research papers\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

IUCrJ
Volume 1| Part 4| July 2014| Pages 228-239
ISSN: 2052-2525

Aniline–phenol recognition: from solution through supramolecular synthons to cocrystals

aSolid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560 012, India, and bMolecular Biophysics Unit, Indian Institute of Science, Bangalore 560 012, India
*Correspondence e-mail: gautam_desiraju@yahoo.com

Edited by A. D. Bond, University of Copenhagen, Denmark (Received 17 February 2014; accepted 24 May 2014; online 12 June 2014)

Aniline–phenol recognition is studied in the crystal engineering context in several 1:1 cocrystals that contain a closed cyclic hydrogen-bonded [⋯O—H⋯N—H⋯]2 tetramer supramolecular synthon (II). Twelve cocrystals of 3,4,5- and 2,3,4-trichlorophenol with one of eight halogenated anilines have been characterized. Ten of these cocrystals contain an extended octamer synthon that is assembled with hydrogen bonding and ππ stacking that defines a Long-Range Synthon Aufbau Module (LSAM). The design strategy is, therefore, based on the construction and transferability of the LSAM, which is a dimer of tetramers. Using the LSAM concept, two short cell axes in the crystal structures can be predicted. Whilst one of them is dictated by synthon II, the other one is dominated by ππ interactions. The third cell axis can also be predicted, in some cases, by systematic tuning of the halogen bonds. The design strategy is also verified in cocrystals of non-halogenated precursors. The observation of this large synthon in so many structures points to its stability and possible existence in solution. To this end, one-dimensional 1H and 15N NMR studies, performed on the 3,4,5-trichlorophenol–3,5-dichloroaniline cocrystal in CDCl3, show characteristic downfield shifts that point to a ππ stacked structure and to the robustness of the hydrogen-bonded aggregates. Nuclear Overhauser effects point to hydrogen bonding between aniline and phenol molecules in the aggregates. Diffusion-ordered spectroscopy and T1 inversion recovery experiments show that stacking is present in concentrated solution and lost at a certain dilution. A sequence of events is therefore established: molecules of the aniline and the phenol associate via hydrogen bonding to form tetramers, and tetramers subsequently stack to form octamers.

1. Introduction

The study of aniline–phenol recognition, in the context of crystal engineering and supramolecular synthons, has been an unusually complex exercise, considering the small size and relative simplicity of the —NH2 and —OH functional groups. At the first level, only the hydrogen-bonding capabilities of the amino and hydroxyl groups appear to be important; Ermer & Eling (1994[Ermer, O. & Eling, A. (1994). J. Chem. Soc. Perkin Trans. 2, pp. 925-944.]) and Hanessian et al. (1994[Hanessian, S., Gomtsyan, A., Simard, M. & Roelens, S. (1994). J. Am. Chem. Soc. 116, 4495-4496.], 1995[Hanessian, S., Simard, M. & Roelens, S. (1995). J. Am. Chem. Soc. 117, 7630-7645.], 1999[Hanessian, S., Saladino, R., Margarita, R. & Simard, M. (1999). Chem. Eur. J. 5, 2169-2183.]) independently predicted that in systems with an equal stoichiometry of —OH and —NH2 groups, there are equal numbers of O—H⋯N and N—H⋯O hydrogen bonds, leading to tetrahedral configurations at both N and O atoms. Allen et al. (1997[Allen, F. H., Hoy, V. J., Howard, J. A. K., Thalladi, V. R., Desiraju, G. R., Wilson, C. C. & McIntyre, G. J. (1997). J. Am. Chem. Soc. 119, 3477-3480.]) showed, however, that this seemingly simple model, which was applied to 4-aminophenol by Ermer, ignores the herringbone interactions of the phenyl rings, as seen in the N—H⋯π-based structures of 2- and 3-aminophenol. The appearance of N—H⋯π interactions in many of these structures is a manifestation of interference between hydrocarbon residues and the hydrogen-bonding groups (Desiraju, 2001[Desiraju, G. R. (2001). Nature 412, 397-400.]). This is a real issue in many aminophenols. Vangala et al. (2003[Vangala, V. R., Bhogala, B. R., Dey, A., Desiraju, G. R., Broder, C. K., Smith, P. S., Mondal, R., Howard, J. A. K. & Wilson, C. C. (2003). J. Am. Chem. Soc. 125, 14495-14509.]) demonstrated that 3-aminophenol is a prototype and that an entire family of methylene-linked aminophenols can be understood as a balance between the infinite ⋯O—H⋯N—H⋯ synthon and various hydrocarbon interactions, including the non-conventional N—H⋯π hydrogen bond. Also described by them is the concept of synthon evolution which may be examined in systems of large enough size and complexity. Dey et al. (2005[Dey, A., Kirchner, M. T., Vangala, V. R., Desiraju, G. R., Mondal, R. & Howard, J. A. K. (2005). J. Am. Chem. Soc. 127, 10545-10559.]) hinted at the importance of large synthons (containing both hydrogen bonds and C—H⋯π herringbone interactions) in the context of crystallization mechanisms in a crystal structure prediction of isomeric methyl aminophenols. The conjoining of hydrogen bonds and hydrocarbon interactions leads to an increase in both complexity and size of certain important synthons in this system and these have been referred to as Long Range Synthon Aufbau Modules (LSAM) by Ganguly & Desiraju (2010[Ganguly, P. & Desiraju, G. R. (2010). CrystEngComm, 12, 817-833.]). These guidelines apply equally well to multi-component systems: Vangala et al. (2004[Vangala, V. R., Mondal, R., Broder, C. K., Howard, J. A. K. & Desiraju, G. R. (2004). Cryst. Growth Des. 5, 99-104.]) studied a series of dianiline–diphenol molecular complexes or cocrystals in this regard. Desiraju (2013[Desiraju, G. R. (2013). J. Am. Chem. Soc. 135, 9952-9967.]) suggested recently that the so-called large synthons or LSAMs in the aminophenols could be a sought-after bridge between small synthons and crystal growth units.

Intermolecular association and aggregation in solution may be probed by NMR spectroscopic methods in a facile manner (Spitaleri et al., 2004[Spitaleri, A., Hunter, C. A., McCabe, J. F., Packer, M. J. & Cockroft, S. L. (2004). CrystEngComm, 6, 490-493.]; Chiarella et al., 2007[Chiarella, R. A., Gillon, A. L., Burton, R. C., Davey, R. J., Sadiq, G., Auffret, A., Cioffi, M. & Hunter, C. A. (2007). Faraday Discuss. 136, 179-193.]; Chadwick et al., 2009[Chadwick, K., Davey, R. J., Dent, G., Pritchard, R. G., Hunter, C. A. & Musumeci, D. (2009). Cryst. Growth Des. 9, 1990-1999.]; Schneider, 2009[Schneider, H.-J. (2009). Angew. Chem. Int. Ed. Engl. 48, 3924-3977.]). The most direct evidence for molecular association/aggregation comes from perturbations in chemical shifts (δ) between the free and the associated form of interacting solutes (Saito et al., 2002[Saito, A., Igarashi, K., Azuma, M. & Ooshima, H. (2002). J. Chem. Eng. Jpn, 35, 1133-1139.]; Spitaleri et al., 2004[Spitaleri, A., Hunter, C. A., McCabe, J. F., Packer, M. J. & Cockroft, S. L. (2004). CrystEngComm, 6, 490-493.]). Perturbations in chemical shifts arise from differences in the magnetic environment that the nuclear spins experience in the free and associated forms. Molecular association may also be inferred from other well established NMR parameters such as the spin-lattice relaxation time constants (T1) (a measure of the time required for the nuclear spins under investigation to return to thermal equilibrium after a perturbation) (Claridge, 2008[Claridge, T. D. W. (2008). High Resolution NMR Techniques in Organic Chemistry, 2nd ed. Amsterdam: Elsevier.]) and from estimates of translational diffusion coefficients (Ds) (Diffusion Ordered Spectroscopy, DOSY, is an experimental method designed to estimate the translational diffusion coefficient of solutes) (Barjat et al., 1995[Barjat, H., Morris, G. A., Smart, S., Swanson, A. G. & Williams, S. C. R. (1995). J. Magn. Reson. Ser. B, 108, 170-172.]; Cohen et al., 2005[Cohen, Y., Avram, L. & Frish, L. (2005). Angew. Chem. Int. Ed. Engl. 44, 520-554.]). The magnitude of Nuclear Overhauser effect (NOE) enhancement is dependent on the fact that the distance of separation between the nuclear magnetic moments must lie within ∼5 Å (Neuhaus & Williamson, 2000[Neuhaus, D. & Williamson, M. P. (2000). The Nuclear Overhauser Effect in Structural and Conformational Analysis, 2nd ed. New York: Wiley-VCH.]). Fortunately, the weak forces that stabilize intermolecular interactions such as hydrogen bonding, van der Waals interactions, hydrophobic interactions or salt bridges act over short distances. Thus, the existence of intermolecular associations may be established by assignment of the NOE between the interacting species. The longitudinal relaxation rates are sensitive to the rotational correlation time (τc) and thus proportional to the molecular size. Similarly, the translational diffusion coefficient is also proportional to the molecular size. A significant advantage of solution NMR methods lies in their ability to explore association/aggregation properties of solutes as a function of solute concentration, and whether or not association/aggregation occurs.

With this background, we initiated a study of the crystal chemistry of a series of phenol–aniline cocrystals based mostly on 3,4,5-trichlorophenol, 1, and halogenated anilines, 310. Phenol 1 has a highly modular crystal structure that may be developed (unusually) from the crystal structures of 4-chloro­phenol and 3,5-dichlorophenol (Mukherjee & Desiraju, 2011[Mukherjee, A. & Desiraju, G. R. (2011). Cryst. Growth Des. 11, 3735-3739.]). It must be noted here that modularity is an inherent property of supramolecular synthons and, in that sense, every crystal structure has certain modular features. However, as weak interactions play a major role at the end stages of crystallization, this modularity is often restricted to the primary synthon level. The unusual feature of phenol 1 is that it shows the rare phenomenon of modularity at a large synthon level. This type of modularity is indicative of high structural insulation, which is useful for the type of study performed here. The family of structures studied here, therefore, lends itself particularly well to the principles of crystal engineering and also provides an opportunity for the study of large synthons in solution and their evaluation as intermediates during crystallization.[link]

[Scheme 1]

2. Experimental

2.1. Synthesis and single-crystal X-ray diffraction

The cocrystals were prepared generally via solvent drop grinding (see supporting information for details), except those with 3-chloroaniline, which is a liquid at ambient conditions. Single crystals were obtained mostly by solvent evaporation except in a few cases where crystals were obtained by sublimation. The details of the crystallization procedure for each cocrystal are given in the supporting information . After obtaining crystals of suitable size and quality, single-crystal X-ray data were collected on a Rigaku Mercury375R/M CCD (XtaLAB mini) diffractometer using graphite-monochromated Mo Kα radiation. The instrument was attached to a Rigaku low-temperature gas-spray cooler. The data were processed with the CrystalClear software (Rigaku, 2009[Rigaku (2009). Crystal Clear-SM Expert 2.0. Rigaku Corporation, Tokyo, Japan.]). Structure solution and refinements were performed using SHELX97 incorporated within the WinGX suite (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]; Farrugia, 1999[Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.]).

2.2. Database studies

A search of the Cambridge Structural Database (CSD, Version 5.34, with updates to May 2013; Allen, 2002[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]) was performed to find crystal structures which contain both aniline and phenol residues. The search was restricted according to the following criteria: three-dimensional structures determined, R < 0.075, not disordered, no errors, not polymeric, no ions, no powder structures, only organics. The resulting structures were analysed manually to identify synthon patterns and their relative frequencies.

2.3. NMR spectroscopic techniques

NMR spectra were acquired on Bruker 400 or 500 MHz NMR spectrometers or on an Agilent 600 MHz NMR spectrometer. All spectra were acquired at 298 K. A 1H spectral width of 10 p.p.m. was sampled at all field strengths. A 13C spectral width of 100 p.p.m. was sampled at all field strengths. One-dimensional 15N spectra were recorded at 600 MHz at natural abundance, using a spectral width of 12 019 Hz. Urea (BrukerBiospin Standard, 0.1 M 15N-urea in dimethyl sulfoxide) was taken as a reference compound. A total of 64, 8192, 16 384 and 81 920 transients were recorded for the urea reference, and for samples A, E and F (see below). During acquisition, a 5 kHz field was applied to achieve proton decoupling. 15N chemical shifts are referenced to external DSS (Cavanagh et al., 2007[Cavanagh, J., Fairbrother, W. J., Palmer, A. G., Rance, M. & Skelton, N. J. (2007). Protein NMR Spectroscopy, Principles and Practice. New York: Elsevier Academic Press.]). 1H and 13C chemical shifts are referenced to internal TMS (0.0 p.p.m.) and CDCl3 (solvent, 77 p.p.m.), respectively.

2.3.1. Sample preparation

3,4,5-Trichlorophenol and 3,5-dichloroaniline were taken in a 1:1 molar ratio and ground together in a mortar to obtain cocrystal 14. The resulting powder was dissolved in CDCl3 to obtain a concentration of 1.25 M. This concentration is taken as the starting point in the dilution study and is called A. This solution was then diluted gradually from A to B (1 M) to C (0.8 M) to D (0.7 M) to E (0.625 M) and finally to F (0.125 M). Solutions of 1,2,3-trichlorobenzene were prepared in a similar manner from a stock solution (1.25 M) and labelled A1 to F1.

2.3.2. Chemical shift perturbation

One-dimensional NMR spectra of solutions A to F (14) and A1 to F1 (1,2,3-trichloro­benzene) were recorded on the Bruker 400 MHz NMR spectrometer using a BBI probe fitted with a single (z-axis) pulsed field gradient (PFG) accessory. All spectra were processed using TopSpin 3.2 software (Bruker, 2014[Bruker (2014). TopSpin 3.2. Bruker BioSpin GmbH, Rheinstetten, Germany.]).

2.3.3. Estimation of longitudinal relaxation time constants (T1)

Data for T1 estimation of 13C in samples of A, E and F (14) and A1, E1 and F1 (1,2,3-trichlorobenzene) were acquired using the T1 inversion recovery method (Claridge, 2008[Claridge, T. D. W. (2008). High Resolution NMR Techniques in Organic Chemistry, 2nd ed. Amsterdam: Elsevier.]). Data were acquired on the Bruker 500 MHz spectrometer using a TXI probe fitted with a z-axis PFG accessory and the Agilent 600 MHz NMR spectrometer using an IDTRPFG probe fitted with a z-axis gradient accessory. Interscan delays of 15 and 25 s were maintained at 500 and 600 MHz, respectively. 13C T1 values were measured from spectra recorded with 25 different durations of the recovery delay at 500 MHz: τ = 50, 100, 500 ms, 1.0–8.0 s in steps of 0.5, 9, 10, 12, 15, 18, 21 and 25 s. T1 values at 600 MHz were measured from 13 different durations of the recovery delay for sample A: τ = 100, 500 ms, 1.0–5.0 s in steps of 0.5, 7.5 and 10 s; and from 11 different durations of the recovery delay for samples E and F: τ = 0.1, 0.5, 1, 2, 4, 6, 8, 10, 12.5, 15 and 20 s. Spectra were processed using the VnmrJ 3.2A software (Agilent, 2012[Agilent (2012). VnmrJ 3.2A. Agilent Technologies Inc., Santa Clara, California, USA.]). The peak heights were fitted to the equation

[I_t = I_0+ A \exp(-t/T_{1}),]

where It is the peak height at time t, I0 is the peak height at t = 0 and A is a constant. T1 values were calculated using peak-fitting routines in VnmrJ 3.2A.

2.3.4. Difference NOE experiments

Difference NOE spectra (Neuhaus & Williamson, 2000[Neuhaus, D. & Williamson, M. P. (2000). The Nuclear Overhauser Effect in Structural and Conformational Analysis, 2nd ed. New York: Wiley-VCH.]) on solutions A, E and F (14) and A1, E1 and F1 (1,2,3-trichlorobenzene) were acquired on the Agilent 600 MHz NMR spectrometer using the IDTRPFG probe fitted with a z-axis PFG accessory. Low power saturation was applied for 3 s followed by data acquisition. In the case of the no-saturation experiment, the transmitter was placed at −2 p.p.m. A relaxation delay of 25 s was maintained between transients.

2.3.5. Estimation of translational diffusion coefficients

Translational diffusion coefficients were measured using the one-dimensional DOSY bipolar pulsed pair gradient stimulated echo experiment (Stejskal & Tanner, 1965[Stejskal, E. O. & Tanner, J. E. (1965). J. Chem. Phys. 42, 288-292.]; Johnson, 1999[Johnson, C. S. (1999). Prog. Nucl. Magn. Reson. Spectrosc. 34, 203-256.]) on the Agilent 600 MHz NMR spectrometer. All spectra were acquired using the IDTRPFG probe fitted with a z-axis PFG accessory. Data were acquired at three values of the diffusion delay (75, 85 and 100 ms) for gradient strengths (G cm−1) of 2.10, 2.73, 4.62, 10.07, 18.55, 25.02, 30.60, 35.29, 39.43, 43.18, 46.63, 49.84, 52.85, 55.70, 58.41, 61.00, 63.49, 65.88 and 68.20. A relaxation delay of 25 s was maintained between successive transients. Bipolar pulsed field gradients were applied for a total duration of 2 ms and a gradient recovery delay time of 500 µs introduced prior to application of RF pulses. Spectra were processed using VnmrJ 32A software. The translational diffusion coefficient (D) was obtained by fitting to the equation

[I_G = I_{G = 0} \exp[-(\gamma \delta G)^{2} D (\Delta -\delta/3- \tau_{\rm g}/2)],]

where IG is the observed signal intensity, IG=0 is the signal intensity in the absence of the gradient spin-echo, G is the gradient strength (Gauss cm−1), D is the diffusion coefficient (m2 s−1), γ is the gyromagnetic ratio of the observed nucleus, τg is the gradient recovery delay (s), Δ is the diffusion time (s) and δ is the duration of the gradient pulse (s).

3. Results and discussion

The supramolecular synthons referred to in this study are shown in Fig. 1[link]. The main patterns are synthons I and II. Synthon I, which is an infinite open ⋯O—H⋯N—H⋯ chain, is the most common pattern in the family and is found in both 3- and 4-aminophenol prototypes. In 3-aminophenol, the second `free' N—H group is involved in an N—H⋯π interaction. In 4-aminophenol, the infinite chains criss-cross each other to give closed hexamers, III, with a cooperative [⋯O—H⋯N—H⋯]3 arrangement. The main closed pattern in the family is the tetramer synthon II, [⋯O—H⋯N—H⋯]2, which is the target synthon in the present study.

[Figure 1]
Figure 1
Supramolecular synthon possibilities in the aniline–phenol cocrystals in this study.

3.1. Aniline–phenol recognition: general considerations

A CSD study was performed to examine aniline–phenol recognition in aromatic compounds. A total of 176 hits were obtained that contain both aniline (—NH2) and phenol (—OH) fragments. Of this number, 77 (44%) contain O—H⋯N hydrogen bonds, the strongest hydrogen bond possible in this family. These 77 hits may be divided into 48 single-component and 29 multi-component structures. Analysis of the 48 single-component structures shows that 19 have the 3-aminophenol structure. Ten structures take the 4-aminophenol structure, which includes synthon III. Synthon III arises due to the compatibility between geometric and chemical factors of the —OH and —NH2 groups at the 1- and 4-positions of the aromatic ring. In the 3-aminophenol structure, the positional compatibility between —NH2 and —OH is lost, and geometrical factors play a major role in determining the final herringbone structure. As a result, the synthon pattern deviates from III and an additional N—H⋯π interaction is observed in this structure. The structure of 3-aminophenol is indicative of the fact that if the cooperativity between —NH2 and —OH groups is perturbed, the synthon pattern deviates from synthon III. Seven structures have the closed tetramer structure, II, while three have infinite ⋯O—H⋯N—H⋯ chains (synthon I) without N—H⋯π interactions. The remaining nine structures show interaction interference: absence of N—H⋯O [CSD refcodes AMNPHA (Haisa et al., 1980[Haisa, M., Kashino, S. & Kawashima, T. (1980). Acta Cryst. B36, 1598-1601.]), NODTIJ (Blagden et al., 2001[Blagden, N., Cross, W. I., Davey, R. J., Broderick, M., Pritchard, R. G., Roberts, R. J. & Rowe, R. C. (2001). Phys. Chem. Chem. Phys. 3, 3819-3825.]) and HIWNEH (Largeron et al., 2008[Largeron, M., Chiaroni, A. & Fleury, M.-B. (2008). Chem. Eur. J. 14, 996-1003.])]; finite chains [CSD refcodes GIVRIM (Mahmoud et al., 1998[Mahmoud, H., Han, Y., Segal, B. M. & Cai, L. (1998). Tetrahedron Asymm. 9, 2035-2042.]), SADJAK (Kar et al., 2010[Kar, G. P., Karmakar, A. & Baruah, J. B. (2010). J. Chem. Cryst. 40, 702-706.]), UHEVOT (Bacchi et al., 2009[Bacchi, A., Carcelli, M., Chiodo, T., Cantoni, G., De Filippo, C. & Pipolo, S. (2009). CrystEngComm, 11, 1433-1441.]) and WURNHZ (Lu et al., 2010[Lu, H., Xue, Z., Mack, J., Shen, Z., You, X. & Kobayashi, N. (2010). Chem. Commun. 46, 3565-3567.])]; hexamer synthon composed of O—H⋯N, N—H⋯O, O—H⋯O, N—H⋯N [CSD refcodes PEJCAJ and PEJCAJ01 (Dey & Desiraju, 2006[Dey, A. & Desiraju, G. R. (2006). CrystEngComm, 8, 477-481.])].

The 29 multi-component structures are distinct in that 14 of them are quite free from interference from other functionalities and show clear structural preferences. Ten of them have the [⋯O—H⋯N—H⋯]3 hexamer in the 4-aminophenol structure and three have the [⋯O—H⋯N—H⋯]2 tetramer (Van Bellingen et al., 1971[Van Bellingen, I., Germain, G., Piret, P. & Van Meerssche, M. (1971). Acta Cryst. B27, 553-559.]). The infinite ⋯O—H⋯N—H⋯ chain, without N—H⋯π interactions and without hexamers, is seen in one structure. Generally, the multi-component crystals take the 4-aminophenol structure; the tetramer is uncommon and other outlier structures are rarely seen. Could it be that the very formation of a multi-component crystal is already accompanied in the early stages with a funnelling into a certain pathway that is mediated by ⋯O—H⋯N—H⋯ hydrogen bonding? The following observations on the ten tetramer structures (seven single-component and three multi-component) are relevant: (i) in all three multi-component crystals [CSD refcodes FIDLIO, FIDLOU (Vangala et al., 2004[Vangala, V. R., Mondal, R., Broder, C. K., Howard, J. A. K. & Desiraju, G. R. (2004). Cryst. Growth Des. 5, 99-104.]) and SARLEC (Loehlin et al., 1998[Loehlin, J. H., Franz, K. J., Gist, L. & Moore, R. H. (1998). Acta Cryst. B54, 695-704.])], the aniline contains more than one —NH2 group and/or the phenol contains more than one —OH group; (ii) in five of the seven single-component crystals, ππ interactions (stacking of aromatic rings) are present. With these observations, we attempted to formulate a design strategy for aniline–phenol cocrystals that would lend themselves to NMR study in solution, in order that the presence of large synthons (LSAMs) might be detected in solution prior to crystallization. A synthon consisting of both hydrogen-bonded and π-stacked regions, as shown in Fig. 2[link], was identified as one such strategy.

[Figure 2]
Figure 2
Construction of the target LSAM by amalgamation of hydrogen bonding and ππ stacking.

3.2. Aniline–phenol recognition: crystal engineering

3.2.1. Design strategy for cocrystals

The ability to anticipate packing patterns in crystal structures based on known structures is a daunting task when the database of known structures is small. It is even more difficult to design structures that are based on synthons which are not the most common ones in the respective family. CSD studies showed that tetramer structures are not the most common but that they may be favoured when there is an additional stability from ππ stacking (Hunter & Sanders, 1990[Hunter, C. A. & Sanders, J. K. M. (1990). J. Am. Chem. Soc. 112, 5525-5534.]). Given that we were searching for a synthon of the type shown in Fig. 2[link], our attention shifted naturally to synthon II. The design of aniline–phenol cocrystals based on synthon II is difficult because the aromatic rings can themselves be a part of a synthon (say with N—H⋯π) and interfere with other functionalities, notably the —NH2 group. Therefore, successful design of crystal structures containing synthon II may need steering groups which can form strong ππ interactions that may eventually decrease the interference from the rest of the molecule (Desiraju et al., 2011[Desiraju, G. R., Vittal, J. J. & Ramanan, A. (2011). Crystal Engineering: a Textbook. Singapore: World Scientific.]). In this context, we chose 3,4,5-trichlorophenol, 1, as the main compound in this study. The 2,3,4 isomer, 2, was also used in some experiments. In 1, the phenolic —OH group and the Cl atoms are well separated. The electron-deficient nature of the aromatic ring was also expected to favour ππ stacking. For steric and electronic reasons, phenol 1 was selected for cocrystallization with several halogenated anilines in order to obtain recurring packing patterns in the respective cocrystals. The coformers used are anilines 310.

Phenol 1 was taken with 4-chloroaniline (3) in 1:1 n-hexane–MeOH in an equimolar ratio to give cocrystal 11 (Table 1[link]). The primary synthon in this structure is the desired closed tetramer II (Fig. 3[link]a) which consists of alternating aniline and phenol molecules. The aniline ring is tilted at an angle of 53.4° to the phenol ring. The phenol rings in adjacent tetramers are stacked in an antiparallel manner roughly down the a axis (Fig. 3[link]b). The stacked dimer (octamer) in Fig. 3[link](b) is of great importance because it corresponds to the LSAM that is monitored with NMR in the second part of this study. The extended structure propagates in a sort of double layer that is aligned along [210] as shown in Fig. 3[link](c). The double layers are themselves loosely associated in the c-axis direction with halogen atom interactions (Fig. 3[link]d). The periphery of the double layer is halogen-rich.

Table 1
Summary of crystallographic information for cocrystals 1125

  11 12 13 14 15
Formula C6H3Cl3O·C6H6ClN C6H3Cl3O·C6H6ClN C6H3Cl3O·C6H5Cl2N C6H3Cl3O·C6H5Cl2N C6H3Cl3O·C6H5Cl2N
Crystal system Triclinic Monoclinic Monoclinic Monoclinic Triclinic
Space group [{P\bar 1}] P21/c P21 I2/a [{P\bar 1}]
a (Å) 7.0243 (14) 6.9676 (7) 7.0572 (6) 22.638 (5) 7.0681 (6)
b (Å) 9.4152 (18) 21.336 (2) 15.4665 (13) 7.2553 (11) 9.5008 (8)
c (Å) 10.928 (2) 9.1861 (10) 13.2112 (11) 18.013 (3) 11.4095 (9)
α (°) 82.750 (6) 90 90 90 85.402 (6)
β (°) 79.147 (6) 99.139 (7) 98.980 (7) 90.767 (9) 83.071 (6)
γ (°) 76.703 (5) 90 90 90 71.211 (5)
Volume (Å3) 688.2 (2) 1348.3 (2) 1424.3 (2) 2958.3 (9) 719.36 (11)
Z 2 4 4 8 2
CCDC No. 962085 962086 962087 962088 962089
  16 17 18 19 20
Formula C6H3Cl3O·C6H6BrN C6H3Cl3O·C6H6IN C6H4ClIN·C6H3Cl3O C6H3Cl3O·C6H6ClN C6H3Cl3O·C6H6ClN
Crystal system Triclinic Triclinic Triclinic Monoclinic Triclinic
Space group [{P\bar 1}] [{P\bar 1}] [{P\bar 1}] P21/c [{P\bar 1}]
a (Å) 7.0562 (15) 7.083 (3) 7.107 (2) 7.851 (5) 7.208 (9)
b (Å) 9.373 (2) 9.354 (4) 9.498 (3) 11.865 (7) 9.333 (10)
c (Å) 11.110 (2) 11.456 (5) 11.827 (3) 14.891 (8) 10.884 (13)
α (°) 83.358 (6) 84.118 (7) 85.425 (6) 90 99.035 (14)
β (°) 79.173 (6) 79.555 (7) 81.804 (6) 106.79 (3) 107.107 (6)
γ (°) 76.588 (5) 76.553 (7) 71.851 (5) 90 102.219 (10)
Volume (Å3) 700.0 (2) 724.5 (5) 750.4 (4) 1328.0 (14) 664.8 (14)
Z 2 2 2 4 2
CCDC No. 962090 962091 962092 962094 962093
  21 22 23 24 25
Formula C6H3Cl3O·C6H5Cl2N C6H3Cl3O·C6H5Cl2N C7H6O3·C7H8N2O C7H6O3·C7H8N2O C14H12O8·2C7H8N2O
Crystal system Triclinic Triclinic Monoclinic Monoclinic Triclinic
Space group [{P\bar 1}] [{P\bar 1}] C2/c P21/c [{P\bar 1}]
a (Å) 7.1441 (8) 7.2060 (8) 24.698 (2) 12.410 (15) 4.760 (2)
b (Å) 9.3027 (10) 9.2558 (10) 5.1072 (5) 5.124 (6) 11.501 (6)
c (Å) 11.8726 (13) 11.3203 (12) 20.6682 (19) 20.06 (2) 12.539 (6)
α (°) 77.966 (5) 99.693 (7) 90 90 77.081 (6)
β (°) 74.889 (5) 99.616 (7) 99.673 (12) 92.901 (14) 86.975 (6)
γ (°) 77.979 (5) 101.387 (7) 90 90 81.302 (6)
Volume (Å3) 735.06 (14) 713.76 (14) 2570.0 (4) 1274 (2) 661.3 (5)
Z 2 2 8 4 1
CCDC No. 962095 967791 962096 962097 962098
†Structures 20 and 22 are reported using their formal reduced cells, which have obtuse rather than acute angles. The cells are nonetheless comparable with those of 11, 15, 16, 17, 18 and 21; all of these cocrystals are essentially isostructural.
[Figure 3]
Figure 3
(a) Hydrogen-bonded tetramer synthon, II, in cocrystal 11; (b) antiparallel ππ stacking of trichlorophenol rings in adjacent tetramers to give the LSAM (compare with Fig. 2[link]); (c) arrangement of the LSAMs along [210]; (d) association of the LSAMs along [001] with halogen atom synthons (shown in green).

Synthon II was expected to be of high modularity. The chloro-substitution pattern of the aniline may change the width of the module slightly but its length remains almost the same because it is a function of the molecular size of phenol 1. This means that cocrystals that may be obtained when phenol 1 is taken with other related anilines should have nearly the same crystal structure as 11 with the a and b axes practically the same (within a particular crystal system or space group), and with the c axis varying slightly depending on the substitution pattern in the aniline. This expectation was borne out in practice (Table 1[link]).

3.2.2. Significance of LSAMs

Crystal engineering seeks a modular way to describe a structure. Transfer of smaller structural units (synthons, LSAMs) simplifies the complex task of comparing interaction strengths to one of putting structural modules together. To this end, and analogous to the Aufbau modules proposed originally by Kitaigorodskii (1961[Kitaigorodskii, A. I. (1961). Organic Chemical Crystallography. New York: Consultants Bureau.]), Ganguly & Desiraju (2010[Ganguly, P. & Desiraju, G. R. (2010). CrystEngComm, 12, 817-833.]) proposed the concept of the LSAM. In this notation, a crystal can be dissected into long-range larger synthons which are modular and therefore the crystal structure can be described by different arrangements of these modules. Long-range synthons can be formed by various combinations of different small/large synthons. In the context of this paper, we consider O—H⋯N and N—H⋯O as the primary synthons, the tetramer synthon (II) as the larger secondary synthon and a combination of two tetramers through ππ interactions as the octamer LSAM. One of the objectives of this work is to find out how the LSAMs can be transferred from one structure to another and how this transferability contributes to the overall predictability of the crystal structures. The cocrystallization of 1 with 4, 6 and 7 produced cocrystals 12, 14 and 15, respectively. As hypothesized in the preceding paragraph, all four structures adopt structures similar to that of 11 (Fig. 4[link]).

[Figure 4]
Figure 4
Octamer LSAMs in cocrystals 12 (a), 14 (b) and 15 (c). The width shown in these figures is calculated as the distances between the 4-substituents in two aniline molecules in the tetramer II. Compare with Fig. 3[link](b) and Fig. 2[link].

In cocrystal 12, the change in position of the Cl atom on the aniline periphery causes a structural variation in the long direction. In 11, Cl in the 4-position forms Cl⋯Cl halogen bonds with neighbouring LSAMs whereas in 12, Cl in the 3-position forms an intra-LSAM halogen bond. Cocrystal 14 shows similarity with 12 in the organization along the long-axis dimension because the Cl-substituent positioning in 6 is similar to 4. Curiously, this structure shows an unusually large excess electron density in the Fourier map in the 4-position of the aniline. This excess density may arise from a small number of domains of pure 3,4,5-trichlorophenol which have an O—H⋯O tetramer in its native structure. The implication is that tetramers of pure 1 and of the aniline–phenol adduct (II) are present in solution and that a small amount of the former is included in the cocrystal in a solid solution manner. Cocrystal 15 contains an aniline analogue, 7, which is also substituted with Cl in 3- and 4-positions. The Cl in the 3-position shows partial occupancy and, therefore, 7 behaves like a 3,4,5-trichloroaniline. This substitution pattern favours antiparallel stacking (Fig. 5[link]). Therefore, in 15, there is stacking of both phenol and aniline rings. A very short Cl⋯Cl type I contact of length 3.078 (1) Å is observed which connects two LSAMs.

[Figure 5]
Figure 5
Cocrystal 15. (a) LSAM formed by ππ stacking between molecules of 3,4,5-trichlorophenol, (b) alternative LSAM formed by ππ stacking between molecules of 3,4-dichloroaniline, (c) combination LSAM.
3.2.3. LSAM organization: tuning with halogen bonds

The structure of the octamer LSAM in cocrystal 11 indicates that Cl in the 4-position in 3, which lies on the periphery of the LSAM, controls the organization of the LSAMs in the direction of the long axis. In this context, it was assumed that replacing Cl with Br or I may lead to better control in the long-axis direction. Accordingly, cocrystals 16 and 17 were prepared. When 1 is cocrystallized with 8, it gives 16 (Table 1[link]). The LSAM remains intact as reflected in the a- and b directions. The c direction (which is longer than the corresponding length in 11) is controlled by a Br⋯Cl type II interaction which is 3.489 (1) Å in length. With the success of the hypothesis that the halogen bond can control the strength and directionality in the long crystal axis direction, we tried to cocrystallize 9 with 1 in the next step, resulting in cocrystal 17. The replacement of Br with I results in a cocrystal with a similar structure (Table 1[link]). The c direction is determined by an I⋯Cl interaction of 3.583 (1) Å in length. When 1 is crystallized with 10 it results in 18, which has a longer c axis than 15 (Table 1[link]). These results show that the increased control in engineering the packing in the longer crystal axis direction (mostly the c axis in our study) can be obtained by introducing halogen bonds (Metrangolo et al., 2005[Metrangolo, P., Neukirch, H., Pilati, T. & Resnati, G. (2005). Acc. Chem. Res. 38, 386-395.]) oriented in that direction (Fig. 6[link]). It is also shown that if insulating interactions with variable strengths are incorporated in almost perpendicular directions, it is possible to predict the crystal structures. The notable point in these structures is that the common structural part is not restricted to tetramer synthon II. The larger octamer LSAM, which is obtained by ππ stacking of two tetramers, is impressively repeated in as many as seven cocrystal structures. This observation leads to the possibility that LSAMs may also exist in solution.

[Figure 6]
Figure 6
Halogen bonds used in tuning the longer direction in the cocrystals (a) 16, (b) 17 and (c) 18.
3.2.4. Transferability of tetramer and LSAM

The octamer LSAM remains intact even when phenol 2 is cocrystallized with 3, 6 and 7 to produce 20, 21 and 22 (Fig. 7[link]). The tetramer II is translated to LSAMs with an inversion centre between two molecules of 2 to facilitate the stacking. The increase in the c-axis length in 21 compared with 20 (Table 1[link]) results from the symmetric arrangement of Cl atoms in 6, which gives rise to an extra Cl⋯Cl type I contact, compatible with triclinic inversion symmetry. It is important to note that the same LSAM is found in cocrystals formed by phenols 1 and 2, as manifested in the lengths of the two shorter cell axes in cocrystals 20, 21 and 22 being practically the same as the corresponding ones in cocrystals 11, 12 and 1418.

[Figure 7]
Figure 7
Cocrystal structures formed with 2 and showing the presence of the octamer LSAM: (a) 20, (b) 21, (c) 22.

Cocrystal 19, on the other hand, shows the presence of tetramer II but the LSAM is not the same (Fig. 8[link]). Instead of phenol–phenol antiparallel stacking as in 20, 21 and 22, there is phenol–aniline stacking between molecules of 2 and 4. Although only four cocrystals of phenol 2 were studied, it appears that there is more structural variability in these structures compared with the seven cocrystals formed by phenol 1. Perhaps the more distant positioning of the —OH group and Cl atoms in 1 leads to a certain amount of insulation and consequent predictability of the crystal structures.

[Figure 8]
Figure 8
Tetramer synthons observed in cocrystal 19. The LSAM is not observed.
3.2.5. Distorted LSAMs

The LSAM is a finite entity and its size and shape depends on the positioning of the functional groups. When 1 is cocrystallized with 5 it gives 13, which contains distorted LSAMs (Fig. 9[link]). The uneven positioning of Cl atoms on the ring periphery of 2,5-dichloroaniline restricts the structure from adopting the common LSAM observed in cocrystals 11, 12, 14, 15, 16, 17 and 18. Two 3,4,5-trichloro­phenol molecules are still stacked with each other by ππ interactions, but unlike the other structures, they are not stacked in an antiparallel fashion. Therefore, the distorted LSAM in this structure may be attributed to the uneven positioning of Cl atoms on the aniline periphery, which facilitates the formation of C—H⋯Cl hydrogen bonds. Perhaps this hints that hydrogen bonding precedes stacking in solution.

[Figure 9]
Figure 9
Distorted LSAM observed in cocrystal 13.
3.2.6. Transferability of the tetramer synthon to other cocrystals

The next objective of the study was to test the applicability of the proposed design strategy: the transferability of the tetrameric synthons was checked in more complex multi-functional non-halogenated cocrystals where other hydrogen bonding is possible. In other words, what is the robustness of synthon II in the presence of other strong hydrogen bonds? The coformers used in these studies contain functional groups like amides and acids which are able to form strong hydrogen bonds. The observation of the tetrameric synthon in these cocrystals would depend upon the relative positions of the functional groups as they are not completely insulated from each other. It is well known that functional groups in 1- and 4- positions often interfere, especially if both of them are quite strong and directional in nature. Keeping this aspect of crystal design in mind, we chose 3-aminobenzamide for crystallization with 4-hydroxybenzoic acid and 3-aminobenzoic acid. When 3-aminobenzamide was cocrystallized with 4-hydroxybenzoic acid, it resulted in the formation of a 1:1 cocrystal (23) which shows the presence of a tetramer synthon (Fig. 10[link]). The cocrystallization of 3-aminobenzamide with 3-aminobenzoic acid gives cocrystal 24 which also sustains tetramer II (Fig. 10[link]).

[Figure 10]
Figure 10
Transferability of the tetrameric synthon to other cocrystals: (a) 23, (b) 24.

When 4-aminobenzamide is cocrystallized with 3,5-dihydroxybenzoic acid, it results in cocrystal 25, which is also sustained by the aniline–phenol tetramer II (Fig. 11[link]). The interesting aspect in this structure is the presence of amide–amide and acid–acid interactions. This is very rare in the sense that when acid and amide are present in a cocrystal system they usually tend to form acid–amide heterosynthons in lieu of homosynthons (Allen et al., 1999[Allen, F. H., Motherwell, W. D. S., Raithby, P. R., Shields, G. P. & Taylor, R. (1999). New J. Chem. 23, 25-34.]). A CSD search performed on the aromatic acid–aromatic amide multi-component crystals gave 37 hits, among which 13 (35.1%) structures have amide–amide dimers. A manual analysis of these 13 structures revealed that there is no structure wherein the acid–acid dimer is also present. This implies that aniline–phenol recognition is so persistent that even the `normal' behaviour of acid and amide functionalities is modified. This observation also reinforces the strength and robustness of the tetramer synthon.

[Figure 11]
Figure 11
The cocrystal of 3,5-dihydroxybenzoic acid and 4-aminobenzamide (25) shows the formation of the tetrameric synthon. Thereafter, it translates into the formation of a predictable network.

3.3. Synthon structure in solution

The understanding of crystal nucleation and growth is still at a nascent stage (Davey et al., 2013[Davey, R. J., Schroeder, S. L. M. & ter Horst, J. H. (2013). Angew. Chem. Int. Ed. Engl. 52, 2166-2179.]; Erdemir et al., 2009[Erdemir, D., Lee, A. Y. & Myerson, A. S. (2009). Acc. Chem. Res. 42, 621-629.]; Weissbuch et al., 2003[Weissbuch, I., Lahav, M. & Leiserowitz, L. (2003). Cryst. Growth Des. 3, 125-150.]; Derdour & Skliar, 2012[Derdour, L. & Skliar, D. (2012). Cryst. Growth Des. 12, 5180-5187.]; Vekilov, 2010[Vekilov, P. G. (2010). Cryst. Growth Des. 10, 5007-5019.]). The region of the crystallization reaction coordinate (structural landscape) between the late stages of nucleation and the early stages of growth is still far from understood (Desiraju, 2007[Desiraju, G. R. (2007). Angew. Chem. Int. Ed. Engl. 46, 8342-8356.]). In this context, it is of interest to know whether synthons that have been identified in crystals may actually be defined in solution. There are very few studies available to this end. An FTIR study by Davey and co-workers of tetrolic acid shows the presence of dimer and catemer synthons in solution (Parveen et al., 2005[Parveen, S., Davey, R. J., Dent, G. & Pritchard, R. G. (2005). Chem. Commun. pp. 1531-1533.]). In a more recent study, ter Horst and co-workers performed an FTIR and Raman study on isonicotin­amide to probe the formation of homo- and heterosynthons in solution (Kulkarni et al., 2012[Kulkarni, S. A., McGarrity, E. S., Meekes, H. & ter Horst, J. H. (2012). Chem. Commun. 48, 4983-4985.]). Both of these studies indicate that there is a possibility of carry-over of the small synthons from solution to the crystal if classical nucleation theory operates. However, these studies are silent about larger synthons and LSAMs. In the present study, the robustness of the tetramer synthon II and corresponding octamer LSAM prompted us to look at the aggregation behaviour in solution, through the following NMR studies.

3.3.1. Chemical shift perturbation as a function of concentration

Fig. 12[link] shows one-dimensional 1H NMR spectra of 14 in CDCl3 at various dilutions. A single set of resonances that can be assigned to the aniline and phenol fragments is observed. This indicates that in solution the sample is homogeneous and that the fragments do not exhibit conformational exchange. A downfield shift of the 2, 6 protons (δ ∼ 6.8 p.p.m.) of 1 as a function of dilution (AE) is clearly observed, indicating stacking of the aromatic rings. The abrupt shift in going from E to F shows that aromatic stacking interactions are lost at this point. The aromatic protons of aniline (δ ∼ 6.55 and ∼ 6.74 p.p.m.) are largely unaffected upon dilution. Noting that the phenol rings are stacked in the crystal structure of 14, the downfield shift of the phenol protons may arise from the presence of the octamer species in solution, or it may arise from a simple stacking of isolated phenol molecules. To distinguish between these possibilities, samples A, E and F were studied to estimate association and comparative molecular sizes using NOEs, measurement of T1 relaxation rates and translational diffusion coefficients.

[Figure 12]
Figure 12
Chemical shift as a function of dilution (AF) of 14 in CDCl3. In F, δ 6.88 (H2, H6 of 1), δ 6.74 (H4 of 6), δ 6.55 (H2, H6 of 6). A significant upfield shift of the H2, H6 protons of 1, combined with overall line-narrowing is observed upon dilution from E to F.
3.3.2. One-dimensional difference NOE experiments

Having established the aromatic stacking interactions in solution, we proceeded to an NOE (Neuhaus & Williamson, 2000[Neuhaus, D. & Williamson, M. P. (2000). The Nuclear Overhauser Effect in Structural and Conformational Analysis, 2nd ed. New York: Wiley-VCH.]) study of 14, to examine the possibility of aniline–phenol hydrogen bonding in solution, and in turn the presence of tetramer II. Saturation of the H2, H6 protons of 6 and the resulting NOE on the proximal H2, H6 protons of 1 (Fig. 13[link]a) confirms hydrogen bonding between —NH2 and —OH groups. The peaks at δ 6.7 and 6.9 p.p.m. are the NOE difference peaks of the H2, H6 protons of 1. The presence of these peaks at all three dilutions indicate that the hydrogen bonding between 1 and 6 is intact in solution. Based on the robustness of tetramer synthon II in the crystal structures in this study, the CSD results on earlier aniline–phenol cocrystals, and the CSP results given by Dey et al. (2005[Dey, A., Kirchner, M. T., Vangala, V. R., Desiraju, G. R., Mondal, R. & Howard, J. A. K. (2005). J. Am. Chem. Soc. 127, 10545-10559.]), we conclude that the hydrogen bonding is prevalent in a cyclic closed tetramer, II, in solution (Fig. 13[link]b). Finally these data, when taken in conjunction with the chemical shift data discussed above, would indicate that the stacking interactions responsible for the formation of the LSAM is preceded by the hydrogen-bonded association of 1 and 6 to form the tetramer synthon.

[Figure 13]
Figure 13
(a) NOE difference spectra of solutions A, E and F. Negative NOE peaks are observed in the difference spectra at all three dilutions. The difference NOE peaks indicate that the hydrogen bonding between 1 and 6 is intact. (b) The saturation of the H2, H6 protons of 6 should result in a NOE effect on the H2, H6 protons of 1.
3.3.3. Longitudinal relaxation time constants (T1)

13C T1 relaxation time constants (Table 2[link]) were measured using the T1 inversion recovery pulsed method (Claridge, 2008[Claridge, T. D. W. (2008). High Resolution NMR Techniques in Organic Chemistry, 2nd ed. Amsterdam: Elsevier.]). In general, for solutes in non-viscous solvents, the T1 relaxation time constant increases as the molecular size decreases. This is due to a decrease in the rotational correlation time. From the values in Table 2[link], it is clear that T1 increases from AEF, in other words with increasing dilution; this is strongly suggestive of dissociation from octamer to tetramer species.

Table 2
T1 relaxation time constants (s) for solutions A, E and F

  3,4,5-Trichlorophenol 3,5-Dichloroaniline
  C2, C6 C2, C6 C4
A 3.60 2.15 3.05
E 4.31 2.77 3.58
F 5.64 3.42 4.85
3.3.4. Estimation of translational diffusion coefficients (Ds)

To differentiate the sizes of various molecular aggregates in solution, the translational diffusion coefficients of molecular species in solutions A, E and F were measured using the bipolar pulsed gradient stimulated echo sequence (Stejskal & Tanner, 1965[Stejskal, E. O. & Tanner, J. E. (1965). J. Chem. Phys. 42, 288-292.]; Johnson, 1999[Johnson, C. S. (1999). Prog. Nucl. Magn. Reson. Spectrosc. 34, 203-256.]). Fig. S4 in the supporting information is an example of the one-dimensional diffusion NMR spectra obtained at 600 MHz. Fig. S5 shows the two-dimensional representation of the experimentally derived translational diffusion coefficients. Since the translational diffusion coefficient is inversely proportional to the radius of the molecule that is diffusing, a decrease in radius should result in an increase in Ds. This is exactly what is observed in going from AEF (Table 3[link]).

Table 3
Translational diffusion coefficients (Ds × 10−10 m2 s−1) measured for 14

Sample Translational diffusion coefficient
A 12.63 ± 0.21
E 16.19 ± 0.11
F 20.69 ± 0.25
Ds values are reported for experiments carried out with a diffusion delay period of 100 ms.
3.3.5. 1,2,3-Trichlorobenzene: a control compound to identify stacking in the LSAM

1,2,3-Trichlorobenzene, 26, was chosen as a test compound to probe changes in chemical shifts that can arise from the stacking of the 1,2,3-trichlorophenyl rings. In the crystal, 26 exists as a two-molecule antiparallel stack (see supporting information ) (Hazell et al., 1972[Hazell, R. G., Lehmann, M. S. & Pawley, G. S. (1972). Acta Cryst. B28, 1388-1394.]). It was anticipated that this antiparallel stack would persist in solution but obviously there would be no hydrogen bonding as seen in cocrystal 14. The effect of concentration on this stacking interaction was studied in a manner similar to that for 14. Fig. 14[link] shows one-dimensional 1H NMR spectra of 26 at different dilutions. The molar concentration of 26 in each sample was identical to that of 1 and 6 in each of the corresponding samples (AF) of 14. The abrupt change in chemical shift in going from EF once again indicates that the stacking interaction in lost upon dilution, at a definite point. The translational diffusion coefficients measured for 26 (Table 4[link]) indicate no change at dilutions A1 and E1 and a small change in F1, in accordance with the above interpretation.

Table 4
Measured T1 (s) and Ds (×10−10 m2 s−1) values for 1,2,3-trichlorobenzene, 26

  T1 Ds
  C5 C4, C6  
A1 6.16 5.90 20.51 ± 0.25
E1 6.44 6.81 20.59 ± 0.14
F1 5.68 5.83 23.47 ± 0.17
Ds values are reported for experiments carried out with a diffusion delay period of 100 ms.
[Figure 14]
Figure 14
1H chemical shifts in dilution experiments (A1F1) for 1,2,3-trichloro­benzene, 26, in CDCl3.

The measured values of T1 and Ds for 26 in samples A1, E1 and F1 are given in Table 4[link]. The two-dimensional DOSY plots for A1, E1 and F1 are shown in the supporting information (§S4). The larger values of T1 in the case of 26 strongly suggest that the aggregates in A1 and E1 are smaller than the corresponding aggregates in A and E of 14, as would be expected. The size of the dimer of 26 is roughly four times smaller than the octamer LSAM derived from 14. Additional evidence for this interpretation comes from the values of the measured translational diffusion coefficients. From the values given in Table 4[link], it is clear that the species in A1 and E1 are significantly smaller in size than those in A and E, although it is not possible to state that it is exactly four times smaller. As mentioned above, crystallographic studies have established that 1,2,3-trichlorobenzene forms a stacked antiparallel dimer in the solid state. Thus, it may be concluded that A1 and E1 represent the stacked antiparallel dimers of 1,2,3-trichloro­benzene, and F1 the monomer form. In summary, the solution NMR studies indicate that in the phenol–aniline system investigated here, the LSAMs are assembled via stacking interactions of tetramer synthons. The sequence of events is therefore established: hydrogen bonding between aniline and phenol comes first and ππ stacking follows.

One-dimensional 15N spectra (supporting information ) recorded on samples A, E and F show no change in the chemical shift positions as a function of concentration. Since 15N chemical shifts are very sensitive to the environment, this observation reinforces the conclusion that hydrogen bonding persists in F. The absence of other peaks in the 15N spectrum of F further points towards the presence of a single species within the limits of detection.

3.3.6. Presence of a hydrogen-bonded tetramer in solution

The NMR experiments point to a hydrogen-bonded and stacked aggregate at higher concentrations that loses the stacking interactions upon dilution to give a hydrogen-bonded aggregate. This indicates that hydrogen bonding in this system is stronger than stacking. We have interpreted these results in terms of a hydrogen-bonded tetramer which is stacked to form dimers, trimers and in the limit of high concentrations n-mers of tetramers. It is desirable to rule out a trivial scenario in which the highest concentration species is a stacked structure of hydrogen-bonded dimers. The evidence for this is as follows: T1 values in A through to E indicate that the species size is gradually decreasing. This is corroborated by the diffusion coefficients and is in accord with a stacked n-mer in A reducing to a stacked dimer in E. It is highly unlikely that the stacked n-mers are constituted with hydrogen-bonded dimers or even trimers because hydrogen bonding is a stronger interaction than stacking. The tetramer structure, which is `saturated' with respect to hydrogen-bonded capability, is a far more likely candidate to be the basic synthon in the structure. Circumstantial evidence for this is also provided by the distorted LSAM in 13, which is a high-Zcrystal structure where stacking is distorted but where the hydrogen-bonded tetramer is preserved fully.

4. Conclusions

The rational synthesis of cocrystals is a difficult task. It becomes even more difficult when there are multiple synthon possibilities in the system and one tries to design a cocrystal wherein the desired synthon is not the most probable one. In this study, a number of aniline–phenol cocrystals have been isolated and shown to contain a large but robust octamer synthon, or LSAM, stabilized by cooperative N—H⋯O—H⋯ hydrogen bonding and ππ stacking, and where the hydrogen bonding defines a closed tetramer. It is noteworthy that a synthon this large and complex is repeated in so many crystal structures. NMR experiments in solution demonstrate conclusively the presence of hydrogen bonding and stacking interactions in solution, the likely presence of a tetramer and octamer and the preferred aggregation via hydrogen bonding as compared with stacking. The NMR studies are a way of establishing the hierarchy in which the various intermolecular interactions are established in the molecular association process. This could be a reason why the tetramers are transferrable even to cocrystals that are dominated by strong hydrogen bonds (23, 24, 25). To our knowledge, this is the first time that such stepwise formation of intermolecular interactions has been monitored. The LSAM is, in a true sense, an additive representation of supramolecular synthons because the geometrical and chemical information implied in supramolecular synthons add up to make a LSAM, which is significant in the very late stages of nucleation. Therefore, it is reasonable to assume that LSAMs can be more useful than individual supramolecular synthons in crystal design, especially when the finer details like unit-cell dimensions are sought to be engineered. The observation of a LSAM in solution and its use in crystal engineering in a predictable way may therefore pave the way for control of crystal packing with greater predictability and precision.

Supporting information


Computing details top

Data collection: CrystalClear-SM Expert 2.0 r4 (Rigaku, 2009) for (11), (12), (13), (14), (15), (16), (17), (21), (23), (24), (25); CrystalClear-SM Expert 2.0 rc14 (Rigaku, 2009) for (18), (19), (20), (22). Cell refinement: CrystalClear-SM Expert 2.0 r4 (Rigaku, 2009) for (11), (12), (13), (14), (15), (16), (17), (21), (23), (24), (25); CrystalClear-SM Expert 2.0 rc14 (Rigaku, 2009) for (18), (19), (20), (22). Data reduction: CrystalClear-SM Expert 2.0 r4 (Rigaku, 2009) for (11), (12), (13), (14), (15), (16), (17), (21), (23), (24), (25); CrystalClear-SM Expert 2.0 rc14 (Rigaku, 2009) for (18), (19), (20), (22). For all compounds, program(s) used to solve structure: SHELXL97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1]
[Figure 2]
[Figure 3]
[Figure 4]
[Figure 5]
[Figure 6]
[Figure 7]
[Figure 8]
[Figure 9]
[Figure 10]
[Figure 11]
[Figure 12]
[Figure 13]
[Figure 14]
(11) top
Crystal data top
C6H3Cl3O·C6H6ClNZ = 2
Mr = 325.00F(000) = 328
Triclinic, P1Dx = 1.569 Mg m3
a = 7.0243 (14) ÅMo Kα radiation, λ = 0.71073 Å
b = 9.4152 (18) ÅCell parameters from 6653 reflections
c = 10.928 (2) Åθ = 3.0–27.5°
α = 82.750 (6)°µ = 0.85 mm1
β = 79.147 (6)°T = 150 K
γ = 76.703 (5)°0.3 × 0.2 × 0.1 mm
V = 688.1 (2) Å3
Data collection top
Rigaku Mercury375R (2x2 bin mode)
diffractometer
3144 independent reflections
Radiation source: fine-focus sealed tube2604 reflections with I > 2σ(I)
Graphite Monochromator monochromatorRint = 0.025
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan
Jacobson, R. (1998) Private communication
h = 99
Tmin = 0.787, Tmax = 1.000k = 1212
7315 measured reflectionsl = 1414
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.084H atoms treated by a mixture of independent and constrained refinement
S = 1.09 w = 1/[σ2(Fo2) + (0.0386P)2 + 0.1418P]
where P = (Fo2 + 2Fc2)/3
3144 reflections(Δ/σ)max = 0.001
175 parametersΔρmax = 0.31 e Å3
0 restraintsΔρmin = 0.32 e Å3
Crystal data top
C6H3Cl3O·C6H6ClNγ = 76.703 (5)°
Mr = 325.00V = 688.1 (2) Å3
Triclinic, P1Z = 2
a = 7.0243 (14) ÅMo Kα radiation
b = 9.4152 (18) ŵ = 0.85 mm1
c = 10.928 (2) ÅT = 150 K
α = 82.750 (6)°0.3 × 0.2 × 0.1 mm
β = 79.147 (6)°
Data collection top
Rigaku Mercury375R (2x2 bin mode)
diffractometer
3144 independent reflections
Absorption correction: multi-scan
Jacobson, R. (1998) Private communication
2604 reflections with I > 2σ(I)
Tmin = 0.787, Tmax = 1.000Rint = 0.025
7315 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0320 restraints
wR(F2) = 0.084H atoms treated by a mixture of independent and constrained refinement
S = 1.09Δρmax = 0.31 e Å3
3144 reflectionsΔρmin = 0.32 e Å3
175 parameters
Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
H1O0.002 (4)1.327 (3)0.538 (2)0.045 (7)*
H1B0.248 (3)1.390 (2)0.718 (2)0.032 (6)*
H1A0.172 (3)1.507 (2)0.6634 (19)0.027 (6)*
Cl20.46442 (7)0.68283 (5)0.49717 (5)0.03745 (14)
Cl10.25550 (8)0.83391 (5)0.74496 (5)0.03588 (14)
Cl40.39502 (8)1.30305 (6)1.06286 (5)0.04031 (15)
Cl30.44791 (8)0.87407 (6)0.23894 (5)0.04020 (15)
O10.05506 (19)1.30340 (13)0.47157 (12)0.0252 (3)
C20.1557 (2)1.07825 (18)0.59699 (16)0.0210 (3)
H20.09641.12090.67090.025*
C50.3358 (2)0.95040 (19)0.37796 (17)0.0243 (4)
C60.2394 (2)1.09626 (19)0.37203 (16)0.0226 (4)
H60.23561.15090.29510.027*
N10.1507 (3)1.4197 (2)0.69092 (16)0.0283 (4)
C40.3440 (2)0.86558 (18)0.49145 (18)0.0244 (4)
C10.1482 (2)1.16040 (17)0.48193 (16)0.0199 (3)
C100.2280 (3)1.3406 (2)0.95682 (16)0.0271 (4)
C80.1121 (3)1.47989 (19)0.77659 (17)0.0272 (4)
H80.12121.55430.71250.033*
C70.0291 (3)1.39656 (19)0.78544 (16)0.0239 (4)
C30.2526 (3)0.93224 (19)0.59986 (17)0.0224 (4)
C120.0410 (3)1.2849 (2)0.88099 (17)0.0298 (4)
H120.13631.22900.88750.036*
C90.2404 (3)1.4527 (2)0.86321 (17)0.0279 (4)
H90.33411.50970.85820.033*
C110.0889 (3)1.2565 (2)0.96680 (17)0.0321 (4)
H110.08181.18141.03040.039*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl20.0276 (3)0.0177 (2)0.0683 (4)0.00021 (18)0.0130 (2)0.0089 (2)
Cl10.0432 (3)0.0280 (2)0.0370 (3)0.0107 (2)0.0144 (2)0.0127 (2)
Cl40.0395 (3)0.0513 (3)0.0297 (3)0.0042 (2)0.0140 (2)0.0005 (2)
Cl30.0394 (3)0.0409 (3)0.0411 (3)0.0111 (2)0.0077 (2)0.0232 (2)
O10.0288 (7)0.0180 (6)0.0262 (7)0.0014 (5)0.0065 (6)0.0006 (5)
C20.0184 (8)0.0207 (8)0.0245 (8)0.0045 (7)0.0043 (7)0.0020 (7)
C50.0175 (8)0.0274 (9)0.0304 (9)0.0075 (7)0.0000 (7)0.0125 (8)
C60.0209 (9)0.0250 (9)0.0234 (8)0.0077 (7)0.0040 (7)0.0021 (7)
N10.0286 (9)0.0253 (9)0.0329 (9)0.0040 (7)0.0097 (7)0.0056 (7)
C40.0160 (8)0.0164 (8)0.0425 (10)0.0030 (6)0.0079 (7)0.0051 (8)
C10.0160 (8)0.0177 (8)0.0274 (9)0.0036 (6)0.0067 (7)0.0023 (7)
C100.0273 (10)0.0314 (10)0.0201 (8)0.0012 (8)0.0044 (7)0.0064 (7)
C80.0345 (11)0.0195 (8)0.0274 (9)0.0038 (8)0.0077 (8)0.0010 (7)
C70.0249 (9)0.0226 (8)0.0237 (9)0.0000 (7)0.0035 (7)0.0094 (7)
C30.0195 (9)0.0210 (8)0.0289 (9)0.0077 (7)0.0087 (7)0.0029 (7)
C120.0313 (10)0.0339 (10)0.0257 (9)0.0134 (8)0.0008 (8)0.0041 (8)
C90.0313 (10)0.0233 (9)0.0306 (10)0.0060 (8)0.0073 (8)0.0046 (8)
C110.0381 (11)0.0342 (10)0.0210 (9)0.0085 (9)0.0002 (8)0.0030 (8)
Geometric parameters (Å, º) top
Cl2—C41.7330 (17)C6—C11.390 (2)
Cl1—C31.7334 (18)N1—C71.426 (2)
Cl4—C101.7499 (19)C4—C31.388 (3)
Cl3—C51.7346 (18)C10—C111.374 (3)
O1—C11.3556 (19)C10—C91.380 (3)
C2—C31.386 (2)C8—C71.383 (3)
C2—C11.394 (2)C8—C91.388 (3)
C5—C61.384 (2)C7—C121.390 (3)
C5—C41.391 (3)C12—C111.389 (3)
C3—C2—C1119.15 (16)C11—C10—Cl4119.50 (15)
C6—C5—C4121.67 (16)C9—C10—Cl4119.40 (15)
C6—C5—Cl3118.20 (14)C7—C8—C9120.13 (17)
C4—C5—Cl3120.13 (14)C8—C7—C12119.63 (17)
C5—C6—C1119.48 (16)C8—C7—N1119.26 (17)
C3—C4—C5117.77 (15)C12—C7—N1120.95 (17)
C3—C4—Cl2121.15 (14)C2—C3—C4121.91 (16)
C5—C4—Cl2121.08 (14)C2—C3—Cl1117.50 (14)
O1—C1—C6117.43 (15)C4—C3—Cl1120.59 (13)
O1—C1—C2122.55 (15)C11—C12—C7120.26 (18)
C6—C1—C2120.02 (15)C10—C9—C8119.54 (18)
C11—C10—C9121.09 (17)C10—C11—C12119.33 (18)
(12) top
Crystal data top
C6H3Cl3O·C6H6ClNF(000) = 656
Mr = 325.00Dx = 1.601 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 6.9676 (7) ÅCell parameters from 12676 reflections
b = 21.336 (2) Åθ = 3.1–27.6°
c = 9.1861 (10) ŵ = 0.86 mm1
β = 99.139 (7)°T = 150 K
V = 1348.3 (2) Å30.3 × 0.2 × 0.1 mm
Z = 4
Data collection top
Rigaku Mercury375R (2x2 bin mode)
diffractometer
3066 independent reflections
Radiation source: fine-focus sealed tube2703 reflections with I > 2σ(I)
Graphite Monochromator monochromatorRint = 0.032
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan
Jacobson, R. (1998) Private communication
h = 99
Tmin = 0.777, Tmax = 1.000k = 2727
13875 measured reflectionsl = 1111
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.033Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.085H atoms treated by a mixture of independent and constrained refinement
S = 1.09 w = 1/[σ2(Fo2) + (0.0371P)2 + 0.7069P]
where P = (Fo2 + 2Fc2)/3
3066 reflections(Δ/σ)max = 0.001
175 parametersΔρmax = 0.42 e Å3
0 restraintsΔρmin = 0.46 e Å3
Crystal data top
C6H3Cl3O·C6H6ClNV = 1348.3 (2) Å3
Mr = 325.00Z = 4
Monoclinic, P21/cMo Kα radiation
a = 6.9676 (7) ŵ = 0.86 mm1
b = 21.336 (2) ÅT = 150 K
c = 9.1861 (10) Å0.3 × 0.2 × 0.1 mm
β = 99.139 (7)°
Data collection top
Rigaku Mercury375R (2x2 bin mode)
diffractometer
3066 independent reflections
Absorption correction: multi-scan
Jacobson, R. (1998) Private communication
2703 reflections with I > 2σ(I)
Tmin = 0.777, Tmax = 1.000Rint = 0.032
13875 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0330 restraints
wR(F2) = 0.085H atoms treated by a mixture of independent and constrained refinement
S = 1.09Δρmax = 0.42 e Å3
3066 reflectionsΔρmin = 0.46 e Å3
175 parameters
Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
H1A0.741 (4)0.3939 (11)0.451 (3)0.040 (6)*
H1B0.588 (3)0.4188 (11)0.546 (3)0.041 (6)*
H1O0.405 (4)0.4798 (12)1.347 (3)0.045 (7)*
Cl10.02886 (7)0.28694 (2)0.54553 (6)0.03685 (13)
Cl20.13436 (8)0.63084 (2)0.84685 (6)0.04161 (14)
Cl30.20997 (8)0.37843 (3)0.85082 (6)0.04445 (15)
Cl40.08451 (7)0.50261 (3)0.67545 (5)0.04329 (15)
O10.40912 (18)0.51300 (6)1.30530 (13)0.0273 (3)
N10.6231 (3)0.40358 (7)0.46088 (18)0.0279 (3)
C20.2762 (2)0.56365 (8)1.08480 (18)0.0235 (3)
H20.29020.60201.13360.028*
C10.3321 (2)0.50850 (8)1.16050 (18)0.0210 (3)
C120.3200 (3)0.34473 (8)0.49862 (18)0.0241 (3)
H120.26520.37360.56890.029*
C90.4779 (3)0.25816 (8)0.2870 (2)0.0306 (4)
H90.53110.22950.21550.037*
C70.5124 (3)0.35105 (8)0.42951 (18)0.0238 (3)
C60.3111 (2)0.45141 (8)1.08699 (19)0.0238 (3)
H60.34860.41441.13700.029*
C30.1999 (2)0.56122 (8)0.93703 (19)0.0251 (4)
C100.2866 (3)0.25088 (8)0.3553 (2)0.0284 (4)
H100.21100.21770.33110.034*
C50.2338 (2)0.45008 (9)0.93884 (19)0.0257 (4)
C110.2124 (3)0.29461 (8)0.46036 (19)0.0250 (4)
C40.1777 (2)0.50462 (9)0.86114 (18)0.0262 (4)
C80.5909 (3)0.30724 (8)0.3235 (2)0.0285 (4)
H80.71920.31110.27750.034*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0267 (2)0.0395 (3)0.0424 (3)0.00050 (18)0.00049 (19)0.0010 (2)
Cl20.0484 (3)0.0408 (3)0.0347 (3)0.0062 (2)0.0039 (2)0.0177 (2)
Cl30.0511 (3)0.0406 (3)0.0416 (3)0.0035 (2)0.0070 (2)0.0221 (2)
Cl40.0345 (3)0.0764 (4)0.0171 (2)0.0079 (2)0.00163 (18)0.0050 (2)
O10.0318 (7)0.0276 (7)0.0195 (6)0.0023 (5)0.0050 (5)0.0003 (5)
N10.0310 (9)0.0281 (8)0.0241 (8)0.0016 (6)0.0030 (6)0.0027 (6)
C20.0223 (8)0.0245 (8)0.0235 (8)0.0025 (6)0.0033 (6)0.0014 (6)
C10.0179 (8)0.0259 (8)0.0189 (8)0.0014 (6)0.0017 (6)0.0009 (6)
C120.0311 (9)0.0236 (8)0.0173 (8)0.0054 (7)0.0034 (6)0.0002 (6)
C90.0359 (10)0.0249 (9)0.0297 (10)0.0069 (7)0.0015 (8)0.0062 (7)
C70.0300 (9)0.0216 (8)0.0203 (8)0.0012 (7)0.0059 (6)0.0031 (6)
C60.0217 (8)0.0242 (8)0.0257 (9)0.0022 (6)0.0042 (6)0.0004 (6)
C30.0204 (8)0.0318 (9)0.0237 (9)0.0031 (7)0.0053 (6)0.0076 (7)
C100.0349 (10)0.0208 (8)0.0301 (10)0.0005 (7)0.0074 (7)0.0012 (7)
C50.0200 (8)0.0314 (9)0.0263 (9)0.0014 (7)0.0053 (6)0.0088 (7)
C110.0253 (9)0.0257 (8)0.0237 (9)0.0040 (7)0.0028 (7)0.0042 (6)
C40.0176 (8)0.0437 (10)0.0167 (8)0.0007 (7)0.0014 (6)0.0018 (7)
C80.0292 (9)0.0279 (9)0.0269 (9)0.0046 (7)0.0003 (7)0.0017 (7)
Geometric parameters (Å, º) top
Cl1—C111.7455 (18)C12—C111.383 (3)
Cl2—C31.7265 (17)C12—C71.396 (2)
Cl3—C51.7250 (18)C9—C81.383 (3)
Cl4—C41.7266 (17)C9—C101.389 (3)
O1—C11.356 (2)C7—C81.397 (2)
N1—C71.416 (2)C6—C51.382 (2)
C2—C31.378 (2)C3—C41.391 (3)
C2—C11.391 (2)C10—C111.383 (2)
C1—C61.389 (2)C5—C41.388 (3)
C3—C2—C1119.63 (16)C4—C3—Cl2120.44 (13)
O1—C1—C6122.25 (15)C11—C10—C9117.75 (17)
O1—C1—C2117.79 (15)C6—C5—C4121.53 (16)
C6—C1—C2119.95 (15)C6—C5—Cl3118.24 (14)
C11—C12—C7118.63 (16)C4—C5—Cl3120.23 (14)
C8—C9—C10121.17 (17)C10—C11—C12122.79 (17)
C12—C7—C8119.59 (16)C10—C11—Cl1118.47 (14)
C12—C7—N1119.92 (16)C12—C11—Cl1118.73 (13)
C8—C7—N1120.39 (17)C5—C4—C3118.05 (16)
C5—C6—C1119.42 (16)C5—C4—Cl4121.21 (14)
C2—C3—C4121.42 (16)C3—C4—Cl4120.75 (14)
C2—C3—Cl2118.14 (14)C9—C8—C7120.06 (17)
(13) top
Crystal data top
C6H3Cl3O·C6H5Cl2NF(000) = 720
Mr = 359.44Dx = 1.676 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
a = 7.0572 (6) ÅCell parameters from 14958 reflections
b = 15.4665 (13) Åθ = 3.1–27.5°
c = 13.2112 (11) ŵ = 1.01 mm1
β = 98.980 (7)°T = 150 K
V = 1424.3 (2) Å30.3 × 0.2 × 0.1 mm
Z = 4
Data collection top
Rigaku Mercury375R (2x2 bin mode)
diffractometer
6493 independent reflections
Radiation source: fine-focus sealed tube6193 reflections with I > 2σ(I)
Graphite Monochromator monochromatorRint = 0.023
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan
Jacobson, R. (1998) Private communication
h = 99
Tmin = 0.772, Tmax = 1.000k = 2020
15205 measured reflectionsl = 1717
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.026H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.056 w = 1/[σ2(Fo2) + (0.0228P)2 + 0.3139P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.001
6493 reflectionsΔρmax = 0.38 e Å3
367 parametersΔρmin = 0.25 e Å3
1 restraintAbsolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.03 (3)
Crystal data top
C6H3Cl3O·C6H5Cl2NV = 1424.3 (2) Å3
Mr = 359.44Z = 4
Monoclinic, P21Mo Kα radiation
a = 7.0572 (6) ŵ = 1.01 mm1
b = 15.4665 (13) ÅT = 150 K
c = 13.2112 (11) Å0.3 × 0.2 × 0.1 mm
β = 98.980 (7)°
Data collection top
Rigaku Mercury375R (2x2 bin mode)
diffractometer
6493 independent reflections
Absorption correction: multi-scan
Jacobson, R. (1998) Private communication
6193 reflections with I > 2σ(I)
Tmin = 0.772, Tmax = 1.000Rint = 0.023
15205 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.026H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.056Δρmax = 0.38 e Å3
S = 1.06Δρmin = 0.25 e Å3
6493 reflectionsAbsolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
367 parametersAbsolute structure parameter: 0.03 (3)
1 restraint
Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
H2B0.790 (4)0.6482 (18)0.077 (2)0.039 (8)*
H1A0.845 (3)0.3095 (16)0.1180 (19)0.030 (6)*
H2A0.902 (4)0.6730 (17)0.1488 (18)0.030 (7)*
H1B0.944 (4)0.285 (2)0.214 (2)0.051 (8)*
H1O0.209 (4)0.197 (2)0.077 (2)0.042 (8)*
H2O0.797 (4)0.161 (2)0.131 (2)0.040 (8)*
Cl10.23666 (8)0.16589 (3)0.04147 (4)0.03325 (12)
Cl80.14020 (7)0.53302 (3)0.23536 (4)0.03090 (11)
Cl60.69544 (9)0.19777 (4)0.15903 (5)0.03846 (13)
Cl30.29897 (8)0.01657 (4)0.39458 (4)0.03099 (12)
Cl20.29478 (8)0.16329 (3)0.28225 (4)0.03445 (12)
Cl70.86753 (8)0.71523 (3)0.34275 (4)0.03328 (12)
Cl40.82810 (8)0.02746 (4)0.47583 (4)0.03454 (12)
Cl50.73955 (8)0.16320 (4)0.39542 (4)0.03550 (13)
Cl90.17446 (8)0.42597 (4)0.11905 (5)0.04232 (14)
Cl100.89857 (11)0.29635 (5)0.40595 (5)0.05823 (19)
O10.2104 (2)0.15902 (11)0.04406 (12)0.0290 (3)
N10.8364 (3)0.28576 (13)0.17706 (15)0.0307 (4)
C40.2676 (3)0.06808 (13)0.21328 (15)0.0219 (4)
N20.7986 (3)0.67400 (13)0.13019 (15)0.0269 (4)
O20.7657 (3)0.12012 (12)0.10219 (13)0.0353 (4)
C60.2514 (3)0.08872 (13)0.20845 (15)0.0214 (4)
H60.25440.14130.24280.026*
C20.2245 (3)0.00767 (13)0.05134 (15)0.0226 (4)
H20.20960.00600.01980.027*
C30.2433 (3)0.06827 (13)0.10715 (15)0.0216 (4)
C220.3543 (3)0.60266 (14)0.36698 (16)0.0276 (4)
H220.25360.58870.41850.033*
C80.7362 (3)0.02742 (14)0.13807 (16)0.0258 (4)
H80.71890.03880.06810.031*
C50.2702 (3)0.01175 (13)0.26251 (13)0.0200 (4)
C100.7576 (3)0.07927 (13)0.31157 (16)0.0227 (4)
C200.6643 (3)0.66388 (13)0.31244 (15)0.0243 (4)
C140.5224 (3)0.35229 (13)0.15740 (16)0.0261 (4)
H140.51330.34910.08650.031*
C110.7895 (3)0.00541 (13)0.34575 (14)0.0228 (4)
C190.6541 (3)0.64636 (12)0.20982 (15)0.0221 (4)
C70.7654 (3)0.05717 (14)0.17340 (16)0.0254 (4)
C120.7946 (3)0.07324 (13)0.27838 (16)0.0245 (4)
H120.81730.12930.30290.029*
C210.5176 (3)0.64228 (14)0.38990 (16)0.0289 (5)
H210.52860.65440.45770.035*
C230.3441 (3)0.58429 (13)0.26604 (16)0.0246 (4)
C240.4908 (3)0.60528 (13)0.18724 (15)0.0237 (4)
H240.47990.59190.11980.028*
C160.3773 (4)0.39078 (16)0.30534 (19)0.0409 (6)
H160.27410.41300.33300.049*
C10.2279 (3)0.08614 (13)0.10172 (15)0.0209 (4)
C90.7331 (3)0.09350 (13)0.20637 (16)0.0243 (4)
C180.6911 (4)0.32839 (15)0.32645 (17)0.0358 (5)
C130.6861 (3)0.32261 (13)0.22005 (16)0.0269 (5)
C150.3728 (3)0.38670 (14)0.20101 (17)0.0318 (5)
C170.5382 (4)0.36114 (16)0.36756 (18)0.0435 (7)
H170.54410.36320.43830.052*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0416 (3)0.0242 (2)0.0328 (3)0.0051 (2)0.0022 (2)0.0085 (2)
Cl80.0282 (2)0.0278 (3)0.0372 (3)0.0001 (2)0.0071 (2)0.0004 (2)
Cl60.0440 (3)0.0249 (3)0.0444 (3)0.0023 (2)0.0002 (2)0.0094 (2)
Cl30.0363 (3)0.0407 (3)0.0156 (2)0.0060 (2)0.00275 (19)0.0010 (2)
Cl20.0422 (3)0.0259 (3)0.0337 (3)0.0005 (2)0.0013 (2)0.0089 (2)
Cl70.0377 (3)0.0307 (3)0.0354 (3)0.0023 (2)0.0181 (2)0.0007 (2)
Cl40.0393 (3)0.0428 (3)0.0222 (2)0.0001 (3)0.0070 (2)0.0054 (2)
Cl50.0394 (3)0.0297 (3)0.0384 (3)0.0023 (2)0.0094 (2)0.0100 (2)
Cl90.0326 (3)0.0445 (3)0.0527 (4)0.0007 (3)0.0155 (3)0.0010 (3)
Cl100.0726 (5)0.0659 (4)0.0285 (3)0.0182 (4)0.0163 (3)0.0093 (3)
O10.0434 (9)0.0220 (7)0.0205 (8)0.0002 (7)0.0017 (6)0.0007 (6)
N10.0323 (10)0.0322 (11)0.0265 (10)0.0043 (9)0.0014 (8)0.0089 (8)
C40.0195 (9)0.0224 (9)0.0231 (10)0.0009 (8)0.0007 (7)0.0035 (8)
N20.0292 (10)0.0256 (9)0.0261 (10)0.0014 (8)0.0051 (8)0.0013 (8)
O20.0485 (11)0.0293 (9)0.0287 (9)0.0028 (8)0.0078 (7)0.0045 (7)
C60.0197 (9)0.0226 (10)0.0217 (10)0.0011 (8)0.0025 (8)0.0037 (8)
C20.0211 (9)0.0289 (10)0.0174 (9)0.0020 (8)0.0013 (7)0.0009 (8)
C30.0185 (9)0.0207 (9)0.0255 (10)0.0012 (8)0.0027 (8)0.0036 (8)
C220.0307 (11)0.0254 (10)0.0260 (10)0.0054 (9)0.0022 (8)0.0067 (9)
C80.0231 (10)0.0320 (12)0.0219 (10)0.0005 (9)0.0017 (8)0.0045 (9)
C50.0176 (9)0.0292 (10)0.0127 (8)0.0018 (8)0.0010 (7)0.0006 (8)
C100.0176 (9)0.0230 (10)0.0278 (10)0.0013 (8)0.0046 (8)0.0046 (8)
C200.0292 (10)0.0196 (9)0.0265 (10)0.0020 (9)0.0115 (8)0.0018 (8)
C140.0341 (11)0.0238 (10)0.0220 (10)0.0110 (9)0.0090 (8)0.0022 (8)
C110.0178 (9)0.0302 (11)0.0208 (9)0.0013 (8)0.0039 (7)0.0021 (8)
C190.0284 (10)0.0154 (9)0.0229 (10)0.0058 (8)0.0057 (8)0.0020 (7)
C70.0195 (9)0.0282 (11)0.0286 (11)0.0001 (8)0.0039 (8)0.0056 (8)
C120.0244 (10)0.0209 (10)0.0295 (11)0.0020 (8)0.0080 (8)0.0036 (8)
C210.0389 (12)0.0297 (11)0.0191 (10)0.0084 (9)0.0079 (8)0.0004 (8)
C230.0265 (10)0.0180 (9)0.0303 (11)0.0035 (8)0.0080 (8)0.0018 (8)
C240.0320 (11)0.0190 (9)0.0215 (9)0.0062 (8)0.0086 (8)0.0006 (8)
C160.0601 (17)0.0308 (12)0.0368 (14)0.0135 (12)0.0229 (12)0.0090 (10)
C10.0200 (9)0.0236 (10)0.0183 (9)0.0018 (8)0.0002 (7)0.0011 (8)
C90.0178 (9)0.0228 (10)0.0310 (11)0.0004 (8)0.0001 (8)0.0044 (8)
C180.0551 (15)0.0291 (12)0.0210 (11)0.0175 (11)0.0007 (10)0.0013 (9)
C130.0367 (12)0.0216 (10)0.0222 (10)0.0131 (9)0.0038 (9)0.0004 (8)
C150.0398 (13)0.0263 (11)0.0317 (12)0.0118 (10)0.0132 (10)0.0044 (9)
C170.0753 (19)0.0380 (13)0.0202 (11)0.0263 (13)0.0164 (12)0.0106 (9)
Geometric parameters (Å, º) top
Cl1—C31.7385 (19)C2—C11.382 (3)
Cl8—C231.745 (2)C22—C231.376 (3)
Cl6—C91.735 (2)C22—C211.379 (3)
Cl3—C51.7264 (18)C8—C91.366 (3)
Cl2—C41.727 (2)C8—C71.393 (3)
Cl7—C201.740 (2)C10—C91.391 (3)
Cl4—C111.731 (2)C10—C111.392 (3)
Cl5—C101.724 (2)C20—C211.379 (3)
Cl9—C151.740 (3)C20—C191.395 (3)
Cl10—C181.736 (3)C14—C151.385 (3)
O1—C11.355 (2)C14—C131.390 (3)
N1—C131.400 (3)C11—C121.380 (3)
C4—C31.386 (3)C19—C241.388 (3)
C4—C51.394 (3)C7—C121.392 (3)
N2—C191.412 (3)C23—C241.387 (3)
O2—C71.354 (3)C16—C171.373 (4)
C6—C51.384 (3)C16—C151.375 (3)
C6—C11.394 (3)C18—C171.378 (4)
C2—C31.382 (3)C18—C131.403 (3)
C3—C4—C5117.67 (17)O2—C7—C12123.2 (2)
C3—C4—Cl2121.21 (15)O2—C7—C8117.29 (19)
C5—C4—Cl2121.12 (15)C12—C7—C8119.50 (19)
C5—C6—C1118.94 (17)C11—C12—C7119.47 (18)
C3—C2—C1119.75 (17)C20—C21—C22120.06 (19)
C2—C3—C4121.62 (18)C22—C23—C24122.20 (19)
C2—C3—Cl1118.62 (15)C22—C23—Cl8119.26 (17)
C4—C3—Cl1119.76 (15)C24—C23—Cl8118.54 (16)
C23—C22—C21118.4 (2)C23—C24—C19119.54 (18)
C9—C8—C7119.87 (19)C17—C16—C15118.2 (2)
C6—C5—C4121.85 (16)O1—C1—C2117.80 (18)
C6—C5—Cl3118.11 (15)O1—C1—C6122.04 (18)
C4—C5—Cl3120.04 (15)C2—C1—C6120.16 (18)
C9—C10—C11117.48 (18)C8—C9—C10121.96 (19)
C9—C10—Cl5120.84 (16)C8—C9—Cl6118.34 (16)
C11—C10—Cl5121.63 (16)C10—C9—Cl6119.69 (16)
C21—C20—C19121.84 (19)C17—C18—C13121.3 (2)
C21—C20—Cl7119.36 (16)C17—C18—Cl10120.33 (18)
C19—C20—Cl7118.79 (16)C13—C18—Cl10118.3 (2)
C15—C14—C13119.7 (2)C14—C13—N1120.31 (19)
C12—C11—C10121.68 (18)C14—C13—C18117.6 (2)
C12—C11—Cl4118.33 (16)N1—C13—C18122.0 (2)
C10—C11—Cl4119.98 (15)C16—C15—C14122.3 (2)
C24—C19—C20117.91 (18)C16—C15—Cl9119.9 (2)
C24—C19—N2120.35 (19)C14—C15—Cl9117.80 (17)
C20—C19—N2121.62 (19)C16—C17—C18120.8 (2)
(14) top
Crystal data top
C6H3Cl3O·C6H5Cl2NF(000) = 1440
Mr = 359.44Dx = 1.614 Mg m3
Monoclinic, I2/aMo Kα radiation, λ = 0.71073 Å
a = 22.638 (5) ÅCell parameters from 14187 reflections
b = 7.2553 (11) Åθ = 3.0–27.6°
c = 18.013 (3) ŵ = 0.97 mm1
β = 90.767 (9)°T = 150 K
V = 2958.2 (9) Å30.6 × 0.3 × 0.2 mm
Z = 8
Data collection top
Rigaku Mercury375R (2x2 bin mode)
diffractometer
2662 independent reflections
Radiation source: fine-focus sealed tube2516 reflections with I > 2σ(I)
Graphite Monochromator monochromatorRint = 0.033
Detector resolution: 13.6612 pixels mm-1θmax = 25.2°, θmin = 3.0°
Absorption correction: multi-scan
Jacobson, R. (1998) Private communication
h = 2727
Tmin = 0.766, Tmax = 1.000k = 88
12389 measured reflectionsl = 2121
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.093Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.202H atoms treated by a mixture of independent and constrained refinement
S = 1.21 w = 1/[σ2(Fo2) + (0.0317P)2 + 62.0784P]
where P = (Fo2 + 2Fc2)/3
2662 reflections(Δ/σ)max < 0.001
182 parametersΔρmax = 3.00 e Å3
2 restraintsΔρmin = 0.57 e Å3
Crystal data top
C6H3Cl3O·C6H5Cl2NV = 2958.2 (9) Å3
Mr = 359.44Z = 8
Monoclinic, I2/aMo Kα radiation
a = 22.638 (5) ŵ = 0.97 mm1
b = 7.2553 (11) ÅT = 150 K
c = 18.013 (3) Å0.6 × 0.3 × 0.2 mm
β = 90.767 (9)°
Data collection top
Rigaku Mercury375R (2x2 bin mode)
diffractometer
2662 independent reflections
Absorption correction: multi-scan
Jacobson, R. (1998) Private communication
2516 reflections with I > 2σ(I)
Tmin = 0.766, Tmax = 1.000Rint = 0.033
12389 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0932 restraints
wR(F2) = 0.202H atoms treated by a mixture of independent and constrained refinement
S = 1.21 w = 1/[σ2(Fo2) + (0.0317P)2 + 62.0784P]
where P = (Fo2 + 2Fc2)/3
2662 reflectionsΔρmax = 3.00 e Å3
182 parametersΔρmin = 0.57 e Å3
Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
H1O0.268 (3)0.334 (8)0.417 (3)0.008 (15)*
H1B0.173 (2)0.744 (9)0.5198 (15)0.010*
H1A0.154 (2)0.856 (4)0.455 (3)0.010*
Cl10.12726 (9)0.6276 (3)0.17802 (10)0.0431 (5)
Cl20.06752 (9)0.1127 (3)0.51615 (11)0.0450 (5)
Cl30.24729 (11)0.6278 (3)0.09208 (9)0.0515 (6)
Cl40.02151 (9)0.5883 (4)0.31950 (12)0.0611 (7)
Cl50.36222 (9)0.4972 (4)0.17707 (11)0.0554 (6)
O10.2350 (2)0.3736 (8)0.4013 (2)0.0318 (11)
N10.1611 (3)0.7428 (9)0.4728 (3)0.0330 (13)
C10.2400 (3)0.4334 (9)0.3301 (3)0.0267 (14)
C70.1142 (3)0.6209 (11)0.4577 (4)0.0300 (15)
C20.2933 (3)0.4364 (10)0.2935 (3)0.0279 (14)
H20.32850.39770.31810.034*
C110.0299 (3)0.5376 (12)0.3874 (4)0.0345 (17)
C100.0267 (3)0.3653 (12)0.4201 (4)0.0371 (18)
H100.00270.27810.40700.045*
C80.1123 (3)0.4498 (10)0.4923 (3)0.0256 (14)
H80.14060.41820.52860.031*
C30.2947 (3)0.4966 (11)0.2203 (4)0.0335 (16)
C60.1885 (3)0.4930 (10)0.2944 (3)0.0278 (14)
H60.15180.49170.31940.033*
C50.1917 (3)0.5544 (10)0.2214 (4)0.0297 (15)
C90.0689 (3)0.3269 (10)0.4735 (4)0.0294 (15)
C40.2445 (3)0.5542 (10)0.1834 (4)0.0332 (16)
C120.0725 (3)0.6662 (11)0.4042 (4)0.0365 (17)
H120.07350.78260.38000.044*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0479 (11)0.0482 (11)0.0328 (9)0.0021 (9)0.0172 (8)0.0059 (9)
Cl20.0493 (11)0.0385 (11)0.0470 (11)0.0042 (9)0.0031 (8)0.0045 (9)
Cl30.0787 (15)0.0572 (13)0.0187 (9)0.0191 (12)0.0012 (8)0.0054 (9)
Cl40.0397 (11)0.103 (2)0.0411 (11)0.0194 (12)0.0140 (9)0.0103 (12)
Cl50.0433 (11)0.0832 (17)0.0404 (10)0.0185 (11)0.0206 (9)0.0073 (11)
O10.024 (2)0.049 (3)0.022 (2)0.004 (2)0.0020 (18)0.008 (2)
N10.029 (3)0.033 (3)0.036 (3)0.001 (3)0.003 (2)0.002 (3)
C10.032 (3)0.028 (4)0.020 (3)0.005 (3)0.001 (3)0.003 (3)
C70.023 (3)0.040 (4)0.027 (3)0.006 (3)0.007 (3)0.001 (3)
C20.026 (3)0.034 (4)0.024 (3)0.000 (3)0.001 (3)0.001 (3)
C110.022 (3)0.054 (5)0.028 (3)0.013 (3)0.000 (3)0.001 (3)
C100.025 (3)0.057 (5)0.029 (4)0.009 (3)0.001 (3)0.008 (4)
C80.019 (3)0.034 (4)0.024 (3)0.007 (3)0.002 (2)0.001 (3)
C30.034 (4)0.040 (4)0.027 (3)0.013 (3)0.009 (3)0.003 (3)
C60.027 (3)0.034 (4)0.023 (3)0.001 (3)0.001 (3)0.001 (3)
C50.036 (4)0.027 (4)0.026 (3)0.002 (3)0.008 (3)0.002 (3)
C90.027 (3)0.037 (4)0.024 (3)0.005 (3)0.006 (3)0.002 (3)
C40.050 (4)0.031 (4)0.018 (3)0.012 (3)0.001 (3)0.001 (3)
C120.034 (4)0.046 (5)0.029 (4)0.010 (3)0.009 (3)0.011 (3)
Geometric parameters (Å, º) top
Cl1—C51.730 (7)C7—C121.397 (10)
Cl2—C91.734 (7)C2—C31.389 (9)
Cl3—C41.731 (7)C11—C121.379 (11)
Cl4—C111.738 (7)C11—C101.384 (11)
Cl5—C31.725 (7)C10—C91.392 (10)
O1—C11.360 (8)C8—C91.372 (10)
N1—C71.410 (9)C3—C41.375 (10)
C1—C21.383 (9)C6—C51.391 (9)
C1—C61.393 (9)C5—C41.384 (10)
C7—C81.390 (10)
O1—C1—C2122.6 (6)C4—C3—Cl5120.8 (5)
O1—C1—C6117.2 (6)C2—C3—Cl5117.5 (6)
C2—C1—C6120.3 (6)C5—C6—C1118.8 (6)
C8—C7—C12120.1 (7)C4—C5—C6121.6 (6)
C8—C7—N1119.5 (6)C4—C5—Cl1120.3 (5)
C12—C7—N1120.2 (7)C6—C5—Cl1118.1 (5)
C1—C2—C3119.3 (6)C8—C9—C10122.7 (7)
C12—C11—C10123.4 (6)C8—C9—Cl2118.8 (5)
C12—C11—Cl4119.2 (6)C10—C9—Cl2118.5 (6)
C10—C11—Cl4117.4 (6)C3—C4—C5118.3 (6)
C11—C10—C9116.3 (7)C3—C4—Cl3120.9 (6)
C9—C8—C7119.2 (6)C5—C4—Cl3120.8 (6)
C4—C3—C2121.7 (6)C11—C12—C7118.3 (7)
(15) top
Crystal data top
C6H3Cl3O·C6H4Cl2NZ = 2
Mr = 358.44F(000) = 358
Triclinic, P1Dx = 1.655 Mg m3
a = 7.0681 (6) ÅMo Kα radiation, λ = 0.71073 Å
b = 9.5008 (8) ÅCell parameters from 7095 reflections
c = 11.4095 (9) Åθ = 3.1–27.5°
α = 85.402 (6)°µ = 1.00 mm1
β = 83.071 (6)°T = 150 K
γ = 71.211 (5)°0.5 × 0.3 × 0.2 mm
V = 719.36 (10) Å3
Data collection top
Rigaku Mercury375R (2x2 bin mode)
diffractometer
3293 independent reflections
Radiation source: fine-focus sealed tube2949 reflections with I > 2σ(I)
Graphite Monochromator monochromatorRint = 0.016
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan
Jacobson, R. (1998) Private communication
h = 99
Tmin = 0.826, Tmax = 1.000k = 1212
7652 measured reflectionsl = 1414
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.064Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.150H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0452P)2 + 2.5468P]
where P = (Fo2 + 2Fc2)/3
3293 reflections(Δ/σ)max < 0.001
194 parametersΔρmax = 2.21 e Å3
0 restraintsΔρmin = 1.74 e Å3
Crystal data top
C6H3Cl3O·C6H4Cl2Nγ = 71.211 (5)°
Mr = 358.44V = 719.36 (10) Å3
Triclinic, P1Z = 2
a = 7.0681 (6) ÅMo Kα radiation
b = 9.5008 (8) ŵ = 1.00 mm1
c = 11.4095 (9) ÅT = 150 K
α = 85.402 (6)°0.5 × 0.3 × 0.2 mm
β = 83.071 (6)°
Data collection top
Rigaku Mercury375R (2x2 bin mode)
diffractometer
3293 independent reflections
Absorption correction: multi-scan
Jacobson, R. (1998) Private communication
2949 reflections with I > 2σ(I)
Tmin = 0.826, Tmax = 1.000Rint = 0.016
7652 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0640 restraints
wR(F2) = 0.150H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 2.21 e Å3
3293 reflectionsΔρmin = 1.74 e Å3
194 parameters
Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
C10.3681 (4)1.1658 (3)0.9778 (3)0.0236 (6)
C20.3447 (5)1.0815 (4)1.0834 (3)0.0273 (6)
H20.40391.12471.15470.033*
C30.2316 (5)0.9319 (4)1.0814 (3)0.0304 (7)
C40.1393 (5)0.8651 (3)0.9765 (3)0.0308 (7)
C50.1636 (5)0.9524 (4)0.8724 (3)0.0288 (7)
C60.2772 (5)1.1009 (3)0.8719 (3)0.0255 (6)
H60.29291.15710.80110.031*
C70.5446 (6)0.5887 (4)1.7238 (3)0.0436 (10)
C80.4006 (6)0.5216 (5)1.7164 (3)0.0437 (10)
H80.38680.44701.77150.052*
C90.2764 (6)0.5664 (5)1.6259 (3)0.0473 (10)
C100.2955 (7)0.6789 (5)1.5434 (3)0.0481 (11)
C110.4396 (8)0.7448 (5)1.5508 (4)0.0524 (11)
C120.5649 (7)0.6998 (5)1.6404 (4)0.0507 (11)
H120.66330.74411.64500.061*
O10.4772 (4)1.3120 (3)0.9718 (2)0.0312 (5)
Cl10.04927 (16)0.87615 (11)0.73917 (9)0.0482 (3)
Cl20.00093 (15)0.67852 (10)0.97457 (11)0.0494 (3)
Cl30.20748 (17)0.82959 (12)1.21357 (9)0.0504 (3)
Cl40.1081 (3)0.49479 (18)1.61913 (15)0.0323 (3)0.50
Cl50.1329 (2)0.73989 (16)1.43400 (9)0.0680 (4)
Cl60.4440 (5)0.8717 (3)1.4549 (2)0.0745 (8)0.50
N10.6626 (6)0.5510 (5)1.8203 (3)0.0464 (9)
H1A0.682 (9)0.455 (8)1.850 (6)0.09 (2)*
H1B0.770 (8)0.569 (6)1.799 (5)0.062 (17)*
H70.527 (8)1.343 (6)1.036 (5)0.057 (15)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0199 (13)0.0234 (14)0.0270 (15)0.0051 (11)0.0053 (11)0.0007 (11)
C20.0246 (15)0.0339 (17)0.0259 (15)0.0124 (13)0.0037 (12)0.0005 (13)
C30.0278 (16)0.0330 (17)0.0353 (17)0.0155 (13)0.0140 (13)0.0117 (14)
C40.0234 (15)0.0204 (14)0.051 (2)0.0071 (12)0.0125 (14)0.0015 (14)
C50.0235 (15)0.0281 (16)0.0352 (17)0.0074 (12)0.0020 (12)0.0081 (13)
C60.0243 (14)0.0249 (15)0.0272 (15)0.0070 (12)0.0041 (12)0.0014 (12)
C70.049 (2)0.040 (2)0.0251 (17)0.0131 (17)0.0051 (15)0.0120 (14)
C80.048 (2)0.040 (2)0.0280 (17)0.0103 (17)0.0060 (16)0.0071 (15)
C90.046 (2)0.047 (2)0.0309 (19)0.0134 (18)0.0054 (16)0.0110 (16)
C100.054 (2)0.048 (2)0.0209 (16)0.0167 (19)0.0060 (16)0.0078 (15)
C110.064 (3)0.048 (2)0.0282 (19)0.006 (2)0.0021 (18)0.0069 (17)
C120.058 (3)0.048 (2)0.034 (2)0.001 (2)0.0031 (18)0.0139 (18)
O10.0336 (12)0.0260 (12)0.0272 (12)0.0010 (9)0.0034 (10)0.0043 (9)
Cl10.0496 (6)0.0409 (5)0.0481 (6)0.0058 (4)0.0075 (4)0.0221 (4)
Cl20.0407 (5)0.0213 (4)0.0866 (8)0.0051 (3)0.0237 (5)0.0015 (4)
Cl30.0577 (6)0.0537 (6)0.0487 (6)0.0297 (5)0.0259 (5)0.0288 (5)
Cl40.0344 (8)0.0299 (8)0.0346 (8)0.0129 (6)0.0066 (6)0.0035 (6)
Cl50.0694 (8)0.0761 (8)0.0321 (5)0.0179 (6)0.0173 (5)0.0021 (5)
Cl60.102 (2)0.0624 (15)0.0409 (12)0.0123 (14)0.0100 (12)0.0224 (11)
N10.046 (2)0.049 (2)0.0303 (17)0.0072 (17)0.0095 (15)0.0105 (15)
Geometric parameters (Å, º) top
C1—O11.355 (4)C7—C81.377 (7)
C1—C61.389 (4)C7—C121.394 (6)
C1—C21.389 (4)C7—N11.415 (5)
C2—C31.388 (5)C8—C91.389 (5)
C3—C41.388 (5)C9—C101.395 (6)
C3—Cl31.723 (3)C9—Cl41.561 (5)
C4—C51.388 (5)C10—C111.370 (7)
C4—Cl21.731 (3)C10—Cl51.736 (4)
C5—C61.380 (4)C11—C121.384 (6)
C5—Cl11.730 (3)C11—Cl61.568 (5)
O1—C1—C6117.0 (3)C8—C7—C12119.9 (4)
O1—C1—C2123.0 (3)C8—C7—N1119.7 (4)
C6—C1—C2120.1 (3)C12—C7—N1120.3 (5)
C3—C2—C1119.2 (3)C7—C8—C9119.3 (4)
C4—C3—C2121.6 (3)C8—C9—C10120.7 (5)
C4—C3—Cl3120.3 (3)C8—C9—Cl4119.7 (4)
C2—C3—Cl3118.2 (3)C10—C9—Cl4119.6 (3)
C3—C4—C5118.0 (3)C11—C10—C9119.8 (4)
C3—C4—Cl2121.3 (3)C11—C10—Cl5119.7 (3)
C5—C4—Cl2120.7 (3)C9—C10—Cl5120.5 (4)
C6—C5—C4121.5 (3)C10—C11—C12119.8 (4)
C6—C5—Cl1118.3 (3)C10—C11—Cl6115.2 (4)
C4—C5—Cl1120.1 (3)C12—C11—Cl6125.0 (5)
C5—C6—C1119.6 (3)C11—C12—C7120.5 (5)
(16) top
Crystal data top
C6H3Cl3O·C6H6BrNZ = 2
Mr = 369.46F(000) = 364
Triclinic, P1Dx = 1.753 Mg m3
a = 7.0562 (15) ÅMo Kα radiation, λ = 0.71073 Å
b = 9.373 (2) ÅCell parameters from 6533 reflections
c = 11.110 (2) Åθ = 3.0–27.6°
α = 83.358 (6)°µ = 3.49 mm1
β = 79.173 (6)°T = 150 K
γ = 76.588 (5)°0.3 × 0.2 × 0.1 mm
V = 700.0 (3) Å3
Data collection top
Rigaku Mercury375R (2x2 bin mode)
diffractometer
3204 independent reflections
Radiation source: fine-focus sealed tube2717 reflections with I > 2σ(I)
Graphite Monochromator monochromatorRint = 0.036
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan
Jacobson, R. (1998) Private communication
h = 99
Tmin = 0.540, Tmax = 1.000k = 1212
7199 measured reflectionsl = 1414
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0434P)2 + 0.6163P]
where P = (Fo2 + 2Fc2)/3
3204 reflections(Δ/σ)max < 0.001
175 parametersΔρmax = 1.24 e Å3
0 restraintsΔρmin = 0.66 e Å3
Crystal data top
C6H3Cl3O·C6H6BrNγ = 76.588 (5)°
Mr = 369.46V = 700.0 (3) Å3
Triclinic, P1Z = 2
a = 7.0562 (15) ÅMo Kα radiation
b = 9.373 (2) ŵ = 3.49 mm1
c = 11.110 (2) ÅT = 150 K
α = 83.358 (6)°0.3 × 0.2 × 0.1 mm
β = 79.173 (6)°
Data collection top
Rigaku Mercury375R (2x2 bin mode)
diffractometer
3204 independent reflections
Absorption correction: multi-scan
Jacobson, R. (1998) Private communication
2717 reflections with I > 2σ(I)
Tmin = 0.540, Tmax = 1.000Rint = 0.036
7199 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.098H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 1.24 e Å3
3204 reflectionsΔρmin = 0.66 e Å3
175 parameters
Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
H2B0.675 (6)0.012 (5)1.345 (4)0.039 (10)*
H1A0.760 (6)0.106 (4)1.291 (4)0.045 (12)*
H1O0.505 (6)0.831 (4)0.539 (4)0.042 (11)*
Br10.10078 (5)0.20720 (4)0.93630 (3)0.04047 (13)
Cl20.03637 (12)0.18035 (8)0.50580 (9)0.0394 (2)
Cl30.25341 (13)0.33750 (9)0.74615 (8)0.0381 (2)
Cl10.04579 (13)0.36577 (10)0.25074 (8)0.0408 (2)
O10.4463 (3)0.8015 (2)0.4726 (2)0.0260 (4)
C60.3482 (4)0.5794 (3)0.5978 (3)0.0216 (6)
H60.40980.62440.66950.026*
C20.2584 (4)0.5919 (3)0.3777 (3)0.0233 (6)
H20.26030.64520.30180.028*
C10.3529 (4)0.6578 (3)0.4853 (3)0.0209 (5)
N10.6537 (4)0.0755 (3)1.3132 (3)0.0302 (6)
C100.2818 (4)0.1611 (3)1.0498 (3)0.0276 (6)
C70.5344 (4)0.1003 (3)1.2198 (3)0.0253 (6)
C40.1559 (4)0.3636 (3)0.4976 (3)0.0250 (6)
C90.4224 (5)0.2430 (4)1.0422 (3)0.0325 (7)
H90.43120.31880.98100.039*
C50.2509 (4)0.4328 (3)0.6034 (3)0.0245 (6)
C30.1616 (4)0.4455 (3)0.3857 (3)0.0263 (6)
C120.3916 (5)0.0191 (3)1.2254 (3)0.0281 (6)
H120.38020.05591.28720.034*
C80.5511 (5)0.2117 (3)1.1268 (3)0.0314 (7)
H80.64850.26531.12130.038*
C110.2659 (5)0.0490 (3)1.1397 (3)0.0295 (6)
H110.17130.00651.14300.035*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0381 (2)0.0539 (2)0.02721 (19)0.00325 (16)0.01176 (14)0.00268 (14)
Cl20.0304 (4)0.0184 (3)0.0709 (6)0.0007 (3)0.0165 (4)0.0057 (3)
Cl30.0480 (5)0.0303 (4)0.0375 (5)0.0116 (3)0.0177 (4)0.0152 (3)
Cl10.0391 (5)0.0426 (5)0.0414 (5)0.0117 (4)0.0059 (4)0.0207 (4)
O10.0296 (11)0.0185 (10)0.0268 (12)0.0007 (8)0.0064 (9)0.0016 (8)
C60.0212 (13)0.0208 (13)0.0235 (14)0.0059 (11)0.0045 (11)0.0011 (11)
C20.0224 (14)0.0250 (14)0.0239 (14)0.0079 (11)0.0061 (11)0.0012 (11)
C10.0176 (13)0.0195 (13)0.0270 (15)0.0055 (10)0.0077 (10)0.0026 (11)
N10.0294 (14)0.0277 (14)0.0342 (15)0.0027 (12)0.0109 (11)0.0027 (11)
C100.0273 (15)0.0337 (16)0.0181 (14)0.0005 (12)0.0024 (11)0.0032 (12)
C70.0268 (15)0.0240 (14)0.0234 (15)0.0002 (12)0.0041 (11)0.0054 (11)
C40.0161 (13)0.0194 (13)0.0414 (18)0.0052 (11)0.0080 (12)0.0023 (12)
C90.0361 (17)0.0372 (17)0.0207 (15)0.0095 (14)0.0011 (12)0.0054 (12)
C50.0233 (14)0.0226 (14)0.0309 (16)0.0104 (11)0.0115 (11)0.0069 (11)
C30.0204 (14)0.0281 (15)0.0329 (16)0.0083 (12)0.0016 (11)0.0104 (12)
C120.0364 (17)0.0222 (14)0.0264 (15)0.0073 (12)0.0090 (12)0.0040 (11)
C80.0334 (17)0.0327 (16)0.0290 (16)0.0145 (14)0.0009 (13)0.0007 (13)
C110.0331 (16)0.0268 (15)0.0303 (17)0.0090 (13)0.0063 (13)0.0026 (12)
Geometric parameters (Å, º) top
Br1—C101.906 (3)N1—C71.422 (4)
Cl2—C41.729 (3)C10—C111.372 (4)
Cl3—C51.727 (3)C10—C91.374 (5)
Cl1—C31.729 (3)C7—C121.385 (4)
O1—C11.360 (3)C7—C81.391 (4)
C6—C11.377 (4)C4—C31.386 (4)
C6—C51.386 (4)C4—C51.390 (4)
C2—C31.384 (4)C9—C81.388 (5)
C2—C11.391 (4)C12—C111.383 (4)
C1—C6—C5119.5 (3)C3—C4—Cl2121.2 (2)
C3—C2—C1118.8 (3)C5—C4—Cl2120.8 (2)
O1—C1—C6122.8 (3)C10—C9—C8119.5 (3)
O1—C1—C2116.6 (2)C6—C5—C4121.3 (3)
C6—C1—C2120.6 (3)C6—C5—Cl3118.0 (2)
C11—C10—C9121.2 (3)C4—C5—Cl3120.7 (2)
C11—C10—Br1119.3 (2)C2—C3—C4121.8 (3)
C9—C10—Br1119.5 (2)C2—C3—Cl1118.0 (2)
C12—C7—C8119.5 (3)C4—C3—Cl1120.2 (2)
C12—C7—N1119.9 (3)C11—C12—C7120.4 (3)
C8—C7—N1120.5 (3)C9—C8—C7120.0 (3)
C3—C4—C5118.0 (3)C10—C11—C12119.5 (3)
(17) top
Crystal data top
C6H3Cl3O·C6H6INZ = 2
Mr = 416.45F(000) = 400
Triclinic, P1Dx = 1.909 Mg m3
a = 7.083 (3) ÅMo Kα radiation, λ = 0.71073 Å
b = 9.354 (4) ÅCell parameters from 4784 reflections
c = 11.456 (5) Åθ = 3.2–27.6°
α = 84.118 (7)°µ = 2.75 mm1
β = 79.555 (7)°T = 150 K
γ = 76.553 (7)°0.3 × 0.2 × 0.1 mm
V = 724.5 (5) Å3
Data collection top
Rigaku Mercury375R (2x2 bin mode)
diffractometer
3313 independent reflections
Radiation source: fine-focus sealed tube3105 reflections with I > 2σ(I)
Graphite Monochromator monochromatorRint = 0.024
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.2°
Absorption correction: multi-scan
Jacobson, R. (1998) Private communication
h = 99
Tmin = 0.614, Tmax = 1.000k = 1212
7553 measured reflectionsl = 1414
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.028Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.070H atoms treated by a mixture of independent and constrained refinement
S = 1.12 w = 1/[σ2(Fo2) + (0.0143P)2 + 1.5784P]
where P = (Fo2 + 2Fc2)/3
3313 reflections(Δ/σ)max < 0.001
172 parametersΔρmax = 0.84 e Å3
0 restraintsΔρmin = 1.18 e Å3
Crystal data top
C6H3Cl3O·C6H6INγ = 76.553 (7)°
Mr = 416.45V = 724.5 (5) Å3
Triclinic, P1Z = 2
a = 7.083 (3) ÅMo Kα radiation
b = 9.354 (4) ŵ = 2.75 mm1
c = 11.456 (5) ÅT = 150 K
α = 84.118 (7)°0.3 × 0.2 × 0.1 mm
β = 79.555 (7)°
Data collection top
Rigaku Mercury375R (2x2 bin mode)
diffractometer
3313 independent reflections
Absorption correction: multi-scan
Jacobson, R. (1998) Private communication
3105 reflections with I > 2σ(I)
Tmin = 0.614, Tmax = 1.000Rint = 0.024
7553 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0280 restraints
wR(F2) = 0.070H atoms treated by a mixture of independent and constrained refinement
S = 1.12Δρmax = 0.84 e Å3
3313 reflectionsΔρmin = 1.18 e Å3
172 parameters
Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.6466 (4)1.1554 (3)0.0111 (3)0.0205 (5)
C20.7447 (4)1.0845 (3)0.1130 (3)0.0234 (6)
H20.74561.13480.18740.028*
C30.8410 (4)0.9382 (3)0.1022 (3)0.0250 (6)
C40.8409 (4)0.8593 (3)0.0074 (3)0.0249 (6)
C50.7416 (4)0.9327 (3)0.1072 (3)0.0239 (6)
C60.6457 (4)1.0797 (3)0.0998 (3)0.0218 (6)
H60.58151.12700.16820.026*
C70.4596 (4)0.4029 (3)0.2715 (3)0.0243 (6)
C80.6048 (5)0.4814 (3)0.2703 (3)0.0279 (6)
H80.61930.55700.21220.033*
C90.7271 (5)0.4474 (4)0.3549 (3)0.0294 (7)
H90.82430.49980.35350.035*
C100.7055 (5)0.3358 (4)0.4417 (3)0.0273 (6)
C110.5604 (5)0.2571 (4)0.4449 (3)0.0332 (7)
H110.54660.18140.50290.040*
C120.4364 (5)0.2931 (4)0.3605 (3)0.0312 (7)
H120.33640.24290.36370.037*
Cl10.96210 (13)0.85307 (10)0.23056 (8)0.0398 (2)
Cl20.95991 (12)0.67672 (8)0.01919 (9)0.0391 (2)
Cl30.73172 (14)0.84277 (9)0.24748 (8)0.0387 (2)
I10.90135 (3)0.27572 (3)0.564201 (19)0.03831 (8)
N10.3459 (4)0.4307 (3)0.1790 (3)0.0289 (6)
O10.5534 (3)1.2988 (2)0.02595 (19)0.0260 (4)
H1O0.48841.32680.03760.039*
H1A0.328 (6)0.515 (5)0.147 (3)0.033 (10)*
H1B0.243 (6)0.401 (4)0.195 (3)0.028 (10)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0175 (13)0.0210 (14)0.0237 (14)0.0052 (10)0.0055 (11)0.0008 (11)
C20.0225 (14)0.0262 (15)0.0228 (14)0.0080 (11)0.0040 (11)0.0013 (11)
C30.0172 (13)0.0288 (15)0.0302 (16)0.0067 (11)0.0005 (11)0.0102 (12)
C40.0184 (13)0.0150 (13)0.0426 (18)0.0016 (10)0.0083 (12)0.0072 (12)
C50.0225 (14)0.0242 (14)0.0272 (15)0.0079 (11)0.0094 (12)0.0047 (11)
C60.0191 (13)0.0252 (14)0.0210 (14)0.0050 (11)0.0034 (11)0.0003 (11)
C70.0252 (14)0.0250 (15)0.0202 (14)0.0009 (11)0.0002 (11)0.0069 (11)
C80.0344 (17)0.0203 (14)0.0281 (16)0.0051 (12)0.0057 (13)0.0013 (12)
C90.0314 (16)0.0284 (16)0.0291 (16)0.0062 (13)0.0050 (13)0.0060 (12)
C100.0285 (15)0.0321 (16)0.0174 (14)0.0019 (12)0.0022 (12)0.0061 (12)
C110.0380 (18)0.0388 (18)0.0197 (15)0.0106 (14)0.0022 (13)0.0048 (13)
C120.0307 (16)0.0354 (17)0.0278 (16)0.0116 (13)0.0010 (13)0.0043 (13)
Cl10.0348 (4)0.0425 (5)0.0429 (5)0.0103 (4)0.0062 (4)0.0237 (4)
Cl20.0305 (4)0.0174 (3)0.0706 (6)0.0005 (3)0.0166 (4)0.0066 (4)
Cl30.0521 (5)0.0298 (4)0.0358 (4)0.0105 (4)0.0176 (4)0.0127 (3)
I10.03512 (13)0.05327 (16)0.02303 (12)0.00223 (10)0.00657 (9)0.00009 (9)
N10.0284 (14)0.0276 (15)0.0298 (15)0.0035 (11)0.0065 (11)0.0011 (11)
O10.0290 (11)0.0205 (10)0.0251 (11)0.0001 (8)0.0045 (9)0.0022 (8)
Geometric parameters (Å, º) top
C1—O11.358 (3)C7—N11.412 (4)
C1—C61.390 (4)C8—C91.380 (4)
C1—C21.391 (4)C8—H80.9300
C2—C31.384 (4)C9—C101.382 (5)
C2—H20.9300C9—H90.9300
C3—C41.390 (5)C10—C111.390 (5)
C3—Cl11.731 (3)C10—I12.095 (3)
C4—C51.385 (4)C11—C121.387 (5)
C4—Cl21.723 (3)C11—H110.9300
C5—C61.386 (4)C12—H120.9300
C5—Cl31.733 (3)N1—H1A0.83 (4)
C6—H60.9300N1—H1B0.82 (4)
C7—C121.388 (4)O1—H1O0.8200
C7—C81.393 (4)
O1—C1—C6122.7 (3)C8—C7—N1119.7 (3)
O1—C1—C2117.2 (3)C9—C8—C7120.2 (3)
C6—C1—C2120.2 (3)C9—C8—H8119.9
C3—C2—C1119.2 (3)C7—C8—H8119.9
C3—C2—H2120.4C8—C9—C10120.2 (3)
C1—C2—H2120.4C8—C9—H9119.9
C2—C3—C4122.0 (3)C10—C9—H9119.9
C2—C3—Cl1118.1 (2)C9—C10—C11120.4 (3)
C4—C3—Cl1120.0 (2)C9—C10—I1120.2 (2)
C5—C4—C3117.6 (3)C11—C10—I1119.3 (2)
C5—C4—Cl2121.1 (3)C12—C11—C10119.1 (3)
C3—C4—Cl2121.4 (2)C12—C11—H11120.4
C4—C5—C6122.0 (3)C10—C11—H11120.4
C4—C5—Cl3120.8 (2)C11—C12—C7120.9 (3)
C6—C5—Cl3117.2 (2)C11—C12—H12119.6
C5—C6—C1119.1 (3)C7—C12—H12119.6
C5—C6—H6120.4C7—N1—H1A117 (3)
C1—C6—H6120.4C7—N1—H1B114 (3)
C12—C7—C8119.2 (3)H1A—N1—H1B112 (4)
C12—C7—N1121.1 (3)C1—O1—H1O109.5
O1—C1—C2—C3179.7 (3)Cl3—C5—C6—C1178.8 (2)
C6—C1—C2—C30.1 (4)O1—C1—C6—C5178.9 (3)
C1—C2—C3—C40.7 (4)C2—C1—C6—C50.7 (4)
C1—C2—C3—Cl1179.9 (2)C12—C7—C8—C91.7 (5)
C2—C3—C4—C50.5 (4)N1—C7—C8—C9175.0 (3)
Cl1—C3—C4—C5179.9 (2)C7—C8—C9—C100.4 (5)
C2—C3—C4—Cl2179.5 (2)C8—C9—C10—C110.2 (5)
Cl1—C3—C4—Cl20.1 (4)C8—C9—C10—I1176.4 (2)
C3—C4—C5—C60.3 (4)C9—C10—C11—C120.6 (5)
Cl2—C4—C5—C6179.7 (2)I1—C10—C11—C12177.2 (2)
C3—C4—C5—Cl3179.4 (2)C10—C11—C12—C72.0 (5)
Cl2—C4—C5—Cl30.6 (4)C8—C7—C12—C112.6 (5)
C4—C5—C6—C10.9 (4)N1—C7—C12—C11174.1 (3)
(18) top
Crystal data top
C6H4ClIN·C6H3Cl3OZ = 2
Mr = 449.89F(000) = 430
Triclinic, P1Dx = 1.991 Mg m3
a = 7.107 (2) ÅMo Kα radiation, λ = 0.71073 Å
b = 9.498 (3) ÅCell parameters from 7098 reflections
c = 11.827 (3) Åθ = 3.0–27.5°
α = 85.425 (6)°µ = 2.84 mm1
β = 81.804 (6)°T = 150 K
γ = 71.851 (5)°0.3 × 0.2 × 0.1 mm
V = 750.4 (4) Å3
Data collection top
Radiation source: fine-focus sealed tube3038 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.026
Absorption correction: multi-scan
Jacobson, R. (1998) Private communication
θmax = 27.5°, θmin = 3.0°
Tmin = 0.578, Tmax = 1.000h = 99
7564 measured reflectionsk = 1212
3429 independent reflectionsl = 1515
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.048H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.124 w = 1/[σ2(Fo2) + (0.0419P)2 + 1.7038P]
where P = (Fo2 + 2Fc2)/3
S = 1.20(Δ/σ)max < 0.001
3429 reflectionsΔρmax = 1.01 e Å3
201 parametersΔρmin = 0.88 e Å3
0 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0057 (17)
Crystal data top
C6H4ClIN·C6H3Cl3Oγ = 71.851 (5)°
Mr = 449.89V = 750.4 (4) Å3
Triclinic, P1Z = 2
a = 7.107 (2) ÅMo Kα radiation
b = 9.498 (3) ŵ = 2.84 mm1
c = 11.827 (3) ÅT = 150 K
α = 85.425 (6)°0.3 × 0.2 × 0.1 mm
β = 81.804 (6)°
Data collection top
Absorption correction: multi-scan
Jacobson, R. (1998) Private communication
3429 independent reflections
Tmin = 0.578, Tmax = 1.0003038 reflections with I > 2σ(I)
7564 measured reflectionsRint = 0.026
Refinement top
R[F2 > 2σ(F2)] = 0.0480 restraints
wR(F2) = 0.124H atoms treated by a mixture of independent and constrained refinement
S = 1.20Δρmax = 1.01 e Å3
3429 reflectionsΔρmin = 0.88 e Å3
201 parameters
Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
C90.0478 (9)0.7585 (7)0.4339 (4)0.0576 (15)
C40.3545 (6)1.6353 (4)0.0128 (5)0.0369 (10)
C10.1354 (5)1.3366 (4)0.0168 (3)0.0261 (7)
C20.2313 (6)1.4048 (4)0.1180 (4)0.0305 (8)
H20.22241.35130.18750.037*
C30.3398 (6)1.5529 (5)0.1137 (4)0.0364 (10)
C100.1956 (9)0.8232 (6)0.4415 (4)0.0535 (15)
C60.1475 (6)1.4163 (4)0.0864 (4)0.0285 (8)
H60.08321.37090.15410.034*
C70.0516 (6)0.9123 (5)0.2678 (4)0.0356 (9)
C80.0739 (8)0.8023 (6)0.3494 (4)0.0473 (12)
H80.17290.75820.34640.057*
C110.2145 (7)0.9344 (6)0.3621 (4)0.0473 (12)
C50.2574 (6)1.5655 (5)0.0868 (4)0.0341 (9)
C120.0938 (7)0.9789 (5)0.2751 (4)0.0375 (10)
H120.11051.05310.22210.045*
Cl90.0426 (4)0.6367 (3)0.5358 (2)0.0572 (7)0.50
H1A0.177 (9)1.042 (8)0.141 (6)0.060 (18)*
H1B0.264 (10)0.942 (8)0.186 (6)0.06 (2)*
Cl20.49031 (19)1.82135 (12)0.01099 (16)0.0602 (4)
Cl30.2662 (2)1.66233 (15)0.21655 (13)0.0586 (4)
Cl40.4604 (2)1.63364 (15)0.24184 (13)0.0582 (4)
Cl50.3820 (3)1.0050 (2)0.37402 (17)0.0305 (4)0.50
O10.0298 (4)1.1907 (3)0.0256 (2)0.0311 (6)
H1O0.01971.16030.03820.047*
N10.1658 (7)0.9488 (5)0.1758 (3)0.0371 (8)
I1A0.42335 (19)0.7807 (3)0.55954 (8)0.0356 (5)0.405 (5)
I1B0.3726 (2)0.72527 (18)0.56697 (5)0.0421 (4)0.595 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C90.065 (3)0.055 (3)0.029 (2)0.010 (3)0.003 (2)0.004 (2)
C40.0239 (18)0.0195 (18)0.071 (3)0.0064 (15)0.0157 (19)0.0066 (19)
C10.0215 (16)0.0220 (17)0.035 (2)0.0062 (13)0.0058 (15)0.0005 (15)
C20.0285 (18)0.0272 (19)0.036 (2)0.0087 (15)0.0026 (16)0.0053 (16)
C30.0256 (19)0.029 (2)0.055 (3)0.0065 (16)0.0047 (18)0.0175 (19)
C100.059 (3)0.050 (3)0.022 (2)0.026 (2)0.005 (2)0.0046 (19)
C60.0259 (18)0.0274 (19)0.034 (2)0.0096 (15)0.0058 (15)0.0012 (16)
C70.035 (2)0.033 (2)0.027 (2)0.0060 (17)0.0004 (16)0.0077 (16)
C80.053 (3)0.044 (3)0.034 (2)0.002 (2)0.004 (2)0.003 (2)
C110.044 (3)0.050 (3)0.033 (2)0.011 (2)0.0067 (19)0.016 (2)
C50.0300 (19)0.0274 (19)0.051 (3)0.0139 (16)0.0195 (18)0.0104 (18)
C120.041 (2)0.031 (2)0.029 (2)0.0059 (17)0.0062 (17)0.0033 (17)
Cl90.0626 (16)0.0589 (16)0.0512 (15)0.0267 (13)0.0074 (12)0.0254 (12)
Cl20.0452 (6)0.0198 (5)0.1186 (13)0.0016 (4)0.0368 (7)0.0068 (6)
Cl30.0736 (9)0.0462 (7)0.0682 (9)0.0294 (6)0.0412 (7)0.0310 (6)
Cl40.0484 (7)0.0505 (7)0.0715 (9)0.0056 (6)0.0047 (6)0.0372 (7)
Cl50.0331 (9)0.0282 (9)0.0347 (10)0.0140 (7)0.0107 (8)0.0032 (7)
O10.0350 (15)0.0213 (13)0.0313 (14)0.0010 (11)0.0023 (12)0.0015 (11)
N10.037 (2)0.037 (2)0.033 (2)0.0039 (17)0.0046 (16)0.0050 (16)
I1A0.0354 (5)0.0376 (9)0.0330 (4)0.0082 (4)0.0100 (3)0.0010 (4)
I1B0.0549 (6)0.0354 (5)0.0274 (3)0.0004 (4)0.0097 (2)0.0028 (2)
Geometric parameters (Å, º) top
C9—C81.370 (8)C10—C111.382 (8)
C9—C101.389 (9)C10—I1B2.057 (5)
C9—Cl91.607 (6)C10—I1A2.209 (6)
C4—C31.372 (7)C6—C51.389 (6)
C4—C51.383 (7)C7—C121.385 (7)
C4—Cl21.730 (4)C7—C81.395 (7)
C1—O11.359 (4)C7—N11.407 (6)
C1—C61.382 (6)C11—C121.389 (6)
C1—C21.391 (6)C11—Cl51.565 (6)
C2—C31.378 (6)C5—Cl31.723 (5)
C3—Cl41.739 (5)Cl9—I1B2.805 (4)
C8—C9—C10121.0 (5)C9—C10—I1B113.2 (4)
C8—C9—Cl9128.1 (6)C11—C10—I1A110.1 (5)
C10—C9—Cl9110.9 (4)C9—C10—I1A132.0 (4)
C3—C4—C5118.1 (4)C1—C6—C5118.7 (4)
C3—C4—Cl2120.7 (4)C12—C7—C8118.7 (4)
C5—C4—Cl2121.1 (4)C12—C7—N1120.4 (4)
O1—C1—C6122.8 (4)C8—C7—N1120.8 (5)
O1—C1—C2116.6 (3)C9—C8—C7121.0 (5)
C6—C1—C2120.5 (4)C10—C11—C12121.7 (5)
C3—C2—C1118.9 (4)C10—C11—Cl5116.4 (4)
C4—C3—C2122.0 (4)C12—C11—Cl5121.9 (5)
C4—C3—Cl4120.4 (3)C4—C5—C6121.7 (4)
C2—C3—Cl4117.6 (4)C4—C5—Cl3120.8 (3)
C11—C10—C9118.0 (5)C6—C5—Cl3117.5 (4)
C11—C10—I1B128.7 (5)C7—C12—C11119.7 (5)
(19) top
Crystal data top
C6H3Cl3O·C6H6ClNF(000) = 656
Mr = 325.00Dx = 1.626 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 7.851 (5) ÅCell parameters from 4028 reflections
b = 11.865 (7) Åθ = 2.2–27.5°
c = 14.891 (8) ŵ = 0.88 mm1
β = 106.79 (3)°T = 150 K
V = 1328.0 (14) Å30.20 × 0.20 × 0.20 mm
Z = 4
Data collection top
Rigaku Mercury375R (2x2 bin mode)
diffractometer
3068 independent reflections
Radiation source: fine-focus sealed tube2843 reflections with I > 2σ(I)
Graphite Monochromator monochromatorRint = 0.157
Detector resolution: 13.6612 pixels mm-1θmax = 27.6°, θmin = 2.2°
Absorption correction: multi-scan
Jacobson, R. (1998) Private communication
h = 1010
Tmin = 0.804, Tmax = 1.000k = 1515
13867 measured reflectionsl = 1919
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.144H-atom parameters constrained
S = 1.14 w = 1/[σ2(Fo2) + (0.0657P)2 + 0.229P]
where P = (Fo2 + 2Fc2)/3
3068 reflections(Δ/σ)max < 0.001
163 parametersΔρmax = 0.43 e Å3
0 restraintsΔρmin = 0.67 e Å3
Crystal data top
C6H3Cl3O·C6H6ClNV = 1328.0 (14) Å3
Mr = 325.00Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.851 (5) ŵ = 0.88 mm1
b = 11.865 (7) ÅT = 150 K
c = 14.891 (8) Å0.20 × 0.20 × 0.20 mm
β = 106.79 (3)°
Data collection top
Rigaku Mercury375R (2x2 bin mode)
diffractometer
3068 independent reflections
Absorption correction: multi-scan
Jacobson, R. (1998) Private communication
2843 reflections with I > 2σ(I)
Tmin = 0.804, Tmax = 1.000Rint = 0.157
13867 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0420 restraints
wR(F2) = 0.144H-atom parameters constrained
S = 1.14Δρmax = 0.43 e Å3
3068 reflectionsΔρmin = 0.67 e Å3
163 parameters
Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl10.80413 (7)0.33847 (4)0.02255 (3)0.02673 (17)
Cl20.49563 (7)0.47342 (4)0.33598 (3)0.02614 (17)
Cl30.59367 (7)0.52098 (4)0.11800 (3)0.03092 (18)
O10.87627 (19)0.13477 (12)0.06494 (10)0.0263 (3)
H1O0.92500.08250.07780.039*
C10.7878 (2)0.21061 (16)0.12872 (13)0.0193 (4)
C20.7412 (3)0.19133 (16)0.22498 (13)0.0206 (4)
H20.77070.12310.24740.025*
C30.6517 (2)0.27218 (17)0.28749 (13)0.0203 (4)
H30.62280.25850.35160.024*
C40.6050 (2)0.37335 (16)0.25525 (13)0.0188 (4)
C50.6479 (2)0.39438 (15)0.15920 (13)0.0190 (4)
C60.7396 (2)0.31274 (16)0.09657 (13)0.0188 (4)
Cl40.34428 (7)0.20566 (5)0.03592 (4)0.03470 (19)
N10.0477 (2)0.46511 (15)0.37280 (12)0.0253 (4)
H1A0.13640.49610.37270.030*
H1B0.08260.42750.42730.030*
C70.0448 (2)0.40235 (17)0.29246 (13)0.0206 (4)
C80.0453 (3)0.43822 (17)0.20308 (14)0.0220 (4)
H80.01730.50270.19640.026*
C90.1383 (3)0.37849 (18)0.12416 (13)0.0240 (4)
H90.13800.40230.06470.029*
C100.2316 (3)0.28310 (17)0.13490 (13)0.0231 (4)
C110.2369 (3)0.24761 (18)0.22285 (14)0.0255 (4)
H110.30240.18430.22900.031*
C120.1430 (3)0.30787 (17)0.30155 (14)0.0231 (4)
H120.14590.28480.36080.028*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0356 (3)0.0287 (3)0.0148 (3)0.00280 (19)0.00550 (19)0.00239 (17)
Cl20.0325 (3)0.0219 (3)0.0208 (3)0.00374 (17)0.0026 (2)0.00311 (16)
Cl30.0423 (3)0.0231 (3)0.0243 (3)0.0112 (2)0.0047 (2)0.00520 (17)
O10.0355 (8)0.0225 (7)0.0195 (7)0.0099 (6)0.0055 (6)0.0016 (6)
C10.0199 (8)0.0185 (9)0.0189 (9)0.0001 (6)0.0049 (7)0.0021 (7)
C20.0223 (9)0.0189 (9)0.0214 (9)0.0000 (7)0.0077 (7)0.0030 (7)
C30.0206 (8)0.0240 (9)0.0166 (8)0.0020 (7)0.0061 (7)0.0026 (7)
C40.0178 (8)0.0199 (9)0.0186 (9)0.0011 (7)0.0049 (6)0.0021 (7)
C50.0195 (8)0.0189 (8)0.0194 (9)0.0011 (7)0.0070 (7)0.0033 (7)
C60.0209 (8)0.0209 (9)0.0156 (8)0.0016 (7)0.0066 (7)0.0011 (7)
Cl40.0343 (3)0.0378 (3)0.0253 (3)0.0013 (2)0.0020 (2)0.0060 (2)
N10.0273 (8)0.0259 (9)0.0207 (8)0.0038 (7)0.0039 (6)0.0010 (6)
C70.0209 (8)0.0206 (9)0.0202 (9)0.0085 (7)0.0056 (7)0.0005 (7)
C80.0242 (9)0.0200 (9)0.0226 (9)0.0043 (7)0.0080 (7)0.0026 (7)
C90.0259 (9)0.0280 (10)0.0183 (9)0.0070 (8)0.0066 (7)0.0037 (7)
C100.0207 (9)0.0257 (9)0.0211 (9)0.0057 (7)0.0035 (7)0.0027 (7)
C110.0218 (9)0.0262 (10)0.0293 (10)0.0018 (8)0.0087 (8)0.0028 (8)
C120.0239 (9)0.0261 (10)0.0210 (9)0.0044 (7)0.0093 (7)0.0041 (7)
Geometric parameters (Å, º) top
Cl1—C61.725 (2)N1—C71.418 (3)
Cl2—C41.731 (2)N1—H1A0.7881
Cl3—C51.722 (2)N1—H1B0.8964
O1—C11.346 (2)C7—C121.389 (3)
O1—H1O0.7811C7—C81.396 (3)
C1—C21.392 (3)C8—C91.386 (3)
C1—C61.395 (3)C8—H80.9300
C2—C31.379 (3)C9—C101.382 (3)
C2—H20.9300C9—H90.9300
C3—C41.381 (3)C10—C111.388 (3)
C3—H30.9300C11—C121.389 (3)
C4—C51.394 (3)C11—H110.9300
C5—C61.392 (3)C12—H120.9300
Cl4—C101.745 (2)
C1—O1—H1O123.1C7—N1—H1B116.7
O1—C1—C2123.04 (17)H1A—N1—H1B101.3
O1—C1—C6118.32 (17)C12—C7—C8119.34 (18)
C2—C1—C6118.64 (17)C12—C7—N1120.33 (18)
C3—C2—C1120.79 (17)C8—C7—N1120.25 (18)
C3—C2—H2119.6C9—C8—C7120.55 (19)
C1—C2—H2119.6C9—C8—H8119.7
C2—C3—C4120.30 (18)C7—C8—H8119.7
C2—C3—H3119.9C10—C9—C8119.18 (18)
C4—C3—H3119.9C10—C9—H9120.4
C3—C4—C5120.16 (17)C8—C9—H9120.4
C3—C4—Cl2118.88 (15)C9—C10—C11121.25 (18)
C5—C4—Cl2120.95 (15)C9—C10—Cl4119.31 (15)
C6—C5—C4119.20 (17)C11—C10—Cl4119.43 (16)
C6—C5—Cl3120.09 (14)C10—C11—C12119.15 (19)
C4—C5—Cl3120.69 (14)C10—C11—H11120.4
C5—C6—C1120.90 (17)C12—C11—H11120.4
C5—C6—Cl1120.48 (14)C7—C12—C11120.49 (18)
C1—C6—Cl1118.57 (15)C7—C12—H12119.8
C7—N1—H1A118.7C11—C12—H12119.8
O1—C1—C2—C3179.49 (17)C2—C1—C6—C50.5 (3)
C6—C1—C2—C31.1 (3)O1—C1—C6—Cl12.8 (2)
C1—C2—C3—C40.8 (3)C2—C1—C6—Cl1177.80 (14)
C2—C3—C4—C50.0 (3)C12—C7—C8—C91.9 (3)
C2—C3—C4—Cl2179.09 (14)N1—C7—C8—C9178.74 (17)
C3—C4—C5—C60.6 (3)C7—C8—C9—C100.3 (3)
Cl2—C4—C5—C6178.53 (14)C8—C9—C10—C111.4 (3)
C3—C4—C5—Cl3178.96 (14)C8—C9—C10—Cl4178.39 (14)
Cl2—C4—C5—Cl30.1 (2)C9—C10—C11—C121.5 (3)
C4—C5—C6—C10.3 (3)Cl4—C10—C11—C12178.27 (14)
Cl3—C5—C6—C1178.68 (14)C8—C7—C12—C111.8 (3)
C4—C5—C6—Cl1176.92 (13)N1—C7—C12—C11178.62 (17)
Cl3—C5—C6—Cl11.5 (2)C10—C11—C12—C70.1 (3)
O1—C1—C6—C5179.98 (16)
(20) top
Crystal data top
C6H3Cl3O·C6H6ClNZ = 2
Mr = 325.00F(000) = 328
Triclinic, P1Dx = 1.623 Mg m3
a = 7.208 (9) ÅMo Kα radiation, λ = 0.71073 Å
b = 9.333 (10) ÅCell parameters from 2132 reflections
c = 10.884 (13) Åθ = 3.1–27.5°
α = 99.035 (14)°µ = 0.88 mm1
β = 107.107 (6)°T = 150 K
γ = 102.219 (10)°0.20 × 0.20 × 0.20 mm
V = 664.9 (13) Å3
Data collection top
Rigaku Mercury375R (2x2 bin mode)
diffractometer
2397 independent reflections
Radiation source: fine-focus sealed tube2240 reflections with I > 2σ(I)
Graphite Monochromator monochromatorRint = 0.156
Detector resolution: 13.6612 pixels mm-1θmax = 25.2°, θmin = 2.0°
Absorption correction: multi-scan
Jacobson, R. (1998) Private communication
h = 88
Tmin = 0.844, Tmax = 1.000k = 1111
5849 measured reflectionsl = 1313
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.139H atoms treated by a mixture of independent and constrained refinement
S = 1.14 w = 1/[σ2(Fo2) + (0.0565P)2 + 0.0167P]
where P = (Fo2 + 2Fc2)/3
2397 reflections(Δ/σ)max < 0.001
175 parametersΔρmax = 0.45 e Å3
0 restraintsΔρmin = 0.45 e Å3
Crystal data top
C6H3Cl3O·C6H6ClNγ = 102.219 (10)°
Mr = 325.00V = 664.9 (13) Å3
Triclinic, P1Z = 2
a = 7.208 (9) ÅMo Kα radiation
b = 9.333 (10) ŵ = 0.88 mm1
c = 10.884 (13) ÅT = 150 K
α = 99.035 (14)°0.20 × 0.20 × 0.20 mm
β = 107.107 (6)°
Data collection top
Rigaku Mercury375R (2x2 bin mode)
diffractometer
2397 independent reflections
Absorption correction: multi-scan
Jacobson, R. (1998) Private communication
2240 reflections with I > 2σ(I)
Tmin = 0.844, Tmax = 1.000Rint = 0.156
5849 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0420 restraints
wR(F2) = 0.139H atoms treated by a mixture of independent and constrained refinement
S = 1.14Δρmax = 0.45 e Å3
2397 reflectionsΔρmin = 0.45 e Å3
175 parameters
Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
H1A0.070 (4)0.868 (3)0.286 (3)0.026 (8)*
H1O0.049 (4)0.185 (3)0.557 (3)0.031 (7)*
H1B0.019 (4)0.984 (3)0.333 (3)0.019 (6)*
Cl10.27595 (9)0.59690 (6)0.24122 (6)0.0263 (2)
Cl20.46362 (8)0.83079 (5)0.51627 (7)0.0277 (2)
Cl30.07242 (9)0.25908 (6)0.22791 (6)0.0260 (2)
Cl40.71511 (9)0.95479 (7)0.10761 (7)0.0302 (2)
O10.0510 (2)0.20209 (15)0.47606 (18)0.0211 (4)
N10.0066 (3)0.8943 (2)0.3094 (2)0.0208 (5)
C70.1900 (3)0.8492 (2)0.2005 (2)0.0185 (5)
C30.2616 (3)0.5415 (2)0.3828 (2)0.0180 (5)
C90.5251 (3)0.8671 (2)0.1026 (2)0.0210 (5)
C80.3424 (3)0.9193 (2)0.2042 (2)0.0201 (5)
H80.32070.99970.27400.024*
C40.3422 (3)0.6451 (2)0.5047 (3)0.0186 (5)
C50.3273 (3)0.6014 (2)0.6184 (2)0.0209 (5)
H50.38220.67110.69960.025*
C10.1492 (3)0.3480 (2)0.4901 (2)0.0171 (5)
C20.1676 (3)0.3918 (2)0.3767 (2)0.0172 (5)
C120.2251 (4)0.7309 (2)0.0940 (3)0.0241 (5)
H120.12360.68520.09010.029*
C60.2299 (3)0.4534 (2)0.6103 (2)0.0206 (5)
H60.21870.42450.68640.025*
C100.5644 (4)0.7485 (2)0.0034 (3)0.0255 (5)
H100.68930.71500.07060.031*
C110.4110 (4)0.6810 (2)0.0062 (3)0.0268 (6)
H110.43340.60100.07640.032*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0375 (4)0.0253 (3)0.0281 (4)0.0143 (2)0.0191 (3)0.0167 (3)
Cl20.0295 (4)0.0138 (3)0.0415 (5)0.0041 (2)0.0146 (3)0.0093 (3)
Cl30.0366 (4)0.0204 (3)0.0194 (4)0.0061 (2)0.0092 (3)0.0031 (3)
Cl40.0298 (4)0.0360 (4)0.0382 (5)0.0175 (3)0.0211 (3)0.0166 (3)
O10.0273 (8)0.0147 (7)0.0223 (9)0.0020 (6)0.0119 (7)0.0059 (7)
N10.0227 (10)0.0173 (10)0.0253 (12)0.0050 (8)0.0124 (9)0.0054 (8)
C70.0236 (11)0.0143 (10)0.0222 (13)0.0044 (8)0.0131 (9)0.0082 (9)
C30.0177 (11)0.0188 (10)0.0246 (14)0.0095 (8)0.0116 (10)0.0102 (10)
C90.0276 (12)0.0200 (10)0.0270 (14)0.0099 (8)0.0203 (10)0.0118 (10)
C80.0291 (12)0.0153 (10)0.0214 (13)0.0048 (8)0.0165 (10)0.0061 (9)
C40.0168 (10)0.0153 (10)0.0271 (13)0.0071 (8)0.0089 (9)0.0076 (9)
C50.0221 (11)0.0194 (11)0.0227 (13)0.0072 (8)0.0096 (9)0.0032 (9)
C10.0161 (10)0.0160 (10)0.0237 (13)0.0069 (7)0.0095 (9)0.0088 (9)
C20.0165 (10)0.0182 (10)0.0191 (12)0.0081 (8)0.0066 (8)0.0052 (9)
C120.0313 (12)0.0217 (11)0.0269 (14)0.0122 (9)0.0160 (10)0.0088 (10)
C60.0211 (11)0.0207 (11)0.0235 (13)0.0074 (8)0.0102 (10)0.0076 (10)
C100.0259 (12)0.0280 (11)0.0224 (13)0.0058 (9)0.0077 (10)0.0083 (10)
C110.0355 (13)0.0213 (11)0.0219 (14)0.0070 (9)0.0105 (11)0.0000 (10)
Geometric parameters (Å, º) top
Cl1—C31.724 (3)C3—C21.400 (3)
Cl2—C41.735 (3)C9—C81.377 (4)
Cl3—C21.728 (3)C9—C101.383 (4)
Cl4—C91.747 (3)C4—C51.389 (4)
O1—C11.357 (3)C5—C61.387 (3)
N1—C71.420 (3)C1—C61.387 (4)
C7—C121.391 (3)C1—C21.393 (4)
C7—C81.400 (3)C12—C111.384 (4)
C3—C41.392 (4)C10—C111.389 (4)
C12—C7—C8119.5 (2)C3—C4—Cl2120.24 (18)
C12—C7—N1121.1 (2)C6—C5—C4119.7 (2)
C8—C7—N1119.2 (2)O1—C1—C6123.4 (2)
C4—C3—C2119.0 (2)O1—C1—C2117.3 (2)
C4—C3—Cl1120.53 (17)C6—C1—C2119.3 (2)
C2—C3—Cl1120.47 (17)C1—C2—C3120.6 (2)
C8—C9—C10122.8 (2)C1—C2—Cl3119.20 (17)
C8—C9—Cl4118.64 (18)C3—C2—Cl3120.22 (18)
C10—C9—Cl4118.59 (19)C11—C12—C7120.1 (2)
C9—C8—C7118.7 (2)C5—C6—C1120.8 (2)
C5—C4—C3120.6 (2)C9—C10—C11117.8 (2)
C5—C4—Cl2119.13 (18)C12—C11—C10121.1 (2)
(21) top
Crystal data top
C6H3Cl3O·C6H5Cl2NZ = 2
Mr = 359.44F(000) = 360
Triclinic, P1Dx = 1.624 Mg m3
a = 7.1441 (8) ÅMo Kα radiation, λ = 0.71073 Å
b = 9.3027 (10) ÅCell parameters from 7290 reflections
c = 11.8726 (13) Åθ = 3.0–27.5°
α = 77.966 (5)°µ = 0.98 mm1
β = 74.889 (5)°T = 150 K
γ = 77.979 (5)°0.3 × 0.2 × 0.1 mm
V = 735.06 (14) Å3
Data collection top
Rigaku Mercury375R (2x2 bin mode)
diffractometer
3366 independent reflections
Radiation source: fine-focus sealed tube3035 reflections with I > 2σ(I)
Graphite Monochromator monochromatorRint = 0.022
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan
Jacobson, R. (1998) Private communication
h = 99
Tmin = 0.761, Tmax = 1.000k = 1212
7780 measured reflectionsl = 1515
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099H atoms treated by a mixture of independent and constrained refinement
S = 1.09 w = 1/[σ2(Fo2) + (0.0443P)2 + 0.5725P]
where P = (Fo2 + 2Fc2)/3
3366 reflections(Δ/σ)max < 0.001
181 parametersΔρmax = 0.58 e Å3
0 restraintsΔρmin = 0.66 e Å3
Crystal data top
C6H3Cl3O·C6H5Cl2Nγ = 77.979 (5)°
Mr = 359.44V = 735.06 (14) Å3
Triclinic, P1Z = 2
a = 7.1441 (8) ÅMo Kα radiation
b = 9.3027 (10) ŵ = 0.98 mm1
c = 11.8726 (13) ÅT = 150 K
α = 77.966 (5)°0.3 × 0.2 × 0.1 mm
β = 74.889 (5)°
Data collection top
Rigaku Mercury375R (2x2 bin mode)
diffractometer
3366 independent reflections
Absorption correction: multi-scan
Jacobson, R. (1998) Private communication
3035 reflections with I > 2σ(I)
Tmin = 0.761, Tmax = 1.000Rint = 0.022
7780 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0370 restraints
wR(F2) = 0.099H atoms treated by a mixture of independent and constrained refinement
S = 1.09Δρmax = 0.58 e Å3
3366 reflectionsΔρmin = 0.66 e Å3
181 parameters
Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.3440 (3)0.3479 (2)0.01244 (17)0.0203 (4)
C20.2305 (3)0.4010 (2)0.11532 (17)0.0205 (4)
C30.1375 (3)0.5493 (2)0.11040 (17)0.0215 (4)
C40.1565 (3)0.6433 (2)0.00203 (19)0.0231 (4)
C50.2672 (3)0.5915 (2)0.09991 (18)0.0237 (4)
H50.27920.65550.17200.028*
C60.3606 (3)0.4445 (2)0.09522 (18)0.0223 (4)
H60.43470.41030.16420.027*
C70.4223 (3)0.1218 (2)0.72918 (16)0.0205 (4)
C80.3499 (3)0.2238 (2)0.63179 (18)0.0266 (4)
H80.24430.26830.63090.032*
C90.4374 (4)0.2575 (2)0.53649 (19)0.0352 (5)
C100.5968 (4)0.1954 (3)0.5351 (2)0.0390 (6)
H100.65520.21990.47070.047*
C110.6655 (3)0.0954 (3)0.6337 (2)0.0322 (5)
C120.5822 (3)0.0569 (2)0.73044 (19)0.0257 (4)
H120.63160.01100.79530.031*
N10.3397 (3)0.0894 (2)0.82956 (16)0.0258 (4)
O10.4330 (2)0.20375 (14)0.02337 (12)0.0235 (3)
H1O0.50630.18760.04000.035*
Cl10.20849 (9)0.27996 (6)0.24730 (4)0.03356 (15)
Cl20.00063 (8)0.61395 (6)0.23798 (5)0.03226 (14)
Cl30.04117 (8)0.82751 (5)0.00705 (5)0.03299 (15)
Cl40.33851 (13)0.37939 (8)0.41388 (5)0.0610 (2)
Cl50.86496 (9)0.01310 (9)0.63571 (8)0.0576 (2)
H1A0.225 (5)0.109 (3)0.813 (3)0.043 (8)*
H1B0.344 (4)0.001 (3)0.861 (2)0.037 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0178 (8)0.0188 (9)0.0258 (9)0.0028 (7)0.0067 (7)0.0054 (7)
C20.0200 (9)0.0210 (9)0.0213 (9)0.0041 (7)0.0064 (7)0.0024 (7)
C30.0167 (8)0.0231 (9)0.0270 (10)0.0043 (7)0.0040 (7)0.0094 (7)
C40.0202 (9)0.0171 (8)0.0347 (11)0.0025 (7)0.0106 (8)0.0049 (7)
C50.0243 (9)0.0212 (9)0.0257 (10)0.0057 (7)0.0091 (8)0.0021 (7)
C60.0196 (9)0.0224 (9)0.0248 (9)0.0038 (7)0.0045 (7)0.0038 (7)
C70.0207 (9)0.0174 (8)0.0193 (9)0.0016 (7)0.0004 (7)0.0039 (7)
C80.0287 (10)0.0214 (9)0.0242 (10)0.0033 (8)0.0021 (8)0.0030 (7)
C90.0486 (14)0.0266 (10)0.0200 (10)0.0045 (10)0.0010 (9)0.0028 (8)
C100.0464 (14)0.0418 (13)0.0268 (11)0.0158 (11)0.0161 (10)0.0143 (10)
C110.0233 (10)0.0342 (11)0.0412 (12)0.0056 (8)0.0082 (9)0.0199 (10)
C120.0232 (9)0.0216 (9)0.0279 (10)0.0012 (7)0.0016 (8)0.0063 (8)
N10.0263 (9)0.0241 (9)0.0241 (9)0.0002 (7)0.0046 (7)0.0028 (7)
O10.0242 (7)0.0190 (6)0.0234 (7)0.0015 (5)0.0020 (6)0.0039 (5)
Cl10.0463 (3)0.0284 (3)0.0204 (2)0.0008 (2)0.0050 (2)0.00056 (19)
Cl20.0332 (3)0.0313 (3)0.0322 (3)0.0026 (2)0.0007 (2)0.0161 (2)
Cl30.0330 (3)0.0173 (2)0.0500 (3)0.00116 (19)0.0157 (2)0.0056 (2)
Cl40.0959 (6)0.0402 (3)0.0229 (3)0.0009 (4)0.0094 (3)0.0071 (2)
Cl50.0275 (3)0.0733 (5)0.0863 (6)0.0015 (3)0.0142 (3)0.0494 (4)
Geometric parameters (Å, º) top
C1—O11.355 (2)C7—C81.393 (3)
C1—C61.393 (3)C7—C121.394 (3)
C1—C21.400 (3)C7—N11.415 (3)
C2—C31.398 (3)C8—C91.382 (3)
C2—Cl11.7195 (19)C9—C101.386 (4)
C3—C41.388 (3)C9—Cl41.736 (2)
C3—Cl21.725 (2)C10—C111.383 (4)
C4—C51.381 (3)C11—C121.378 (3)
C4—Cl31.7344 (19)C11—Cl51.745 (2)
C5—C61.388 (3)
O1—C1—C6123.27 (17)C5—C6—C1120.28 (18)
O1—C1—C2117.63 (17)C8—C7—C12120.21 (19)
C6—C1—C2119.10 (17)C8—C7—N1119.94 (19)
C3—C2—C1120.48 (18)C12—C7—N1119.78 (18)
C3—C2—Cl1120.89 (15)C9—C8—C7118.9 (2)
C1—C2—Cl1118.63 (14)C8—C9—C10122.4 (2)
C4—C3—C2119.28 (18)C8—C9—Cl4118.0 (2)
C4—C3—Cl2120.66 (15)C10—C9—Cl4119.63 (19)
C2—C3—Cl2120.06 (15)C11—C10—C9117.1 (2)
C5—C4—C3120.54 (17)C12—C11—C10122.7 (2)
C5—C4—Cl3119.12 (16)C12—C11—Cl5118.41 (19)
C3—C4—Cl3120.34 (16)C10—C11—Cl5118.84 (19)
C4—C5—C6120.31 (18)C11—C12—C7118.7 (2)
(22) top
Crystal data top
C6H3Cl3O·C6H5Cl2NZ = 2
Mr = 359.44F(000) = 360
Triclinic, P1Dx = 1.672 Mg m3
a = 7.2060 (8) ÅMo Kα radiation, λ = 0.71073 Å
b = 9.2558 (10) ÅCell parameters from 7284 reflections
c = 11.3203 (12) Åθ = 3.1–27.5°
α = 99.693 (7)°µ = 1.00 mm1
β = 99.616 (7)°T = 150 K
γ = 101.387 (7)°0.4 × 0.3 × 0.2 mm
V = 713.76 (13) Å3
Data collection top
Rigaku Mercury375R (2x2 bin mode)
diffractometer
3265 independent reflections
Radiation source: fine-focus sealed tube3023 reflections with I > 2σ(I)
Graphite Monochromator monochromatorRint = 0.018
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.2°
Absorption correction: multi-scan
Jacobson, R. (1998) Private communication
h = 99
Tmin = 0.833, Tmax = 1.000k = 1211
7624 measured reflectionsl = 1414
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.025Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.067H atoms treated by a mixture of independent and constrained refinement
S = 1.07 w = 1/[σ2(Fo2) + (0.0309P)2 + 0.2835P]
where P = (Fo2 + 2Fc2)/3
3265 reflections(Δ/σ)max < 0.001
184 parametersΔρmax = 0.30 e Å3
0 restraintsΔρmin = 0.32 e Å3
Crystal data top
C6H3Cl3O·C6H5Cl2Nγ = 101.387 (7)°
Mr = 359.44V = 713.76 (13) Å3
Triclinic, P1Z = 2
a = 7.2060 (8) ÅMo Kα radiation
b = 9.2558 (10) ŵ = 1.00 mm1
c = 11.3203 (12) ÅT = 150 K
α = 99.693 (7)°0.4 × 0.3 × 0.2 mm
β = 99.616 (7)°
Data collection top
Rigaku Mercury375R (2x2 bin mode)
diffractometer
3265 independent reflections
Absorption correction: multi-scan
Jacobson, R. (1998) Private communication
3023 reflections with I > 2σ(I)
Tmin = 0.833, Tmax = 1.000Rint = 0.018
7624 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0250 restraints
wR(F2) = 0.067H atoms treated by a mixture of independent and constrained refinement
S = 1.07Δρmax = 0.30 e Å3
3265 reflectionsΔρmin = 0.32 e Å3
184 parameters
Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
H1A1.059 (3)0.488 (2)0.3514 (18)0.032 (5)*
H2A1.118 (3)0.370 (2)0.2993 (17)0.027 (5)*
H1O0.036 (3)0.319 (2)0.542 (2)0.043 (6)*
Cl10.46298 (5)0.32531 (4)0.50451 (4)0.02765 (10)
Cl20.10518 (6)0.23495 (4)0.24189 (3)0.02723 (10)
Cl30.31723 (6)0.09853 (4)0.25146 (3)0.02790 (10)
O10.05066 (15)0.29800 (11)0.47493 (10)0.0221 (2)
C30.27860 (19)0.04084 (15)0.38408 (12)0.0184 (3)
C60.21323 (19)0.05145 (15)0.59749 (13)0.0197 (3)
H60.19180.08160.66930.024*
C40.34224 (19)0.14147 (14)0.49635 (13)0.0191 (3)
C20.18280 (19)0.10706 (15)0.37928 (12)0.0175 (3)
C10.14761 (19)0.15406 (15)0.48612 (13)0.0174 (3)
C50.3102 (2)0.09525 (16)0.60257 (13)0.0211 (3)
H50.35380.16270.67760.025*
Cl40.37051 (6)0.48964 (5)0.15315 (4)0.03222 (10)
Cl50.30744 (6)0.20678 (5)0.06122 (4)0.03879 (11)
N11.02843 (19)0.39459 (15)0.32117 (12)0.0232 (3)
C70.8640 (2)0.35684 (15)0.22471 (13)0.0207 (3)
C80.7180 (2)0.43430 (15)0.23094 (13)0.0216 (3)
H80.73390.51620.29490.026*
C100.5228 (2)0.26698 (17)0.04680 (13)0.0257 (3)
C110.6696 (2)0.19171 (17)0.03919 (14)0.0293 (3)
H110.65380.11060.02540.035*
C90.5493 (2)0.38996 (16)0.14236 (13)0.0224 (3)
C120.8395 (2)0.23600 (17)0.12683 (14)0.0267 (3)
H120.93780.18520.12060.032*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.02880 (19)0.01358 (16)0.0396 (2)0.00100 (13)0.00831 (15)0.00618 (14)
Cl20.0378 (2)0.02049 (17)0.01959 (17)0.00234 (14)0.00313 (14)0.00169 (13)
Cl30.0405 (2)0.02329 (17)0.02578 (18)0.00850 (15)0.01433 (15)0.01264 (14)
O10.0258 (5)0.0158 (5)0.0240 (5)0.0003 (4)0.0071 (4)0.0065 (4)
C30.0190 (6)0.0185 (6)0.0217 (6)0.0074 (5)0.0078 (5)0.0083 (5)
C60.0213 (7)0.0197 (6)0.0198 (6)0.0052 (5)0.0065 (5)0.0063 (5)
C40.0180 (6)0.0121 (6)0.0281 (7)0.0040 (5)0.0061 (5)0.0049 (5)
C20.0177 (6)0.0160 (6)0.0188 (6)0.0047 (5)0.0036 (5)0.0032 (5)
C10.0152 (6)0.0152 (6)0.0233 (7)0.0044 (5)0.0049 (5)0.0066 (5)
C50.0216 (7)0.0189 (6)0.0216 (7)0.0048 (5)0.0036 (5)0.0012 (5)
Cl40.0290 (2)0.0348 (2)0.0397 (2)0.01293 (16)0.01230 (16)0.01473 (17)
Cl50.0366 (2)0.0446 (2)0.0269 (2)0.00049 (18)0.00341 (16)0.00646 (17)
N10.0233 (6)0.0203 (6)0.0263 (6)0.0033 (5)0.0069 (5)0.0061 (5)
C70.0251 (7)0.0181 (6)0.0205 (6)0.0016 (5)0.0090 (5)0.0080 (5)
C80.0276 (7)0.0163 (6)0.0215 (7)0.0017 (5)0.0100 (6)0.0051 (5)
C100.0297 (8)0.0265 (7)0.0190 (7)0.0004 (6)0.0040 (6)0.0076 (6)
C110.0415 (9)0.0245 (7)0.0207 (7)0.0058 (7)0.0094 (6)0.0004 (6)
C90.0255 (7)0.0220 (7)0.0241 (7)0.0053 (6)0.0108 (6)0.0112 (5)
C120.0332 (8)0.0240 (7)0.0259 (7)0.0101 (6)0.0110 (6)0.0044 (6)
Geometric parameters (Å, º) top
Cl1—C41.7311 (13)Cl4—C91.7349 (15)
Cl2—C21.7208 (14)Cl5—C101.7347 (16)
Cl3—C31.7226 (14)N1—C71.4124 (19)
O1—C11.3510 (16)C7—C81.390 (2)
C3—C41.390 (2)C7—C121.396 (2)
C3—C21.3938 (18)C8—C91.382 (2)
C6—C51.3860 (19)C10—C111.383 (2)
C6—C11.3911 (19)C10—C91.390 (2)
C4—C51.382 (2)C11—C121.382 (2)
C2—C11.3973 (19)
C4—C3—C2119.63 (12)C4—C5—C6120.12 (13)
C4—C3—Cl3120.24 (10)C8—C7—C12119.24 (14)
C2—C3—Cl3120.13 (10)C8—C7—N1119.70 (13)
C5—C6—C1120.74 (13)C12—C7—N1120.92 (14)
C5—C4—C3120.17 (12)C9—C8—C7120.16 (13)
C5—C4—Cl1119.44 (11)C11—C10—C9119.29 (14)
C3—C4—Cl1120.39 (11)C11—C10—Cl5120.09 (12)
C3—C2—C1120.52 (12)C9—C10—Cl5120.62 (12)
C3—C2—Cl2120.71 (10)C12—C11—C10120.55 (14)
C1—C2—Cl2118.78 (10)C8—C9—C10120.56 (14)
O1—C1—C6123.59 (12)C8—C9—Cl4118.82 (11)
O1—C1—C2117.60 (12)C10—C9—Cl4120.62 (12)
C6—C1—C2118.81 (12)C11—C12—C7120.16 (14)
(23) top
Crystal data top
C7H6O3·C7H8N2OF(000) = 1152
Mr = 274.27Dx = 1.418 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 24.698 (2) ÅCell parameters from 11883 reflections
b = 5.1072 (5) Åθ = 3.2–27.5°
c = 20.6682 (19) ŵ = 0.11 mm1
β = 99.673 (12)°T = 150 K
V = 2570.0 (4) Å30.3 × 0.2 × 0.1 mm
Z = 8
Data collection top
Rigaku Mercury375R (2x2 bin mode)
diffractometer
2944 independent reflections
Radiation source: fine-focus sealed tube2635 reflections with I > 2σ(I)
Graphite Monochromator monochromatorRint = 0.026
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.4°
Absorption correction: multi-scan
Jacobson, R. (1998) Private communication
h = 3232
Tmin = 0.894, Tmax = 1.000k = 66
12832 measured reflectionsl = 2626
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.109H atoms treated by a mixture of independent and constrained refinement
S = 1.10 w = 1/[σ2(Fo2) + (0.0529P)2 + 2.1818P]
where P = (Fo2 + 2Fc2)/3
2944 reflections(Δ/σ)max < 0.001
205 parametersΔρmax = 0.30 e Å3
0 restraintsΔρmin = 0.23 e Å3
Crystal data top
C7H6O3·C7H8N2OV = 2570.0 (4) Å3
Mr = 274.27Z = 8
Monoclinic, C2/cMo Kα radiation
a = 24.698 (2) ŵ = 0.11 mm1
b = 5.1072 (5) ÅT = 150 K
c = 20.6682 (19) Å0.3 × 0.2 × 0.1 mm
β = 99.673 (12)°
Data collection top
Rigaku Mercury375R (2x2 bin mode)
diffractometer
2944 independent reflections
Absorption correction: multi-scan
Jacobson, R. (1998) Private communication
2635 reflections with I > 2σ(I)
Tmin = 0.894, Tmax = 1.000Rint = 0.026
12832 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.109H atoms treated by a mixture of independent and constrained refinement
S = 1.10Δρmax = 0.30 e Å3
2944 reflectionsΔρmin = 0.23 e Å3
205 parameters
Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.45088 (5)1.1446 (3)0.09912 (6)0.0196 (3)
C20.39455 (5)1.1515 (3)0.10112 (6)0.0214 (3)
H20.37221.27650.07720.026*
C30.37234 (5)0.9699 (3)0.13922 (6)0.0208 (3)
H30.33500.97500.14100.025*
C40.40522 (5)0.7802 (2)0.17479 (6)0.0186 (3)
C50.46132 (5)0.7741 (3)0.17188 (6)0.0211 (3)
H50.48350.64650.19490.025*
C60.48396 (5)0.9566 (3)0.13493 (6)0.0223 (3)
H60.52150.95370.13400.027*
C70.38037 (5)0.5890 (2)0.21521 (6)0.0190 (3)
C80.33328 (5)1.0227 (2)0.32768 (6)0.0192 (3)
C90.32422 (5)0.8114 (2)0.37531 (6)0.0186 (3)
C100.27339 (5)0.7660 (3)0.39413 (6)0.0236 (3)
H100.24270.86330.37600.028*
C110.26932 (5)0.5729 (3)0.44047 (7)0.0272 (3)
H110.23560.54190.45350.033*
C120.31450 (6)0.4261 (3)0.46758 (7)0.0256 (3)
H120.31100.29810.49860.031*
C130.36536 (5)0.4691 (2)0.44852 (6)0.0199 (3)
C140.36963 (5)0.6627 (2)0.40213 (6)0.0192 (3)
H140.40330.69280.38900.023*
N10.41256 (5)0.3348 (2)0.47945 (6)0.0238 (2)
N20.29025 (4)1.1577 (2)0.29704 (6)0.0233 (3)
O10.47578 (4)1.3140 (2)0.06279 (5)0.0276 (2)
O20.33057 (4)0.56511 (19)0.21281 (5)0.0237 (2)
O30.41681 (4)0.44658 (19)0.25387 (5)0.0246 (2)
O40.38075 (4)1.06761 (19)0.31828 (5)0.0259 (2)
H1A0.4074 (8)0.181 (4)0.5004 (10)0.046 (5)*
H1B0.4406 (8)0.314 (4)0.4554 (9)0.038 (5)*
H1O0.4517 (8)1.432 (4)0.0404 (10)0.047 (6)*
H2A0.2566 (7)1.136 (4)0.3048 (8)0.030 (4)*
H2B0.2970 (7)1.293 (4)0.2705 (9)0.034 (4)*
H3O0.4005 (8)0.319 (4)0.2746 (10)0.048 (5)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0201 (6)0.0205 (6)0.0187 (6)0.0030 (5)0.0049 (4)0.0014 (5)
C20.0197 (6)0.0213 (6)0.0229 (6)0.0034 (5)0.0024 (5)0.0023 (5)
C30.0143 (5)0.0231 (6)0.0251 (6)0.0006 (5)0.0032 (4)0.0007 (5)
C40.0164 (6)0.0187 (6)0.0207 (6)0.0018 (4)0.0031 (4)0.0009 (5)
C50.0168 (6)0.0229 (6)0.0228 (6)0.0020 (5)0.0012 (4)0.0020 (5)
C60.0151 (5)0.0276 (7)0.0247 (6)0.0005 (5)0.0045 (5)0.0013 (5)
C70.0170 (5)0.0191 (6)0.0209 (6)0.0006 (4)0.0029 (4)0.0005 (5)
C80.0169 (5)0.0184 (6)0.0224 (6)0.0014 (4)0.0031 (4)0.0006 (5)
C90.0189 (6)0.0180 (6)0.0190 (5)0.0032 (5)0.0036 (4)0.0008 (5)
C100.0163 (6)0.0274 (7)0.0268 (6)0.0013 (5)0.0032 (5)0.0027 (5)
C110.0193 (6)0.0343 (8)0.0288 (7)0.0077 (5)0.0068 (5)0.0046 (6)
C120.0260 (7)0.0248 (7)0.0262 (6)0.0066 (5)0.0055 (5)0.0056 (5)
C130.0217 (6)0.0177 (6)0.0197 (6)0.0019 (5)0.0019 (5)0.0019 (5)
C140.0169 (6)0.0190 (6)0.0223 (6)0.0029 (5)0.0052 (4)0.0009 (5)
N10.0247 (6)0.0217 (6)0.0249 (6)0.0022 (4)0.0036 (4)0.0042 (4)
N20.0166 (5)0.0248 (6)0.0283 (6)0.0002 (4)0.0035 (4)0.0075 (5)
O10.0233 (5)0.0286 (5)0.0326 (5)0.0003 (4)0.0091 (4)0.0101 (4)
O20.0154 (4)0.0260 (5)0.0296 (5)0.0007 (3)0.0040 (4)0.0047 (4)
O30.0172 (4)0.0261 (5)0.0298 (5)0.0018 (4)0.0020 (4)0.0102 (4)
O40.0168 (4)0.0274 (5)0.0342 (5)0.0002 (4)0.0064 (4)0.0121 (4)
Geometric parameters (Å, º) top
C1—O11.3588 (15)C8—O41.2414 (15)
C1—C61.3906 (18)C8—N21.3341 (16)
C1—C21.3993 (17)C8—C91.5026 (17)
C2—C31.3880 (18)C9—C141.3904 (18)
C3—C41.3922 (17)C9—C101.3946 (17)
C4—C51.3973 (16)C10—C111.3904 (19)
C4—C71.4834 (17)C11—C121.383 (2)
C5—C61.3813 (18)C12—C131.3957 (18)
C7—O21.2287 (15)C13—C141.3934 (18)
C7—O31.3173 (15)C13—N11.4099 (17)
O1—C1—C6116.99 (11)O4—C8—N2121.88 (12)
O1—C1—C2123.01 (12)O4—C8—C9118.93 (11)
C6—C1—C2119.99 (11)N2—C8—C9119.18 (11)
C3—C2—C1119.31 (11)C14—C9—C10120.11 (12)
C2—C3—C4120.90 (11)C14—C9—C8117.03 (11)
C3—C4—C5119.17 (11)C10—C9—C8122.83 (11)
C3—C4—C7119.72 (11)C11—C10—C9118.86 (12)
C5—C4—C7121.11 (11)C12—C11—C10121.14 (12)
C6—C5—C4120.35 (12)C11—C12—C13120.24 (12)
C5—C6—C1120.26 (11)C14—C13—C12118.80 (12)
O2—C7—O3123.15 (11)C14—C13—N1120.33 (11)
O2—C7—C4123.27 (11)C12—C13—N1120.67 (12)
O3—C7—C4113.57 (10)C9—C14—C13120.84 (11)
(24) top
Crystal data top
C7H6O3·C7H8N2OF(000) = 576
Mr = 274.27Dx = 1.430 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 12.410 (15) ÅCell parameters from 3168 reflections
b = 5.124 (6) Åθ = 1.9–27.5°
c = 20.06 (2) ŵ = 0.11 mm1
β = 92.901 (14)°T = 150 K
V = 1274 (3) Å30.5 × 0.3 × 0.2 mm
Z = 4
Data collection top
Rigaku Mercury375R (2x2 bin mode)
diffractometer
2914 independent reflections
Radiation source: fine-focus sealed tube2416 reflections with I > 2σ(I)
Graphite Monochromator monochromatorRint = 0.066
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 1.6°
Absorption correction: multi-scan
Jacobson, R. (1998) Private communication
h = 1616
Tmin = 0.795, Tmax = 1.000k = 66
12530 measured reflectionsl = 2626
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.169H atoms treated by a mixture of independent and constrained refinement
S = 1.14 w = 1/[σ2(Fo2) + (0.0947P)2]
where P = (Fo2 + 2Fc2)/3
2914 reflections(Δ/σ)max < 0.001
202 parametersΔρmax = 0.29 e Å3
0 restraintsΔρmin = 0.32 e Å3
Crystal data top
C7H6O3·C7H8N2OV = 1274 (3) Å3
Mr = 274.27Z = 4
Monoclinic, P21/cMo Kα radiation
a = 12.410 (15) ŵ = 0.11 mm1
b = 5.124 (6) ÅT = 150 K
c = 20.06 (2) Å0.5 × 0.3 × 0.2 mm
β = 92.901 (14)°
Data collection top
Rigaku Mercury375R (2x2 bin mode)
diffractometer
2914 independent reflections
Absorption correction: multi-scan
Jacobson, R. (1998) Private communication
2416 reflections with I > 2σ(I)
Tmin = 0.795, Tmax = 1.000Rint = 0.066
12530 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0480 restraints
wR(F2) = 0.169H atoms treated by a mixture of independent and constrained refinement
S = 1.14Δρmax = 0.29 e Å3
2914 reflectionsΔρmin = 0.32 e Å3
202 parameters
Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
H1B0.048 (2)0.597 (5)0.2128 (13)0.038 (7)*
H1A0.138 (2)0.751 (6)0.2499 (13)0.040 (7)*
H2B0.470 (2)0.707 (5)0.4327 (13)0.041 (7)*
H1O0.366 (2)0.454 (6)0.5023 (16)0.053 (8)*
H2A0.366 (2)0.824 (5)0.4251 (12)0.032 (6)*
O20.00183 (10)0.2796 (3)0.40432 (6)0.0273 (3)
H2O0.03800.28060.36900.041*
O40.13450 (10)0.1862 (2)0.20172 (6)0.0241 (3)
O10.36355 (10)0.3407 (3)0.53328 (7)0.0287 (3)
O30.08217 (10)0.0484 (3)0.35493 (6)0.0307 (4)
C90.26914 (13)0.3714 (3)0.27586 (8)0.0195 (4)
C50.27405 (14)0.0140 (4)0.58023 (9)0.0249 (4)
H50.31830.00520.61870.030*
C20.13962 (12)0.0677 (3)0.46615 (8)0.0199 (4)
C110.43991 (15)0.1618 (4)0.30069 (9)0.0266 (4)
H110.49070.03570.29090.032*
N20.40137 (14)0.6769 (3)0.42639 (8)0.0264 (4)
N10.10796 (13)0.6013 (3)0.23451 (8)0.0253 (4)
C10.07015 (13)0.0919 (3)0.40321 (8)0.0204 (4)
C40.19796 (15)0.2132 (4)0.57602 (9)0.0262 (4)
H40.19230.32830.61150.031*
C130.38557 (13)0.5228 (3)0.36837 (8)0.0206 (4)
C70.21616 (14)0.1320 (3)0.46995 (9)0.0211 (4)
H70.22170.24790.43460.025*
C120.46071 (14)0.3310 (4)0.35375 (9)0.0245 (4)
H120.52480.31670.37960.029*
C140.29054 (13)0.5444 (3)0.32859 (9)0.0211 (4)
H140.24110.67490.33730.025*
C30.13031 (14)0.2416 (4)0.51912 (9)0.0231 (4)
H30.07940.37490.51640.028*
C80.16497 (13)0.3820 (3)0.23456 (8)0.0200 (4)
C60.28407 (14)0.1567 (3)0.52692 (9)0.0220 (4)
C100.34378 (15)0.1784 (3)0.26179 (9)0.0239 (4)
H100.32970.06200.22690.029*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O20.0288 (7)0.0277 (7)0.0244 (7)0.0087 (5)0.0072 (5)0.0048 (5)
O40.0263 (7)0.0211 (6)0.0242 (6)0.0003 (5)0.0051 (5)0.0024 (5)
O10.0236 (7)0.0322 (8)0.0295 (7)0.0056 (5)0.0063 (5)0.0011 (6)
O30.0284 (7)0.0407 (8)0.0221 (7)0.0118 (6)0.0056 (5)0.0082 (6)
C90.0185 (8)0.0202 (8)0.0198 (8)0.0018 (6)0.0015 (6)0.0018 (6)
C50.0223 (8)0.0310 (10)0.0210 (8)0.0049 (7)0.0028 (6)0.0043 (7)
C20.0169 (8)0.0232 (9)0.0195 (8)0.0018 (6)0.0002 (6)0.0026 (6)
C110.0238 (9)0.0269 (10)0.0290 (9)0.0079 (7)0.0015 (7)0.0007 (7)
N20.0226 (8)0.0277 (9)0.0282 (8)0.0007 (6)0.0056 (6)0.0059 (6)
N10.0242 (8)0.0231 (8)0.0278 (8)0.0028 (6)0.0073 (6)0.0041 (6)
C10.0184 (8)0.0229 (8)0.0201 (8)0.0002 (6)0.0012 (6)0.0018 (6)
C40.0290 (9)0.0300 (10)0.0197 (8)0.0032 (7)0.0006 (7)0.0032 (7)
C130.0203 (8)0.0202 (8)0.0214 (8)0.0023 (6)0.0005 (6)0.0008 (6)
C70.0194 (8)0.0240 (9)0.0198 (8)0.0014 (6)0.0001 (6)0.0007 (7)
C120.0191 (8)0.0263 (9)0.0278 (9)0.0012 (6)0.0011 (6)0.0018 (7)
C140.0191 (8)0.0198 (8)0.0242 (9)0.0011 (6)0.0003 (6)0.0002 (6)
C30.0226 (8)0.0237 (9)0.0229 (8)0.0002 (7)0.0006 (6)0.0005 (7)
C80.0209 (8)0.0215 (8)0.0175 (8)0.0004 (6)0.0015 (6)0.0013 (6)
C60.0176 (8)0.0244 (9)0.0237 (9)0.0020 (6)0.0005 (6)0.0053 (7)
C100.0254 (9)0.0231 (9)0.0234 (9)0.0009 (7)0.0018 (7)0.0028 (7)
Geometric parameters (Å, º) top
O2—C11.314 (2)C2—C71.396 (3)
O4—C81.248 (2)C2—C11.497 (3)
O1—C61.366 (2)C11—C121.387 (3)
O3—C11.221 (2)C11—C101.395 (3)
C9—C101.393 (3)N2—C131.412 (3)
C9—C141.395 (3)N1—C81.328 (3)
C9—C81.501 (3)C4—C31.390 (3)
C5—C41.390 (3)C13—C141.394 (3)
C5—C61.392 (3)C13—C121.396 (3)
C2—C31.396 (3)C7—C61.391 (3)
C10—C9—C14120.09 (16)C14—C13—N2120.36 (16)
C10—C9—C8118.48 (16)C12—C13—N2120.03 (16)
C14—C9—C8121.40 (15)C6—C7—C2119.59 (17)
C4—C5—C6120.10 (17)C11—C12—C13120.06 (17)
C3—C2—C7120.58 (16)C13—C14—C9120.42 (16)
C3—C2—C1121.52 (16)C4—C3—C2119.23 (17)
C7—C2—C1117.89 (16)O4—C8—N1122.18 (17)
C12—C11—C10120.79 (17)O4—C8—C9119.45 (15)
O3—C1—O2123.69 (16)N1—C8—C9118.37 (16)
O3—C1—C2122.13 (16)O1—C6—C7122.97 (17)
O2—C1—C2114.16 (15)O1—C6—C5117.02 (16)
C3—C4—C5120.47 (17)C7—C6—C5120.00 (17)
C14—C13—C12119.36 (17)C9—C10—C11119.25 (17)
(25) top
Crystal data top
C14H12O8·2(C7H8N2O)Z = 1
Mr = 580.54F(000) = 304
Triclinic, P1Dx = 1.458 Mg m3
a = 4.760 (2) ÅMo Kα radiation, λ = 0.71073 Å
b = 11.501 (6) ÅCell parameters from 5373 reflections
c = 12.539 (6) Åθ = 3.3–27.7°
α = 77.081 (6)°µ = 0.11 mm1
β = 86.975 (6)°T = 150 K
γ = 81.302 (6)°0.3 × 0.2 × 0.1 mm
V = 661.3 (6) Å3
Data collection top
Rigaku Mercury375R (2x2 bin mode)
diffractometer
3013 independent reflections
Radiation source: fine-focus sealed tube2472 reflections with I > 2σ(I)
Graphite Monochromator monochromatorRint = 0.021
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.3°
Absorption correction: multi-scan
Jacobson, R. (1998) Private communication
h = 66
Tmin = 0.837, Tmax = 1.000k = 1414
6973 measured reflectionsl = 1616
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.108H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 1/[σ2(Fo2) + (0.0573P)2 + 0.2205P]
where P = (Fo2 + 2Fc2)/3
3013 reflections(Δ/σ)max < 0.001
218 parametersΔρmax = 0.28 e Å3
0 restraintsΔρmin = 0.28 e Å3
Crystal data top
C14H12O8·2(C7H8N2O)γ = 81.302 (6)°
Mr = 580.54V = 661.3 (6) Å3
Triclinic, P1Z = 1
a = 4.760 (2) ÅMo Kα radiation
b = 11.501 (6) ŵ = 0.11 mm1
c = 12.539 (6) ÅT = 150 K
α = 77.081 (6)°0.3 × 0.2 × 0.1 mm
β = 86.975 (6)°
Data collection top
Rigaku Mercury375R (2x2 bin mode)
diffractometer
3013 independent reflections
Absorption correction: multi-scan
Jacobson, R. (1998) Private communication
2472 reflections with I > 2σ(I)
Tmin = 0.837, Tmax = 1.000Rint = 0.021
6973 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0400 restraints
wR(F2) = 0.108H atoms treated by a mixture of independent and constrained refinement
S = 1.03Δρmax = 0.28 e Å3
3013 reflectionsΔρmin = 0.28 e Å3
218 parameters
Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.2322 (3)0.40273 (12)0.57907 (11)0.0153 (3)
C20.0373 (3)0.31886 (12)0.63581 (11)0.0153 (3)
C30.0758 (3)0.25007 (12)0.57508 (11)0.0164 (3)
H30.03310.25890.50070.020*
C40.2527 (3)0.16833 (12)0.62638 (11)0.0162 (3)
C50.3172 (3)0.15646 (12)0.73683 (11)0.0181 (3)
H50.43590.10150.77120.022*
C60.2052 (3)0.22653 (13)0.79674 (11)0.0186 (3)
C70.0250 (3)0.30816 (12)0.74690 (11)0.0176 (3)
H70.05180.35440.78680.021*
C80.4836 (3)0.14805 (12)0.26271 (11)0.0173 (3)
C90.5281 (3)0.15221 (13)0.15308 (11)0.0199 (3)
H90.41180.10030.11680.024*
C100.7442 (3)0.23322 (13)0.09805 (11)0.0193 (3)
H100.77200.23540.02470.023*
C110.9213 (3)0.31173 (12)0.15029 (11)0.0164 (3)
C120.8704 (3)0.30901 (13)0.25907 (11)0.0190 (3)
H120.98360.36240.29470.023*
C130.6545 (3)0.22832 (13)0.31491 (11)0.0193 (3)
H130.62340.22770.38770.023*
C141.1568 (3)0.39359 (12)0.08734 (11)0.0162 (3)
N10.2820 (3)0.05905 (11)0.32326 (11)0.0206 (3)
N21.3288 (3)0.46829 (11)0.13609 (10)0.0200 (3)
O10.3550 (2)0.10123 (9)0.56436 (8)0.0225 (2)
O20.2794 (3)0.20984 (11)0.90389 (8)0.0294 (3)
O30.2816 (2)0.40852 (9)0.47822 (8)0.0204 (2)
O40.3433 (2)0.46551 (9)0.63323 (8)0.0201 (2)
O51.1936 (2)0.39137 (9)0.00998 (8)0.0204 (2)
H1A0.141 (4)0.0340 (18)0.2831 (16)0.034 (5)*
H1B0.221 (4)0.0821 (18)0.3809 (17)0.033 (5)*
H1O0.476 (4)0.0587 (19)0.6005 (16)0.038 (5)*
H2A1.306 (4)0.4721 (17)0.2044 (17)0.030 (5)*
H2B1.472 (4)0.5143 (17)0.0960 (15)0.030 (5)*
H2O0.221 (5)0.270 (2)0.932 (2)0.063 (7)*
H4O0.522 (8)0.525 (3)0.575 (3)0.132 (13)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0144 (6)0.0159 (6)0.0150 (6)0.0004 (5)0.0008 (5)0.0041 (5)
C20.0132 (6)0.0154 (6)0.0169 (6)0.0011 (5)0.0001 (5)0.0032 (5)
C30.0176 (6)0.0187 (7)0.0129 (6)0.0013 (5)0.0009 (5)0.0042 (5)
C40.0164 (6)0.0158 (6)0.0169 (6)0.0014 (5)0.0032 (5)0.0045 (5)
C50.0189 (7)0.0175 (6)0.0181 (7)0.0055 (5)0.0028 (5)0.0028 (5)
C60.0208 (7)0.0210 (7)0.0144 (6)0.0029 (5)0.0028 (5)0.0051 (5)
C70.0194 (7)0.0194 (7)0.0157 (6)0.0039 (5)0.0011 (5)0.0067 (5)
C80.0154 (6)0.0166 (6)0.0197 (7)0.0061 (5)0.0005 (5)0.0014 (5)
C90.0212 (7)0.0203 (7)0.0185 (7)0.0020 (5)0.0036 (5)0.0066 (5)
C100.0229 (7)0.0224 (7)0.0134 (6)0.0054 (6)0.0008 (5)0.0047 (5)
C110.0165 (6)0.0171 (6)0.0156 (6)0.0058 (5)0.0003 (5)0.0017 (5)
C120.0202 (7)0.0207 (7)0.0168 (7)0.0017 (5)0.0008 (5)0.0066 (5)
C130.0220 (7)0.0226 (7)0.0139 (6)0.0037 (6)0.0014 (5)0.0045 (5)
C140.0172 (6)0.0172 (6)0.0149 (6)0.0074 (5)0.0003 (5)0.0020 (5)
N10.0182 (6)0.0207 (6)0.0221 (6)0.0006 (5)0.0022 (5)0.0042 (5)
N20.0201 (6)0.0226 (6)0.0169 (6)0.0000 (5)0.0036 (5)0.0045 (5)
O10.0293 (6)0.0247 (5)0.0175 (5)0.0136 (4)0.0005 (4)0.0067 (4)
O20.0442 (7)0.0344 (6)0.0154 (5)0.0209 (5)0.0094 (5)0.0097 (5)
O30.0223 (5)0.0234 (5)0.0163 (5)0.0065 (4)0.0036 (4)0.0048 (4)
O40.0196 (5)0.0235 (5)0.0204 (5)0.0085 (4)0.0015 (4)0.0080 (4)
O50.0238 (5)0.0224 (5)0.0151 (5)0.0025 (4)0.0034 (4)0.0043 (4)
Geometric parameters (Å, º) top
C1—O31.2627 (17)C8—C131.389 (2)
C1—O41.2787 (16)C8—C91.391 (2)
C1—C21.4804 (19)C8—N11.4060 (19)
C2—C71.391 (2)C9—C101.379 (2)
C2—C31.3919 (19)C10—C111.390 (2)
C3—C41.3849 (19)C11—C121.390 (2)
C4—O11.3636 (16)C11—C141.486 (2)
C4—C51.384 (2)C12—C131.380 (2)
C5—C61.3932 (19)C14—O51.2482 (17)
C6—O21.3496 (18)C14—N21.3234 (18)
C6—C71.3902 (19)
O3—C1—O4122.86 (12)C6—C7—C2118.29 (12)
O3—C1—C2117.80 (11)C13—C8—C9119.23 (13)
O4—C1—C2119.34 (12)C13—C8—N1119.49 (13)
C7—C2—C3121.49 (12)C9—C8—N1121.14 (13)
C7—C2—C1120.54 (12)C10—C9—C8120.12 (13)
C3—C2—C1117.96 (12)C9—C10—C11121.11 (13)
C4—C3—C2119.41 (12)C10—C11—C12118.31 (13)
O1—C4—C5122.52 (12)C10—C11—C14118.33 (12)
O1—C4—C3117.54 (12)C12—C11—C14123.36 (12)
C5—C4—C3119.94 (12)C13—C12—C11121.03 (13)
C4—C5—C6120.26 (13)C12—C13—C8120.16 (13)
O2—C6—C7122.80 (13)O5—C14—N2120.35 (13)
O2—C6—C5116.59 (13)O5—C14—C11120.53 (12)
C7—C6—C5120.61 (13)N2—C14—C11119.12 (12)

Experimental details

(11)(12)(13)(14)
Crystal data
Chemical formulaC6H3Cl3O·C6H6ClNC6H3Cl3O·C6H6ClNC6H3Cl3O·C6H5Cl2NC6H3Cl3O·C6H5Cl2N
Mr325.00325.00359.44359.44
Crystal system, space groupTriclinic, P1Monoclinic, P21/cMonoclinic, P21Monoclinic, I2/a
Temperature (K)150150150150
a, b, c (Å)7.0243 (14), 9.4152 (18), 10.928 (2)6.9676 (7), 21.336 (2), 9.1861 (10)7.0572 (6), 15.4665 (13), 13.2112 (11)22.638 (5), 7.2553 (11), 18.013 (3)
α, β, γ (°)82.750 (6), 79.147 (6), 76.703 (5)90, 99.139 (7), 9090, 98.980 (7), 9090, 90.767 (9), 90
V3)688.1 (2)1348.3 (2)1424.3 (2)2958.2 (9)
Z2448
Radiation typeMo KαMo KαMo KαMo Kα
µ (mm1)0.850.861.010.97
Crystal size (mm)0.3 × 0.2 × 0.10.3 × 0.2 × 0.10.3 × 0.2 × 0.10.6 × 0.3 × 0.2
Data collection
DiffractometerRigaku Mercury375R (2x2 bin mode)
diffractometer
Rigaku Mercury375R (2x2 bin mode)
diffractometer
Rigaku Mercury375R (2x2 bin mode)
diffractometer
Rigaku Mercury375R (2x2 bin mode)
diffractometer
Absorption correctionMulti-scan
Jacobson, R. (1998) Private communication
Multi-scan
Jacobson, R. (1998) Private communication
Multi-scan
Jacobson, R. (1998) Private communication
Multi-scan
Jacobson, R. (1998) Private communication
Tmin, Tmax0.787, 1.0000.777, 1.0000.772, 1.0000.766, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
7315, 3144, 2604 13875, 3066, 2703 15205, 6493, 6193 12389, 2662, 2516
Rint0.0250.0320.0230.033
(sin θ/λ)max1)0.6490.6490.6490.599
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.032, 0.084, 1.09 0.033, 0.085, 1.09 0.026, 0.056, 1.06 0.093, 0.202, 1.21
No. of reflections3144306664932662
No. of parameters175175367182
No. of restraints0012
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
w = 1/[σ2(Fo2) + (0.0386P)2 + 0.1418P]
where P = (Fo2 + 2Fc2)/3
w = 1/[σ2(Fo2) + (0.0371P)2 + 0.7069P]
where P = (Fo2 + 2Fc2)/3
w = 1/[σ2(Fo2) + (0.0228P)2 + 0.3139P]
where P = (Fo2 + 2Fc2)/3
w = 1/[σ2(Fo2) + (0.0317P)2 + 62.0784P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)0.31, 0.320.42, 0.460.38, 0.253.00, 0.57
Absolute structure??Flack H D (1983), Acta Cryst. A39, 876-881?
Absolute structure parameter??0.03 (3)?


(15)(16)(17)(18)
Crystal data
Chemical formulaC6H3Cl3O·C6H4Cl2NC6H3Cl3O·C6H6BrNC6H3Cl3O·C6H6INC6H4ClIN·C6H3Cl3O
Mr358.44369.46416.45449.89
Crystal system, space groupTriclinic, P1Triclinic, P1Triclinic, P1Triclinic, P1
Temperature (K)150150150150
a, b, c (Å)7.0681 (6), 9.5008 (8), 11.4095 (9)7.0562 (15), 9.373 (2), 11.110 (2)7.083 (3), 9.354 (4), 11.456 (5)7.107 (2), 9.498 (3), 11.827 (3)
α, β, γ (°)85.402 (6), 83.071 (6), 71.211 (5)83.358 (6), 79.173 (6), 76.588 (5)84.118 (7), 79.555 (7), 76.553 (7)85.425 (6), 81.804 (6), 71.851 (5)
V3)719.36 (10)700.0 (3)724.5 (5)750.4 (4)
Z2222
Radiation typeMo KαMo KαMo KαMo Kα
µ (mm1)1.003.492.752.84
Crystal size (mm)0.5 × 0.3 × 0.20.3 × 0.2 × 0.10.3 × 0.2 × 0.10.3 × 0.2 × 0.1
Data collection
DiffractometerRigaku Mercury375R (2x2 bin mode)
diffractometer
Rigaku Mercury375R (2x2 bin mode)
diffractometer
Rigaku Mercury375R (2x2 bin mode)
diffractometer
?
Absorption correctionMulti-scan
Jacobson, R. (1998) Private communication
Multi-scan
Jacobson, R. (1998) Private communication
Multi-scan
Jacobson, R. (1998) Private communication
Multi-scan
Jacobson, R. (1998) Private communication
Tmin, Tmax0.826, 1.0000.540, 1.0000.614, 1.0000.578, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
7652, 3293, 2949 7199, 3204, 2717 7553, 3313, 3105 7564, 3429, 3038
Rint0.0160.0360.0240.026
(sin θ/λ)max1)0.6490.6490.6490.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.064, 0.150, 1.04 0.039, 0.098, 1.04 0.028, 0.070, 1.12 0.048, 0.124, 1.20
No. of reflections3293320433133429
No. of parameters194175172201
No. of restraints0000
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
w = 1/[σ2(Fo2) + (0.0452P)2 + 2.5468P]
where P = (Fo2 + 2Fc2)/3
w = 1/[σ2(Fo2) + (0.0434P)2 + 0.6163P]
where P = (Fo2 + 2Fc2)/3
w = 1/[σ2(Fo2) + (0.0143P)2 + 1.5784P]
where P = (Fo2 + 2Fc2)/3
w = 1/[σ2(Fo2) + (0.0419P)2 + 1.7038P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)2.21, 1.741.24, 0.660.84, 1.181.01, 0.88
Absolute structure????
Absolute structure parameter????


(19)(20)(21)(22)
Crystal data
Chemical formulaC6H3Cl3O·C6H6ClNC6H3Cl3O·C6H6ClNC6H3Cl3O·C6H5Cl2NC6H3Cl3O·C6H5Cl2N
Mr325.00325.00359.44359.44
Crystal system, space groupMonoclinic, P21/cTriclinic, P1Triclinic, P1Triclinic, P1
Temperature (K)150150150150
a, b, c (Å)7.851 (5), 11.865 (7), 14.891 (8)7.208 (9), 9.333 (10), 10.884 (13)7.1441 (8), 9.3027 (10), 11.8726 (13)7.2060 (8), 9.2558 (10), 11.3203 (12)
α, β, γ (°)90, 106.79 (3), 9099.035 (14), 107.107 (6), 102.219 (10)77.966 (5), 74.889 (5), 77.979 (5)99.693 (7), 99.616 (7), 101.387 (7)
V3)1328.0 (14)664.9 (13)735.06 (14)713.76 (13)
Z4222
Radiation typeMo KαMo KαMo KαMo Kα
µ (mm1)0.880.880.981.00
Crystal size (mm)0.20 × 0.20 × 0.200.20 × 0.20 × 0.200.3 × 0.2 × 0.10.4 × 0.3 × 0.2
Data collection
DiffractometerRigaku Mercury375R (2x2 bin mode)
diffractometer
Rigaku Mercury375R (2x2 bin mode)
diffractometer
Rigaku Mercury375R (2x2 bin mode)
diffractometer
Rigaku Mercury375R (2x2 bin mode)
diffractometer
Absorption correctionMulti-scan
Jacobson, R. (1998) Private communication
Multi-scan
Jacobson, R. (1998) Private communication
Multi-scan
Jacobson, R. (1998) Private communication
Multi-scan
Jacobson, R. (1998) Private communication
Tmin, Tmax0.804, 1.0000.844, 1.0000.761, 1.0000.833, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
13867, 3068, 2843 5849, 2397, 2240 7780, 3366, 3035 7624, 3265, 3023
Rint0.1570.1560.0220.018
(sin θ/λ)max1)0.6510.5990.6490.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.144, 1.14 0.042, 0.139, 1.14 0.037, 0.099, 1.09 0.025, 0.067, 1.07
No. of reflections3068239733663265
No. of parameters163175181184
No. of restraints0000
H-atom treatmentH-atom parameters constrainedH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
w = 1/[σ2(Fo2) + (0.0657P)2 + 0.229P]
where P = (Fo2 + 2Fc2)/3
w = 1/[σ2(Fo2) + (0.0565P)2 + 0.0167P]
where P = (Fo2 + 2Fc2)/3
w = 1/[σ2(Fo2) + (0.0443P)2 + 0.5725P]
where P = (Fo2 + 2Fc2)/3
w = 1/[σ2(Fo2) + (0.0309P)2 + 0.2835P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)0.43, 0.670.45, 0.450.58, 0.660.30, 0.32
Absolute structure????
Absolute structure parameter????


(23)(24)(25)
Crystal data
Chemical formulaC7H6O3·C7H8N2OC7H6O3·C7H8N2OC14H12O8·2(C7H8N2O)
Mr274.27274.27580.54
Crystal system, space groupMonoclinic, C2/cMonoclinic, P21/cTriclinic, P1
Temperature (K)150150150
a, b, c (Å)24.698 (2), 5.1072 (5), 20.6682 (19)12.410 (15), 5.124 (6), 20.06 (2)4.760 (2), 11.501 (6), 12.539 (6)
α, β, γ (°)90, 99.673 (12), 9090, 92.901 (14), 9077.081 (6), 86.975 (6), 81.302 (6)
V3)2570.0 (4)1274 (3)661.3 (6)
Z841
Radiation typeMo KαMo KαMo Kα
µ (mm1)0.110.110.11
Crystal size (mm)0.3 × 0.2 × 0.10.5 × 0.3 × 0.20.3 × 0.2 × 0.1
Data collection
DiffractometerRigaku Mercury375R (2x2 bin mode)
diffractometer
Rigaku Mercury375R (2x2 bin mode)
diffractometer
Rigaku Mercury375R (2x2 bin mode)
diffractometer
Absorption correctionMulti-scan
Jacobson, R. (1998) Private communication
Multi-scan
Jacobson, R. (1998) Private communication
Multi-scan
Jacobson, R. (1998) Private communication
Tmin, Tmax0.894, 1.0000.795, 1.0000.837, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
12832, 2944, 2635 12530, 2914, 2416 6973, 3013, 2472
Rint0.0260.0660.021
(sin θ/λ)max1)0.6490.6490.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.109, 1.10 0.048, 0.169, 1.14 0.040, 0.108, 1.03
No. of reflections294429143013
No. of parameters205202218
No. of restraints000
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
w = 1/[σ2(Fo2) + (0.0529P)2 + 2.1818P]
where P = (Fo2 + 2Fc2)/3
w = 1/[σ2(Fo2) + (0.0947P)2]
where P = (Fo2 + 2Fc2)/3
w = 1/[σ2(Fo2) + (0.0573P)2 + 0.2205P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)0.30, 0.230.29, 0.320.28, 0.28
Absolute structure???
Absolute structure parameter???

Computer programs: CrystalClear-SM Expert 2.0 r4 (Rigaku, 2009), CrystalClear-SM Expert 2.0 rc14 (Rigaku, 2009), SHELXL97 (Sheldrick, 2008).

 

Acknowledgements

AM and KD thank CSIR for a SRF. SPS thanks DST for the NMR facility in MBU. GRD thanks DST for award of a J. C. Bose fellowship.

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IUCrJ
Volume 1| Part 4| July 2014| Pages 228-239
ISSN: 2052-2525