Reaction of 4-methyl benzyl chloride with barbituric acid gave 5,5-bis(4-methylbenzyl)pyrimidine-2,4,6(1H,3H,5H)-trione, which crystallized with two molecules in its asymmetric unit along with two solvent water molecules. A hydrogen-bonded sheet is formed by a combination of N—H⋯O and Owater—H⋯O hydrogen bonds, which are further interconnected by C—H⋯πaryl interactions, leading to a three-dimensional supramolecular architecture.
Keywords: crystal structure, hydrogen-bonded sheets, pyrimidine, C—H⋯π interactions, Knoevenagel condensation, three-dimensional structure
Abstract
The asymmetric unit of the title compound, C20H20N2O3·H2O, contains two independent molecules (A and B), with similar conformations and two independent water molecules. In the crystal, N—H⋯O and Owater—H⋯O hydrogen bonds link all moieties into two crystallographically independent kinds of sheets parallel to the ac plane. These independent sheets, each containing either A or B molecules, are further alternately stacked along the b axis and interconnected via C—H⋯πaryl interactions.
Chemical Context
Barbituric acid and its derivatives have historically been classified as compounds which act on the central nervous system (Barbachyn et al., 2007 ▸). These compounds have been widely used as therapeutic drugs such as anxiolytics, sedatives, hypnotics and anti-convulsants (Coupey, 1997 ▸). Recent investigations on barbituric acid derivatives revealed the applications of these compounds as antibacterial (Yilmaz et al., 2006 ▸; Sweidan et al., 2011 ▸), anti-viral (Clercq, 1986a
▸,b
▸; Baba et al., 1987 ▸), analgesic (Vida et al., 1975 ▸), anti-hypertensive (Bassin & Bleck, 2008 ▸) and as anti-cancer (Humar et al., 2004 ▸; Singh et al., 2009 ▸) agents. 5-Fluorouracil is a barbituric acid analogue, which has been widely employed as a clinically useful anti-cancer drug (Heidelberger & Arafield, 1963 ▸).
Inspired by the above facts, the title compound was synthesized by Knoevenagel condensation reaction (Prajapati and Gohain, 2006 ▸). A double-benzylated product of barbituric acid was obtained by using two equivalents of 4-methyl benzyl chloride in the presence of catalytic amounts of 1,8-diazabicycloundec-7-ene (DBU) and solvent acetonitrile. The obtained compound was characterized by 1H-NMR and mass spectroscopy. We report herein on its crystal structure.
Structural commentary
The title compound (I) (Fig. 1 ▸) crystallizes with two molecules, A and B, in the asymmetric unit along with two water molecules of crystallization. In both molecules, the pyrimidine rings are nearly planar [r.m.s. deviations of 0.039 and 0.040 Å] and can be considered as a pseudo-mirror plane for each molecule. In A, the benzene rings form dihedral angles of 49.70 (17) and 51.66 (17)° with the pyrimidine ring and are inclined each to other by 62.9 (2)°. In B, the corresponding angles are 50.44 (18), 69.90 (19) and 59.8 (2)°, respectively. In the related compound 5,5-dibenzylbarbituric acid monohydrate (II) (Bhatt et al., 2007 ▸), which crystallizes with one independent molecule and one water molecule in the asymmetric unit, the dihedral angles between the pyrimidine and two benzene rings are 54.09 (11) and 62.71 (11)°.
Figure 1.
A view of (I), showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.
Supramolecular features
In the first level of packing, the independent molecules are linked directly to their symmetry equivalents via strong N2—HN2⋯O4 (A) and N3—HN3⋯O7 (B) hydrogen bonds (Table 1 ▸), forming chains running along a-axis direction. Thus, the graph set motif is C(6)C(6). Six chains pass through the unit cell. These chains are linked via water molecules through N1—H1⋯O1 and O1—H1B⋯O5 (for A) and N4—HN4⋯O2 and O2—H2A⋯O8 (for B) hydrogen bonds (Table 1 ▸), each forming graph set motif D(2). In addition, the symmetry-dependent parallel chains are interconnected via bridging water molecules through O—H⋯O3 and O1—HIB⋯O5 (for A) and O2—H2B⋯O6 and O2—H2A⋯O8 (for B) hydrogen bonds (Table 1 ▸), forming sheets parallel to the ac plane (Fig. 2 ▸). The alternate sheets formed by A or B molecules and water molecules are interconnected via C—H⋯π interactions (Fig. 3 ▸, Table 1 ▸), thus forming a three-dimensional structure.
Table 1. Hydrogen-bond geometry (, ).
Cg is the centroid of the C13C18 benzene ring.
| DHA | DH | HA | D A | DHA |
|---|---|---|---|---|
| N1HN1O1 | 0.86 | 1.94 | 2.787(4) | 167 |
| O1H1AO3i | 0.84(3) | 2.13(3) | 2.949(3) | 162 |
| O1H1BO5ii | 0.90(3) | 1.90(3) | 2.794(4) | 175 |
| N2HN2O4iii | 0.86 | 1.94 | 2.767(2) | 162 |
| O2H2AO8iv | 0.86(6) | 1.88(6) | 2.739(4) | 177 |
| O2H2BO6v | 0.82(3) | 2.16(3) | 2.961(3) | 169 |
| N3HN3O7vi | 0.86 | 1.90 | 2.739(2) | 164 |
| N4HN4O2 | 0.86 | 1.92 | 2.761(4) | 166 |
| C22H22Cg vii | 0.93 | 2.97 | 3.5693 | 124 |
Symmetry codes: (i) 
; (ii) 
; (iii) 
; (iv) 
; (v) 
; (vi) 
; (vii) 
.
Figure 2.
A portion of the crystal packing viewed along [100] and showing two kinds of hydrogen-bonded (thin blue lines) sheets, each containing either A or B molecules. H atoms not involved in hydrogen bonding have been omitted for clarity.
Figure 3.
A portion of the crystal packing viewed along [100] and showing C—H⋯π interactions as dotted lines. Magenta dots show the centroids of aryl rings. Thin blue lines denote hydrogen bonds. H atoms not involved in intermolecular interactions were omitted for clarity.
There are several interesting differences between the two chemically closely related structures (I) and (II) (differing only by a methyl group on the two benzene rings). Firstly, (I) crystallizes in the orthorhombic space group Pca21, whereas (II) crystallizes in the monoclinic space group P21/n. Secondly, (I) crystallizes with two molecules in its asymmetric unit, while (II) crystallizes with one independent molecule. Lastly, in the crystal of compound (II), hydrogen bonding leads to a two-dimensional network in contrast to the three-dimensional architecture formed in (I).
Synthesis and crystallization
To an ice-cooled stirring solution of acetonitrile (5 ml), 4-methyl benzyl chloride (0.5 g, 0.0035 mol), 1,8-diazabicycloundec-7-ene (DBU) (0.5 g, 0.0035 mol) and barbituric acid (0.22 g, 0.0017 mol) were added. The reaction mixture was stirred to the room temperature and then refluxed for 8 h. Thin-layer chromatography showed the absence of any starting material. The reaction mixture was cooled and poured into ice-cold water. The solid obtained was extracted with ethyl acetate and the organic layer was washed with saturated ammonium chloride solution and dried over anhydrous sodium sulphate. The solvent was removed under reduced pressure to give the title compound as a white solid (Yield 0.54 g, 91.83%).
Colourless prisms of the title compound suitable for diffraction studies were grown from an ethyl acetate–petroleum ether solvent system in the ratio 2.5:7.5, by the solvent evaporation technique.
Refinement
Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. The water H atoms were located in a difference Fourier map and freely refined. The amino and C-bound H atoms were fixed geometrically (N—H = 0.86, C—H = 0.93–0.97 Å) and allowed to ride on their parent atoms with 1.5U eq(C) for methyl H atoms and = 1.2U eq(N,C) for other H atoms.
Table 2. Experimental details.
| Crystal data | |
| Chemical formula | C20H20N2O3H2O |
| M r | 354.40 |
| Crystal system, space group | Orthorhombic, P c a21 |
| Temperature (K) | 296 |
| a, b, c () | 13.0920(17), 19.198(3), 15.827(2) |
| V (3) | 3978.1(9) |
| Z | 8 |
| Radiation type | Mo K |
| (mm1) | 0.08 |
| Crystal size (mm) | 0.39 0.27 0.19 |
| Data collection | |
| Diffractometer | Bruker APEXII |
| Absorption correction | Multi-scan (SADABS; Bruker, 2009 ▸) |
| T min, T max | 0.973, 0.984 |
| No. of measured, independent and observed [I > 2(I)] reflections | 61392, 8543, 4909 |
| R int | 0.057 |
| (sin /)max (1) | 0.649 |
| Refinement | |
| R[F 2 > 2(F 2)], wR(F 2), S | 0.049, 0.135, 0.98 |
| No. of reflections | 8543 |
| No. of parameters | 489 |
| No. of restraints | 29 |
| H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
| max, min (e 3) | 0.20, 0.14 |
| Absolute structure | Flack (1983 ▸), 4587 Friedel pairs |
| Absolute structure parameter | 0.1(1) |
Supplementary Material
Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S205698901402619X/cv5478sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S205698901402619X/cv5478Isup2.hkl
Supporting information file. DOI: 10.1107/S205698901402619X/cv5478Isup3.cml
CCDC reference: 1036677
Additional supporting information: crystallographic information; 3D view; checkCIF report
Acknowledgments
The authors thank the Department of Science and Technology, New Delhi, for financial support under the DST–SERB scheme (grant No. SR/FT/CS-145/2010). The support and encouragement of Tumkur University administration is also acknowledged. In addition, the authors thank Sapala Organics Pvt. Ltd, Hyderabad, for recording the 1H NMR and MS spectra of the title compound.
supplementary crystallographic information
Crystal data
| C20H20N2O3·H2O | Prism |
| Mr = 354.40 | Dx = 1.183 Mg m−3 |
| Orthorhombic, Pca21 | Melting point: 443 K |
| Hall symbol: P 2c -2ac | Mo Kα radiation, λ = 0.71073 Å |
| a = 13.0920 (17) Å | Cell parameters from 138 reflections |
| b = 19.198 (3) Å | θ = 1.9–27.5° |
| c = 15.827 (2) Å | µ = 0.08 mm−1 |
| V = 3978.1 (9) Å3 | T = 296 K |
| Z = 8 | Prism, colourless |
| F(000) = 1504 | 0.39 × 0.27 × 0.19 mm |
Data collection
| Bruker APEXII diffractometer | 4909 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.057 |
| Graphite monochromator | θmax = 27.5°, θmin = 1.9° |
| phi and φ scans | h = −16→16 |
| Absorption correction: multi-scan (SADABS; Bruker, 2009) | k = −24→24 |
| Tmin = 0.973, Tmax = 0.984 | l = −19→20 |
| 61392 measured reflections | 1 standard reflections every 1 reflections |
| 8543 independent reflections | intensity decay: 1% |
Refinement
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.049 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.135 | w = 1/[σ2(Fo2) + (0.0724P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 0.98 | (Δ/σ)max < 0.001 |
| 8543 reflections | Δρmax = 0.20 e Å−3 |
| 489 parameters | Δρmin = −0.14 e Å−3 |
| 29 restraints | Absolute structure: Flack (1983), 4587 Friedel pairs |
| Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.1 (1) |
Special details
| Experimental. All the solvents employed were of analytical grade. Starting materials and reagents were purchased from Sigma Chemical co. (Saint Louis, USA). The reaction progress was monitored by thin layer chromatography using TLC Silica gel 60 F254 (Merck), and spots were visualized by using ultraviolet light of 254 nm. Melting point was determined by using open capillary and uncorrected value is given. 1H-NMR spectrum was recorded on Jeol-400 MHz NMR instrument using CDCl3/DMSO-d6 as solvent. Chemical shift values were expressed in δ (p.p.m.) relative to tetramethylsilane (TMS) as an internal reference standard. Mass spectrum of the compound was recorded on Shimadzu LC-2010EV with ESI probe.1H-NMR spectral data of I clearly indicated the formation of I. In the spectrum, a singlet at δ (p.p.m.) value 2.23 corresponds to the two para-methyl groups, while, a singlet signal at δ (p.p.m.) value 3.22 is for four alkyl protons (two CH2 groups) and two doublets at 6.93 and 7.07 corresponds to the eight aromatic protons. Two NH protons of the barbituric acid moiety appeared at δ value 7.85 as a singlet. Mass spectrum of I gave a peak with (m/z) value = 335.0 which exactly matches with its calculated mass. |
| Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes. |
| Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | ||
| C6 | 0.8772 (3) | 0.7536 (2) | 0.0448 (3) | 0.1148 (12) | |
| H6 | 0.8098 | 0.7382 | 0.0448 | 0.138* | |
| C19 | 0.9200 (4) | 0.6505 (2) | 0.1358 (3) | 0.174 (2) | |
| H19A | 0.9340 | 0.6568 | 0.1949 | 0.262* | |
| H19B | 0.9595 | 0.6122 | 0.1147 | 0.262* | |
| H19C | 0.8487 | 0.6409 | 0.1281 | 0.262* | |
| C39 | 0.8413 (4) | 0.8470 (2) | 0.2588 (3) | 0.205 (3) | |
| H39A | 0.8257 | 0.8861 | 0.2944 | 0.308* | |
| H39B | 0.8045 | 0.8512 | 0.2066 | 0.308* | |
| H39C | 0.9133 | 0.8461 | 0.2474 | 0.308* | |
| C40 | 0.7798 (5) | 0.1883 (2) | 0.2643 (4) | 0.192 (2) | |
| H40A | 0.8105 | 0.1576 | 0.3049 | 0.288* | |
| H40B | 0.8263 | 0.1956 | 0.2182 | 0.288* | |
| H40C | 0.7179 | 0.1678 | 0.2434 | 0.288* | |
| H2B | 0.520 (2) | 0.5106 (14) | 0.109 (2) | 0.088 (10)* | |
| H2A | 0.583 (3) | 0.513 (2) | 0.036 (4) | 0.156 (19)* | |
| H1A | 1.225 (2) | 0.9802 (12) | 0.272 (2) | 0.092 (10)* | |
| H1B | 1.1706 (19) | 1.0021 (12) | 0.342 (2) | 0.070 (8)* | |
| C1 | 0.9482 (4) | 0.7161 (2) | 0.0883 (3) | 0.1193 (12) | |
| C2 | 1.0471 (4) | 0.7405 (2) | 0.0846 (2) | 0.1205 (13) | |
| H2 | 1.0982 | 0.7152 | 0.1115 | 0.145* | |
| C3 | 1.0739 (3) | 0.8016 (2) | 0.0421 (2) | 0.1027 (11) | |
| H3 | 1.1413 | 0.8168 | 0.0427 | 0.123* | |
| C4 | 1.0001 (2) | 0.83994 (14) | −0.00130 (15) | 0.0727 (7) | |
| C5 | 0.9012 (2) | 0.81420 (17) | 0.0001 (2) | 0.0877 (9) | |
| H5 | 0.8500 | 0.8376 | −0.0291 | 0.105* | |
| C7 | 1.02806 (17) | 0.90622 (13) | −0.04658 (16) | 0.0715 (7) | |
| H7A | 0.9901 | 0.9082 | −0.0992 | 0.086* | |
| H7B | 1.1001 | 0.9044 | −0.0608 | 0.086* | |
| C8 | 1.00757 (17) | 0.97436 (13) | 0.00349 (16) | 0.0563 (6) | |
| C9 | 0.89331 (16) | 0.98272 (13) | 0.01741 (17) | 0.0522 (6) | |
| C10 | 0.91876 (18) | 1.00450 (11) | 0.1679 (2) | 0.0510 (6) | |
| C11 | 1.06796 (15) | 0.97321 (12) | 0.08499 (16) | 0.0561 (6) | |
| C12 | 1.04400 (17) | 1.03834 (13) | −0.04920 (18) | 0.0678 (7) | |
| H12A | 1.1174 | 1.0350 | −0.0565 | 0.081* | |
| H12B | 1.0132 | 1.0356 | −0.1048 | 0.081* | |
| C13 | 1.01968 (17) | 1.10829 (15) | −0.01215 (17) | 0.0685 (7) | |
| C14 | 0.9285 (2) | 1.14188 (16) | −0.0302 (2) | 0.0845 (8) | |
| H14 | 0.8828 | 1.1210 | −0.0673 | 0.101* | |
| C15 | 0.9035 (3) | 1.2049 (2) | 0.0051 (3) | 0.1032 (11) | |
| H15 | 0.8415 | 1.2257 | −0.0085 | 0.124* | |
| C16 | 0.9688 (4) | 1.23778 (19) | 0.0602 (3) | 0.1149 (12) | |
| C17 | 1.0608 (4) | 1.2054 (2) | 0.0784 (3) | 0.1245 (14) | |
| H17 | 1.1066 | 1.2268 | 0.1152 | 0.149* | |
| C18 | 1.0859 (2) | 1.14120 (18) | 0.0425 (2) | 0.0941 (9) | |
| H18 | 1.1481 | 1.1204 | 0.0556 | 0.113* | |
| C20 | 0.9419 (4) | 1.3093 (2) | 0.0984 (4) | 0.180 (2) | |
| H20A | 0.9712 | 1.3131 | 0.1538 | 0.270* | |
| H20B | 0.8690 | 1.3139 | 0.1022 | 0.270* | |
| H20C | 0.9687 | 1.3456 | 0.0629 | 0.270* | |
| C21 | 0.8100 (4) | 0.7794 (2) | 0.3035 (3) | 0.1294 (14) | |
| C22 | 0.8734 (3) | 0.7433 (2) | 0.3546 (3) | 0.1207 (12) | |
| H22 | 0.9391 | 0.7598 | 0.3642 | 0.145* | |
| C23 | 0.8418 (2) | 0.68184 (19) | 0.3932 (2) | 0.0984 (11) | |
| H23 | 0.8869 | 0.6585 | 0.4287 | 0.118* | |
| C24 | 0.7465 (2) | 0.65484 (16) | 0.38039 (18) | 0.0820 (8) | |
| C25 | 0.6804 (3) | 0.6924 (2) | 0.3298 (2) | 0.1110 (12) | |
| H25 | 0.6142 | 0.6764 | 0.3210 | 0.133* | |
| C26 | 0.7127 (4) | 0.7546 (2) | 0.2916 (3) | 0.1376 (16) | |
| H26 | 0.6674 | 0.7794 | 0.2577 | 0.165* | |
| C27 | 0.71252 (17) | 0.58865 (16) | 0.42374 (18) | 0.0824 (9) | |
| H27A | 0.6397 | 0.5916 | 0.4342 | 0.099* | |
| H27B | 0.7464 | 0.5857 | 0.4781 | 0.099* | |
| C28 | 0.73450 (17) | 0.52040 (14) | 0.37356 (17) | 0.0655 (7) | |
| C29 | 0.67384 (16) | 0.52234 (14) | 0.29184 (18) | 0.0635 (6) | |
| C30 | 0.82374 (18) | 0.49247 (12) | 0.20860 (19) | 0.0514 (6) | |
| C31 | 0.84770 (17) | 0.51243 (15) | 0.35966 (18) | 0.0630 (7) | |
| C32 | 0.69710 (19) | 0.45597 (16) | 0.42547 (17) | 0.0812 (8) | |
| H32A | 0.7295 | 0.4571 | 0.4806 | 0.097* | |
| H32B | 0.6240 | 0.4601 | 0.4342 | 0.097* | |
| C33 | 0.7185 (2) | 0.38700 (16) | 0.38549 (18) | 0.0784 (8) | |
| C34 | 0.8099 (2) | 0.3523 (2) | 0.3962 (2) | 0.1020 (10) | |
| H34 | 0.8596 | 0.3716 | 0.4311 | 0.122* | |
| C35 | 0.8296 (4) | 0.2887 (3) | 0.3557 (4) | 0.1307 (16) | |
| H35 | 0.8928 | 0.2673 | 0.3622 | 0.157* | |
| C36 | 0.7556 (5) | 0.2579 (2) | 0.3061 (3) | 0.1243 (12) | |
| C37 | 0.6641 (4) | 0.2918 (2) | 0.2993 (3) | 0.1226 (13) | |
| H37 | 0.6127 | 0.2711 | 0.2676 | 0.147* | |
| C38 | 0.6443 (2) | 0.3541 (2) | 0.3365 (2) | 0.0993 (10) | |
| H38 | 0.5808 | 0.3750 | 0.3293 | 0.119* | |
| N1 | 1.01988 (13) | 0.98950 (10) | 0.15858 (17) | 0.0572 (6) | |
| HN1 | 1.0568 | 0.9904 | 0.2035 | 0.069* | |
| N2 | 0.85962 (14) | 0.99882 (10) | 0.09608 (16) | 0.0534 (5) | |
| HN2 | 0.7952 | 1.0062 | 0.1017 | 0.064* | |
| N3 | 0.88084 (14) | 0.49787 (10) | 0.28006 (15) | 0.0558 (6) | |
| HN3 | 0.9455 | 0.4913 | 0.2743 | 0.067* | |
| N4 | 0.72171 (13) | 0.50664 (10) | 0.21786 (16) | 0.0584 (6) | |
| HN4 | 0.6847 | 0.5055 | 0.1730 | 0.070* | |
| O1 | 1.16630 (18) | 0.99390 (14) | 0.2863 (2) | 0.0976 (8) | |
| O2 | 0.57806 (19) | 0.51299 (15) | 0.0904 (2) | 0.1084 (10) | |
| O3 | 0.88202 (13) | 1.02084 (10) | 0.23583 (12) | 0.0709 (5) | |
| O4 | 1.15820 (10) | 0.95863 (10) | 0.08464 (13) | 0.0775 (5) | |
| O5 | 0.83276 (12) | 0.97775 (9) | −0.04055 (11) | 0.0726 (5) | |
| O6 | 0.86065 (13) | 0.47823 (10) | 0.14088 (12) | 0.0709 (5) | |
| O7 | 0.58342 (12) | 0.53645 (12) | 0.29178 (14) | 0.0953 (6) | |
| O8 | 0.90867 (13) | 0.51705 (12) | 0.41774 (13) | 0.0874 (6) |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C6 | 0.137 (3) | 0.088 (3) | 0.119 (3) | −0.038 (2) | −0.003 (2) | −0.026 (2) |
| C19 | 0.312 (6) | 0.093 (3) | 0.119 (3) | −0.044 (3) | 0.006 (4) | −0.005 (2) |
| C39 | 0.362 (8) | 0.094 (3) | 0.159 (4) | −0.046 (4) | 0.014 (5) | −0.006 (3) |
| C40 | 0.294 (7) | 0.109 (3) | 0.172 (5) | 0.019 (4) | 0.044 (5) | 0.025 (3) |
| C1 | 0.190 (4) | 0.088 (3) | 0.080 (2) | −0.001 (3) | −0.010 (3) | −0.019 (2) |
| C2 | 0.179 (4) | 0.103 (3) | 0.079 (2) | 0.028 (3) | −0.022 (3) | 0.003 (2) |
| C3 | 0.113 (2) | 0.108 (3) | 0.087 (2) | 0.022 (2) | −0.009 (2) | −0.009 (2) |
| C4 | 0.0893 (18) | 0.0841 (18) | 0.0448 (15) | 0.0125 (16) | 0.0001 (14) | −0.0115 (14) |
| C5 | 0.094 (2) | 0.087 (2) | 0.082 (2) | −0.0126 (17) | −0.0143 (17) | −0.0221 (18) |
| C7 | 0.0651 (14) | 0.105 (2) | 0.0445 (16) | 0.0115 (13) | 0.0061 (12) | −0.0133 (15) |
| C8 | 0.0431 (11) | 0.0879 (17) | 0.0379 (13) | −0.0012 (12) | 0.0014 (10) | 0.0050 (13) |
| C9 | 0.0401 (12) | 0.0792 (15) | 0.0375 (16) | −0.0035 (10) | −0.0045 (11) | 0.0052 (11) |
| C10 | 0.0432 (12) | 0.0672 (15) | 0.0426 (18) | −0.0026 (9) | 0.0024 (13) | 0.0077 (11) |
| C11 | 0.0365 (11) | 0.0798 (16) | 0.0520 (15) | −0.0043 (11) | 0.0038 (11) | 0.0030 (13) |
| C12 | 0.0529 (12) | 0.097 (2) | 0.0537 (16) | −0.0022 (12) | 0.0092 (12) | 0.0155 (15) |
| C13 | 0.0573 (13) | 0.094 (2) | 0.0543 (18) | −0.0113 (13) | −0.0003 (12) | 0.0191 (15) |
| C14 | 0.0796 (18) | 0.086 (2) | 0.088 (2) | −0.0055 (15) | −0.0074 (15) | 0.0160 (17) |
| C15 | 0.101 (2) | 0.099 (3) | 0.110 (3) | −0.002 (2) | 0.006 (2) | 0.029 (2) |
| C16 | 0.172 (4) | 0.086 (3) | 0.086 (3) | 0.002 (3) | 0.017 (3) | 0.014 (2) |
| C17 | 0.178 (4) | 0.114 (3) | 0.082 (3) | −0.035 (3) | −0.038 (3) | 0.011 (2) |
| C18 | 0.095 (2) | 0.098 (2) | 0.089 (2) | −0.0124 (18) | −0.0202 (17) | 0.0148 (18) |
| C20 | 0.275 (6) | 0.117 (3) | 0.148 (4) | 0.007 (3) | 0.036 (4) | −0.011 (3) |
| C21 | 0.192 (4) | 0.114 (3) | 0.083 (3) | −0.010 (3) | −0.015 (3) | −0.039 (2) |
| C22 | 0.140 (3) | 0.099 (3) | 0.123 (3) | −0.013 (2) | −0.010 (3) | −0.030 (3) |
| C23 | 0.095 (2) | 0.108 (3) | 0.091 (3) | 0.004 (2) | −0.0182 (18) | −0.036 (2) |
| C24 | 0.0795 (17) | 0.115 (2) | 0.0511 (16) | 0.0048 (17) | −0.0033 (15) | −0.0236 (17) |
| C25 | 0.114 (2) | 0.130 (3) | 0.089 (3) | 0.009 (2) | −0.034 (2) | −0.026 (2) |
| C26 | 0.203 (5) | 0.109 (3) | 0.100 (3) | 0.015 (3) | −0.054 (3) | −0.018 (3) |
| C27 | 0.0600 (15) | 0.135 (3) | 0.0525 (18) | 0.0095 (15) | 0.0060 (12) | −0.0218 (18) |
| C28 | 0.0446 (12) | 0.114 (2) | 0.0377 (15) | −0.0038 (13) | 0.0058 (11) | −0.0082 (15) |
| C29 | 0.0391 (12) | 0.1030 (19) | 0.0486 (15) | −0.0098 (12) | −0.0013 (11) | 0.0014 (14) |
| C30 | 0.0467 (13) | 0.0750 (16) | 0.0327 (16) | −0.0054 (10) | −0.0042 (12) | 0.0004 (10) |
| C31 | 0.0447 (13) | 0.108 (2) | 0.0363 (16) | −0.0031 (12) | −0.0027 (12) | −0.0025 (13) |
| C32 | 0.0672 (14) | 0.133 (3) | 0.0432 (15) | −0.0126 (16) | 0.0118 (13) | 0.0041 (17) |
| C33 | 0.0753 (17) | 0.112 (2) | 0.0479 (17) | −0.0106 (16) | 0.0049 (14) | 0.0165 (17) |
| C34 | 0.084 (2) | 0.125 (3) | 0.096 (2) | −0.0012 (19) | −0.0010 (18) | 0.034 (2) |
| C35 | 0.127 (3) | 0.118 (4) | 0.147 (4) | 0.027 (3) | 0.024 (3) | 0.053 (3) |
| C36 | 0.171 (4) | 0.105 (3) | 0.097 (3) | −0.002 (3) | 0.026 (3) | 0.011 (2) |
| C37 | 0.146 (4) | 0.123 (3) | 0.099 (3) | −0.004 (3) | −0.008 (3) | 0.008 (3) |
| C38 | 0.101 (2) | 0.113 (3) | 0.084 (2) | −0.0056 (19) | −0.0081 (18) | 0.004 (2) |
| N1 | 0.0406 (10) | 0.0901 (14) | 0.0408 (15) | −0.0008 (8) | −0.0098 (10) | 0.0026 (10) |
| N2 | 0.0325 (9) | 0.0872 (14) | 0.0405 (14) | 0.0011 (7) | −0.0005 (10) | 0.0027 (8) |
| N3 | 0.0336 (10) | 0.0979 (15) | 0.0360 (15) | −0.0022 (8) | 0.0001 (10) | −0.0017 (9) |
| N4 | 0.0423 (11) | 0.0982 (15) | 0.0347 (14) | −0.0044 (8) | −0.0038 (10) | −0.0027 (9) |
| O1 | 0.0577 (12) | 0.192 (2) | 0.0431 (15) | 0.0075 (11) | −0.0041 (12) | −0.0181 (12) |
| O2 | 0.0582 (13) | 0.223 (3) | 0.0443 (16) | 0.0125 (12) | −0.0046 (12) | 0.0058 (14) |
| O3 | 0.0593 (10) | 0.1132 (14) | 0.0402 (11) | 0.0041 (9) | 0.0053 (8) | −0.0093 (9) |
| O4 | 0.0389 (8) | 0.1202 (15) | 0.0733 (12) | 0.0012 (8) | −0.0007 (8) | −0.0006 (11) |
| O5 | 0.0535 (9) | 0.1195 (15) | 0.0448 (11) | −0.0020 (9) | −0.0080 (9) | −0.0004 (10) |
| O6 | 0.0649 (10) | 0.1105 (14) | 0.0373 (11) | 0.0007 (9) | 0.0047 (8) | −0.0088 (10) |
| O7 | 0.0366 (9) | 0.174 (2) | 0.0751 (13) | −0.0020 (10) | −0.0013 (9) | −0.0119 (13) |
| O8 | 0.0517 (9) | 0.1655 (18) | 0.0449 (11) | 0.0017 (10) | −0.0126 (9) | −0.0159 (11) |
Geometric parameters (Å, º)
| C6—C1 | 1.363 (5) | C16—C20 | 1.541 (6) |
| C6—C5 | 1.397 (5) | C17—C18 | 1.396 (5) |
| C19—C1 | 1.513 (6) | C21—C22 | 1.351 (6) |
| C39—C21 | 1.534 (6) | C21—C26 | 1.373 (5) |
| C40—C36 | 1.524 (6) | C22—C23 | 1.392 (5) |
| C1—C2 | 1.378 (6) | C23—C24 | 1.367 (4) |
| C2—C3 | 1.396 (5) | C24—C25 | 1.383 (5) |
| C3—C4 | 1.396 (4) | C24—C27 | 1.511 (4) |
| C4—C5 | 1.386 (4) | C25—C26 | 1.403 (6) |
| C4—C7 | 1.506 (4) | C27—C28 | 1.559 (4) |
| C7—C8 | 1.553 (3) | C28—C31 | 1.506 (3) |
| C8—C11 | 1.513 (3) | C28—C29 | 1.518 (4) |
| C8—C9 | 1.521 (3) | C28—C32 | 1.564 (4) |
| C8—C12 | 1.559 (4) | C29—O7 | 1.214 (3) |
| C9—O5 | 1.216 (3) | C29—N4 | 1.362 (4) |
| C9—N2 | 1.357 (3) | C30—O6 | 1.207 (3) |
| C10—O3 | 1.218 (3) | C30—N3 | 1.360 (3) |
| C10—N1 | 1.363 (3) | C30—N4 | 1.371 (3) |
| C10—N2 | 1.380 (4) | C31—O8 | 1.221 (3) |
| C11—O4 | 1.214 (2) | C31—N3 | 1.361 (4) |
| C11—N1 | 1.360 (3) | C32—C33 | 1.494 (4) |
| C12—C13 | 1.500 (4) | C33—C34 | 1.380 (4) |
| C13—C18 | 1.378 (4) | C33—C38 | 1.393 (4) |
| C13—C14 | 1.386 (4) | C34—C35 | 1.403 (6) |
| C14—C15 | 1.372 (5) | C35—C36 | 1.380 (6) |
| C15—C16 | 1.374 (5) | C36—C37 | 1.368 (6) |
| C16—C17 | 1.387 (6) | C37—C38 | 1.358 (6) |
| C1—C6—C5 | 122.8 (4) | C26—C21—C39 | 118.6 (5) |
| C6—C1—C2 | 116.1 (4) | C21—C22—C23 | 121.0 (4) |
| C6—C1—C19 | 121.7 (5) | C24—C23—C22 | 121.9 (3) |
| C2—C1—C19 | 122.2 (5) | C23—C24—C25 | 117.3 (3) |
| C1—C2—C3 | 122.8 (4) | C23—C24—C27 | 121.4 (3) |
| C4—C3—C2 | 120.4 (4) | C25—C24—C27 | 121.2 (3) |
| C5—C4—C3 | 116.8 (3) | C24—C25—C26 | 120.4 (4) |
| C5—C4—C7 | 122.4 (3) | C21—C26—C25 | 121.0 (4) |
| C3—C4—C7 | 120.8 (3) | C24—C27—C28 | 114.9 (2) |
| C4—C5—C6 | 121.0 (3) | C31—C28—C29 | 113.1 (2) |
| C4—C7—C8 | 115.3 (2) | C31—C28—C27 | 110.0 (2) |
| C11—C8—C9 | 113.1 (2) | C29—C28—C27 | 108.5 (2) |
| C11—C8—C7 | 109.4 (2) | C31—C28—C32 | 107.7 (2) |
| C9—C8—C7 | 109.44 (19) | C29—C28—C32 | 107.7 (2) |
| C11—C8—C12 | 107.91 (19) | C27—C28—C32 | 109.8 (2) |
| C9—C8—C12 | 107.17 (18) | O7—C29—N4 | 119.8 (2) |
| C7—C8—C12 | 109.7 (2) | O7—C29—C28 | 121.1 (2) |
| O5—C9—N2 | 119.9 (2) | N4—C29—C28 | 119.10 (19) |
| O5—C9—C8 | 121.6 (2) | O6—C30—N3 | 122.4 (2) |
| N2—C9—C8 | 118.5 (2) | O6—C30—N4 | 122.0 (2) |
| O3—C10—N1 | 122.3 (3) | N3—C30—N4 | 115.6 (2) |
| O3—C10—N2 | 121.7 (2) | O8—C31—N3 | 120.2 (2) |
| N1—C10—N2 | 116.0 (2) | O8—C31—C28 | 121.7 (2) |
| O4—C11—N1 | 120.5 (2) | N3—C31—C28 | 118.0 (2) |
| O4—C11—C8 | 120.5 (2) | C33—C32—C28 | 114.8 (2) |
| N1—C11—C8 | 119.00 (18) | C34—C33—C38 | 117.0 (3) |
| C13—C12—C8 | 115.6 (2) | C34—C33—C32 | 122.5 (3) |
| C18—C13—C14 | 117.2 (3) | C38—C33—C32 | 120.5 (3) |
| C18—C13—C12 | 121.5 (2) | C33—C34—C35 | 121.6 (4) |
| C14—C13—C12 | 121.3 (3) | C36—C35—C34 | 120.3 (4) |
| C15—C14—C13 | 122.2 (3) | C37—C36—C35 | 117.0 (4) |
| C14—C15—C16 | 121.0 (4) | C37—C36—C40 | 124.4 (6) |
| C15—C16—C17 | 117.8 (4) | C35—C36—C40 | 118.5 (6) |
| C15—C16—C20 | 121.1 (4) | C38—C37—C36 | 123.6 (4) |
| C17—C16—C20 | 121.1 (5) | C37—C38—C33 | 120.5 (3) |
| C16—C17—C18 | 121.0 (4) | C11—N1—C10 | 126.2 (2) |
| C13—C18—C17 | 120.8 (3) | C9—N2—C10 | 126.29 (19) |
| C22—C21—C26 | 118.3 (5) | C30—N3—C31 | 127.6 (2) |
| C22—C21—C39 | 123.1 (5) | C29—N4—C30 | 125.7 (2) |
| C5—C6—C1—C2 | −1.3 (5) | C39—C21—C26—C25 | 179.0 (4) |
| C5—C6—C1—C19 | −179.7 (3) | C24—C25—C26—C21 | 0.0 (6) |
| C6—C1—C2—C3 | 2.7 (6) | C23—C24—C27—C28 | −90.5 (3) |
| C19—C1—C2—C3 | −178.9 (3) | C25—C24—C27—C28 | 93.0 (3) |
| C1—C2—C3—C4 | −2.0 (5) | C24—C27—C28—C31 | 60.9 (3) |
| C2—C3—C4—C5 | −0.2 (4) | C24—C27—C28—C29 | −63.3 (3) |
| C2—C3—C4—C7 | 179.4 (3) | C24—C27—C28—C32 | 179.3 (2) |
| C3—C4—C5—C6 | 1.5 (4) | C31—C28—C29—O7 | −171.5 (3) |
| C7—C4—C5—C6 | −178.1 (3) | C27—C28—C29—O7 | −49.2 (3) |
| C1—C6—C5—C4 | −0.7 (5) | C32—C28—C29—O7 | 69.6 (3) |
| C5—C4—C7—C8 | 82.6 (3) | C31—C28—C29—N4 | 9.8 (3) |
| C3—C4—C7—C8 | −97.0 (3) | C27—C28—C29—N4 | 132.0 (2) |
| C4—C7—C8—C11 | 59.5 (3) | C32—C28—C29—N4 | −109.2 (3) |
| C4—C7—C8—C9 | −64.9 (3) | C29—C28—C31—O8 | 172.4 (3) |
| C4—C7—C8—C12 | 177.7 (2) | C27—C28—C31—O8 | 50.9 (3) |
| C11—C8—C9—O5 | −172.6 (2) | C32—C28—C31—O8 | −68.7 (3) |
| C7—C8—C9—O5 | −50.3 (3) | C29—C28—C31—N3 | −9.4 (3) |
| C12—C8—C9—O5 | 68.6 (3) | C27—C28—C31—N3 | −130.8 (3) |
| C11—C8—C9—N2 | 10.0 (3) | C32—C28—C31—N3 | 109.5 (3) |
| C7—C8—C9—N2 | 132.3 (2) | C31—C28—C32—C33 | −57.5 (3) |
| C12—C8—C9—N2 | −108.8 (2) | C29—C28—C32—C33 | 64.8 (3) |
| C9—C8—C11—O4 | 171.2 (2) | C27—C28—C32—C33 | −177.3 (2) |
| C7—C8—C11—O4 | 48.9 (3) | C28—C32—C33—C34 | 86.1 (3) |
| C12—C8—C11—O4 | −70.4 (3) | C28—C32—C33—C38 | −95.3 (3) |
| C9—C8—C11—N1 | −9.5 (3) | C38—C33—C34—C35 | 3.6 (5) |
| C7—C8—C11—N1 | −131.8 (2) | C32—C33—C34—C35 | −177.7 (3) |
| C12—C8—C11—N1 | 108.9 (2) | C33—C34—C35—C36 | −2.5 (6) |
| C11—C8—C12—C13 | −66.5 (2) | C34—C35—C36—C37 | −0.3 (7) |
| C9—C8—C12—C13 | 55.6 (3) | C34—C35—C36—C40 | −179.1 (4) |
| C7—C8—C12—C13 | 174.32 (19) | C35—C36—C37—C38 | 1.9 (7) |
| C8—C12—C13—C18 | 89.4 (3) | C40—C36—C37—C38 | −179.4 (4) |
| C8—C12—C13—C14 | −89.2 (3) | C36—C37—C38—C33 | −0.6 (7) |
| C18—C13—C14—C15 | −0.7 (4) | C34—C33—C38—C37 | −2.1 (5) |
| C12—C13—C14—C15 | 178.0 (3) | C32—C33—C38—C37 | 179.2 (3) |
| C13—C14—C15—C16 | 0.2 (5) | O4—C11—N1—C10 | −177.7 (2) |
| C14—C15—C16—C17 | 0.5 (6) | C8—C11—N1—C10 | 3.0 (3) |
| C14—C15—C16—C20 | 178.6 (4) | O3—C10—N1—C11 | −177.6 (2) |
| C15—C16—C17—C18 | −0.6 (6) | N2—C10—N1—C11 | 3.6 (3) |
| C20—C16—C17—C18 | −178.7 (4) | O5—C9—N2—C10 | 178.3 (2) |
| C14—C13—C18—C17 | 0.6 (4) | C8—C9—N2—C10 | −4.3 (3) |
| C12—C13—C18—C17 | −178.1 (3) | O3—C10—N2—C9 | 178.3 (2) |
| C16—C17—C18—C13 | 0.0 (6) | N1—C10—N2—C9 | −2.9 (3) |
| C26—C21—C22—C23 | 1.2 (6) | O6—C30—N3—C31 | −178.9 (3) |
| C39—C21—C22—C23 | −179.4 (4) | N4—C30—N3—C31 | 3.3 (3) |
| C21—C22—C23—C24 | 0.8 (6) | O8—C31—N3—C30 | −178.5 (2) |
| C22—C23—C24—C25 | −2.4 (5) | C28—C31—N3—C30 | 3.3 (4) |
| C22—C23—C24—C27 | −179.0 (3) | O7—C29—N4—C30 | 177.3 (2) |
| C23—C24—C25—C26 | 1.9 (5) | C28—C29—N4—C30 | −3.9 (4) |
| C27—C24—C25—C26 | 178.5 (3) | O6—C30—N4—C29 | 179.2 (2) |
| C22—C21—C26—C25 | −1.6 (6) | N3—C30—N4—C29 | −2.9 (3) |
Hydrogen-bond geometry (Å, º)
Cg is the centroid of the C13–C18 benzene ring.
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—HN1···O1 | 0.86 | 1.94 | 2.787 (4) | 167 |
| O1—H1A···O3i | 0.84 (3) | 2.13 (3) | 2.949 (3) | 162 |
| O1—H1B···O5ii | 0.90 (3) | 1.90 (3) | 2.794 (4) | 175 |
| N2—HN2···O4iii | 0.86 | 1.94 | 2.767 (2) | 162 |
| O2—H2A···O8iv | 0.86 (6) | 1.88 (6) | 2.739 (4) | 177 |
| O2—H2B···O6v | 0.82 (3) | 2.16 (3) | 2.961 (3) | 169 |
| N3—HN3···O7vi | 0.86 | 1.90 | 2.739 (2) | 164 |
| N4—HN4···O2 | 0.86 | 1.92 | 2.761 (4) | 166 |
| C22—H22···Cgvii | 0.93 | 2.97 | 3.5693 | 124 |
Symmetry codes: (i) x+1/2, −y+2, z; (ii) −x+2, −y+2, z+1/2; (iii) x−1/2, −y+2, z; (iv) −x+3/2, y, z−1/2; (v) x−1/2, −y+1, z; (vi) x+1/2, −y+1, z; (vii) −x+1, −y, z+1/2.
References
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Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S205698901402619X/cv5478sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S205698901402619X/cv5478Isup2.hkl
Supporting information file. DOI: 10.1107/S205698901402619X/cv5478Isup3.cml
CCDC reference: 1036677
Additional supporting information: crystallographic information; 3D view; checkCIF report