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The NNO2 group of the title compound is significantly less twisted with respect to the aromatic ring in comparison to a typical secondary nitramine. The amide nitrogen is trigonally hybridized. The nitramino group is almost planar. The C-C-N-N torsion angles vary between ca 13 and 42°, whereas the twist along the N-N bond is much smaller and amounts to between ca 1 and 15°. Those twist angles are governed by a crystal packing and are much larger in the case of crystals of pure N,4-dinitroaniline in comparison to that of its complex with sulfolane. The deviations of the internal angles of the aromatic ring from 120° do not exceed 3°. The presence of the nitro group increases the C-C-C valence angle of ca 2.0-2.6°, whereas an analogous effect associated with the nitramino group is much smaller (ca 0.3-1.3°), pointing to its weak electron-withdrawing properties. The nitramino group displays no tendency to conjugate with an electron-demanding substituent across the ring. It participates in hydrogen bonding only as a hydrogen-bonding donor. It does not act as a proton acceptor, despite the fact that nitramine rearrangement is catalysed by acids.
Supporting information
 | Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768101016548/lc0040sup1.cif |
 | Structure factor file (CIF format) https://doi.org/10.1107/S0108768101016548/lc00401sup2.fcf |
| Structure factor file (CIF format) https://doi.org/10.1107/S0108768101016548/lc00402sup3.fcf |
CCDC references: 180196; 180197
Computing details top
For both compounds, cell refinement: KUMA Diffraction Software, ver. KM4b8 (KUMA, 1997); data reduction: KUMA Diffraction Software, DATARED9 (KUMA, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1990); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
(1) 'N,4-Dinitroaniline-sulpholane complex' top
Crystal data top
| C16H18N6O10S | F(000) = 1008 |
| Mr = 486.42 | Dx = 1.605 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
| a = 10.043 (3) Å | Cell parameters from 24 reflections |
| b = 17.131 (4) Å | θ = 16–23° |
| c = 12.299 (4) Å | µ = 0.23 mm−1 |
| β = 107.95 (3)° | T = 85 K |
| V = 2013.1 (10) Å3 | Plates, yellow |
| Z = 4 | 0.5 × 0.3 × 0.25 mm |
Data collection top
| KUMA KM4 diffractometer | Rint = 0.061 |
| Radiation source: fine-focus sealed tube | θmax = 27.0°, θmin = 2.1° |
| Graphite monochromator | h = −12→0 |
| ω scans | k = −21→0 |
| 4440 measured reflections | l = −14→14 |
| 4200 independent reflections | 2 standard reflections every 50 reflections |
| 3360 reflections with I > 2σ(I) | intensity decay: 0.5% |
Refinement top
| 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)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.165 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.19 | w = 1/[σ2(Fo2) + (0.0489P)2 + 7.0136P] where P = (Fo2 + 2Fc2)/3 |
| 4200 reflections | (Δ/σ)max = 0.033 |
| 298 parameters | Δρmax = 0.61 e Å−3 |
| 0 restraints | Δρmin = −0.41 e Å−3 |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > σ(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) top
| x | y | z | Uiso*/Ueq | ||
| S1 | 0.65278 (8) | 0.01688 (4) | 0.80618 (7) | 0.0157 (2) | |
| O1 | 0.6048 (3) | −0.05541 (14) | 0.8433 (2) | 0.0223 (5) | |
| O2 | 0.5821 (2) | 0.08743 (13) | 0.8226 (2) | 0.0214 (5) | |
| C1 | 0.8364 (3) | 0.02269 (19) | 0.8692 (3) | 0.0189 (7) | |
| H11 | 0.8659 | 0.0056 | 0.9426 | 0.023* | |
| H12 | 0.8717 | 0.0745 | 0.8666 | 0.023* | |
| C2 | 0.8871 (4) | −0.0359 (2) | 0.7970 (3) | 0.0207 (7) | |
| H21 | 0.8695 | −0.0884 | 0.8142 | 0.025* | |
| H22 | 0.9891 | −0.0302 | 0.8128 | 0.025* | |
| C3 | 0.8024 (4) | −0.0203 (2) | 0.6703 (3) | 0.0251 (8) | |
| H31 | 0.7977 | −0.0672 | 0.6297 | 0.030* | |
| H32 | 0.8502 | 0.0192 | 0.6441 | 0.030* | |
| C4 | 0.6538 (4) | 0.0056 (2) | 0.6619 (3) | 0.0202 (7) | |
| H41 | 0.6311 | 0.0545 | 0.6244 | 0.024* | |
| H42 | 0.5833 | −0.0322 | 0.6230 | 0.024* | |
| C1A | 1.1712 (3) | −0.29214 (18) | 0.6125 (3) | 0.0144 (6) | |
| C2A | 1.0785 (3) | −0.24838 (18) | 0.6525 (3) | 0.0152 (6) | |
| H2A | 1.0115 | −0.2744 | 0.6789 | 0.018* | |
| C3A | 1.0862 (3) | −0.16805 (19) | 0.6527 (3) | 0.0159 (6) | |
| H3A | 1.0241 | −0.1370 | 0.6783 | 0.019* | |
| C4A | 1.1875 (3) | −0.13295 (18) | 0.6148 (3) | 0.0160 (6) | |
| C5A | 1.2795 (3) | −0.17510 (19) | 0.5740 (3) | 0.0158 (6) | |
| H5A | 1.3464 | −0.1485 | 0.5482 | 0.019* | |
| C6A | 1.2710 (3) | −0.25614 (19) | 0.5717 (3) | 0.0157 (6) | |
| H6A | 1.3310 | −0.2868 | 0.5436 | 0.019* | |
| N11A | 1.1999 (3) | −0.04765 (16) | 0.6187 (2) | 0.0184 (6) | |
| O12A | 1.1064 (3) | −0.00980 (14) | 0.6383 (2) | 0.0263 (6) | |
| O13A | 1.3040 (3) | −0.01820 (14) | 0.6027 (2) | 0.0250 (6) | |
| N7A | 1.1520 (3) | −0.37359 (16) | 0.6142 (2) | 0.0175 (6) | |
| H7A | 1.0694 | −0.3902 | 0.6214 | 0.021* | |
| N8A | 1.2441 (3) | −0.42869 (16) | 0.6061 (2) | 0.0167 (6) | |
| O9A | 1.3564 (2) | −0.40954 (14) | 0.5942 (2) | 0.0224 (5) | |
| O10A | 1.2065 (3) | −0.49686 (13) | 0.6103 (2) | 0.0233 (5) | |
| C1B | 1.9499 (3) | −0.26226 (19) | 0.3552 (3) | 0.0153 (6) | |
| C2B | 1.8840 (3) | −0.32530 (18) | 0.3899 (3) | 0.0166 (6) | |
| H2B | 1.9146 | −0.3776 | 0.3833 | 0.020* | |
| C3B | 1.7752 (3) | −0.31299 (18) | 0.4335 (3) | 0.0162 (6) | |
| H3B | 1.7310 | −0.3561 | 0.4564 | 0.019* | |
| C4B | 1.7329 (3) | −0.23653 (19) | 0.4426 (3) | 0.0154 (6) | |
| C5B | 1.7961 (3) | −0.17351 (19) | 0.4083 (3) | 0.0166 (6) | |
| H5B | 1.7648 | −0.1214 | 0.4148 | 0.020* | |
| C6B | 1.9054 (3) | −0.18586 (19) | 0.3644 (3) | 0.0162 (6) | |
| H6B | 1.9486 | −0.1426 | 0.3411 | 0.019* | |
| N11B | 1.6158 (3) | −0.22361 (17) | 0.4873 (2) | 0.0204 (6) | |
| O13B | 1.5785 (3) | −0.15586 (15) | 0.4957 (2) | 0.0263 (6) | |
| O12B | 1.5595 (3) | −0.28042 (16) | 0.5148 (3) | 0.0310 (6) | |
| N7B | 2.0568 (3) | −0.28484 (16) | 0.3103 (2) | 0.0186 (6) | |
| H7B | 2.0588 | −0.3358 | 0.2948 | 0.022* | |
| N8B | 2.1553 (3) | −0.23913 (17) | 0.2881 (2) | 0.0199 (6) | |
| O9B | 2.1476 (3) | −0.16799 (14) | 0.2972 (2) | 0.0239 (6) | |
| O10B | 2.2467 (3) | −0.27356 (15) | 0.2595 (2) | 0.0273 (6) |
Atomic displacement parameters (Å2) top
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S1 | 0.0167 (4) | 0.0109 (4) | 0.0227 (4) | −0.0013 (3) | 0.0107 (3) | −0.0020 (3) |
| O1 | 0.0234 (13) | 0.0129 (11) | 0.0349 (14) | −0.0030 (9) | 0.0152 (11) | −0.0002 (10) |
| O2 | 0.0231 (12) | 0.0126 (11) | 0.0343 (14) | 0.0004 (9) | 0.0173 (11) | −0.0039 (10) |
| C1 | 0.0171 (16) | 0.0173 (16) | 0.0230 (17) | −0.0026 (12) | 0.0073 (13) | −0.0021 (13) |
| C2 | 0.0169 (16) | 0.0168 (16) | 0.0285 (19) | −0.0007 (12) | 0.0070 (14) | −0.0045 (13) |
| C3 | 0.0221 (18) | 0.0264 (18) | 0.030 (2) | −0.0009 (14) | 0.0136 (15) | −0.0088 (15) |
| C4 | 0.0200 (17) | 0.0228 (17) | 0.0186 (16) | −0.0011 (13) | 0.0071 (13) | −0.0016 (13) |
| C1A | 0.0154 (15) | 0.0137 (15) | 0.0144 (15) | −0.0022 (12) | 0.0049 (12) | 0.0000 (12) |
| C2A | 0.0146 (15) | 0.0143 (15) | 0.0162 (15) | −0.0006 (12) | 0.0041 (12) | −0.0009 (12) |
| C3A | 0.0158 (15) | 0.0151 (15) | 0.0162 (15) | 0.0035 (12) | 0.0040 (12) | 0.0011 (12) |
| C4A | 0.0192 (16) | 0.0127 (15) | 0.0149 (15) | 0.0018 (12) | 0.0034 (13) | 0.0011 (12) |
| C5A | 0.0161 (15) | 0.0147 (15) | 0.0166 (15) | −0.0017 (12) | 0.0050 (12) | 0.0026 (12) |
| C6A | 0.0149 (15) | 0.0155 (15) | 0.0175 (16) | 0.0018 (12) | 0.0063 (13) | 0.0005 (12) |
| N11A | 0.0199 (14) | 0.0148 (13) | 0.0204 (14) | 0.0011 (11) | 0.0061 (12) | 0.0038 (11) |
| O12A | 0.0299 (14) | 0.0158 (12) | 0.0391 (16) | 0.0024 (10) | 0.0194 (12) | −0.0006 (11) |
| O13A | 0.0257 (13) | 0.0177 (12) | 0.0353 (15) | −0.0030 (10) | 0.0148 (11) | 0.0028 (10) |
| N7A | 0.0149 (13) | 0.0107 (13) | 0.0278 (15) | 0.0003 (10) | 0.0080 (11) | −0.0003 (11) |
| N8A | 0.0168 (14) | 0.0146 (13) | 0.0190 (14) | 0.0020 (10) | 0.0056 (11) | −0.0003 (11) |
| O9A | 0.0168 (12) | 0.0179 (12) | 0.0355 (14) | 0.0017 (9) | 0.0124 (10) | −0.0001 (10) |
| O10A | 0.0281 (13) | 0.0108 (11) | 0.0331 (14) | −0.0012 (9) | 0.0124 (11) | −0.0012 (10) |
| C1B | 0.0156 (15) | 0.0167 (16) | 0.0127 (15) | −0.0005 (12) | 0.0031 (12) | −0.0007 (11) |
| C2B | 0.0194 (16) | 0.0103 (14) | 0.0173 (16) | 0.0001 (12) | 0.0017 (13) | 0.0012 (12) |
| C3B | 0.0164 (15) | 0.0128 (15) | 0.0173 (16) | −0.0018 (12) | 0.0023 (13) | 0.0015 (12) |
| C4B | 0.0153 (15) | 0.0167 (16) | 0.0149 (15) | 0.0008 (12) | 0.0055 (13) | −0.0019 (12) |
| C5B | 0.0202 (16) | 0.0123 (14) | 0.0152 (15) | 0.0018 (12) | 0.0025 (13) | −0.0003 (12) |
| C6B | 0.0198 (16) | 0.0128 (15) | 0.0152 (15) | −0.0010 (12) | 0.0040 (13) | −0.0001 (12) |
| N11B | 0.0201 (14) | 0.0202 (14) | 0.0220 (15) | −0.0006 (11) | 0.0079 (12) | −0.0029 (12) |
| O13B | 0.0263 (13) | 0.0208 (13) | 0.0364 (15) | 0.0038 (10) | 0.0162 (12) | −0.0042 (11) |
| O12B | 0.0278 (14) | 0.0239 (13) | 0.0478 (17) | −0.0016 (11) | 0.0212 (13) | 0.0032 (12) |
| N7B | 0.0230 (15) | 0.0119 (13) | 0.0236 (15) | −0.0005 (11) | 0.0110 (12) | 0.0002 (11) |
| N8B | 0.0211 (15) | 0.0191 (14) | 0.0199 (14) | 0.0015 (11) | 0.0072 (12) | 0.0029 (11) |
| O9B | 0.0301 (14) | 0.0137 (12) | 0.0330 (14) | −0.0001 (10) | 0.0174 (11) | 0.0037 (10) |
| O10B | 0.0264 (13) | 0.0247 (13) | 0.0373 (15) | 0.0068 (11) | 0.0194 (12) | 0.0057 (11) |
Geometric parameters (Å, º) top
| S1—O2 | 1.447 (2) | N7A—N8A | 1.346 (4) |
| S1—O1 | 1.453 (2) | N8A—O9A | 1.226 (4) |
| S1—C1 | 1.769 (3) | N8A—O10A | 1.233 (4) |
| S1—C4 | 1.788 (3) | C1B—C6B | 1.399 (4) |
| C1—C2 | 1.528 (5) | C1B—C2B | 1.400 (4) |
| C2—C3 | 1.551 (5) | C1B—N7B | 1.404 (4) |
| C3—C4 | 1.530 (5) | C2B—C3B | 1.375 (5) |
| C1A—C6A | 1.395 (4) | C3B—C4B | 1.392 (4) |
| C1A—C2A | 1.398 (4) | C4B—C5B | 1.382 (4) |
| C1A—N7A | 1.410 (4) | C4B—N11B | 1.460 (4) |
| C2A—C3A | 1.378 (4) | C5B—C6B | 1.381 (5) |
| C3A—C4A | 1.380 (5) | N11B—O12B | 1.225 (4) |
| C4A—C5A | 1.383 (5) | N11B—O13B | 1.234 (4) |
| C4A—N11A | 1.466 (4) | N7B—N8B | 1.355 (4) |
| C5A—C6A | 1.391 (4) | N8B—O9B | 1.229 (4) |
| N11A—O12A | 1.225 (4) | N8B—O10B | 1.230 (4) |
| N11A—O13A | 1.230 (4) | ||
| O2—S1—O1 | 116.32 (14) | O13A—N11A—C4A | 118.1 (3) |
| O2—S1—C1 | 112.43 (15) | N8A—N7A—C1A | 126.3 (3) |
| O1—S1—C1 | 108.20 (16) | O9A—N8A—O10A | 124.3 (3) |
| O2—S1—C4 | 112.44 (16) | O9A—N8A—N7A | 120.0 (3) |
| O1—S1—C4 | 108.93 (16) | O10A—N8A—N7A | 115.8 (3) |
| C1—S1—C4 | 96.70 (16) | C6B—C1B—C2B | 120.3 (3) |
| C2—C1—S1 | 101.4 (2) | C6B—C1B—N7B | 126.3 (3) |
| C1—C2—C3 | 107.0 (3) | C2B—C1B—N7B | 113.4 (3) |
| C4—C3—C2 | 109.9 (3) | C3B—C2B—C1B | 120.5 (3) |
| C3—C4—S1 | 105.5 (2) | C2B—C3B—C4B | 118.3 (3) |
| C6A—C1A—C2A | 121.3 (3) | C5B—C4B—C3B | 122.0 (3) |
| C6A—C1A—N7A | 124.1 (3) | C5B—C4B—N11B | 119.7 (3) |
| C2A—C1A—N7A | 114.6 (3) | C3B—C4B—N11B | 118.3 (3) |
| C3A—C2A—C1A | 119.5 (3) | C6B—C5B—C4B | 119.6 (3) |
| C2A—C3A—C4A | 118.8 (3) | C5B—C6B—C1B | 119.2 (3) |
| C3A—C4A—C5A | 122.6 (3) | O12B—N11B—O13B | 123.1 (3) |
| C3A—C4A—N11A | 119.2 (3) | O12B—N11B—C4B | 118.6 (3) |
| C5A—C4A—N11A | 118.2 (3) | O13B—N11B—C4B | 118.3 (3) |
| C4A—C5A—C6A | 119.0 (3) | N8B—N7B—C1B | 127.9 (3) |
| C5A—C6A—C1A | 118.7 (3) | O9B—N8B—O10B | 125.2 (3) |
| O12A—N11A—O13A | 123.7 (3) | O9B—N8B—N7B | 118.9 (3) |
| O12A—N11A—C4A | 118.1 (3) | O10B—N8B—N7B | 115.9 (3) |
| O2—S1—C1—C2 | −154.9 (2) | C6A—C1A—N7A—N8A | 18.1 (5) |
| O1—S1—C1—C2 | 75.3 (2) | C2A—C1A—N7A—N8A | −163.6 (3) |
| C4—S1—C1—C2 | −37.2 (2) | C1A—N7A—N8A—O9A | −1.2 (5) |
| S1—C1—C2—C3 | 44.9 (3) | C1A—N7A—N8A—O10A | 179.5 (3) |
| C1—C2—C3—C4 | −34.1 (4) | C6B—C1B—C2B—C3B | −0.2 (5) |
| C2—C3—C4—S1 | 6.5 (3) | N7B—C1B—C2B—C3B | −178.6 (3) |
| O2—S1—C4—C3 | 136.1 (2) | C1B—C2B—C3B—C4B | −0.2 (5) |
| O1—S1—C4—C3 | −93.5 (3) | C2B—C3B—C4B—C5B | 0.6 (5) |
| C1—S1—C4—C3 | 18.4 (3) | C2B—C3B—C4B—N11B | 179.0 (3) |
| C6A—C1A—C2A—C3A | −0.5 (5) | C3B—C4B—C5B—C6B | −0.5 (5) |
| N7A—C1A—C2A—C3A | −178.9 (3) | N11B—C4B—C5B—C6B | −179.0 (3) |
| C1A—C2A—C3A—C4A | −1.0 (5) | C4B—C5B—C6B—C1B | 0.1 (5) |
| C2A—C3A—C4A—C5A | 1.6 (5) | C2B—C1B—C6B—C5B | 0.2 (5) |
| C2A—C3A—C4A—N11A | −177.8 (3) | N7B—C1B—C6B—C5B | 178.4 (3) |
| C3A—C4A—C5A—C6A | −0.6 (5) | C5B—C4B—N11B—O12B | 178.4 (3) |
| N11A—C4A—C5A—C6A | 178.8 (3) | C3B—C4B—N11B—O12B | −0.1 (5) |
| C4A—C5A—C6A—C1A | −1.0 (5) | C5B—C4B—N11B—O13B | −1.7 (5) |
| C2A—C1A—C6A—C5A | 1.6 (5) | C3B—C4B—N11B—O13B | 179.8 (3) |
| N7A—C1A—C6A—C5A | 179.7 (3) | C6B—C1B—N7B—N8B | 14.2 (5) |
| C3A—C4A—N11A—O12A | −11.3 (5) | C2B—C1B—N7B—N8B | −167.5 (3) |
| C5A—C4A—N11A—O12A | 169.3 (3) | C1B—N7B—N8B—O9B | −7.3 (5) |
| C3A—C4A—N11A—O13A | 168.3 (3) | C1B—N7B—N8B—O10B | 172.9 (3) |
| C5A—C4A—N11A—O13A | −11.1 (4) |
Hydrogen-bond geometry (Å, º) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| C2B—H2B···O1i | 0.96 | 2.41 | 3.194 (4) | 139 |
| C2B—H2B···O10Aii | 0.96 | 2.48 | 3.179 (4) | 129 |
| C5B—H5B···O13Aiii | 0.96 | 2.48 | 3.425 (4) | 169 |
| N7A—H7A···O2iv | 0.91 | 1.89 | 2.776 (4) | 164 |
| N7B—H7B···O1i | 0.89 | 1.97 | 2.787 (4) | 151 |
| C2A—H2A···O2iv | 0.94 | 2.55 | 3.303 (4) | 138 |
| Symmetry codes: (i) x+3/2, −y−1/2, z−1/2; (ii) −x+3, −y−1, −z+1; (iii) −x+3, −y, −z+1; (iv) −x+3/2, y−1/2, −z+3/2. |
(2) N,4-Dinitroaniline top
Crystal data top
| C6H5N3O4 | Z = 4 |
| Mr = 183.13 | F(000) = 376 |
| Triclinic, P1 | Dx = 1.679 Mg m−3 |
| a = 6.947 (1) Å | Mo Kα radiation, λ = 0.71073 Å |
| b = 7.773 (2) Å | Cell parameters from 28 reflections |
| c = 13.836 (3) Å | θ = 17–24° |
| α = 84.25 (3)° | µ = 0.14 mm−1 |
| β = 79.77 (3)° | T = 85 K |
| γ = 81.27 (3)° | Plates, yellow |
| V = 724.7 (3) Å3 | 0.5 × 0.45 × 0.4 mm |
Data collection top
| KUMA KM4 diffractometer | Rint = 0.018 |
| Radiation source: fine-focus sealed tube | θmax = 28.1°, θmin = 1.5° |
| Graphite monochromator | h = −9→0 |
| ω scans | k = −9→9 |
| 3500 measured reflections | l = −18→18 |
| 3255 independent reflections | 2 standard reflections every 50 reflections |
| 2972 reflections with I > 2σ(I) | intensity decay: −0.5% |
Refinement top
| 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)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.090 | All H-atom parameters refined |
| S = 1.05 | w = 1/[σ2(Fo2) + (0.0488P)2 + 0.318P] where P = (Fo2 + 2Fc2)/3 |
| 3255 reflections | (Δ/σ)max = 0.009 |
| 265 parameters | Δρmax = 0.33 e Å−3 |
| 2 restraints | Δρmin = −0.25 e Å−3 |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > σ(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) top
| x | y | z | Uiso*/Ueq | ||
| C1A | 0.26811 (16) | −0.31451 (15) | 0.35902 (8) | 0.0142 (2) | |
| C2A | 0.24181 (16) | −0.28904 (15) | 0.26047 (8) | 0.0142 (2) | |
| C3A | 0.18037 (16) | −0.12358 (16) | 0.22120 (8) | 0.0144 (2) | |
| C4A | 0.14768 (16) | 0.01378 (15) | 0.28144 (8) | 0.0142 (2) | |
| C5A | 0.17609 (17) | −0.00885 (16) | 0.37901 (8) | 0.0160 (2) | |
| C6A | 0.23772 (17) | −0.17429 (16) | 0.41815 (8) | 0.0164 (2) | |
| N7A | 0.34002 (15) | −0.48561 (13) | 0.39180 (7) | 0.0169 (2) | |
| H7A | 0.383 (2) | −0.5656 (17) | 0.3501 (10) | 0.024* | |
| N8A | 0.27305 (15) | −0.56295 (13) | 0.48208 (7) | 0.0166 (2) | |
| O9A | −0.33747 (13) | 0.58521 (12) | −0.05994 (6) | 0.02013 (19) | |
| O10A | 0.32033 (14) | −0.72185 (11) | 0.49187 (6) | 0.0219 (2) | |
| N11A | 0.07702 (14) | 0.18810 (13) | 0.24168 (7) | 0.0150 (2) | |
| O12A | 0.01170 (12) | 0.20082 (11) | 0.16300 (6) | 0.01833 (19) | |
| O13A | 0.08106 (13) | 0.31379 (11) | 0.28740 (7) | 0.02034 (19) | |
| C1B | −0.25805 (16) | 0.67362 (15) | 0.11991 (8) | 0.0140 (2) | |
| C2B | −0.24633 (16) | 0.66383 (15) | 0.22035 (8) | 0.0140 (2) | |
| C3B | −0.28485 (16) | 0.81371 (16) | 0.27012 (8) | 0.0147 (2) | |
| C4B | −0.33955 (16) | 0.97061 (15) | 0.21920 (8) | 0.0139 (2) | |
| C5B | −0.35205 (17) | 0.98318 (16) | 0.11969 (8) | 0.0160 (2) | |
| C6B | −0.30861 (18) | 0.83405 (16) | 0.06899 (8) | 0.0167 (2) | |
| N7B | −0.20445 (15) | 0.51396 (13) | 0.07679 (7) | 0.0164 (2) | |
| H7B | −0.155 (2) | 0.4194 (16) | 0.1115 (11) | 0.026* | |
| N8B | −0.25262 (14) | 0.47271 (13) | −0.00817 (7) | 0.0155 (2) | |
| O9B | 0.17861 (16) | −0.47260 (13) | 0.54623 (7) | 0.0283 (2) | |
| O10B | −0.20143 (13) | 0.31906 (11) | −0.02665 (6) | 0.02079 (19) | |
| N11B | −0.37953 (14) | 1.12878 (13) | 0.27200 (7) | 0.0153 (2) | |
| O12B | −0.31808 (13) | 1.12592 (12) | 0.34980 (6) | 0.0211 (2) | |
| O13B | −0.47274 (13) | 1.25969 (11) | 0.23512 (6) | 0.0212 (2) | |
| H2A | 0.262 (2) | −0.384 (2) | 0.2209 (12) | 0.021* | |
| H3A | 0.160 (2) | −0.103 (2) | 0.1552 (12) | 0.022* | |
| H5A | 0.157 (2) | 0.088 (2) | 0.4181 (12) | 0.023* | |
| H6A | 0.262 (2) | −0.196 (2) | 0.4836 (13) | 0.028* | |
| H2B | −0.217 (2) | 0.555 (2) | 0.2566 (12) | 0.023* | |
| H3B | −0.279 (3) | 0.809 (2) | 0.3407 (13) | 0.030* | |
| H5B | −0.383 (2) | 1.094 (2) | 0.0857 (13) | 0.027* | |
| H6B | −0.309 (2) | 0.840 (2) | 0.0010 (12) | 0.022* |
Atomic displacement parameters (Å2) top
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1A | 0.0129 (5) | 0.0140 (5) | 0.0154 (5) | −0.0001 (4) | −0.0027 (4) | −0.0020 (4) |
| C2A | 0.0139 (5) | 0.0142 (5) | 0.0148 (5) | −0.0008 (4) | −0.0022 (4) | −0.0053 (4) |
| C3A | 0.0135 (5) | 0.0164 (6) | 0.0137 (5) | −0.0009 (4) | −0.0034 (4) | −0.0028 (4) |
| C4A | 0.0119 (5) | 0.0133 (6) | 0.0172 (5) | −0.0002 (4) | −0.0031 (4) | −0.0020 (4) |
| C5A | 0.0163 (5) | 0.0153 (6) | 0.0164 (5) | 0.0001 (4) | −0.0023 (4) | −0.0065 (4) |
| C6A | 0.0183 (5) | 0.0172 (6) | 0.0144 (5) | −0.0003 (4) | −0.0046 (4) | −0.0043 (4) |
| N7A | 0.0219 (5) | 0.0136 (5) | 0.0133 (4) | 0.0030 (4) | −0.0012 (4) | −0.0034 (4) |
| N8A | 0.0201 (5) | 0.0160 (5) | 0.0145 (4) | −0.0008 (4) | −0.0059 (4) | −0.0016 (4) |
| O9A | 0.0260 (4) | 0.0185 (4) | 0.0171 (4) | −0.0026 (4) | −0.0080 (3) | 0.0001 (3) |
| O10A | 0.0318 (5) | 0.0142 (4) | 0.0194 (4) | 0.0008 (4) | −0.0081 (4) | 0.0007 (3) |
| N11A | 0.0121 (4) | 0.0142 (5) | 0.0179 (4) | 0.0001 (4) | −0.0017 (3) | −0.0026 (4) |
| O12A | 0.0199 (4) | 0.0171 (4) | 0.0179 (4) | 0.0008 (3) | −0.0064 (3) | −0.0006 (3) |
| O13A | 0.0237 (4) | 0.0132 (4) | 0.0245 (4) | 0.0016 (3) | −0.0056 (3) | −0.0069 (3) |
| C1B | 0.0127 (5) | 0.0148 (6) | 0.0143 (5) | −0.0007 (4) | −0.0016 (4) | −0.0037 (4) |
| C2B | 0.0136 (5) | 0.0142 (6) | 0.0137 (5) | 0.0009 (4) | −0.0033 (4) | −0.0006 (4) |
| C3B | 0.0135 (5) | 0.0179 (6) | 0.0126 (5) | −0.0003 (4) | −0.0033 (4) | −0.0016 (4) |
| C4B | 0.0121 (5) | 0.0142 (6) | 0.0155 (5) | −0.0003 (4) | −0.0018 (4) | −0.0043 (4) |
| C5B | 0.0182 (5) | 0.0146 (6) | 0.0148 (5) | −0.0006 (4) | −0.0037 (4) | 0.0002 (4) |
| C6B | 0.0206 (5) | 0.0164 (6) | 0.0127 (5) | −0.0008 (4) | −0.0031 (4) | −0.0010 (4) |
| N7B | 0.0216 (5) | 0.0133 (5) | 0.0143 (4) | 0.0023 (4) | −0.0063 (4) | −0.0029 (4) |
| N8B | 0.0160 (4) | 0.0172 (5) | 0.0135 (4) | −0.0034 (4) | −0.0008 (3) | −0.0041 (4) |
| O9B | 0.0437 (6) | 0.0218 (5) | 0.0148 (4) | 0.0018 (4) | 0.0035 (4) | −0.0042 (4) |
| O10B | 0.0256 (4) | 0.0160 (4) | 0.0210 (4) | −0.0006 (3) | −0.0032 (3) | −0.0071 (3) |
| N11B | 0.0136 (4) | 0.0156 (5) | 0.0166 (4) | −0.0012 (4) | −0.0013 (3) | −0.0041 (4) |
| O12B | 0.0229 (4) | 0.0235 (5) | 0.0185 (4) | −0.0001 (4) | −0.0071 (3) | −0.0076 (3) |
| O13B | 0.0257 (5) | 0.0141 (4) | 0.0225 (4) | 0.0044 (3) | −0.0057 (3) | −0.0025 (3) |
Geometric parameters (Å, º) top
| C1A—C6A | 1.396 (2) | N11A—O12A | 1.241 (1) |
| C1A—C2A | 1.398 (2) | C1B—C6B | 1.398 (2) |
| C1A—N7A | 1.408 (2) | C1B—C2B | 1.400 (2) |
| C2A—C3A | 1.381 (2) | C1B—N7B | 1.401 (2) |
| C3A—C4A | 1.387 (2) | C2B—C3B | 1.380 (2) |
| C4A—C5A | 1.389 (2) | C3B—C4B | 1.382 (2) |
| C4A—N11A | 1.457 (2) | C4B—C5B | 1.388 (2) |
| C5A—C6A | 1.381 (2) | C4B—N11B | 1.458 (2) |
| N7A—N8A | 1.366 (1) | C5B—C6B | 1.381 (2) |
| N8A—O9B | 1.221 (1) | N7B—N8B | 1.358 (1) |
| N8A—O10A | 1.229 (1) | N8B—O10B | 1.232 (1) |
| O9A—N8B | 1.222 (1) | N11B—O12B | 1.224 (1) |
| N11A—O13A | 1.222 (1) | N11B—O13B | 1.236 (1) |
| C6A—C1A—C2A | 121.0 (1) | C6B—C1B—C2B | 120.8 (1) |
| C6A—C1A—N7A | 122.7 (1) | C6B—C1B—N7B | 124.8 (1) |
| C2A—C1A—N7A | 116.1 (1) | C2B—C1B—N7B | 114.4 (1) |
| C3A—C2A—C1A | 119.8 (1) | C3B—C2B—C1B | 120.0 (1) |
| C2A—C3A—C4A | 118.4 (1) | C2B—C3B—C4B | 118.5 (1) |
| C3A—C4A—C5A | 122.5 (1) | C3B—C4B—C5B | 122.5 (1) |
| C3A—C4A—N11A | 118.9 (1) | C3B—C4B—N11B | 118.3 (1) |
| C5A—C4A—N11A | 118.6 (1) | C5B—C4B—N11B | 119.2 (1) |
| C6A—C5A—C4A | 119.0 (1) | C6B—C5B—C4B | 119.2 (1) |
| C5A—C6A—C1A | 119.2 (1) | C5B—C6B—C1B | 119.1 (1) |
| N8A—N7A—C1A | 123.5 (1) | N8B—N7B—C1B | 126.9 (1) |
| O9B—N8A—O10A | 125.4 (1) | O9A—N8B—O10B | 125.4 (1) |
| O9B—N8A—N7A | 119.4 (1) | O9A—N8B—N7B | 120.0 (1) |
| O10A—N8A—N7A | 115.2 (1) | O10B—N8B—N7B | 114.6 (1) |
| O13A—N11A—O12A | 123.1 (1) | O12B—N11B—O13B | 123.4 (1) |
| O13A—N11A—C4A | 119.2 (1) | O12B—N11B—C4B | 118.6 (1) |
| O12A—N11A—C4A | 117.7 (1) | O13B—N11B—C4B | 118.0 (1) |
| C6A—C1A—C2A—C3A | −1.54 (16) | C6B—C1B—C2B—C3B | −0.02 (17) |
| N7A—C1A—C2A—C3A | −177.06 (10) | N7B—C1B—C2B—C3B | 176.47 (10) |
| C1A—C2A—C3A—C4A | 0.44 (16) | C1B—C2B—C3B—C4B | 1.66 (16) |
| C2A—C3A—C4A—C5A | 0.59 (17) | C2B—C3B—C4B—C5B | −1.70 (17) |
| C2A—C3A—C4A—N11A | −178.15 (9) | C2B—C3B—C4B—N11B | −179.81 (9) |
| C3A—C4A—C5A—C6A | −0.52 (17) | C3B—C4B—C5B—C6B | 0.04 (17) |
| N11A—C4A—C5A—C6A | 178.22 (10) | N11B—C4B—C5B—C6B | 178.13 (10) |
| C4A—C5A—C6A—C1A | −0.58 (17) | C4B—C5B—C6B—C1B | 1.62 (17) |
| C2A—C1A—C6A—C5A | 1.60 (17) | C2B—C1B—C6B—C5B | −1.64 (17) |
| N7A—C1A—C6A—C5A | 176.82 (10) | N7B—C1B—C6B—C5B | −177.75 (10) |
| C6A—C1A—N7A—N8A | 44.8 (2) | C6B—C1B—N7B—N8B | −23.8 (2) |
| C2A—C1A—N7A—N8A | −139.7 (1) | C2B—C1B—N7B—N8B | 159.9 (1) |
| C1A—N7A—N8A—O9B | −16.2 (2) | C1B—N7B—N8B—O9A | 6.7 (2) |
| C1A—N7A—N8A—O10A | 165.8 (1) | C1B—N7B—N8B—O10B | −174.3 (1) |
| C3A—C4A—N11A—O13A | −167.2 (1) | C3B—C4B—N11B—O12B | 17.8 (2) |
| C5A—C4A—N11A—O13A | 14.1 (2) | C5B—C4B—N11B—O12B | −160.4 (1) |
| C3A—C4A—N11A—O12A | 14.2 (2) | C3B—C4B—N11B—O13B | −162.8 (1) |
| C5A—C4A—N11A—O12A | −164.6 (1) | C5B—C4B—N11B—O13B | 19.0 (2) |
Hydrogen-bond geometry (Å, º) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| C3A—H3A···O10Bi | 0.94 (2) | 2.52 (2) | 3.192 (2) | 128 (1) |
| C3B—H3B···O10Aii | 0.98 (2) | 2.33 (2) | 3.272 (2) | 161 (1) |
| C5A—H5A···O10Aiii | 0.95 (2) | 2.40 (2) | 3.217 (2) | 145 (1) |
| C5B—H5B···O10Biii | 0.95 (2) | 2.55 (2) | 3.321 (2) | 138 (1) |
| C6A—H6A···O12Biv | 0.94 (2) | 2.53 (2) | 3.421 (2) | 157 (1) |
| N7A—H7A···O13Bv | 0.87 (1) | 2.20 (1) | 3.064 (2) | 171 (2) |
| N7B—H7B···O12A | 0.90 (1) | 2.05 (1) | 2.924 (2) | 167 (2) |
| Symmetry codes: (i) −x, −y, −z; (ii) −x, −y, −z+1; (iii) x, y+1, z; (iv) −x, −y+1, −z+1; (v) x+1, y−2, z. |
