The asymmetric unit of the title carbamate, contains two independent molecules (A and B) with similar conformations. In the crystal, they are arranged alternately, forming –A–B–A–B– chains linked by N—H⋯O(carbonyl) hydrogen bonds, which extend along the a-axis direction.
Keywords: crystal structure, carbamate, ester, (dimethylphenyl)carbamate, N—H⋯O hydrogen bonding, C—H⋯π interactions, π–π interactions
Abstract
The asymmetric unit of the title compound, C15H15NO2, contains two independent molecules (A and B). The dimethylphenyl ring, the phenyl ring and the central carbamate N—C(=O)—O group are not coplanar. In molecule A, the dimethylphenyl and phenyl rings are inclined to the carbamate group mean plane by 27.71 (13) and 71.70 (4)°, respectively, and to one another by 84.53 (13)°. The corresponding dihedral angles in molecule B are 34.33 (11), 66.32 (13) and 85.48 (12)°, respectively. In the crystal, the A and B molecules are arranged alternately linked through N—H⋯O(carbonyl) hydrogen bonds, forming –A–B–A–B– chains, which extend along [100]. Within the chains and linking neighbouring chains there are C—H⋯π interactions present, forming columns along the a-axis direction. The columns are linked by offset π–π stacking interactions, forming a three-dimensional network [shortest centroid–centroid distance = 3.606 (1) Å].
Chemical context
The The carbamate group is known in biochemistry for its role in biological processes. For example it tunes haemoglobin affinity for O2 during physiological respiration (O’Donnell et al., 1979 ▸). Carbamates are widely employed as pharmacological and therapeutic agents (Greig et al., 2005 ▸), to inhibit different enzymes such as acetyl- and butyrylcholinesterases (Darvesh et al., 2008 ▸), cholesterol esterase (Hosie et al., 1987 ▸), elastase (Digenis et al., 1986 ▸), chymotrypsin (Lin et al., 2006 ▸) and fatty acid amide hydrolase (FAAH) (Kathuria et al., 2003 ▸). In the solid state, the carbamate group acts as both donor and acceptor in hydrogen bonding, favouring the formation of highly stable synthons. Thus, the carbamate group has been proposed as a building block for hydrogen-bonded solids in crystal engineering (Ghosh et al., 2006 ▸). Most carbamate compounds of interest are phenyl derivatives, similar to the title compound whose synthesis and crystal structure are reported on herein.
Structural commentary
The asymmetric unit of the title compound, Fig. 1 ▸, contains two crystallographically independent molecules (A and B), with similar conformations. In molecule A, the dimethylphenyl ring (C1–C6) makes a dihedral angle of 84.53 (13)° with the phenyl ring (C10–C15), and in molecule B the dimethylphenyl ring (C16–C21) makes a dihedral angle of 85.48 (12)° with the phenyl ring (C25–C30). In molecule A, the aryl rings (C1–C6 and C10–C15) are inclined to the the mean plane of the carbamate N1—C9(=O2)—O1 unit by 27.71 (13) and 71.70 (14)°, respectively. In molecule B, rings C16–C21 and C25–C39 are inclined to the the mean plane of the carbamate N2—C24(=O24)—O13 unit by 34.33 (11) and 66.32 (13)°, respectively. The C9—N1 and C24—N2 distances are 1.336 (3) and 1.335 (3) Å, respectively, indicating partial double-bond character in the carbamate unit.
Figure 1.
A view of the two independent molecules (A and B) of the title compound, with the atom labelling. Displacement ellipsoids are drawn at the 30% probability level.
Supramolecular features
In the crystal, N—H⋯O(carbonyl) hydrogen bonds link the molecules to form –A–B–A–B– chains, propagating along the a-axis direction (Table 1 ▸ and Fig. 2 ▸). Within the chains and linking neighbouring chains there are C—H⋯π interactions, between the H16 and H29 hydrogen atoms of the aromatic and phenyl rings (C10–C15, centroid Cg2 and C16–C21, centroid Cg3; see Table 1 ▸ and Fig. 3 ▸ a). These interactions form columns along the a-axis direction, which are linked by offset π–π stacking interactions (Fig. 3 ▸ b), forming a three-dimensional network, as illustrated in Fig. 4 ▸ [Cg1⋯Cg1iii = 3.738 (2) Å, interplanar distance = 3.521 (1) Å, slippage = 1.257 Å; Cg3⋯Cg3 iv = 3.606 (1) Å, interplanar distance = 3.462 (1) Å, slippage = 1.007 Å; Cg1 and Cg3 are the centroids of the C1–C6 and C16–C21 rings, respectively; symmetry codes: (iii) −x + 3, −y, −z + 1; (iv) −x + 2, −y + 1, −z + 1].
Table 1. Hydrogen-bond geometry (Å, °).
Cg2 and Cg3 are the centroids of rings C10–C15 and C16–C21, respectively.
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| N1—H1⋯O4i | 0.86 | 2.14 | 2.957 (2) | 159 |
| N2—H2⋯O2 | 0.86 | 2.06 | 2.896 (2) | 164 |
| C16—H16⋯Cg2 | 0.93 | 2.93 | 3.659 (2) | 136 |
| C29—H29⋯Cg3ii | 0.93 | 2.59 | 3.508 (3) | 173 |
Symmetry codes: (i) 
; (ii) 
.
Figure 2.
A view along the b axis of the crystal packing of the title compound, with the N—H⋯O hydrogen bonds (see Table 1 ▸) shown as dashed lines. For clarity, H atoms not involved in hydrogen bonding have been omitted.
Figure 3.
Details of (a) the C—H⋯π interactions (thin lines; see Table 1 ▸) involving adjacent aromatic rings of the title compound, and (b) the offset π–π interactions [dotted lines; Cg1 and Cg3 are the centroids of rings C1–C6 and C16–C21, respectively]. For clarity, H atoms are not involved in these interactions have been omitted.
Figure 4.
A view along the a axis of the crystal packing of the title compound. The hydrogen bonds are shown as dashed lines and examples of the C—H⋯π interactions as black arrows (see Table 1 ▸). The rings involved in π–π interactions are blue⋯blue (Cg1; molecule A) and red⋯red (Cg3; molecule B). For clarity, H atoms are not involved in these interactions have been omitted.
Database survey
A search of the Cambridge Structural Database (Version 5.38, update February 2017; Groom et al., 2016 ▸) for the skeleton phenyl phenylcarbamate yielded 42 hits. Among these structures there are reports of two Pna21 polymorphs of phenyl phenylcarbamate itself, viz. YEHPOQ (Lehr et al., 2001 ▸) and YEHPOQ01 (Shahwar et al., 2009a ▸), and those of phenyl (4-methylphenyl)carbamate (YOVHOH; Bao et al., 2009 ▸) and phenyl(2-methylphenyl)carbamate (YOVLIF; Shahwar et al., 2009b ▸). The conformations of all four reported molecules are different. For example, the aromatic rings are inclined to one another by ca 25.8° in YEHPOQ, 42.5° in YEHPOQ01, 59.0° in YOVHOH and 39.2° in YOVLIF, compared to 84.5 (1) and 85.5 (1)°, respectively, in molecules A and B of the title compound.
Synthesis and crystallization
To a stirred solution of 1.0 g (5.45 mmol) of 3,5 dimethyl aniline dissolved in 100 ml of dry THF was added a calculated 5% excess of phenylchloroforamate in 50 ml of dry THF. The addition rate was such that it took 1.5 h for complete transfer. After the addition was complete, stirring was continued overnight. Excess THF was removed under vacuum at room temperature. The crude product was extracted with ethyl acetate (3 × 100 ml), and then the organic layer was dried over anhydrous sodium sulfate. Removing the solvent under vacuum at room temperature, yielded a light-yellow product which was dried under vacuum to constant weight. Yellow block-like crystals were obtained by slow evaporation of an ethyl acetate solution at room temperature (yield 99%).
Refinement
Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. The N– and C-bound H atoms were positioned geometrically (N—H = 0.86 Å and C—H = 0.93–0.96 Å) and allowed to ride on their parent atoms, with U iso(H) = 1.5U eq(C-methyl) and 1.2U eq(N,C) for the H atoms.
Table 2. Experimental details.
| Crystal data | |
| Chemical formula | C15H15NO2 |
| M r | 241.28 |
| Crystal system, space group | Triclinic, P
|
| Temperature (K) | 293 |
| a, b, c (Å) | 9.4257 (4), 12.2054 (5), 13.2067 (6) |
| α, β, γ (°) | 62.979 (3), 82.329 (3), 87.145 (3) |
| V (Å3) | 1341.29 (10) |
| Z | 4 |
| Radiation type | Mo Kα |
| μ (mm−1) | 0.08 |
| Crystal size (mm) | 0.20 × 0.18 × 0.17 |
| Data collection | |
| Diffractometer | Bruker SMART APEXII CCD |
| Absorption correction | Multi-scan (SADABS; Bruker, 2008 ▸) |
| T min, T max | 0.984, 0.987 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 31199, 4723, 3376 |
| R int | 0.031 |
| (sin θ/λ)max (Å−1) | 0.595 |
| Refinement | |
| R[F 2 > 2σ(F 2)], wR(F 2), S | 0.046, 0.143, 1.09 |
| No. of reflections | 4723 |
| No. of parameters | 325 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.25, −0.20 |
Supplementary Material
Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989017006922/su5370sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989017006922/su5370Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989017006922/su5370Isup3.cml
CCDC reference: 1548793
Additional supporting information: crystallographic information; 3D view; checkCIF report
Acknowledgments
The authors thank Dr Babu Varghese, SAIF, IIT, Chennai, India, for the data collection.
supplementary crystallographic information
Crystal data
| C15H15NO2 | Z = 4 |
| Mr = 241.28 | F(000) = 512 |
| Triclinic, P1 | Dx = 1.195 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
| a = 9.4257 (4) Å | Cell parameters from 3376 reflections |
| b = 12.2054 (5) Å | θ = 1.7–25.0° |
| c = 13.2067 (6) Å | µ = 0.08 mm−1 |
| α = 62.979 (3)° | T = 293 K |
| β = 82.329 (3)° | Block, yellow |
| γ = 87.145 (3)° | 0.20 × 0.18 × 0.17 mm |
| V = 1341.29 (10) Å3 |
Data collection
| Bruker SMART APEXII CCD diffractometer | 4723 independent reflections |
| Radiation source: fine-focus sealed tube | 3376 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.031 |
| ω and φ scans | θmax = 25.0°, θmin = 1.7° |
| Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −11→11 |
| Tmin = 0.984, Tmax = 0.987 | k = −14→14 |
| 31199 measured reflections | l = −15→15 |
Refinement
| Refinement on F2 | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Secondary atom site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.143 | H-atom parameters constrained |
| S = 1.09 | w = 1/[σ2(Fo2) + (0.0578P)2 + 0.5754P] where P = (Fo2 + 2Fc2)/3 |
| 4723 reflections | (Δ/σ)max < 0.001 |
| 325 parameters | Δρmax = 0.25 e Å−3 |
| 0 restraints | Δρmin = −0.20 e Å−3 |
Special details
| Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles |
| 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 > 2sigma(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 | ||
| O1 | 1.58017 (15) | 0.50462 (14) | 0.15809 (14) | 0.0562 (5) | |
| O2 | 1.41427 (14) | 0.39474 (15) | 0.30750 (13) | 0.0566 (6) | |
| N1 | 1.64082 (17) | 0.32555 (16) | 0.29043 (15) | 0.0457 (6) | |
| C1 | 1.7338 (2) | 0.1239 (2) | 0.3932 (2) | 0.0532 (8) | |
| C2 | 1.7388 (3) | 0.0131 (2) | 0.4911 (3) | 0.0626 (9) | |
| C3 | 1.6482 (3) | −0.0046 (2) | 0.5884 (2) | 0.0642 (9) | |
| O3 | 1.16793 (15) | 0.29093 (14) | 0.18417 (14) | 0.0529 (6) | |
| C4 | 1.5555 (3) | 0.0854 (2) | 0.5912 (2) | 0.0590 (8) | |
| O4 | 0.94345 (14) | 0.36607 (14) | 0.18663 (13) | 0.0491 (5) | |
| C5 | 1.5507 (2) | 0.1955 (2) | 0.4921 (2) | 0.0503 (8) | |
| C6 | 1.6388 (2) | 0.21386 (19) | 0.39347 (19) | 0.0435 (7) | |
| C7 | 1.8376 (4) | −0.0869 (3) | 0.4895 (3) | 0.0977 (13) | |
| C8 | 1.4618 (4) | 0.0653 (3) | 0.6999 (2) | 0.0914 (13) | |
| C9 | 1.5337 (2) | 0.40501 (19) | 0.25803 (18) | 0.0420 (7) | |
| C10 | 1.4810 (2) | 0.5974 (2) | 0.10787 (19) | 0.0505 (7) | |
| C11 | 1.5007 (3) | 0.7082 (2) | 0.1060 (3) | 0.0703 (10) | |
| C12 | 1.4096 (4) | 0.8039 (3) | 0.0507 (3) | 0.0948 (13) | |
| C13 | 1.3023 (4) | 0.7864 (3) | −0.0004 (3) | 0.0933 (12) | |
| C14 | 1.2842 (3) | 0.6744 (3) | 0.0022 (2) | 0.0795 (12) | |
| C15 | 1.3748 (2) | 0.5789 (3) | 0.0561 (2) | 0.0595 (9) | |
| N2 | 1.11656 (17) | 0.40705 (15) | 0.27069 (15) | 0.0425 (6) | |
| C16 | 1.1256 (2) | 0.58070 (18) | 0.30825 (17) | 0.0422 (7) | |
| C17 | 1.0624 (2) | 0.66070 (19) | 0.34863 (18) | 0.0468 (7) | |
| C18 | 0.9176 (2) | 0.6468 (2) | 0.38825 (19) | 0.0505 (8) | |
| C19 | 0.8359 (2) | 0.5547 (2) | 0.39031 (18) | 0.0467 (7) | |
| C20 | 0.9016 (2) | 0.47436 (19) | 0.35201 (17) | 0.0418 (7) | |
| C21 | 1.0452 (2) | 0.48834 (17) | 0.30963 (16) | 0.0365 (6) | |
| C22 | 1.1512 (3) | 0.7594 (2) | 0.3502 (3) | 0.0725 (10) | |
| C23 | 0.6792 (3) | 0.5403 (3) | 0.4352 (3) | 0.0721 (10) | |
| C24 | 1.0631 (2) | 0.35729 (17) | 0.21212 (17) | 0.0382 (6) | |
| C25 | 1.1406 (2) | 0.24132 (19) | 0.11142 (18) | 0.0417 (7) | |
| C26 | 1.1482 (3) | 0.1170 (2) | 0.1526 (2) | 0.0724 (10) | |
| C27 | 1.1370 (4) | 0.0660 (3) | 0.0796 (3) | 0.0925 (13) | |
| C28 | 1.1152 (3) | 0.1379 (3) | −0.0306 (3) | 0.0758 (12) | |
| C29 | 1.1068 (3) | 0.2615 (3) | −0.0702 (2) | 0.0630 (9) | |
| C30 | 1.1207 (2) | 0.3150 (2) | 0.0001 (2) | 0.0522 (8) | |
| H1 | 1.71910 | 0.34390 | 0.24420 | 0.0550* | |
| H1A | 1.79470 | 0.13780 | 0.32690 | 0.0640* | |
| H3 | 1.64960 | −0.07930 | 0.65390 | 0.0770* | |
| H5 | 1.48810 | 0.25680 | 0.49240 | 0.0600* | |
| H7A | 1.89210 | −0.05870 | 0.41510 | 0.1470* | |
| H7B | 1.78230 | −0.15830 | 0.50600 | 0.1470* | |
| H7C | 1.90150 | −0.10750 | 0.54620 | 0.1470* | |
| H8A | 1.40440 | 0.13660 | 0.68630 | 0.1370* | |
| H8B | 1.52060 | 0.05130 | 0.75850 | 0.1370* | |
| H8C | 1.40060 | −0.00500 | 0.72410 | 0.1370* | |
| H11 | 1.57400 | 0.71960 | 0.14110 | 0.0840* | |
| H12 | 1.42170 | 0.88010 | 0.04850 | 0.1140* | |
| H13 | 1.24120 | 0.85060 | −0.03710 | 0.1120* | |
| H14 | 1.21060 | 0.66280 | −0.03260 | 0.0950* | |
| H15 | 1.36370 | 0.50310 | 0.05710 | 0.0710* | |
| H2 | 1.20280 | 0.38790 | 0.28630 | 0.0510* | |
| H16 | 1.22240 | 0.58930 | 0.28020 | 0.0510* | |
| H18 | 0.87400 | 0.70090 | 0.41420 | 0.0610* | |
| H20 | 0.84890 | 0.41050 | 0.35480 | 0.0500* | |
| H22A | 1.24840 | 0.75510 | 0.31950 | 0.1090* | |
| H22B | 1.14850 | 0.74710 | 0.42760 | 0.1090* | |
| H22C | 1.11320 | 0.83870 | 0.30460 | 0.1090* | |
| H23A | 0.65130 | 0.60320 | 0.45820 | 0.1080* | |
| H23B | 0.66170 | 0.46090 | 0.49980 | 0.1080* | |
| H23C | 0.62440 | 0.54770 | 0.37610 | 0.1080* | |
| H26 | 1.16080 | 0.06710 | 0.22880 | 0.0870* | |
| H27 | 1.14440 | −0.01860 | 0.10650 | 0.1110* | |
| H28 | 1.10600 | 0.10280 | −0.07880 | 0.0910* | |
| H29 | 1.09160 | 0.31090 | −0.14580 | 0.0760* | |
| H30 | 1.11650 | 0.40000 | −0.02780 | 0.0630* |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0349 (8) | 0.0558 (9) | 0.0593 (10) | 0.0080 (7) | −0.0001 (7) | −0.0123 (8) |
| O2 | 0.0302 (8) | 0.0715 (11) | 0.0554 (10) | 0.0058 (7) | −0.0035 (7) | −0.0187 (8) |
| N1 | 0.0295 (8) | 0.0500 (10) | 0.0534 (11) | 0.0029 (7) | −0.0028 (8) | −0.0207 (9) |
| C1 | 0.0442 (12) | 0.0516 (13) | 0.0670 (15) | 0.0033 (10) | −0.0101 (11) | −0.0291 (12) |
| C2 | 0.0626 (15) | 0.0462 (14) | 0.0798 (19) | 0.0059 (11) | −0.0270 (14) | −0.0250 (13) |
| C3 | 0.0729 (17) | 0.0495 (14) | 0.0649 (17) | −0.0067 (13) | −0.0275 (14) | −0.0155 (13) |
| O3 | 0.0406 (8) | 0.0657 (10) | 0.0743 (11) | 0.0177 (7) | −0.0184 (7) | −0.0493 (9) |
| C4 | 0.0623 (15) | 0.0627 (15) | 0.0514 (14) | −0.0125 (12) | −0.0131 (12) | −0.0223 (12) |
| O4 | 0.0303 (7) | 0.0692 (10) | 0.0590 (10) | 0.0036 (7) | −0.0066 (6) | −0.0388 (8) |
| C5 | 0.0461 (12) | 0.0536 (13) | 0.0551 (14) | −0.0013 (10) | −0.0083 (11) | −0.0272 (12) |
| C6 | 0.0359 (10) | 0.0447 (12) | 0.0534 (13) | −0.0014 (9) | −0.0127 (10) | −0.0231 (11) |
| C7 | 0.101 (2) | 0.0603 (18) | 0.126 (3) | 0.0280 (17) | −0.033 (2) | −0.0349 (19) |
| C8 | 0.108 (3) | 0.099 (2) | 0.0551 (17) | −0.0149 (19) | −0.0002 (17) | −0.0254 (17) |
| C9 | 0.0308 (11) | 0.0498 (12) | 0.0473 (12) | 0.0006 (9) | −0.0068 (9) | −0.0230 (11) |
| C10 | 0.0377 (11) | 0.0548 (14) | 0.0459 (13) | 0.0068 (10) | 0.0015 (10) | −0.0138 (11) |
| C11 | 0.0558 (15) | 0.0610 (16) | 0.087 (2) | 0.0000 (12) | −0.0054 (14) | −0.0282 (15) |
| C12 | 0.084 (2) | 0.0554 (18) | 0.120 (3) | 0.0092 (16) | 0.006 (2) | −0.0237 (18) |
| C13 | 0.075 (2) | 0.086 (2) | 0.077 (2) | 0.0306 (18) | −0.0041 (17) | −0.0048 (18) |
| C14 | 0.0532 (15) | 0.123 (3) | 0.0531 (16) | 0.0237 (17) | −0.0125 (12) | −0.0324 (18) |
| C15 | 0.0443 (13) | 0.0827 (18) | 0.0530 (14) | 0.0074 (12) | −0.0024 (11) | −0.0337 (13) |
| N2 | 0.0291 (8) | 0.0530 (10) | 0.0556 (11) | 0.0062 (7) | −0.0086 (7) | −0.0332 (9) |
| C16 | 0.0387 (11) | 0.0465 (12) | 0.0404 (12) | −0.0029 (9) | −0.0024 (9) | −0.0192 (10) |
| C17 | 0.0582 (13) | 0.0401 (11) | 0.0411 (12) | −0.0021 (10) | −0.0078 (10) | −0.0169 (10) |
| C18 | 0.0579 (14) | 0.0536 (13) | 0.0463 (13) | 0.0118 (11) | −0.0064 (11) | −0.0291 (11) |
| C19 | 0.0407 (11) | 0.0610 (14) | 0.0447 (12) | 0.0064 (10) | −0.0052 (9) | −0.0299 (11) |
| C20 | 0.0358 (10) | 0.0506 (12) | 0.0431 (12) | −0.0009 (9) | −0.0025 (9) | −0.0252 (10) |
| C21 | 0.0345 (10) | 0.0395 (10) | 0.0353 (11) | 0.0036 (8) | −0.0058 (8) | −0.0168 (9) |
| C22 | 0.090 (2) | 0.0568 (15) | 0.0774 (19) | −0.0152 (14) | −0.0020 (15) | −0.0368 (15) |
| C23 | 0.0452 (13) | 0.105 (2) | 0.085 (2) | 0.0088 (13) | 0.0023 (13) | −0.0629 (18) |
| C24 | 0.0307 (10) | 0.0400 (11) | 0.0419 (11) | 0.0010 (8) | −0.0021 (8) | −0.0176 (9) |
| C25 | 0.0350 (10) | 0.0473 (12) | 0.0492 (13) | 0.0049 (9) | −0.0086 (9) | −0.0269 (11) |
| C26 | 0.118 (2) | 0.0460 (14) | 0.0578 (16) | 0.0122 (14) | −0.0381 (16) | −0.0215 (12) |
| C27 | 0.156 (3) | 0.0517 (16) | 0.090 (2) | 0.0190 (18) | −0.057 (2) | −0.0402 (16) |
| C28 | 0.095 (2) | 0.081 (2) | 0.077 (2) | 0.0157 (16) | −0.0331 (16) | −0.0534 (17) |
| C29 | 0.0631 (15) | 0.0784 (18) | 0.0446 (14) | 0.0112 (13) | −0.0104 (11) | −0.0253 (13) |
| C30 | 0.0514 (13) | 0.0453 (12) | 0.0529 (14) | 0.0058 (10) | −0.0045 (11) | −0.0172 (11) |
Geometric parameters (Å, º)
| O1—C9 | 1.361 (3) | C11—H11 | 0.9300 |
| O1—C10 | 1.405 (3) | C12—H12 | 0.9300 |
| O2—C9 | 1.205 (2) | C13—H13 | 0.9300 |
| N1—C6 | 1.422 (3) | C14—H14 | 0.9300 |
| N1—C9 | 1.336 (3) | C15—H15 | 0.9300 |
| C1—C2 | 1.387 (4) | N2—H2 | 0.8600 |
| C1—C6 | 1.383 (3) | C16—C21 | 1.381 (3) |
| N1—H1 | 0.8600 | C16—C17 | 1.387 (3) |
| C2—C3 | 1.379 (4) | C17—C18 | 1.385 (3) |
| C2—C7 | 1.504 (5) | C17—C22 | 1.510 (4) |
| O3—C25 | 1.402 (3) | C18—C19 | 1.382 (3) |
| O3—C24 | 1.365 (3) | C19—C20 | 1.381 (3) |
| C3—C4 | 1.380 (4) | C19—C23 | 1.504 (4) |
| C4—C5 | 1.390 (3) | C20—C21 | 1.382 (3) |
| C4—C8 | 1.505 (4) | C25—C30 | 1.364 (3) |
| O4—C24 | 1.206 (2) | C25—C26 | 1.361 (4) |
| C5—C6 | 1.379 (3) | C26—C27 | 1.381 (5) |
| C10—C15 | 1.366 (3) | C27—C28 | 1.354 (5) |
| C10—C11 | 1.363 (4) | C28—C29 | 1.356 (5) |
| C11—C12 | 1.388 (5) | C29—C30 | 1.378 (4) |
| C12—C13 | 1.363 (5) | C16—H16 | 0.9300 |
| C13—C14 | 1.370 (6) | C18—H18 | 0.9300 |
| C14—C15 | 1.380 (4) | C20—H20 | 0.9300 |
| C1—H1A | 0.9300 | C22—H22A | 0.9600 |
| N2—C24 | 1.335 (3) | C22—H22B | 0.9600 |
| N2—C21 | 1.416 (3) | C22—H22C | 0.9600 |
| C3—H3 | 0.9300 | C23—H23A | 0.9600 |
| C5—H5 | 0.9300 | C23—H23B | 0.9600 |
| C7—H7C | 0.9600 | C23—H23C | 0.9600 |
| C7—H7B | 0.9600 | C26—H26 | 0.9300 |
| C7—H7A | 0.9600 | C27—H27 | 0.9300 |
| C8—H8A | 0.9600 | C28—H28 | 0.9300 |
| C8—H8C | 0.9600 | C29—H29 | 0.9300 |
| C8—H8B | 0.9600 | C30—H30 | 0.9300 |
| C9—O1—C10 | 117.78 (16) | C14—C15—H15 | 120.00 |
| C6—N1—C9 | 126.72 (17) | C10—C15—H15 | 121.00 |
| C2—C1—C6 | 120.4 (2) | C21—N2—H2 | 117.00 |
| C6—N1—H1 | 117.00 | C24—N2—H2 | 117.00 |
| C9—N1—H1 | 117.00 | C17—C16—C21 | 120.19 (18) |
| C3—C2—C7 | 120.9 (3) | C18—C17—C22 | 121.3 (2) |
| C1—C2—C3 | 118.6 (3) | C16—C17—C18 | 118.5 (2) |
| C1—C2—C7 | 120.5 (3) | C16—C17—C22 | 120.18 (19) |
| C2—C3—C4 | 121.8 (2) | C17—C18—C19 | 121.9 (2) |
| C24—O3—C25 | 118.46 (16) | C20—C19—C23 | 120.4 (2) |
| C3—C4—C5 | 118.9 (2) | C18—C19—C20 | 118.64 (19) |
| C3—C4—C8 | 120.6 (2) | C18—C19—C23 | 121.0 (2) |
| C5—C4—C8 | 120.4 (3) | C19—C20—C21 | 120.4 (2) |
| C4—C5—C6 | 120.0 (2) | C16—C21—C20 | 120.3 (2) |
| C1—C6—C5 | 120.2 (2) | N2—C21—C20 | 122.0 (2) |
| N1—C6—C5 | 122.4 (2) | N2—C21—C16 | 117.65 (17) |
| N1—C6—C1 | 117.29 (19) | O3—C24—O4 | 123.5 (2) |
| O1—C9—O2 | 123.5 (2) | O3—C24—N2 | 108.53 (17) |
| O1—C9—N1 | 109.16 (17) | O4—C24—N2 | 127.9 (2) |
| O2—C9—N1 | 127.3 (2) | O3—C25—C26 | 117.45 (19) |
| C11—C10—C15 | 121.6 (3) | C26—C25—C30 | 120.9 (2) |
| O1—C10—C11 | 117.6 (2) | O3—C25—C30 | 121.4 (2) |
| O1—C10—C15 | 120.6 (3) | C25—C26—C27 | 119.0 (2) |
| C10—C11—C12 | 118.9 (3) | C26—C27—C28 | 120.7 (4) |
| C11—C12—C13 | 120.2 (4) | C27—C28—C29 | 119.6 (3) |
| C12—C13—C14 | 120.2 (3) | C28—C29—C30 | 120.9 (3) |
| C13—C14—C15 | 120.2 (3) | C25—C30—C29 | 118.9 (3) |
| C10—C15—C14 | 119.0 (3) | C17—C16—H16 | 120.00 |
| C6—C1—H1A | 120.00 | C21—C16—H16 | 120.00 |
| C2—C1—H1A | 120.00 | C17—C18—H18 | 119.00 |
| C21—N2—C24 | 126.38 (17) | C19—C18—H18 | 119.00 |
| C2—C3—H3 | 119.00 | C19—C20—H20 | 120.00 |
| C4—C3—H3 | 119.00 | C21—C20—H20 | 120.00 |
| C6—C5—H5 | 120.00 | C17—C22—H22A | 109.00 |
| C4—C5—H5 | 120.00 | C17—C22—H22B | 109.00 |
| C2—C7—H7C | 110.00 | C17—C22—H22C | 110.00 |
| H7A—C7—H7B | 109.00 | H22A—C22—H22B | 109.00 |
| H7A—C7—H7C | 109.00 | H22A—C22—H22C | 110.00 |
| H7B—C7—H7C | 109.00 | H22B—C22—H22C | 109.00 |
| C2—C7—H7A | 109.00 | C19—C23—H23A | 109.00 |
| C2—C7—H7B | 109.00 | C19—C23—H23B | 110.00 |
| C4—C8—H8A | 109.00 | C19—C23—H23C | 109.00 |
| H8A—C8—H8B | 110.00 | H23A—C23—H23B | 110.00 |
| H8A—C8—H8C | 109.00 | H23A—C23—H23C | 109.00 |
| H8B—C8—H8C | 109.00 | H23B—C23—H23C | 109.00 |
| C4—C8—H8B | 109.00 | C25—C26—H26 | 121.00 |
| C4—C8—H8C | 109.00 | C27—C26—H26 | 120.00 |
| C10—C11—H11 | 121.00 | C26—C27—H27 | 120.00 |
| C12—C11—H11 | 121.00 | C28—C27—H27 | 120.00 |
| C11—C12—H12 | 120.00 | C27—C28—H28 | 120.00 |
| C13—C12—H12 | 120.00 | C29—C28—H28 | 120.00 |
| C14—C13—H13 | 120.00 | C28—C29—H29 | 120.00 |
| C12—C13—H13 | 120.00 | C30—C29—H29 | 119.00 |
| C13—C14—H14 | 120.00 | C25—C30—H30 | 120.00 |
| C15—C14—H14 | 120.00 | C29—C30—H30 | 121.00 |
| C10—O1—C9—N1 | 178.0 (2) | C10—C11—C12—C13 | 0.2 (5) |
| C9—O1—C10—C15 | −72.6 (3) | C11—C12—C13—C14 | −0.3 (5) |
| C9—O1—C10—C11 | 111.8 (3) | C12—C13—C14—C15 | −0.3 (5) |
| C10—O1—C9—O2 | −3.0 (3) | C13—C14—C15—C10 | 0.9 (4) |
| C6—N1—C9—O2 | −3.2 (4) | C21—N2—C24—O4 | −4.3 (4) |
| C9—N1—C6—C1 | 156.0 (2) | C24—N2—C21—C16 | −144.0 (2) |
| C9—N1—C6—C5 | −26.5 (4) | C24—N2—C21—C20 | 38.5 (3) |
| C6—N1—C9—O1 | 175.8 (2) | C21—N2—C24—O3 | 176.05 (18) |
| C6—C1—C2—C3 | −0.6 (4) | C21—C16—C17—C18 | −1.0 (3) |
| C6—C1—C2—C7 | 177.4 (3) | C21—C16—C17—C22 | 178.3 (2) |
| C2—C1—C6—N1 | 179.3 (2) | C17—C16—C21—N2 | −178.04 (18) |
| C2—C1—C6—C5 | 1.7 (4) | C17—C16—C21—C20 | −0.5 (3) |
| C7—C2—C3—C4 | −179.2 (3) | C22—C17—C18—C19 | −178.2 (2) |
| C1—C2—C3—C4 | −1.2 (4) | C16—C17—C18—C19 | 1.1 (3) |
| C2—C3—C4—C8 | −177.7 (3) | C17—C18—C19—C23 | 179.2 (2) |
| C25—O3—C24—O4 | 7.3 (3) | C17—C18—C19—C20 | 0.3 (3) |
| C2—C3—C4—C5 | 1.9 (4) | C18—C19—C20—C21 | −1.8 (3) |
| C24—O3—C25—C26 | −120.5 (2) | C23—C19—C20—C21 | 179.3 (2) |
| C25—O3—C24—N2 | −173.11 (18) | C19—C20—C21—N2 | 179.34 (19) |
| C24—O3—C25—C30 | 65.6 (3) | C19—C20—C21—C16 | 1.9 (3) |
| C3—C4—C5—C6 | −0.7 (4) | O3—C25—C26—C27 | −173.2 (3) |
| C8—C4—C5—C6 | 178.9 (3) | C30—C25—C26—C27 | 0.7 (4) |
| C4—C5—C6—C1 | −1.1 (3) | O3—C25—C30—C29 | 174.3 (2) |
| C4—C5—C6—N1 | −178.5 (2) | C26—C25—C30—C29 | 0.7 (3) |
| C11—C10—C15—C14 | −1.0 (4) | C25—C26—C27—C28 | −1.6 (5) |
| O1—C10—C15—C14 | −176.5 (2) | C26—C27—C28—C29 | 1.2 (5) |
| O1—C10—C11—C12 | 176.1 (3) | C27—C28—C29—C30 | 0.3 (4) |
| C15—C10—C11—C12 | 0.5 (4) | C28—C29—C30—C25 | −1.2 (4) |
Hydrogen-bond geometry (Å, º)
Cg2 and Cg3 are the centroids of rings C10–C15 and C16–C21, respectively.
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···O4i | 0.86 | 2.14 | 2.957 (2) | 159 |
| N2—H2···O2 | 0.86 | 2.06 | 2.896 (2) | 164 |
| C16—H16···Cg2 | 0.93 | 2.93 | 3.659 (2) | 136 |
| C29—H29···Cg3ii | 0.93 | 2.59 | 3.508 (3) | 173 |
Symmetry codes: (i) x+1, y, z; (ii) −x+2, −y+1, −z.
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) global, I. DOI: 10.1107/S2056989017006922/su5370sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989017006922/su5370Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989017006922/su5370Isup3.cml
CCDC reference: 1548793
Additional supporting information: crystallographic information; 3D view; checkCIF report