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

Journal logoSTRUCTURAL SCIENCE
CRYSTAL ENGINEERING
MATERIALS
ISSN: 2052-5206

Formation of quinol co-crystals with hydrogen-bond acceptors

aSchool of Chemistry, The University of Edinburgh, King's Buildings, West Mains Road, Edinburgh EH9 3JJ, Scotland, and bCambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, England
*Correspondence e-mail: i.d.h.oswald@sms.ed.ac.uk

(Received 21 June 2004; accepted 6 November 2004)

The crystal structures of eight new co-crystals of quinol with pyrazine, piperazine, morpholine, pyridine, piperidine, 4,4′-bipyridine, N-methylmorpholine and N,N′-dimethylpiperazine are reported. Quinol forms 1:1 co-crystals with pyrazine, piperazine and N,N′-dimethylpiperazine, but 1:2 co-crystals with morpholine, 4,4′-bipyridine, N-methylmorpholine, pyridine and piperidine. This difference can be rationalized in most cases by the presence of, respectively, two or one strong hydrogen-bond acceptor(s) in the guest molecule. The exception to this generalization is 4,4′-bipyridine, which forms a 1:2 co-crystal, possibly to optimize crystal packing. All structures are dominated by hydrogen bonding between quinol and the guest molecules. A doubly bridging motif, which connects pairs of quinol and guest molecules via NH⋯O or CH⋯O interactions, is present in all but the sterically hindered N,N′-dimethylpiperazine and N-methylmorpholine co-crystals.

1. Introduction

Quinol, or hydroquinone, is widely used to stabilize compounds that are susceptible to polymerization. It has been shown to crystallize in three polymorphic forms. The structure of the α-polymorph (R[\bar 3]) was determined by Bolte & Lerner (2001[Bolte, M. & Lerner, H.-W. (2001). Private Communication to CSD, CCDC 161816.]); the β-polymorph was determined by Lindeman et al. (1981[Lindeman, S. V., Shklover, V. E. & Struchkov, Yu. T. (1981). Cryst. Struct. Commun. 10, 1173-1179.]) and found to belong to the same space group, but with a smaller cell (Z′ = ½ rather than Z′ = 3). These two polymorphs were previously identified by Caspari (1926[Caspari, W. A. (1926). J. Chem. Soc. pp. 2944-2948.], 1927[Caspari, W. A. (1927). J. Chem. Soc. pp. 1093-1095.]), but there was some ambiguity in the determination of the space group. The γ-polymorph was found to crystallize in space group P21/c (Maartmann-Moe, 1966[Maartmann-Moe, K. (1966). Acta Cryst. 21, 979-982.]).

Quinol shows a great propensity for co-crystallizing with a variety of different compounds. A search of the Cambridge Structural Database, Version 5.25 (CSD: Allen & Motherwell, 2002[Allen, F. H. & Motherwell, W. D. S. (2002). Acta Cryst. B58, 407-422.]) shows that there are 92 co-crystals of quinol with a range of organic compounds. Of all the structures in the database over half were co-crystals of quinol with hydrogen-bond acceptors, including 1,4-dioxane (Barnes et al., 1990[Barnes, J. C., Paton, J. D. & Blyth, C. S. (1990). Acta Cryst. C46, 1183-1184.]). A previous paper by our group (Oswald et al., 2002[Oswald, I. D. H., Allan, D. R., McGregor, P. A., Motherwell, W. D. S., Parsons, S. & Pulham, C. R. (2002). Acta Cryst. B58, 1057-1066.]) described how molecules analogous to dioxane yielded a series of crystal structures with closely related packing motifs, and in this paper we report the crystal structures of co-crystals of quinol with pyrazine, piperazine, morpholine, pyridine, piperidine and 4,4′-bipyridine (hereafter referred to as guest molecules). These all crystallize in a manner related to that of the dioxane co-crystal. The structures of the N-methylmorpholine and N,N′-dimethylpiperazine co-crystals, which were also determined, highlight the effect of steric hindrance on the common structural motifs present for the unsubstituted guest molecules. Fig. 1[link] shows all the guest molecules used in the series.

[Figure 1]
Figure 1
Guest molecules used to form co-crystals with quinol. From left to right the structures show: top: dioxane, pyrazine, piperazine, morpholine, pyridine; bottom: piperidine, 4,4′-bipyridine, N-methylmorpholine and N,N-dimethylpiperazine. The structure numbers, (1)–(8) refer to the adducts that these molecules form with quinol.

2. Experimental

2.1. Synthesis

All starting materials were obtained from Sigma–Aldrich and used as received.

2.1.1. Quinol–pyrazine (1/1) (1)

Quinol (0.70 g, 6.36 mmol) was refluxed with pyrazine (0.51 g, 6.38 mmol) in ethanol (3 cm3) until the solid dissolved. The solution was allowed to cool to room temperature to produce crystals as colourless blocks.

2.1.2. Quinol–piperazine (1/1) (2)

Quinol (0.60 g, 5.45 mmol) was refluxed with piperazine (0.50 g, 5.81 mmol) in ethanol (3 cm3) until the solid dissolved. The solution was allowed to cool to room temperature to produce crystals in the form of colourless blocks.

2.1.3. Quinol–morpholine (1/2) (3)

Quinol (0.65 g, 5.90 mmol) was refluxed with morpholine (0.53 g, 5.95 mmol) with a little ethanol until the solid dissolved. Colourless, crystalline blocks were obtained on cooling to 277 K.

2.1.4. Quinol–pyridine (1/2) (4)

Quinol (0.49 g, 4.45 mmol) was dissolved in an excess of pyridine and drawn into a glass capillary (o.d. 0.32 mm). A polycrystalline sample was obtained on freezing the sample at 253 K and a crystal grown using the laser-assisted zone-refinement procedure of Boese & Nussbaumer (1994[Boese, R. & Nussbaumer, M. (1994). Correlations, Transformations, and Interactions in Organic Crystal Chemistry, edited by D. W. Jones & A. Katrusiak, Vol. 7, pp. 20-37. IUCr Crystallographic Symposia 7. IUCr and Oxford University Press.]).

2.1.5. Quinol–piperidine (1/2) (5)

Quinol (0.49 g, 4.45 mmol) was refluxed in a minimum volume of piperidine to dissolve the solid. The solution was allowed to cool to room temperature to produce crystals as colourless blocks.

2.1.6. Quinol–bipyridine (1/2) (6)

Quinol (0.59 g, 5.84 mmol) was refluxed with 4,4′-bipyridine (0.87 g, 5.58 mmol) in 3 cm3 of ethanol until the solid dissolved. The solution was allowed to cool to room temperature to produce colourless laths. An attempt was made to prepare a 1:1 adduct using the method employed by Corradi et al. (2000[Corradi, E., Meille, S. V., Messina, M. T., Metrangolo, P. & Resnati, G. (2000). Angew. Chem. Int. Ed. 39, 1782-1786.]): quinol (0.53 g, 4.82 mmol) and 4,4′-bipyridine (0.80 g, 5.13 mmol) were dissolved in hot acetone (40 cm3), and the mixture allowed to cool to room temperature. The colourless crystals were identified as (6) from their unit-cell dimensions.

2.1.7. Quinol–N-methylmorpholine (1/2) (7)

Quinol (0.55 g, 5.00 mmol) was dissolved in N-methylmorpholine (1.00 g, 10.30 mmol) and drawn into a glass capillary (o.d. 0.38 mm). A crystal was grown at 240 K from a polycrystalline sample of the frozen liquid by Boese's method (see above).

2.1.8. Quinol–N,N′-dimethylpiperazine (1/1) (8)

Quinol (0.65 g, 5.90 mmol) was refluxed with dimethylpiperazine (3 cm3, 20.10 mmol) in a little ethanol until the solid dissolved. The solution was held at 277 K to produce colourless crystalline blocks.

2.2. Crystallography

X-ray diffraction intensities were collected with Mo Kα radiation on a Bruker SMART APEX CCD diffractometer equipped with an Oxford Cryosystems low-temperature device (Cosier & Glazer, 1986[Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst. 19, 105-107.]). Absorption corrections were carried out using the multiscan procedure SADABS (Sheldrick, 1997a[Sheldrick, G. M. (1997a). SADABS. Bruker-AXS, Madison, Wisconsin, USA.]; based on the procedure described by Blessing, 1995[Blessing, R. H. (1995). Acta Cryst. A51, 33-38.]). All structures were solved by direct methods and refined by full-matrix least-squares against F2 using all data (SHELXTL; Sheldrick, 1997b[Sheldrick, G. M. (1997b). SHELXTL. Bruker-AXS, Madison, Wisconsin, USA.]). H atoms were placed on C atoms in calculated positions and allowed to ride on their parent atoms. Methyl groups were treated with the Sheldrick (1997b[Sheldrick, G. M. (1997b). SHELXTL. Bruker-AXS, Madison, Wisconsin, USA.]) rotating rigid-group model, except one methyl group in the dimethylpiperazine co-crystal which exhibited high thermal motion or some disorder (not modelled), where the positions were calculated purely on stereochemical grounds. H atoms involved in hydrogen bonding were located in difference maps and refined freely. All non-H atoms were modelled with anisotropic displacement parameters.

The diffraction pattern of the piperazine co-crystal indexed readily on the cell with a = 7.1977 (18), b = 8.859 (2), c = 13.247 (4) Å, α = 80.420 (6), β = 74.400 (4), γ = 66.153 (4)°. This can be transformed to a pseudo-monoclinic C-centred cell, although the Laue symmetry was clearly [\bar 1] and not 2/m. While the structure solved and refined without difficulty, it appeared to be twinned by a twofold rotation about [100] – the pseudo-monoclinic b axis. The R factor was 0.06, and bond distances and angles were normal. Symmetry checking (PLATON; Spek, 2002[Spek, A. L. (2002). PLATON. Utrecht University, The Netherlands.]) implied that the structure could be described using a smaller unit cell and closer inspection of the intensities revealed that data with k + l = 3n had an average I/σ(I) some eight times larger than the rest of the data. [This could also be readily recognized in the Patterson function, which had a peak with a height of about two-thirds that of the origin peak at approximately (0, ⅓, ⅓).] The data set was transformed using the matrix

[\left({\matrix{ 0 & {{1 \over 3}} & {{1 \over 3}} \cr 0 & { - {2 \over 3}} & {{1 \over 3}} \cr 1 & { - {1 \over 3}} & { - {1 \over 3}} \cr } } \right),]

and refined using a twofold rotation about [101], which corresponds to the matrix

[\left({\matrix{ { - {1 \over 3}} & 0 & {{2 \over 3}} \cr { - {1 \over 3}} & { - 1} & { - {1 \over 3}} \cr {{4 \over 3}} & 0 & {{1 \over 3}} \cr } } \right).]

Reflections where h+l = 3n contain contributions from both twin domains; the twin scale factor was 0.1185 (16).

A consistent numbering scheme was used for the quinol molecules in all structures and this is shown in the following scheme[link]. Where there is more than one quinol molecule in the asymmetric unit the labels shown are augmented with the letters A and B. Labels for atoms forming part of the guest molecules carry the letters S, T etc. A full listing of crystal, data collection and refinement parameters is given in Table 1[link]1 and a set of hydrogen-bonding parameters is given in Table 2[link]. Structures were visualized using SHELXTL or MERCURY (Taylor & Macrae, 2001[Taylor, R. & Macrae, C. F. (2001). Acta Cryst. B57, 815-827.]; Bruno et al., 2002[Bruno, I. J., Cole, J. C., Edgington, P. R., Kessler, M., Macrae, C. F., McCabe, P., Pearson, J. & Taylor, R. (2002). Acta Cryst. B58, 389-397.]); the figures were produced using CAMERON (Watkin et al., 1993[Watkin, D. J., Pearce, L. & Prout, C. K. (1993). CAMERON. Chemical Crystallography Laboratory, University of Oxford, England.]). Other analyses utilized the p.c. version of the program PLATON (Spek, 2002[Spek, A. L. (2002). PLATON. Utrecht University, The Netherlands.]; Farrugia, 1999[Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.]). Searches of the Cambridge Crystallographic Database (Allen & Motherwell, 2002[Allen, F. H. & Motherwell, W. D. S. (2002). Acta Cryst. B58, 407-422.]) were carried out with the program CONQUEST, utilizing Version 5.25 of the database. Graph-set assignments were confirmed using the GSET routine in RPLUTO (Motherwell et al., 1999[Motherwell, W. D. S., Shields, G. P. & Allen, F. H. (1999). Acta Cryst. B55, 1044-1056.]).

[Scheme 1]

Table 1
Crystallographic data for the co-crystals of quinol with pyrazine, piperazine, morpholine, pyridine, piperidine, 4,4′-bipyridine, N-methylmorpholine and N,N′-dimethylpiperazine

All data were collected at 150 K.

  (1) (2) (3) (4)
Crystal data
Chemical formula C6H6O2·C4H4N2 C4H10N2·C6H6O2 2C4H9NO·C6H6O2 C3H3O·C5H5N
Mr 190.20 196.25 284.36 268.31
Cell setting, space group Monoclinic, P21/c Triclinic twin, [P\bar 1] Monoclinic, P21/n Monoclinic, P21/c
a, b, c (Å) 8.901 (3), 7.666 (2), 6.984 (2) 5.7060 (15), 6.7599 (19), 7.0771 (18) 6.6652 (13), 5.5881 (11), 20.034 (4) 6.4990 (9), 16.459 (2), 7.1794 (10)
α, β, γ (°) 90.00, 90.091 (6), 90.00 100.269 (4), 112.446 (3), 90.163 (3) 90.00, 94.942 (4), 90.00 90.00, 112.986 (3), 90.00
V3) 476.6 (3) 247.50 (11) 743.4 (3) 707.00 (17)
Z 2 1 2 2
Dx (Mg m−3) 1.325 1.317 1.270 1.260
Radiation type Mo Kα Mo Kα Mo Kα Mo Kα
No. of reflections for cell parameters 834 2430 1472 1519
θ range (°) 2.3–26.7 3.1–28.7 3.3–28.3 2.4–28.5
μ (mm−1) 0.10 0.09 0.09 0.08
Temperature (K) 150 (2) 150 (2) 150 (2) 150 (2)
Crystal form, colour Plate, colourless Block, colourless Block, colourless Cylinder, colourless
Crystal size (mm) 0.39 × 0.28 × 0.10 0.27 × 0.23 × 0.06 0.31 × 0.22 × 0.09 1 × 0.32 × 0.32
         
Data collection
Diffractometer CCD area detector CCD area detector CCD area detector CCD area detector
Data collection method ω scans ω scans ω scans ω scans
Absorption correction Multi-scan Multi-scan Multi-scan Multi-scan
Tmin 0.787 0.874 0.675 0.593
Tmax 1 1 1 1
No. of measured, independent and observed reflections 2873, 1141, 926 3814, 1194, 1117 4226, 1730, 1427 5091, 1700, 1345
Criterion for observed reflections I > 2σ(I) I > 2σ(I) I > 2σ(I) I > 2σ(I)
Rint 0.023 0.029 0.038 0.031
θmax (°) 28.8 28.8 28.5 28.9
Range of h, k, l −10 → h → 11 −7 → h → 7 −8 → h → 8 −8 → h → 7
  −9 → k → 10 −9 → k → 8 −7 → k → 6 −21 → k → 21
  −8 → l → 9 −9 → l → 9 −26 → l → 19 −8 → l → 9
         
Refinement
Refinement on F2 F2 F2 F2
R[F2 > 2σ(F2)], wR(F2), S 0.047, 0.115, 1.07 0.051, 0.118, 1.09 0.085, 0.211, 1.18 0.083, 0.172, 1.33
No. of reflections 1141 1194 1730 1700
No. of parameters 68 73 99 95
H-atom treatment Mixture of independent and constrained refinement Mixture of independent and constrained refinement Mixture of independent and constrained refinement Mixture of independent and constrained refinement
Weighting scheme w = 1/[σ2(Fo2) + (0.0544P)2 + 0.1051P], where P = (Fo2 + 2Fc2)/3 w = 1/[σ2(Fo2) + (0.0269P)2 + 0.1505P], where P = (Fo2 + 2Fc2)/3 w = 1/[σ2(Fo2) + (0.0914P)2 + 0.6423P], where P = (Fo2 + 2Fc2)/3 w = 1/[σ2(Fo2) + (0.0363P)2 + 0.5217P], where P = (Fo2 + 2Fc2)/3
(Δ/σ)max <0.0001 <0.0001 <0.0001 <0.0001
Δρmax, Δρmin (e Å−3) 0.26, −0.30 0.32, −0.33 0.44, −0.30 0.28, −0.39
Extinction method None None None None
  (5) (6) (7) (8)
Crystal data
Chemical formula 2C5H11N·C6H6O2 2C10H8N2·C6H6O2 2C5H11NO·C6H6O2 C6H14N2·C6H6O2
Mr 280.40 422.49 312.41 224.30
Cell setting, space group Monoclinic, P21/c Triclinic, [P\bar 1] Triclinic, [P\bar 1] Triclinic, [P\bar 1]
a, b, c (Å) 10.4230 (15), 5.2619 (7), 15.221 (2) 7.820 (4), 8.619 (4), 9.201 (4) 6.9612 (10), 7.3146 (11), 9.659 (2) 8.9620 (8), 9.4944 (8), 14.7119 (13)
α, β, γ (°) 90.00, 109.920 (3), 90.00 111.897 (7), 109.851 (7), 94.657 (8) 106.182 (3), 104.481 (3), 106.201 (2) 90.501 (2), 92.919 (2), 99.664 (2)
V3) 784.84 (19) 525.7 (4) 423.94 (12) 1232.26 (19)
Z 2 1 1 4
Dx (Mg m−3) 1.187 1.335 1.224 1.209
Radiation type Mo Kα Mo Kα Mo Kα Mo Kα
No. of reflections for cell parameters 774 2247 2797 1812
θ range (°) 2.9–25.3 2.6–28.4 2.4–28.8 2.6–24.4
μ (mm−1) 0.08 0.09 0.09 0.08
Temperature (K) 150 (2) 150 (2) 150 (2) 150 (2)
Crystal form, colour Block, colourless Lath, colourless Cylinder, colourless Block, colourless
Crystal size (mm) 0.33 × 0.18 × 0.18 0.77 × 0.22 × 0.15 1 × 0.38 × 0.38 0.34 × 0.20 × 0.11
         
Data collection
Diffractometer CCD area detector CCD area detector CCD area detector CCD area detector
Data collection method ω scans ω scans ω scans ω scans
Absorption correction Multi-scan Multi-scan Multi-scan Multi-scan
Tmin 0.661 0.763 0.774 0.898
Tmax 1 1 1 1
No. of measured, independent and observed reflections 4754, 1896, 1327 4641, 2428, 2067 3788, 1972, 1794 11 345, 5844, 3873
Criterion for observed reflections I > 2σ(I) I > 2σ(I) I > 2σ(I) I > 2σ(I)
Rint 0.028 0.031 0.020 0.039
θmax (°) 29.0 28.7 28.8 28.9
Range of h, k, l −14 → h → 7 −10 → h → 10 −9 → h → 9 −12 → h → 12
  −7 → k → 7 −11 → k → 11 −9 → k → 9 −12 → k → 12
  −17 → l → 19 −12 → l → 12 −12 → l → 13 −19 → l → 19
         
Refinement
Refinement on F2 F2 F2 F2
R[F2 > 2σ(F2)], wR(F2), S 0.056, 0.136, 1.04 0.054, 0.144, 1.04 0.045, 0.120, 1.07 0.074, 0.162, 1.03
No. of reflections 1896 2428 1972 5844
No. of parameters 99 150 106 308
H-atom treatment Mixture of independent and constrained refinement Mixture of independent and constrained refinement Mixture of independent and constrained refinement Mixture of independent and constrained refinement
Weighting scheme w = 1/[σ2(Fo2) + (0.0582P)2 + 0.1207P], where P = (Fo2 + 2Fc2)/3 w = 1/[σ2(Fo2) + (0.0803P)2 + 0.1067P], where P = (Fo2 + 2Fc2)/3 w = 1/[σ2(Fo2) + (0.063P)2 + 0.0864P], where P = (Fo2 + 2Fc2)/3 w = 1/[σ2(Fo2) + (0.0536P)2 + 0.587P], where P = (Fo2 + 2Fc2)/3
(Δ/σ)max <0.0001 <0.0001 <0.0001 <0.0001
Δρmax, Δρmin (e Å−3) 0.24, −0.19 0.31, −0.26 0.24, −0.26 0.50, −0.43
Extinction method None SHELXL SHELXL None
Extinction coefficient 0.013 (9) 0.29 (4)
Computer programs used: Bruker SMART, Bruker SHELXTL, SHELXS97 (Sheldrick, 1997b[Sheldrick, G. M. (1997b). SHELXTL. Bruker-AXS, Madison, Wisconsin, USA.]), SHELXL97 (Sheldrick, 1997b[Sheldrick, G. M. (1997b). SHELXTL. Bruker-AXS, Madison, Wisconsin, USA.]).

Table 2
Table of hydrogen-bonding parameters C—H, N—H and O—H distances were normalized to 1.083, 1.009 and 0.983 Å, respectively, to aid comparison with Cambridge Database search results (Table 3[link])

Co-crystal Donor Acceptor DA distance (Å) Obs. distance/normalized distance (Å) Typical normalized distance (Å) Angle DHA (°)
Pyrazine (1) O1A—H1A N1S 2.7585 (17) 1.85 (2) 1.78 1.81 177 (2)
  C3S—H3S O1Ai 3.347 (2) 2.40 2.27 2.52 177
Piperazine (2) N1S—H1S O1Aii 3.0498 (19) 2.35 (2) 2.25 1.94 138.1 (17)
  O1A—H1A N1S 2.6708 (18) 1.80 (3) 1.71 1.83 167 (2)
Morpholine (3) N1S—H1S O1A 3.032 (3) 2.36 (3) 2.24 1.94 137 (3)
  O1A—H1A N1Siii 2.686 (3) 1.85 (4) 1.73 1.83 164 (3)
  C2S—H2S2 O4Siv 3.693 (3) 2.75 2.66 2.60 160
  C3S—H3S1 O4Sv 3.672 (4) 2.81 2.73 2.60 147
Pyridine (4) O1A—H1A N1S 2.728 (3) 1.88 (3) 1.75 1.83 174 (3)
  C2S—H2S O1Avi 3.385 (3) 2.49 2.37 2.52 156
Piperidine (5) N1S—H1S O1Avii 3.2782 (19) 2.43 (2) 2.28 1.94 168.8 (18)
  O1A—H1A N1Svii 2.747 (2) 1.82 (2) 1.77 1.83 173 (2)
4,4′-Bipyridine (6) O1A—H1A N1S 2.740 (2) 1.84 (2) 1.76 1.81 176 (2)
  C5S—H5S O1Aviii 3.456 (2) 2.59 2.47 2.52 152
  C9S—H9S O1Aix 3.394 (2) 2.46 2.33 2.52 169
N-Methyl-morpholine (7) O1A—H1A N1S 2.7367 (12) 1.87 (2) 1.77 1.83 167 (2)
  C1S—H1S3 O4Sx 3.4115 (15) 2.61 2.54 2.60 139
  C6S—H6S1 O4Sxi 3.5646 (14) 2.60 2.52 2.60 163
Dimethyl-piperazine (8) O1A—H1A N1T 2.733 (3) 1.86 (3) 1.77 1.83 167 (3)
  O4A—H4A N1Uxii 2.744 (3) 1.79 (3) 1.78 1.83 166 (3)
  O1B—H1B N1V 2.765 (3) 1.83 (3) 1.79 1.83 169 (3)
  O4B—H4B N1Sxiii 2.739 (3) 1.84 (3) 1.79 1.83 163 (3)
  C2A—H2A O1B 3.446 (3) 2.67 2.57 2.60 139
  C2B—H2B O1Ai 3.328 (3) 2.60 2.51 2.60 133
  C5B—H5B O4Bxiii 3.442 (3) 2.65 2.54 2.60 142
  C1S—H1S1 O4Axiv 3.560 (3) 2.63 2.53 2.60 159
  C3T—H3T2 O1Bxv 3.405 (3) 2.71 2.65 2.60 128
Symmetry operators: (i) x, y-1, z; (ii) -x+1, -y+1, -z+2; (iii) -x+2, -y+2, -z; (iv) [-x+{3\over 2}, y+{1\over 2},-z+{1\over 2}]; (v) [-x+{3\over 2}, y-{1\over 2}, -z+1/2]; (vi) -x, -y+1, -z+1; (vii) [-x+2, y+{1\over 2}, -z+{1\over 2}]; (viii) x-1, y, z; (ix) -x, -y+1, -z+2; (x) x, y+1, z; (xi) -x, -y, -z+2; (xii) x-1, y-1, z; (xiii) -x+1, -y, -z+1; (xiv) x+1, y, z; (xv) -x+1, -y+1, -z.

3. Results

3.1. Quinol–dioxane (1/1)

The structure of the quinol–dioxane co-crystal has been determined by Barnes et al. (1990[Barnes, J. C., Paton, J. D. & Blyth, C. S. (1990). Acta Cryst. C46, 1183-1184.]; CSD Refcode SENJOK). In this paper we report co-crystals of quinol with several compounds which are related to dioxane by their hydrogen-bonding properties; we discuss the structure of the quinol–dioxane co-crystal here in order to be able to make comparisons with the co-crystals that form the subject of the rest of this paper.

The asymmetric unit of quinol–dioxane (space group P21/a) consists of half-molecules of each component. The primary hydrogen-bonding motif in the structure is a C22(12) (Bernstein et al., 1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]) chain formed by O—H⋯O(ether) hydrogen bonds which connect alternating quinol and dioxane molecules; these chains run from the top left to the lower right in Fig. 2[link]. The chains are staggered, which allows the acceptor functionality of the hydroxyl to be filled by a close contact with a C—H moiety of a dioxane molecule in a neighbouring chain (CH⋯O 2.60 Å; the sum of the van der Waals radii of H and O is 2.72 Å). Interactions of this type link the chains together into a layer. CH⋯O interactions of similar dimensions are observed in both phases of dioxane (Buschmann et al., 1986[Buschmann, J., Müller, E. & Luger, P. (1986). Acta Cryst. C42, 873-876.]) and in morpholine (Parkin et al., 2004[Parkin, A., Oswald, I. D. H. & Parsons, S. (2004). Acta Cryst. B60, 219-227.]).

[Figure 2]
Figure 2
Quinol–dioxane (1/1) (CSD refcode: SENJOK) viewed perpendicular to the (100) planes. Colour scheme: C green, H grey and O red. The bridging motif through OH⋯O interactions and a close contact between a CH and the O of the hydroxyl group gives a R44(10) graph set (circled). The layers occupy the (200) planes in the structure, and alternate layers have chains running along the [011] and [0[\bar 1]1] directions.

A doubly bridging subunit composed of two quinol molecules and two dioxane molecules is presented in Fig. 2[link]. Each quinol is hydrogen bonded to one of the dioxane molecules, but it also accepts a CH⋯O interaction from the second. At this level of graph-set analysis there are four donors consisting of pairs of OH and CH moieties, and four acceptors formed by pairs of ether and phenol O atoms. It is useful for the purposes of drawing comparisons with the other structures in this series to highlight this secondary level, R44(10) ring motif in which two quinol molecules are doubly bridged by two dioxane molecules.

3.2. Quinol–pyrazine (1/1) (1)

Although pyrazine is chemically rather different to dioxane, the two molecules are similar in that they both consist of six-membered rings with centrosymmetrically related hydrogen-bond acceptors in the 1 and 4 positions. In addition, although ether oxygen can potentially act as a double acceptor, it rarely does so, and so the N atoms in pyrazine and the O atoms in dioxane can both be considered to be monofunctional hydrogen-bond acceptors.

The asymmetric unit of quinol–pyrazine (1/1) contains half-molecules of quinol and pyrazine, both occupying inversion centres in the space group P21/c. The primary bond distances and angles are normal for this and all the other structures reported here, and they are listed in the supplementary data . The structure is very similar to that of the dioxane co-crystal and the primary graph set consists of a C22(12) chain formed by alternating quinol and pyrazine molecules, which are hydrogen-bonded via OH⋯N interactions [H⋯N 1.85 (2) Å, see Table 2[link]]; the chains run from the top left to the lower right in Fig. 3[link]. The orientation of pyrazine enables a close contact to be formed between a C—H and the O of the hydroxyl group (2.40 Å), which serves to link chains to form a layer. Thus, an R44(10) subunit (Fig. 3[link]) composed of two quinol molecules doubly bridged by two guest molecules, which characterized the dioxane co-crystal, is also observed here.

[Figure 3]
Figure 3
Quinol–pyrazine (1/1) (1) viewed perpendicular to the (001) planes. Colour scheme: C green, H grey, O red and N blue. A similar doubly bridging motif to the dioxane structure is observed (circled). The layers occupy the (002) planes, and alternate layers contain chains passing along the [110] and [1[\bar 1]0] directions (note that the source of the differences in Miller indices between the dioxane and this pyrazine co-crystals is that the former has published coordinates referred to P21/a, while the latter is in P21/c).

3.3. Quinol–piperazine (1/1) (2)

In quinol–piperazine (1/1) both components are located on inversion centres. The amine H atom (the position of which was derived from a difference-Fourier map) favours the axial position in the piperazine molecule. The structure is depicted in Fig. 4[link].

[Figure 4]
Figure 4
Quinol–piperazine (1/1) (2) viewed perpendicular to the (110) planes. The donor–acceptor function of the amine moiety allows the co-crystal to form an R44(8) hydrogen-bonded doubly bridging motif (circled).

Piperazine is related to dioxane by the substitution of two NH groups for the ether O atoms. As in dioxane and pyrazine the N atoms act as monofunctional hydrogen-bond acceptors, but they can, in addition, act as hydrogen-bond donors. C22(12) chains are formed via OH⋯N hydrogen bonds and run from top left to lower right in Fig. 4[link]. NH⋯O hydrogen bonds are formed between the quinol and piperazine molecules in neighbouring chains, forming layers. The doubly bridging subunit (Fig. 4[link]), which was observed in the dioxane and pyrazine co-crystals, is also observed here, although it forms an R44(8) graph, rather than R44(10), because the donor capacity of piperazine is `built into' the amine group.

3.4. Quinol–morpholine (1/2) (3)

Morpholine is related to dioxane through the substitution of one of the O atoms with protonated nitrogen. This co-crystal crystallizes with one molecule of morpholine and half a molecule of quinol in the asymmetric unit, and in this respect it differs from the dioxane, pyrazine and piperazine co-crystals which all have 1:1 stoichometry. The quinol resides on a crystallographic inversion centre. The H atom (H1S) attached to the N atom in the morpholine molecule was located in a difference-Fourier map and found to occupy the less favourable axial position.

The hydrogen-bonding functionality of the quinol molecules, which form OH⋯N hydrogen bonds to the morpholine molecules, resembles that in the piperazine co-crystal. However, the ether O atoms do not participate in hydrogen bonding and the C22(12) chain motif observed in the piperazine co-crystal corresponds to a discrete D22(10) motif consisting of one quinol and two morpholine molecules in this co-crystal (see Fig. 5[link]a running diagonally from top left to lower right): the ether O atoms act like chain-stoppers. Neighbouring quinol–morpholine (1/2) units are linked by NH⋯O hydrogen-bonding interactions. A doubly bridging subunit (Fig. 5[link]a) analogous to those observed in the structures described above therefore also appears in this co-crystal. As in the piperazine co-crystal its secondary level graph-set descriptor is R44(8).

[Figure 5]
Figure 5
(a) Quinol–morpholine (1/2) (3) ribbon viewed perpendicular to the (112) planes. The ribbon does not extend into layers because of the relatively weak acceptor ability of the ether oxygen, which does not take part in hydrogen bonding. (b) The structure of quinol–morpholine (1/2) (3) viewed down the a axis showing the interleaved morpholine molecules. The ribbons at c = 0, 1…etc. run parallel to [110] and the second set of ribbons at c = 0.5 run parallel to [[\bar 1]10].

The ether O atom does not participate in any interactions which would be considered significant using a criterion based on the sums of the van der Waals radii, with the result that the structure is based on ribbons and not layers. The structure partitions into one set of regions at c = 0, 1…etc., where the ribbons run parallel to [110], and a second set through the middle of the unit cell (c = 0.5), where the ribbons run parallel to [[\bar 1]10] (Fig. 5[link]b). The overall effect is to interleave morpholine molecules. The angle between the mean planes of morpholine molecules in neighbouring ribbons passing along [110] and [[\bar 1]10] is 78.4 (4)° and the closest contacts made by O4S are to H atoms attached to C2S and C3S (2.75 and 2.81 Å, respectively)

3.5. Quinol–pyridine (1/2) (4)

Pyridine is related to pyrazine through the substitution of one of the N atoms by CH. This co-crystal crystallizes with one molecule of pyridine and a half molecule of quinol in the asymmetric unit. The quinol molecule resides on a crystallographic inversion centre. The stoichiometry of this co-crystal is 1:2, although we have recently shown that quinol also forms a 1:1 co-crystal with pyridine (Oswald, Motherwell & Parsons, 2004[Oswald, I. D. H., Motherwell, W. D. S. & Parsons, S. (2004). Acta Cryst. E60, o1967-o1969.]).

The hydrogen-bonding activity in the quinol molecules is identical to that observed in the pyrazine co-crystal (see above and Fig. 3[link]). The quinol donates to two symmetrically equivalent pyridine molecules through OH⋯N interactions (Fig. 6[link]a) to form a discrete D22(10) motif consisting of one quinol and two pyridine molecules. This is analogous to the structure of the morpholine co-crystal, with the CH group in the 4-position of the pyridine acting as a chain-stopper and, as a result, this structure consists of ribbons. The CH adjacent to the N atom of a pyridine in a neighbouring quinol–pyridine (1/2) unit acts as the donor group to the phenolic oxygen, yielding the same doubly bridging R44(10) motif as observed in the pyrazine co-crystal (Fig. 6[link]a). Neighbouring ribbons interact with each other through π-stacking of the pyridine molecules in which the stacking distance is 3.45 Å and the angle between the mean planes of stacked pyridine molecules is 5.32 (6)° (Fig. 6[link]b).

[Figure 6]
Figure 6
(a) Quinol–pyridine (1/2) (4) structure viewed perpendicular to the (21[\bar 2]) planes. The doubly bridging motif gives a R44(10) graph set (cf. pyrazine, circled). (b) Quinol–pyridine (1/2) (4) viewed down the a axis. Colour scheme: C green, H grey, O red and N blue. The π-stacking of pyridine molecules from neighbouring ribbons can clearly be seen.

3.6. Quinol–piperidine (1/2) (5)

Piperidine is related to morpholine through the substitution of the O atom with a methylene group. This co-crystal crystallizes with one molecule of piperidine and half a molecule of quinol in the asymmetric unit (cf. the morpholine and pyridine co-crystals). The quinol resides on a crystallographic inversion centre. The H atom (H1S) attached to the nitrogen in the piperidine molecule was located in a difference-Fourier map and occupies the axial position.

This co-crystal forms a similar structure to morpholine and pyridine in that it consists of discrete D22(10) units, consisting of one quinol and two piperidine molecules, which are linked into a ribbon via NH⋯O hydrogen bonds. Rather than forming an R22(8) motif the doubly bridging subunit forms an R44(18) graph set (Fig. 7[link]a, see also Table 2[link]). There are a larger number of atoms in this graph-set descriptor than in the structures discussed previously, because of the difference in the relative orientations of the quinol and piperidine molecules: cf., for example, Figs. 4[link], 6[link](a) and 7[link](a). A view of the packing along the direction of the ribbons ([010]) is shown in Fig. 7[link](b).

[Figure 7]
Figure 7
(a) Quinol–piperidine (1/2) (5) viewed perpendicular to the ([\bar 1]01) planes. Ribbons are formed rather than an extended layer motif, which follows from the absence of strong hydrogen-bonding functions in the 4-position in piperidine. (b) Quinol–piperidine (1/2) (5) viewed down the b axis. Colour scheme: C green, H grey, O red and N blue. The structure is based on ribbons which form along the [010] direction and are arranged in the ([\bar 2]02) planes. Piperidine molecules in neighbouring chains occupying the same ([\bar 2]02) plane are interleaved.

3.7. Quinol–(4,4′-bipyridine) (1/2) (6)

Co-crystals of quinol with 4,4′-bipyridine, N-methylmorpholine and N,N′-dimethylpiperazine were studied in order to investigate the effect of steric hindrance on the doubly bridging motif that has been observed in all the structures described so far. Like morpholine, 4,4′-bipyridine forms a 1:2 co-crystal with quinol, and the asymmetric unit contains half a molecule of quinol and one molecule of 4,4′-bipyridine. The angle between the C5N planes in the 4,4′-bipyridine molecules is 28.59 (6)°.

Predictably, the quinol interacts with the 4,4′-bipyridine molecule through the hydrogen bond between O1A and N1B. In terms of the symmetry of its hydrogen-bond acceptor functions bipyridine resembles dioxane, pyrazine and piperazine. An attempt was made to obtain a 1:1 co-crystal by recrystallization of a stoichiometric mixture of the components from acetone. This procedure has been used for the preparation of a 1:1 co-crystal of quinol and 4,4′-(bipyridyl)ethane, but in the case of 4,4′-bipyridine the same 1:2 co-crystal was obtained as from ethanol.

As in the other 1:2 co-crystals in this series, the structure contains a D22(10) unit consisting of one quinol and two bipyridine molecules. These are then linked into ribbons via a subunit (Fig. 8[link]a) in which two quinol molecules are doubly bridged by CH⋯O interactions with two bipyridine molecules. The C—H groups adjacent to the N atoms in bipyridine sometimes act as donors. This is not at all uncommon and it has even been used in crystal structure design, but it is not observed here. Instead, the quinol O atom acts as an acceptor for the H atom adjacent to the central C—C bond of the bipyridine (C9S—H9S⋯O1A, 2.46 Å, 169°).

[Figure 8]
Figure 8
(a) Quinol–(4,4′-bipyridine) (1/2) (6) viewed perpendicular to the (11[\bar 2]) planes. The graph set for this motif is the same as the piperidine structure, R44(18) (circled). (b) Quinol–(4,4′-bipyridine) (1/2) (6) viewed perpendicular to the b axis showing the interleaving between layers. Colour scheme: C green, H grey, O red and N blue. The different regions of quinol molecules at c = 0, 1... etc. and bipyridine molecules at c = ½.

A second CH⋯O bond exists between C5S—H5S and O1A (2.59 Å, 152°) that connects the ribbons together to form layers. When viewed along the b axis the structure consists of regions of quinol molecules occupying different layers at c = 0, 1…etc. and regions of bipyridine molecules at c = ½ in which bipyridine molecules in different layers interleave (Fig. 8[link]b). The pyridine moieties based on N7S are involved in offset stacks disposed about inversion centres, in which the distance between the ring planes is 3.62 Å with an offset of 1.77 Å (Hunter et al., 2001[Hunter, C. A., Lawson, K. R., Perkins, J. & Urch, C. J. (2001). J. Chem. Soc. Perkin Trans. 2, pp. 651-669.]). The layers are additionally connected by weak N⋯H interactions measuring 2.9–3.0 Å, involving N7S in one layer and H atoms in another (these contacts are not shown in Fig. 8[link]b for the sake of clarity).

3.8. Quinol–N-methylmorpholine (1/2) (7)

Crystals of N-methylmorpholine were grown by Boese's laser-assisted zone refinement method from a 1:2 mixture of quinol and N-methylmorpholine held in a capillary mounted on the diffractometer. Crystal growth experiments by more conventional procedures failed to yield anything but crystals of quinol.

The crystal structure contains half a molecule of quinol and a whole molecule of N-methylmorpholine in the asymmetric unit. The methyl group of the N-methylmorpholine molecule adopts the expected equatorial position, and bond distances and angles are normal. As in the other 1:2 co-crystals there is a D22(10) motif consisting of one quinol and two N-methylmorpholine molecules connected by centrosymmetrically related OH⋯N hydrogen bonds (Fig. 9[link]). In the morpholine co-crystal (see above) the D22(10) units were linked together via a doubly bridging subunit involving NH⋯O interactions, but substitution of the NH group by N(CH3) means that this type of bridging cannot occur in the N-methylmorpholine co-crystal. The steric bulk of the methyl group also forces a change in the relative orientation of the quinol and guest molecules, preventing the alternative O⋯CH(ring) interaction seen elsewhere in this series. The steric effect of the N-methyl group has therefore been to disrupt the formation of the doubly bridging unit highlighted in Figs. 2–8[link][link][link][link][link][link][link]. D22(10) units are instead linked via CH3⋯O interactions between N-methylmorpholine molecules, forming ribbons. The ribbons are then linked into a layer by further CH⋯O interactions between N-methylmorpholine molecules.

[Figure 9]
Figure 9
Quinol–N-methylmorpholine (1/2) (7) viewed perpendicular to the (101) planes.

3.9. Quinol–N,N′-dimethylpiperazine (1/1) (8)

In the asymmetric unit of the dimethylpiperazine co-crystal there are two molecules of quinol and four half-molecules of dimethylpiperazine, so that the co-crystal has overall 1:1 stoichiometry. In all cases the methyl groups of the dimethylpiperazine are in the expected equatorial positions.

The strongest intermolecular interactions are OH⋯N hydrogen bonds which build up C22(12) chains (Fig. 10[link]), similar to those observed in the quinol–piperazine (1/1) co-crystal. There are two symmetrically inequivalent chains present in the structure, both involving one quinol molecule and two independent guest molecules. The quinol is present in a non-centrosymmetric conformer, which results in the chains becoming more sinusoidal than in the piperazine co-crystal. As in the N-methylmorpholine co-crystal described above, the N-methyl groups prevent the formation of bridging interactions between chains, which are instead linked by CH⋯O interactions with other chains that pass through the rather open structure depicted in Fig. 10[link].

[Figure 10]
Figure 10
Quinol–N,N′-dimethylpiperazine (1/1) (8). The inequivalent chains run perpendicular to these chains filling the space between the two chains.

4. Discussion and conclusions

4.1. Hydrogen-bond formation in co-crystals of quinol

Our previous paper on paracetamol co-crystals utilized the Cambridge Structural Database (CSD) in rationalizing the formation of a series of co-crystals from pure paracetamol (Oswald et al., 2002[Oswald, I. D. H., Allan, D. R., McGregor, P. A., Motherwell, W. D. S., Parsons, S. & Pulham, C. R. (2002). Acta Cryst. B58, 1057-1066.]; Oswald, Motherwell, Parsons, Pidcock & Pulham, 2004[Oswald, I. D. H., Motherwell, W. D. S., Parsons, S., Pidcock, E. & Pulham, C. R. (2004). Cryst. Rev. 10, 57-66.]) and a similar procedure can be used for this series of compounds. There are only two classical hydrogen-bond donor groups in this series: the phenol OH and a secondary amine NH. The aromatic or aliphatic CH groups adjacent to the heteroatom with the phenolic oxygen can also act as donors. The acceptor groups in the series are a phenolic O, secondary or tertiary amine N, ether O and pyridine N. The results of searches of the CSD for typical hydrogen-bond geometries involving these functionalities are listed in Table 3[link]; searching criteria are given in the legend to that table.

Table 3
Summary of the results of searches of the CSD (Version 5.25, November 2003) for typical distances in hydrogen-bonded systems containing identical functional groups to the quinol co-crystals studied

The distances to H atoms were normalized to typical neutron distances (C—H 1.083, N—H 1.009 and O—H 0.983 Å). Only `organic' structures where the R factor is less than 0.05, with no errors or disorder, were included, and ionic or polymeric structures were excluded. The C atoms attached to the amine moieties were specified to be sp2 or sp3 hybridized. The donor-H–acceptor distance was specified to be 1.50–2.20 or 1.50–2.75 Å in the case of the CH donor atoms.

  Acceptor (O or N in each case)
Donor (NH or OH)  
[Scheme 2]
[Scheme 3]
[Scheme 4]
[Scheme 5]
[Scheme 6]
Sample size (Å) 334 54 57 95
Max OH⋯A 2.20 2.19 2.20 2.18
Min OH⋯A 1.67 1.66 1.62 1.53
Mean OH⋯A 1.87 1.82 1.90 1.81
[Scheme 7]
Sample size 3 15 5 Not applicable
Max NH⋯A 2.03 2.20 2.18
Min NH⋯A 1.87 2.00 2.11
Mean NH⋯A 1.94 2.14 2.13
[Scheme 8]
Sample size 217 109 4273 Not applicable
Max CH⋯A 2.75 2.75 2.75  
Min CH⋯A 2.13 2.40 1.87  
Mean CH⋯A 2.60 2.64 2.58  
[Scheme 9]
Sample size 67 Not applicable Not applicable 328
Max CH⋯A 2.75 2.75
Min CH⋯A 2.18 2.26
Mean CH⋯A 2.52 2.59

In interpreting the data in Table 3[link] we assume that the strength of hydrogen bonds is related to the donor-hydrogen–acceptor distance with the D—H bond normalized to typical neutron distances (O—H 0.983, N—H 1.009 and C—H 1.083 Å). Amine N atoms are more strongly basic than phenolic or ether O atoms, and the strongest bonds in Table 3[link] are those from a phenol donor to a secondary or tertiary amine, or a pyridine N. In co-crystals of this type hydrogen bonds are formed to the guest rather than to the weaker OH⋯O(H) found in pure quinol, and where N atoms are present in the 1 and 4 positions of the guest (i.e. in pyrazine, piperazine and N,N′-dimethylpiperazine), 1:1 co-crystals are formed. Hydrogen bonds in which the phenolic and ether O atoms act as acceptors to weak CH donors are similar in strength. This observation helps to rationalize the formation of the dioxane co-crystal. It was formed from a solution of quinol in dioxane that was allowed to evaporate at room temperature. Under these conditions there is excess dioxane present in the system, which would favour the OH⋯O(ether) interaction, leading to a 1:1 co-crystal of quinol and dioxane.

In the co-crystals of quinol with molecules with N, NH or NMe and O, CH or CH2, respectively, in the 1 and 4 positions, the quinol hydrogen bonds exclusively to the nitrogen moiety. In the case of morpholine and N-methylmorpholine the ether O atom is a much less effective acceptor than the amine nitrogen (Table 3[link]); in piperidine and pyridine the CH2 and CH groups in the 4-positions can, of course, fail to act as acceptors at all. Quinol selectively binds to the nitrogen group and, in order to satisfy the hydrogen-bonding capacity of quinol, all four of these co-crystals crystallize in a 1:2 quinol-to-guest ratio.

4.2. The co-crystal of quinol with 4,4′-bipyridine

Considerations of hydrogen-bonding strength based on the data in Table 3[link] enable the stoichiometries of the majority of co-crystals studied here to be rationalized. The exception is the co-crystal of quinol with 4,4′-bipyridine, which would be predicted to form a 1:1 co-crystal, whereas the observed stoichiometry is 1:2, with only one of the two N atoms in each bipyridine molecule being used in hydrogen bonding. An attempt to obtain a 1:1 co-crystal under the same conditions as employed in the synthesis of quinol–1,2-bis(4-pyridyl)ethane (Corradi et al., 2000[Corradi, E., Meille, S. V., Messina, M. T., Metrangolo, P. & Resnati, G. (2000). Angew. Chem. Int. Ed. 39, 1782-1786.]) was not successful. It is possible that a substantial change of crystallization conditions (e.g. solvothermal methods or high pressure) would lead to substantially different behaviour: paracetamol, for example, forms a methanol solvate which can be prepared at 0.62 GPa, but undergoes desolvation at ambient pressure (Fabbiani et al., 2003[Fabbiani, F. P. A., Allan, D. R., Dawson, A., David, W. I. F., McGregor, P. A., Oswald, I. D. H., Parsons, S. & Pulham, C. R. (2003). Chem. Commun. pp. 3004-3005.]). It is possible that the anomalous behaviour of 4,4′-bipyridine occurs as a result of competition between hydrogen bonding (leading to a 1:1 co-crystal) and π-stacking (leading to a 1:2 co-crystal).

Pyrazine is similar to 4,4′-bipyridine in that it contains two aromatic N-acceptor sites, yet this forms a 1:1 co-crystal with quinol; pyrazine (pKa 0.6) is also less basic than 4,4′-bipyridine (pKa 4.8). This trend is observed in other co-crystals: a search of the CSD reveals that pyrazine always acts as a double acceptor for hydroxyl-containing moieties, whereas for 4,4′-bipyidine both π-stacking and hydrogen-bonding interactions are observed. Theoretical values of the polarizabilities of neutral and protonated versions of pyridine and pyrazine have recently been published (Soscùn et al., 2004[Soscùn, H., Bermúdez, Y., Castellano, O. & Hernández, J. (2004). Chem. Phys. Lett. 396, 117-121.]) and values (in a.u.) are: pyridine, 61.14; pyridine-H+, 54.30; pyrazine, 56.38; pyrazine-H+, 50.67. The non-hydrogen-bonded ring of 4,4′-bipyridine in the co-crystal with quinol plausibly has a polarizability similar to pyridine (61.14 a.u.), whereas a singly coordinated pyrazine ring would have a polarizability somewhere between 56.38 and 50.57 a.u. The higher polarizability of the former would tend to promote π-stacking. This may be enough to make this interaction competitive with hydrogen bonding for 4,4′-bipyridine.

We have recently shown that quinol forms a 1:1 co-crystal with pyridine (Oswald, Motherwell & Parsons, 2004[Oswald, I. D. H., Motherwell, W. D. S. & Parsons, S. (2004). Acta Cryst. E60, o1967-o1969.]), whereas a 1:2 co-crystal would normally have been anticipated. The formation of this co-crystal could also be ascribed to competition between hydrogen bonding with a combination of CH⋯O, CH⋯π and π-stacking.

4.3. Hydrogen-bonding patterns

All the 1:1 co-crystals described here are based on C22(12) chains of alternating quinol and guest molecules. All the 1:2 co-crystals are based on discrete D22(10) motifs containing one quinol and two guest molecules. In all but the two sterically hindered cases (N-methylmorpholine and N,N′-dimethylpiperazine) the C22(12) chains or D22(10)-based motifs are linked about an inversion centre by NH⋯O or CH⋯O interactions in which quinol molecules are doubly bridged by pairs of guest molecules. This linking of chains builds layers in the 1:1 co-crystals; linking of the discrete units in the 1:2 co-crystals builds ribbons.

These observations also apply to the crystal structure of quinol itself. Three polymorphs of quinol are known, but the simplest is the monoclinic γ-polymorph, and the co-crystals discussed in this paper are related to this structure. In the asymmetric unit there are two half molecules of quinol residing on inversion centres. The primary graph set is C22(14) formed by OH⋯O(H) hydrogen bonds; this corresponds to the C22(12) chains of the 1:1 co-crystals described above. These chains are parallel to one another and hydrogen bond together to form a doubly bridging R44(18) graph set at the secondary level (Fig. 11[link]).

[Figure 11]
Figure 11
γ-Quinol viewed down the a axis. γ-Quinol is a layered structure where the primary graph set is C22(14); these chains are parallel to one another and hydrogen bond together to form an R44(18) graph set.

4.4. Co-crystals of resorcinol and catechol

Co-crystal formation by the isomers of quinol, resorcinol (1,3-dihyroxybenzene) and catechol (1,2-dihydroxybenzene) has been more lightly investigated than those of quinol itself. There have been no systematic studies of the type presented here for quinol for either compound, although we are currently investigating the formation of such compounds.

There are 13 chemically distinct co-crystals of resorcinol in Version 5.25 of the CSD. Seven of these form hydrogen-bonded chains similar to those observed for quinol (for example, CSD refcodes ACOYOG and VAKTUX). The non-linear arrangement of the OH donor sites in resorcinol also allows resorcinol to build discrete hydrogen-bonded clusters rather than infinite motifs (e.g. refcodes ABEKUN and TAHVII). This feature has found application in forming clusters in which C=C bonds are bought into close proximity so that 2 + 2-cycloadditions occur on UV irradiation (MacGillivray et al., 2000[MacGillivray, L. R., Reid, J. &. Ripmeester, J. A. (2000). J. Am. Chem. Soc. 122, 7817-7818.]). Resorcinol itself (RESORA03) forms a three-dimensional network based on rings of molecules. Similar remarks apply to co-crystals of catechol. The crystal structure of catechol itself contains hydrogen-bonded dimers and these are linked, pairwise, into chains. Clusters of varying sizes are observed in eight out of 16 co-crystals in the CSD; chain motifs account for most of the remainder.

4.5. Inversion symmetry in quinol co-crystals

In all but one co-crystal described here (8) the quinol is present in its centrosymmetric conformer. This preference is reflected in other quinol co-crystals in the CSD; out of 108 structures only seven have quinol in the non-centrosymmetric form (CABWAD, COBMOV, GUSSES, IDUMUP, KEFBEC, QUNNEC, SUWGOG); there does not appear to be any common feature in these structures that might have explained the adoption of the less usual conformation. It is possible that the adoption by quinol of its centrosymmetric conformer is related to the general preference for centrosymmetric packing in crystal structures. In fact, quinol has a tendency to occupy crystallographic inversion centres in its co-crystals: of the 71 quinol molecules in the relational database CSD symmetry (Yao et al., 2002[Yao, J. W., Cole, J. C., Pidcock, E., Allen, F. H., Howard, J. A. K. & Motherwell, W. D. S. (2002). Acta Cryst. B58, 640-646.]; this was built using version 5.19 of the CSD), 46 occupy Wyckoff positions [\bar 1]. This is consistent with the behaviour of centrosymmetric molecules in general. In a recent survey Pidcock et al. (2003[Pidcock, E., Motherwell, W. D. S. & Cole, J. C. (2003). Acta Cryst. B59, 634-640.]) showed that molecules with an inversion centre retain this symmetry element in their crystal structures in over 80% of cases. This bias towards centrosymmetry is related to the promotion of dense packing by crystallographic inversion centres. Similar features are observed in the retention in crystal structures of other `point-acting' symmetry elements 3 and 4 (Pidcock et al., 2003[Pidcock, E., Motherwell, W. D. S. & Cole, J. C. (2003). Acta Cryst. B59, 634-640.]).

Supporting information


Computing details top

For all compounds, data collection: Bruker SMART; cell refinement: Bruker SMART; data reduction: Bruker SHELXTL; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997b); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997b); molecular graphics: Bruker SHELXTL; software used to prepare material for publication: Bruker SHELXTL.

Figures top
[Figure 1]
[Figure 2]
[Figure 3]
[Figure 4]
[Figure 5]
[Figure 6]
[Figure 7]
[Figure 8]
[Figure 9]
[Figure 10]
[Figure 11]
(1) top
Crystal data top
C6H6O2.C4H4N2F(000) = 200
Mr = 190.20Dx = 1.325 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 8.901 (3) ÅCell parameters from 834 reflections
b = 7.666 (2) Åθ = 2.3–26.7°
c = 6.984 (2) ŵ = 0.10 mm1
β = 90.091 (6)°T = 150 K
V = 476.6 (3) Å3Plate, colourless
Z = 20.39 × 0.28 × 0.10 mm
Data collection top
CCD area detector
diffractometer
1141 independent reflections
Radiation source: fine-focus sealed tube926 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.023
ω scansθmax = 28.8°, θmin = 3.5°
Absorption correction: multi-scan
SADABS
h = 1011
Tmin = 0.787, Tmax = 1k = 910
2873 measured reflectionsl = 89
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)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.115H atoms treated by a mixture of independent and constrained refinement
S = 1.07 w = 1/[σ2(Fo2) + (0.0544P)2 + 0.1051P]
where P = (Fo2 + 2Fc2)/3
1141 reflections(Δ/σ)max < 0.001
68 parametersΔρmax = 0.26 e Å3
0 restraintsΔρmin = 0.30 e Å3
Crystal data top
C6H6O2.C4H4N2V = 476.6 (3) Å3
Mr = 190.20Z = 2
Monoclinic, P21/cMo Kα radiation
a = 8.901 (3) ŵ = 0.10 mm1
b = 7.666 (2) ÅT = 150 K
c = 6.984 (2) Å0.39 × 0.28 × 0.10 mm
β = 90.091 (6)°
Data collection top
CCD area detector
diffractometer
1141 independent reflections
Absorption correction: multi-scan
SADABS
926 reflections with I > 2σ(I)
Tmin = 0.787, Tmax = 1Rint = 0.023
2873 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0470 restraints
wR(F2) = 0.115H atoms treated by a mixture of independent and constrained refinement
S = 1.07Δρmax = 0.26 e Å3
1141 reflectionsΔρmin = 0.30 e Å3
68 parameters
Special details top

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

Refinement. 125_ALERT_4_C No _symmetry_space_group_name_Hall Given ···.. ?

-P 2ybc

152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ··· ?

Volume Reported 476.6 (3) Calculated 476.6 (2) Probably a rounding error

061_ALERT_3_C Tmax/Tmin Range Test RR' too Large ·········.. 0.81 764_ALERT_4_C Overcomplete CIF Bond list Detected (Rep/Expd) 1.29 Ratio

No action taken.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O1A0.71445 (11)0.46037 (14)0.14967 (15)0.0260 (3)
C1A0.85553 (15)0.47662 (18)0.0737 (2)0.0199 (3)
C2A0.94287 (15)0.61663 (18)0.1331 (2)0.0216 (3)
H2A0.90430.69670.22450.026*
C3A1.08664 (15)0.64018 (18)0.05933 (19)0.0219 (3)
H3A1.14560.73660.10020.026*
N1S0.57307 (13)0.15072 (16)0.05990 (17)0.0258 (3)
C2S0.62719 (17)0.0078 (2)0.0975 (2)0.0279 (4)
H2S0.71850.01800.16710.033*
C3S0.55474 (16)0.15751 (19)0.0385 (2)0.0259 (4)
H3S0.59710.26790.06880.031*
H1A0.670 (2)0.358 (3)0.117 (3)0.049 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O1A0.0221 (5)0.0202 (6)0.0358 (6)0.0040 (4)0.0053 (4)0.0034 (4)
C1A0.0204 (7)0.0179 (7)0.0215 (6)0.0003 (5)0.0016 (5)0.0031 (5)
C2A0.0255 (7)0.0168 (7)0.0224 (7)0.0007 (5)0.0000 (5)0.0036 (5)
C3A0.0236 (7)0.0163 (7)0.0256 (7)0.0037 (5)0.0035 (5)0.0016 (5)
N1S0.0261 (7)0.0216 (7)0.0297 (7)0.0054 (5)0.0046 (5)0.0035 (5)
C2S0.0245 (7)0.0293 (9)0.0297 (8)0.0009 (6)0.0023 (6)0.0013 (6)
C3S0.0270 (8)0.0217 (8)0.0292 (8)0.0012 (6)0.0054 (6)0.0024 (6)
Geometric parameters (Å, º) top
O1A—C1A1.3696 (17)C3A—H3A0.9500
O1A—H1A0.91 (2)N1S—C3Sii1.3291 (19)
C1A—C2A1.3882 (19)N1S—C2S1.333 (2)
C1A—C3Ai1.390 (2)C2S—C3S1.379 (2)
C2A—C3A1.392 (2)C2S—H2S0.9500
C2A—H2A0.9500C3S—N1Sii1.3291 (19)
C3A—C1Ai1.390 (2)C3S—H3S0.9500
C1A—O1A—H1A112.1 (13)C2A—C3A—H3A119.8
O1A—C1A—C2A117.91 (12)C3Sii—N1S—C2S116.50 (12)
O1A—C1A—C3Ai122.76 (12)N1S—C2S—C3S122.08 (14)
C2A—C1A—C3Ai119.33 (13)N1S—C2S—H2S119.0
C1A—C2A—C3A120.30 (13)C3S—C2S—H2S119.0
C1A—C2A—H2A119.8N1Sii—C3S—C2S121.42 (14)
C3A—C2A—H2A119.8N1Sii—C3S—H3S119.3
C1Ai—C3A—C2A120.37 (12)C2S—C3S—H3S119.3
C1Ai—C3A—H3A119.8
Symmetry codes: (i) x+2, y+1, z; (ii) x+1, y, z.
(2) top
Crystal data top
C4H10N2·C6H6O2Z = 1
Mr = 196.25F(000) = 106
Triclinic twin, P1Dx = 1.317 Mg m3
a = 5.7060 (15) ÅMo Kα radiation, λ = 0.71073 Å
b = 6.7599 (19) ÅCell parameters from 2430 reflections
c = 7.0771 (18) Åθ = 3.1–28.7°
α = 100.269 (4)°µ = 0.09 mm1
β = 112.446 (3)°T = 150 K
γ = 90.163 (3)°Block, colourless
V = 247.50 (11) Å30.27 × 0.23 × 0.06 mm
Data collection top
CCD area detector
diffractometer
1194 independent reflections
Radiation source: fine-focus sealed tube1117 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.029
ω scansθmax = 28.8°, θmin = 3.1°
Absorption correction: multi-scan
SADABS
h = 77
Tmin = 0.874, Tmax = 1k = 98
3814 measured reflectionsl = 99
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)] = 0.051Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.118H atoms treated by a mixture of independent and constrained refinement
S = 1.09 w = 1/[σ2(Fo2) + (0.0269P)2 + 0.1505P]
where P = (Fo2 + 2Fc2)/3
1194 reflections(Δ/σ)max < 0.001
73 parametersΔρmax = 0.32 e Å3
0 restraintsΔρmin = 0.33 e Å3
Crystal data top
C4H10N2·C6H6O2γ = 90.163 (3)°
Mr = 196.25V = 247.50 (11) Å3
Triclinic twin, P1Z = 1
a = 5.7060 (15) ÅMo Kα radiation
b = 6.7599 (19) ŵ = 0.09 mm1
c = 7.0771 (18) ÅT = 150 K
α = 100.269 (4)°0.27 × 0.23 × 0.06 mm
β = 112.446 (3)°
Data collection top
CCD area detector
diffractometer
1194 independent reflections
Absorption correction: multi-scan
SADABS
1117 reflections with I > 2σ(I)
Tmin = 0.874, Tmax = 1Rint = 0.029
3814 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0510 restraints
wR(F2) = 0.118H atoms treated by a mixture of independent and constrained refinement
S = 1.09Δρmax = 0.32 e Å3
1194 reflectionsΔρmin = 0.33 e Å3
73 parameters
Special details top

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

Refinement. 029_ALERT_3_A _diffrn_measured_fraction_theta_full Low ······. 0.93

The data set is 99.8% complete to 0.6 Å.

================================================================================ Resolution & Completeness Statistics (Cumulative) ================================================================================ Theta sin(th)/Lambda Complete Expected Measured Missing ——————————————————————————– 20.82 0.500 0.998 518 517 1 23.01 0.550 0.999 691 690 1 25.24 0.600 0.998 893 891 2 ———————————————————— ACTA Min. Res. —- 27.51 0.650 0.988 1145 1131 14 29.84 0.700 0.928 1286 1194 92

417_ALERT_2_C Short Inter D—H.·H—D H1A.. H1S.. 2.12 A ng.

H1A is hydrogen-bonding to N1S. H1S is attached to N1S hence the close contact

061_ALERT_3_C Tmax/Tmin Range Test RR' too Large ············. 0.89 125_ALERT_4_C No _symmetry_space_group_name_Hall Given ······. ? 720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ······.. 4 764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd). 1.29 Ratio 911_ALERT_3_C Missing FCF Refl. Between TH(Min) & STH/L=0.6.. 2 912_ALERT_3_C Missing FCF Reflections Above STH/L=0.6 ······.. 90

Noted, but no action taken.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O1A0.2196 (2)0.64145 (17)0.94863 (19)0.0256 (3)
C1A0.1153 (3)0.8206 (2)0.9723 (2)0.0181 (3)
C2A0.1463 (3)0.9795 (2)0.8811 (2)0.0188 (3)
H2A0.24670.96650.79970.023*
C3A0.0313 (3)1.1566 (2)0.9084 (2)0.0183 (3)
H3A0.05311.26390.84480.022*
N1S0.4720 (3)0.5682 (2)0.6971 (2)0.0204 (3)
C2S0.5026 (3)0.7117 (2)0.5742 (2)0.0207 (3)
H2S10.59740.83690.66970.025*
H2S20.33260.74680.48560.025*
C3S0.6429 (3)0.6288 (2)0.4364 (3)0.0234 (4)
H3S10.64330.72610.34730.028*
H3S20.82190.61470.52560.028*
H1S0.619 (4)0.548 (3)0.789 (3)0.028 (5)*
H1A0.306 (5)0.637 (4)0.868 (4)0.048 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O1A0.0375 (7)0.0196 (6)0.0312 (7)0.0116 (5)0.0236 (6)0.0103 (5)
C1A0.0205 (7)0.0164 (7)0.0171 (7)0.0032 (5)0.0073 (6)0.0026 (5)
C2A0.0204 (7)0.0202 (7)0.0182 (7)0.0019 (6)0.0101 (6)0.0036 (6)
C3A0.0215 (7)0.0170 (7)0.0173 (7)0.0009 (5)0.0077 (6)0.0048 (5)
N1S0.0236 (7)0.0203 (6)0.0179 (6)0.0041 (5)0.0094 (5)0.0023 (5)
C2S0.0245 (8)0.0188 (7)0.0196 (7)0.0036 (6)0.0100 (6)0.0021 (6)
C3S0.0281 (8)0.0220 (8)0.0242 (8)0.0007 (6)0.0156 (7)0.0021 (6)
Geometric parameters (Å, º) top
O1A—C1A1.3626 (18)N1S—C3Sii1.473 (2)
O1A—H1A0.88 (3)N1S—H1S0.87 (2)
C1A—C3Ai1.390 (2)C2S—C3S1.520 (2)
C1A—C2A1.391 (2)C2S—H2S10.9900
C2A—C3A1.386 (2)C2S—H2S20.9900
C2A—H2A0.9500C3S—N1Sii1.473 (2)
C3A—C1Ai1.390 (2)C3S—H3S10.9900
C3A—H3A0.9500C3S—H3S20.9900
N1S—C2S1.465 (2)
C1A—O1A—H1A112.6 (16)N1S—C2S—C3S112.59 (13)
O1A—C1A—C3Ai117.95 (13)N1S—C2S—H2S1109.1
O1A—C1A—C2A123.23 (14)C3S—C2S—H2S1109.1
C3Ai—C1A—C2A118.82 (14)N1S—C2S—H2S2109.1
C3A—C2A—C1A120.35 (14)C3S—C2S—H2S2109.1
C3A—C2A—H2A119.8H2S1—C2S—H2S2107.8
C1A—C2A—H2A119.8N1Sii—C3S—C2S112.70 (13)
C2A—C3A—C1Ai120.84 (14)N1Sii—C3S—H3S1109.1
C2A—C3A—H3A119.6C2S—C3S—H3S1109.1
C1Ai—C3A—H3A119.6N1Sii—C3S—H3S2109.1
C2S—N1S—C3Sii111.17 (12)C2S—C3S—H3S2109.1
C2S—N1S—H1S110.5 (14)H3S1—C3S—H3S2107.8
C3Sii—N1S—H1S107.5 (13)
Symmetry codes: (i) x, y+2, z+2; (ii) x+1, y+1, z+1.
(3) top
Crystal data top
2(C4H9NO)(C6H6O2)F(000) = 308
Mr = 284.36Dx = 1.270 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 6.6652 (13) ÅCell parameters from 1472 reflections
b = 5.5881 (11) Åθ = 3.3–28.3°
c = 20.034 (4) ŵ = 0.09 mm1
β = 94.942 (4)°T = 150 K
V = 743.4 (3) Å3Block, colourless
Z = 20.31 × 0.22 × 0.09 mm
Data collection top
CCD area detector
diffractometer
1730 independent reflections
Radiation source: fine-focus sealed tube1427 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.038
ω scansθmax = 28.5°, θmin = 2.0°
Absorption correction: multi-scan
SADABS
h = 88
Tmin = 0.675, Tmax = 1k = 76
4226 measured reflectionsl = 2619
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)] = 0.085Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.211H atoms treated by a mixture of independent and constrained refinement
S = 1.18 w = 1/[σ2(Fo2) + (0.0914P)2 + 0.6423P]
where P = (Fo2 + 2Fc2)/3
1730 reflections(Δ/σ)max < 0.001
99 parametersΔρmax = 0.44 e Å3
0 restraintsΔρmin = 0.31 e Å3
Crystal data top
2(C4H9NO)(C6H6O2)V = 743.4 (3) Å3
Mr = 284.36Z = 2
Monoclinic, P21/nMo Kα radiation
a = 6.6652 (13) ŵ = 0.09 mm1
b = 5.5881 (11) ÅT = 150 K
c = 20.034 (4) Å0.31 × 0.22 × 0.09 mm
β = 94.942 (4)°
Data collection top
CCD area detector
diffractometer
1730 independent reflections
Absorption correction: multi-scan
SADABS
1427 reflections with I > 2σ(I)
Tmin = 0.675, Tmax = 1Rint = 0.038
4226 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0850 restraints
wR(F2) = 0.211H atoms treated by a mixture of independent and constrained refinement
S = 1.18Δρmax = 0.44 e Å3
1730 reflectionsΔρmin = 0.31 e Å3
99 parameters
Special details top

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

Refinement. 061_ALERT_3_B Tmax/Tmin Range Test RR' too Large ·········.. 0.69

SADABS corrects for all systematic errors, not just absorption. Crystal decay or mounting oil could account for this.

041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ.. ? 042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ.. ? 045_ALERT_1_C Calculated and Reported Z Differ by ·········. 2.00 Ratio

These alerts are due to the formula unit chosen. We have chosen the formula unit to consist of one whole quinol molecule and two morpholine molecules.

125_ALERT_4_C No _symmetry_space_group_name_Hall Given ···.. ? –P 2yn

145_ALERT_4_C su on beta Small or Missing (x 10000) ··· 40 Deg.

Noted; unit cell s.u.s taken from SAINT output.

417_ALERT_2_C Short Inter D—H.·H—D H1A.. H1S = 2.13 A ng.

H1A is hydrogen-bonding to N1S. H1S is attached to N1S hence the close contact

720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ······ 8 790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.# 2 C6 H6 O2

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O1A1.1444 (3)0.7562 (4)0.01502 (10)0.0291 (5)
H1A1.148 (5)0.861 (7)0.0466 (18)0.038 (9)*
C1A1.3221 (3)0.6347 (5)0.00838 (12)0.0199 (5)
C2A1.4933 (3)0.7076 (4)0.03813 (12)0.0203 (5)
H2A1.48950.84970.06420.024*
C3A1.6694 (3)0.5742 (5)0.02995 (12)0.0206 (5)
H3A1.78510.62550.05060.025*
N1S0.9012 (3)0.8769 (4)0.10161 (11)0.0233 (5)
H1S0.927 (5)0.777 (6)0.0715 (16)0.030 (8)*
C2S0.7391 (4)0.7839 (5)0.13987 (13)0.0260 (6)
H2S10.62380.73470.10840.031*
H2S20.69230.91260.16870.031*
C3S0.8086 (5)0.5731 (6)0.18289 (15)0.0359 (7)
H3S10.69730.51910.20900.043*
H3S20.84440.43920.15380.043*
O4S0.9797 (3)0.6344 (4)0.22794 (10)0.0371 (6)
C5S1.1419 (4)0.7109 (6)0.19133 (14)0.0341 (7)
H5S11.18420.57710.16330.041*
H5S21.25800.75540.22310.041*
C6S1.0827 (4)0.9228 (5)0.14695 (14)0.0314 (7)
H6S11.05831.06270.17550.038*
H6S21.19570.96310.12000.038*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O1A0.0197 (9)0.0267 (11)0.0417 (11)0.0056 (8)0.0073 (7)0.0141 (9)
C1A0.0171 (11)0.0176 (12)0.0245 (12)0.0008 (9)0.0007 (8)0.0004 (9)
C2A0.0213 (12)0.0155 (12)0.0241 (12)0.0003 (9)0.0013 (9)0.0023 (9)
C3A0.0172 (11)0.0206 (13)0.0244 (12)0.0027 (9)0.0035 (8)0.0007 (9)
N1S0.0243 (11)0.0204 (12)0.0247 (11)0.0034 (9)0.0004 (8)0.0008 (9)
C2S0.0244 (12)0.0275 (14)0.0261 (12)0.0021 (11)0.0024 (9)0.0011 (10)
C3S0.0392 (16)0.0321 (16)0.0367 (15)0.0015 (13)0.0046 (12)0.0109 (12)
O4S0.0404 (12)0.0414 (13)0.0286 (10)0.0061 (10)0.0019 (8)0.0092 (9)
C5S0.0323 (14)0.0334 (17)0.0349 (15)0.0055 (12)0.0068 (11)0.0035 (12)
C6S0.0269 (13)0.0269 (15)0.0389 (15)0.0008 (11)0.0055 (11)0.0055 (12)
Geometric parameters (Å, º) top
O1A—C1A1.362 (3)C2S—H2S10.9900
O1A—H1A0.86 (4)C2S—H2S20.9900
C1A—C2A1.393 (3)C3S—O4S1.433 (4)
C1A—C3Ai1.396 (3)C3S—H3S10.9900
C2A—C3A1.388 (3)C3S—H3S20.9900
C2A—H2A0.9500O4S—C5S1.424 (4)
C3A—C1Ai1.396 (3)C5S—C6S1.513 (4)
C3A—H3A0.9500C5S—H5S10.9900
N1S—C6S1.471 (3)C5S—H5S20.9900
N1S—C2S1.472 (3)C6S—H6S10.9900
N1S—H1S0.85 (3)C6S—H6S20.9900
C2S—C3S1.509 (4)
C1A—O1A—H1A109 (2)O4S—C3S—C2S111.2 (2)
O1A—C1A—C2A123.4 (2)O4S—C3S—H3S1109.4
O1A—C1A—C3Ai117.7 (2)C2S—C3S—H3S1109.4
C2A—C1A—C3Ai118.9 (2)O4S—C3S—H3S2109.4
C3A—C2A—C1A120.5 (2)C2S—C3S—H3S2109.4
C3A—C2A—H2A119.7H3S1—C3S—H3S2108.0
C1A—C2A—H2A119.7C5S—O4S—C3S110.2 (2)
C2A—C3A—C1Ai120.5 (2)O4S—C5S—C6S111.5 (2)
C2A—C3A—H3A119.7O4S—C5S—H5S1109.3
C1Ai—C3A—H3A119.7C6S—C5S—H5S1109.3
C6S—N1S—C2S110.0 (2)O4S—C5S—H5S2109.3
C6S—N1S—H1S110 (2)C6S—C5S—H5S2109.3
C2S—N1S—H1S110 (2)H5S1—C5S—H5S2108.0
N1S—C2S—C3S111.7 (2)N1S—C6S—C5S112.7 (2)
N1S—C2S—H2S1109.3N1S—C6S—H6S1109.1
C3S—C2S—H2S1109.3C5S—C6S—H6S1109.1
N1S—C2S—H2S2109.3N1S—C6S—H6S2109.1
C3S—C2S—H2S2109.3C5S—C6S—H6S2109.1
H2S1—C2S—H2S2107.9H6S1—C6S—H6S2107.8
Symmetry code: (i) x+3, y+1, z.
(4) top
Crystal data top
C3H3O(C5H5N)F(000) = 284
Mr = 268.31Dx = 1.260 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 6.4990 (9) ÅCell parameters from 1519 reflections
b = 16.459 (2) Åθ = 2.4–28.5°
c = 7.1794 (10) ŵ = 0.08 mm1
β = 112.986 (3)°T = 150 K
V = 707.00 (17) Å3Cylinder, colourless
Z = 21 × 0.32 × 0.32 mm
Data collection top
CCD area detector
diffractometer
1700 independent reflections
Radiation source: fine-focus sealed tube1345 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
ω scansθmax = 28.9°, θmin = 2.5°
Absorption correction: multi-scan
SADABS
h = 87
Tmin = 0.593, Tmax = 1k = 2121
5091 measured reflectionsl = 89
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)] = 0.083Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.172H atoms treated by a mixture of independent and constrained refinement
S = 1.33 w = 1/[σ2(Fo2) + (0.0363P)2 + 0.5217P]
where P = (Fo2 + 2Fc2)/3
1700 reflections(Δ/σ)max < 0.001
95 parametersΔρmax = 0.28 e Å3
0 restraintsΔρmin = 0.39 e Å3
Crystal data top
C3H3O(C5H5N)V = 707.00 (17) Å3
Mr = 268.31Z = 2
Monoclinic, P21/cMo Kα radiation
a = 6.4990 (9) ŵ = 0.08 mm1
b = 16.459 (2) ÅT = 150 K
c = 7.1794 (10) Å1 × 0.32 × 0.32 mm
β = 112.986 (3)°
Data collection top
CCD area detector
diffractometer
1700 independent reflections
Absorption correction: multi-scan
SADABS
1345 reflections with I > 2σ(I)
Tmin = 0.593, Tmax = 1Rint = 0.031
5091 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0830 restraints
wR(F2) = 0.172H atoms treated by a mixture of independent and constrained refinement
S = 1.33Δρmax = 0.28 e Å3
1700 reflectionsΔρmin = 0.39 e Å3
95 parameters
Special details top

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

Refinement. 028_ALERT_3_A _diffrn_measured_fraction_theta_max Low ···.. 0.91

Data are 99.6% complete to 0.6 Å.

================================================================================ Resolution & Completeness Statistics (Cumulative) ================================================================================ Theta sin(th)/Lambda Complete Expected Measured Missing ——————————————————————————– 20.82 0.500 0.999 740 739 1 23.01 0.550 0.999 980 979 1 25.24 0.600 0.996 1282 1277 5 ———————————————————— ACTA Min. Res. —- 27.51 0.650 0.988 1624 1604 20 29.84 0.700 0.913 1861 1700 161

061_ALERT_3_B Tmax/Tmin Range Test RR' too Large ·········.. 0.63

SADABS corrects for all systematic errors, not just absorption. Crystal decay or mounting oil could account for this.

063_ALERT_3_B Crystal Probably too Large for Beam Size ···.. 1.00 mm

Gorbitz has shown that use of a large crystal does not appear to affect data quality. See C. H. Gorbitz Acta Cryst. (1999). B55, 1090–1098

041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ.. ? 042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ.. ? 045_ALERT_1_C Calculated and Reported Z Differ by ·········. 0.50 Ratio

These alerts are due to the formula unit chosen. We have chosen the formula unit to consist of one whole quinol molecule and two pyridine molecules.

145_ALERT_4_C su on beta Small or Missing (x 10000) ··· 30 Deg.

Noted; unit cell s.u.s taken from SAINT output.

340_ALERT_3_C Low Bond Precision on C—C bonds (x 1000) Ang.. 5

This is a crystal-quality issue, also reflected in the highish value of R1 (8%).

062_ALERT_4_C Rescale T(min) & T(max) by ··················. 0.97 125_ALERT_4_C No _symmetry_space_group_name_Hall Given ···.. ? 790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.# 2 C5 H5 N

Noted, but no action taken.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O1A0.2880 (3)0.55053 (12)0.6023 (3)0.0386 (5)
H1A0.185 (5)0.5848 (19)0.587 (5)0.047 (9)*
C1A0.3901 (4)0.52595 (13)0.7995 (4)0.0289 (6)
C2A0.5991 (4)0.49064 (14)0.8625 (4)0.0311 (6)
H2A0.66760.48350.76840.037*
C3A0.7104 (4)0.46540 (13)1.0613 (4)0.0298 (6)
H3A0.85530.44221.10290.036*
N1S0.0211 (4)0.66756 (14)0.5710 (3)0.0391 (6)
C2S0.2294 (5)0.64719 (17)0.5387 (4)0.0411 (7)
H2S0.26810.59120.52680.049*
C3S0.3923 (5)0.7035 (2)0.5217 (5)0.0490 (8)
H3S0.54010.68670.49910.059*
C4S0.3371 (6)0.7842 (2)0.5381 (5)0.0529 (9)
H4S0.44650.82430.52620.064*
C5S0.1237 (6)0.80628 (17)0.5715 (5)0.0478 (8)
H5S0.08160.86190.58430.057*
C6S0.0292 (5)0.74662 (19)0.5864 (4)0.0424 (7)
H6S0.17770.76220.60870.051*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O1A0.0470 (12)0.0361 (10)0.0359 (11)0.0159 (9)0.0196 (9)0.0060 (8)
C1A0.0372 (14)0.0188 (10)0.0339 (14)0.0007 (10)0.0174 (11)0.0000 (9)
C2A0.0400 (14)0.0241 (11)0.0379 (15)0.0003 (10)0.0248 (12)0.0000 (10)
C3A0.0287 (13)0.0226 (11)0.0413 (15)0.0040 (9)0.0173 (11)0.0016 (10)
N1S0.0489 (14)0.0387 (12)0.0299 (13)0.0180 (11)0.0157 (11)0.0046 (9)
C2S0.064 (2)0.0326 (13)0.0267 (14)0.0033 (13)0.0174 (14)0.0020 (11)
C3S0.0378 (16)0.077 (2)0.0375 (17)0.0067 (15)0.0199 (13)0.0143 (15)
C4S0.073 (2)0.0548 (18)0.0429 (19)0.0372 (17)0.0354 (17)0.0204 (15)
C5S0.085 (2)0.0278 (13)0.0393 (17)0.0038 (14)0.0337 (17)0.0009 (11)
C6S0.0404 (16)0.0544 (17)0.0340 (16)0.0028 (13)0.0164 (13)0.0018 (13)
Geometric parameters (Å, º) top
O1A—C1A1.370 (3)C2S—C3S1.376 (4)
O1A—H1A0.85 (3)C2S—H2S0.9500
C1A—C2A1.382 (3)C3S—C4S1.368 (5)
C1A—C3Ai1.398 (3)C3S—H3S0.9500
C2A—C3A1.388 (4)C4S—C5S1.361 (5)
C2A—H2A0.9500C4S—H4S0.9500
C3A—C1Ai1.398 (3)C5S—C6S1.371 (4)
C3A—H3A0.9500C5S—H5S0.9500
N1S—C2S1.324 (4)C6S—H6S0.9500
N1S—C6S1.336 (4)
C1A—O1A—H1A111 (2)C3S—C2S—H2S118.5
O1A—C1A—C2A118.7 (2)C4S—C3S—C2S118.6 (3)
O1A—C1A—C3Ai122.4 (2)C4S—C3S—H3S120.7
C2A—C1A—C3Ai118.9 (2)C2S—C3S—H3S120.7
C1A—C2A—C3A120.9 (2)C5S—C4S—C3S119.3 (3)
C1A—C2A—H2A119.6C5S—C4S—H4S120.3
C3A—C2A—H2A119.6C3S—C4S—H4S120.3
C2A—C3A—C1Ai120.2 (2)C4S—C5S—C6S118.7 (3)
C2A—C3A—H3A119.9C4S—C5S—H5S120.7
C1Ai—C3A—H3A119.9C6S—C5S—H5S120.7
C2S—N1S—C6S117.5 (2)N1S—C6S—C5S123.0 (3)
N1S—C2S—C3S122.9 (3)N1S—C6S—H6S118.5
N1S—C2S—H2S118.5C5S—C6S—H6S118.5
Symmetry code: (i) x+1, y+1, z+2.
(5) top
Crystal data top
2(C5H11N)(C6H6O2)F(000) = 308
Mr = 280.40Dx = 1.187 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 10.4230 (15) ÅCell parameters from 774 reflections
b = 5.2619 (7) Åθ = 2.9–25.3°
c = 15.221 (2) ŵ = 0.08 mm1
β = 109.920 (3)°T = 150 K
V = 784.84 (19) Å3Block, colourless
Z = 20.33 × 0.18 × 0.18 mm
Data collection top
CCD area detector
diffractometer
1896 independent reflections
Radiation source: fine-focus sealed tube1327 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.028
ω scansθmax = 29.0°, θmin = 2.1°
Absorption correction: multi-scan
SADABS
h = 147
Tmin = 0.661, Tmax = 1k = 77
4754 measured reflectionsl = 1719
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)] = 0.056Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.136H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0582P)2 + 0.1207P]
where P = (Fo2 + 2Fc2)/3
1896 reflections(Δ/σ)max < 0.001
99 parametersΔρmax = 0.24 e Å3
0 restraintsΔρmin = 0.19 e Å3
Crystal data top
2(C5H11N)(C6H6O2)V = 784.84 (19) Å3
Mr = 280.40Z = 2
Monoclinic, P21/cMo Kα radiation
a = 10.4230 (15) ŵ = 0.08 mm1
b = 5.2619 (7) ÅT = 150 K
c = 15.221 (2) Å0.33 × 0.18 × 0.18 mm
β = 109.920 (3)°
Data collection top
CCD area detector
diffractometer
1896 independent reflections
Absorption correction: multi-scan
SADABS
1327 reflections with I > 2σ(I)
Tmin = 0.661, Tmax = 1Rint = 0.028
4754 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0560 restraints
wR(F2) = 0.136H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.24 e Å3
1896 reflectionsΔρmin = 0.19 e Å3
99 parameters
Special details top

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

Refinement. 061_ALERT_3_B Tmax/Tmin Range Test RR' too Large ·········.. 0.67

SADABS corrects for all systematic errors, not just absorption. Crystal decay or mounting oil could account for this.

041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ.. ? 042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ.. ? 045_ALERT_1_C Calculated and Reported Z Differ by ·········. 2.00 Ratio

These alerts are due to the formula unit chosen. We have chosen the formula unit to consist of one whole quinol molecule and two piperidine molecules.

125_ALERT_4_C No _symmetry_space_group_name_Hall Given ···.. ?

-P 2ybc

145_ALERT_4_C su on beta Small or Missing (x 10000) ··· 30 Deg.

Noted; unit cell s.u.s taken from SAINT output.

062_ALERT_4_C Rescale T(min) & T(max) by ··················. 0.99 720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ······ 10 790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.# 1 C5 H11 N

Noted, but no action taken.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C1A0.87876 (17)0.0277 (3)0.42372 (10)0.0315 (4)
O1A0.75868 (13)0.0445 (2)0.34998 (8)0.0396 (3)
H1A0.754 (2)0.195 (5)0.3174 (15)0.069 (7)*
C2A0.98205 (17)0.2081 (3)0.44194 (10)0.0319 (4)
H2A0.97050.35160.40210.038*
C3A1.10111 (17)0.1811 (3)0.51729 (10)0.0324 (4)
H3A1.17020.30710.52900.039*
N1S1.27883 (15)0.0133 (3)0.25158 (10)0.0363 (4)
H1S1.274 (2)0.123 (4)0.2191 (13)0.057 (6)*
C2S1.41806 (17)0.0256 (3)0.31858 (14)0.0417 (5)
H2S11.43700.12730.35890.050*
H2S21.48400.02940.28470.050*
C3S1.43466 (17)0.2609 (3)0.37798 (13)0.0432 (5)
H3S11.52760.26400.42510.052*
H3S21.42400.41350.33810.052*
C4S1.3303 (2)0.2683 (3)0.42704 (11)0.0462 (5)
H4S11.33660.43290.45980.055*
H4S21.34990.13110.47430.055*
C5S1.18863 (17)0.2353 (3)0.35791 (11)0.0379 (4)
H5S11.16430.38460.31590.045*
H5S21.12260.22440.39160.045*
C6S1.18007 (16)0.0017 (3)0.30107 (11)0.0361 (4)
H6S11.08660.02020.25540.043*
H6S21.20010.15220.34260.043*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C1A0.0443 (10)0.0314 (8)0.0235 (7)0.0110 (7)0.0179 (7)0.0094 (6)
O1A0.0490 (8)0.0376 (7)0.0303 (6)0.0175 (6)0.0111 (6)0.0033 (5)
C2A0.0500 (10)0.0258 (8)0.0261 (8)0.0132 (7)0.0209 (7)0.0075 (6)
C3A0.0462 (10)0.0276 (8)0.0302 (8)0.0173 (7)0.0219 (8)0.0093 (7)
N1S0.0476 (9)0.0318 (8)0.0342 (7)0.0126 (7)0.0201 (7)0.0134 (6)
C2S0.0323 (9)0.0279 (9)0.0709 (12)0.0043 (7)0.0256 (9)0.0007 (8)
C3S0.0268 (9)0.0313 (9)0.0551 (11)0.0045 (7)0.0073 (8)0.0029 (8)
C4S0.0694 (13)0.0312 (9)0.0275 (8)0.0078 (9)0.0030 (9)0.0075 (7)
C5S0.0400 (10)0.0449 (10)0.0358 (9)0.0195 (8)0.0222 (8)0.0145 (8)
C6S0.0265 (8)0.0492 (11)0.0292 (8)0.0125 (7)0.0049 (7)0.0048 (7)
Geometric parameters (Å, º) top
C1A—O1A1.370 (2)C2S—H2S20.9900
C1A—C3Ai1.389 (2)C3S—C4S1.515 (3)
C1A—C2A1.391 (2)C3S—H3S10.9900
O1A—H1A0.93 (2)C3S—H3S20.9900
C2A—C3A1.380 (2)C4S—C5S1.503 (2)
C2A—H2A0.9500C4S—H4S10.9900
C3A—C1Ai1.389 (2)C4S—H4S20.9900
C3A—H3A0.9500C5S—C6S1.503 (2)
N1S—C2S1.463 (2)C5S—H5S10.9900
N1S—C6S1.470 (2)C5S—H5S20.9900
N1S—H1S0.86 (2)C6S—H6S10.9900
C2S—C3S1.508 (2)C6S—H6S20.9900
C2S—H2S10.9900
O1A—C1A—C3Ai118.39 (14)C2S—C3S—H3S2109.4
O1A—C1A—C2A123.25 (14)C4S—C3S—H3S2109.4
C3Ai—C1A—C2A118.36 (15)H3S1—C3S—H3S2108.0
C1A—O1A—H1A111.1 (14)C5S—C4S—C3S110.55 (13)
C3A—C2A—C1A120.74 (15)C5S—C4S—H4S1109.5
C3A—C2A—H2A119.6C3S—C4S—H4S1109.5
C1A—C2A—H2A119.6C5S—C4S—H4S2109.5
C2A—C3A—C1Ai120.90 (14)C3S—C4S—H4S2109.5
C2A—C3A—H3A119.6H4S1—C4S—H4S2108.1
C1Ai—C3A—H3A119.6C6S—C5S—C4S110.51 (13)
C2S—N1S—C6S110.27 (13)C6S—C5S—H5S1109.5
C2S—N1S—H1S106.8 (14)C4S—C5S—H5S1109.5
C6S—N1S—H1S109.2 (14)C6S—C5S—H5S2109.5
N1S—C2S—C3S109.75 (13)C4S—C5S—H5S2109.5
N1S—C2S—H2S1109.7H5S1—C5S—H5S2108.1
C3S—C2S—H2S1109.7N1S—C6S—C5S109.62 (13)
N1S—C2S—H2S2109.7N1S—C6S—H6S1109.7
C3S—C2S—H2S2109.7C5S—C6S—H6S1109.7
H2S1—C2S—H2S2108.2N1S—C6S—H6S2109.7
C2S—C3S—C4S111.19 (14)C5S—C6S—H6S2109.7
C2S—C3S—H3S1109.4H6S1—C6S—H6S2108.2
C4S—C3S—H3S1109.4
Symmetry code: (i) x+2, y, z+1.
(6) top
Crystal data top
2(C10H8N2)(C6H6O2)Z = 1
Mr = 422.49F(000) = 222
Triclinic, P1Dx = 1.335 Mg m3
a = 7.820 (4) ÅMo Kα radiation, λ = 0.71073 Å
b = 8.619 (4) ÅCell parameters from 2247 reflections
c = 9.201 (4) Åθ = 2.6–28.4°
α = 111.897 (7)°µ = 0.09 mm1
β = 109.851 (7)°T = 150 K
γ = 94.657 (8)°Lath, colourless
V = 525.7 (4) Å30.77 × 0.22 × 0.15 mm
Data collection top
CCD area detector
diffractometer
2428 independent reflections
Radiation source: fine-focus sealed tube2067 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
ω scansθmax = 28.7°, θmin = 2.6°
Absorption correction: multi-scan
SADABS
h = 1010
Tmin = 0.763, Tmax = 1k = 1111
4641 measured reflectionsl = 1212
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)] = 0.054H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.144 w = 1/[σ2(Fo2) + (0.0803P)2 + 0.1067P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
2428 reflectionsΔρmax = 0.31 e Å3
150 parametersΔρmin = 0.26 e Å3
0 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.013 (9)
Crystal data top
2(C10H8N2)(C6H6O2)γ = 94.657 (8)°
Mr = 422.49V = 525.7 (4) Å3
Triclinic, P1Z = 1
a = 7.820 (4) ÅMo Kα radiation
b = 8.619 (4) ŵ = 0.09 mm1
c = 9.201 (4) ÅT = 150 K
α = 111.897 (7)°0.77 × 0.22 × 0.15 mm
β = 109.851 (7)°
Data collection top
CCD area detector
diffractometer
2428 independent reflections
Absorption correction: multi-scan
SADABS
2067 reflections with I > 2σ(I)
Tmin = 0.763, Tmax = 1Rint = 0.031
4641 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0540 restraints
wR(F2) = 0.144H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.31 e Å3
2428 reflectionsΔρmin = 0.26 e Å3
150 parameters
Special details top

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

Refinement. 041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ.. ? 042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ.. ? 045_ALERT_1_C Calculated and Reported Z Differ by ·········. 2.00 Ratio

These alerts are due to the formula unit chosen. We have chosen the formula unit to consist of one whole quinol molecule and two dipyridyl molecules.

031_ALERT_4_B Refined Extinction Parameter within Range ···. 1.44 Sigma 061_ALERT_3_C Tmax/Tmin Range Test RR' too Large ·········.. 0.81 062_ALERT_4_C Rescale T(min) & T(max) by ··················. 0.99

Noted, but no action taken.

063_ALERT_3_C Crystal Probably too Large for Beam Size ···.. 0.77 mm

Gorbitz has shown that use of a large crystal does not appear to affect data quality. See C. H. Gorbitz Acta Cryst. (1999). B55, 1090–1098

125_ALERT_4_C No _symmetry_space_group_name_Hall Given ···.. ?

Hall space group –P 1

150_ALERT_1_C Volume as Calculated Differs from that Given = 525.70 A ng-3

Volume Reported 525.7 (4) Calculated 525.6 (4) This is probably a rounding error.

790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.# 1 C10 H8 N2

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O1A0.39246 (15)0.29172 (13)0.97975 (14)0.0289 (3)
H1A0.267 (3)0.272 (3)0.928 (3)0.051 (6)*
C1A0.44173 (19)0.14592 (18)0.98779 (18)0.0218 (3)
C2A0.31417 (19)0.01306 (18)0.90679 (17)0.0223 (3)
H2A0.18650.02270.84250.027*
C3A0.37157 (19)0.15719 (18)0.91898 (18)0.0226 (3)
H3A0.28290.26470.86330.027*
N1S0.01390 (17)0.24543 (17)0.81825 (18)0.0292 (3)
C2S0.0475 (2)0.1999 (2)0.6504 (2)0.0304 (4)
H2S0.03430.16140.59550.036*
C3S0.2233 (2)0.2057 (2)0.5520 (2)0.0282 (3)
H3S0.26080.17100.43270.034*
C4S0.34486 (19)0.26309 (18)0.63051 (19)0.0223 (3)
C5S0.2830 (2)0.30806 (19)0.80472 (19)0.0253 (3)
H5S0.36200.34600.86290.030*
C6S0.1046 (2)0.2968 (2)0.8925 (2)0.0276 (3)
H6S0.06450.32711.01130.033*
N7S0.87985 (18)0.32257 (18)0.34555 (17)0.0319 (3)
C8S0.7857 (2)0.4193 (2)0.5134 (2)0.0295 (4)
H8S0.84020.50430.56950.035*
C9S0.6146 (2)0.40417 (19)0.6110 (2)0.0258 (3)
H9S0.55460.47680.73000.031*
C10S0.53146 (19)0.28020 (18)0.53159 (18)0.0220 (3)
C11S0.6276 (2)0.17840 (19)0.35718 (19)0.0265 (3)
H11S0.57700.09200.29750.032*
C12S0.7979 (2)0.2046 (2)0.2717 (2)0.0308 (4)
H12S0.86100.13410.15250.037*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O1A0.0203 (6)0.0278 (6)0.0358 (6)0.0086 (4)0.0068 (5)0.0140 (5)
C1A0.0200 (7)0.0269 (7)0.0207 (7)0.0098 (5)0.0090 (6)0.0107 (6)
C2A0.0151 (6)0.0305 (8)0.0199 (7)0.0072 (5)0.0061 (5)0.0098 (6)
C3A0.0171 (7)0.0254 (7)0.0205 (7)0.0031 (5)0.0056 (5)0.0069 (5)
N1S0.0211 (6)0.0301 (7)0.0368 (8)0.0107 (5)0.0088 (6)0.0162 (6)
C2S0.0246 (8)0.0338 (8)0.0374 (9)0.0142 (6)0.0155 (7)0.0158 (7)
C3S0.0266 (8)0.0324 (8)0.0267 (8)0.0110 (6)0.0112 (6)0.0127 (6)
C4S0.0194 (7)0.0212 (7)0.0272 (8)0.0067 (5)0.0079 (6)0.0123 (6)
C5S0.0232 (7)0.0277 (7)0.0281 (8)0.0094 (6)0.0114 (6)0.0134 (6)
C6S0.0243 (7)0.0314 (8)0.0287 (8)0.0102 (6)0.0081 (6)0.0160 (6)
N7S0.0206 (6)0.0366 (8)0.0320 (8)0.0071 (5)0.0044 (6)0.0135 (6)
C8S0.0221 (7)0.0304 (8)0.0324 (8)0.0106 (6)0.0077 (6)0.0116 (7)
C9S0.0211 (7)0.0266 (7)0.0252 (7)0.0063 (6)0.0062 (6)0.0092 (6)
C10S0.0174 (7)0.0245 (7)0.0261 (8)0.0055 (5)0.0077 (6)0.0137 (6)
C11S0.0233 (7)0.0270 (7)0.0275 (8)0.0070 (6)0.0092 (6)0.0106 (6)
C12S0.0218 (7)0.0356 (8)0.0260 (8)0.0036 (6)0.0040 (6)0.0097 (6)
Geometric parameters (Å, º) top
O1A—C1A1.3644 (18)C4S—C10S1.487 (2)
O1A—H1A0.90 (2)C5S—C6S1.387 (2)
C1A—C2A1.393 (2)C5S—H5S0.9500
C1A—C3Ai1.393 (2)C6S—H6S0.9500
C2A—C3A1.385 (2)N7S—C8S1.338 (2)
C2A—H2A0.9500N7S—C12S1.339 (2)
C3A—C1Ai1.393 (2)C8S—C9S1.384 (2)
C3A—H3A0.9500C8S—H8S0.9500
N1S—C2S1.335 (2)C9S—C10S1.397 (2)
N1S—C6S1.339 (2)C9S—H9S0.9500
C2S—C3S1.383 (2)C10S—C11S1.391 (2)
C2S—H2S0.9500C11S—C12S1.383 (2)
C3S—C4S1.395 (2)C11S—H11S0.9500
C3S—H3S0.9500C12S—H12S0.9500
C4S—C5S1.390 (2)
C1A—O1A—H1A110.5 (13)C6S—C5S—H5S120.4
O1A—C1A—C2A122.99 (13)C4S—C5S—H5S120.4
O1A—C1A—C3Ai118.27 (13)N1S—C6S—C5S123.30 (15)
C2A—C1A—C3Ai118.74 (13)N1S—C6S—H6S118.3
C3A—C2A—C1A120.68 (13)C5S—C6S—H6S118.3
C3A—C2A—H2A119.7C8S—N7S—C12S115.72 (13)
C1A—C2A—H2A119.7N7S—C8S—C9S124.54 (14)
C2A—C3A—C1Ai120.58 (13)N7S—C8S—H8S117.7
C2A—C3A—H3A119.7C9S—C8S—H8S117.7
C1Ai—C3A—H3A119.7C8S—C9S—C10S118.85 (14)
C2S—N1S—C6S117.15 (13)C8S—C9S—H9S120.6
N1S—C2S—C3S123.70 (14)C10S—C9S—H9S120.6
N1S—C2S—H2S118.1C11S—C10S—C9S117.33 (13)
C3S—C2S—H2S118.1C11S—C10S—C4S122.01 (13)
C2S—C3S—C4S118.98 (15)C9S—C10S—C4S120.64 (13)
C2S—C3S—H3S120.5C12S—C11S—C10S119.10 (14)
C4S—C3S—H3S120.5C12S—C11S—H11S120.5
C5S—C4S—C3S117.62 (13)C10S—C11S—H11S120.5
C5S—C4S—C10S121.48 (13)N7S—C12S—C11S124.47 (15)
C3S—C4S—C10S120.87 (14)N7S—C12S—H12S117.8
C6S—C5S—C4S119.21 (14)C11S—C12S—H12S117.8
Symmetry code: (i) x+1, y, z+2.
(7) 'N-methylmorpholine hemi-quinol' top
Crystal data top
2(C5H11NO)(C6H6O2)Z = 1
Mr = 312.41F(000) = 170
Triclinic, P1Dx = 1.224 Mg m3
a = 6.9612 (10) ÅMo Kα radiation, λ = 0.71073 Å
b = 7.3146 (11) ÅCell parameters from 2797 reflections
c = 9.659 (2) Åθ = 2.4–28.8°
α = 106.182 (3)°µ = 0.09 mm1
β = 104.481 (3)°T = 150 K
γ = 106.201 (2)°Cylinder, colourless
V = 423.94 (12) Å31 × 0.38 × 0.38 mm
Data collection top
CCD area detector
diffractometer
1972 independent reflections
Radiation source: fine-focus sealed tube1794 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.020
ω scansθmax = 28.8°, θmin = 2.4°
Absorption correction: multi-scan
SADABS
h = 99
Tmin = 0.774, Tmax = 1k = 99
3788 measured reflectionsl = 1213
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)] = 0.045H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.120 w = 1/[σ2(Fo2) + (0.063P)2 + 0.0864P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max < 0.001
1972 reflectionsΔρmax = 0.24 e Å3
106 parametersΔρmin = 0.27 e Å3
0 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.29 (4)
Crystal data top
2(C5H11NO)(C6H6O2)γ = 106.201 (2)°
Mr = 312.41V = 423.94 (12) Å3
Triclinic, P1Z = 1
a = 6.9612 (10) ÅMo Kα radiation
b = 7.3146 (11) ŵ = 0.09 mm1
c = 9.659 (2) ÅT = 150 K
α = 106.182 (3)°1 × 0.38 × 0.38 mm
β = 104.481 (3)°
Data collection top
CCD area detector
diffractometer
1972 independent reflections
Absorption correction: multi-scan
SADABS
1794 reflections with I > 2σ(I)
Tmin = 0.774, Tmax = 1Rint = 0.020
3788 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.120H atoms treated by a mixture of independent and constrained refinement
S = 1.07Δρmax = 0.24 e Å3
1972 reflectionsΔρmin = 0.27 e Å3
106 parameters
Special details top

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

Refinement. 063_ALERT_3_B Crystal Probably too Large for Beam Size ···.. 1.00 mm

This crystal was grown by laser (see text) in a capilliary. It was very difficult to the precise length of the crystal grown. Gorbitz has shown that use of a large crystal does not appear to affect data quality. See C. H. Gorbitz Acta Cryst. (1999). B55, 1090–1098

041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ.. ? 042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ.. ? 045_ALERT_1_C Calculated and Reported Z Differ by ·········. 2.00 Ratio

These alerts are due to the formula unit chosen. We have chosen the formula unit to consist of one whole quinol molecule and two N-methylmorpholine molecules.

125_ALERT_4_C No _symmetry_space_group_name_Hall Given ···.. ?

-P 1

144_ALERT_4_C su on alpha Small or Missing (x 10000) ··· 30 Deg. 145_ALERT_4_C su on beta Small or Missing (x 10000) ··· 30 Deg. 146_ALERT_4_C su on gamma Small or Missing (x 10000) ··· 20 Deg.

Noted; unit cell s.u.s taken from SAINT output.

061_ALERT_3_C Tmax/Tmin Range Test RR' too Large ·········.. 0.82 062_ALERT_4_C Rescale T(min) & T(max) by ··················. 0.97 720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ······ 11

Noted, no action taken.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O1A0.41864 (14)0.24781 (13)0.66204 (10)0.0372 (3)
H1A0.332 (3)0.269 (3)0.712 (2)0.061 (5)*
C1A0.45668 (16)0.37535 (16)0.58385 (12)0.0281 (3)
C2A0.40603 (17)0.54952 (16)0.60802 (12)0.0289 (3)
H2A0.34140.58440.68210.035*
C3A0.44913 (17)0.67307 (16)0.52471 (12)0.0293 (3)
H3A0.41370.79180.54230.035*
C1S0.0212 (2)0.39650 (18)0.79816 (15)0.0369 (3)
H1S10.09520.36820.83850.055*
H1S20.03700.38360.69090.055*
H1S30.12600.53620.86050.055*
N1S0.12536 (14)0.24977 (13)0.80499 (10)0.0254 (2)
C2S0.03361 (18)0.03902 (16)0.72026 (13)0.0311 (3)
H2S10.10060.01870.61110.037*
H2S20.14740.01690.76510.037*
C3S0.0714 (2)0.11455 (16)0.72879 (13)0.0345 (3)
H3S10.03840.25530.67340.041*
H3S20.17750.09880.67690.041*
O4S0.17518 (14)0.08750 (12)0.88378 (10)0.0349 (2)
C5S0.32736 (19)0.11710 (17)0.96806 (13)0.0340 (3)
H5S10.44060.14220.92300.041*
H5S20.39550.13411.07630.041*
C6S0.22386 (18)0.27224 (16)0.96507 (12)0.0291 (3)
H6S10.11340.25071.01290.035*
H6S20.33280.41271.02500.035*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O1A0.0437 (5)0.0412 (5)0.0438 (5)0.0203 (4)0.0265 (4)0.0267 (4)
C1A0.0256 (5)0.0294 (5)0.0264 (5)0.0057 (4)0.0082 (4)0.0120 (4)
C2A0.0273 (5)0.0305 (5)0.0258 (5)0.0071 (4)0.0113 (4)0.0080 (4)
C3A0.0279 (5)0.0283 (5)0.0302 (5)0.0090 (4)0.0105 (4)0.0101 (4)
C1S0.0399 (6)0.0317 (6)0.0490 (7)0.0206 (5)0.0191 (5)0.0195 (5)
N1S0.0283 (4)0.0215 (4)0.0296 (5)0.0108 (3)0.0117 (4)0.0114 (3)
C2S0.0301 (5)0.0256 (5)0.0320 (5)0.0079 (4)0.0060 (4)0.0097 (4)
C3S0.0426 (6)0.0226 (5)0.0346 (6)0.0115 (4)0.0111 (5)0.0087 (4)
O4S0.0409 (5)0.0250 (4)0.0393 (5)0.0114 (3)0.0107 (4)0.0168 (3)
C5S0.0335 (6)0.0299 (6)0.0350 (6)0.0101 (4)0.0056 (5)0.0146 (5)
C6S0.0332 (5)0.0238 (5)0.0277 (5)0.0079 (4)0.0109 (4)0.0089 (4)
Geometric parameters (Å, º) top
O1A—C1A1.3659 (13)N1S—C2S1.4706 (13)
O1A—H1A0.887 (19)C2S—C3S1.5110 (15)
C1A—C3Ai1.3861 (16)C2S—H2S10.9900
C1A—C2A1.3886 (16)C2S—H2S20.9900
C2A—C3A1.3889 (15)C3S—O4S1.4199 (14)
C2A—H2A0.9500C3S—H3S10.9900
C3A—C1Ai1.3861 (16)C3S—H3S20.9900
C3A—H3A0.9500O4S—C5S1.4246 (14)
C1S—N1S1.4599 (13)C5S—C6S1.5072 (15)
C1S—H1S10.9800C5S—H5S10.9900
C1S—H1S20.9800C5S—H5S20.9900
C1S—H1S30.9800C6S—H6S10.9900
N1S—C6S1.4674 (14)C6S—H6S20.9900
C1A—O1A—H1A113.1 (12)N1S—C2S—H2S2109.6
O1A—C1A—C3Ai117.77 (10)C3S—C2S—H2S2109.6
O1A—C1A—C2A123.32 (10)H2S1—C2S—H2S2108.1
C3Ai—C1A—C2A118.91 (10)O4S—C3S—C2S111.62 (9)
C1A—C2A—C3A120.48 (10)O4S—C3S—H3S1109.3
C1A—C2A—H2A119.8C2S—C3S—H3S1109.3
C3A—C2A—H2A119.8O4S—C3S—H3S2109.3
C1Ai—C3A—C2A120.60 (10)C2S—C3S—H3S2109.3
C1Ai—C3A—H3A119.7H3S1—C3S—H3S2108.0
C2A—C3A—H3A119.7C3S—O4S—C5S110.45 (8)
N1S—C1S—H1S1109.5O4S—C5S—C6S111.47 (9)
N1S—C1S—H1S2109.5O4S—C5S—H5S1109.3
H1S1—C1S—H1S2109.5C6S—C5S—H5S1109.3
N1S—C1S—H1S3109.5O4S—C5S—H5S2109.3
H1S1—C1S—H1S3109.5C6S—C5S—H5S2109.3
H1S2—C1S—H1S3109.5H5S1—C5S—H5S2108.0
C1S—N1S—C6S110.85 (9)N1S—C6S—C5S109.56 (9)
C1S—N1S—C2S109.85 (9)N1S—C6S—H6S1109.8
C6S—N1S—C2S107.86 (8)C5S—C6S—H6S1109.8
N1S—C2S—C3S110.40 (9)N1S—C6S—H6S2109.8
N1S—C2S—H2S1109.6C5S—C6S—H6S2109.8
C3S—C2S—H2S1109.6H6S1—C6S—H6S2108.2
Symmetry code: (i) x+1, y+1, z+1.
(8) top
Crystal data top
C6H14N2.C6H6O2Z = 4
Mr = 224.30F(000) = 488
Triclinic, P1Dx = 1.209 Mg m3
a = 8.9620 (8) ÅMo Kα radiation, λ = 0.71073 Å
b = 9.4944 (8) ÅCell parameters from 1812 reflections
c = 14.7119 (13) Åθ = 2.6–24.4°
α = 90.501 (2)°µ = 0.08 mm1
β = 92.919 (2)°T = 150 K
γ = 99.664 (2)°Block, colourless
V = 1232.26 (19) Å30.34 × 0.20 × 0.11 mm
Data collection top
CCD area detector
diffractometer
5844 independent reflections
Radiation source: fine-focus sealed tube3873 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.039
ω scansθmax = 28.9°, θmin = 1.4°
Absorption correction: multi-scan
SADABS
h = 1212
Tmin = 0.898, Tmax = 1k = 1212
11345 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)] = 0.074Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.162H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 1/[σ2(Fo2) + (0.0536P)2 + 0.587P]
where P = (Fo2 + 2Fc2)/3
5844 reflections(Δ/σ)max < 0.001
308 parametersΔρmax = 0.50 e Å3
0 restraintsΔρmin = 0.43 e Å3
Crystal data top
C6H14N2.C6H6O2γ = 99.664 (2)°
Mr = 224.30V = 1232.26 (19) Å3
Triclinic, P1Z = 4
a = 8.9620 (8) ÅMo Kα radiation
b = 9.4944 (8) ŵ = 0.08 mm1
c = 14.7119 (13) ÅT = 150 K
α = 90.501 (2)°0.34 × 0.20 × 0.11 mm
β = 92.919 (2)°
Data collection top
CCD area detector
diffractometer
5844 independent reflections
Absorption correction: multi-scan
SADABS
3873 reflections with I > 2σ(I)
Tmin = 0.898, Tmax = 1Rint = 0.039
11345 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0740 restraints
wR(F2) = 0.162H atoms treated by a mixture of independent and constrained refinement
S = 1.03Δρmax = 0.50 e Å3
5844 reflectionsΔρmin = 0.43 e Å3
308 parameters
Special details top

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

Refinement. 125_ALERT_4_C No _symmetry_space_group_name_Hall Given ···.. ?

Hall: –P 1

144_ALERT_4_C su on alpha Small or Missing (x 10000) ··· 20 Deg. 145_ALERT_4_C su on beta Small or Missing (x 10000) ··· 20 Deg. 146_ALERT_4_C su on gamma Small or Missing (x 10000) ··· 20 Deg.

Noted; unit cell s.u.s taken from SAINT output.

244_ALERT_4_C Low Solvent U(eq) as Compared to Neighbors.. N1V

The terminal methyl group based on C1V seems to librating more than the ring-atoms, this is not especially unusual.

720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ······ 29 764_ALERT_4_C Overcomplete CIF Bond list Detected (Rep/Expd) 1.13 Ratio

No action taken

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O1A0.1999 (2)0.55595 (18)0.10784 (12)0.0303 (4)
C1A0.1227 (2)0.4712 (2)0.17097 (15)0.0225 (5)
C2A0.1675 (3)0.3471 (2)0.20331 (15)0.0228 (5)
H2A0.25680.31870.18250.027*
C3A0.0827 (3)0.2642 (2)0.26600 (15)0.0240 (5)
H3A0.11490.17970.28780.029*
C4A0.0481 (3)0.3030 (2)0.29706 (15)0.0239 (5)
O4A0.13639 (19)0.22739 (19)0.35842 (12)0.0321 (4)
C5A0.0917 (3)0.4278 (3)0.26438 (17)0.0287 (6)
H5A0.18090.45650.28510.034*
C6A0.0074 (3)0.5104 (3)0.20244 (17)0.0294 (6)
H6A0.03920.59540.18110.035*
O1B0.3462 (2)0.08746 (19)0.11340 (12)0.0335 (4)
C1B0.3689 (3)0.0181 (2)0.19305 (15)0.0240 (5)
C2B0.3072 (3)0.1238 (2)0.20638 (16)0.0247 (5)
H2B0.24510.17660.15930.030*
C3B0.3356 (3)0.1891 (2)0.28792 (15)0.0238 (5)
H3B0.29240.28620.29640.029*
C4B0.4263 (3)0.1139 (2)0.35694 (15)0.0218 (5)
O4B0.4586 (2)0.17203 (19)0.43913 (11)0.0320 (4)
C5B0.4880 (3)0.0278 (3)0.34385 (16)0.0290 (6)
H5B0.54990.08080.39100.035*
C6B0.4598 (3)0.0924 (3)0.26233 (16)0.0302 (6)
H6B0.50350.18940.25380.036*
C1S0.8070 (3)0.4747 (3)0.53140 (17)0.0293 (6)
H1S10.84130.39910.49630.044*
H1S20.84300.47100.59520.044*
H1S30.84760.56800.50670.044*
N1S0.6414 (2)0.4539 (2)0.52553 (13)0.0216 (4)
C2S0.5855 (3)0.5654 (2)0.57718 (15)0.0235 (5)
H2S10.62720.66040.55340.028*
H2S20.62060.56280.64190.028*
C3S0.4148 (3)0.5441 (2)0.56985 (15)0.0221 (5)
H3S10.37310.45140.59670.027*
H3S20.37950.62080.60470.027*
C1T0.5811 (3)0.6117 (3)0.17652 (17)0.0365 (6)
H1T10.55420.54720.22700.055*
H1T20.55170.70440.18930.055*
H1T30.69070.62450.16960.055*
N1T0.5015 (2)0.5503 (2)0.09256 (13)0.0265 (5)
C2T0.5346 (3)0.6488 (3)0.01698 (16)0.0282 (5)
H2T10.64510.66700.00870.034*
H2T20.50290.74110.03130.034*
C3T0.4516 (3)0.5856 (3)0.06968 (16)0.0281 (6)
H3T10.34100.57000.06190.034*
H3T20.47370.65320.12000.034*
C1U0.8613 (4)0.8646 (3)0.33895 (19)0.0454 (7)
H1U10.86640.76720.35890.068*
H1U20.91730.88380.28370.068*
H1U30.75510.87440.32620.068*
N1U0.9284 (2)0.9667 (2)0.41090 (13)0.0259 (5)
C2U0.8448 (3)0.9402 (3)0.49425 (17)0.0285 (6)
H2U10.84810.84160.51470.034*
H2U20.73740.94920.48120.034*
C3U0.9125 (3)1.0445 (3)0.56829 (16)0.0282 (6)
H3U10.90531.14280.54880.034*
H3U20.85471.02510.62370.034*
C1V0.2262 (4)0.1396 (5)0.0664 (3)0.0975 (18)
H1V40.25780.21310.02690.146*
H1V50.31610.07790.08760.146*
H1V60.16470.18550.11890.146*
N1V0.1361 (2)0.0532 (3)0.01501 (14)0.0364 (6)
C2V0.0881 (3)0.0589 (3)0.06965 (17)0.0420 (7)
H2V10.02570.01600.12360.050*
H2V20.17810.12210.09130.050*
C3V0.0015 (3)0.1443 (3)0.0158 (2)0.0429 (8)
H3V10.06140.18900.03750.051*
H3V20.03190.22150.05370.051*
H4B0.422 (4)0.269 (3)0.439 (2)0.058 (10)*
H1A0.295 (4)0.541 (3)0.106 (2)0.054 (9)*
H4A0.101 (4)0.138 (3)0.371 (2)0.062 (10)*
H1B0.273 (4)0.030 (3)0.074 (2)0.068 (11)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O1A0.0245 (10)0.0326 (10)0.0353 (10)0.0060 (8)0.0095 (8)0.0121 (8)
C1A0.0182 (11)0.0281 (13)0.0202 (11)0.0014 (9)0.0016 (9)0.0012 (10)
C2A0.0203 (11)0.0255 (12)0.0234 (12)0.0065 (9)0.0006 (9)0.0032 (10)
C3A0.0283 (13)0.0201 (12)0.0238 (12)0.0052 (10)0.0013 (10)0.0010 (10)
C4A0.0245 (12)0.0266 (13)0.0200 (12)0.0024 (10)0.0025 (10)0.0010 (10)
O4A0.0315 (10)0.0315 (10)0.0356 (10)0.0081 (8)0.0135 (8)0.0119 (8)
C5A0.0216 (12)0.0308 (14)0.0366 (14)0.0103 (10)0.0073 (11)0.0075 (11)
C6A0.0265 (13)0.0264 (13)0.0374 (14)0.0088 (10)0.0051 (11)0.0092 (11)
O1B0.0453 (11)0.0289 (10)0.0243 (9)0.0035 (8)0.0105 (8)0.0038 (8)
C1B0.0263 (12)0.0250 (13)0.0217 (12)0.0073 (10)0.0008 (10)0.0011 (10)
C2B0.0248 (12)0.0266 (13)0.0225 (12)0.0054 (10)0.0034 (10)0.0040 (10)
C3B0.0244 (12)0.0196 (12)0.0267 (12)0.0011 (9)0.0032 (10)0.0002 (10)
C4B0.0222 (12)0.0239 (12)0.0201 (11)0.0058 (9)0.0014 (9)0.0020 (9)
O4B0.0405 (11)0.0246 (10)0.0268 (9)0.0039 (8)0.0085 (8)0.0068 (8)
C5B0.0329 (14)0.0259 (13)0.0244 (13)0.0024 (10)0.0091 (10)0.0016 (10)
C6B0.0393 (15)0.0202 (12)0.0290 (13)0.0004 (11)0.0055 (11)0.0040 (10)
C1S0.0220 (12)0.0277 (13)0.0376 (14)0.0032 (10)0.0017 (11)0.0029 (11)
N1S0.0184 (10)0.0223 (10)0.0234 (10)0.0023 (8)0.0014 (8)0.0013 (8)
C2S0.0243 (12)0.0247 (12)0.0204 (12)0.0015 (10)0.0012 (9)0.0007 (10)
C3S0.0257 (12)0.0212 (12)0.0185 (11)0.0008 (9)0.0022 (9)0.0007 (9)
C1T0.0329 (15)0.0500 (17)0.0286 (14)0.0123 (13)0.0021 (11)0.0016 (13)
N1T0.0241 (11)0.0347 (12)0.0222 (10)0.0079 (9)0.0041 (8)0.0056 (9)
C2T0.0254 (13)0.0298 (13)0.0304 (13)0.0058 (10)0.0042 (10)0.0086 (11)
C3T0.0253 (13)0.0324 (14)0.0284 (13)0.0088 (10)0.0045 (10)0.0138 (11)
C1U0.059 (2)0.0378 (17)0.0365 (16)0.0015 (14)0.0056 (14)0.0013 (13)
N1U0.0274 (11)0.0247 (11)0.0251 (11)0.0030 (8)0.0020 (9)0.0010 (8)
C2U0.0214 (12)0.0279 (13)0.0361 (14)0.0026 (10)0.0050 (11)0.0085 (11)
C3U0.0313 (13)0.0282 (13)0.0290 (13)0.0126 (10)0.0117 (11)0.0084 (11)
C1V0.062 (2)0.167 (4)0.075 (3)0.065 (3)0.028 (2)0.082 (3)
N1V0.0310 (12)0.0523 (15)0.0290 (12)0.0199 (11)0.0083 (10)0.0148 (11)
C2V0.0357 (15)0.061 (2)0.0234 (14)0.0088 (14)0.0022 (12)0.0107 (13)
C3V0.0529 (18)0.0207 (13)0.0510 (18)0.0051 (12)0.0330 (15)0.0020 (12)
Geometric parameters (Å, º) top
O1A—C1A1.371 (3)C3S—H3S10.9900
O1A—H1A0.89 (3)C3S—H3S20.9900
C1A—C6A1.382 (3)C1T—N1T1.460 (3)
C1A—C2A1.387 (3)C1T—H1T10.9800
C2A—C3A1.390 (3)C1T—H1T20.9800
C2A—H2A0.9500C1T—H1T30.9800
C3A—C4A1.384 (3)N1T—C3Tii1.465 (3)
C3A—H3A0.9500N1T—C2T1.468 (3)
C4A—O4A1.360 (3)C2T—C3T1.509 (3)
C4A—C5A1.390 (3)C2T—H2T10.9900
O4A—H4A0.97 (3)C2T—H2T20.9900
C5A—C6A1.379 (3)C3T—N1Tii1.465 (3)
C5A—H5A0.9500C3T—H3T10.9900
C6A—H6A0.9500C3T—H3T20.9900
O1B—C1B1.372 (3)C1U—N1U1.464 (3)
O1B—H1B0.95 (3)C1U—H1U10.9800
C1B—C6B1.382 (3)C1U—H1U20.9800
C1B—C2B1.387 (3)C1U—H1U30.9800
C2B—C3B1.387 (3)N1U—C3Uiii1.465 (3)
C2B—H2B0.9500N1U—C2U1.471 (3)
C3B—C4B1.382 (3)C2U—C3U1.499 (3)
C3B—H3B0.9500C2U—H2U10.9900
C4B—O4B1.371 (3)C2U—H2U20.9900
C4B—C5B1.386 (3)C3U—N1Uiii1.465 (3)
O4B—H4B0.92 (3)C3U—H3U10.9900
C5B—C6B1.383 (3)C3U—H3U20.9900
C5B—H5B0.9500C1V—N1V1.474 (4)
C6B—H6B0.9500C1V—H1V40.9800
C1S—N1S1.462 (3)C1V—H1V50.9800
C1S—H1S10.9800C1V—H1V60.9800
C1S—H1S20.9800N1V—C2V1.448 (3)
C1S—H1S30.9800N1V—C3Viv1.457 (4)
N1S—C2S1.467 (3)C2V—C3V1.484 (4)
N1S—C3Si1.468 (3)C2V—H2V10.9900
C2S—C3S1.507 (3)C2V—H2V20.9900
C2S—H2S10.9900C3V—N1Viv1.457 (4)
C2S—H2S20.9900C3V—H3V10.9900
C3S—N1Si1.468 (3)C3V—H3V20.9900
C1A—O1A—H1A111.1 (19)N1T—C1T—H1T2109.5
O1A—C1A—C6A118.1 (2)H1T1—C1T—H1T2109.5
O1A—C1A—C2A123.2 (2)N1T—C1T—H1T3109.5
C6A—C1A—C2A118.7 (2)H1T1—C1T—H1T3109.5
C1A—C2A—C3A120.4 (2)H1T2—C1T—H1T3109.5
C1A—C2A—H2A119.8C1T—N1T—C3Tii110.62 (19)
C3A—C2A—H2A119.8C1T—N1T—C2T110.2 (2)
C4A—C3A—C2A120.9 (2)C3Tii—N1T—C2T108.72 (18)
C4A—C3A—H3A119.6N1T—C2T—C3T110.19 (19)
C2A—C3A—H3A119.6N1T—C2T—H2T1109.6
O4A—C4A—C3A124.1 (2)C3T—C2T—H2T1109.6
O4A—C4A—C5A117.7 (2)N1T—C2T—H2T2109.6
C3A—C4A—C5A118.2 (2)C3T—C2T—H2T2109.6
C4A—O4A—H4A109.7 (18)H2T1—C2T—H2T2108.1
C6A—C5A—C4A121.0 (2)N1Tii—C3T—C2T110.37 (19)
C6A—C5A—H5A119.5N1Tii—C3T—H3T1109.6
C4A—C5A—H5A119.5C2T—C3T—H3T1109.6
C5A—C6A—C1A120.8 (2)N1Tii—C3T—H3T2109.6
C5A—C6A—H6A119.6C2T—C3T—H3T2109.6
C1A—C6A—H6A119.6H3T1—C3T—H3T2108.1
C1B—O1B—H1B110.4 (19)N1U—C1U—H1U1109.5
O1B—C1B—C6B118.3 (2)N1U—C1U—H1U2109.5
O1B—C1B—C2B123.0 (2)H1U1—C1U—H1U2109.5
C6B—C1B—C2B118.7 (2)N1U—C1U—H1U3109.5
C1B—C2B—C3B120.5 (2)H1U1—C1U—H1U3109.5
C1B—C2B—H2B119.7H1U2—C1U—H1U3109.5
C3B—C2B—H2B119.7C1U—N1U—C3Uiii111.1 (2)
C4B—C3B—C2B120.4 (2)C1U—N1U—C2U110.2 (2)
C4B—C3B—H3B119.8C3Uiii—N1U—C2U108.81 (18)
C2B—C3B—H3B119.8N1U—C2U—C3U110.66 (19)
O4B—C4B—C3B123.4 (2)N1U—C2U—H2U1109.5
O4B—C4B—C5B117.5 (2)C3U—C2U—H2U1109.5
C3B—C4B—C5B119.2 (2)N1U—C2U—H2U2109.5
C4B—O4B—H4B111.0 (19)C3U—C2U—H2U2109.5
C6B—C5B—C4B120.2 (2)H2U1—C2U—H2U2108.1
C6B—C5B—H5B119.9N1Uiii—C3U—C2U110.72 (19)
C4B—C5B—H5B119.9N1Uiii—C3U—H3U1109.5
C1B—C6B—C5B121.0 (2)C2U—C3U—H3U1109.5
C1B—C6B—H6B119.5N1Uiii—C3U—H3U2109.5
C5B—C6B—H6B119.5C2U—C3U—H3U2109.5
N1S—C1S—H1S1109.5H3U1—C3U—H3U2108.1
N1S—C1S—H1S2109.5N1V—C1V—H1V4109.5
H1S1—C1S—H1S2109.5N1V—C1V—H1V5109.5
N1S—C1S—H1S3109.5H1V4—C1V—H1V5109.5
H1S1—C1S—H1S3109.5N1V—C1V—H1V6109.5
H1S2—C1S—H1S3109.5H1V4—C1V—H1V6109.5
C1S—N1S—C2S111.13 (17)H1V5—C1V—H1V6109.5
C1S—N1S—C3Si110.22 (18)C2V—N1V—C3Viv108.3 (2)
C2S—N1S—C3Si109.13 (17)C2V—N1V—C1V112.0 (3)
N1S—C2S—C3S110.75 (18)C3Viv—N1V—C1V109.7 (3)
N1S—C2S—H2S1109.5N1V—C2V—C3V110.6 (2)
C3S—C2S—H2S1109.5N1V—C2V—H2V1109.5
N1S—C2S—H2S2109.5C3V—C2V—H2V1109.5
C3S—C2S—H2S2109.5N1V—C2V—H2V2109.5
H2S1—C2S—H2S2108.1C3V—C2V—H2V2109.5
N1Si—C3S—C2S110.94 (18)H2V1—C2V—H2V2108.1
N1Si—C3S—H3S1109.5N1Viv—C3V—C2V110.1 (2)
C2S—C3S—H3S1109.5N1Viv—C3V—H3V1109.6
N1Si—C3S—H3S2109.5C2V—C3V—H3V1109.6
C2S—C3S—H3S2109.5N1Viv—C3V—H3V2109.6
H3S1—C3S—H3S2108.0C2V—C3V—H3V2109.6
N1T—C1T—H1T1109.5H3V1—C3V—H3V2108.2
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y+1, z; (iii) x+2, y+2, z+1; (iv) x, y, z.

Experimental details

(1)(2)(3)(4)
Crystal data
Chemical formulaC6H6O2.C4H4N2C4H10N2·C6H6O22(C4H9NO)(C6H6O2)C3H3O(C5H5N)
Mr190.20196.25284.36268.31
Crystal system, space groupMonoclinic, P21/cTriclinic twin, P1Monoclinic, P21/nMonoclinic, P21/c
Temperature (K)150150150150
a, b, c (Å)8.901 (3), 7.666 (2), 6.984 (2)5.7060 (15), 6.7599 (19), 7.0771 (18)6.6652 (13), 5.5881 (11), 20.034 (4)6.4990 (9), 16.459 (2), 7.1794 (10)
α, β, γ (°)90, 90.091 (6), 90100.269 (4), 112.446 (3), 90.163 (3)90, 94.942 (4), 9090, 112.986 (3), 90
V3)476.6 (3)247.50 (11)743.4 (3)707.00 (17)
Z2122
Radiation typeMo KαMo KαMo KαMo Kα
µ (mm1)0.100.090.090.08
Crystal size (mm)0.39 × 0.28 × 0.100.27 × 0.23 × 0.060.31 × 0.22 × 0.091 × 0.32 × 0.32
Data collection
DiffractometerCCD area detector
diffractometer
CCD area detector
diffractometer
CCD area detector
diffractometer
CCD area detector
diffractometer
Absorption correctionMulti-scan
SADABS
Multi-scan
SADABS
Multi-scan
SADABS
Multi-scan
SADABS
Tmin, Tmax0.787, 10.874, 10.675, 10.593, 1
No. of measured, independent and
observed [I > 2σ(I)] reflections
2873, 1141, 926 3814, 1194, 1117 4226, 1730, 1427 5091, 1700, 1345
Rint0.0230.0290.0380.031
(sin θ/λ)max1)0.6770.6770.6710.679
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.047, 0.115, 1.07 0.051, 0.118, 1.09 0.085, 0.211, 1.18 0.083, 0.172, 1.33
No. of reflections1141119417301700
No. of parameters68739995
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
Δρmax, Δρmin (e Å3)0.26, 0.300.32, 0.330.44, 0.310.28, 0.39


(5)(6)(7)(8)
Crystal data
Chemical formula2(C5H11N)(C6H6O2)2(C10H8N2)(C6H6O2)2(C5H11NO)(C6H6O2)C6H14N2.C6H6O2
Mr280.40422.49312.41224.30
Crystal system, space groupMonoclinic, P21/cTriclinic, P1Triclinic, P1Triclinic, P1
Temperature (K)150150150150
a, b, c (Å)10.4230 (15), 5.2619 (7), 15.221 (2)7.820 (4), 8.619 (4), 9.201 (4)6.9612 (10), 7.3146 (11), 9.659 (2)8.9620 (8), 9.4944 (8), 14.7119 (13)
α, β, γ (°)90, 109.920 (3), 90111.897 (7), 109.851 (7), 94.657 (8)106.182 (3), 104.481 (3), 106.201 (2)90.501 (2), 92.919 (2), 99.664 (2)
V3)784.84 (19)525.7 (4)423.94 (12)1232.26 (19)
Z2114
Radiation typeMo KαMo KαMo KαMo Kα
µ (mm1)0.080.090.090.08
Crystal size (mm)0.33 × 0.18 × 0.180.77 × 0.22 × 0.151 × 0.38 × 0.380.34 × 0.20 × 0.11
Data collection
DiffractometerCCD area detector
diffractometer
CCD area detector
diffractometer
CCD area detector
diffractometer
CCD area detector
diffractometer
Absorption correctionMulti-scan
SADABS
Multi-scan
SADABS
Multi-scan
SADABS
Multi-scan
SADABS
Tmin, Tmax0.661, 10.763, 10.774, 10.898, 1
No. of measured, independent and
observed [I > 2σ(I)] reflections
4754, 1896, 1327 4641, 2428, 2067 3788, 1972, 1794 11345, 5844, 3873
Rint0.0280.0310.0200.039
(sin θ/λ)max1)0.6830.6760.6770.681
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.056, 0.136, 1.04 0.054, 0.144, 1.04 0.045, 0.120, 1.07 0.074, 0.162, 1.03
No. of reflections1896242819725844
No. of parameters99150106308
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
Δρmax, Δρmin (e Å3)0.24, 0.190.31, 0.260.24, 0.270.50, 0.43

Computer programs: Bruker SMART, Bruker SHELXTL, SHELXS97 (Sheldrick, 1997b), SHELXL97 (Sheldrick, 1997b).

 

Footnotes

1Supplementary data for this paper are available from the IUCr electronic archives (Reference: WS5013 ). Services for accessing these data are described at the back of the journal.

Acknowledgements

We thank the EPSRC, the Cambridge Crystallographic Data Centre and the University of Edinburgh for funding. We also thank the referees for their careful reading of the draft manuscript.

References

First citationAllen, F. H. & Motherwell, W. D. S. (2002). Acta Cryst. B58, 407–422.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationBarnes, J. C., Paton, J. D. & Blyth, C. S. (1990). Acta Cryst. C46, 1183–1184.  CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationBernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.  CrossRef CAS Web of Science Google Scholar
First citationBlessing, R. H. (1995). Acta Cryst. A51, 33–38.  CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationBoese, R. & Nussbaumer, M. (1994). Correlations, Transformations, and Interactions in Organic Crystal Chemistry, edited by D. W. Jones & A. Katrusiak, Vol. 7, pp. 20–37. IUCr Crystallographic Symposia 7. IUCr and Oxford University Press.  Google Scholar
First citationBolte, M. & Lerner, H.-W. (2001). Private Communication to CSD, CCDC 161816.  Google Scholar
First citationBruno, I. J., Cole, J. C., Edgington, P. R., Kessler, M., Macrae, C. F., McCabe, P., Pearson, J. & Taylor, R. (2002). Acta Cryst. B58, 389–397.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationBuschmann, J., Müller, E. & Luger, P. (1986). Acta Cryst. C42, 873–876.  CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationCaspari, W. A. (1926). J. Chem. Soc. pp. 2944–2948.  CrossRef Google Scholar
First citationCaspari, W. A. (1927). J. Chem. Soc. pp. 1093–1095.  CrossRef Google Scholar
First citationCorradi, E., Meille, S. V., Messina, M. T., Metrangolo, P. & Resnati, G. (2000). Angew. Chem. Int. Ed. 39, 1782–1786.  Web of Science CrossRef CAS Google Scholar
First citationCosier, J. & Glazer, A. M. (1986). J. Appl. Cryst. 19, 105–107.  CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationFabbiani, F. P. A., Allan, D. R., Dawson, A., David, W. I. F., McGregor, P. A., Oswald, I. D. H., Parsons, S. & Pulham, C. R. (2003). Chem. Commun. pp. 3004–3005.  Web of Science CSD CrossRef Google Scholar
First citationFarrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.  CrossRef CAS IUCr Journals Google Scholar
First citationHunter, C. A., Lawson, K. R., Perkins, J. & Urch, C. J. (2001). J. Chem. Soc. Perkin Trans. 2, pp. 651–669.  Web of Science CrossRef Google Scholar
First citationLindeman, S. V., Shklover, V. E. & Struchkov, Yu. T. (1981). Cryst. Struct. Commun. 10, 1173–1179.  CAS Google Scholar
First citationMaartmann-Moe, K. (1966). Acta Cryst. 21, 979–982.  CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
First citationMacGillivray, L. R., Reid, J. &. Ripmeester, J. A. (2000). J. Am. Chem. Soc. 122, 7817–7818.  Web of Science CSD CrossRef CAS Google Scholar
First citationMotherwell, W. D. S., Shields, G. P. & Allen, F. H. (1999). Acta Cryst. B55, 1044–1056.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationOswald, I. D. H., Allan, D. R., McGregor, P. A., Motherwell, W. D. S., Parsons, S. & Pulham, C. R. (2002). Acta Cryst. B58, 1057–1066.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
First citationOswald, I. D. H., Motherwell, W. D. S. & Parsons, S. (2004). Acta Cryst. E60, o1967–o1969.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationOswald, I. D. H., Motherwell, W. D. S., Parsons, S., Pidcock, E. & Pulham, C. R. (2004). Cryst. Rev. 10, 57–66.  CrossRef CAS Google Scholar
First citationParkin, A., Oswald, I. D. H. & Parsons, S. (2004). Acta Cryst. B60, 219–227.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
First citationPidcock, E., Motherwell, W. D. S. & Cole, J. C. (2003). Acta Cryst. B59, 634–640.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSheldrick, G. M. (1997a). SADABS. Bruker-AXS, Madison, Wisconsin, USA.  Google Scholar
First citationSheldrick, G. M. (1997b). SHELXTL. Bruker-AXS, Madison, Wisconsin, USA.  Google Scholar
First citationSoscùn, H., Bermúdez, Y., Castellano, O. & Hernández, J. (2004). Chem. Phys. Lett. 396, 117–121.  Web of Science CrossRef CAS Google Scholar
First citationSpek, A. L. (2002). PLATON. Utrecht University, The Netherlands.  Google Scholar
First citationTaylor, R. & Macrae, C. F. (2001). Acta Cryst. B57, 815–827.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationWatkin, D. J., Pearce, L. & Prout, C. K. (1993). CAMERON. Chemical Crystallography Laboratory, University of Oxford, England.  Google Scholar
First citationYao, J. W., Cole, J. C., Pidcock, E., Allen, F. H., Howard, J. A. K. & Motherwell, W. D. S. (2002). Acta Cryst. B58, 640–646.  Web of Science CrossRef CAS IUCr Journals Google Scholar

© International Union of Crystallography. Prior permission is not required to reproduce short quotations, tables and figures from this article, provided the original authors and source are cited. For more information, click here.

Journal logoSTRUCTURAL SCIENCE
CRYSTAL ENGINEERING
MATERIALS
ISSN: 2052-5206
Follow Acta Cryst. B
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds