In the title compounds, the planes of the two aromatic rings are inclined to one another by 7.60 (8) and76.19 (8)°. In the crystals of both compounds, molecules are linked via N—H⋯O hydrogen bonds, forming chains along [010].
Keywords: crystal structure; carbamate; 3,5-dinitrophenylcarbamate; hydrogen bonding
Abstract
The title compounds, C13H8ClN3O6, (I), and C13H9N3O6, (II), differ in the orientation of the two aromatic rings. In (I), they are essentially coplanar, making a dihedral angle of 8.2 (1)°, while in (II), they are inclined to one another by 76.2 (1)°. The two nitro groups are essentially coplanar with the attached benzene rings, as indicated by the dihedral angles of 1.4 (2) and 2.3 (2)° in (I), and 4.96 (18) and 5.4 (2)° in (II). The carbamate group is twisted slightly from the attached benzene ring, with a C—N—C—O torsion angle of −170.17 (15)° for (I) and 168.91 (13)° for (II). In the crystals of of both compounds, molecules are linked via N—H⋯O hydrogen bonds, forming chains propagating along [010]. In (I), C—H⋯O hydrogen bonds also link molecules within the chains. The crystal packing in (I) also features a very weak π–π interaction [centroid–centroid distance = 3.7519 (9) Å].
Chemical context
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 ▸). The therapeutic exploitation of the endocannabinoid system with exogenous agonists is limited by the undesired side effects caused by indiscriminate activation of cannabinoid type-1 (CB1) receptors, particularly in the brain (Mechoulam & Parker, 2013 ▸). An alternative strategy to direct CB1 receptor targeting is to increase the signaling activity of the endogenous cannabinoid ligands, arachidonoylethanolamide (anandamide) (Di Marzo et al., 1994 ▸) and 2-arachidonoyl-sn-glycerol (2-AG) (Stella et al., 1997 ▸), by blocking their intracellular degradation. As part of our studies in this area, we report herein on the syntheses and crystal structures of two 3,5-dinitrophenylcarbamate derivatives, (I) and (II).
Structural commentary
The molecular structures of the title compounds, (I) and (II), are shown in Figs. 1 ▸ and 2 ▸, respectively. The molecules have different conformations. In compound (I), the benzene rings (C1–C6 and C8–C13) are almost coplanar, making a dihedral angle of 7.60 (8)°. The mean plane of the carbamate group (N3/C7/O5/O6) is twisted out of the planes of the rings by 14.00 (9) and 20.96 (9)°, respectively. In compound (II), the benzene and phenyl rings (C1–C6 and C8–C13, respectively) are roughly normal to one another, making a dihedral angle of 76.19 (8)°. Here, the mean plane of the carbamate group (N3/C7/O5/O6) is twisted out of the planes of the rings by 37.51 (8) and 80.90 (9)°, respectively.
Figure 1.
The molecular structure of compound (I), showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.
Figure 2.
The molecular structure of compound (II), showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.
Supramolecular features
In the crystal of (I), N—H⋯O hydrogen bonds, involving a nitro O atom, O3, link adjacent molecules into zigzag chains along the b axis (Table 1 ▸ and Fig. 3 ▸). Within the chain molecules are also linked by C—H⋯O hydrogen bonds. The packing also features a very weak π–π interaction [Cg1⋯Cg2i = 3.7519 (9) Å; Cg1 and Cg2 are the centroids of rings C1–C6 and C8–C13, respectively; symmetry code: (i) −x + 
, y + 
, −z + ].
Table 1. Hydrogen-bond geometry (Å, °) for (I) .
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| N3—H3A⋯O3i | 0.86 | 2.18 | 3.0286 (19) | 168 |
| C12—H12⋯O1ii | 0.93 | 2.54 | 3.428 (2) | 159 |
Symmetry codes: (i) 
; (ii) 
.
Figure 3.
The crystal packing of compound (I), viewed along the c axis. The hydrogen bonds are shown as dashed lines (see Table 1 ▸ for details).
In the crystal of (II), molecules are again linked via N—H⋯O hydrogen bonds, this time involving the carbonyl O atom O5, forming chains propagating along the b axis; see Table 2 ▸ and Fig. 4 ▸.
Table 2. Hydrogen-bond geometry (Å, °) for (II) .
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| N3—H3A⋯O5i | 0.86 | 2.07 | 2.8836 (15) | 157 |
Symmetry code: (i) 
.
Figure 4.
A view along the a axis of the crystal packing of compound (II). The hydrogen bonds are shown as dashed lines (see Table 2 ▸ for details).
Database survey
A search of the Cambridge Structural Database (Version 5.36, February 2015; Groom & Allen, 2014 ▸) for phenyl N-phenylcarbamate gave 16 hits for similar compounds, including two orthorhombic poylmorphs of phenyl N-phenylcarbamate itself (YEHPOQ: Lehr et al., 2001 ▸; YEHPOQ01; Shahwar et al., 2009 ▸). In the first polymorph (YEHPOQ), the phenyl rings are inclined to one another by 25.76°, while in the latter (YEHPOQ01) the equivalent dihedral angle is 42.50°. These values are quite different to those observed for compounds (I) and (II); cf. 7.60 (8)° in (I), and 76.19 (8)° in (II).
Synthesis and crystallization
The title compounds were prepared in a similar manner using a stirred solution of of 3,5 dinitroaniline (1.0 g, 5.45 mmol) dissolved in 100 ml of dry THF, and to it was added the calculated amount (with 5% excess) of 4-chlorophenylchloroformate for compound (I), or phenylchloroformate for compound (II), dissolved in 50 ml of dry THF. The addition rate was such that it took 90 min for complete transfer of 4-chlorophenylchloroformate for compound (I), and phenylchloroformate for compound (II). After the addition was over, stirring was continued overnight. Excess THF was removed under vacuum at room temperature. The crude product was extracted with ethyl acetate (3 × 100 ml). The organic layer was dried over anhydrous sodium sulfate. Removal of solvent under vacuum at room temperature yielded a light-yellow product. It was dried under vacuum to constant weight. It was dissolved in ethyl acetate and just warmed-up using a water bath, and then kept at room temperature. The solvent was slowly evaporated and light-yellow crystals of each of the title compounds were obtained (yields 99%).
Refinement details
Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. The N- and C-bound H atoms were positioned geometrically (N—H = 0.86 Å, C—H = 0.93 Å) and allowed to ride on their parent atoms, with U iso(H) = 1.2U eq(N,C).
Table 3. Experimental details.
| (I) | (II) | |
|---|---|---|
| Crystal data | ||
| Chemical formula | C13H8ClN3O6 | C13H9N3O6 |
| M r | 337.67 | 303.23 |
| Crystal system, space group | Monoclinic, P21/n | Monoclinic, P21/c |
| Temperature (K) | 293 | 293 |
| a, b, c (Å) | 9.9103 (4), 12.5791 (4), 10.9772 (5) | 12.2549 (4), 8.8717 (4), 12.1470 (5) |
| β (°) | 94.183 (2) | 91.673 (2) |
| V (Å3) | 1364.80 (9) | 1320.08 (9) |
| Z | 4 | 4 |
| Radiation type | Mo Kα | Mo Kα |
| μ (mm−1) | 0.32 | 0.12 |
| Crystal size (mm) | 0.35 × 0.30 × 0.25 | 0.35 × 0.30 × 0.25 |
| Data collection | ||
| Diffractometer | Bruker SMART APEXII CCD | Bruker SMART APEXII CCD |
| Absorption correction | Multi-scan (SADABS; Bruker, 2008 ▸) | Multi-scan (SADABS; Bruker, 2008 ▸) |
| T min, T max | 0.938, 0.944 | 0.969, 0.976 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 8697, 2584, 2134 | 11395, 2925, 2355 |
| R int | 0.015 | 0.020 |
| (sin θ/λ)max (Å−1) | 0.610 | 0.642 |
| Refinement | ||
| R[F 2 > 2σ(F 2)], wR(F 2), S | 0.033, 0.086, 1.04 | 0.044, 0.122, 1.03 |
| No. of reflections | 2584 | 2925 |
| No. of parameters | 208 | 199 |
| H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.18, −0.20 | 0.23, −0.27 |
Supplementary Material
Crystal structure: contains datablock(s) global, I, II. DOI: 10.1107/S2056989015010245/su5141sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015010245/su5141Isup2.hkl
Structure factors: contains datablock(s) II. DOI: 10.1107/S2056989015010245/su5141IIsup3.hkl
Supporting information file. DOI: 10.1107/S2056989015010245/su5141Isup4.cml
Supporting information file. DOI: 10.1107/S2056989015010245/su5141IIsup5.cml
Additional supporting information: crystallographic information; 3D view; checkCIF report
Acknowledgments
RR thanks the Department of Chemistry, IIT, Chennai, 600 025, India, for the X-ray intensity data collection.
supplementary crystallographic information
(I) 4-Chlorophenyl N-(3,5-dinitrophenyl)carbamate . Crystal data
| C13H8ClN3O6 | F(000) = 688 |
| Mr = 337.67 | Dx = 1.643 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
| a = 9.9103 (4) Å | Cell parameters from 2013 reflections |
| b = 12.5791 (4) Å | θ = 2.5–25.0° |
| c = 10.9772 (5) Å | µ = 0.32 mm−1 |
| β = 94.183 (2)° | T = 293 K |
| V = 1364.80 (9) Å3 | Block, yellow |
| Z = 4 | 0.35 × 0.30 × 0.25 mm |
(I) 4-Chlorophenyl N-(3,5-dinitrophenyl)carbamate . Data collection
| Bruker SMART APEXII CCD diffractometer | 2584 independent reflections |
| Radiation source: fine-focus sealed tube | 2134 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.015 |
| ω and φ scans | θmax = 25.7°, θmin = 2.5° |
| Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −12→12 |
| Tmin = 0.938, Tmax = 0.944 | k = −15→9 |
| 8697 measured reflections | l = −13→11 |
(I) 4-Chlorophenyl N-(3,5-dinitrophenyl)carbamate . 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)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.086 | H-atom parameters constrained |
| S = 1.04 | w = 1/[σ2(Fo2) + (0.0379P)2 + 0.4574P] where P = (Fo2 + 2Fc2)/3 |
| 2584 reflections | (Δ/σ)max = 0.001 |
| 208 parameters | Δρmax = 0.18 e Å−3 |
| 0 restraints | Δρmin = −0.20 e Å−3 |
(I) 4-Chlorophenyl N-(3,5-dinitrophenyl)carbamate . Special details
| 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. |
(I) 4-Chlorophenyl N-(3,5-dinitrophenyl)carbamate . Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | ||
| Cl1 | 1.06146 (5) | −0.35304 (4) | 1.04085 (5) | 0.06328 (18) | |
| O1 | 0.9159 (2) | 0.44697 (12) | 0.70274 (14) | 0.0966 (7) | |
| O2 | 0.86323 (17) | 0.55251 (10) | 0.55446 (13) | 0.0687 (4) | |
| O3 | 0.69275 (17) | 0.41624 (12) | 0.16853 (12) | 0.0701 (4) | |
| O4 | 0.66305 (14) | 0.24728 (12) | 0.14188 (12) | 0.0629 (4) | |
| O5 | 0.88633 (15) | 0.10055 (9) | 0.73898 (11) | 0.0570 (4) | |
| O6 | 0.89504 (13) | −0.05893 (9) | 0.64269 (10) | 0.0471 (3) | |
| N1 | 0.87388 (17) | 0.46386 (12) | 0.59848 (14) | 0.0514 (4) | |
| N2 | 0.69860 (15) | 0.32352 (13) | 0.20431 (13) | 0.0472 (4) | |
| N3 | 0.83153 (15) | 0.07996 (10) | 0.53417 (12) | 0.0421 (3) | |
| H3A | 0.8133 | 0.0312 | 0.4806 | 0.051* | |
| C1 | 0.76419 (15) | 0.20217 (13) | 0.37383 (14) | 0.0367 (4) | |
| H1 | 0.7386 | 0.1452 | 0.3234 | 0.044* | |
| C2 | 0.75199 (15) | 0.30533 (13) | 0.33135 (14) | 0.0369 (4) | |
| C3 | 0.78764 (16) | 0.39277 (13) | 0.40121 (15) | 0.0403 (4) | |
| H3 | 0.7800 | 0.4615 | 0.3704 | 0.048* | |
| C4 | 0.83533 (16) | 0.37228 (12) | 0.51973 (14) | 0.0376 (4) | |
| C5 | 0.85006 (16) | 0.27193 (12) | 0.56865 (14) | 0.0367 (4) | |
| H5 | 0.8822 | 0.2623 | 0.6496 | 0.044* | |
| C6 | 0.81578 (15) | 0.18518 (12) | 0.49431 (14) | 0.0344 (3) | |
| C7 | 0.87274 (16) | 0.04673 (12) | 0.64903 (14) | 0.0362 (4) | |
| C8 | 0.93362 (16) | −0.12190 (12) | 0.74459 (14) | 0.0347 (4) | |
| C9 | 1.00067 (18) | −0.08512 (13) | 0.85107 (16) | 0.0441 (4) | |
| H9 | 1.0194 | −0.0131 | 0.8613 | 0.053* | |
| C10 | 1.03967 (18) | −0.15731 (14) | 0.94259 (16) | 0.0454 (4) | |
| H10 | 1.0840 | −0.1339 | 1.0153 | 0.054* | |
| C11 | 1.01246 (16) | −0.26366 (13) | 0.92519 (15) | 0.0400 (4) | |
| C12 | 0.94754 (17) | −0.30018 (13) | 0.81784 (16) | 0.0420 (4) | |
| H12 | 0.9309 | −0.3724 | 0.8067 | 0.050* | |
| C13 | 0.90742 (16) | −0.22847 (12) | 0.72698 (15) | 0.0396 (4) | |
| H13 | 0.8630 | −0.2520 | 0.6544 | 0.048* |
(I) 4-Chlorophenyl N-(3,5-dinitrophenyl)carbamate . Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cl1 | 0.0702 (3) | 0.0569 (3) | 0.0615 (3) | 0.0118 (2) | −0.0038 (2) | 0.0230 (2) |
| O1 | 0.192 (2) | 0.0443 (8) | 0.0469 (9) | −0.0131 (10) | −0.0372 (11) | −0.0008 (7) |
| O2 | 0.1083 (12) | 0.0319 (7) | 0.0639 (9) | −0.0004 (7) | −0.0065 (8) | 0.0048 (6) |
| O3 | 0.1021 (12) | 0.0657 (9) | 0.0412 (8) | 0.0195 (8) | −0.0030 (7) | 0.0199 (7) |
| O4 | 0.0672 (9) | 0.0793 (10) | 0.0400 (7) | 0.0021 (7) | −0.0117 (6) | −0.0028 (7) |
| O5 | 0.0993 (11) | 0.0377 (7) | 0.0322 (7) | 0.0145 (7) | −0.0061 (6) | −0.0037 (5) |
| O6 | 0.0763 (9) | 0.0307 (6) | 0.0328 (6) | 0.0004 (5) | −0.0069 (6) | −0.0011 (5) |
| N1 | 0.0727 (11) | 0.0354 (8) | 0.0450 (9) | −0.0033 (7) | −0.0017 (8) | 0.0009 (7) |
| N2 | 0.0461 (8) | 0.0636 (10) | 0.0318 (8) | 0.0092 (7) | 0.0012 (6) | 0.0052 (7) |
| N3 | 0.0630 (9) | 0.0325 (7) | 0.0297 (7) | −0.0024 (6) | −0.0047 (6) | −0.0033 (6) |
| C1 | 0.0384 (8) | 0.0430 (9) | 0.0288 (8) | −0.0005 (7) | 0.0023 (6) | −0.0025 (7) |
| C2 | 0.0338 (8) | 0.0497 (9) | 0.0274 (8) | 0.0056 (7) | 0.0030 (6) | 0.0057 (7) |
| C3 | 0.0440 (9) | 0.0392 (9) | 0.0378 (9) | 0.0038 (7) | 0.0042 (7) | 0.0075 (7) |
| C4 | 0.0428 (9) | 0.0352 (8) | 0.0347 (9) | −0.0007 (7) | 0.0025 (7) | −0.0001 (7) |
| C5 | 0.0420 (9) | 0.0371 (8) | 0.0305 (8) | −0.0006 (7) | −0.0012 (6) | 0.0025 (7) |
| C6 | 0.0375 (8) | 0.0348 (8) | 0.0311 (8) | 0.0004 (6) | 0.0030 (6) | 0.0019 (6) |
| C7 | 0.0464 (9) | 0.0310 (8) | 0.0310 (9) | 0.0007 (7) | 0.0011 (7) | 0.0006 (7) |
| C8 | 0.0411 (9) | 0.0305 (8) | 0.0325 (8) | 0.0012 (6) | 0.0027 (7) | 0.0006 (6) |
| C9 | 0.0571 (11) | 0.0307 (8) | 0.0430 (10) | −0.0022 (7) | −0.0068 (8) | −0.0027 (7) |
| C10 | 0.0516 (10) | 0.0453 (10) | 0.0375 (9) | 0.0033 (8) | −0.0085 (8) | −0.0023 (8) |
| C11 | 0.0390 (9) | 0.0389 (9) | 0.0422 (9) | 0.0054 (7) | 0.0041 (7) | 0.0070 (7) |
| C12 | 0.0467 (9) | 0.0295 (8) | 0.0498 (10) | −0.0020 (7) | 0.0041 (8) | −0.0005 (7) |
| C13 | 0.0448 (9) | 0.0341 (8) | 0.0394 (9) | −0.0028 (7) | −0.0010 (7) | −0.0055 (7) |
(I) 4-Chlorophenyl N-(3,5-dinitrophenyl)carbamate . Geometric parameters (Å, º)
| Cl1—C11 | 1.7384 (16) | C2—C3 | 1.372 (2) |
| O1—N1 | 1.208 (2) | C3—C4 | 1.376 (2) |
| O2—N1 | 1.2169 (19) | C3—H3 | 0.9300 |
| O3—N2 | 1.231 (2) | C4—C5 | 1.375 (2) |
| O4—N2 | 1.216 (2) | C5—C6 | 1.390 (2) |
| O5—C7 | 1.1967 (19) | C5—H5 | 0.9300 |
| O6—C7 | 1.3500 (19) | C8—C13 | 1.376 (2) |
| O6—C8 | 1.4009 (19) | C8—C9 | 1.381 (2) |
| N1—C4 | 1.474 (2) | C9—C10 | 1.388 (2) |
| N2—C2 | 1.473 (2) | C9—H9 | 0.9300 |
| N3—C7 | 1.362 (2) | C10—C11 | 1.375 (2) |
| N3—C6 | 1.399 (2) | C10—H10 | 0.9300 |
| N3—H3A | 0.8600 | C11—C12 | 1.380 (2) |
| C1—C2 | 1.381 (2) | C12—C13 | 1.382 (2) |
| C1—C6 | 1.399 (2) | C12—H12 | 0.9300 |
| C1—H1 | 0.9300 | C13—H13 | 0.9300 |
| C7—O6—C8 | 123.48 (12) | C5—C6—N3 | 122.83 (14) |
| O1—N1—O2 | 123.46 (16) | C5—C6—C1 | 119.46 (15) |
| O1—N1—C4 | 118.36 (14) | N3—C6—C1 | 117.71 (14) |
| O2—N1—C4 | 118.17 (15) | O5—C7—O6 | 126.20 (15) |
| O4—N2—O3 | 124.24 (15) | O5—C7—N3 | 126.73 (15) |
| O4—N2—C2 | 118.71 (15) | O6—C7—N3 | 107.07 (13) |
| O3—N2—C2 | 117.05 (16) | C13—C8—C9 | 121.28 (15) |
| C7—N3—C6 | 126.78 (13) | C13—C8—O6 | 113.63 (14) |
| C7—N3—H3A | 116.6 | C9—C8—O6 | 124.94 (14) |
| C6—N3—H3A | 116.6 | C8—C9—C10 | 118.99 (15) |
| C2—C1—C6 | 118.66 (15) | C8—C9—H9 | 120.5 |
| C2—C1—H1 | 120.7 | C10—C9—H9 | 120.5 |
| C6—C1—H1 | 120.7 | C11—C10—C9 | 119.63 (16) |
| C3—C2—C1 | 123.49 (15) | C11—C10—H10 | 120.2 |
| C3—C2—N2 | 117.68 (15) | C9—C10—H10 | 120.2 |
| C1—C2—N2 | 118.83 (15) | C10—C11—C12 | 121.14 (15) |
| C2—C3—C4 | 115.78 (15) | C10—C11—Cl1 | 119.09 (13) |
| C2—C3—H3 | 122.1 | C12—C11—Cl1 | 119.77 (13) |
| C4—C3—H3 | 122.1 | C11—C12—C13 | 119.40 (15) |
| C5—C4—C3 | 124.09 (15) | C11—C12—H12 | 120.3 |
| C5—C4—N1 | 118.22 (14) | C13—C12—H12 | 120.3 |
| C3—C4—N1 | 117.69 (14) | C8—C13—C12 | 119.55 (15) |
| C4—C5—C6 | 118.48 (14) | C8—C13—H13 | 120.2 |
| C4—C5—H5 | 120.8 | C12—C13—H13 | 120.2 |
| C6—C5—H5 | 120.8 | ||
| C6—C1—C2—C3 | −0.1 (2) | C7—N3—C6—C1 | −176.15 (15) |
| C6—C1—C2—N2 | 179.58 (14) | C2—C1—C6—C5 | 1.6 (2) |
| O4—N2—C2—C3 | −178.06 (15) | C2—C1—C6—N3 | −177.90 (14) |
| O3—N2—C2—C3 | 1.7 (2) | C8—O6—C7—O5 | 2.4 (3) |
| O4—N2—C2—C1 | 2.2 (2) | C8—O6—C7—N3 | −177.36 (14) |
| O3—N2—C2—C1 | −177.98 (15) | C6—N3—C7—O5 | 10.1 (3) |
| C1—C2—C3—C4 | −1.1 (2) | C6—N3—C7—O6 | −170.17 (15) |
| N2—C2—C3—C4 | 179.18 (14) | C7—O6—C8—C13 | 159.36 (15) |
| C2—C3—C4—C5 | 1.0 (2) | C7—O6—C8—C9 | −25.2 (2) |
| C2—C3—C4—N1 | −179.54 (14) | C13—C8—C9—C10 | −1.3 (3) |
| O1—N1—C4—C5 | −0.5 (3) | O6—C8—C9—C10 | −176.42 (15) |
| O2—N1—C4—C5 | 178.63 (16) | C8—C9—C10—C11 | 0.8 (3) |
| O1—N1—C4—C3 | 179.99 (19) | C9—C10—C11—C12 | 0.4 (3) |
| O2—N1—C4—C3 | −0.9 (2) | C9—C10—C11—Cl1 | −179.80 (14) |
| C3—C4—C5—C6 | 0.4 (2) | C10—C11—C12—C13 | −1.0 (3) |
| N1—C4—C5—C6 | −179.06 (14) | Cl1—C11—C12—C13 | 179.19 (13) |
| C4—C5—C6—N3 | 177.72 (15) | C9—C8—C13—C12 | 0.7 (2) |
| C4—C5—C6—C1 | −1.7 (2) | O6—C8—C13—C12 | 176.33 (15) |
| C7—N3—C6—C5 | 4.4 (3) | C11—C12—C13—C8 | 0.4 (2) |
(I) 4-Chlorophenyl N-(3,5-dinitrophenyl)carbamate . Hydrogen-bond geometry (Å, º)
| D—H···A | D—H | H···A | D···A | D—H···A |
| N3—H3A···O3i | 0.86 | 2.18 | 3.0286 (19) | 168 |
| C12—H12···O1ii | 0.93 | 2.54 | 3.428 (2) | 159 |
Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) x, y−1, z.
(II) Phenyl N-(3,5-dinitrophenyl)carbamate . Crystal data
| C13H9N3O6 | F(000) = 624 |
| Mr = 303.23 | Dx = 1.526 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| a = 12.2549 (4) Å | Cell parameters from 1992 reflections |
| b = 8.8717 (4) Å | θ = 1.7–25.0° |
| c = 12.1470 (5) Å | µ = 0.12 mm−1 |
| β = 91.673 (2)° | T = 293 K |
| V = 1320.08 (9) Å3 | Block, yellow |
| Z = 4 | 0.35 × 0.30 × 0.25 mm |
(II) Phenyl N-(3,5-dinitrophenyl)carbamate . Data collection
| Bruker SMART APEXII CCD diffractometer | 2925 independent reflections |
| Radiation source: fine-focus sealed tube | 2355 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.020 |
| ω and φ scans | θmax = 27.1°, θmin = 1.7° |
| Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −13→15 |
| Tmin = 0.969, Tmax = 0.976 | k = −7→11 |
| 11395 measured reflections | l = −15→15 |
(II) Phenyl N-(3,5-dinitrophenyl)carbamate . 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)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.122 | H-atom parameters constrained |
| S = 1.03 | w = 1/[σ2(Fo2) + (0.0617P)2 + 0.328P] where P = (Fo2 + 2Fc2)/3 |
| 2925 reflections | (Δ/σ)max < 0.001 |
| 199 parameters | Δρmax = 0.23 e Å−3 |
| 0 restraints | Δρmin = −0.27 e Å−3 |
(II) Phenyl N-(3,5-dinitrophenyl)carbamate . Special details
| 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. |
(II) Phenyl N-(3,5-dinitrophenyl)carbamate . Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | ||
| O1 | 0.61513 (10) | 0.32392 (15) | 0.60653 (10) | 0.0637 (4) | |
| O2 | 0.79022 (12) | 0.31538 (18) | 0.63113 (11) | 0.0785 (4) | |
| O3 | 1.00811 (10) | 0.0409 (2) | 0.37541 (12) | 0.0824 (5) | |
| O4 | 0.93014 (11) | −0.11517 (17) | 0.26319 (12) | 0.0722 (4) | |
| O5 | 0.42568 (8) | 0.16533 (11) | 0.29697 (8) | 0.0433 (3) | |
| O6 | 0.38141 (10) | −0.04444 (13) | 0.20033 (12) | 0.0667 (4) | |
| N1 | 0.70568 (11) | 0.27772 (15) | 0.58344 (10) | 0.0488 (3) | |
| N2 | 0.92743 (10) | −0.01973 (18) | 0.33498 (11) | 0.0522 (4) | |
| N3 | 0.53349 (9) | −0.04417 (13) | 0.30003 (10) | 0.0416 (3) | |
| H3A | 0.5327 | −0.1390 | 0.2852 | 0.050* | |
| C1 | 0.72796 (11) | −0.03251 (16) | 0.32278 (11) | 0.0382 (3) | |
| H5 | 0.7340 | −0.1028 | 0.2665 | 0.046* | |
| C2 | 0.81974 (11) | 0.02594 (17) | 0.37459 (11) | 0.0397 (3) | |
| C3 | 0.81594 (12) | 0.12779 (17) | 0.46001 (11) | 0.0423 (3) | |
| H3 | 0.8789 | 0.1657 | 0.4944 | 0.051* | |
| C4 | 0.71342 (12) | 0.17011 (15) | 0.49145 (11) | 0.0382 (3) | |
| C5 | 0.61827 (11) | 0.11716 (15) | 0.44186 (11) | 0.0370 (3) | |
| H1 | 0.5506 | 0.1491 | 0.4655 | 0.044* | |
| C6 | 0.62602 (11) | 0.01493 (14) | 0.35580 (11) | 0.0352 (3) | |
| C7 | 0.44606 (11) | 0.03875 (15) | 0.26836 (12) | 0.0383 (3) | |
| C8 | 0.29939 (12) | 0.03219 (17) | 0.13844 (14) | 0.0475 (4) | |
| C9 | 0.19265 (13) | 0.0095 (2) | 0.16418 (15) | 0.0569 (4) | |
| H13 | 0.1747 | −0.0481 | 0.2250 | 0.068* | |
| C10 | 0.11244 (14) | 0.0740 (2) | 0.09776 (16) | 0.0644 (5) | |
| H12 | 0.0394 | 0.0593 | 0.1137 | 0.077* | |
| C11 | 0.13885 (15) | 0.1595 (2) | 0.00871 (15) | 0.0610 (5) | |
| H11 | 0.0839 | 0.2024 | −0.0354 | 0.073* | |
| C12 | 0.24650 (15) | 0.1821 (2) | −0.01578 (14) | 0.0590 (4) | |
| H10 | 0.2643 | 0.2407 | −0.0761 | 0.071* | |
| C13 | 0.32810 (14) | 0.1174 (2) | 0.04939 (15) | 0.0548 (4) | |
| H9 | 0.4011 | 0.1314 | 0.0333 | 0.066* |
(II) Phenyl N-(3,5-dinitrophenyl)carbamate . Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0677 (8) | 0.0644 (8) | 0.0598 (7) | 0.0019 (6) | 0.0147 (6) | −0.0192 (6) |
| O2 | 0.0757 (9) | 0.0913 (11) | 0.0673 (8) | −0.0013 (8) | −0.0177 (7) | −0.0362 (8) |
| O3 | 0.0406 (6) | 0.1277 (14) | 0.0791 (9) | −0.0059 (7) | 0.0041 (6) | −0.0198 (9) |
| O4 | 0.0600 (8) | 0.0823 (10) | 0.0753 (8) | 0.0092 (7) | 0.0192 (6) | −0.0170 (8) |
| O5 | 0.0452 (6) | 0.0320 (5) | 0.0525 (6) | 0.0027 (4) | −0.0015 (4) | −0.0037 (4) |
| O6 | 0.0591 (7) | 0.0358 (6) | 0.1029 (10) | 0.0050 (5) | −0.0356 (7) | −0.0157 (6) |
| N1 | 0.0620 (8) | 0.0448 (7) | 0.0395 (6) | −0.0031 (6) | −0.0005 (6) | −0.0039 (6) |
| N2 | 0.0439 (7) | 0.0672 (9) | 0.0459 (7) | 0.0044 (7) | 0.0064 (6) | 0.0044 (7) |
| N3 | 0.0427 (6) | 0.0257 (6) | 0.0559 (7) | −0.0010 (5) | −0.0061 (5) | −0.0023 (5) |
| C1 | 0.0466 (7) | 0.0346 (7) | 0.0334 (6) | 0.0033 (6) | 0.0020 (6) | 0.0020 (5) |
| C2 | 0.0394 (7) | 0.0435 (8) | 0.0363 (7) | 0.0038 (6) | 0.0033 (5) | 0.0081 (6) |
| C3 | 0.0428 (7) | 0.0469 (8) | 0.0369 (7) | −0.0040 (6) | −0.0053 (6) | 0.0043 (6) |
| C4 | 0.0484 (7) | 0.0344 (7) | 0.0319 (6) | −0.0004 (6) | 0.0000 (5) | 0.0018 (5) |
| C5 | 0.0418 (7) | 0.0318 (7) | 0.0376 (7) | 0.0009 (6) | 0.0027 (5) | 0.0044 (5) |
| C6 | 0.0411 (7) | 0.0272 (6) | 0.0371 (7) | −0.0011 (5) | −0.0019 (5) | 0.0055 (5) |
| C7 | 0.0381 (7) | 0.0293 (7) | 0.0475 (7) | −0.0052 (5) | −0.0012 (6) | 0.0007 (6) |
| C8 | 0.0434 (8) | 0.0373 (8) | 0.0610 (9) | 0.0015 (6) | −0.0114 (7) | −0.0130 (7) |
| C9 | 0.0516 (9) | 0.0643 (11) | 0.0546 (9) | −0.0033 (8) | −0.0007 (7) | 0.0016 (8) |
| C10 | 0.0403 (8) | 0.0860 (14) | 0.0667 (11) | 0.0024 (8) | −0.0011 (8) | −0.0057 (10) |
| C11 | 0.0602 (10) | 0.0674 (12) | 0.0545 (10) | 0.0101 (9) | −0.0143 (8) | −0.0082 (9) |
| C12 | 0.0751 (12) | 0.0563 (10) | 0.0457 (9) | −0.0051 (9) | 0.0018 (8) | −0.0071 (8) |
| C13 | 0.0453 (8) | 0.0522 (9) | 0.0670 (10) | −0.0069 (7) | 0.0061 (7) | −0.0168 (8) |
(II) Phenyl N-(3,5-dinitrophenyl)carbamate . Geometric parameters (Å, º)
| O1—N1 | 1.2232 (17) | C3—C4 | 1.376 (2) |
| O2—N1 | 1.2188 (17) | C3—H3 | 0.9300 |
| O3—N2 | 1.2165 (19) | C4—C5 | 1.3791 (19) |
| O4—N2 | 1.2167 (19) | C5—C6 | 1.3894 (19) |
| O5—C7 | 1.2039 (16) | C5—H1 | 0.9300 |
| O6—C7 | 1.3480 (17) | C8—C9 | 1.369 (2) |
| O6—C8 | 1.4119 (18) | C8—C13 | 1.374 (3) |
| N1—C4 | 1.4748 (18) | C9—C10 | 1.378 (2) |
| N2—C2 | 1.4745 (18) | C9—H13 | 0.9300 |
| N3—C7 | 1.3465 (18) | C10—C11 | 1.368 (3) |
| N3—C6 | 1.4054 (17) | C10—H12 | 0.9300 |
| N3—H3A | 0.8600 | C11—C12 | 1.376 (3) |
| C1—C2 | 1.374 (2) | C11—H11 | 0.9300 |
| C1—C6 | 1.3885 (19) | C12—C13 | 1.382 (2) |
| C1—H5 | 0.9300 | C12—H10 | 0.9300 |
| C2—C3 | 1.378 (2) | C13—H9 | 0.9300 |
| C7—O6—C8 | 117.34 (11) | C1—C6—C5 | 119.81 (12) |
| O2—N1—O1 | 124.29 (14) | C1—C6—N3 | 117.89 (12) |
| O2—N1—C4 | 117.71 (13) | C5—C6—N3 | 122.30 (12) |
| O1—N1—C4 | 118.00 (13) | O5—C7—N3 | 126.67 (13) |
| O3—N2—O4 | 123.94 (14) | O5—C7—O6 | 124.37 (13) |
| O3—N2—C2 | 118.12 (14) | N3—C7—O6 | 108.94 (12) |
| O4—N2—C2 | 117.94 (14) | C9—C8—C13 | 121.95 (15) |
| C7—N3—C6 | 123.92 (11) | C9—C8—O6 | 118.54 (16) |
| C7—N3—H3A | 118.0 | C13—C8—O6 | 119.31 (15) |
| C6—N3—H3A | 118.0 | C8—C9—C10 | 118.38 (17) |
| C2—C1—C6 | 118.98 (13) | C8—C9—H13 | 120.8 |
| C2—C1—H5 | 120.5 | C10—C9—H13 | 120.8 |
| C6—C1—H5 | 120.5 | C11—C10—C9 | 120.82 (16) |
| C1—C2—C3 | 123.17 (13) | C11—C10—H12 | 119.6 |
| C1—C2—N2 | 118.37 (13) | C9—C10—H12 | 119.6 |
| C3—C2—N2 | 118.44 (13) | C10—C11—C12 | 120.16 (17) |
| C4—C3—C2 | 116.06 (13) | C10—C11—H11 | 119.9 |
| C4—C3—H3 | 122.0 | C12—C11—H11 | 119.9 |
| C2—C3—H3 | 122.0 | C11—C12—C13 | 119.89 (17) |
| C3—C4—C5 | 123.57 (13) | C11—C12—H10 | 120.1 |
| C3—C4—N1 | 117.80 (13) | C13—C12—H10 | 120.1 |
| C5—C4—N1 | 118.63 (12) | C8—C13—C12 | 118.81 (16) |
| C4—C5—C6 | 118.39 (13) | C8—C13—H9 | 120.6 |
| C4—C5—H1 | 120.8 | C12—C13—H9 | 120.6 |
| C6—C5—H1 | 120.8 | ||
| C6—C1—C2—C3 | 1.4 (2) | C4—C5—C6—C1 | 0.73 (19) |
| C6—C1—C2—N2 | −177.01 (12) | C4—C5—C6—N3 | −179.58 (12) |
| O3—N2—C2—C1 | 174.49 (15) | C7—N3—C6—C1 | −137.09 (14) |
| O4—N2—C2—C1 | −5.0 (2) | C7—N3—C6—C5 | 43.2 (2) |
| O3—N2—C2—C3 | −4.0 (2) | C6—N3—C7—O5 | −12.7 (2) |
| O4—N2—C2—C3 | 176.50 (14) | C6—N3—C7—O6 | 168.91 (13) |
| C1—C2—C3—C4 | −0.4 (2) | C8—O6—C7—O5 | 15.9 (2) |
| N2—C2—C3—C4 | 178.04 (12) | C8—O6—C7—N3 | −165.73 (14) |
| C2—C3—C4—C5 | −0.5 (2) | C7—O6—C8—C9 | −110.20 (18) |
| C2—C3—C4—N1 | 179.34 (12) | C7—O6—C8—C13 | 74.81 (19) |
| O2—N1—C4—C3 | −4.8 (2) | C13—C8—C9—C10 | 0.4 (3) |
| O1—N1—C4—C3 | 174.88 (14) | O6—C8—C9—C10 | −174.48 (15) |
| O2—N1—C4—C5 | 175.11 (14) | C8—C9—C10—C11 | −0.4 (3) |
| O1—N1—C4—C5 | −5.3 (2) | C9—C10—C11—C12 | 0.0 (3) |
| C3—C4—C5—C6 | 0.3 (2) | C10—C11—C12—C13 | 0.4 (3) |
| N1—C4—C5—C6 | −179.52 (12) | C9—C8—C13—C12 | 0.1 (2) |
| C2—C1—C6—C5 | −1.57 (19) | O6—C8—C13—C12 | 174.88 (14) |
| C2—C1—C6—N3 | 178.72 (12) | C11—C12—C13—C8 | −0.5 (2) |
(II) Phenyl N-(3,5-dinitrophenyl)carbamate . Hydrogen-bond geometry (Å, º)
| D—H···A | D—H | H···A | D···A | D—H···A |
| N3—H3A···O5i | 0.86 | 2.07 | 2.8836 (15) | 157 |
Symmetry code: (i) −x+1, y−1/2, −z+1/2.
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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, II. DOI: 10.1107/S2056989015010245/su5141sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015010245/su5141Isup2.hkl
Structure factors: contains datablock(s) II. DOI: 10.1107/S2056989015010245/su5141IIsup3.hkl
Supporting information file. DOI: 10.1107/S2056989015010245/su5141Isup4.cml
Supporting information file. DOI: 10.1107/S2056989015010245/su5141IIsup5.cml
Additional supporting information: crystallographic information; 3D view; checkCIF report