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In the two title compounds, N-methylcarbazole-3,5-dinitrobenzonitrile (1/1), C13H11N·C7H3N3O4, (I), and N-ethylcarbazole-3,5-dinitrobenzonitrile (1/1), C14H13N·C7H3N3O4, (II), the donor and acceptor molecules are stacked alternately to form one-dimensional columns. In (I), the N-methyl group of the donor is nearly eclipsed with respect to one of the nitro groups of the neighboring acceptor in a column, whereas the N-ethyl group is anti with respect to the cyano group of the neighboring acceptor in (II).
Supporting information
 | Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100003851/qa0230sup1.cif |
 | Structure factor file (CIF format) https://doi.org/10.1107/S0108270100003851/qa0230Isup2.hkl |
| Structure factor file (CIF format) https://doi.org/10.1107/S0108270100003851/qa0230IIsup3.hkl |
CCDC references: 144705; 144706
Experimental top
Equimolecular mixtures of N-alkylcarbazoles and 3,5-dinitrobenzonitrile were recrystallized from methylene chloride [for (I)] and ethyl acetate [for (II)].
Refinement top
All H-atom positional parameters were calculated geometrically and fixed with Uiso(H) = 1.2Ueq(parent atom).
Computing details top
For both compounds, data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1999); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: TEXSAN.
(I) top
Crystal data top
| C13H11N·C7H3N3O4 | Dx = 1.382 Mg m−3 |
| Mr = 374.35 | Mo Kα radiation, λ = 0.71073 Å |
| Orthorhombic, P212121 | Cell parameters from 25 reflections |
| a = 8.339 (2) Å | θ = 10.0–15.0° |
| b = 27.604 (4) Å | µ = 0.10 mm−1 |
| c = 7.817 (2) Å | T = 293 K |
| V = 1799.4 (7) Å3 | Prism, red |
| Z = 4 | 0.55 × 0.3 × 0.2 mm |
Data collection top
| Rigaku AFC5 diffractometer | h = 0→10 |
| ω scans | k = 0→35 |
| 2384 measured reflections | l = 0→10 |
| 2384 independent reflections | 3 standard reflections every 100 reflections |
| 1034 reflections with I > 2σ(I) | intensity decay: 1.1% |
| θmax = 27.5°, θmin = 2.0° |
Refinement top
| Refinement on F2 | H-atom parameters not refined |
| R[F2 > 2σ(F2)] = 0.063 | w = 1/[σ2(Fo2) + (0.0604P)2] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.162 | (Δ/σ)max = 0.001 |
| S = 1.00 | Δρmax = 0.21 e Å−3 |
| 2384 reflections | Δρmin = −0.16 e Å−3 |
| 253 parameters |
Crystal data top
| C13H11N·C7H3N3O4 | V = 1799.4 (7) Å3 |
| Mr = 374.35 | Z = 4 |
| Orthorhombic, P212121 | Mo Kα radiation |
| a = 8.339 (2) Å | µ = 0.10 mm−1 |
| b = 27.604 (4) Å | T = 293 K |
| c = 7.817 (2) Å | 0.55 × 0.3 × 0.2 mm |
Data collection top
| Rigaku AFC5 diffractometer | 1034 reflections with I > 2σ(I) |
| 2384 measured reflections | 3 standard reflections every 100 reflections |
| 2384 independent reflections | intensity decay: 1.1% |
Refinement top
| R[F2 > 2σ(F2)] = 0.063 | 253 parameters |
| wR(F2) = 0.162 | H-atom parameters not refined |
| S = 1.00 | Δρmax = 0.21 e Å−3 |
| 2384 reflections | Δρmin = −0.16 e Å−3 |
Special details top
Refinement. Refinement was based on F2 against all reflections. The weighted R-factor (wR) and goodness of fit (S) were based on F2, and conventional R-factor (R) was calculated on F, with F set to zero for negative F2. The threshold expression of I > 2σ(I) was used only for calculating R-factor(gt). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
| x | y | z | Uiso*/Ueq | ||
| O1 | −0.0700 (7) | 0.3442 (2) | 1.0078 (7) | 0.125 (2) | |
| O2 | 0.1186 (7) | 0.3062 (2) | 0.8773 (8) | 0.121 (2) | |
| O3 | 0.2399 (6) | 0.3501 (2) | 0.2930 (6) | 0.100 (2) | |
| O4 | 0.1621 (7) | 0.4184 (2) | 0.1971 (6) | 0.114 (2) | |
| N5 | 0.0202 (8) | 0.3382 (2) | 0.8871 (8) | 0.085 (2) | |
| N6 | 0.1671 (7) | 0.3876 (2) | 0.3075 (7) | 0.071 (1) | |
| N7 | −0.2374 (8) | 0.5283 (2) | 0.6566 (9) | 0.113 (2) | |
| N8 | −0.4414 (6) | 0.3313 (2) | 0.8117 (6) | 0.065 (1) | |
| C9 | −0.1754 (7) | 0.4932 (2) | 0.6482 (9) | 0.074 (2) | |
| C10 | −0.0869 (7) | 0.4477 (2) | 0.6324 (8) | 0.059 (2) | |
| C11 | −0.0796 (7) | 0.4155 (2) | 0.7695 (6) | 0.066 (2) | |
| C12 | 0.0086 (7) | 0.3742 (2) | 0.7454 (8) | 0.061 (2) | |
| C13 | 0.0914 (6) | 0.3628 (2) | 0.5968 (8) | 0.059 (2) | |
| C14 | 0.0796 (7) | 0.3966 (2) | 0.4685 (7) | 0.056 (1) | |
| C15 | −0.0078 (7) | 0.4392 (2) | 0.4776 (6) | 0.056 (1) | |
| C16 | −0.5011 (7) | 0.3748 (2) | 0.7579 (9) | 0.063 (2) | |
| C17 | −0.5956 (8) | 0.4083 (3) | 0.8453 (6) | 0.092 (2) | |
| C18 | −0.6378 (8) | 0.4503 (3) | 0.760 (1) | 0.113 (3) | |
| C19 | −0.5899 (9) | 0.4592 (2) | 0.595 (1) | 0.096 (3) | |
| C20 | −0.4951 (7) | 0.4265 (2) | 0.5055 (6) | 0.077 (2) | |
| C21 | −0.4517 (6) | 0.3836 (2) | 0.5885 (8) | 0.054 (1) | |
| C22 | −0.3520 (7) | 0.3429 (2) | 0.5402 (7) | 0.056 (1) | |
| C23 | −0.2661 (8) | 0.3322 (2) | 0.3944 (6) | 0.069 (2) | |
| C24 | −0.1792 (7) | 0.2896 (3) | 0.3903 (8) | 0.081 (2) | |
| C25 | −0.1767 (7) | 0.2585 (2) | 0.530 (1) | 0.085 (2) | |
| C26 | −0.2608 (8) | 0.2688 (2) | 0.6794 (7) | 0.069 (2) | |
| C27 | −0.3481 (7) | 0.3117 (2) | 0.6822 (8) | 0.056 (1) | |
| C28 | −0.4730 (5) | 0.3082 (2) | 0.9785 (6) | 0.100 (2) | |
| H11 | −0.1351 | 0.4226 | 0.8758 | 0.0789* | |
| H13 | 0.1536 | 0.3335 | 0.5840 | 0.0688* | |
| H15 | −0.0102 | 0.4619 | 0.3819 | 0.0658* | |
| H17 | −0.6270 | 0.4023 | 0.9624 | 0.1090* | |
| H18 | −0.7025 | 0.4734 | 0.8222 | 0.1281* | |
| H19 | −0.6247 | 0.4892 | 0.5439 | 0.1203* | |
| H20 | −0.4582 | 0.4336 | 0.3893 | 0.0942* | |
| H23 | −0.2730 | 0.3528 | 0.2948 | 0.0828* | |
| H24 | −0.1117 | 0.2806 | 0.2948 | 0.0934* | |
| H25 | −0.1206 | 0.2279 | 0.5229 | 0.0971* | |
| H26 | −0.2554 | 0.2460 | 0.7720 | 0.0857* | |
| H28A | −0.4363 | 0.3286 | 1.0714 | 0.1166* | |
| H28B | −0.4185 | 0.2772 | 0.9878 | 0.1166* | |
| H28C | −0.5868 | 0.3024 | 0.9943 | 0.1166* |
Atomic displacement parameters (Å2) top
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.124 (5) | 0.171 (5) | 0.079 (3) | −0.024 (4) | 0.017 (4) | 0.033 (4) |
| O2 | 0.136 (5) | 0.101 (4) | 0.127 (5) | 0.011 (4) | −0.015 (5) | 0.037 (4) |
| O3 | 0.117 (4) | 0.076 (3) | 0.106 (4) | 0.022 (3) | 0.023 (4) | −0.012 (3) |
| O4 | 0.158 (5) | 0.105 (3) | 0.078 (3) | 0.032 (4) | 0.051 (4) | 0.021 (3) |
| N5 | 0.086 (5) | 0.098 (5) | 0.070 (4) | −0.027 (4) | −0.006 (4) | 0.021 (4) |
| N6 | 0.086 (4) | 0.061 (3) | 0.065 (3) | 0.001 (3) | 0.016 (4) | −0.001 (3) |
| N7 | 0.084 (4) | 0.106 (4) | 0.149 (6) | 0.024 (4) | −0.008 (5) | −0.038 (5) |
| N8 | 0.065 (3) | 0.083 (3) | 0.048 (3) | −0.008 (3) | 0.004 (3) | 0.000 (3) |
| C9 | 0.050 (4) | 0.081 (4) | 0.091 (5) | 0.002 (4) | 0.002 (4) | −0.027 (4) |
| C10 | 0.046 (3) | 0.065 (3) | 0.066 (4) | −0.010 (3) | −0.004 (3) | −0.012 (3) |
| C11 | 0.051 (4) | 0.092 (4) | 0.056 (4) | −0.012 (4) | 0.006 (3) | −0.014 (4) |
| C12 | 0.054 (3) | 0.077 (4) | 0.051 (3) | −0.024 (4) | −0.004 (3) | 0.008 (3) |
| C13 | 0.057 (4) | 0.054 (3) | 0.066 (4) | −0.014 (3) | −0.008 (3) | 0.004 (3) |
| C14 | 0.052 (4) | 0.062 (3) | 0.054 (3) | −0.011 (3) | 0.005 (3) | −0.006 (3) |
| C15 | 0.052 (4) | 0.062 (3) | 0.055 (4) | −0.004 (3) | 0.003 (3) | −0.007 (3) |
| C16 | 0.047 (3) | 0.064 (4) | 0.079 (4) | −0.011 (3) | −0.005 (3) | −0.018 (4) |
| C17 | 0.061 (4) | 0.091 (5) | 0.124 (6) | −0.011 (4) | 0.020 (5) | −0.052 (5) |
| C18 | 0.059 (5) | 0.083 (5) | 0.199 (10) | −0.004 (5) | 0.002 (7) | −0.065 (7) |
| C19 | 0.059 (5) | 0.068 (4) | 0.162 (8) | −0.003 (4) | −0.016 (6) | 0.001 (5) |
| C20 | 0.057 (4) | 0.066 (3) | 0.108 (5) | −0.018 (4) | −0.006 (5) | 0.006 (4) |
| C21 | 0.042 (3) | 0.050 (3) | 0.070 (4) | −0.009 (3) | −0.005 (3) | 0.000 (3) |
| C22 | 0.050 (3) | 0.060 (3) | 0.057 (3) | −0.013 (3) | −0.005 (3) | −0.004 (3) |
| C23 | 0.065 (4) | 0.082 (4) | 0.059 (4) | −0.011 (4) | 0.000 (4) | −0.003 (4) |
| C24 | 0.074 (5) | 0.090 (4) | 0.080 (4) | −0.020 (4) | 0.017 (4) | −0.022 (5) |
| C25 | 0.067 (5) | 0.067 (4) | 0.121 (6) | 0.005 (4) | 0.009 (5) | −0.033 (4) |
| C26 | 0.060 (4) | 0.053 (3) | 0.094 (5) | −0.003 (3) | −0.011 (4) | 0.006 (3) |
| C27 | 0.051 (4) | 0.059 (3) | 0.059 (3) | −0.011 (3) | −0.001 (3) | 0.003 (3) |
| C28 | 0.098 (6) | 0.142 (6) | 0.061 (4) | −0.009 (5) | 0.014 (5) | 0.007 (4) |
Geometric parameters (Å, º) top
| O1—N5 | 1.218 (9) | C17—C18 | 1.38 (1) |
| O2—N5 | 1.209 (9) | C17—H17 | 0.966 |
| O3—N6 | 1.204 (7) | C18—C19 | 1.37 (1) |
| O4—N6 | 1.212 (7) | C18—H18 | 0.968 |
| N5—C12 | 1.490 (9) | C19—C20 | 1.389 (9) |
| N6—C14 | 1.476 (8) | C19—H19 | 0.963 |
| N7—C9 | 1.099 (9) | C20—C21 | 1.397 (8) |
| N8—C16 | 1.365 (8) | C20—H20 | 0.979 |
| N8—C27 | 1.387 (7) | C21—C22 | 1.449 (8) |
| N8—C28 | 1.475 (7) | C22—C23 | 1.378 (8) |
| C9—C10 | 1.462 (9) | C22—C27 | 1.405 (8) |
| C10—C11 | 1.393 (8) | C23—C24 | 1.380 (9) |
| C10—C15 | 1.397 (8) | C23—H23 | 0.966 |
| C11—C12 | 1.371 (9) | C24—C25 | 1.389 (10) |
| C11—H11 | 0.971 | C24—H24 | 0.968 |
| C12—C13 | 1.388 (8) | C25—C26 | 1.393 (10) |
| C13—C14 | 1.372 (8) | C25—H25 | 0.968 |
| C13—H13 | 0.967 | C26—C27 | 1.390 (8) |
| C14—C15 | 1.386 (7) | C26—H26 | 0.961 |
| C15—H15 | 0.977 | C28—H28A | 0.969 |
| C16—C17 | 1.393 (9) | C28—H28B | 0.971 |
| C16—C21 | 1.409 (9) | C28—H28C | 0.970 |
| O1—N5—O2 | 124.5 (7) | C17—C18—H18 | 116.8 |
| O1—N5—C12 | 116.4 (6) | C19—C18—H18 | 121.1 |
| O2—N5—C12 | 119.0 (6) | C18—C19—C20 | 121.4 (6) |
| O3—N6—O4 | 123.5 (6) | C18—C19—H19 | 117.1 |
| O3—N6—C14 | 118.3 (5) | C20—C19—H19 | 121.5 |
| O4—N6—C14 | 118.2 (5) | C19—C20—C21 | 117.7 (5) |
| C16—N8—C27 | 108.8 (5) | C19—C20—H20 | 121.0 |
| C16—N8—C28 | 126.0 (5) | C21—C20—H20 | 121.3 |
| C27—N8—C28 | 125.2 (5) | C16—C21—C20 | 120.5 (5) |
| N7—C9—C10 | 177.3 (7) | C16—C21—C22 | 106.1 (5) |
| C9—C10—C11 | 120.3 (5) | C20—C21—C22 | 133.3 (5) |
| C9—C10—C15 | 117.2 (5) | C21—C22—C23 | 132.9 (5) |
| C11—C10—C15 | 122.5 (5) | C21—C22—C27 | 106.4 (5) |
| C10—C11—C12 | 116.6 (5) | C23—C22—C27 | 120.7 (5) |
| C10—C11—H11 | 120.6 | C22—C23—C24 | 118.4 (5) |
| C12—C11—H11 | 122.7 | C22—C23—H23 | 120.6 |
| N5—C12—C11 | 119.2 (5) | C24—C23—H23 | 120.9 |
| N5—C12—C13 | 116.0 (5) | C23—C24—C25 | 121.0 (5) |
| C11—C12—C13 | 124.8 (5) | C23—C24—H24 | 122.9 |
| C12—C13—C14 | 115.0 (5) | C25—C24—H24 | 116.0 |
| C12—C13—H13 | 122.9 | C24—C25—C26 | 121.7 (5) |
| C14—C13—H13 | 122.1 | C24—C25—H25 | 120.2 |
| N6—C14—C13 | 118.3 (5) | C26—C25—H25 | 118.0 |
| N6—C14—C15 | 116.5 (5) | C25—C26—C27 | 116.8 (5) |
| C13—C14—C15 | 125.2 (5) | C25—C26—H26 | 118.3 |
| C10—C15—C14 | 115.8 (5) | C27—C26—H26 | 124.9 |
| C10—C15—H15 | 123.0 | N8—C27—C22 | 109.0 (5) |
| C14—C15—H15 | 121.1 | N8—C27—C26 | 129.6 (5) |
| N8—C16—C17 | 129.7 (6) | C22—C27—C26 | 121.4 (5) |
| N8—C16—C21 | 109.6 (5) | N8—C28—H28A | 110.8 |
| C17—C16—C21 | 120.7 (5) | N8—C28—H28B | 111.3 |
| C16—C17—C18 | 117.6 (6) | N8—C28—H28C | 111.0 |
| C16—C17—H17 | 120.3 | H28A—C28—H28B | 107.9 |
| C18—C17—H17 | 122.1 | H28A—C28—H28C | 108.0 |
| C17—C18—C19 | 122.0 (7) | H28B—C28—H28C | 107.8 |
(II) top
Crystal data top
| C14H13N·C7H3N3O4 | Dx = 1.368 Mg m−3 |
| Mr = 388.38 | Mo Kα radiation, λ = 0.71073 Å |
| Monoclinic, P21/a | Cell parameters from 25 reflections |
| a = 16.227 (2) Å | θ = 10.0–15.0° |
| b = 6.982 (2) Å | µ = 0.10 mm−1 |
| c = 17.435 (2) Å | T = 293 K |
| β = 107.30 (1)° | Prism, orange |
| V = 1886.0 (6) Å3 | 0.5 × 0.35 × 0.3 mm |
| Z = 4 |
Data collection top
| Rigaku AFC5 diffractometer | θmax = 27.5°, θmin = 2.0° |
| θ–2θ scans | h = 0→21 |
| 4482 measured reflections | k = 0→9 |
| 4322 independent reflections | l = −22→22 |
| 1585 reflections with I > 2σ(I) | 3 standard reflections every 100 reflections |
| Rint = 0.020 | intensity decay: 2.8% |
Refinement top
| Refinement on F2 | w = 1/[σ2(Fo2) + (0.0549P)2] where P = (Fo2 + 2Fc2)/3 |
| R[F2 > 2σ(F2)] = 0.064 | (Δ/σ)max = 0.001 |
| wR(F2) = 0.160 | Δρmax = 0.13 e Å−3 |
| S = 0.97 | Δρmin = −0.13 e Å−3 |
| 4322 reflections | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| 263 parameters | Extinction coefficient: 0.0071 (10) |
| H-atom parameters not refined |
Crystal data top
| C14H13N·C7H3N3O4 | V = 1886.0 (6) Å3 |
| Mr = 388.38 | Z = 4 |
| Monoclinic, P21/a | Mo Kα radiation |
| a = 16.227 (2) Å | µ = 0.10 mm−1 |
| b = 6.982 (2) Å | T = 293 K |
| c = 17.435 (2) Å | 0.5 × 0.35 × 0.3 mm |
| β = 107.30 (1)° |
Data collection top
| Rigaku AFC5 diffractometer | Rint = 0.020 |
| 4482 measured reflections | 3 standard reflections every 100 reflections |
| 4322 independent reflections | intensity decay: 2.8% |
| 1585 reflections with I > 2σ(I) |
Refinement top
| R[F2 > 2σ(F2)] = 0.064 | 263 parameters |
| wR(F2) = 0.160 | H-atom parameters not refined |
| S = 0.97 | Δρmax = 0.13 e Å−3 |
| 4322 reflections | Δρmin = −0.13 e Å−3 |
Special details top
Refinement. Refinement was based on F2 against all reflections. The weighted R-factor (wR) and goodness of fit (S) were based on F2, and conventional R-factor (R) was calculated on F, with F set to zero for negative F2. The threshold expression of I > 2σ(I) was used only for calculating R-factor(gt). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
| x | y | z | Uiso*/Ueq | ||
| O1 | 0.5497 (2) | 0.8484 (4) | 0.9271 (2) | 0.0994 (9) | |
| O2 | 0.5317 (2) | 0.8096 (4) | 0.8004 (2) | 0.0933 (9) | |
| O3 | 0.2550 (2) | 0.9426 (4) | 0.6110 (1) | 0.1023 (10) | |
| O4 | 0.1440 (2) | 0.9922 (4) | 0.6523 (2) | 0.1003 (9) | |
| N5 | 0.5045 (2) | 0.8442 (4) | 0.8574 (2) | 0.0715 (8) | |
| N6 | 0.2203 (2) | 0.9591 (4) | 0.6640 (2) | 0.0749 (9) | |
| N7 | 0.2286 (2) | 0.9773 (6) | 1.0053 (2) | 0.126 (1) | |
| N8 | 0.3681 (2) | 0.3832 (4) | 0.6538 (2) | 0.0662 (8) | |
| C9 | 0.2554 (2) | 0.9581 (6) | 0.9534 (2) | 0.083 (1) | |
| C10 | 0.2907 (2) | 0.9364 (5) | 0.8868 (2) | 0.0622 (9) | |
| C11 | 0.3784 (2) | 0.9040 (5) | 0.9038 (2) | 0.0629 (9) | |
| C12 | 0.4114 (2) | 0.8838 (4) | 0.8400 (2) | 0.0549 (8) | |
| C13 | 0.3619 (2) | 0.8997 (4) | 0.7610 (2) | 0.0570 (8) | |
| C14 | 0.2753 (2) | 0.9348 (4) | 0.7476 (2) | 0.0584 (8) | |
| C15 | 0.2380 (2) | 0.9524 (5) | 0.8088 (2) | 0.0630 (9) | |
| C16 | 0.4163 (2) | 0.3694 (4) | 0.7341 (2) | 0.0582 (8) | |
| C17 | 0.5036 (2) | 0.3290 (5) | 0.7664 (2) | 0.0706 (10) | |
| C18 | 0.5370 (2) | 0.3223 (5) | 0.8488 (2) | 0.080 (1) | |
| C19 | 0.4841 (3) | 0.3556 (6) | 0.8974 (2) | 0.085 (1) | |
| C20 | 0.3970 (3) | 0.3917 (5) | 0.8660 (2) | 0.074 (1) | |
| C21 | 0.3621 (2) | 0.3992 (4) | 0.7823 (2) | 0.0593 (9) | |
| C22 | 0.2774 (2) | 0.4341 (4) | 0.7289 (2) | 0.0625 (9) | |
| C23 | 0.1964 (3) | 0.4741 (5) | 0.7397 (2) | 0.078 (1) | |
| C24 | 0.1269 (2) | 0.5054 (6) | 0.6727 (3) | 0.092 (1) | |
| C25 | 0.1347 (2) | 0.4988 (6) | 0.5953 (2) | 0.096 (1) | |
| C26 | 0.2134 (3) | 0.4591 (6) | 0.5828 (2) | 0.085 (1) | |
| C27 | 0.2836 (2) | 0.4260 (5) | 0.6504 (2) | 0.0645 (9) | |
| C28 | 0.4035 (2) | 0.3946 (6) | 0.5860 (2) | 0.084 (1) | |
| C29 | 0.4271 (2) | 0.5972 (6) | 0.5716 (2) | 0.105 (1) | |
| H11 | 0.4162 | 0.8943 | 0.9591 | 0.0697* | |
| H13 | 0.3871 | 0.8851 | 0.7165 | 0.0634* | |
| H15 | 0.1757 | 0.9662 | 0.7968 | 0.0689* | |
| H17 | 0.5394 | 0.3043 | 0.7316 | 0.0798* | |
| H18 | 0.5983 | 0.2948 | 0.8727 | 0.0942* | |
| H19 | 0.5097 | 0.3513 | 0.9560 | 0.0988* | |
| H20 | 0.3601 | 0.4117 | 0.9005 | 0.0871* | |
| H23 | 0.1905 | 0.4778 | 0.7935 | 0.0918* | |
| H24 | 0.0716 | 0.5396 | 0.6799 | 0.1041* | |
| H25 | 0.0836 | 0.5218 | 0.5489 | 0.1120* | |
| H26 | 0.2208 | 0.4558 | 0.5290 | 0.1007* | |
| H28A | 0.4543 | 0.3147 | 0.5961 | 0.0943* | |
| H28B | 0.3611 | 0.3471 | 0.5379 | 0.0943* | |
| H29A | 0.4501 | 0.6068 | 0.5274 | 0.1170* | |
| H29B | 0.4692 | 0.6476 | 0.6195 | 0.1170* | |
| H29C | 0.3761 | 0.6798 | 0.5609 | 0.1170* |
Atomic displacement parameters (Å2) top
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.080 (2) | 0.117 (2) | 0.088 (2) | 0.009 (2) | 0.005 (2) | 0.003 (2) |
| O2 | 0.088 (2) | 0.101 (2) | 0.104 (2) | 0.009 (2) | 0.051 (2) | 0.004 (2) |
| O3 | 0.123 (2) | 0.123 (3) | 0.060 (2) | 0.007 (2) | 0.026 (2) | −0.005 (2) |
| O4 | 0.078 (2) | 0.109 (2) | 0.101 (2) | 0.002 (2) | 0.006 (2) | 0.004 (2) |
| N5 | 0.073 (2) | 0.061 (2) | 0.086 (2) | −0.001 (2) | 0.033 (2) | 0.006 (2) |
| N6 | 0.086 (2) | 0.067 (2) | 0.067 (2) | −0.006 (2) | 0.015 (2) | −0.007 (2) |
| N7 | 0.134 (3) | 0.167 (4) | 0.105 (3) | −0.024 (3) | 0.076 (2) | −0.021 (3) |
| N8 | 0.067 (2) | 0.074 (2) | 0.065 (2) | −0.002 (2) | 0.032 (1) | −0.012 (2) |
| C9 | 0.084 (3) | 0.098 (3) | 0.079 (3) | −0.006 (2) | 0.039 (2) | −0.003 (2) |
| C10 | 0.072 (2) | 0.057 (2) | 0.064 (2) | −0.004 (2) | 0.030 (2) | 0.000 (2) |
| C11 | 0.074 (2) | 0.060 (2) | 0.056 (2) | −0.002 (2) | 0.021 (2) | 0.008 (2) |
| C12 | 0.058 (2) | 0.047 (2) | 0.063 (2) | −0.002 (2) | 0.023 (2) | 0.000 (2) |
| C13 | 0.075 (2) | 0.042 (2) | 0.060 (2) | −0.007 (2) | 0.029 (2) | −0.005 (2) |
| C14 | 0.073 (2) | 0.047 (2) | 0.053 (2) | −0.007 (2) | 0.015 (2) | −0.003 (2) |
| C15 | 0.061 (2) | 0.059 (2) | 0.072 (2) | −0.007 (2) | 0.023 (2) | −0.001 (2) |
| C16 | 0.072 (2) | 0.046 (2) | 0.061 (2) | −0.005 (2) | 0.026 (2) | −0.005 (2) |
| C17 | 0.078 (3) | 0.058 (2) | 0.080 (3) | −0.006 (2) | 0.031 (2) | −0.003 (2) |
| C18 | 0.088 (3) | 0.064 (3) | 0.085 (3) | −0.005 (2) | 0.020 (2) | 0.011 (2) |
| C19 | 0.121 (3) | 0.064 (3) | 0.068 (2) | −0.004 (3) | 0.023 (2) | 0.014 (2) |
| C20 | 0.116 (3) | 0.050 (2) | 0.071 (2) | −0.001 (2) | 0.048 (2) | 0.007 (2) |
| C21 | 0.081 (3) | 0.040 (2) | 0.066 (2) | −0.009 (2) | 0.036 (2) | −0.004 (2) |
| C22 | 0.076 (2) | 0.042 (2) | 0.083 (2) | −0.010 (2) | 0.045 (2) | −0.006 (2) |
| C23 | 0.095 (3) | 0.053 (2) | 0.107 (3) | −0.003 (2) | 0.061 (3) | 0.002 (2) |
| C24 | 0.077 (3) | 0.074 (3) | 0.139 (4) | 0.002 (2) | 0.055 (3) | 0.007 (3) |
| C25 | 0.073 (3) | 0.091 (3) | 0.123 (4) | −0.005 (3) | 0.025 (3) | 0.004 (3) |
| C26 | 0.075 (3) | 0.092 (3) | 0.090 (3) | −0.008 (2) | 0.026 (2) | −0.005 (2) |
| C27 | 0.070 (2) | 0.055 (2) | 0.075 (2) | −0.009 (2) | 0.031 (2) | −0.011 (2) |
| C28 | 0.084 (3) | 0.112 (3) | 0.064 (2) | 0.006 (2) | 0.033 (2) | −0.016 (2) |
| C29 | 0.101 (3) | 0.131 (4) | 0.099 (3) | 0.003 (3) | 0.052 (3) | 0.026 (3) |
Geometric parameters (Å, º) top
| O1—N5 | 1.219 (4) | C18—C19 | 1.395 (6) |
| O2—N5 | 1.225 (5) | C18—H18 | 0.976 |
| O3—N6 | 1.222 (5) | C19—C20 | 1.379 (6) |
| O4—N6 | 1.216 (5) | C19—H19 | 0.981 |
| N5—C12 | 1.476 (4) | C20—C21 | 1.400 (5) |
| N6—C14 | 1.475 (4) | C20—H20 | 0.977 |
| N7—C9 | 1.123 (6) | C21—C22 | 1.434 (4) |
| N8—C16 | 1.390 (4) | C22—C23 | 1.409 (6) |
| N8—C27 | 1.387 (5) | C22—C27 | 1.403 (6) |
| N8—C28 | 1.463 (5) | C23—C24 | 1.378 (5) |
| C9—C10 | 1.447 (6) | C23—H23 | 0.972 |
| C10—C11 | 1.383 (5) | C24—C25 | 1.393 (7) |
| C10—C15 | 1.379 (4) | C24—H24 | 0.972 |
| C11—C12 | 1.378 (5) | C25—C26 | 1.386 (6) |
| C11—H11 | 0.980 | C25—H25 | 0.985 |
| C12—C13 | 1.376 (4) | C26—C27 | 1.394 (4) |
| C13—C14 | 1.376 (5) | C26—H26 | 0.980 |
| C13—H13 | 0.984 | C28—C29 | 1.506 (6) |
| C14—C15 | 1.380 (5) | C28—H28A | 0.966 |
| C15—H15 | 0.976 | C28—H28B | 0.971 |
| C16—C17 | 1.390 (5) | C29—H29A | 0.953 |
| C16—C21 | 1.401 (6) | C29—H29B | 0.974 |
| C17—C18 | 1.376 (5) | C29—H29C | 0.979 |
| C17—H17 | 0.971 | ||
| O1—N5—O2 | 123.9 (3) | C18—C19—H19 | 118.8 |
| O1—N5—C12 | 118.5 (3) | C20—C19—H19 | 119.1 |
| O2—N5—C12 | 117.6 (3) | C19—C20—C21 | 118.1 (4) |
| O3—N6—O4 | 124.5 (3) | C19—C20—H20 | 121.6 |
| O3—N6—C14 | 117.2 (3) | C21—C20—H20 | 120.3 |
| O4—N6—C14 | 118.3 (3) | C16—C21—C20 | 119.2 (3) |
| C16—N8—C27 | 108.1 (3) | C16—C21—C22 | 106.7 (3) |
| C16—N8—C28 | 125.4 (3) | C20—C21—C22 | 134.1 (4) |
| C27—N8—C28 | 125.1 (2) | C21—C22—C23 | 134.3 (3) |
| N7—C9—C10 | 179.0 (4) | C21—C22—C27 | 107.1 (3) |
| C9—C10—C11 | 118.2 (3) | C23—C22—C27 | 118.6 (3) |
| C9—C10—C15 | 120.3 (3) | C22—C23—C24 | 118.6 (4) |
| C11—C10—C15 | 121.4 (3) | C22—C23—H23 | 119.8 |
| C10—C11—C12 | 117.8 (3) | C24—C23—H23 | 121.6 |
| C10—C11—H11 | 121.6 | C23—C24—C25 | 121.9 (4) |
| C12—C11—H11 | 120.6 | C23—C24—H24 | 118.9 |
| N5—C12—C11 | 118.2 (3) | C25—C24—H24 | 119.1 |
| N5—C12—C13 | 118.6 (3) | C24—C25—C26 | 120.8 (3) |
| C11—C12—C13 | 123.2 (3) | C24—C25—H25 | 119.6 |
| C12—C13—C14 | 116.6 (3) | C26—C25—H25 | 119.6 |
| C12—C13—H13 | 121.6 | C25—C26—C27 | 117.4 (4) |
| C14—C13—H13 | 121.8 | C25—C26—H26 | 122.4 |
| N6—C14—C13 | 118.4 (3) | C27—C26—H26 | 120.2 |
| N6—C14—C15 | 118.6 (3) | N8—C27—C22 | 109.0 (3) |
| C13—C14—C15 | 123.0 (3) | N8—C27—C26 | 128.3 (4) |
| C10—C15—C14 | 118.0 (3) | C22—C27—C26 | 122.7 (4) |
| C10—C15—H15 | 121.3 | N8—C28—C29 | 111.5 (3) |
| C14—C15—H15 | 120.6 | N8—C28—H28A | 109.8 |
| N8—C16—C17 | 128.5 (3) | N8—C28—H28B | 109.3 |
| N8—C16—C21 | 109.2 (3) | C29—C28—H28A | 109.2 |
| C17—C16—C21 | 122.3 (3) | C29—C28—H28B | 109.1 |
| C16—C17—C18 | 117.8 (4) | H28A—C28—H28B | 108.0 |
| C16—C17—H17 | 120.7 | C28—C29—H29A | 112.3 |
| C18—C17—H17 | 121.5 | C28—C29—H29B | 110.2 |
| C17—C18—C19 | 120.5 (3) | C28—C29—H29C | 110.0 |
| C17—C18—H18 | 119.1 | H29A—C29—H29B | 108.9 |
| C19—C18—H18 | 120.4 | H29A—C29—H29C | 108.4 |
| C18—C19—C20 | 122.1 (3) | H29B—C29—H29C | 106.8 |
Experimental details
| (I) | (II) | |
| Crystal data | ||
| Chemical formula | C13H11N·C7H3N3O4 | C14H13N·C7H3N3O4 |
| Mr | 374.35 | 388.38 |
| Crystal system, space group | Orthorhombic, P212121 | Monoclinic, P21/a |
| Temperature (K) | 293 | 293 |
| a, b, c (Å) | 8.339 (2), 27.604 (4), 7.817 (2) | 16.227 (2), 6.982 (2), 17.435 (2) |
| α, β, γ (°) | 90, 90, 90 | 90, 107.30 (1), 90 |
| V (Å3) | 1799.4 (7) | 1886.0 (6) |
| Z | 4 | 4 |
| Radiation type | Mo Kα | Mo Kα |
| µ (mm−1) | 0.10 | 0.10 |
| Crystal size (mm) | 0.55 × 0.3 × 0.2 | 0.5 × 0.35 × 0.3 |
| Data collection | ||
| Diffractometer | Rigaku AFC5 diffractometer | Rigaku AFC5 diffractometer |
| Absorption correction | – | – |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 2384, 2384, 1034 | 4482, 4322, 1585 |
| Rint | ? | 0.020 |
| (sin θ/λ)max (Å−1) | 0.650 | 0.650 |
| Refinement | ||
| R[F2 > 2σ(F2)], wR(F2), S | 0.063, 0.162, 1.00 | 0.064, 0.160, 0.97 |
| No. of reflections | 2384 | 4322 |
| No. of parameters | 253 | 263 |
| No. of restraints | ? | ? |
| H-atom treatment | H-atom parameters not refined | H-atom parameters not refined |
| Δρmax, Δρmin (e Å−3) | 0.21, −0.16 | 0.13, −0.13 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993), MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1999), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), TEXSAN.
Selected geometric parameters (Å, º) for (I) top
| O1—N5 | 1.218 (9) | N7—C9 | 1.099 (9) |
| O2—N5 | 1.209 (9) | N8—C28 | 1.475 (7) |
| O3—N6 | 1.204 (7) | C9—C10 | 1.462 (9) |
| O4—N6 | 1.212 (7) | ||
| O1—N5—O2 | 124.5 (7) | N7—C9—C10 | 177.3 (7) |
| O3—N6—O4 | 123.5 (6) |
Selected geometric parameters (Å, º) for (II) top
| O1—N5 | 1.219 (4) | N7—C9 | 1.123 (6) |
| O2—N5 | 1.225 (5) | N8—C28 | 1.463 (5) |
| O3—N6 | 1.222 (5) | C9—C10 | 1.447 (6) |
| O4—N6 | 1.216 (5) | C28—C29 | 1.506 (6) |
| O1—N5—O2 | 123.9 (3) | N7—C9—C10 | 179.0 (4) |
| O3—N6—O4 | 124.5 (3) | N8—C28—C29 | 111.5 (3) |
Crystals of (I) underwent photoredox reactions initiated by the excited nitro group, leading to α-oxidation of the N-alkyl groups. However, no photoreaction was observed for (II) (Ito et al., 1998).
In (I), the N-methyl group of the donor is nearly eclipsed with respect to one of the nitro groups of the neighboring acceptor in a column, whereas the N-ethyl group is anti with respect to the cyano group of the neighboring acceptor in (II).