research communications
N,N′-bis[(pyridin-4-yl)methyl]ethanediamide and 3-chlorobenzoic acid
Hirshfeld surface analysis and computational study of the 1:2 formed betweenaResearch Centre for Crystalline Materials, School of Science and Technology, Sunway University, 47500 Bandar Sunway, Selangor Darul Ehsan, Malaysia
*Correspondence e-mail: edwardt@sunway.edu.my
The 14H14N4O2·2C7H5ClO2, comprises a half-molecule of oxalamide (4LH2), being located about a centre of inversion, and a molecule of3-chlorobenzoic acid (3-ClBA) in a general position. From symmetry, the 4LH2 molecule has a (+)antiperiplanar conformation with the 4-pyridyl residues lying to either side of the central, planar C2N2O2 chromophore with the dihedral angle between the core and pyridyl ring being 74.69 (11)°; intramolecular amide-N—H⋯O(amide) hydrogen bonds are noted. The 3-ClBA molecule exhibits a small twist as seen in the C6/CO2 dihedral angle of 8.731 (12)°. In the molecular packing, three-molecule aggregates are formed via carboxylic acid-O—H⋯N(pyridyl) hydrogen bonding. These are connected into a supramolecular tape along [111] through amide-N—H⋯O(carbonyl) hydrogen bonding. Additional points of contact between molecules include pyridyl and benzoic acid-C—H⋯O(amide), methylene-C—H⋯O(carbonyl) and C—Cl⋯π(pyridyl) interactions so a three-dimensional architecture results. The contributions to the calculated Hirshfeld surface are dominated by H⋯H (28.5%), H⋯O/O⋯H (23.2%), H⋯C/C⋯H (23.3%), H⋯Cl/Cl⋯H (10.0%) and C⋯Cl/C⋯Cl (6.2%) contacts. Computational chemistry confirms the C—Cl⋯π interaction is weak, and the importance of both electrostatic and dispersion terms in sustaining the molecular packing despite the strong electrostatic term provided by the carboxylic acid-O—H⋯N(pyridyl) hydrogen bonds.
of the title 1:2 CKeywords: crystal structure; oxalamide; benzoic acid derivative; hydrogen bonding; Hirshfeld surface analysis; computational chemistry.
CCDC reference: 2004094
1. Chemical context
Herein, the X-ray -ylmethyl)ethanediamide and 3-chlorobenzoic acid, (I), is described. The present crystallographic study continues recent studies into the structural chemistry of the isomeric bis(pyridin-n-ylmethyl)ethanediamide molecules, i.e. species with the general formula n-NC5H4CH2N(H)C(=O)C(=O)CH2C5H4N-n, for n = 2, 3 and 4, and hereafter, abbreviated as nLH2 (Tiekink, 2017). These molecules have interest as co-formers as they possess both hydrogen-bonding donating and accepting sites, i.e. amide and pyridyl functionalities. A particular focus of these studies has been upon co-crystals formed with carboxylic acids (Arman et al., 2012, 2014; Tan, Halcovitch et al., 2019; Tan & Tiekink, 2019), directed by the reliability of the carboxylic acid-O—H⋯N(pyridyl) synthon (Shattock et al., 2008). A common thread of recent investigations has been upon benzoic acid (Tan & Tiekink, 2020a) and derivatives (Syed et al., 2016), in particular halide-substituted species (Tan & Tiekink, 2020b) in order to probe for the possibility of competing/complementary halogen-bonding interactions. In connection with this theme, this report describes the crystal and molecular structures of (I), along with a detailed analysis of the supramolecular association through the calculation of the Hirshfeld surface and computational chemistry.
determination of the 1:2 formed between bis(pyridin-42. Structural commentary
The comprises a molecule of 4-chlorobenzoic acid (3-ClBA) in a general position and one-half molecule of 4LH2, being disposed about a centre of inversion, Fig. 1. In the acid, 3-ClBA, there is a definitive disparity in the C8—O2 [1.225 (2) Å] and C8—O3 [1.308 (2) Å] bond lengths entirely consistent with the localization of the acidic proton on the O3 atom. This is also borne out in the angles subtended at the C8 atom with the widest angle involving the oxygen atoms [O2—C8—O3 = 123.38 (17)°] and the narrowest involving the atoms connected by a single bond [O3—C8—C9 = 114.23 (15)°]. A small twist in the molecule is evident as seen in the dihedral angle of 8.731 (12)° formed between the CO2/C6 residues; the O2—C8—C9—C10 torsion angle = 171.79 (19) Å.
of (I)The 4LH2 molecule is situated about a centre of inversion so the central C2N2O2 chromophore is constrained to be planar. As is normal for nLH2 molecules (Tiekink, 2017), the central C7—C7i [1.539 (3) Å; symmetry code: (i) 1 − x, − y, − z] bond length is considered long, an observation ascribed to the electronegative substituents bound to the sp2-C7 atom. The conformation of the 4LH2 molecule is (+)antiperiplanar so the 4-pyridyl residues lie to either side of the planar region of the molecule. The dihedral angle between the central core and the N1-pyridyl ring is 74.69 (11)°. Owing to the anti-disposition of the amide groups intramolecular amide-N—H⋯O(amide) hydrogen bonds are formed which complete S(5) loops, Table 1.
3. Supramolecular features
The most distinctive feature of the molecular packing is the association between 4LH2 and two symmetry-related 3-ClBA molecules via carboxylic acid-O—H⋯N(pyridyl) hydrogen bonding, Table 1, to generate a three-molecule aggregate. These three-molecule aggregates are connected into a linear tape along [111] via amide-N—H⋯O(carbonyl) hydrogen bonds Fig. 2(a). These give rise to 22-membered {⋯NC4NH⋯OCOH}2 synthons. Additional stability to the hydrogen-bonding arrangement is provided by supporting benzoic acid-C14—H⋯O(amide) interaction which lead to non-symmetric 10-membered {⋯HC3O⋯HNC2O}2 synthons, which flank the larger 22-membered rings. Further, a complementary C—Cl⋯π(pyridyl) contact is noted, as detailed in Table 1. A survey of the literature (Imai et al., 2008) as well as the Cambridge Structural Database (Groom et al., 2016) shows that the average Cl⋯π distance is about 3.6 Å, which is shorter than the contact distance in (I). An end-on view of the tape is shown in Fig. 2(b). The tapes are connected into a supramolecular layer by relatively short pyridyl-C1—H⋯O(amide) contacts, Fig. 2(c). A three-dimensional architecture results when benzoic acid-C12—H⋯O(amide) and methylene-C—H⋯O(carbonyl) interactions are taken into consideration, Fig. 2(d). In this scheme, the amide-O1 atom participates in three pivotal C—H⋯O interactions.
4. Hirshfeld surface analysis
The Hirshfeld surface analysis was performed for the three-molecule aggregate of (I), i.e. that sustained by the carboxylic acid-O—H⋯N(pyridyl) hydrogen bonds, and for the individual components, viz. the full molecule of 4LH2 and 3-ClBA, with the use of CrystalExplorer17 (Turner et al., 2017) and based on established methods (Tan, Jotani et al., 2019). As shown in the images of Fig. 3, the analysis reveals there are several red spots of variable intensity observed on the dnorm maps calculated for 4LH2 and 3-ClBA. These are indicative of close contact distances shorter than the van der Waals radii (Spackman & Jayatilaka, 2009). Specifically, red spots with intensity in decreasing order are observed for hydroxyl-O3—H3O⋯N1(pyridyl), amide-N2—H2N⋯O2(carbonyl), pyridyl-C1—H1⋯O1(amide), benzene-C14—H14⋯O1(amide), benzene-C12—H12⋯O1(amide) and methylene-C6—H6A⋯O3(hydroxyl); the dnorm distances for these short contacts are given in Table 2. While the identified close contacts are consistent with those obtained from PLATON analysis (Spek, 2020), additional red spots are noted for pyridyl-C4—H4⋯C11(benzene) as well as benzyl-C10⋯C10(benzene), albeit with relatively weaker intensity than the other interactions mentioned above. As for the C13–Cl1⋯π(N1,C1–C5) contact, Table 2, the Hirshfeld surface analysis reveals only a faint-blue spot around the tip of Cl1 in Fig. 3(b) indicating the contact distance that is slightly less than the sum of the van der Waals radii (Spackman & Jayatilaka, 2009).
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To verify the nature of the Cl⋯π contact in (I), the co-formers were subjected to electrostatic potential mapping through DFT-B3LYP/6-31G(d,p), as available in CrystalExplorer17. The analysis indicates that the Cl⋯π interaction is weak in nature as evidenced from the white spot around the σ-hole region about the Cl1 atom in Fig. 4(a) as well as the faint-red spot around the centre of the π-ring centre, Fig. 4(b). A detailed study on the localized electrostatic charges shows that the σ-hole of Cl1 is about −0.0072 a.u. while the pyridyl π-hole is about −0.1270 a.u. indicating that the interaction is rather dispersive in nature. This observation is in contrast with other charge complementary interactions as shown from the intense blue (i.e. electropositive) and red (i.e. electronegative) regions on the electrostatic surface map. For instance, the amide-N2—H2N⋯O2(carbonyl) hydrogen bond has a point-to-point electrostatic charge of 0.1438 a.u. for H2N and −0.0622 a.u. for O2, suggestive of a strong interaction, while benzene-C14—H14⋯O1(amide) shows complementary charges of 0.0427 and −0.0486 a.u. for H14 and O1, respectively, being indicative of a relatively weaker interaction. Among all the identified close contacts, hydroxyl-O3—H3O⋯N1(pyridyl) is considered to be the strongest exhibiting a marked difference in the electrostatic charge of 0.2919 a.u. for H3O and −0.0727 a.u. for N1.
The three-molecule-aggregate of (I) as well as its individual co-formers, i.e. 4LH2 and 3-ClBA, were subjected to fingerprint analysis for quantification of the close contacts for each entity, Fig. 5(a). Overall (I) exhibits a paw-like fingerprint profile which can be delineated into H⋯H (28.5%), H⋯O/O⋯H (23.2%), H⋯C/C⋯H (23.3%), H⋯N/N⋯H (2.2%), H⋯Cl/Cl⋯H (10.0%) and C⋯Cl/C⋯Cl (6.2%), as illustrated in Fig. 5(b)–(f); others contacts amount to 6.6%, constituting contacts less than 2.0% each. Among those contacts for (I), only H⋯O/O⋯H and H⋯C/C⋯H exhibit minimum di + de contact distances tipped at ca 1.94 and 2.08 Å, respectively, significantly less than their respective sums of van der Waals radii of 2.61 and 2.79 Å; the remaining contacts occur at distances greater than their corresponding sums of van der Waals radii.
A similar paw-like fingerprint profile is observed for the overall fingerprint plots of the individual 4LH2 and 3-ClBA molecules. The key difference between these and that for (I) is the asymmetry in the distributions owing to the interdependency of the intermolecular interactions between the two co-formers. For 4LH2, the major contacts comprise H⋯H (34.5%), H⋯O/O⋯H (22.1%), H⋯C/C⋯H (20.3%), H⋯N/N⋯H (8.4%), H⋯Cl/Cl⋯H (6.4%) and C⋯Cl (5.0%). A detailed analysis on the corresponding contacts reveals that the (internal)-H⋯O-(external) and (internal)-H⋯C-(external) contacts are slightly more dominant over the (internal)-O⋯H-(external) and (internal)-C⋯H-(external) counterparts with the distribution of the contacts being 12.7 and 11.2% versus 9.4 and 9.1%, while the opposite is true for the (internal)-H⋯N-(external) contact with a distribution of 0.6% as compared to 7.8% for (internal)-N⋯H-(external). The stark difference in the dominance for H⋯N/N⋯H is likely due to the amide-H forming a hydrogen bond to O(carbonyl) rather than to a nitrogen acceptor. Among the major contacts, (internal)-H⋯O-(external) and (internal)-N⋯H-(external) display minimum di + de distances of about 1.94 and 1.60 Å, respectively, which are significantly shorter than the sums of the respective van der Waals radii as compared to the (internal)-O⋯H-(external) and (internal)-H⋯N-(external) counterparts of 2.24 and 3.62 Å, respectively. A similar observation is noted for (internal)-H⋯C-(external) (∼2.66 Å) despite the deviation from the sum of the van der Waals radii (2.79 Å) being less significant.
As for the individual 3-ClBA molecule, the major contacts in the overall fingerprint plot can be delineated into H⋯O/O⋯H (23.5%), H⋯C/C⋯H (22.9%), H⋯H (21.8%), H⋯Cl/Cl⋯H (11.9%), C⋯Cl/Cl⋯C (6.5%) and H⋯N/N⋯H (4.6%). The trend of dominance is more inclined towards (internal)-X⋯Y-(external) for some close contacts (X = O, C and Cl; Y = H and C), with the distribution being 15.0, 14.4, 10.5 and 5.5% for O⋯H, C⋯H, Cl⋯H and Cl⋯C, respectively, compared to 8.5, 8.5, 1.4 and 1.0% for the corresponding H⋯O, H⋯C, H⋯Cl and C⋯Cl counterparts. In term of di + de contact distances, the key values are reciprocal to those for 4LH2 owing to the interdependency of interactions as mentioned previously.
5. Computational chemistry
The calculation of the interaction energy for all pairwise molecules in (I) was performed through CrystalExplorer17 (Turner et al., 2017) following reported procedures (Tan, Jotani et al., 2019) with the purpose of studying the strength of each interaction identified from the Hirshfeld surface analysis. The results tabulated in Table 3 show that the carboxylic acid-O3—H3O⋯N1(pyridyl) hydrogen bond has the greatest interaction energy (Eint) with the value being −48.0 kJ mol−1, and this is followed by the dimeric amide-N2—H2N⋯O2(carbonyl), benzene-C14—H14⋯O1(amide) and Cl1⋯π(N1,C1–C5) interactions, with a combined Eint of −38.7 kJ mol−1, the 16-membered {⋯OCNC3CH⋯} heterosynthon involving pyridyl-C1—H1⋯O1(amide) interactions (−24.6 kJ mol−1), benzene-C12—H12⋯O1(amide) and pyridyl-C4—H4⋯C11(benzene) with a combined Eint of −24.0 kJ mol−1, methylene-C6—H6A⋯O3(hydroxyl) (−15.8 kJ mol−1) as well as the benzene-C10⋯C10(benzene) interaction with (−15.0 kJ mol−1). Interestingly, the strongest hydroxyl-O3—H3O⋯N1(pyridyl) interaction in this crystal has an Eint value that is only slightly less than that of −49.4 and −52.0 kJ mol−1) (two independent molecules) displayed by an equivalent O—H⋯N hydrogen bond complemented by a supporting pyridyl-C—H⋯O(carbonyl) interaction in the isomeric 2:1 of 4LH2 with 4-ClBA (Tan & Tiekink, 2020b); the supporting C—H⋯O(carbonyl) contact is absent in (I).
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The . In the electrostatic energy framework, the hydroxyl-O3—H3O⋯N1(pyridyl) interaction is the main foundation of the framework as evidenced from the thick cylindrical rods with other, relatively, thinner rods which ramify owing to various other O⋯H interactions, Fig. 6(a). The O⋯H interactions together with other complementary interactions are found to contribute to the dispersion energy framework which forms a similar topology as the electrostatic energy framework, Fig. 6(b). The combination of the other electrostatic and dispersion forces supersedes the strong interaction energy from the hydroxyl-O3—H3O⋯N1(pyridyl) hydrogen bonding and leads to the overall energy framework illustrated in Fig. 6(c) without dominant interactions in a given direction. It is interesting to note that despite being an isomeric analogue to the 4LH2·2(4-ClBA) (Tan & Tiekink, 2020b), (I) exhibits completely different topological frameworks as compared to the ladder-like frameworks of 4LH2·2(4-ClBA).
system is governed by a combination of electrostatic and dispersion forces leading to a three-dimensional wire mesh-like energy framework as shown in Fig. 66. Database survey
The aforementioned analogue of (I), 4LH2·2(4-ClBA) (Tan & Tiekink, 2020b), is the most closely related, and indeed, isomeric available for comparison; this too has been subjected to a detailed analysis of the molecular packing. Co-crystals (I) and (II) are not isostructural, with the of (II) comprising two half-molecules of 4LH2, i.e. 4LH2-IIa and 4LH2-IIb, as each is disposed about a centre of inversion, and two symmetry-independent molecules of 4-ClBA, i.e. 4-ClBA-IIa and 4-ClBA-IIb. The common feature of the molecular packing of (I) and (II) is the formation of two three-molecule aggregates. The key difference in the molecular packing relates to the nature of the supramolecular tapes: in (II), the tapes are sustained by a sequence of ten-membered {⋯HNCCO}2 synthons, as highlighted in Fig. 7.
A comparison of the percentage contributions by the most prominent contacts to the respective Hirshfeld surfaces of (I) and (II), and including their individual components has been made (Jotani et al., 2019). The results are summarized in Fig. 8 and suggest that to a first approximation there are no dramatic variations between the contacts made to the Hirshfeld surfaces calculated for (I) and (II). Among the noticeable differences are due to the H⋯O/O⋯H contacts which are greater for 3-ClBA, by 5.8 and 5.6%, respectively than for 4-ClBA-IIa and IIb. This is compensated by a reduction in the H⋯Cl/Cl⋯H contacts by 4.9 and 5.6%. One possible reason for the increase in O⋯H/H⋯O contacts in (I) cf. (II) relates to the participation of the carbonyl-O atom in formal hydrogen bonding to the amide-N—H group and the prominent role of the amide-O1 atom in providing points of contact between molecules.
7. Synthesis and crystallization
The precursor, N,N′-bis[(pyridin-4-yl)methyl]oxalamide (4LH2) was prepared according to a literature procedure: M.p. 486.3–487.6 K; lit. 486–487 K (Nguyen et al., 1998). 3-Chlorobenzoic acid (Merck; 3-ClBA) was of reagent grade and used as received without further purification. The co-former 4LH2 (0.271 g, 0.001 mol) was mixed with 3-ClBA (0.157 g, 0.001 mol) and the mixture was then ground for 15 min in the presence of a few drops of methanol. The procedure was repeated twice. Colourless blocks were obtained through careful layering of toluene (1 ml) on an N,N-dimethylformamide solution (1 ml) of the ground mixture. M.p. 436.6–437.7 K. IR (cm−1): 3280 ν(N—H), 3070–2919 ν(C—H), 1703–1656 ν(C=O), 1524 ν(C=C), 1415 ν(C—N), 753 ν(C—Cl).
8. Refinement
Crystal data, data collection and structure . The carbon-bound H atoms were placed in calculated positions (C—H = 0.95–0.99 Å) and were included in the in the riding-model approximation, with Uiso(H) set to 1.2Ueq(C). The oxygen- and nitrogen-bound H atoms were located from a difference-Fourier map and refined with O—H = 0.84±0.01 Å and N—H = 0.86±0.01 Å, respectively, and with Uiso(H) set to 1.5Ueq(O) or 1.2Ueq(N).
details are summarized in Table 4
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Supporting information
CCDC reference: 2004094
https://doi.org/10.1107/S2056989020006568/wm5558sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989020006568/wm5558Isup2.hkl
Data collection: CrysAlis PRO (Rigaku OD, 2018); cell
CrysAlis PRO (Rigaku OD, 2018); data reduction: CrysAlis PRO (Rigaku OD, 2018); program(s) used to solve structure: SHELXS (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2017/1 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012), DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).C7H5ClO2·C7H7N2O | Z = 2 |
Mr = 291.71 | F(000) = 302 |
Triclinic, P1 | Dx = 1.401 Mg m−3 |
a = 7.7817 (2) Å | Cu Kα radiation, λ = 1.54184 Å |
b = 9.5743 (3) Å | Cell parameters from 7027 reflections |
c = 11.1516 (4) Å | θ = 5.4–76.0° |
α = 113.721 (3)° | µ = 2.54 mm−1 |
β = 90.064 (2)° | T = 100 K |
γ = 112.397 (3)° | Rhombohedral, colourless |
V = 691.47 (4) Å3 | 0.17 × 0.07 × 0.06 mm |
XtaLAB Synergy, Dualflex, AtlasS2 diffractometer | 2873 independent reflections |
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source | 2589 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.043 |
Detector resolution: 5.2558 pixels mm-1 | θmax = 76.6°, θmin = 4.4° |
ω scans | h = −9→9 |
Absorption correction: gaussian (CrysAlisPro; Rigaku OD, 2018) | k = −12→12 |
Tmin = 0.604, Tmax = 1.000 | l = −13→13 |
17474 measured reflections |
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.047 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.128 | w = 1/[σ2(Fo2) + (0.0629P)2 + 0.363P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
2873 reflections | Δρmax = 0.61 e Å−3 |
189 parameters | Δρmin = −0.47 e Å−3 |
2 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 | ||
Cl1 | 1.16272 (7) | 1.19147 (7) | 0.97323 (5) | 0.04950 (19) | |
O2 | 0.52027 (18) | 0.7929 (2) | 0.61549 (14) | 0.0462 (4) | |
O3 | 0.61166 (18) | 0.70870 (18) | 0.41896 (13) | 0.0379 (3) | |
H3O | 0.4966 (19) | 0.676 (4) | 0.389 (3) | 0.080 (10)* | |
C8 | 0.6450 (2) | 0.7875 (2) | 0.54909 (18) | 0.0323 (4) | |
C9 | 0.8502 (2) | 0.8715 (2) | 0.61122 (18) | 0.0314 (4) | |
C10 | 0.9858 (3) | 0.8450 (2) | 0.5341 (2) | 0.0337 (4) | |
H10 | 0.949112 | 0.774182 | 0.441116 | 0.040* | |
C11 | 1.1744 (3) | 0.9230 (3) | 0.5943 (2) | 0.0383 (4) | |
H11 | 1.266423 | 0.903127 | 0.542180 | 0.046* | |
C12 | 1.2306 (3) | 1.0291 (3) | 0.7289 (2) | 0.0385 (4) | |
H12 | 1.360150 | 1.082595 | 0.769580 | 0.046* | |
C13 | 1.0942 (3) | 1.0560 (2) | 0.8034 (2) | 0.0358 (4) | |
C14 | 0.9041 (2) | 0.9776 (2) | 0.74687 (19) | 0.0341 (4) | |
H14 | 0.812284 | 0.996077 | 0.799770 | 0.041* | |
O1 | 0.62312 (17) | 0.12645 (16) | −0.07710 (13) | 0.0330 (3) | |
N1 | 1.2621 (2) | 0.5924 (2) | 0.31316 (17) | 0.0383 (4) | |
N2 | 0.5685 (2) | 0.2032 (2) | 0.13447 (16) | 0.0328 (3) | |
H2N | 0.522 (3) | 0.167 (3) | 0.1913 (19) | 0.045 (7)* | |
C1 | 1.1930 (3) | 0.6341 (3) | 0.22886 (19) | 0.0388 (4) | |
H1 | 1.278903 | 0.712666 | 0.201889 | 0.047* | |
C2 | 1.0017 (3) | 0.5676 (2) | 0.17938 (19) | 0.0365 (4) | |
H2 | 0.958087 | 0.600506 | 0.119978 | 0.044* | |
C3 | 0.8745 (3) | 0.4522 (2) | 0.21761 (18) | 0.0339 (4) | |
C4 | 0.9465 (3) | 0.4093 (3) | 0.3046 (2) | 0.0444 (5) | |
H4 | 0.863962 | 0.330319 | 0.332615 | 0.053* | |
C5 | 1.1384 (3) | 0.4818 (3) | 0.3502 (2) | 0.0459 (5) | |
H5 | 1.185252 | 0.452059 | 0.410711 | 0.055* | |
C6 | 0.6630 (3) | 0.3820 (2) | 0.1718 (2) | 0.0381 (4) | |
H6A | 0.608278 | 0.441956 | 0.244426 | 0.046* | |
H6B | 0.639555 | 0.402602 | 0.094503 | 0.046* | |
C7 | 0.5558 (2) | 0.0917 (2) | 0.01203 (17) | 0.0291 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0348 (3) | 0.0602 (3) | 0.0397 (3) | 0.0143 (2) | −0.0083 (2) | 0.0140 (2) |
O2 | 0.0246 (6) | 0.0723 (10) | 0.0315 (7) | 0.0152 (6) | 0.0036 (5) | 0.0177 (7) |
O3 | 0.0292 (7) | 0.0445 (8) | 0.0298 (7) | 0.0093 (6) | 0.0013 (5) | 0.0124 (6) |
C8 | 0.0287 (9) | 0.0384 (9) | 0.0297 (9) | 0.0112 (7) | 0.0039 (7) | 0.0173 (8) |
C9 | 0.0262 (8) | 0.0363 (9) | 0.0333 (9) | 0.0109 (7) | 0.0041 (7) | 0.0187 (8) |
C10 | 0.0323 (9) | 0.0355 (9) | 0.0369 (10) | 0.0145 (7) | 0.0081 (8) | 0.0189 (8) |
C11 | 0.0286 (9) | 0.0456 (11) | 0.0496 (12) | 0.0176 (8) | 0.0127 (8) | 0.0269 (10) |
C12 | 0.0241 (8) | 0.0452 (10) | 0.0515 (12) | 0.0113 (7) | 0.0023 (8) | 0.0289 (10) |
C13 | 0.0286 (9) | 0.0414 (10) | 0.0371 (10) | 0.0114 (7) | −0.0005 (7) | 0.0199 (8) |
C14 | 0.0259 (8) | 0.0426 (10) | 0.0354 (10) | 0.0132 (7) | 0.0043 (7) | 0.0194 (8) |
O1 | 0.0242 (6) | 0.0417 (7) | 0.0306 (7) | 0.0080 (5) | 0.0035 (5) | 0.0186 (6) |
N1 | 0.0319 (8) | 0.0360 (8) | 0.0355 (9) | 0.0028 (6) | −0.0022 (6) | 0.0155 (7) |
N2 | 0.0246 (7) | 0.0362 (8) | 0.0278 (8) | 0.0053 (6) | 0.0000 (6) | 0.0117 (6) |
C1 | 0.0372 (10) | 0.0420 (10) | 0.0309 (9) | 0.0058 (8) | 0.0040 (8) | 0.0199 (8) |
C2 | 0.0387 (10) | 0.0393 (10) | 0.0290 (9) | 0.0107 (8) | 0.0017 (7) | 0.0177 (8) |
C3 | 0.0320 (9) | 0.0301 (9) | 0.0284 (9) | 0.0057 (7) | −0.0022 (7) | 0.0091 (7) |
C4 | 0.0342 (10) | 0.0393 (10) | 0.0503 (12) | −0.0023 (8) | −0.0080 (9) | 0.0273 (10) |
C5 | 0.0380 (11) | 0.0423 (11) | 0.0511 (13) | 0.0019 (8) | −0.0099 (9) | 0.0284 (10) |
C6 | 0.0318 (9) | 0.0365 (10) | 0.0366 (10) | 0.0095 (8) | −0.0019 (8) | 0.0117 (8) |
C7 | 0.0169 (7) | 0.0381 (9) | 0.0279 (8) | 0.0069 (7) | −0.0012 (6) | 0.0146 (7) |
Cl1—C13 | 1.746 (2) | N1—C5 | 1.340 (3) |
O2—C8 | 1.225 (2) | N2—H2N | 0.857 (10) |
O3—H3O | 0.846 (10) | N2—C6 | 1.453 (2) |
O3—C8 | 1.308 (2) | N2—C7 | 1.326 (2) |
C8—C9 | 1.499 (2) | C1—H1 | 0.9500 |
C9—C10 | 1.395 (3) | C1—C2 | 1.385 (3) |
C9—C14 | 1.391 (3) | C2—H2 | 0.9500 |
C10—H10 | 0.9500 | C2—C3 | 1.389 (3) |
C10—C11 | 1.386 (3) | C3—C4 | 1.385 (3) |
C11—H11 | 0.9500 | C3—C6 | 1.517 (3) |
C11—C12 | 1.382 (3) | C4—H4 | 0.9500 |
C12—H12 | 0.9500 | C4—C5 | 1.376 (3) |
C12—C13 | 1.386 (3) | C5—H5 | 0.9500 |
C13—C14 | 1.386 (3) | C6—H6A | 0.9900 |
C14—H14 | 0.9500 | C6—H6B | 0.9900 |
O1—C7 | 1.228 (2) | C7—C7i | 1.539 (3) |
N1—C1 | 1.340 (3) | ||
C8—O3—H3O | 110 (2) | C7—N2—C6 | 120.72 (16) |
O2—C8—O3 | 123.38 (17) | N1—C1—H1 | 118.6 |
O2—C8—C9 | 122.38 (17) | N1—C1—C2 | 122.84 (17) |
O3—C8—C9 | 114.23 (15) | C2—C1—H1 | 118.6 |
C10—C9—C8 | 120.62 (17) | C1—C2—H2 | 120.4 |
C14—C9—C8 | 119.03 (16) | C1—C2—C3 | 119.22 (18) |
C14—C9—C10 | 120.35 (17) | C3—C2—H2 | 120.4 |
C9—C10—H10 | 120.3 | C2—C3—C6 | 121.38 (18) |
C11—C10—C9 | 119.44 (19) | C4—C3—C2 | 117.76 (17) |
C11—C10—H10 | 120.3 | C4—C3—C6 | 120.78 (17) |
C10—C11—H11 | 119.5 | C3—C4—H4 | 120.2 |
C12—C11—C10 | 121.04 (18) | C5—C4—C3 | 119.60 (18) |
C12—C11—H11 | 119.5 | C5—C4—H4 | 120.2 |
C11—C12—H12 | 120.7 | N1—C5—C4 | 122.98 (19) |
C11—C12—C13 | 118.63 (17) | N1—C5—H5 | 118.5 |
C13—C12—H12 | 120.7 | C4—C5—H5 | 118.5 |
C12—C13—Cl1 | 119.31 (15) | N2—C6—C3 | 112.60 (16) |
C14—C13—Cl1 | 118.88 (15) | N2—C6—H6A | 109.1 |
C14—C13—C12 | 121.81 (19) | N2—C6—H6B | 109.1 |
C9—C14—H14 | 120.6 | C3—C6—H6A | 109.1 |
C13—C14—C9 | 118.72 (18) | C3—C6—H6B | 109.1 |
C13—C14—H14 | 120.6 | H6A—C6—H6B | 107.8 |
C5—N1—C1 | 117.60 (17) | O1—C7—N2 | 124.94 (17) |
C6—N2—H2N | 120.9 (16) | O1—C7—C7i | 121.2 (2) |
C7—N2—H2N | 118.3 (16) | N2—C7—C7i | 113.87 (19) |
Cl1—C13—C14—C9 | 179.18 (14) | N1—C1—C2—C3 | −0.2 (3) |
O2—C8—C9—C10 | 171.79 (19) | C1—N1—C5—C4 | 0.7 (3) |
O2—C8—C9—C14 | −8.8 (3) | C1—C2—C3—C4 | 0.1 (3) |
O3—C8—C9—C10 | −8.1 (2) | C1—C2—C3—C6 | 176.96 (19) |
O3—C8—C9—C14 | 171.32 (17) | C2—C3—C4—C5 | 0.4 (3) |
C8—C9—C10—C11 | −179.40 (17) | C2—C3—C6—N2 | 138.48 (19) |
C8—C9—C14—C13 | −179.43 (17) | C3—C4—C5—N1 | −0.8 (4) |
C9—C10—C11—C12 | −1.3 (3) | C4—C3—C6—N2 | −44.8 (3) |
C10—C9—C14—C13 | 0.0 (3) | C5—N1—C1—C2 | −0.2 (3) |
C10—C11—C12—C13 | 0.3 (3) | C6—N2—C7—O1 | 1.8 (3) |
C11—C12—C13—Cl1 | −179.29 (15) | C6—N2—C7—C7i | −177.61 (17) |
C11—C12—C13—C14 | 1.0 (3) | C6—C3—C4—C5 | −176.5 (2) |
C12—C13—C14—C9 | −1.1 (3) | C7—N2—C6—C3 | −86.3 (2) |
C14—C9—C10—C11 | 1.2 (3) |
Symmetry code: (i) −x+1, −y, −z. |
Cg1 is the centroid of the (N1,C1–C5) ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···O1i | 0.86 (2) | 2.34 (3) | 2.717 (2) | 107 (2) |
N2—H2N···O2ii | 0.86 (2) | 2.08 (2) | 2.863 (2) | 151 (2) |
O3—H3O···N1iii | 0.84 (2) | 1.74 (2) | 2.581 (2) | 174 (4) |
C14—H14···O1iv | 0.95 | 2.37 | 3.286 (2) | 161 |
C1—H1···O1v | 0.95 | 2.39 | 3.286 (3) | 157 |
C12—H12···O1vi | 0.95 | 2.46 | 3.328 (3) | 152 |
C6—H6A···O3 | 0.99 | 2.50 | 3.400 (3) | 151 |
C13—Cl1···Cg1 | 1.75 (1) | 3.83 (1) | 5.358 (2) | 145 (1) |
Symmetry codes: (i) −x+1, −y, −z; (ii) −x+1, −y+1, −z+1; (iii) x−1, y, z; (iv) x, y+1, z+1; (v) −x+2, −y+1, −z; (vi) x+1, y+1, z+1. |
Contact | Distance | Symmetry operation |
H2N···O2b | 1.95 | 1 - x, 2 - y, 1 - z |
H3O···N1b | 1.60 | 1 - x, 2 - y, 1 - z |
H1···O1 | 2.27 | -1 + x, -1 + y, 1 + z |
H6A···O3 | 2.42 | -1 + x, -1 + y, 1 + z |
H12···O1 | 2.34 | 1 - x, 1 - y, 1 - z |
H14···O1 | 2.25 | x, y, z |
H4···C11 | 2.66 | 1 - x, 1 - y, 1 - z |
C10···C10 | 3.28 | 2 - x, 2 - y, 1 - z |
Notes: (a) The interatomic distances are calculated in Crystal Explorer 17 (Turner et al., 2017) whereby the X—H bond lengths are adjusted to their neutron values; (b) these interactions correspond to conventional hydrogen bonds. |
Contact | Eele | Epol | Edis | Erep | Etot | Symmetry operation |
N2—H2N···O2 + | ||||||
C14—H14···O1 + | ||||||
Cl1···π(N1,C1–C5) | -39.1 | -6.6 | -21.6 | 28.7 | -38.7 | 1 - x, 1 - y, 1 - z |
O3—H3O···N1 | -102.5 | -17.5 | -10.2 | 82.2 | -48.0 | -1 + x, y, z |
C1—H1···O1 (×2) | -22.0 | -3.4 | -16.1 | 16.9 | -24.6 | 2 - x, 1 - y, -z |
C6—H6A···O3 | -7.7 | -0.9 | -18.3 | 11.2 | -15.8 | x, y, z |
C12—H12···O1+ | ||||||
C4—H4···C11 | -12.9 | -1.6 | -31.0 | 21.6 | -24.0 | 1 + x, 1 + y, 1 + z |
C10···C10 | -2.4 | -0.4 | -26.0 | 13.7 | -15.0 | 2 - x, 2 - y, 1 - z |
Funding information
Crystallographic research at Sunway University is supported by Sunway University Sdn Bhd (grant No. STR-RCTR-RCCM-001-2019).
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