research papers
The synthesis and characterization of a series of cocrystals of an isoniazid derivative with butan-2-one and propan-2-one
aMolecular Sciences Institute, School of Chemistry, University of the Witwatersrand, Private Bag 3, Johannesburg, Gauteng 2050, South Africa
*Correspondence e-mail: andreas.lemmerer@wits.ac.za
This article is part of a collection of articles to commemorate the founding of the African Crystallographic Association and the 75th anniversary of the IUCr.
Four cocrystals containing N′-(butan-2-ylidene)pyridine-4-carbohydrazide (izbt) and one cocrystal containing N′-isopropylideneisonicotinohydrazide (izact) were synthesized by reacting isoniazid with either butan-2-one (for the former) or acetone (for the latter). The coformers used to synthesize the izbt cocrystals were 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2-chloro-4-nitrobenzoic acid and 1-naphthoic acid. 1-Naphthoic acid was also used with izact to form a cocrystal. The 1:1 cocrystals are: N′-(butan-2-ylidene)pyridine-4-carbohydrazide–1-naphthoic acid (izbt–1nta), C10H13N3O·C11H8O2, N′-(butan-2-ylidene)pyridine-4-carbohydrazide–2,4-dihydroxybenzoic acid (izbt–2,4-dhba), C10H13N3O·C7H6O4, N′-(propan-2-ylidene)pyridine-4-carbohydrazide–1-naphthoic acid (izact–1nta), C9H11N3O·C11H8O2, N′-(butan-2-ylidene)pyridine-4-carbohydrazide–2-chloro-4-nitrobenzoic acid (izbt–2c4n), C10H13N3O·C7H4ClNO4, and N′-(butan-2-ylidene)pyridine-4-carbohydrazide–2,5-dihydroxybenzoic acid (izbt–2,5-dhba), C10H13N3O·C7H6O4. The cocrystals containing izbt were compared to those containing the same (or similar) coformers with izact that have been reported either here or in the Cambridge Structural Database (CSD). Most of the cocrystals showed different packing despite having the same hydrogen-bonding motifs. The cocrystals were characterized by single-crystal X-ray diffraction (SC-XRD), powder X-ray diffraction (PXRD) and (DSC).
1. Introduction
In the pharmaceutical industry, it is often typical for new and existing drugs to have poor physicochemical properties. The poor performance from these drugs can hamper their success on the market. The modification of an existing drug can yield a new product with possibly improved properties compared to the original drug molecule. Although this would require new clinical trials, it could prove to be advantageous for long-term success. From a crystal engineering perspective, this could prove to be an opportunity to explore new solid-state structural landscapes.
One approach of crystal engineering with repsect to changing the solid-state form of active pharmaceutical ingredients (APIs) is to use cocrystals. Although no universal definition of a cocrystal exists, several different definitions have been proposed by different authors. The definition proposed by Aitipamula et al. (2012) is as follows: `cocrystals are solids that are crystalline single phase materials composed of two or more different molecular and/or ionic compounds generally in a stoichiometric ratio.' Grothe defines a cocrystal as `a crystal with a coformer molecule plus either another coformer or at least two ions,' with further classifications depending on whether the crystal also contains ions, solvate molecules or water (Grothe et al., 2016). Cocrystals have been proven to have new properties, such as having a different solubility or bioavailability over the starting material (Karimi-Jafari et al., 2018). It can even lead to the possibility of having multiple drugs in one crystal form (Wang et al., 2021). Unfortunately, cocrystal design and synthesis is not straightforward; it is possible to fail creating a cocrystal despite using a reasonable cocrystal design methodology (Bučar et al., 2013).
Isoniazid (inh) is an antibacterial drug used to treat Mycobacterium tuberculosis bacteria (TB). It is often combined with several different drugs in a fixed-dose combination (FDC) as part of the treatment for this disease (Murray et al., 2015). However, inh has been known to undergo degradation in the presence of other drugs (Bhutani et al., 2005). Inh is a fairly simple drug molecule, consisting of a pyridine ring, an amide group and a hydrazine group. One way to modify inh is to employ a Schiff base reaction using inh and either an aldehyde or a ketone. In previous work, we modified isoniazid with acetone, butan-2-one, 4-hydroxy-4-methylpentan-2-one and benzophenone, and explored a different number of cocrystal and molecular salt crystal structures (Lemmerer et al., 2010; Madeley et al., 2019; Scheepers & Lemmerer, 2022; Lemmerer, 2012). In particular, a decent number of cocrystals and molecular salts with isoniazid derived from acetone and butan-2-one have been reported, with seven crystal structures containing N′-(butan-2-ylidene)pyridine-4-carbohydrazide (butan-2-one-based derivative, izbt) and 15 containing N′-isopropylideneisonicotinohydrazide (acetone-based derivative, izact). Out of these, only five pairs share the same coformer, of which, three pairs are isostructural (Table 1). It should not be too surprising to find crystal structures becoming isostructural when certain functional groups are exchanged with a similar one, for example, changing a chlorine to a bromine or methyl to an amino group (Clarke et al., 2012). However, it is still possible that exchanging one for another can yield a completely different structure. In the case of izact and izbt, the difference is the presence or absence of the methylene group in the alkyl group. In three of the cases, this had no effect, but in the case of the anyhydrous forms of izact– and izbt–3-hydroxybenzoic acid, and izact– and izbt–2-hydrobenzoic acid, there was a significant difference in the packing. Based on the structures listed in Table 1, we would expect that the methylene group would very likely have a small or even insignificant effect on the overall packing of the molecules in the however, with a small sample size it is difficult to assess if this is a reasonable assertion. Therefore, the aim of this work is to expand the number of multicomponent pairs and compare them, in order to confirm whether the addition of the methylene group can have a significant impact of the packing of these structures. The simplest way to achieve this is to expand the number of izbt cocrystals using coformers that worked for izact; the coformers used include: 2,4-dihydroxybenzoic acid (2,4-dhba), 2,5-dihydroxybenzoic acid (2,5-dhba) and 2-chloro-4-nitrobenzoic acid (2c4n). In addition, cocrystals containing 1-naphthoic acid (1nta) with izact and izbt, respectively, were synthesized and characterized. 1nta was used to observe the effect of using a bulky double ring as opposed to using coformers consisting of a single ring. The structures of these compounds are represented in Scheme 1.
2. Experimental
2.1. Materials
All materials were purchased from Sigma–Aldrich and were used without further purification.
2.2. General procedure for the synthesis of izbt and izact cocrystals
The general procedure for synthesizing cocrystals featuring either izbt or izact is as follows: stoichiometric ratios of inh and the respective coformer (1:1 ratio) were dissolved in absolute ethanol (5 ml) in a small vial. The deriving ketone (acetone or butan-2-one) (1 ml) was added. This vial was closed and the mixture stirred for 4 h. Afterwards, the lid on the vial was replaced with a lid with a hole in it and the vial kept in a dark cupboard. After several days, crystals remained after the solvent evaporated.
2.3. Powder X-ray diffraction (PXRD)
PXRD was used to determine the bulk phase purity of each sample. PXRD data for all forms were measured at 293 K on a Bruker D2 Phaser diffractometer which employs a sealed tube Co X-ray source (λ = 1.78896 Å), operating at 30 kV and 10 mA, and a LynxEye PSD detector in Bragg–Brentano geometry. The powder patterns for the cocrystals are presented in the supporting information, where the experimentally measured pattern is compared to the calculated patterns obtained from the single-crystal X-ray diffraction (SC-XRD) data, as well as the calculated patterns of its components using data from the Cambridge Structural Database (CSD, Version 2022.1.0; Groom et al., 2016).
2.4. Single-crystal X-ray diffraction (SC-XRD) and refinement
Crystal data, data collection and structure . All carbon-bound H atoms were placed in idealized positions and refined as riding atoms, with Uiso(H) parameters 1.2 or 1.5 times those of the parent atoms. Most nitrogen- and oxygen-bound H atoms were located in difference Fourier maps, and their coordinates and isotropic displacement parameters were refined freely.
details are summarized in Table 2
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2.5. The Cambridge Structural Database (CSD)
The CSD (Version 2022.1.0; Groom et al., 2016) was used to compare the cocrystals presented in this work with the cocrystals of izact. The only restriction was that entries must be classified as being organic. Mercury (Macrae et al., 2020) was used to inspect the crystal structures. The Similarity tool was used to compare the structural similarity of selected structures.
2.6. (DSC)
DSC data were collected using a Mettler Toledo DSC 3 with aluminium pans under nitrogen gas (flow rate = 10 ml min−1). Exothermic events were shown as peaks. Samples were heated and cooled to determine the melting points, as well as any additional phase transitions. The temperature and energy calibrations were performed using pure indium (purity 99.99%, m.p. 156.6 °C, heat of fusion: 28.45 J g−1) and pure zinc (purity 99.99%, m.p. 479.5 °C, heat of fusion: 107.5 J g−1). Samples were heated to 250 °C from 25 °C before being cooled back down to 25 °C at a heating or cooling rate of 10 °C min−1.
3. Results and discussion
3.1. Synthesis of cocrystals
In this work, six cocrystals were synthesized and characterized. Five of these cocrystals contained izbt and one contained izact. The four coformers chosen were: 2,4-dihydroxybenzoic acid (2,4-dhba), 2,5-dihydroxybenzoic acid (gentisic acid, abbreviated as 2,5-dhba), 2-chloro-4-nitrobenzoic acid (2c4n) and 1-naphthoic acid (1nta). The first three coformers were chosen because previous cocrystals containing said coformers with izact had been synthesized and characterized previously, and it would be a good reference to compare the respective corystals. 1nta was chosen due to its naphthalene ring, as it would be interesting to see if its bulky nature had an effect on the overall packing. These cocrystals are described below, together with that of izbt compared to its izact counterpart, as well as any other notable cocrystal of izact. The data are given in Table 2, while the displacement ellipsoid plots are shown in Fig. 1. Hydrogen-bond tables can be found in the supporting information.
Powder patterns were collected for each sample and were compared to the powder patterns calculated from the single-crystal structural data. These powder patterns are also compared to the powder patterns of each of the components, including the polymorphic forms of the components which are polymorphic. It should be noted that we are comparing the hydrated form of izbt to the powder patterns of the cocrystals presented here. This was done because it was the closest form to a `pure' component we can get, and in our own investigations, we have obtained the hydrated form of izbt exclusively when using the same crystallizing conditions we used to obtain the cocrystals presented here, which indicates that izbt is most likely highly hygroscopic, obtaining the water from either the waters of reaction or atmospheric moisture, or both. This comparison between the experimental and calculated patterns was made to confirm the bulk phase purity. These patterns are presented in the supporting information.
3.2. of izbt–2,4-dhba
Izbt formed a cocrystal with 2,4-dhba which crystallized as colourless blocks in the P21/n, with the consisting of one molecule each of izbt and 2,4-dhba. A disorder model is present, where two C atoms (C9 and C10) of the alkyl portion of izbt were split over two different positions, respectively. The pyridine ring of izbt forms a hydrogen bond with the carboxylic acid group of 2,4-dhba, while the hydroxy group at the 4-position of the 2,4-dhba molecule (O5—H5) forms two different hydrogen bonds with the amide group of izbt, one where the hydroxy group is the hydrogen-bond donor, forming a hydrogen bond with the O atom of the amide group [O5—H5⋯O1i; symmetry code: (i) x + , −y + , z + ], and one where the hydroxy group is the hydrogen-bond acceptor, forming a hydrogen bond with the amine portion of the amide group [N1—H1⋯O5ii; symmetry code: (ii) −x + , y + , −z + ] [Fig. 2(a)]. This hydrogen-bond arrangement ultimately forms a tetramer with an R44(12) ring hydrogen-bond motif. The hydroxy group at the 2-position of 2,4-dhba does not form any strong hydrogen bonds other than the typical intramolecular hydrogen bond with the carboxylic acid group. The overall packing of the structure resembles a herringbone-type structure [Fig. 2(b)].
Although there is no equivalent cocrystal featuring 2,4-dhba and izact, the of izbt–2,4-dhba may be compared to that of izact–4hba (CSD refcode LATKOI). Fig. 2(c) shows the overlay of these two structures using the Similarity tool of Mercury (Macrae et al., 2020). The parameters of izact–4hba match closely with those of izbt–2,4-dhba, and when the Similarity tool of Mercury was used, it showed that the respective molecules matched up well, indicating that they were isostructural. This implies that, in this case, the hydroxy group at the 2-position and the extra methyl group on the alkyl chain did not have any significant effect on the overall packing on the structure.
3.3. of izbt–2,5-dhba
Izbt formed a cocrystal with 2,5-dhba which crystallized as colourless blocks in the P, with the consisting of two molecules each of izbt and 2,5-dhba. A disorder model exists where the methylene group of one of the izbt molecules has been split into two different sites (C26A and C26B). Like izbt–2,4-dhba, the corystals of izbt–2,5-dhba exhibit a similar hydrogen-bonding trend: a hydrogen bond is formed between the pyridine ring of izbt and the carboxylic acid group of 2,5-dhba, while the hydroxy group at the 5-position of 2,5-dhba forms a C22(11) chain–ring hydrogen-bond motif with the O and H atom of the amide group of adjacent izbt molecules [Fig. 3(a)]. The overall packing is a layered-type structure, with the alkyl group separating the ring layers [Fig. 3(b)]. In comparison, the structure of izact–2,5-dhba (refcode NAKYOQ; Oruganti et al., 2016) is very similar to its izbt counterpart. Both exhibit the same hydrogen-bond pattern, as well as the overall packing pattern, and the reduced unit-cell lengths of NAKYOQ are comparable (a = 9.119, b = 11.581 and c = 15.273 Å) [Fig. 3(c)].
3.4. of izbt–2c4n
Izbt and 2c4n formed a cocrystal, crystallizing as yellow plates. The consists of one molecule each of izbt and 2c4n, crystallizing in the P21/n. The hydrogen bonding observed in izact–2c4n consists of the typical scheme observed for these types of structures: the carboxylic acid group of 2c4n forms a hydrogen bond with the pyridine ring of izbt, while the amide group of izbt forms a C(4) chain hydrogen-bond motif between the H atom of the amide group and the O atom of the amide group of another izbt molecule [Fig. 4(a)]. This chain hydrogen-bond motif causes the molecules of izbt to lie almost perpendicular with respect to each other in an alternating pattern, and extends along the a and c axes. This ultimately forms a series of ribbons which pack together to form the observed in Fig. 4(c).
The izact–2c4n cocrystal (refcode LATLID) is much different in comparison. According to Grothe et al. (2016), this can be defined as a `cocrystal salt', since its consists of three neutral molecules of 2c4n and one ion of 2c4n, with three neutral molecules of izact and one protonated ion of izact [Fig. 4(b)]. This crystallizes in the P21. Like the structure of izbt–2c4n, molecules and ions of izact are connected to each other via a series of C44(16) chain hydrogen-bond motifs involving the H atom of the amide group forming a hydrogen bond with the O atom of the amide group from another izact molecule. The carboxylic acid group of 2c4n also forms a hydrogen bond with the pyridine ring of izact (charge-assisted for the cation–anion pair). The overall packing of izact–2c4n also consists of ribbons, but these differ from the structure of izbt–2c4n [Fig. 4(d)]. Unlike in the of izbt–2c4n, the arrangement of the izbt–2c4n bonded pairs lie almost parallel to each other, instead of the rotation of almost 90° seen in izbt–2c4n.
3.5. Crystal structures of izact–1nta and izbt–1nta
Izact and izbt each formed a cocrystal with 1nta, both crystallizing as colourless plates. Despite sharing similar unit-cell parameters, the structures are not isostructural, as the of izact–1nta crystallizes in the Cc, while the of izbt–1nta crystallizes in the P21/n. These structures are also not isostructural with izbt–2c4n, despite sharing similar unit-cell parameters, as can be seen in Fig. 5(d). Both crystal structures share the same hydrogen-bonding patterns. 1nta forms a hydrogen bond with the isoniazid derivative, while the isoniazid derivative forms a C(4) chain hydrogen-bond motif involving the H atom of the amide group and the O atom of the amide group from a neighbouring molecule of the isoniazid derivative [Fig. 5(a)], which expands generally in the direction of the a axis as ribbons. The key difference between the two structures lies in the packing, where the difference between the P21/n and Cc space groups is that the inversion centres in P21/n [Fig. 5(b)] are replaced by glide planes in Cc [Fig. 5(c)]. This changes the orientation of the molecules existing in both structures with respect to the Overall, the packing of both structures may be described as herringbone.
3.6. Thermal analysis
DSC curves were collected for all ten cocrystals. The DSC curve of izbt–1nta is presented in Fig. 6 as a representative curve, while the remaining DSC curves can be found in the supporting information. The onset and values are presented in Table 3. The melting points and enthalpies of some of the cocrystals related to the cocrystals presented in this work are also included. In each of the curves, only one large distinct peak was observed on the heating stage, which correlates to the melting/decomposition of the sample. No peaks were observed on the cooling stage of the DSC curves, indicating that no recrystallization occurred. A common feature between the cocrystals is that their melting points are much lower than the melting points of the acid coformers. This makes sense since the R22(8) hydrogen-bond ring motif formed between the carboxylic acid pairs is expected to be stronger than that formed by carboxylic acid–pyridine. From a pharmaceutical point of view, a lower melting point is usually indicative of a product that has a better drug solubility, which indicates the possibility of having better pharmaceutical properties compared to their individual components (Chu & Yalkowsky, 2009). A comparison of the melting/decomposition points and enthalpies of the izact cocrystals with those of their izbt counterparts indicates that the values tend to be similar to each other, which would make sense considering their overall similar hydrogen-bond schemes.
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4. Conclusions
Four cocrystals containing izbt and one cocrystal containing izact were synthesized and characterized. The structures of the cocrystals containing izbt were compared to their izact counterparts, except for izbt–2,4-dhba, which was instead compared to izact–4hba. Most of the structures of the cocrystals of izbt were different compared to their izact counterparts in terms of packing, despite sharing similar hydrogen-bond patterns. This would imply that the presence or absence of a methylene group can have a significant impact on the overall packing, contrary to our initial assumption that the methylene group has a small or even insignificant effect on the packing of molecules in the The melting/decomposition points were found to be much lower than those of the coformers. The overall result shows that many crystal systems are temperamental: small differences between molecules can lead to big changes in the overall packing.
Supporting information
https://doi.org/10.1107/S2053229623007179/dv3024sup1.cif
contains datablocks izbt1nta, izbt24dhba, izact1nta, izbt2c4n, izbt25dhba, global. DOI:Structure factors: contains datablock izbt1nta. DOI: https://doi.org/10.1107/S2053229623007179/dv3024izbt1ntasup2.hkl
Structure factors: contains datablock izbt24dhba. DOI: https://doi.org/10.1107/S2053229623007179/dv3024izbt24dhbasup3.hkl
Structure factors: contains datablock izact1nta. DOI: https://doi.org/10.1107/S2053229623007179/dv3024izact1ntasup4.hkl
Structure factors: contains datablock izbt2c4n. DOI: https://doi.org/10.1107/S2053229623007179/dv3024izbt2c4nsup5.hkl
Structure factors: contains datablock izbt25dhba. DOI: https://doi.org/10.1107/S2053229623007179/dv3024izbt25dhbasup6.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2053229623007179/dv3024izbt1ntasup7.cml
Supporting information file. DOI: https://doi.org/10.1107/S2053229623007179/dv3024izbt24dhbasup8.cml
Supporting information file. DOI: https://doi.org/10.1107/S2053229623007179/dv3024izact1ntasup9.cml
Supporting information file. DOI: https://doi.org/10.1107/S2053229623007179/dv3024izbt2c4nsup10.cml
Supporting information file. DOI: https://doi.org/10.1107/S2053229623007179/dv3024izbt25dhbasup11.cml
Additional tables and figures. DOI: https://doi.org/10.1107/S2053229623007179/dv3024sup12.pdf
Data collection: APEX2 (Bruker, 2012) for izbt1nta, izbt24dhba, izact1nta, izbt2c4n. Cell
SAINT-Plus (Bruker, 2012) for izbt1nta, izbt24dhba, izact1nta, izbt2c4n. Data reduction: SAINT-Plus (Bruker, 2012) for izbt1nta, izbt24dhba, izact1nta, izbt2c4n. For all structures, program(s) used to solve structure: SHELXT2018 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b). Molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2020) for izbt1nta, izbt24dhba, izact1nta, izbt2c4n; ORTEP-3 for Windows (Farrugia, 2012) for izbt25dhba. Software used to prepare material for publication: WinGX (Farrugia, 2012) and XPREP (Bruker, 2012) for izbt1nta, izbt24dhba, izact1nta, izbt2c4n; WinGX (Farrugia, 2012) for izbt25dhba.C10H13N3O·C11H8O2 | F(000) = 768 |
Mr = 363.41 | Dx = 1.33 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 9890 reflections |
a = 7.4355 (13) Å | θ = 2.9–28.3° |
b = 34.195 (6) Å | µ = 0.09 mm−1 |
c = 7.7242 (14) Å | T = 173 K |
β = 112.512 (4)° | Block, colourless |
V = 1814.3 (6) Å3 | 0.34 × 0.28 × 0.12 mm |
Z = 4 |
Bruker APEXII CCD diffractometer | Rint = 0.033 |
φ and ω scans | θmax = 28.3°, θmin = 3.4° |
35501 measured reflections | h = −9→9 |
4511 independent reflections | k = −45→45 |
3552 reflections with I > 2σ(I) | l = −10→10 |
Refinement on F2 | 0 constraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.054 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.142 | w = 1/[σ2(Fo2) + (0.0637P)2 + 1.0375P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.001 |
4511 reflections | Δρmax = 0.54 e Å−3 |
254 parameters | Δρmin = −0.34 e Å−3 |
0 restraints |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.4865 (3) | 0.64234 (5) | 0.5961 (2) | 0.0289 (4) | |
H1 | 0.479346 | 0.614625 | 0.599541 | 0.035* | |
C2 | 0.5137 (2) | 0.66303 (4) | 0.7582 (2) | 0.0244 (3) | |
H2A | 0.528577 | 0.649764 | 0.870961 | 0.029* | |
C3 | 0.5189 (2) | 0.70353 (4) | 0.7527 (2) | 0.0208 (3) | |
C4 | 0.5009 (2) | 0.72157 (5) | 0.5857 (2) | 0.0264 (3) | |
H4 | 0.504198 | 0.749257 | 0.577421 | 0.032* | |
C5 | 0.4780 (3) | 0.69843 (5) | 0.4313 (2) | 0.0300 (4) | |
H5 | 0.467633 | 0.710899 | 0.317944 | 0.036* | |
C6 | 0.5592 (2) | 0.72591 (4) | 0.9309 (2) | 0.0219 (3) | |
C7 | 0.4945 (2) | 0.82004 (5) | 1.0579 (2) | 0.0269 (3) | |
C8 | 0.4585 (3) | 0.84331 (5) | 0.8828 (2) | 0.0367 (4) | |
H8A | 0.514858 | 0.829582 | 0.804171 | 0.055* | |
H8B | 0.519033 | 0.86913 | 0.916433 | 0.055* | |
H8C | 0.317967 | 0.846392 | 0.813647 | 0.055* | |
C9 | 0.5210 (3) | 0.84343 (5) | 1.2308 (2) | 0.0312 (4) | |
H9A | 0.630337 | 0.861863 | 1.253523 | 0.037* | |
H9B | 0.402059 | 0.859191 | 1.20623 | 0.037* | |
C10 | 0.5606 (3) | 0.82005 (6) | 1.4061 (2) | 0.0376 (4) | |
H10A | 0.448383 | 0.803278 | 1.389922 | 0.056* | |
H10B | 0.582875 | 0.837824 | 1.511822 | 0.056* | |
H10C | 0.676282 | 0.80377 | 1.430932 | 0.056* | |
C11 | 0.3204 (2) | 0.54602 (4) | 0.0208 (2) | 0.0218 (3) | |
C12 | 0.3179 (2) | 0.55966 (4) | −0.1480 (2) | 0.0241 (3) | |
H12 | 0.354523 | 0.585992 | −0.156468 | 0.029* | |
C13 | 0.2629 (2) | 0.53579 (5) | −0.3079 (2) | 0.0281 (3) | |
H13 | 0.26264 | 0.545884 | −0.42259 | 0.034* | |
C14 | 0.2099 (2) | 0.49802 (5) | −0.2971 (2) | 0.0289 (4) | |
H14 | 0.172404 | 0.481852 | −0.405159 | 0.035* | |
C15 | 0.2097 (2) | 0.48253 (5) | −0.1277 (2) | 0.0253 (3) | |
C16 | 0.2665 (2) | 0.50632 (4) | 0.0363 (2) | 0.0221 (3) | |
C17 | 0.2661 (2) | 0.48883 (5) | 0.2031 (2) | 0.0282 (3) | |
H17 | 0.304248 | 0.503862 | 0.314877 | 0.034* | |
C18 | 0.2117 (3) | 0.45067 (5) | 0.2051 (3) | 0.0346 (4) | |
H18 | 0.212744 | 0.439598 | 0.318294 | 0.042* | |
C19 | 0.1544 (3) | 0.42767 (5) | 0.0429 (3) | 0.0374 (4) | |
H19 | 0.116051 | 0.401269 | 0.046069 | 0.045* | |
C20 | 0.1539 (3) | 0.44330 (5) | −0.1191 (3) | 0.0334 (4) | |
H20 | 0.115288 | 0.427542 | −0.22866 | 0.04* | |
C21 | 0.3808 (2) | 0.57384 (5) | 0.1818 (2) | 0.0273 (3) | |
N1 | 0.4697 (2) | 0.65943 (4) | 0.43437 (19) | 0.0295 (3) | |
N2 | 0.4799 (2) | 0.76157 (4) | 0.91231 (18) | 0.0261 (3) | |
N3 | 0.5099 (2) | 0.78278 (4) | 1.07692 (18) | 0.0273 (3) | |
O1 | 0.66638 (17) | 0.71153 (3) | 1.08121 (15) | 0.0301 (3) | |
O2 | 0.3999 (2) | 0.61035 (4) | 0.13403 (18) | 0.0412 (3) | |
O3 | 0.4134 (3) | 0.56528 (4) | 0.34138 (18) | 0.0645 (5) | |
H2 | 0.385 (3) | 0.7684 (6) | 0.805 (3) | 0.039 (5)* | |
H2B | 0.432 (4) | 0.6256 (8) | 0.232 (4) | 0.063 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0369 (9) | 0.0208 (8) | 0.0284 (8) | −0.0006 (6) | 0.0117 (7) | −0.0033 (6) |
C2 | 0.0285 (8) | 0.0207 (7) | 0.0221 (7) | −0.0009 (6) | 0.0077 (6) | −0.0003 (6) |
C3 | 0.0202 (7) | 0.0208 (7) | 0.0193 (7) | 0.0001 (5) | 0.0051 (5) | −0.0027 (5) |
C4 | 0.0349 (9) | 0.0202 (7) | 0.0246 (7) | 0.0004 (6) | 0.0119 (6) | 0.0001 (6) |
C5 | 0.0404 (9) | 0.0287 (8) | 0.0232 (7) | −0.0007 (7) | 0.0148 (7) | −0.0006 (6) |
C6 | 0.0232 (7) | 0.0210 (7) | 0.0199 (7) | −0.0030 (6) | 0.0064 (6) | −0.0028 (5) |
C7 | 0.0236 (8) | 0.0261 (8) | 0.0295 (8) | −0.0014 (6) | 0.0085 (6) | −0.0070 (6) |
C8 | 0.0486 (11) | 0.0262 (9) | 0.0314 (9) | −0.0017 (7) | 0.0113 (8) | −0.0017 (7) |
C9 | 0.0349 (9) | 0.0269 (8) | 0.0332 (9) | −0.0017 (7) | 0.0145 (7) | −0.0080 (7) |
C10 | 0.0428 (10) | 0.0366 (10) | 0.0337 (9) | −0.0006 (8) | 0.0150 (8) | −0.0074 (7) |
C11 | 0.0234 (7) | 0.0218 (7) | 0.0201 (7) | 0.0016 (6) | 0.0083 (6) | −0.0012 (5) |
C12 | 0.0283 (8) | 0.0216 (7) | 0.0230 (7) | 0.0012 (6) | 0.0103 (6) | 0.0006 (6) |
C13 | 0.0335 (9) | 0.0307 (8) | 0.0205 (7) | 0.0028 (7) | 0.0106 (6) | 0.0001 (6) |
C14 | 0.0295 (8) | 0.0321 (8) | 0.0224 (7) | 0.0021 (7) | 0.0069 (6) | −0.0077 (6) |
C15 | 0.0219 (7) | 0.0239 (7) | 0.0285 (8) | 0.0016 (6) | 0.0081 (6) | −0.0028 (6) |
C16 | 0.0209 (7) | 0.0216 (7) | 0.0241 (7) | 0.0033 (6) | 0.0090 (6) | 0.0007 (6) |
C17 | 0.0320 (9) | 0.0267 (8) | 0.0294 (8) | 0.0029 (6) | 0.0156 (7) | 0.0021 (6) |
C18 | 0.0378 (10) | 0.0298 (9) | 0.0424 (10) | 0.0037 (7) | 0.0224 (8) | 0.0095 (7) |
C19 | 0.0381 (10) | 0.0232 (8) | 0.0527 (11) | −0.0032 (7) | 0.0195 (9) | 0.0022 (8) |
C20 | 0.0318 (9) | 0.0254 (8) | 0.0408 (10) | −0.0019 (7) | 0.0114 (7) | −0.0065 (7) |
C21 | 0.0344 (9) | 0.0241 (8) | 0.0229 (7) | −0.0005 (6) | 0.0105 (6) | −0.0019 (6) |
N1 | 0.0368 (8) | 0.0279 (7) | 0.0250 (7) | −0.0007 (6) | 0.0130 (6) | −0.0058 (5) |
N2 | 0.0306 (7) | 0.0231 (7) | 0.0194 (6) | 0.0020 (5) | 0.0037 (5) | −0.0051 (5) |
N3 | 0.0294 (7) | 0.0270 (7) | 0.0231 (6) | −0.0010 (5) | 0.0075 (5) | −0.0077 (5) |
O1 | 0.0364 (6) | 0.0266 (6) | 0.0193 (5) | 0.0020 (5) | 0.0017 (5) | −0.0001 (4) |
O2 | 0.0758 (10) | 0.0223 (6) | 0.0276 (6) | −0.0044 (6) | 0.0222 (7) | −0.0052 (5) |
O3 | 0.1335 (16) | 0.0346 (8) | 0.0231 (7) | −0.0192 (9) | 0.0272 (8) | −0.0066 (5) |
C1—N1 | 1.341 (2) | C11—C12 | 1.378 (2) |
C1—C2 | 1.384 (2) | C11—C16 | 1.433 (2) |
C1—H1 | 0.95 | C11—C21 | 1.492 (2) |
C2—C3 | 1.387 (2) | C12—C13 | 1.404 (2) |
C2—H2A | 0.95 | C12—H12 | 0.95 |
C3—C4 | 1.389 (2) | C13—C14 | 1.362 (2) |
C3—C6 | 1.5016 (19) | C13—H13 | 0.95 |
C4—C5 | 1.386 (2) | C14—C15 | 1.412 (2) |
C4—H4 | 0.95 | C14—H14 | 0.95 |
C5—N1 | 1.335 (2) | C15—C20 | 1.413 (2) |
C5—H5 | 0.95 | C15—C16 | 1.427 (2) |
C6—O1 | 1.2311 (18) | C16—C17 | 1.422 (2) |
C6—N2 | 1.338 (2) | C17—C18 | 1.368 (2) |
C7—N3 | 1.283 (2) | C17—H17 | 0.95 |
C7—C8 | 1.502 (2) | C18—C19 | 1.400 (3) |
C7—C9 | 1.504 (2) | C18—H18 | 0.95 |
C8—H8A | 0.98 | C19—C20 | 1.359 (3) |
C8—H8B | 0.98 | C19—H19 | 0.95 |
C8—H8C | 0.98 | C20—H20 | 0.95 |
C9—C10 | 1.501 (2) | C21—O3 | 1.198 (2) |
C9—H9A | 0.99 | C21—O2 | 1.325 (2) |
C9—H9B | 0.99 | N2—N3 | 1.4054 (17) |
C10—H10A | 0.98 | N2—H2 | 0.89 (2) |
C10—H10B | 0.98 | O2—H2B | 0.87 (3) |
C10—H10C | 0.98 | ||
N1—C1—C2 | 123.30 (15) | C12—C11—C16 | 119.79 (13) |
N1—C1—H1 | 118.3 | C12—C11—C21 | 117.61 (14) |
C2—C1—H1 | 118.3 | C16—C11—C21 | 122.60 (13) |
C1—C2—C3 | 118.61 (14) | C11—C12—C13 | 121.94 (14) |
C1—C2—H2A | 120.7 | C11—C12—H12 | 119 |
C3—C2—H2A | 120.7 | C13—C12—H12 | 119 |
C2—C3—C4 | 118.55 (13) | C14—C13—C12 | 119.39 (14) |
C2—C3—C6 | 118.61 (13) | C14—C13—H13 | 120.3 |
C4—C3—C6 | 122.66 (13) | C12—C13—H13 | 120.3 |
C5—C4—C3 | 118.82 (14) | C13—C14—C15 | 121.05 (14) |
C5—C4—H4 | 120.6 | C13—C14—H14 | 119.5 |
C3—C4—H4 | 120.6 | C15—C14—H14 | 119.5 |
N1—C5—C4 | 123.08 (15) | C14—C15—C20 | 120.28 (15) |
N1—C5—H5 | 118.5 | C14—C15—C16 | 120.26 (14) |
C4—C5—H5 | 118.5 | C20—C15—C16 | 119.46 (15) |
O1—C6—N2 | 124.39 (14) | C17—C16—C15 | 117.54 (14) |
O1—C6—C3 | 119.40 (13) | C17—C16—C11 | 124.88 (14) |
N2—C6—C3 | 116.15 (12) | C15—C16—C11 | 117.57 (13) |
N3—C7—C8 | 127.34 (14) | C18—C17—C16 | 120.98 (15) |
N3—C7—C9 | 116.82 (15) | C18—C17—H17 | 119.5 |
C8—C7—C9 | 115.82 (14) | C16—C17—H17 | 119.5 |
C7—C8—H8A | 109.5 | C17—C18—C19 | 121.03 (16) |
C7—C8—H8B | 109.5 | C17—C18—H18 | 119.5 |
H8A—C8—H8B | 109.5 | C19—C18—H18 | 119.5 |
C7—C8—H8C | 109.5 | C20—C19—C18 | 119.72 (16) |
H8A—C8—H8C | 109.5 | C20—C19—H19 | 120.1 |
H8B—C8—H8C | 109.5 | C18—C19—H19 | 120.1 |
C10—C9—C7 | 115.56 (14) | C19—C20—C15 | 121.26 (16) |
C10—C9—H9A | 108.4 | C19—C20—H20 | 119.4 |
C7—C9—H9A | 108.4 | C15—C20—H20 | 119.4 |
C10—C9—H9B | 108.4 | O3—C21—O2 | 121.05 (15) |
C7—C9—H9B | 108.4 | O3—C21—C11 | 125.43 (15) |
H9A—C9—H9B | 107.5 | O2—C21—C11 | 113.50 (13) |
C9—C10—H10A | 109.5 | C5—N1—C1 | 117.61 (14) |
C9—C10—H10B | 109.5 | C6—N2—N3 | 117.53 (12) |
H10A—C10—H10B | 109.5 | C6—N2—H2 | 119.9 (13) |
C9—C10—H10C | 109.5 | N3—N2—H2 | 120.1 (14) |
H10A—C10—H10C | 109.5 | C7—N3—N2 | 115.64 (13) |
H10B—C10—H10C | 109.5 | C21—O2—H2B | 110.2 (17) |
N1—C1—C2—C3 | 1.8 (3) | C12—C11—C16—C17 | 179.06 (15) |
C1—C2—C3—C4 | −1.4 (2) | C21—C11—C16—C17 | −0.8 (2) |
C1—C2—C3—C6 | −176.73 (14) | C12—C11—C16—C15 | −0.7 (2) |
C2—C3—C4—C5 | 0.2 (2) | C21—C11—C16—C15 | 179.46 (14) |
C6—C3—C4—C5 | 175.28 (15) | C15—C16—C17—C18 | −0.5 (2) |
C3—C4—C5—N1 | 0.9 (3) | C11—C16—C17—C18 | 179.73 (16) |
C2—C3—C6—O1 | 32.2 (2) | C16—C17—C18—C19 | −0.1 (3) |
C4—C3—C6—O1 | −142.93 (16) | C17—C18—C19—C20 | 0.4 (3) |
C2—C3—C6—N2 | −150.56 (15) | C18—C19—C20—C15 | −0.2 (3) |
C4—C3—C6—N2 | 34.3 (2) | C14—C15—C20—C19 | 179.39 (16) |
N3—C7—C9—C10 | −0.6 (2) | C16—C15—C20—C19 | −0.4 (2) |
C8—C7—C9—C10 | −178.93 (16) | C12—C11—C21—O3 | −170.22 (19) |
C16—C11—C12—C13 | 0.3 (2) | C16—C11—C21—O3 | 9.6 (3) |
C21—C11—C12—C13 | −179.86 (14) | C12—C11—C21—O2 | 8.6 (2) |
C11—C12—C13—C14 | 0.1 (2) | C16—C11—C21—O2 | −171.56 (15) |
C12—C13—C14—C15 | −0.1 (2) | C4—C5—N1—C1 | −0.7 (3) |
C13—C14—C15—C20 | 179.88 (16) | C2—C1—N1—C5 | −0.7 (3) |
C13—C14—C15—C16 | −0.3 (2) | O1—C6—N2—N3 | −4.8 (2) |
C14—C15—C16—C17 | −179.06 (14) | C3—C6—N2—N3 | 178.06 (13) |
C20—C15—C16—C17 | 0.7 (2) | C8—C7—N3—N2 | −3.4 (2) |
C14—C15—C16—C11 | 0.7 (2) | C9—C7—N3—N2 | 178.55 (14) |
C20—C15—C16—C11 | −179.47 (14) | C6—N2—N3—C7 | 156.63 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···O3 | 0.95 | 2.51 | 3.208 (2) | 130 |
C8—H8C···O1i | 0.98 | 2.62 | 3.128 (2) | 112 |
N2—H2···O1i | 0.89 (2) | 1.98 (2) | 2.8732 (17) | 174 (2) |
O2—H2B···N1 | 0.87 (3) | 1.88 (3) | 2.7472 (18) | 173 (2) |
Symmetry code: (i) x−1/2, −y+3/2, z−1/2. |
C10H13N3O·C7H6O4 | F(000) = 728 |
Mr = 345.35 | Dx = 1.383 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2614 reflections |
a = 11.0834 (6) Å | θ = 2.4–21.7° |
b = 13.8364 (8) Å | µ = 0.10 mm−1 |
c = 12.0014 (7) Å | T = 173 K |
β = 115.710 (3)° | Block, colourless |
V = 1658.26 (17) Å3 | 0.32 × 0.25 × 0.21 mm |
Z = 4 |
Bruker APEXII CCD diffractometer | Rint = 0.092 |
φ and ω scans | θmax = 28.0°, θmin = 2.1° |
25708 measured reflections | h = −14→14 |
4008 independent reflections | k = −14→18 |
1946 reflections with I > 2σ(I) | l = −15→15 |
Refinement on F2 | 0 constraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.061 | H-atom parameters constrained |
wR(F2) = 0.219 | w = 1/[σ2(Fo2) + (0.1075P)2 + 0.2167P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max < 0.001 |
4008 reflections | Δρmax = 0.70 e Å−3 |
248 parameters | Δρmin = −0.27 e Å−3 |
39 restraints |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1 | 0.2256 (3) | 0.3307 (2) | 0.1115 (2) | 0.0462 (7) | |
C2 | 0.3201 (3) | 0.3638 (2) | 0.2233 (3) | 0.0517 (7) | |
H2A | 0.294648 | 0.40267 | 0.274882 | 0.062* | |
C3 | 0.4529 (3) | 0.3395 (2) | 0.2596 (3) | 0.0565 (8) | |
H3 | 0.517455 | 0.363307 | 0.336671 | 0.068* | |
C4 | 0.4034 (3) | 0.2515 (3) | 0.0874 (3) | 0.0656 (9) | |
H4A | 0.431538 | 0.211008 | 0.039242 | 0.079* | |
C5 | 0.2688 (3) | 0.2722 (2) | 0.0432 (3) | 0.0611 (8) | |
H5A | 0.20651 | 0.246347 | −0.033661 | 0.073* | |
C6 | 0.0790 (3) | 0.3539 (2) | 0.0579 (3) | 0.0486 (7) | |
C7 | −0.0363 (4) | 0.4971 (3) | 0.2909 (4) | 0.0926 (13) | |
H7A | −0.085959 | 0.531016 | 0.329609 | 0.139* | |
H7B | −0.00322 | 0.435334 | 0.333219 | 0.139* | |
H7C | 0.03954 | 0.536836 | 0.297237 | 0.139* | |
C8 | −0.1270 (3) | 0.4788 (2) | 0.1576 (4) | 0.0669 (9) | |
C9A | −0.2718 (8) | 0.5139 (7) | 0.0969 (7) | 0.068 (2) | 0.681 (9) |
H9A1 | −0.273761 | 0.584595 | 0.109021 | 0.082* | 0.681 (9) |
H9A2 | −0.310308 | 0.501278 | 0.006909 | 0.082* | 0.681 (9) |
C10A | −0.3526 (6) | 0.4664 (5) | 0.1481 (7) | 0.093 (2) | 0.681 (9) |
H10A | −0.444645 | 0.490666 | 0.107151 | 0.14* | 0.681 (9) |
H10B | −0.352183 | 0.396541 | 0.134913 | 0.14* | 0.681 (9) |
H10C | −0.315658 | 0.479809 | 0.236963 | 0.14* | 0.681 (9) |
C9B | −0.2550 (16) | 0.5059 (17) | 0.1534 (14) | 0.086 (5) | 0.319 (9) |
H9B1 | −0.266817 | 0.476516 | 0.223158 | 0.104* | 0.319 (9) |
H9B2 | −0.261527 | 0.577059 | 0.158046 | 0.104* | 0.319 (9) |
C10B | −0.3542 (15) | 0.4705 (11) | 0.0377 (13) | 0.095 (4) | 0.319 (9) |
H10D | −0.443548 | 0.486929 | 0.029738 | 0.143* | 0.319 (9) |
H10E | −0.340753 | 0.500108 | −0.030243 | 0.143* | 0.319 (9) |
H10F | −0.346015 | 0.400111 | 0.034516 | 0.143* | 0.319 (9) |
N1 | 0.0399 (2) | 0.40980 (18) | 0.1262 (2) | 0.0549 (7) | |
H1 | 0.098313 | 0.429903 | 0.199395 | 0.066* | |
N2 | 0.4951 (2) | 0.28521 (19) | 0.1933 (2) | 0.0582 (7) | |
N3 | −0.0929 (2) | 0.43602 (19) | 0.0816 (3) | 0.0626 (7) | |
O1 | 0.00257 (19) | 0.32187 (16) | −0.0423 (2) | 0.0651 (6) | |
C11 | 0.9062 (2) | 0.17767 (19) | 0.1967 (2) | 0.0437 (6) | |
C12 | 0.9337 (3) | 0.1210 (2) | 0.1135 (3) | 0.0462 (7) | |
C13 | 1.0644 (3) | 0.0963 (2) | 0.1403 (3) | 0.0483 (7) | |
H13 | 1.082847 | 0.058264 | 0.083628 | 0.058* | |
C14 | 1.1674 (2) | 0.1266 (2) | 0.2486 (3) | 0.0461 (7) | |
C15 | 1.1424 (3) | 0.1830 (2) | 0.3328 (3) | 0.0518 (7) | |
H15 | 1.213819 | 0.20393 | 0.407784 | 0.062* | |
C16 | 1.0126 (3) | 0.2074 (2) | 0.3052 (3) | 0.0497 (7) | |
H16 | 0.994989 | 0.245932 | 0.362002 | 0.06* | |
C17 | 0.7666 (3) | 0.2014 (2) | 0.1685 (3) | 0.0473 (7) | |
O2 | 0.74959 (18) | 0.25109 (16) | 0.25335 (18) | 0.0598 (6) | |
H2 | 0.667349 | 0.259116 | 0.231809 | 0.09* | |
O3 | 0.67159 (18) | 0.17496 (15) | 0.07253 (18) | 0.0559 (6) | |
O4 | 0.83565 (18) | 0.08837 (17) | 0.00710 (18) | 0.0614 (6) | |
H4 | 0.760984 | 0.105658 | 0.002523 | 0.092* | |
O5 | 1.29304 (18) | 0.09825 (15) | 0.27164 (19) | 0.0567 (6) | |
H5 | 1.348308 | 0.124958 | 0.336623 | 0.085* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0322 (13) | 0.0605 (18) | 0.0483 (17) | 0.0021 (12) | 0.0197 (13) | 0.0023 (13) |
C2 | 0.0377 (15) | 0.069 (2) | 0.0518 (18) | 0.0077 (13) | 0.0226 (14) | 0.0001 (15) |
C3 | 0.0337 (14) | 0.078 (2) | 0.0557 (18) | 0.0036 (14) | 0.0172 (14) | −0.0056 (16) |
C4 | 0.0418 (16) | 0.097 (3) | 0.066 (2) | 0.0071 (16) | 0.0309 (17) | −0.0140 (18) |
C5 | 0.0379 (15) | 0.088 (2) | 0.0595 (19) | 0.0001 (15) | 0.0230 (15) | −0.0129 (17) |
C6 | 0.0323 (14) | 0.0587 (18) | 0.0574 (19) | 0.0000 (12) | 0.0218 (15) | 0.0013 (14) |
C7 | 0.080 (3) | 0.106 (3) | 0.125 (4) | −0.013 (2) | 0.076 (3) | −0.028 (3) |
C8 | 0.0505 (18) | 0.064 (2) | 0.105 (3) | 0.0021 (15) | 0.050 (2) | 0.0004 (19) |
C9A | 0.056 (4) | 0.088 (4) | 0.071 (5) | 0.016 (3) | 0.037 (4) | 0.006 (4) |
C10A | 0.064 (4) | 0.103 (5) | 0.135 (6) | 0.010 (3) | 0.064 (4) | 0.018 (4) |
C9B | 0.063 (8) | 0.110 (10) | 0.113 (11) | 0.027 (7) | 0.063 (8) | 0.018 (10) |
C10B | 0.098 (9) | 0.086 (9) | 0.132 (10) | 0.009 (7) | 0.079 (8) | −0.007 (8) |
N1 | 0.0325 (12) | 0.0766 (17) | 0.0606 (16) | 0.0031 (11) | 0.0250 (12) | −0.0011 (13) |
N2 | 0.0351 (12) | 0.0826 (19) | 0.0602 (16) | 0.0074 (12) | 0.0237 (13) | −0.0070 (14) |
N3 | 0.0336 (12) | 0.0738 (18) | 0.0819 (19) | 0.0088 (11) | 0.0265 (13) | 0.0040 (14) |
O1 | 0.0379 (11) | 0.0789 (15) | 0.0678 (15) | 0.0051 (10) | 0.0129 (11) | −0.0127 (12) |
C11 | 0.0340 (13) | 0.0511 (17) | 0.0505 (16) | 0.0028 (11) | 0.0226 (13) | 0.0028 (13) |
C12 | 0.0325 (13) | 0.0589 (18) | 0.0467 (17) | −0.0021 (12) | 0.0168 (13) | −0.0012 (13) |
C13 | 0.0383 (14) | 0.0592 (18) | 0.0535 (17) | 0.0019 (12) | 0.0257 (14) | −0.0057 (14) |
C14 | 0.0311 (13) | 0.0525 (17) | 0.0561 (18) | 0.0036 (11) | 0.0201 (14) | −0.0002 (13) |
C15 | 0.0346 (14) | 0.0643 (19) | 0.0531 (18) | −0.0004 (12) | 0.0158 (13) | −0.0096 (14) |
C16 | 0.0364 (14) | 0.0598 (18) | 0.0549 (18) | 0.0042 (12) | 0.0216 (14) | −0.0067 (14) |
C17 | 0.0352 (14) | 0.0590 (18) | 0.0507 (17) | 0.0041 (12) | 0.0215 (14) | 0.0058 (14) |
O2 | 0.0373 (10) | 0.0837 (15) | 0.0614 (13) | 0.0108 (10) | 0.0242 (10) | −0.0097 (11) |
O3 | 0.0325 (10) | 0.0817 (15) | 0.0535 (13) | 0.0023 (9) | 0.0187 (10) | −0.0035 (10) |
O4 | 0.0361 (10) | 0.0921 (16) | 0.0542 (13) | 0.0026 (10) | 0.0179 (10) | −0.0153 (11) |
O5 | 0.0316 (10) | 0.0738 (14) | 0.0651 (14) | 0.0044 (9) | 0.0212 (10) | −0.0110 (10) |
C1—C2 | 1.374 (4) | C9B—C10B | 1.432 (10) |
C1—C5 | 1.378 (4) | C9B—H9B1 | 0.99 |
C1—C6 | 1.500 (4) | C9B—H9B2 | 0.99 |
C2—C3 | 1.383 (4) | C10B—H10D | 0.98 |
C2—H2A | 0.95 | C10B—H10E | 0.98 |
C3—N2 | 1.319 (4) | C10B—H10F | 0.98 |
C3—H3 | 0.95 | N1—N3 | 1.379 (3) |
C4—N2 | 1.321 (4) | N1—H1 | 0.88 |
C4—C5 | 1.379 (4) | C11—C16 | 1.386 (4) |
C4—H4A | 0.95 | C11—C12 | 1.403 (4) |
C5—H5A | 0.95 | C11—C17 | 1.471 (3) |
C6—O1 | 1.215 (3) | C12—O4 | 1.346 (3) |
C6—N1 | 1.329 (4) | C12—C13 | 1.384 (3) |
C7—C8 | 1.496 (5) | C13—C14 | 1.371 (4) |
C7—H7A | 0.98 | C13—H13 | 0.95 |
C7—H7B | 0.98 | C14—O5 | 1.355 (3) |
C7—H7C | 0.98 | C14—C15 | 1.397 (4) |
C8—N3 | 1.273 (4) | C15—C16 | 1.371 (3) |
C8—C9B | 1.447 (18) | C15—H15 | 0.95 |
C8—C9A | 1.526 (9) | C16—H16 | 0.95 |
C9A—C10A | 1.445 (7) | C17—O3 | 1.232 (3) |
C9A—H9A1 | 0.99 | C17—O2 | 1.308 (3) |
C9A—H9A2 | 0.99 | O2—H2 | 0.84 |
C10A—H10A | 0.98 | O4—H4 | 0.84 |
C10A—H10B | 0.98 | O5—H5 | 0.84 |
C10A—H10C | 0.98 | ||
C2—C1—C5 | 117.6 (2) | C10B—C9B—C8 | 105.9 (13) |
C2—C1—C6 | 124.9 (2) | C10B—C9B—H9B1 | 110.6 |
C5—C1—C6 | 117.5 (3) | C8—C9B—H9B1 | 110.6 |
C1—C2—C3 | 118.8 (3) | C10B—C9B—H9B2 | 110.6 |
C1—C2—H2A | 120.6 | C8—C9B—H9B2 | 110.6 |
C3—C2—H2A | 120.6 | H9B1—C9B—H9B2 | 108.7 |
N2—C3—C2 | 123.8 (3) | C9B—C10B—H10D | 109.5 |
N2—C3—H3 | 118.1 | C9B—C10B—H10E | 109.5 |
C2—C3—H3 | 118.1 | H10D—C10B—H10E | 109.5 |
N2—C4—C5 | 123.4 (3) | C9B—C10B—H10F | 109.5 |
N2—C4—H4A | 118.3 | H10D—C10B—H10F | 109.5 |
C5—C4—H4A | 118.3 | H10E—C10B—H10F | 109.5 |
C1—C5—C4 | 119.4 (3) | C6—N1—N3 | 119.5 (3) |
C1—C5—H5A | 120.3 | C6—N1—H1 | 120.2 |
C4—C5—H5A | 120.3 | N3—N1—H1 | 120.2 |
O1—C6—N1 | 123.3 (2) | C3—N2—C4 | 117.0 (2) |
O1—C6—C1 | 120.5 (2) | C8—N3—N1 | 116.2 (3) |
N1—C6—C1 | 116.3 (3) | C16—C11—C12 | 118.4 (2) |
C8—C7—H7A | 109.5 | C16—C11—C17 | 122.1 (2) |
C8—C7—H7B | 109.5 | C12—C11—C17 | 119.5 (2) |
H7A—C7—H7B | 109.5 | O4—C12—C13 | 118.1 (2) |
C8—C7—H7C | 109.5 | O4—C12—C11 | 121.9 (2) |
H7A—C7—H7C | 109.5 | C13—C12—C11 | 120.1 (3) |
H7B—C7—H7C | 109.5 | C14—C13—C12 | 120.1 (2) |
N3—C8—C9B | 133.3 (7) | C14—C13—H13 | 119.9 |
N3—C8—C7 | 125.0 (3) | C12—C13—H13 | 119.9 |
C9B—C8—C7 | 100.8 (6) | O5—C14—C13 | 117.7 (2) |
N3—C8—C9A | 112.6 (4) | O5—C14—C15 | 121.5 (2) |
C7—C8—C9A | 122.4 (4) | C13—C14—C15 | 120.8 (2) |
C10A—C9A—C8 | 111.7 (6) | C16—C15—C14 | 118.7 (3) |
C10A—C9A—H9A1 | 109.3 | C16—C15—H15 | 120.7 |
C8—C9A—H9A1 | 109.3 | C14—C15—H15 | 120.7 |
C10A—C9A—H9A2 | 109.3 | C15—C16—C11 | 122.0 (3) |
C8—C9A—H9A2 | 109.3 | C15—C16—H16 | 119 |
H9A1—C9A—H9A2 | 107.9 | C11—C16—H16 | 119 |
C9A—C10A—H10A | 109.5 | O3—C17—O2 | 122.1 (2) |
C9A—C10A—H10B | 109.5 | O3—C17—C11 | 122.4 (3) |
H10A—C10A—H10B | 109.5 | O2—C17—C11 | 115.5 (3) |
C9A—C10A—H10C | 109.5 | C17—O2—H2 | 109.5 |
H10A—C10A—H10C | 109.5 | C12—O4—H4 | 109.5 |
H10B—C10A—H10C | 109.5 | C14—O5—H5 | 109.5 |
C5—C1—C2—C3 | 2.0 (4) | C9A—C8—N3—N1 | 174.3 (4) |
C6—C1—C2—C3 | −177.7 (3) | C6—N1—N3—C8 | 171.1 (3) |
C1—C2—C3—N2 | −0.6 (5) | C16—C11—C12—O4 | 179.1 (3) |
C2—C1—C5—C4 | −1.7 (5) | C17—C11—C12—O4 | 0.8 (4) |
C6—C1—C5—C4 | 178.1 (3) | C16—C11—C12—C13 | −0.1 (4) |
N2—C4—C5—C1 | −0.1 (5) | C17—C11—C12—C13 | −178.5 (2) |
C2—C1—C6—O1 | 179.6 (3) | O4—C12—C13—C14 | −178.9 (3) |
C5—C1—C6—O1 | −0.2 (4) | C11—C12—C13—C14 | 0.4 (4) |
C2—C1—C6—N1 | −0.9 (4) | C12—C13—C14—O5 | 178.4 (3) |
C5—C1—C6—N1 | 179.4 (3) | C12—C13—C14—C15 | −0.3 (4) |
N3—C8—C9A—C10A | 116.4 (6) | O5—C14—C15—C16 | −178.6 (3) |
C7—C8—C9A—C10A | −65.7 (8) | C13—C14—C15—C16 | 0.1 (4) |
N3—C8—C9B—C10B | 2 (2) | C14—C15—C16—C11 | 0.2 (5) |
C7—C8—C9B—C10B | −166.8 (13) | C12—C11—C16—C15 | −0.1 (4) |
O1—C6—N1—N3 | −2.0 (4) | C17—C11—C16—C15 | 178.2 (3) |
C1—C6—N1—N3 | 178.5 (2) | C16—C11—C17—O3 | −179.7 (3) |
C2—C3—N2—C4 | −1.1 (5) | C12—C11—C17—O3 | −1.4 (4) |
C5—C4—N2—C3 | 1.5 (5) | C16—C11—C17—O2 | −1.0 (4) |
C9B—C8—N3—N1 | −170.6 (12) | C12—C11—C17—O2 | 177.3 (2) |
C7—C8—N3—N1 | −3.6 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O5i | 0.88 | 2.58 | 3.124 (3) | 121 |
O2—H2···N2 | 0.84 | 1.8 | 2.633 (3) | 175 |
C4—H4A···O3 | 0.95 | 2.56 | 3.233 (3) | 128 |
O4—H4···O3 | 0.84 | 1.82 | 2.568 (3) | 147 |
O5—H5···O1ii | 0.84 | 1.85 | 2.665 (3) | 163 |
Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) x+3/2, −y+1/2, z+1/2. |
C9H11N3O·C11H8O2 | F(000) = 736 |
Mr = 349.38 | Dx = 1.354 Mg m−3 |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C -2yc | Cell parameters from 9944 reflections |
a = 7.6312 (3) Å | θ = 2.4–32.0° |
b = 33.5293 (12) Å | µ = 0.09 mm−1 |
c = 7.3493 (3) Å | T = 173 K |
β = 114.298 (1)° | Plate, colourless |
V = 1713.88 (12) Å3 | 0.72 × 0.33 × 0.08 mm |
Z = 4 |
Bruker APEXII CCD diffractometer | 6145 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.056 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001; Krause et al., 2015) | θmax = 33.7°, θmin = 2.4° |
Tmin = 0.684, Tmax = 0.747 | h = −11→11 |
39441 measured reflections | k = −52→52 |
6819 independent reflections | l = −11→11 |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.043 | w = 1/[σ2(Fo2) + (0.0746P)2 + 0.0558P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.122 | (Δ/σ)max = 0.001 |
S = 1.08 | Δρmax = 0.33 e Å−3 |
6819 reflections | Δρmin = −0.17 e Å−3 |
238 parameters | Absolute structure: Flack x determined using 2626 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
2 restraints | Absolute structure parameter: 0.0 (3) |
0 constraints |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.4245 (2) | 0.64077 (4) | 0.5306 (3) | 0.0271 (3) | |
H1 | 0.427394 | 0.612495 | 0.5399 | 0.033* | |
C2 | 0.2532 (2) | 0.66022 (4) | 0.4942 (2) | 0.0245 (3) | |
H2 | 0.140806 | 0.645537 | 0.476333 | 0.029* | |
C3 | 0.2488 (2) | 0.70167 (4) | 0.4844 (2) | 0.0213 (2) | |
C4 | 0.4160 (2) | 0.72176 (4) | 0.5094 (2) | 0.0268 (3) | |
H4 | 0.417923 | 0.750066 | 0.504539 | 0.032* | |
C5 | 0.5808 (2) | 0.69982 (5) | 0.5418 (3) | 0.0294 (3) | |
H5 | 0.694221 | 0.713739 | 0.556449 | 0.035* | |
C6 | 0.0586 (2) | 0.72170 (4) | 0.4316 (2) | 0.0231 (2) | |
C7 | −0.1291 (2) | 0.81130 (4) | 0.4976 (2) | 0.0270 (3) | |
C8 | 0.0322 (3) | 0.84017 (5) | 0.5454 (3) | 0.0378 (4) | |
H8A | 0.099418 | 0.843103 | 0.690592 | 0.057* | |
H8B | −0.018815 | 0.866102 | 0.485523 | 0.057* | |
H8C | 0.122164 | 0.830294 | 0.491653 | 0.057* | |
C9 | −0.3242 (3) | 0.82752 (6) | 0.4609 (3) | 0.0387 (4) | |
H9A | −0.325317 | 0.836275 | 0.587683 | 0.058* | |
H9B | −0.421165 | 0.806654 | 0.402073 | 0.058* | |
H9C | −0.353539 | 0.850212 | 0.369082 | 0.058* | |
C10 | 0.98959 (19) | 0.54175 (4) | 0.6266 (2) | 0.0229 (3) | |
C11 | 1.1694 (2) | 0.55617 (5) | 0.6594 (2) | 0.0275 (3) | |
H11 | 1.18928 | 0.584175 | 0.662443 | 0.033* | |
C12 | 1.3245 (2) | 0.53034 (5) | 0.6887 (3) | 0.0330 (3) | |
H12 | 1.44702 | 0.54094 | 0.710834 | 0.04* | |
C13 | 1.2980 (2) | 0.49021 (5) | 0.6851 (3) | 0.0321 (3) | |
H13 | 1.402665 | 0.472883 | 0.704124 | 0.039* | |
C14 | 1.1176 (2) | 0.47396 (5) | 0.6536 (2) | 0.0263 (3) | |
C15 | 0.9586 (2) | 0.49954 (4) | 0.6251 (2) | 0.0228 (2) | |
C16 | 0.7820 (2) | 0.48134 (5) | 0.5987 (3) | 0.0307 (3) | |
H16 | 0.674184 | 0.497554 | 0.581332 | 0.037* | |
C17 | 0.7649 (3) | 0.44058 (5) | 0.5979 (3) | 0.0362 (4) | |
H17 | 0.645341 | 0.429103 | 0.580891 | 0.043* | |
C18 | 0.9200 (3) | 0.41547 (5) | 0.6216 (3) | 0.0375 (4) | |
H18 | 0.905031 | 0.38732 | 0.618488 | 0.045* | |
C19 | 1.0922 (3) | 0.43199 (5) | 0.6491 (3) | 0.0340 (3) | |
H19 | 1.197449 | 0.415057 | 0.665593 | 0.041* | |
C20 | 0.8321 (2) | 0.57131 (4) | 0.5883 (2) | 0.0249 (3) | |
N1 | 0.58678 (19) | 0.65991 (4) | 0.5534 (2) | 0.0284 (3) | |
N2 | 0.06057 (18) | 0.75731 (4) | 0.5167 (2) | 0.0249 (2) | |
H2A | 0.168276 | 0.76959 | 0.591197 | 0.03* | |
N3 | −0.12045 (19) | 0.77355 (4) | 0.4788 (2) | 0.0270 (3) | |
O1 | −0.08842 (17) | 0.70564 (3) | 0.3110 (2) | 0.0312 (3) | |
O2 | 0.89085 (18) | 0.60918 (3) | 0.6040 (2) | 0.0338 (3) | |
H2B | 0.797958 | 0.62443 | 0.58666 | 0.051* | |
O3 | 0.66461 (19) | 0.56323 (4) | 0.5423 (3) | 0.0446 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0247 (6) | 0.0208 (5) | 0.0370 (7) | 0.0017 (5) | 0.0138 (6) | 0.0004 (5) |
C2 | 0.0205 (6) | 0.0196 (5) | 0.0317 (7) | −0.0001 (4) | 0.0090 (5) | 0.0007 (5) |
C3 | 0.0190 (5) | 0.0195 (5) | 0.0236 (6) | 0.0011 (4) | 0.0069 (5) | 0.0001 (5) |
C4 | 0.0251 (6) | 0.0204 (5) | 0.0359 (8) | −0.0021 (5) | 0.0137 (6) | −0.0015 (5) |
C5 | 0.0240 (7) | 0.0260 (6) | 0.0415 (8) | −0.0031 (5) | 0.0169 (6) | −0.0027 (6) |
C6 | 0.0199 (6) | 0.0187 (5) | 0.0274 (6) | 0.0004 (4) | 0.0064 (5) | 0.0021 (5) |
C7 | 0.0292 (7) | 0.0231 (6) | 0.0262 (6) | 0.0057 (5) | 0.0088 (6) | 0.0027 (5) |
C8 | 0.0355 (9) | 0.0235 (7) | 0.0441 (10) | −0.0003 (6) | 0.0062 (7) | 0.0027 (6) |
C9 | 0.0390 (9) | 0.0343 (8) | 0.0450 (10) | 0.0149 (7) | 0.0195 (8) | 0.0070 (7) |
C10 | 0.0184 (6) | 0.0237 (6) | 0.0272 (6) | 0.0007 (4) | 0.0100 (5) | −0.0006 (5) |
C11 | 0.0196 (6) | 0.0282 (7) | 0.0352 (7) | −0.0008 (5) | 0.0117 (6) | 0.0042 (6) |
C12 | 0.0199 (6) | 0.0389 (8) | 0.0415 (9) | 0.0038 (6) | 0.0138 (6) | 0.0094 (7) |
C13 | 0.0246 (7) | 0.0364 (8) | 0.0373 (8) | 0.0094 (6) | 0.0147 (6) | 0.0083 (6) |
C14 | 0.0266 (7) | 0.0263 (6) | 0.0263 (6) | 0.0056 (5) | 0.0113 (6) | 0.0037 (5) |
C15 | 0.0211 (6) | 0.0223 (6) | 0.0247 (6) | 0.0008 (5) | 0.0091 (5) | −0.0005 (5) |
C16 | 0.0252 (7) | 0.0242 (6) | 0.0422 (9) | −0.0023 (5) | 0.0133 (6) | −0.0025 (6) |
C17 | 0.0316 (8) | 0.0253 (7) | 0.0475 (10) | −0.0054 (6) | 0.0121 (7) | −0.0022 (6) |
C18 | 0.0416 (9) | 0.0223 (7) | 0.0428 (9) | 0.0002 (6) | 0.0115 (8) | −0.0022 (6) |
C19 | 0.0377 (9) | 0.0255 (7) | 0.0368 (8) | 0.0089 (6) | 0.0134 (7) | 0.0025 (6) |
C20 | 0.0212 (6) | 0.0213 (6) | 0.0338 (7) | −0.0011 (5) | 0.0129 (5) | −0.0033 (5) |
N1 | 0.0233 (6) | 0.0260 (6) | 0.0386 (7) | 0.0013 (5) | 0.0155 (5) | −0.0018 (5) |
N2 | 0.0189 (5) | 0.0204 (5) | 0.0307 (6) | 0.0019 (4) | 0.0054 (5) | −0.0012 (4) |
N3 | 0.0214 (5) | 0.0241 (6) | 0.0337 (7) | 0.0038 (4) | 0.0095 (5) | 0.0017 (4) |
O1 | 0.0211 (5) | 0.0240 (5) | 0.0382 (6) | 0.0005 (4) | 0.0017 (4) | −0.0036 (4) |
O2 | 0.0219 (5) | 0.0207 (5) | 0.0578 (8) | −0.0017 (4) | 0.0152 (5) | −0.0047 (5) |
O3 | 0.0235 (6) | 0.0256 (5) | 0.0863 (12) | −0.0018 (4) | 0.0242 (6) | −0.0063 (6) |
C1—N1 | 1.342 (2) | C10—C15 | 1.4344 (19) |
C1—C2 | 1.385 (2) | C10—C20 | 1.4923 (19) |
C1—H1 | 0.95 | C11—C12 | 1.409 (2) |
C2—C3 | 1.3914 (18) | C11—H11 | 0.95 |
C2—H2 | 0.95 | C12—C13 | 1.359 (2) |
C3—C4 | 1.386 (2) | C12—H12 | 0.95 |
C3—C6 | 1.4987 (19) | C13—C14 | 1.409 (2) |
C4—C5 | 1.390 (2) | C13—H13 | 0.95 |
C4—H4 | 0.95 | C14—C19 | 1.419 (2) |
C5—N1 | 1.340 (2) | C14—C15 | 1.4293 (19) |
C5—H5 | 0.95 | C15—C16 | 1.418 (2) |
C6—O1 | 1.2311 (18) | C16—C17 | 1.372 (2) |
C6—N2 | 1.3450 (18) | C16—H16 | 0.95 |
C7—N3 | 1.2778 (19) | C17—C18 | 1.403 (3) |
C7—C8 | 1.490 (2) | C17—H17 | 0.95 |
C7—C9 | 1.501 (2) | C18—C19 | 1.362 (3) |
C8—H8A | 0.98 | C18—H18 | 0.95 |
C8—H8B | 0.98 | C19—H19 | 0.95 |
C8—H8C | 0.98 | C20—O3 | 1.2109 (18) |
C9—H9A | 0.98 | C20—O2 | 1.3357 (17) |
C9—H9B | 0.98 | N2—N3 | 1.4021 (17) |
C9—H9C | 0.98 | N2—H2A | 0.88 |
C10—C11 | 1.3794 (19) | O2—H2B | 0.84 |
N1—C1—C2 | 123.21 (13) | C10—C11—C12 | 121.57 (14) |
N1—C1—H1 | 118.4 | C10—C11—H11 | 119.2 |
C2—C1—H1 | 118.4 | C12—C11—H11 | 119.2 |
C1—C2—C3 | 118.74 (13) | C13—C12—C11 | 119.80 (15) |
C1—C2—H2 | 120.6 | C13—C12—H12 | 120.1 |
C3—C2—H2 | 120.6 | C11—C12—H12 | 120.1 |
C4—C3—C2 | 118.52 (12) | C12—C13—C14 | 120.87 (14) |
C4—C3—C6 | 123.86 (12) | C12—C13—H13 | 119.6 |
C2—C3—C6 | 117.45 (12) | C14—C13—H13 | 119.6 |
C3—C4—C5 | 118.92 (12) | C13—C14—C19 | 120.15 (14) |
C3—C4—H4 | 120.5 | C13—C14—C15 | 120.38 (14) |
C5—C4—H4 | 120.5 | C19—C14—C15 | 119.47 (14) |
N1—C5—C4 | 122.97 (13) | C16—C15—C14 | 117.61 (13) |
N1—C5—H5 | 118.5 | C16—C15—C10 | 124.78 (13) |
C4—C5—H5 | 118.5 | C14—C15—C10 | 117.61 (13) |
O1—C6—N2 | 123.76 (14) | C17—C16—C15 | 120.83 (15) |
O1—C6—C3 | 119.27 (13) | C17—C16—H16 | 119.6 |
N2—C6—C3 | 116.95 (12) | C15—C16—H16 | 119.6 |
N3—C7—C8 | 126.46 (15) | C16—C17—C18 | 121.53 (16) |
N3—C7—C9 | 115.53 (15) | C16—C17—H17 | 119.2 |
C8—C7—C9 | 117.98 (14) | C18—C17—H17 | 119.2 |
C7—C8—H8A | 109.5 | C19—C18—C17 | 119.15 (15) |
C7—C8—H8B | 109.5 | C19—C18—H18 | 120.4 |
H8A—C8—H8B | 109.5 | C17—C18—H18 | 120.4 |
C7—C8—H8C | 109.5 | C18—C19—C14 | 121.39 (15) |
H8A—C8—H8C | 109.5 | C18—C19—H19 | 119.3 |
H8B—C8—H8C | 109.5 | C14—C19—H19 | 119.3 |
C7—C9—H9A | 109.5 | O3—C20—O2 | 120.99 (13) |
C7—C9—H9B | 109.5 | O3—C20—C10 | 125.43 (13) |
H9A—C9—H9B | 109.5 | O2—C20—C10 | 113.56 (12) |
C7—C9—H9C | 109.5 | C5—N1—C1 | 117.63 (13) |
H9A—C9—H9C | 109.5 | C6—N2—N3 | 115.52 (12) |
H9B—C9—H9C | 109.5 | C6—N2—H2A | 122.2 |
C11—C10—C15 | 119.76 (12) | N3—N2—H2A | 122.2 |
C11—C10—C20 | 117.79 (13) | C7—N3—N2 | 117.00 (13) |
C15—C10—C20 | 122.43 (12) | C20—O2—H2B | 109.5 |
N1—C1—C2—C3 | −1.3 (3) | C20—C10—C15—C16 | −3.5 (2) |
C1—C2—C3—C4 | 0.6 (2) | C11—C10—C15—C14 | −1.5 (2) |
C1—C2—C3—C6 | 176.11 (14) | C20—C10—C15—C14 | 176.86 (13) |
C2—C3—C4—C5 | 0.5 (2) | C14—C15—C16—C17 | −0.9 (2) |
C6—C3—C4—C5 | −174.67 (14) | C10—C15—C16—C17 | 179.51 (16) |
C3—C4—C5—N1 | −1.1 (3) | C15—C16—C17—C18 | −0.5 (3) |
C4—C3—C6—O1 | 139.64 (16) | C16—C17—C18—C19 | 1.0 (3) |
C2—C3—C6—O1 | −35.6 (2) | C17—C18—C19—C14 | −0.2 (3) |
C4—C3—C6—N2 | −38.5 (2) | C13—C14—C19—C18 | 179.09 (18) |
C2—C3—C6—N2 | 146.30 (14) | C15—C14—C19—C18 | −1.1 (3) |
C15—C10—C11—C12 | 1.1 (2) | C11—C10—C20—O3 | 174.12 (18) |
C20—C10—C11—C12 | −177.37 (15) | C15—C10—C20—O3 | −4.3 (2) |
C10—C11—C12—C13 | −0.1 (3) | C11—C10—C20—O2 | −4.2 (2) |
C11—C12—C13—C14 | −0.4 (3) | C15—C10—C20—O2 | 177.43 (14) |
C12—C13—C14—C19 | 179.62 (17) | C4—C5—N1—C1 | 0.6 (3) |
C12—C13—C14—C15 | −0.1 (2) | C2—C1—N1—C5 | 0.6 (3) |
C13—C14—C15—C16 | −178.58 (15) | O1—C6—N2—N3 | 7.5 (2) |
C19—C14—C15—C16 | 1.7 (2) | C3—C6—N2—N3 | −174.42 (12) |
C13—C14—C15—C10 | 1.1 (2) | C8—C7—N3—N2 | 3.5 (2) |
C19—C14—C15—C10 | −178.71 (15) | C9—C7—N3—N2 | −178.53 (14) |
C11—C10—C15—C16 | 178.10 (15) | C6—N2—N3—C7 | −157.47 (14) |
C7H4ClNO4·C10H13N3O | F(000) = 816 |
Mr = 392.79 | Dx = 1.483 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 9966 reflections |
a = 7.2682 (3) Å | θ = 2.4–30.8° |
b = 34.0775 (15) Å | µ = 0.26 mm−1 |
c = 7.6124 (3) Å | T = 173 K |
β = 111.081 (2)° | Plate, colourless |
V = 1759.27 (13) Å3 | 0.46 × 0.26 × 0.11 mm |
Z = 4 |
Bruker APEXII CCD diffractometer | Rint = 0.081 |
φ and ω scans | θmax = 31.1°, θmin = 2.4° |
111394 measured reflections | h = −10→10 |
5624 independent reflections | k = −49→49 |
5056 reflections with I > 2σ(I) | l = −11→11 |
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Secondary atom site location: dual |
R[F2 > 2σ(F2)] = 0.047 | Hydrogen site location: mixed |
wR(F2) = 0.129 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0581P)2 + 0.7134P] where P = (Fo2 + 2Fc2)/3 |
5624 reflections | (Δ/σ)max = 0.002 |
250 parameters | Δρmax = 0.41 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
0 constraints |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.34552 (19) | 0.70488 (4) | 0.34294 (16) | 0.0265 (2) | |
H1 | 0.338196 | 0.718339 | 0.231343 | 0.032* | |
C2 | 0.36445 (17) | 0.72661 (3) | 0.50281 (16) | 0.0236 (2) | |
H2A | 0.368392 | 0.754461 | 0.500126 | 0.028* | |
C3 | 0.37753 (15) | 0.70697 (3) | 0.66653 (14) | 0.01940 (19) | |
C4 | 0.37152 (18) | 0.66621 (3) | 0.66495 (16) | 0.0239 (2) | |
H4 | 0.382589 | 0.651968 | 0.77559 | 0.029* | |
C5 | 0.34909 (19) | 0.64679 (4) | 0.49885 (18) | 0.0281 (2) | |
H5 | 0.341789 | 0.61895 | 0.496836 | 0.034* | |
C6 | 0.41408 (16) | 0.72790 (3) | 0.84962 (14) | 0.01968 (19) | |
C7 | 0.35850 (16) | 0.82289 (3) | 0.97889 (16) | 0.0224 (2) | |
C8 | 0.3268 (2) | 0.84432 (4) | 0.79821 (18) | 0.0308 (3) | |
H8A | 0.398513 | 0.830927 | 0.728525 | 0.046* | |
H8B | 0.375439 | 0.871288 | 0.826095 | 0.046* | |
H8C | 0.185714 | 0.844755 | 0.721955 | 0.046* | |
C9 | 0.38785 (18) | 0.84802 (3) | 1.14869 (17) | 0.0252 (2) | |
H9A | 0.270812 | 0.865116 | 1.122133 | 0.03* | |
H9B | 0.502954 | 0.865278 | 1.167495 | 0.03* | |
C10 | 0.4201 (2) | 0.82623 (4) | 1.33066 (18) | 0.0306 (3) | |
H10A | 0.303647 | 0.81027 | 1.317269 | 0.046* | |
H10B | 0.441788 | 0.84514 | 1.43314 | 0.046* | |
H10C | 0.535749 | 0.809159 | 1.35937 | 0.046* | |
C11 | 0.2577 (2) | 0.55646 (4) | −0.06804 (19) | 0.0329 (3) | |
C12 | 0.4153 (2) | 0.55063 (4) | −0.12851 (19) | 0.0359 (3) | |
C13 | 0.4172 (3) | 0.51828 (4) | −0.2402 (2) | 0.0497 (5) | |
H13 | 0.524522 | 0.513935 | −0.281211 | 0.06* | |
C14 | 0.2596 (4) | 0.49280 (4) | −0.2897 (2) | 0.0552 (5) | |
C15 | 0.1001 (3) | 0.49746 (5) | −0.2356 (2) | 0.0532 (5) | |
H15 | −0.006369 | 0.479348 | −0.272787 | 0.064* | |
C16 | 0.1008 (3) | 0.52969 (4) | −0.1245 (2) | 0.0429 (4) | |
H16 | −0.008083 | 0.533764 | −0.085449 | 0.051* | |
C17 | 0.2412 (2) | 0.58813 (4) | 0.0638 (2) | 0.0339 (3) | |
Cl01 | 0.62203 (6) | 0.58034 (2) | −0.06254 (6) | 0.04457 (12) | |
N1 | 0.33722 (16) | 0.66570 (3) | 0.34045 (15) | 0.0273 (2) | |
N2 | 0.33516 (15) | 0.76384 (3) | 0.83540 (13) | 0.02305 (19) | |
H2 | 0.264867 | 0.773703 | 0.724711 | 0.028* | |
N3 | 0.36705 (15) | 0.78542 (3) | 1.00102 (13) | 0.02341 (19) | |
N4 | 0.2662 (4) | 0.45802 (4) | −0.4029 (2) | 0.0803 (8) | |
O1 | 0.51772 (13) | 0.71240 (2) | 0.99850 (11) | 0.02553 (18) | |
O2 | 0.33658 (16) | 0.62034 (3) | 0.06437 (13) | 0.0320 (2) | |
O3 | 0.1408 (3) | 0.58288 (4) | 0.1583 (3) | 0.0712 (5) | |
O4 | 0.4196 (5) | 0.45158 (5) | −0.4308 (3) | 0.1193 (10) | |
O5 | 0.1146 (4) | 0.43750 (4) | −0.4613 (2) | 0.0987 (8) | |
H2B | 0.326 (4) | 0.6369 (7) | 0.163 (4) | 0.075 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0313 (6) | 0.0300 (6) | 0.0208 (5) | 0.0006 (4) | 0.0124 (4) | −0.0006 (4) |
C2 | 0.0288 (5) | 0.0221 (5) | 0.0216 (5) | 0.0003 (4) | 0.0111 (4) | 0.0005 (4) |
C3 | 0.0186 (4) | 0.0216 (5) | 0.0174 (4) | 0.0007 (3) | 0.0058 (4) | −0.0007 (3) |
C4 | 0.0277 (5) | 0.0213 (5) | 0.0217 (5) | 0.0014 (4) | 0.0077 (4) | 0.0004 (4) |
C5 | 0.0338 (6) | 0.0226 (5) | 0.0280 (6) | 0.0006 (4) | 0.0111 (5) | −0.0040 (4) |
C6 | 0.0202 (4) | 0.0208 (5) | 0.0171 (4) | −0.0010 (4) | 0.0055 (4) | −0.0004 (3) |
C7 | 0.0212 (5) | 0.0239 (5) | 0.0210 (5) | −0.0006 (4) | 0.0063 (4) | −0.0018 (4) |
C8 | 0.0407 (7) | 0.0259 (5) | 0.0234 (5) | −0.0039 (5) | 0.0085 (5) | 0.0009 (4) |
C9 | 0.0292 (5) | 0.0228 (5) | 0.0243 (5) | −0.0011 (4) | 0.0107 (4) | −0.0033 (4) |
C10 | 0.0371 (6) | 0.0318 (6) | 0.0242 (5) | −0.0035 (5) | 0.0127 (5) | −0.0014 (4) |
C11 | 0.0482 (8) | 0.0233 (5) | 0.0264 (6) | 0.0043 (5) | 0.0123 (5) | −0.0024 (4) |
C12 | 0.0565 (9) | 0.0266 (6) | 0.0269 (6) | 0.0121 (6) | 0.0178 (6) | 0.0037 (5) |
C13 | 0.0922 (14) | 0.0308 (7) | 0.0333 (7) | 0.0233 (8) | 0.0313 (8) | 0.0064 (6) |
C14 | 0.1142 (17) | 0.0216 (6) | 0.0247 (6) | 0.0129 (8) | 0.0189 (8) | −0.0011 (5) |
C15 | 0.0877 (14) | 0.0268 (7) | 0.0341 (8) | −0.0060 (8) | 0.0087 (8) | −0.0048 (6) |
C16 | 0.0588 (10) | 0.0281 (6) | 0.0367 (7) | −0.0036 (6) | 0.0111 (7) | −0.0052 (5) |
C17 | 0.0411 (7) | 0.0288 (6) | 0.0351 (7) | −0.0022 (5) | 0.0176 (6) | −0.0086 (5) |
Cl01 | 0.0506 (2) | 0.0406 (2) | 0.0516 (2) | 0.01217 (15) | 0.02936 (18) | 0.00589 (15) |
N1 | 0.0296 (5) | 0.0295 (5) | 0.0239 (5) | 0.0001 (4) | 0.0109 (4) | −0.0059 (4) |
N2 | 0.0280 (5) | 0.0215 (4) | 0.0159 (4) | 0.0033 (3) | 0.0035 (3) | −0.0019 (3) |
N3 | 0.0259 (5) | 0.0242 (4) | 0.0180 (4) | 0.0014 (3) | 0.0053 (3) | −0.0039 (3) |
N4 | 0.180 (2) | 0.0260 (7) | 0.0347 (7) | 0.0174 (10) | 0.0383 (11) | −0.0012 (6) |
O1 | 0.0293 (4) | 0.0247 (4) | 0.0179 (4) | 0.0024 (3) | 0.0028 (3) | 0.0015 (3) |
O2 | 0.0455 (5) | 0.0255 (4) | 0.0291 (4) | −0.0021 (4) | 0.0184 (4) | −0.0069 (3) |
O3 | 0.0978 (12) | 0.0514 (8) | 0.0994 (12) | −0.0357 (8) | 0.0777 (11) | −0.0389 (8) |
O4 | 0.243 (3) | 0.0530 (10) | 0.0986 (15) | 0.0310 (14) | 0.1064 (19) | −0.0144 (9) |
O5 | 0.199 (2) | 0.0292 (6) | 0.0447 (8) | 0.0000 (10) | 0.0163 (11) | −0.0110 (6) |
C1—N1 | 1.3361 (16) | C10—H10A | 0.98 |
C1—C2 | 1.3885 (16) | C10—H10B | 0.98 |
C1—H1 | 0.95 | C10—H10C | 0.98 |
C2—C3 | 1.3874 (15) | C11—C12 | 1.394 (2) |
C2—H2A | 0.95 | C11—C16 | 1.402 (2) |
C3—C4 | 1.3897 (15) | C11—C17 | 1.5076 (18) |
C3—C6 | 1.5019 (14) | C12—C13 | 1.396 (2) |
C4—C5 | 1.3838 (16) | C12—Cl01 | 1.7297 (17) |
C4—H4 | 0.95 | C13—C14 | 1.377 (3) |
C5—N1 | 1.3423 (16) | C13—H13 | 0.95 |
C5—H5 | 0.95 | C14—C15 | 1.372 (3) |
C6—O1 | 1.2316 (13) | C14—N4 | 1.476 (2) |
C6—N2 | 1.3400 (14) | C15—C16 | 1.385 (2) |
C7—N3 | 1.2865 (15) | C15—H15 | 0.95 |
C7—C8 | 1.5001 (16) | C16—H16 | 0.95 |
C7—C9 | 1.5004 (16) | C17—O3 | 1.2077 (19) |
C8—H8A | 0.98 | C17—O2 | 1.2974 (17) |
C8—H8B | 0.98 | N2—N3 | 1.4051 (13) |
C8—H8C | 0.98 | N2—H2 | 0.88 |
C9—C10 | 1.5139 (17) | N4—O4 | 1.228 (4) |
C9—H9A | 0.99 | N4—O5 | 1.244 (3) |
C9—H9B | 0.99 | O2—H2B | 0.96 (3) |
N1—C1—C2 | 122.35 (11) | H10A—C10—H10B | 109.5 |
N1—C1—H1 | 118.8 | C9—C10—H10C | 109.5 |
C2—C1—H1 | 118.8 | H10A—C10—H10C | 109.5 |
C3—C2—C1 | 118.89 (11) | H10B—C10—H10C | 109.5 |
C3—C2—H2A | 120.6 | C12—C11—C16 | 118.74 (13) |
C1—C2—H2A | 120.6 | C12—C11—C17 | 126.39 (13) |
C2—C3—C4 | 118.86 (10) | C16—C11—C17 | 114.78 (14) |
C2—C3—C6 | 122.45 (10) | C11—C12—C13 | 120.22 (16) |
C4—C3—C6 | 118.51 (9) | C11—C12—Cl01 | 123.50 (11) |
C5—C4—C3 | 118.61 (11) | C13—C12—Cl01 | 116.19 (14) |
C5—C4—H4 | 120.7 | C14—C13—C12 | 118.36 (18) |
C3—C4—H4 | 120.7 | C14—C13—H13 | 120.8 |
N1—C5—C4 | 122.66 (11) | C12—C13—H13 | 120.8 |
N1—C5—H5 | 118.7 | C15—C14—C13 | 123.66 (14) |
C4—C5—H5 | 118.7 | C15—C14—N4 | 118.4 (2) |
O1—C6—N2 | 124.65 (10) | C13—C14—N4 | 117.9 (2) |
O1—C6—C3 | 119.72 (10) | C14—C15—C16 | 117.22 (18) |
N2—C6—C3 | 115.56 (9) | C14—C15—H15 | 121.4 |
N3—C7—C8 | 125.98 (10) | C16—C15—H15 | 121.4 |
N3—C7—C9 | 117.93 (10) | C15—C16—C11 | 121.79 (18) |
C8—C7—C9 | 116.07 (10) | C15—C16—H16 | 119.1 |
C7—C8—H8A | 109.5 | C11—C16—H16 | 119.1 |
C7—C8—H8B | 109.5 | O3—C17—O2 | 124.04 (13) |
H8A—C8—H8B | 109.5 | O3—C17—C11 | 120.00 (13) |
C7—C8—H8C | 109.5 | O2—C17—C11 | 115.95 (12) |
H8A—C8—H8C | 109.5 | C1—N1—C5 | 118.62 (10) |
H8B—C8—H8C | 109.5 | C6—N2—N3 | 118.58 (9) |
C7—C9—C10 | 115.82 (10) | C6—N2—H2 | 120.7 |
C7—C9—H9A | 108.3 | N3—N2—H2 | 120.7 |
C10—C9—H9A | 108.3 | C7—N3—N2 | 114.68 (10) |
C7—C9—H9B | 108.3 | O4—N4—O5 | 125.48 (19) |
C10—C9—H9B | 108.3 | O4—N4—C14 | 117.8 (2) |
H9A—C9—H9B | 107.4 | O5—N4—C14 | 116.7 (2) |
C9—C10—H10A | 109.5 | C17—O2—H2B | 107.9 (15) |
C9—C10—H10B | 109.5 | ||
N1—C1—C2—C3 | 0.76 (18) | C13—C14—C15—C16 | −0.3 (3) |
C1—C2—C3—C4 | 0.10 (17) | N4—C14—C15—C16 | 178.00 (15) |
C1—C2—C3—C6 | 175.11 (10) | C14—C15—C16—C11 | −0.4 (2) |
C2—C3—C4—C5 | −1.16 (17) | C12—C11—C16—C15 | 1.1 (2) |
C6—C3—C4—C5 | −176.37 (11) | C17—C11—C16—C15 | −175.78 (14) |
C3—C4—C5—N1 | 1.49 (19) | C12—C11—C17—O3 | −153.35 (18) |
C2—C3—C6—O1 | −143.50 (12) | C16—C11—C17—O3 | 23.2 (2) |
C4—C3—C6—O1 | 31.53 (15) | C12—C11—C17—O2 | 27.9 (2) |
C2—C3—C6—N2 | 33.63 (15) | C16—C11—C17—O2 | −155.51 (13) |
C4—C3—C6—N2 | −151.34 (11) | C2—C1—N1—C5 | −0.49 (19) |
N3—C7—C9—C10 | −1.45 (16) | C4—C5—N1—C1 | −0.66 (19) |
C8—C7—C9—C10 | −179.90 (11) | O1—C6—N2—N3 | −1.73 (17) |
C16—C11—C12—C13 | −1.1 (2) | C3—C6—N2—N3 | −178.70 (9) |
C17—C11—C12—C13 | 175.29 (14) | C8—C7—N3—N2 | −2.66 (17) |
C16—C11—C12—Cl01 | −177.59 (11) | C9—C7—N3—N2 | 179.06 (10) |
C17—C11—C12—Cl01 | −1.2 (2) | C6—N2—N3—C7 | 153.96 (11) |
C11—C12—C13—C14 | 0.6 (2) | C15—C14—N4—O4 | −171.23 (19) |
Cl01—C12—C13—C14 | 177.25 (11) | C13—C14—N4—O4 | 7.1 (3) |
C12—C13—C14—C15 | 0.2 (2) | C15—C14—N4—O5 | 8.4 (2) |
C12—C13—C14—N4 | −178.11 (13) | C13—C14—N4—O5 | −173.23 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O1i | 0.88 | 2.05 | 2.8809 (13) | 158 |
C4—H4···O2ii | 0.95 | 2.58 | 3.5082 (15) | 167 |
C1—H1···O1iii | 0.95 | 2.56 | 3.2966 (15) | 135 |
C8—H8B···O5iv | 0.98 | 2.47 | 3.380 (2) | 154 |
C8—H8C···O1i | 0.98 | 2.59 | 3.2095 (15) | 122 |
C13—H13···O4v | 0.95 | 2.64 | 3.297 (3) | 126 |
C15—H15···O3vi | 0.95 | 2.61 | 3.413 (2) | 142 |
O2—H2B···N1 | 0.96 (3) | 1.65 (3) | 2.6076 (13) | 173 (2) |
N2—H2···O1i | 0.88 | 2.05 | 2.8809 (13) | 158 |
C4—H4···O2ii | 0.95 | 2.58 | 3.5082 (15) | 167 |
C1—H1···O1iii | 0.95 | 2.56 | 3.2966 (15) | 135 |
C8—H8B···O5iv | 0.98 | 2.47 | 3.380 (2) | 154 |
C8—H8C···O1i | 0.98 | 2.59 | 3.2095 (15) | 122 |
C13—H13···O4v | 0.95 | 2.64 | 3.297 (3) | 126 |
C15—H15···O3vi | 0.95 | 2.61 | 3.413 (2) | 142 |
O2—H2B···N1 | 0.96 (3) | 1.65 (3) | 2.6076 (13) | 173 (2) |
Symmetry codes: (i) x−1/2, −y+3/2, z−1/2; (ii) x, y, z+1; (iii) x, y, z−1; (iv) −x+1/2, y+1/2, −z+1/2; (v) −x+1, −y+1, −z−1; (vi) −x, −y+1, −z. |
C10H13N3O·C7H6O4 | Z = 4 |
Mr = 345.35 | F(000) = 728 |
Triclinic, P1 | Dx = 1.383 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.2054 (3) Å | Cell parameters from 9903 reflections |
b = 11.5589 (4) Å | θ = 2.2–27.3° |
c = 15.6268 (6) Å | µ = 0.10 mm−1 |
α = 92.383 (2)° | T = 123 K |
β = 93.092 (2)° | Plate, colourless |
γ = 90.666 (2)° | 0.45 × 0.38 × 0.13 mm |
V = 1658.74 (10) Å3 |
Bruker APEXII CCD diffractometer | Rint = 0.079 |
φ and ω scans | θmax = 28°, θmin = 1.8° |
73254 measured reflections | h = −12→12 |
8026 independent reflections | k = −15→15 |
5972 reflections with I > 2σ(I) | l = −20→20 |
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Secondary atom site location: dual |
R[F2 > 2σ(F2)] = 0.068 | Hydrogen site location: mixed |
wR(F2) = 0.191 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0779P)2 + 1.3095P] where P = (Fo2 + 2Fc2)/3 |
8026 reflections | (Δ/σ)max < 0.001 |
506 parameters | Δρmax = 1.33 e Å−3 |
21 restraints | Δρmin = −0.68 e Å−3 |
0 constraints |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1 | 0.2112 (3) | 0.59980 (18) | 0.42485 (14) | 0.0394 (5) | |
H1 | 0.228948 | 0.524065 | 0.444016 | 0.047* | |
C2 | 0.1065 (2) | 0.61362 (17) | 0.36000 (14) | 0.0350 (4) | |
H2 | 0.05337 | 0.548625 | 0.335013 | 0.042* | |
C3 | 0.0796 (2) | 0.72412 (16) | 0.33160 (13) | 0.0302 (4) | |
C4 | 0.1587 (2) | 0.81679 (16) | 0.37099 (13) | 0.0315 (4) | |
H4 | 0.141596 | 0.893651 | 0.354046 | 0.038* | |
C5 | 0.2624 (2) | 0.79498 (17) | 0.43507 (14) | 0.0332 (4) | |
H5 | 0.317352 | 0.858236 | 0.461266 | 0.04* | |
C6 | −0.0350 (2) | 0.75020 (17) | 0.26420 (15) | 0.0349 (4) | |
C7 | −0.2250 (4) | 0.5985 (2) | 0.0953 (2) | 0.0687 (9) | |
C8 | −0.1519 (4) | 0.4878 (2) | 0.0876 (2) | 0.0647 (8) | |
H8A | −0.04954 | 0.501106 | 0.076189 | 0.097* | |
H8B | −0.199055 | 0.440653 | 0.04015 | 0.097* | |
H8C | −0.158024 | 0.447199 | 0.141079 | 0.097* | |
C9 | −0.3335 (6) | 0.6135 (4) | 0.0212 (3) | 0.0541 (16) | 0.625 (10) |
H9A | −0.288822 | 0.587217 | −0.032332 | 0.065* | 0.625 (10) |
H9B | −0.418717 | 0.562531 | 0.028434 | 0.065* | 0.625 (10) |
C10 | −0.3857 (7) | 0.7345 (6) | 0.0110 (4) | 0.074 (2) | 0.625 (10) |
H10A | −0.461649 | 0.734997 | −0.035398 | 0.111* | 0.625 (10) |
H10B | −0.304234 | 0.784378 | −0.002877 | 0.111* | 0.625 (10) |
H10C | −0.425497 | 0.763312 | 0.064652 | 0.111* | 0.625 (10) |
C11 | 0.6568 (2) | 0.73609 (16) | 0.68602 (14) | 0.0332 (4) | |
C12 | 0.7330 (2) | 0.83240 (17) | 0.72385 (17) | 0.0407 (5) | |
C13 | 0.8377 (3) | 0.81677 (18) | 0.78881 (18) | 0.0451 (6) | |
H13 | 0.89199 | 0.881548 | 0.813175 | 0.054* | |
C14 | 0.8644 (3) | 0.70739 (19) | 0.81880 (17) | 0.0423 (5) | |
H14 | 0.936431 | 0.697752 | 0.863681 | 0.051* | |
C15 | 0.7863 (2) | 0.61188 (16) | 0.78356 (14) | 0.0337 (4) | |
C16 | 0.6847 (2) | 0.62589 (16) | 0.71685 (13) | 0.0318 (4) | |
H16 | 0.633109 | 0.560325 | 0.69155 | 0.038* | |
C17 | 0.5472 (3) | 0.75068 (18) | 0.61543 (14) | 0.0375 (5) | |
C18 | 0.2402 (2) | 0.30223 (17) | 0.56766 (15) | 0.0378 (5) | |
H18 | 0.184874 | 0.361575 | 0.541748 | 0.045* | |
C19 | 0.3424 (2) | 0.33290 (17) | 0.63206 (15) | 0.0373 (5) | |
H19 | 0.358276 | 0.411827 | 0.649888 | 0.045* | |
C20 | 0.4225 (2) | 0.24569 (17) | 0.67075 (16) | 0.0365 (5) | |
C21 | 0.3967 (2) | 0.13173 (17) | 0.64134 (17) | 0.0411 (5) | |
H21 | 0.450213 | 0.070407 | 0.665901 | 0.049* | |
C22 | 0.2930 (3) | 0.10924 (18) | 0.57636 (16) | 0.0430 (5) | |
H22 | 0.275925 | 0.031203 | 0.556543 | 0.052* | |
C23 | 0.5371 (2) | 0.28117 (18) | 0.73810 (17) | 0.0405 (5) | |
C24 | 0.7335 (3) | 0.1562 (2) | 0.9060 (2) | 0.0587 (7) | |
C25 | 0.6514 (4) | 0.0440 (2) | 0.9189 (2) | 0.0685 (9) | |
H25A | 0.698797 | 0.00369 | 0.966535 | 0.103* | |
H25B | 0.550861 | 0.061286 | 0.931974 | 0.103* | |
H25C | 0.651695 | −0.005447 | 0.866372 | 0.103* | |
C26 | 0.8651 (4) | 0.1869 (3) | 0.9665 (3) | 0.0792 (10) | |
H26A | 0.896188 | 0.267519 | 0.957394 | 0.095* | |
H26B | 0.836178 | 0.183245 | 1.026426 | 0.095* | |
C27A | 0.9875 (6) | 0.1110 (6) | 0.9547 (4) | 0.108 (2) | 0.773 (9) |
H27A | 1.068248 | 0.135148 | 0.995175 | 0.161* | 0.773 (9) |
H27B | 0.958489 | 0.031188 | 0.964948 | 0.161* | 0.773 (9) |
H27C | 1.018548 | 0.11553 | 0.895861 | 0.161* | 0.773 (9) |
C27B | 0.988 (2) | 0.239 (3) | 0.932 (2) | 0.164 (10) | 0.227 (9) |
H27D | 1.063797 | 0.254299 | 0.977489 | 0.246* | 0.227 (9) |
H27E | 1.025203 | 0.187517 | 0.887217 | 0.246* | 0.227 (9) |
H27F | 0.959234 | 0.312707 | 0.906915 | 0.246* | 0.227 (9) |
C28 | −0.1528 (2) | 0.21103 (17) | 0.31637 (15) | 0.0359 (5) | |
C29 | −0.2306 (3) | 0.30216 (18) | 0.28099 (18) | 0.0444 (6) | |
C30 | −0.3371 (3) | 0.2784 (2) | 0.2164 (2) | 0.0506 (6) | |
H30 | −0.393105 | 0.339704 | 0.193844 | 0.061* | |
C31 | −0.3626 (3) | 0.1658 (2) | 0.18448 (19) | 0.0472 (6) | |
H31 | −0.435107 | 0.150553 | 0.139709 | 0.057* | |
C32 | −0.2823 (2) | 0.07531 (17) | 0.21785 (15) | 0.0374 (5) | |
C33 | −0.1794 (2) | 0.09764 (17) | 0.28375 (14) | 0.0342 (4) | |
H33 | −0.125851 | 0.035639 | 0.307325 | 0.041* | |
C34 | −0.0415 (3) | 0.23411 (18) | 0.38673 (15) | 0.0394 (5) | |
N1 | 0.2889 (2) | 0.68817 (15) | 0.46199 (11) | 0.0370 (4) | |
N2 | −0.0756 (2) | 0.66280 (16) | 0.20764 (14) | 0.0439 (5) | |
N3 | −0.1888 (3) | 0.6817 (2) | 0.1479 (2) | 0.0776 (9) | |
N4 | 0.2149 (2) | 0.19217 (15) | 0.53972 (13) | 0.0401 (4) | |
N5 | 0.5822 (2) | 0.20013 (16) | 0.79252 (15) | 0.0432 (5) | |
N6 | 0.7001 (2) | 0.22903 (18) | 0.84909 (16) | 0.0526 (6) | |
O1 | −0.08959 (17) | 0.84598 (13) | 0.26287 (12) | 0.0440 (4) | |
O2 | 0.49050 (19) | 0.65507 (13) | 0.58071 (10) | 0.0423 (4) | |
H2B | 0.423495 | 0.670814 | 0.544597 | 0.063* | |
O3 | 0.51263 (19) | 0.84794 (13) | 0.59033 (11) | 0.0456 (4) | |
O4 | 0.7059 (2) | 0.94157 (13) | 0.69790 (14) | 0.0548 (5) | |
H4A | 0.644075 | 0.938517 | 0.656275 | 0.082* | |
O5 | 0.81552 (18) | 0.50542 (12) | 0.81722 (10) | 0.0380 (4) | |
O6 | 0.58774 (19) | 0.37970 (14) | 0.74097 (14) | 0.0543 (5) | |
O7 | 0.0166 (2) | 0.14267 (13) | 0.41965 (10) | 0.0448 (4) | |
H7 | 0.080114 | 0.163181 | 0.458094 | 0.067* | |
O8 | −0.0078 (2) | 0.33425 (13) | 0.41276 (11) | 0.0479 (4) | |
O9 | −0.2047 (2) | 0.41438 (14) | 0.30888 (16) | 0.0575 (5) | |
O10 | −0.31118 (18) | −0.03452 (13) | 0.18240 (12) | 0.0434 (4) | |
C9A | −0.4007 (9) | 0.6164 (8) | 0.0684 (6) | 0.061 (3) | 0.375 (10) |
H9AA | −0.456209 | 0.542674 | 0.069361 | 0.074* | 0.375 (10) |
H9AB | −0.444497 | 0.674963 | 0.106875 | 0.074* | 0.375 (10) |
C10A | −0.3944 (13) | 0.6563 (13) | −0.0178 (11) | 0.099 (5) | 0.375 (10) |
H10D | −0.355335 | 0.595055 | −0.054862 | 0.149* | 0.375 (10) |
H10E | −0.331215 | 0.725178 | −0.017286 | 0.149* | 0.375 (10) |
H10F | −0.492491 | 0.67574 | −0.039729 | 0.149* | 0.375 (10) |
H2A | −0.020 (3) | 0.600 (2) | 0.2030 (16) | 0.044 (7)* | |
H5B | 0.742 (3) | 0.460 (3) | 0.7997 (19) | 0.061 (9)* | |
H5A | 0.526 (4) | 0.137 (3) | 0.798 (2) | 0.075 (10)* | |
H9 | −0.134 (5) | 0.409 (4) | 0.349 (3) | 0.127 (19)* | |
H10 | −0.239 (4) | −0.082 (3) | 0.207 (2) | 0.088 (12)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0562 (14) | 0.0226 (9) | 0.0405 (11) | 0.0040 (9) | 0.0094 (10) | 0.0040 (8) |
C2 | 0.0423 (11) | 0.0194 (9) | 0.0440 (11) | −0.0030 (8) | 0.0112 (9) | −0.0006 (8) |
C3 | 0.0279 (9) | 0.0205 (8) | 0.0426 (11) | 0.0002 (7) | 0.0084 (8) | −0.0016 (7) |
C4 | 0.0312 (10) | 0.0189 (8) | 0.0445 (11) | −0.0001 (7) | 0.0042 (8) | 0.0002 (7) |
C5 | 0.0351 (10) | 0.0232 (9) | 0.0413 (11) | 0.0015 (7) | 0.0046 (8) | −0.0025 (8) |
C6 | 0.0260 (9) | 0.0240 (9) | 0.0542 (12) | 0.0000 (7) | 0.0027 (8) | −0.0049 (8) |
C7 | 0.079 (2) | 0.0343 (13) | 0.088 (2) | −0.0137 (13) | −0.0413 (17) | 0.0059 (13) |
C8 | 0.082 (2) | 0.0470 (15) | 0.0618 (17) | −0.0132 (14) | −0.0140 (15) | −0.0107 (13) |
C9 | 0.061 (3) | 0.050 (3) | 0.049 (3) | −0.003 (2) | −0.015 (2) | −0.002 (2) |
C10 | 0.084 (4) | 0.072 (4) | 0.061 (3) | 0.034 (3) | −0.028 (3) | −0.019 (3) |
C11 | 0.0362 (10) | 0.0217 (9) | 0.0433 (11) | 0.0021 (7) | 0.0127 (9) | 0.0043 (8) |
C12 | 0.0391 (11) | 0.0177 (9) | 0.0670 (15) | 0.0003 (8) | 0.0160 (10) | 0.0042 (9) |
C13 | 0.0375 (12) | 0.0206 (9) | 0.0765 (17) | −0.0053 (8) | 0.0063 (11) | −0.0077 (10) |
C14 | 0.0366 (11) | 0.0285 (10) | 0.0609 (14) | 0.0004 (8) | 0.0001 (10) | −0.0061 (9) |
C15 | 0.0353 (10) | 0.0207 (9) | 0.0454 (11) | 0.0022 (7) | 0.0065 (9) | 0.0010 (8) |
C16 | 0.0363 (10) | 0.0188 (8) | 0.0409 (10) | −0.0005 (7) | 0.0085 (8) | 0.0002 (7) |
C17 | 0.0461 (12) | 0.0264 (10) | 0.0420 (11) | 0.0065 (8) | 0.0156 (9) | 0.0077 (8) |
C18 | 0.0384 (11) | 0.0240 (9) | 0.0521 (13) | −0.0012 (8) | 0.0112 (9) | 0.0034 (8) |
C19 | 0.0325 (10) | 0.0203 (9) | 0.0599 (13) | −0.0018 (7) | 0.0092 (9) | 0.0025 (8) |
C20 | 0.0283 (10) | 0.0203 (9) | 0.0622 (14) | −0.0010 (7) | 0.0111 (9) | 0.0056 (8) |
C21 | 0.0371 (11) | 0.0210 (9) | 0.0670 (15) | 0.0033 (8) | 0.0162 (10) | 0.0031 (9) |
C22 | 0.0515 (14) | 0.0219 (9) | 0.0568 (14) | −0.0028 (9) | 0.0186 (11) | −0.0025 (9) |
C23 | 0.0272 (10) | 0.0242 (10) | 0.0710 (15) | 0.0001 (8) | 0.0059 (10) | 0.0094 (9) |
C24 | 0.0481 (15) | 0.0388 (13) | 0.090 (2) | 0.0071 (11) | −0.0034 (14) | 0.0163 (13) |
C25 | 0.070 (2) | 0.0406 (14) | 0.095 (2) | −0.0018 (13) | −0.0085 (17) | 0.0245 (15) |
C26 | 0.0548 (18) | 0.0601 (19) | 0.121 (3) | −0.0008 (14) | −0.0222 (18) | 0.0203 (19) |
C27A | 0.073 (3) | 0.102 (5) | 0.141 (5) | 0.020 (3) | −0.035 (3) | −0.012 (4) |
C27B | 0.123 (16) | 0.15 (2) | 0.23 (2) | −0.035 (14) | 0.033 (15) | 0.029 (18) |
C28 | 0.0381 (11) | 0.0217 (9) | 0.0493 (12) | −0.0007 (8) | 0.0181 (9) | −0.0002 (8) |
C29 | 0.0423 (12) | 0.0195 (9) | 0.0737 (16) | 0.0003 (8) | 0.0236 (11) | 0.0043 (9) |
C30 | 0.0376 (12) | 0.0274 (11) | 0.0890 (19) | 0.0049 (9) | 0.0128 (12) | 0.0173 (11) |
C31 | 0.0340 (11) | 0.0331 (11) | 0.0755 (17) | −0.0022 (9) | 0.0033 (11) | 0.0152 (11) |
C32 | 0.0324 (10) | 0.0243 (9) | 0.0562 (13) | −0.0017 (8) | 0.0072 (9) | 0.0035 (9) |
C33 | 0.0339 (10) | 0.0210 (9) | 0.0488 (12) | 0.0001 (7) | 0.0114 (9) | 0.0022 (8) |
C34 | 0.0510 (13) | 0.0240 (9) | 0.0446 (12) | −0.0058 (9) | 0.0204 (10) | −0.0036 (8) |
N1 | 0.0463 (10) | 0.0283 (9) | 0.0368 (9) | 0.0069 (7) | 0.0054 (8) | 0.0010 (7) |
N2 | 0.0381 (10) | 0.0248 (9) | 0.0662 (13) | 0.0025 (7) | −0.0114 (9) | −0.0091 (8) |
N3 | 0.0660 (16) | 0.0400 (12) | 0.119 (2) | 0.0099 (11) | −0.0517 (16) | −0.0155 (13) |
N4 | 0.0460 (11) | 0.0268 (9) | 0.0483 (10) | −0.0054 (7) | 0.0136 (8) | −0.0004 (7) |
N5 | 0.0358 (10) | 0.0251 (9) | 0.0693 (13) | −0.0005 (7) | 0.0021 (9) | 0.0120 (8) |
N6 | 0.0353 (10) | 0.0390 (11) | 0.0839 (16) | −0.0011 (8) | −0.0041 (10) | 0.0178 (10) |
O1 | 0.0360 (8) | 0.0258 (7) | 0.0684 (11) | 0.0074 (6) | −0.0066 (7) | −0.0091 (7) |
O2 | 0.0569 (10) | 0.0297 (8) | 0.0402 (8) | 0.0081 (7) | −0.0009 (7) | 0.0035 (6) |
O3 | 0.0568 (10) | 0.0285 (8) | 0.0539 (10) | 0.0121 (7) | 0.0133 (8) | 0.0144 (7) |
O4 | 0.0524 (11) | 0.0180 (7) | 0.0956 (15) | −0.0001 (7) | 0.0130 (10) | 0.0095 (8) |
O5 | 0.0407 (8) | 0.0225 (7) | 0.0498 (9) | −0.0005 (6) | −0.0052 (7) | 0.0021 (6) |
O6 | 0.0416 (9) | 0.0256 (8) | 0.0951 (14) | −0.0106 (7) | −0.0117 (9) | 0.0181 (8) |
O7 | 0.0642 (11) | 0.0259 (7) | 0.0438 (9) | −0.0065 (7) | 0.0033 (8) | −0.0013 (6) |
O8 | 0.0626 (11) | 0.0245 (7) | 0.0569 (10) | −0.0098 (7) | 0.0181 (8) | −0.0092 (7) |
O9 | 0.0582 (12) | 0.0171 (7) | 0.0991 (16) | 0.0008 (7) | 0.0220 (11) | 0.0012 (8) |
O10 | 0.0389 (9) | 0.0258 (7) | 0.0644 (11) | −0.0019 (6) | −0.0071 (8) | 0.0010 (7) |
C9A | 0.052 (5) | 0.080 (6) | 0.050 (5) | 0.005 (4) | −0.005 (4) | −0.025 (4) |
C10A | 0.073 (7) | 0.097 (10) | 0.131 (12) | −0.001 (6) | −0.001 (7) | 0.059 (9) |
C1—N1 | 1.334 (3) | C22—H22 | 0.95 |
C1—C2 | 1.376 (3) | C23—O6 | 1.224 (3) |
C1—H1 | 0.95 | C23—N5 | 1.345 (3) |
C2—C3 | 1.390 (3) | C24—N6 | 1.278 (3) |
C2—H2 | 0.95 | C24—C25 | 1.519 (4) |
C3—C4 | 1.391 (3) | C24—C26 | 1.526 (4) |
C3—C6 | 1.492 (3) | C25—H25A | 0.98 |
C4—C5 | 1.379 (3) | C25—H25B | 0.98 |
C4—H4 | 0.95 | C25—H25C | 0.98 |
C5—N1 | 1.342 (3) | C26—C27B | 1.419 (11) |
C5—H5 | 0.95 | C26—C27A | 1.450 (6) |
C6—O1 | 1.222 (2) | C26—H26A | 0.99 |
C6—N2 | 1.350 (3) | C26—H26B | 0.99 |
C7—N3 | 1.268 (4) | C27A—H27A | 0.98 |
C7—C8 | 1.456 (4) | C27A—H27B | 0.98 |
C7—C9 | 1.506 (5) | C27A—H27C | 0.98 |
C7—C9A | 1.667 (9) | C27B—H27D | 0.98 |
C8—H8A | 0.98 | C27B—H27E | 0.98 |
C8—H8B | 0.98 | C27B—H27F | 0.98 |
C8—H8C | 0.98 | C28—C29 | 1.397 (3) |
C9—C10 | 1.496 (8) | C28—C33 | 1.400 (3) |
C9—H9A | 0.99 | C28—C34 | 1.475 (3) |
C9—H9B | 0.99 | C29—O9 | 1.365 (3) |
C10—H10A | 0.98 | C29—C30 | 1.385 (4) |
C10—H10B | 0.98 | C30—C31 | 1.387 (3) |
C10—H10C | 0.98 | C30—H30 | 0.95 |
C11—C12 | 1.401 (3) | C31—C32 | 1.391 (3) |
C11—C16 | 1.402 (3) | C31—H31 | 0.95 |
C11—C17 | 1.471 (3) | C32—C33 | 1.376 (3) |
C12—O4 | 1.363 (2) | C32—O10 | 1.381 (3) |
C12—C13 | 1.381 (4) | C33—H33 | 0.95 |
C13—C14 | 1.387 (3) | C34—O8 | 1.241 (2) |
C13—H13 | 0.95 | C34—O7 | 1.303 (3) |
C14—C15 | 1.388 (3) | N2—N3 | 1.386 (3) |
C14—H14 | 0.95 | N2—H2A | 0.89 (3) |
C15—C16 | 1.378 (3) | N5—N6 | 1.391 (3) |
C15—O5 | 1.382 (2) | N5—H5A | 0.90 (4) |
C16—H16 | 0.95 | O2—H2B | 0.84 |
C17—O3 | 1.245 (2) | O4—H4A | 0.84 |
C17—O2 | 1.302 (3) | O5—H5B | 0.88 (3) |
C18—N4 | 1.341 (3) | O7—H7 | 0.84 |
C18—C19 | 1.373 (3) | O9—H9 | 0.88 (5) |
C18—H18 | 0.95 | O10—H10 | 0.95 (4) |
C19—C20 | 1.395 (3) | C9A—C10A | 1.446 (18) |
C19—H19 | 0.95 | C9A—H9AA | 0.99 |
C20—C21 | 1.390 (3) | C9A—H9AB | 0.99 |
C20—C23 | 1.491 (3) | C10A—H10D | 0.98 |
C21—C22 | 1.371 (4) | C10A—H10E | 0.98 |
C21—H21 | 0.95 | C10A—H10F | 0.98 |
C22—N4 | 1.334 (3) | ||
N1—C1—C2 | 122.84 (19) | N5—C23—C20 | 117.07 (19) |
N1—C1—H1 | 118.6 | N6—C24—C25 | 125.4 (3) |
C2—C1—H1 | 118.6 | N6—C24—C26 | 116.5 (3) |
C1—C2—C3 | 119.01 (19) | C25—C24—C26 | 118.1 (3) |
C1—C2—H2 | 120.5 | C24—C25—H25A | 109.5 |
C3—C2—H2 | 120.5 | C24—C25—H25B | 109.5 |
C2—C3—C4 | 118.4 (2) | H25A—C25—H25B | 109.5 |
C2—C3—C6 | 123.74 (18) | C24—C25—H25C | 109.5 |
C4—C3—C6 | 117.78 (17) | H25A—C25—H25C | 109.5 |
C5—C4—C3 | 118.75 (18) | H25B—C25—H25C | 109.5 |
C5—C4—H4 | 120.6 | C27B—C26—C24 | 118.2 (14) |
C3—C4—H4 | 120.6 | C27A—C26—C24 | 113.4 (4) |
N1—C5—C4 | 122.76 (19) | C27A—C26—H26A | 108.9 |
N1—C5—H5 | 118.6 | C24—C26—H26A | 108.9 |
C4—C5—H5 | 118.6 | C27A—C26—H26B | 108.9 |
O1—C6—N2 | 123.0 (2) | C24—C26—H26B | 108.9 |
O1—C6—C3 | 120.31 (19) | H26A—C26—H26B | 107.7 |
N2—C6—C3 | 116.69 (18) | C26—C27A—H27A | 109.5 |
N3—C7—C8 | 126.1 (3) | C26—C27A—H27B | 109.5 |
N3—C7—C9 | 121.6 (3) | H27A—C27A—H27B | 109.5 |
C8—C7—C9 | 111.3 (3) | C26—C27A—H27C | 109.5 |
N3—C7—C9A | 105.9 (4) | H27A—C27A—H27C | 109.5 |
C8—C7—C9A | 123.6 (4) | H27B—C27A—H27C | 109.5 |
C7—C8—H8A | 109.5 | C26—C27B—H27D | 109.5 |
C7—C8—H8B | 109.5 | C26—C27B—H27E | 109.5 |
H8A—C8—H8B | 109.5 | H27D—C27B—H27E | 109.5 |
C7—C8—H8C | 109.5 | C26—C27B—H27F | 109.5 |
H8A—C8—H8C | 109.5 | H27D—C27B—H27F | 109.5 |
H8B—C8—H8C | 109.5 | H27E—C27B—H27F | 109.5 |
C10—C9—C7 | 115.1 (4) | C29—C28—C33 | 119.6 (2) |
C10—C9—H9A | 108.5 | C29—C28—C34 | 120.31 (19) |
C7—C9—H9A | 108.5 | C33—C28—C34 | 120.1 (2) |
C10—C9—H9B | 108.5 | O9—C29—C30 | 119.1 (2) |
C7—C9—H9B | 108.5 | O9—C29—C28 | 121.5 (2) |
H9A—C9—H9B | 107.5 | C30—C29—C28 | 119.4 (2) |
C9—C10—H10A | 109.5 | C29—C30—C31 | 120.6 (2) |
C9—C10—H10B | 109.5 | C29—C30—H30 | 119.7 |
H10A—C10—H10B | 109.5 | C31—C30—H30 | 119.7 |
C9—C10—H10C | 109.5 | C30—C31—C32 | 120.1 (2) |
H10A—C10—H10C | 109.5 | C30—C31—H31 | 119.9 |
H10B—C10—H10C | 109.5 | C32—C31—H31 | 119.9 |
C12—C11—C16 | 119.4 (2) | C33—C32—O10 | 122.89 (19) |
C12—C11—C17 | 120.30 (18) | C33—C32—C31 | 119.7 (2) |
C16—C11—C17 | 120.32 (19) | O10—C32—C31 | 117.4 (2) |
O4—C12—C13 | 119.1 (2) | C32—C33—C28 | 120.5 (2) |
O4—C12—C11 | 121.4 (2) | C32—C33—H33 | 119.7 |
C13—C12—C11 | 119.49 (19) | C28—C33—H33 | 119.7 |
C12—C13—C14 | 120.6 (2) | O8—C34—O7 | 122.9 (2) |
C12—C13—H13 | 119.7 | O8—C34—C28 | 121.6 (2) |
C14—C13—H13 | 119.7 | O7—C34—C28 | 115.43 (18) |
C13—C14—C15 | 120.3 (2) | C1—N1—C5 | 118.24 (19) |
C13—C14—H14 | 119.8 | C6—N2—N3 | 118.15 (19) |
C15—C14—H14 | 119.8 | C6—N2—H2A | 119.9 (17) |
C16—C15—O5 | 122.69 (18) | N3—N2—H2A | 121.0 (17) |
C16—C15—C14 | 119.58 (19) | C7—N3—N2 | 117.1 (2) |
O5—C15—C14 | 117.7 (2) | C22—N4—C18 | 118.3 (2) |
C15—C16—C11 | 120.56 (19) | C23—N5—N6 | 117.11 (19) |
C15—C16—H16 | 119.7 | C23—N5—H5A | 120 (2) |
C11—C16—H16 | 119.7 | N6—N5—H5A | 122 (2) |
O3—C17—O2 | 122.6 (2) | C24—N6—N5 | 116.7 (2) |
O3—C17—C11 | 122.0 (2) | C17—O2—H2B | 109.5 |
O2—C17—C11 | 115.34 (17) | C12—O4—H4A | 109.5 |
N4—C18—C19 | 122.9 (2) | C15—O5—H5B | 106 (2) |
N4—C18—H18 | 118.6 | C34—O7—H7 | 109.5 |
C19—C18—H18 | 118.6 | C29—O9—H9 | 103 (3) |
C18—C19—C20 | 118.57 (19) | C32—O10—H10 | 106 (2) |
C18—C19—H19 | 120.7 | C10A—C9A—C7 | 101.5 (8) |
C20—C19—H19 | 120.7 | C10A—C9A—H9AA | 111.5 |
C21—C20—C19 | 118.4 (2) | C7—C9A—H9AA | 111.5 |
C21—C20—C23 | 123.8 (2) | C10A—C9A—H9AB | 111.5 |
C19—C20—C23 | 117.71 (18) | C7—C9A—H9AB | 111.5 |
C22—C21—C20 | 119.0 (2) | H9AA—C9A—H9AB | 109.3 |
C22—C21—H21 | 120.5 | C9A—C10A—H10D | 109.5 |
C20—C21—H21 | 120.5 | C9A—C10A—H10E | 109.5 |
N4—C22—C21 | 122.9 (2) | H10D—C10A—H10E | 109.5 |
N4—C22—H22 | 118.6 | C9A—C10A—H10F | 109.5 |
C21—C22—H22 | 118.6 | H10D—C10A—H10F | 109.5 |
O6—C23—N5 | 123.0 (2) | H10E—C10A—H10F | 109.5 |
O6—C23—C20 | 119.9 (2) | ||
N1—C1—C2—C3 | −0.1 (3) | N6—C24—C26—C27B | −39.4 (16) |
C1—C2—C3—C4 | −0.9 (3) | C25—C24—C26—C27B | 141.7 (16) |
C1—C2—C3—C6 | −177.54 (19) | N6—C24—C26—C27A | −112.4 (5) |
C2—C3—C4—C5 | 1.4 (3) | C25—C24—C26—C27A | 68.7 (5) |
C6—C3—C4—C5 | 178.25 (18) | C33—C28—C29—O9 | −177.8 (2) |
C3—C4—C5—N1 | −1.0 (3) | C34—C28—C29—O9 | 1.3 (3) |
C2—C3—C6—O1 | 153.6 (2) | C33—C28—C29—C30 | 2.5 (3) |
C4—C3—C6—O1 | −23.1 (3) | C34—C28—C29—C30 | −178.4 (2) |
C2—C3—C6—N2 | −25.0 (3) | O9—C29—C30—C31 | 177.7 (2) |
C4—C3—C6—N2 | 158.3 (2) | C28—C29—C30—C31 | −2.6 (4) |
N3—C7—C9—C10 | 4.3 (7) | C29—C30—C31—C32 | 0.8 (4) |
C8—C7—C9—C10 | −164.9 (5) | C30—C31—C32—C33 | 1.2 (4) |
C16—C11—C12—O4 | −177.7 (2) | C30—C31—C32—O10 | −179.0 (2) |
C17—C11—C12—O4 | 1.4 (3) | O10—C32—C33—C28 | 178.92 (19) |
C16—C11—C12—C13 | 2.2 (3) | C31—C32—C33—C28 | −1.2 (3) |
C17—C11—C12—C13 | −178.6 (2) | C29—C28—C33—C32 | −0.6 (3) |
O4—C12—C13—C14 | 177.7 (2) | C34—C28—C33—C32 | −179.67 (19) |
C11—C12—C13—C14 | −2.3 (4) | C29—C28—C34—O8 | −4.4 (3) |
C12—C13—C14—C15 | 0.2 (4) | C33—C28—C34—O8 | 174.6 (2) |
C13—C14—C15—C16 | 1.8 (3) | C29—C28—C34—O7 | 174.84 (19) |
C13—C14—C15—O5 | −178.7 (2) | C33—C28—C34—O7 | −6.1 (3) |
O5—C15—C16—C11 | 178.74 (18) | C2—C1—N1—C5 | 0.5 (3) |
C14—C15—C16—C11 | −1.8 (3) | C4—C5—N1—C1 | 0.0 (3) |
C12—C11—C16—C15 | −0.2 (3) | O1—C6—N2—N3 | −2.9 (4) |
C17—C11—C16—C15 | −179.35 (19) | C3—C6—N2—N3 | 175.6 (2) |
C12—C11—C17—O3 | −4.1 (3) | C8—C7—N3—N2 | −4.9 (6) |
C16—C11—C17—O3 | 175.05 (19) | C9—C7—N3—N2 | −172.5 (4) |
C12—C11—C17—O2 | 175.17 (19) | C9A—C7—N3—N2 | 152.1 (5) |
C16—C11—C17—O2 | −5.7 (3) | C6—N2—N3—C7 | 179.9 (3) |
N4—C18—C19—C20 | −0.7 (3) | C21—C22—N4—C18 | 0.4 (3) |
C18—C19—C20—C21 | 1.0 (3) | C19—C18—N4—C22 | 0.0 (3) |
C18—C19—C20—C23 | 177.6 (2) | O6—C23—N5—N6 | −5.6 (4) |
C19—C20—C21—C22 | −0.7 (3) | C20—C23—N5—N6 | 173.0 (2) |
C23—C20—C21—C22 | −177.1 (2) | C25—C24—N6—N5 | −2.7 (5) |
C20—C21—C22—N4 | 0.0 (3) | C26—C24—N6—N5 | 178.5 (3) |
C21—C20—C23—O6 | 155.2 (2) | C23—N5—N6—C24 | 173.4 (3) |
C19—C20—C23—O6 | −21.2 (3) | N3—C7—C9A—C10A | 106.4 (9) |
C21—C20—C23—N5 | −23.4 (3) | C8—C7—C9A—C10A | −95.9 (9) |
C19—C20—C23—N5 | 160.2 (2) |
Coformer | izact refcode | izbt refcode | Isostructural |
4-tert-Butylbenzoic acid | GIYMAF | GIYMEJ | Yes |
2-Hydroxybenzoic acid (salicylic acid)* | LATLAV | UBILAW | No |
3-Hydroxybenzoic acid (anhydrous) | FADHUP | FADHOJ | No |
3-Hydroxybenzoic acid hydrate | SAYPIT | SAYPOZ | Yes |
4-Nitrobenzoic acid | XOPYEJ | XOPYUZ | Yes |
Note: (*) it should be noted that the unit-cell parameters of both structures are similar but the orientation of the molecules with respect to the unit cells differ significantly. |
Thermal event | Onset (°C) | Enthalpy (J g-1) | Enthalpy (kJ mol-1) |
izact–1-nta melting/decomposition | 106.1 ± 0.5 | 170.9 ± 5.2 | 59.7 ± 2 |
izbt–1-nta melting/decomposition | 89.5± 0.1 | 167.8± 2.5 | 61.0 ± 1 |
izbt–2c4n melting/decomposition | 102.1 ± 0.2 | 100.6 ± 2.3 | 39.5 ± 1 |
izbt–2,4-dhba melting/decomposition | 174.8± 0.2 | 226.3 ± 4.3 | 78.2 ± 1 |
izbt–2,5-dhba melting/decomposition | 151.2 ± 0.2 | 132.5 ± 3.2 | 45.8 ± 1 |
izact m.p. (Lemmerer, 2012) | 160.0 | – | 29.7 |
izact–2c4n m.p. (Lemmerer, 2012) | 93.4 | – | 33.4 |
Acknowledgements
The authors acknowledge and thank the DSI/NRF Centre of Excellence in Strong Materials, as well as the NRF, for funding the Bruker D2 Phaser diffractometer.
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