The synthesis, crystal structure studies and solvatochromic behavior of 2-{(2E,4E)-5-[4-(dimethylamino)phenyl]penta-2,4-dien-1-ylidene}malononitrile, C16H15N3 (DCV[3]), and 2-{(2E,4E,6E)-7-[4-(dimethylamino)phenyl]hepta-2,4,6-trien-1-ylidene}malononitrile, C18H17N3 (DCV[4]), are reported and discussed in comparison with their homologs having a shorter length of the π-conjugated bridge. The compounds of this series have potential use as nonlinear materials with second-order effects due to their donor–acceptor structures. However, DCV[3] and DCV[4] crystallized in the centrosymmetric space group P21/c which excludes their application as nonlinear optical materials in the crystalline state. They both crystallize with two independent molecules having the same molecular conformation in the asymmetric unit. The series DCV[1]–DCV[4] demonstrated reversed solvatochromic behavior in toluene, chloroform, and acetonitrile.
Supporting information
CCDC references: 1942063; 1942062
Data collection: CrysAlis PRO (Agilent, 2012) for DCV3; APEX3 (Bruker, 2016) for DCV4. For both structures, cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT2017 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2017 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: Mercury (Macrae et al., 2008).
2-{5-[4-(Dimethylamino)phenyl]penta-2,4-dien-1-ylidene}malononitrile (DCV3)
top
Crystal data top
C16H15N3 | F(000) = 1056 |
Mr = 249.31 | Dx = 1.179 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54184 Å |
a = 16.9417 (3) Å | Cell parameters from 11249 reflections |
b = 7.45114 (13) Å | θ = 3.7–73.5° |
c = 23.0287 (4) Å | µ = 0.56 mm−1 |
β = 104.9826 (18)° | T = 100 K |
V = 2808.20 (9) Å3 | Plate, red |
Z = 8 | 0.35 × 0.14 × 0.02 mm |
Data collection top
Agilent SuperNova Dual Source diffractometer with an Atlas detector | 4914 reflections with I > 2σ(I) |
Radiation source: sealed X-ray tube | Rint = 0.028 |
ω scans | θmax = 73.7°, θmin = 4.0° |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) | h = −20→21 |
Tmin = 0.584, Tmax = 1.000 | k = −9→8 |
27221 measured reflections | l = −28→28 |
5596 independent reflections | |
Refinement top
Refinement on F2 | Primary atom site location: difference Fourier map |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.108 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0561P)2 + 0.6844P] where P = (Fo2 + 2Fc2)/3 |
5596 reflections | (Δ/σ)max = 0.001 |
347 parameters | Δρmax = 0.25 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
Special details top
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. |
Refinement. The single-crystal X-ray diffraction data for DCV[3] and DCV[4] were collected
on a Bruker SMART APEX II CCD diffractometer (l(MoKa)-radiation,
graphite monochromator, w and f scan mode) and corrected for
absorption using the SADABS program (Bruker, 2016). For details, see
Table 4. The structures were solved by the intrinsic phasing
modification of direct methods (Sheldrick, 2015a) and refined by a full-matrix
least square technique on F2 in anisotropic approximation for
non-hydrogen atoms. The hydrogen atoms were placed in calculated positions and
refined within the riding model with fixed isotropic displacement parameters
[Uiso(H) = 1.5Ueq(C) for the methyl groups and 1.2Ueq(C) for the other
groups]. All calculations were carried out using the SHELXTL program suite
(Sheldrick, 2015b). The supplementary crystallographic data can be obtained
free of charge from the Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N2A | 0.06248 (7) | 0.8003 (2) | 0.48608 (6) | 0.0575 (4) | |
N3A | 0.28508 (6) | 0.54591 (15) | 0.46014 (5) | 0.0345 (2) | |
N4A | 0.82798 (5) | 0.68629 (13) | 0.88289 (4) | 0.0245 (2) | |
C1A | 0.21600 (6) | 0.73520 (15) | 0.52699 (5) | 0.0244 (2) | |
C2A | 0.13074 (7) | 0.77210 (18) | 0.50416 (6) | 0.0349 (3) | |
C3A | 0.25380 (6) | 0.63146 (15) | 0.48927 (5) | 0.0257 (2) | |
C4A | 0.75054 (6) | 0.72307 (14) | 0.84932 (5) | 0.0211 (2) | |
C5A | 0.69207 (6) | 0.79987 (14) | 0.87596 (5) | 0.0216 (2) | |
H5A | 0.706959 | 0.828252 | 0.917595 | 0.026* | |
C6A | 0.61369 (6) | 0.83398 (14) | 0.84213 (5) | 0.0219 (2) | |
H6A | 0.575881 | 0.886870 | 0.861154 | 0.026* | |
C7A | 0.58766 (6) | 0.79341 (14) | 0.78057 (5) | 0.0212 (2) | |
C8A | 0.64632 (6) | 0.71854 (14) | 0.75399 (5) | 0.0228 (2) | |
H8A | 0.631024 | 0.690352 | 0.712348 | 0.027* | |
C9A | 0.72528 (6) | 0.68516 (14) | 0.78684 (5) | 0.0233 (2) | |
H9A | 0.763399 | 0.636009 | 0.767350 | 0.028* | |
C10A | 0.85402 (7) | 0.74330 (18) | 0.94531 (5) | 0.0297 (3) | |
H10A | 0.852240 | 0.874562 | 0.947330 | 0.044* | |
H10B | 0.909967 | 0.701822 | 0.963037 | 0.044* | |
H10C | 0.817418 | 0.691944 | 0.967642 | 0.044* | |
C11A | 0.89075 (6) | 0.62695 (17) | 0.85434 (5) | 0.0296 (3) | |
H11A | 0.871072 | 0.521883 | 0.829159 | 0.044* | |
H11B | 0.940306 | 0.595055 | 0.885314 | 0.044* | |
H11C | 0.903123 | 0.723971 | 0.829343 | 0.044* | |
C12A | 0.25913 (6) | 0.79560 (14) | 0.58191 (5) | 0.0236 (2) | |
H12A | 0.230592 | 0.863249 | 0.604962 | 0.028* | |
C13A | 0.34346 (6) | 0.76451 (15) | 0.60694 (5) | 0.0227 (2) | |
H13A | 0.373680 | 0.704052 | 0.583396 | 0.027* | |
C14A | 0.38286 (6) | 0.81798 (14) | 0.66348 (5) | 0.0229 (2) | |
H14A | 0.352602 | 0.882770 | 0.686008 | 0.027* | |
C15A | 0.46695 (6) | 0.78243 (14) | 0.69089 (5) | 0.0231 (2) | |
H15A | 0.498461 | 0.724196 | 0.667806 | 0.028* | |
C16A | 0.50382 (6) | 0.82815 (14) | 0.74843 (5) | 0.0224 (2) | |
H16A | 0.471131 | 0.889509 | 0.769931 | 0.027* | |
N2B | 0.72618 (6) | 0.93541 (15) | 0.54055 (4) | 0.0327 (2) | |
N3B | 0.52014 (6) | 0.62185 (14) | 0.57039 (4) | 0.0311 (2) | |
N4B | −0.05174 (6) | 0.75728 (15) | 0.15912 (4) | 0.0318 (2) | |
C1B | 0.57868 (6) | 0.81905 (15) | 0.49907 (5) | 0.0233 (2) | |
C2B | 0.66068 (6) | 0.88348 (15) | 0.52181 (5) | 0.0257 (2) | |
C3B | 0.54730 (6) | 0.70875 (15) | 0.53908 (5) | 0.0247 (2) | |
C4B | 0.02901 (6) | 0.77346 (15) | 0.18858 (5) | 0.0239 (2) | |
C5B | 0.08427 (7) | 0.86370 (16) | 0.16212 (5) | 0.0269 (2) | |
H5B | 0.065020 | 0.914725 | 0.123211 | 0.032* | |
C6B | 0.16570 (7) | 0.87872 (15) | 0.19195 (5) | 0.0257 (2) | |
H6B | 0.201216 | 0.939349 | 0.172628 | 0.031* | |
C7B | 0.19836 (6) | 0.80834 (14) | 0.24960 (5) | 0.0225 (2) | |
C8B | 0.14345 (7) | 0.71632 (15) | 0.27566 (5) | 0.0248 (2) | |
H8B | 0.163285 | 0.664412 | 0.314380 | 0.030* | |
C9B | 0.06173 (7) | 0.69944 (15) | 0.24660 (5) | 0.0256 (2) | |
H9B | 0.026616 | 0.636962 | 0.265806 | 0.031* | |
C10B | −0.08223 (8) | 0.8355 (2) | 0.09998 (6) | 0.0443 (3) | |
H10D | −0.073492 | 0.965625 | 0.102372 | 0.067* | |
H10E | −0.140778 | 0.810377 | 0.085156 | 0.067* | |
H10F | −0.053054 | 0.783531 | 0.072392 | 0.067* | |
C11B | −0.10912 (8) | 0.6717 (2) | 0.18611 (6) | 0.0450 (4) | |
H11D | −0.088805 | 0.552333 | 0.200560 | 0.067* | |
H11E | −0.161843 | 0.659886 | 0.156271 | 0.067* | |
H11F | −0.115976 | 0.744148 | 0.219980 | 0.067* | |
C12B | 0.53196 (6) | 0.86280 (15) | 0.44324 (5) | 0.0236 (2) | |
H12B | 0.556126 | 0.935891 | 0.418722 | 0.028* | |
C13B | 0.44978 (6) | 0.80712 (15) | 0.41902 (5) | 0.0239 (2) | |
H13B | 0.423801 | 0.738391 | 0.443515 | 0.029* | |
C14B | 0.40695 (6) | 0.84864 (15) | 0.36204 (5) | 0.0246 (2) | |
H14B | 0.433744 | 0.916488 | 0.337859 | 0.030* | |
C15B | 0.32412 (6) | 0.79638 (15) | 0.33637 (5) | 0.0249 (2) | |
H15B | 0.296749 | 0.727550 | 0.359934 | 0.030* | |
C16B | 0.28335 (6) | 0.84161 (15) | 0.27966 (5) | 0.0243 (2) | |
H16B | 0.314240 | 0.902680 | 0.256732 | 0.029* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N2A | 0.0236 (6) | 0.0747 (10) | 0.0646 (8) | 0.0071 (6) | −0.0060 (5) | −0.0144 (7) |
N3A | 0.0345 (5) | 0.0348 (6) | 0.0351 (5) | −0.0030 (4) | 0.0104 (4) | −0.0033 (5) |
N4A | 0.0171 (4) | 0.0298 (5) | 0.0251 (4) | 0.0004 (4) | 0.0025 (3) | −0.0020 (4) |
C1A | 0.0171 (5) | 0.0246 (6) | 0.0294 (5) | −0.0005 (4) | 0.0026 (4) | 0.0021 (4) |
C2A | 0.0233 (6) | 0.0393 (7) | 0.0380 (6) | 0.0004 (5) | 0.0004 (5) | −0.0057 (5) |
C3A | 0.0217 (5) | 0.0260 (6) | 0.0270 (5) | −0.0042 (4) | 0.0017 (4) | 0.0020 (4) |
C4A | 0.0183 (5) | 0.0186 (5) | 0.0253 (5) | −0.0026 (4) | 0.0039 (4) | 0.0008 (4) |
C5A | 0.0208 (5) | 0.0212 (5) | 0.0218 (5) | −0.0030 (4) | 0.0038 (4) | −0.0011 (4) |
C6A | 0.0204 (5) | 0.0197 (5) | 0.0259 (5) | −0.0013 (4) | 0.0064 (4) | −0.0006 (4) |
C7A | 0.0201 (5) | 0.0180 (5) | 0.0242 (5) | −0.0023 (4) | 0.0033 (4) | 0.0010 (4) |
C8A | 0.0227 (5) | 0.0225 (5) | 0.0221 (5) | −0.0024 (4) | 0.0037 (4) | −0.0009 (4) |
C9A | 0.0212 (5) | 0.0224 (5) | 0.0264 (5) | −0.0015 (4) | 0.0064 (4) | −0.0018 (4) |
C10A | 0.0209 (5) | 0.0379 (7) | 0.0273 (5) | −0.0001 (5) | 0.0010 (4) | −0.0042 (5) |
C11A | 0.0201 (5) | 0.0344 (6) | 0.0328 (6) | 0.0042 (5) | 0.0043 (4) | −0.0044 (5) |
C12A | 0.0208 (5) | 0.0211 (5) | 0.0285 (5) | 0.0004 (4) | 0.0057 (4) | 0.0021 (4) |
C13A | 0.0196 (5) | 0.0210 (5) | 0.0266 (5) | −0.0001 (4) | 0.0044 (4) | 0.0012 (4) |
C14A | 0.0208 (5) | 0.0199 (5) | 0.0271 (5) | −0.0002 (4) | 0.0048 (4) | 0.0017 (4) |
C15A | 0.0205 (5) | 0.0218 (5) | 0.0260 (5) | 0.0000 (4) | 0.0040 (4) | 0.0013 (4) |
C16A | 0.0210 (5) | 0.0194 (5) | 0.0265 (5) | −0.0007 (4) | 0.0057 (4) | 0.0016 (4) |
N2B | 0.0248 (5) | 0.0355 (6) | 0.0355 (5) | −0.0016 (4) | 0.0040 (4) | 0.0029 (4) |
N3B | 0.0314 (5) | 0.0312 (5) | 0.0329 (5) | 0.0020 (4) | 0.0121 (4) | 0.0001 (4) |
N4B | 0.0233 (5) | 0.0413 (6) | 0.0277 (5) | −0.0034 (4) | 0.0008 (4) | 0.0043 (4) |
C1B | 0.0197 (5) | 0.0226 (5) | 0.0280 (5) | 0.0005 (4) | 0.0070 (4) | −0.0026 (4) |
C2B | 0.0245 (5) | 0.0257 (6) | 0.0272 (5) | 0.0026 (4) | 0.0074 (4) | 0.0010 (4) |
C3B | 0.0213 (5) | 0.0257 (6) | 0.0265 (5) | 0.0023 (4) | 0.0048 (4) | −0.0039 (4) |
C4B | 0.0230 (5) | 0.0229 (5) | 0.0244 (5) | 0.0004 (4) | 0.0036 (4) | −0.0017 (4) |
C5B | 0.0291 (6) | 0.0262 (6) | 0.0235 (5) | −0.0010 (4) | 0.0036 (4) | 0.0033 (4) |
C6B | 0.0275 (5) | 0.0238 (6) | 0.0264 (5) | −0.0034 (4) | 0.0082 (4) | 0.0011 (4) |
C7B | 0.0232 (5) | 0.0200 (5) | 0.0241 (5) | 0.0005 (4) | 0.0058 (4) | −0.0012 (4) |
C8B | 0.0241 (5) | 0.0266 (6) | 0.0230 (5) | 0.0002 (4) | 0.0047 (4) | 0.0026 (4) |
C9B | 0.0244 (5) | 0.0281 (6) | 0.0247 (5) | −0.0024 (4) | 0.0068 (4) | 0.0019 (4) |
C10B | 0.0299 (6) | 0.0613 (9) | 0.0343 (6) | −0.0056 (6) | −0.0052 (5) | 0.0126 (6) |
C11B | 0.0246 (6) | 0.0655 (10) | 0.0409 (7) | −0.0092 (6) | 0.0016 (5) | 0.0135 (7) |
C12B | 0.0228 (5) | 0.0214 (5) | 0.0278 (5) | 0.0016 (4) | 0.0087 (4) | −0.0022 (4) |
C13B | 0.0218 (5) | 0.0222 (5) | 0.0283 (5) | 0.0007 (4) | 0.0077 (4) | −0.0018 (4) |
C14B | 0.0230 (5) | 0.0228 (5) | 0.0287 (5) | 0.0002 (4) | 0.0080 (4) | −0.0015 (4) |
C15B | 0.0225 (5) | 0.0242 (6) | 0.0281 (5) | −0.0003 (4) | 0.0069 (4) | −0.0002 (4) |
C16B | 0.0233 (5) | 0.0218 (5) | 0.0286 (5) | −0.0009 (4) | 0.0081 (4) | −0.0013 (4) |
Geometric parameters (Å, º) top
N2A—C2A | 1.1429 (16) | N2B—C2B | 1.1488 (14) |
N3A—C3A | 1.1493 (15) | N3B—C3B | 1.1499 (15) |
N4A—C4A | 1.3673 (13) | N4B—C4B | 1.3663 (14) |
N4A—C10A | 1.4538 (14) | N4B—C11B | 1.4321 (16) |
N4A—C11A | 1.4560 (13) | N4B—C10B | 1.4483 (15) |
C1A—C12A | 1.3631 (15) | C1B—C12B | 1.3637 (15) |
C1A—C2A | 1.4304 (15) | C1B—C2B | 1.4348 (14) |
C1A—C3A | 1.4317 (16) | C1B—C3B | 1.4354 (15) |
C4A—C5A | 1.4140 (14) | C4B—C5B | 1.4124 (15) |
C4A—C9A | 1.4195 (14) | C4B—C9B | 1.4189 (15) |
C5A—C6A | 1.3785 (14) | C5B—C6B | 1.3775 (15) |
C5A—H5A | 0.9500 | C5B—H5B | 0.9500 |
C6A—C7A | 1.4044 (14) | C6B—C7B | 1.4014 (15) |
C6A—H6A | 0.9500 | C6B—H6B | 0.9500 |
C7A—C8A | 1.4099 (15) | C7B—C8B | 1.4087 (15) |
C7A—C16A | 1.4453 (14) | C7B—C16B | 1.4487 (14) |
C8A—C9A | 1.3786 (14) | C8B—C9B | 1.3789 (15) |
C8A—H8A | 0.9500 | C8B—H8B | 0.9500 |
C9A—H9A | 0.9500 | C9B—H9B | 0.9500 |
C10A—H10A | 0.9800 | C10B—H10D | 0.9800 |
C10A—H10B | 0.9800 | C10B—H10E | 0.9800 |
C10A—H10C | 0.9800 | C10B—H10F | 0.9800 |
C11A—H11A | 0.9800 | C11B—H11D | 0.9800 |
C11A—H11B | 0.9800 | C11B—H11E | 0.9800 |
C11A—H11C | 0.9800 | C11B—H11F | 0.9800 |
C12A—C13A | 1.4146 (14) | C12B—C13B | 1.4213 (14) |
C12A—H12A | 0.9500 | C12B—H12B | 0.9500 |
C13A—C14A | 1.3603 (15) | C13B—C14B | 1.3609 (15) |
C13A—H13A | 0.9500 | C13B—H13B | 0.9500 |
C14A—C15A | 1.4260 (14) | C14B—C15B | 1.4287 (14) |
C14A—H14A | 0.9500 | C14B—H14B | 0.9500 |
C15A—C16A | 1.3543 (15) | C15B—C16B | 1.3528 (15) |
C15A—H15A | 0.9500 | C15B—H15B | 0.9500 |
C16A—H16A | 0.9500 | C16B—H16B | 0.9500 |
| | | |
C4A—N4A—C10A | 120.13 (9) | C4B—N4B—C11B | 121.91 (10) |
C4A—N4A—C11A | 120.78 (9) | C4B—N4B—C10B | 119.96 (10) |
C10A—N4A—C11A | 117.70 (9) | C11B—N4B—C10B | 118.06 (10) |
C12A—C1A—C2A | 121.72 (10) | C12B—C1B—C2B | 122.37 (10) |
C12A—C1A—C3A | 121.64 (10) | C12B—C1B—C3B | 121.41 (10) |
C2A—C1A—C3A | 116.64 (10) | C2B—C1B—C3B | 116.20 (9) |
N2A—C2A—C1A | 179.47 (17) | N2B—C2B—C1B | 179.34 (12) |
N3A—C3A—C1A | 178.40 (12) | N3B—C3B—C1B | 178.21 (12) |
N4A—C4A—C5A | 120.88 (9) | N4B—C4B—C5B | 121.20 (10) |
N4A—C4A—C9A | 121.80 (9) | N4B—C4B—C9B | 122.05 (10) |
C5A—C4A—C9A | 117.31 (9) | C5B—C4B—C9B | 116.75 (10) |
C6A—C5A—C4A | 120.66 (9) | C6B—C5B—C4B | 120.90 (10) |
C6A—C5A—H5A | 119.7 | C6B—C5B—H5B | 119.6 |
C4A—C5A—H5A | 119.7 | C4B—C5B—H5B | 119.6 |
C5A—C6A—C7A | 122.41 (9) | C5B—C6B—C7B | 122.77 (10) |
C5A—C6A—H6A | 118.8 | C5B—C6B—H6B | 118.6 |
C7A—C6A—H6A | 118.8 | C7B—C6B—H6B | 118.6 |
C6A—C7A—C8A | 116.79 (9) | C6B—C7B—C8B | 116.32 (10) |
C6A—C7A—C16A | 119.26 (9) | C6B—C7B—C16B | 119.26 (9) |
C8A—C7A—C16A | 123.94 (9) | C8B—C7B—C16B | 124.33 (10) |
C9A—C8A—C7A | 121.74 (9) | C9B—C8B—C7B | 121.89 (10) |
C9A—C8A—H8A | 119.1 | C9B—C8B—H8B | 119.1 |
C7A—C8A—H8A | 119.1 | C7B—C8B—H8B | 119.1 |
C8A—C9A—C4A | 121.05 (9) | C8B—C9B—C4B | 121.36 (10) |
C8A—C9A—H9A | 119.5 | C8B—C9B—H9B | 119.3 |
C4A—C9A—H9A | 119.5 | C4B—C9B—H9B | 119.3 |
N4A—C10A—H10A | 109.5 | N4B—C10B—H10D | 109.5 |
N4A—C10A—H10B | 109.5 | N4B—C10B—H10E | 109.5 |
H10A—C10A—H10B | 109.5 | H10D—C10B—H10E | 109.5 |
N4A—C10A—H10C | 109.5 | N4B—C10B—H10F | 109.5 |
H10A—C10A—H10C | 109.5 | H10D—C10B—H10F | 109.5 |
H10B—C10A—H10C | 109.5 | H10E—C10B—H10F | 109.5 |
N4A—C11A—H11A | 109.5 | N4B—C11B—H11D | 109.5 |
N4A—C11A—H11B | 109.5 | N4B—C11B—H11E | 109.5 |
H11A—C11A—H11B | 109.5 | H11D—C11B—H11E | 109.5 |
N4A—C11A—H11C | 109.5 | N4B—C11B—H11F | 109.5 |
H11A—C11A—H11C | 109.5 | H11D—C11B—H11F | 109.5 |
H11B—C11A—H11C | 109.5 | H11E—C11B—H11F | 109.5 |
C1A—C12A—C13A | 124.52 (10) | C1B—C12B—C13B | 124.82 (10) |
C1A—C12A—H12A | 117.7 | C1B—C12B—H12B | 117.6 |
C13A—C12A—H12A | 117.7 | C13B—C12B—H12B | 117.6 |
C14A—C13A—C12A | 122.42 (10) | C14B—C13B—C12B | 122.42 (10) |
C14A—C13A—H13A | 118.8 | C14B—C13B—H13B | 118.8 |
C12A—C13A—H13A | 118.8 | C12B—C13B—H13B | 118.8 |
C13A—C14A—C15A | 123.79 (10) | C13B—C14B—C15B | 123.98 (10) |
C13A—C14A—H14A | 118.1 | C13B—C14B—H14B | 118.0 |
C15A—C14A—H14A | 118.1 | C15B—C14B—H14B | 118.0 |
C16A—C15A—C14A | 122.79 (10) | C16B—C15B—C14B | 122.22 (10) |
C16A—C15A—H15A | 118.6 | C16B—C15B—H15B | 118.9 |
C14A—C15A—H15A | 118.6 | C14B—C15B—H15B | 118.9 |
C15A—C16A—C7A | 126.83 (10) | C15B—C16B—C7B | 127.95 (10) |
C15A—C16A—H16A | 116.6 | C15B—C16B—H16B | 116.0 |
C7A—C16A—H16A | 116.6 | C7B—C16B—H16B | 116.0 |
| | | |
C10A—N4A—C4A—C5A | −6.58 (16) | C11B—N4B—C4B—C5B | −177.81 (12) |
C11A—N4A—C4A—C5A | −172.79 (10) | C10B—N4B—C4B—C5B | −0.83 (18) |
C10A—N4A—C4A—C9A | 173.84 (10) | C11B—N4B—C4B—C9B | 2.91 (18) |
C11A—N4A—C4A—C9A | 7.64 (16) | C10B—N4B—C4B—C9B | 179.89 (12) |
N4A—C4A—C5A—C6A | −178.93 (10) | N4B—C4B—C5B—C6B | −179.66 (11) |
C9A—C4A—C5A—C6A | 0.67 (15) | C9B—C4B—C5B—C6B | −0.35 (16) |
C4A—C5A—C6A—C7A | 0.68 (16) | C4B—C5B—C6B—C7B | −0.58 (18) |
C5A—C6A—C7A—C8A | −1.29 (16) | C5B—C6B—C7B—C8B | 1.36 (16) |
C5A—C6A—C7A—C16A | 178.18 (10) | C5B—C6B—C7B—C16B | −175.39 (10) |
C6A—C7A—C8A—C9A | 0.54 (16) | C6B—C7B—C8B—C9B | −1.25 (16) |
C16A—C7A—C8A—C9A | −178.89 (10) | C16B—C7B—C8B—C9B | 175.31 (10) |
C7A—C8A—C9A—C4A | 0.79 (17) | C7B—C8B—C9B—C4B | 0.38 (17) |
N4A—C4A—C9A—C8A | 178.20 (10) | N4B—C4B—C9B—C8B | 179.75 (11) |
C5A—C4A—C9A—C8A | −1.39 (16) | C5B—C4B—C9B—C8B | 0.44 (16) |
C2A—C1A—C12A—C13A | −179.71 (11) | C2B—C1B—C12B—C13B | −178.17 (10) |
C3A—C1A—C12A—C13A | 0.33 (17) | C3B—C1B—C12B—C13B | 0.21 (17) |
C1A—C12A—C13A—C14A | −175.85 (11) | C1B—C12B—C13B—C14B | −177.27 (10) |
C12A—C13A—C14A—C15A | 177.39 (10) | C12B—C13B—C14B—C15B | −179.43 (10) |
C13A—C14A—C15A—C16A | −176.21 (10) | C13B—C14B—C15B—C16B | 179.43 (11) |
C14A—C15A—C16A—C7A | 178.11 (10) | C14B—C15B—C16B—C7B | −175.48 (10) |
C6A—C7A—C16A—C15A | −173.54 (10) | C6B—C7B—C16B—C15B | 174.95 (11) |
C8A—C7A—C16A—C15A | 5.88 (18) | C8B—C7B—C16B—C15B | −1.52 (19) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C10A—H10B···N2Ai | 0.98 | 2.50 | 3.4270 (16) | 158 |
Symmetry code: (i) x+1, −y+3/2, z+1/2. |
2-{(2
E,4
E,6
E)-7-[4-(Dimethylamino)phenyl]hepta-2,4,6-trien-1-ylidene}malononitrile (DCV4)
top
Crystal data top
C18H17N3 | F(000) = 1168 |
Mr = 275.34 | Dx = 1.205 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 13.6175 (16) Å | Cell parameters from 9945 reflections |
b = 11.6514 (14) Å | θ = 4.2–30.6° |
c = 19.723 (2) Å | µ = 0.07 mm−1 |
β = 104.121 (2)° | T = 100 K |
V = 3034.8 (6) Å3 | Block, black |
Z = 8 | 0.30 × 0.20 × 0.10 mm |
Data collection top
Bruker APEXII CCD diffractometer | 7413 reflections with I > 2σ(I) |
Radiation source: sealed X-ray tube | Rint = 0.028 |
φ and ω scans | θmax = 30.6°, θmin = 4.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | h = −19→18 |
Tmin = 0.662, Tmax = 0.746 | k = −16→16 |
35544 measured reflections | l = −28→28 |
9304 independent reflections | |
Refinement top
Refinement on F2 | Primary atom site location: difference Fourier map |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.132 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0736P)2 + 0.4714P] where P = (Fo2 + 2Fc2)/3 |
9304 reflections | (Δ/σ)max < 0.001 |
383 parameters | Δρmax = 0.44 e Å−3 |
0 restraints | Δρmin = −0.19 e Å−3 |
Special details top
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. |
Refinement. The single-crystal X-ray diffraction data for DCV[3] and DCV[4] were collected
on a Bruker SMART APEX II CCD diffractometer (l(MoKa)-radiation,
graphite monochromator, w and f scan mode) and corrected for
absorption using the SADABS program (Bruker, 2016). For details, see
Table 4. The structures were solved by the intrinsic phasing
modification of direct methods (Sheldrick, 2015a) and refined by a full-matrix
least square technique on F2 in anisotropic approximation for
non-hydrogen atoms. The hydrogen atoms were placed in calculated positions and
refined within the riding model with fixed isotropic displacement parameters
[Uiso(H) = 1.5Ueq(C) for the methyl groups and 1.2Ueq(C) for the other
groups]. All calculations were carried out using the SHELXTL program suite
(Sheldrick, 2015b). The supplementary crystallographic data can be obtained
free of charge from the Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N2A | −0.02331 (8) | 0.44421 (8) | −0.39101 (5) | 0.0317 (2) | |
N3A | −0.06996 (7) | 0.08869 (8) | −0.33804 (5) | 0.0297 (2) | |
N4A | 0.36455 (7) | 0.06076 (8) | 0.42093 (4) | 0.02794 (19) | |
C1A | −0.00139 (7) | 0.28907 (8) | −0.29515 (5) | 0.01924 (17) | |
C2A | −0.01432 (7) | 0.37585 (8) | −0.34834 (5) | 0.02232 (19) | |
C3A | −0.03914 (7) | 0.17756 (8) | −0.31814 (5) | 0.02093 (18) | |
C4A | 0.33609 (7) | 0.10499 (8) | 0.35438 (5) | 0.02077 (18) | |
C5A | 0.36127 (7) | 0.21805 (8) | 0.33948 (5) | 0.02148 (18) | |
H5A | 0.397735 | 0.265699 | 0.376147 | 0.026* | |
C6A | 0.33334 (7) | 0.26013 (8) | 0.27196 (5) | 0.02029 (18) | |
H6A | 0.351300 | 0.336616 | 0.263404 | 0.024* | |
C7A | 0.27938 (7) | 0.19396 (8) | 0.21551 (5) | 0.01866 (17) | |
C8A | 0.25466 (7) | 0.08140 (8) | 0.23071 (5) | 0.01990 (18) | |
H8A | 0.218640 | 0.033881 | 0.193815 | 0.024* | |
C9A | 0.28133 (7) | 0.03790 (8) | 0.29788 (5) | 0.02089 (18) | |
H9A | 0.262594 | −0.038346 | 0.306288 | 0.025* | |
C10A | 0.41401 (8) | 0.13326 (10) | 0.47894 (5) | 0.0294 (2) | |
H10D | 0.474122 | 0.168590 | 0.468738 | 0.044* | |
H10E | 0.434254 | 0.086778 | 0.521481 | 0.044* | |
H10F | 0.367098 | 0.193427 | 0.485829 | 0.044* | |
C11A | 0.32290 (9) | −0.04831 (10) | 0.43636 (6) | 0.0304 (2) | |
H11D | 0.248905 | −0.046153 | 0.420393 | 0.046* | |
H11E | 0.342409 | −0.062091 | 0.486890 | 0.046* | |
H11F | 0.349325 | −0.110217 | 0.412201 | 0.046* | |
C12A | 0.04484 (7) | 0.31391 (8) | −0.22713 (5) | 0.01997 (18) | |
H12A | 0.065701 | 0.391128 | −0.216952 | 0.024* | |
C13A | 0.06481 (7) | 0.23574 (8) | −0.17013 (5) | 0.02033 (18) | |
H13A | 0.045783 | 0.157425 | −0.177487 | 0.024* | |
C14A | 0.11140 (7) | 0.27368 (8) | −0.10487 (5) | 0.02087 (18) | |
H14A | 0.129914 | 0.352427 | −0.100313 | 0.025* | |
C15A | 0.13488 (7) | 0.20602 (9) | −0.04281 (5) | 0.02173 (18) | |
H15A | 0.118784 | 0.126550 | −0.045646 | 0.026* | |
C16A | 0.17979 (7) | 0.25258 (8) | 0.02036 (5) | 0.02101 (18) | |
H16A | 0.195829 | 0.332012 | 0.021376 | 0.025* | |
C17A | 0.20493 (7) | 0.19208 (8) | 0.08542 (5) | 0.02126 (18) | |
H17A | 0.188683 | 0.112848 | 0.085991 | 0.026* | |
C18A | 0.25116 (7) | 0.24417 (8) | 0.14627 (5) | 0.02004 (18) | |
H18A | 0.266975 | 0.323105 | 0.143151 | 0.024* | |
N2B | 0.62142 (7) | 0.34461 (8) | 0.89338 (5) | 0.02768 (19) | |
N3B | 0.49051 (7) | 0.68469 (8) | 0.84150 (5) | 0.02827 (19) | |
N4B | 0.12933 (7) | 0.71560 (8) | 0.08610 (4) | 0.02634 (18) | |
C1B | 0.53305 (7) | 0.48678 (8) | 0.79738 (5) | 0.02034 (18) | |
C2B | 0.58224 (7) | 0.40728 (8) | 0.85038 (5) | 0.02165 (18) | |
C3B | 0.50958 (7) | 0.59688 (8) | 0.82144 (5) | 0.02149 (19) | |
C4B | 0.16278 (7) | 0.67082 (9) | 0.15183 (5) | 0.02140 (18) | |
C5B | 0.14792 (7) | 0.55429 (9) | 0.16558 (5) | 0.02272 (19) | |
H5B | 0.114020 | 0.505526 | 0.128647 | 0.027* | |
C6B | 0.18219 (7) | 0.51006 (9) | 0.23233 (5) | 0.02233 (19) | |
H6B | 0.170750 | 0.431256 | 0.240099 | 0.027* | |
C7B | 0.23323 (7) | 0.57760 (8) | 0.28891 (5) | 0.02023 (18) | |
C8B | 0.24749 (7) | 0.69372 (9) | 0.27485 (5) | 0.02227 (19) | |
H8B | 0.281596 | 0.742086 | 0.311937 | 0.027* | |
C9B | 0.21347 (8) | 0.73975 (9) | 0.20879 (5) | 0.02335 (19) | |
H9B | 0.224220 | 0.818859 | 0.201434 | 0.028* | |
C10B | 0.09193 (10) | 0.64045 (11) | 0.02686 (6) | 0.0350 (3) | |
H10A | 0.144904 | 0.585528 | 0.023213 | 0.053* | |
H10B | 0.073202 | 0.686245 | −0.016044 | 0.053* | |
H10C | 0.032380 | 0.598765 | 0.033345 | 0.053* | |
C11B | 0.14443 (10) | 0.83608 (10) | 0.07314 (6) | 0.0335 (2) | |
H11A | 0.112358 | 0.883169 | 0.102864 | 0.050* | |
H11B | 0.114011 | 0.853685 | 0.023903 | 0.050* | |
H11C | 0.217125 | 0.852801 | 0.083893 | 0.050* | |
C12B | 0.50707 (7) | 0.45684 (8) | 0.72805 (5) | 0.02137 (18) | |
H12B | 0.521142 | 0.380423 | 0.716507 | 0.026* | |
C13B | 0.46095 (7) | 0.53063 (8) | 0.67222 (5) | 0.02143 (18) | |
H13B | 0.449899 | 0.608963 | 0.681481 | 0.026* | |
C14B | 0.43220 (7) | 0.49035 (9) | 0.60521 (5) | 0.02216 (19) | |
H14B | 0.441188 | 0.410833 | 0.597924 | 0.027* | |
C15B | 0.38980 (7) | 0.55889 (9) | 0.54561 (5) | 0.02263 (19) | |
H15B | 0.387356 | 0.639755 | 0.551119 | 0.027* | |
C16B | 0.35260 (7) | 0.51304 (9) | 0.48100 (5) | 0.02246 (19) | |
H16B | 0.353363 | 0.431793 | 0.477096 | 0.027* | |
C17B | 0.31250 (7) | 0.57682 (9) | 0.41857 (5) | 0.02308 (19) | |
H17B | 0.315278 | 0.658265 | 0.420356 | 0.028* | |
C18B | 0.27057 (7) | 0.52474 (9) | 0.35681 (5) | 0.02193 (19) | |
H18B | 0.264996 | 0.443550 | 0.358244 | 0.026* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N2A | 0.0381 (5) | 0.0275 (5) | 0.0293 (5) | 0.0030 (4) | 0.0076 (4) | 0.0066 (4) |
N3A | 0.0312 (5) | 0.0239 (4) | 0.0301 (5) | −0.0008 (4) | 0.0002 (4) | 0.0006 (3) |
N4A | 0.0356 (5) | 0.0284 (4) | 0.0167 (4) | 0.0012 (4) | 0.0005 (3) | 0.0024 (3) |
C1A | 0.0199 (4) | 0.0184 (4) | 0.0190 (4) | 0.0012 (3) | 0.0038 (3) | 0.0024 (3) |
C2A | 0.0234 (4) | 0.0212 (4) | 0.0220 (4) | 0.0012 (3) | 0.0049 (3) | 0.0005 (3) |
C3A | 0.0209 (4) | 0.0215 (4) | 0.0188 (4) | 0.0019 (3) | 0.0018 (3) | 0.0031 (3) |
C4A | 0.0204 (4) | 0.0242 (5) | 0.0170 (4) | 0.0044 (3) | 0.0030 (3) | 0.0007 (3) |
C5A | 0.0218 (4) | 0.0226 (4) | 0.0186 (4) | 0.0020 (3) | 0.0022 (3) | −0.0027 (3) |
C6A | 0.0203 (4) | 0.0193 (4) | 0.0206 (4) | 0.0004 (3) | 0.0038 (3) | −0.0009 (3) |
C7A | 0.0183 (4) | 0.0200 (4) | 0.0170 (4) | 0.0014 (3) | 0.0030 (3) | −0.0001 (3) |
C8A | 0.0193 (4) | 0.0204 (4) | 0.0187 (4) | 0.0000 (3) | 0.0021 (3) | −0.0008 (3) |
C9A | 0.0211 (4) | 0.0202 (4) | 0.0206 (4) | 0.0008 (3) | 0.0037 (3) | 0.0013 (3) |
C10A | 0.0304 (5) | 0.0390 (6) | 0.0168 (4) | 0.0039 (4) | 0.0019 (4) | −0.0019 (4) |
C11A | 0.0299 (5) | 0.0368 (6) | 0.0229 (5) | 0.0001 (4) | 0.0034 (4) | 0.0093 (4) |
C12A | 0.0194 (4) | 0.0202 (4) | 0.0202 (4) | 0.0000 (3) | 0.0045 (3) | 0.0006 (3) |
C13A | 0.0212 (4) | 0.0200 (4) | 0.0191 (4) | −0.0001 (3) | 0.0036 (3) | 0.0014 (3) |
C14A | 0.0210 (4) | 0.0215 (4) | 0.0195 (4) | −0.0013 (3) | 0.0038 (3) | 0.0000 (3) |
C15A | 0.0226 (4) | 0.0219 (4) | 0.0193 (4) | −0.0008 (3) | 0.0023 (3) | 0.0007 (3) |
C16A | 0.0219 (4) | 0.0210 (4) | 0.0192 (4) | −0.0007 (3) | 0.0032 (3) | 0.0012 (3) |
C17A | 0.0229 (4) | 0.0203 (4) | 0.0192 (4) | −0.0010 (3) | 0.0025 (3) | 0.0009 (3) |
C18A | 0.0208 (4) | 0.0199 (4) | 0.0186 (4) | −0.0006 (3) | 0.0032 (3) | 0.0011 (3) |
N2B | 0.0302 (4) | 0.0273 (4) | 0.0257 (4) | 0.0031 (3) | 0.0072 (3) | 0.0022 (3) |
N3B | 0.0355 (5) | 0.0237 (4) | 0.0247 (4) | 0.0007 (4) | 0.0054 (4) | 0.0013 (3) |
N4B | 0.0315 (4) | 0.0287 (4) | 0.0181 (4) | 0.0007 (3) | 0.0049 (3) | 0.0014 (3) |
C1B | 0.0210 (4) | 0.0200 (4) | 0.0199 (4) | −0.0014 (3) | 0.0048 (3) | 0.0014 (3) |
C2B | 0.0221 (4) | 0.0219 (4) | 0.0218 (4) | −0.0012 (3) | 0.0070 (3) | −0.0012 (3) |
C3B | 0.0229 (4) | 0.0227 (4) | 0.0181 (4) | −0.0024 (3) | 0.0036 (3) | 0.0023 (3) |
C4B | 0.0206 (4) | 0.0252 (5) | 0.0191 (4) | 0.0015 (3) | 0.0063 (3) | 0.0000 (3) |
C5B | 0.0236 (4) | 0.0232 (4) | 0.0201 (4) | −0.0005 (4) | 0.0030 (3) | −0.0033 (3) |
C6B | 0.0233 (4) | 0.0202 (4) | 0.0228 (4) | −0.0002 (3) | 0.0044 (3) | −0.0017 (3) |
C7B | 0.0196 (4) | 0.0219 (4) | 0.0188 (4) | 0.0015 (3) | 0.0040 (3) | −0.0010 (3) |
C8B | 0.0230 (4) | 0.0225 (4) | 0.0208 (4) | −0.0014 (3) | 0.0043 (3) | −0.0028 (3) |
C9B | 0.0261 (5) | 0.0213 (4) | 0.0226 (4) | −0.0017 (4) | 0.0059 (4) | −0.0004 (3) |
C10B | 0.0445 (6) | 0.0386 (6) | 0.0199 (5) | 0.0064 (5) | 0.0038 (4) | −0.0045 (4) |
C11B | 0.0392 (6) | 0.0330 (6) | 0.0276 (5) | −0.0020 (5) | 0.0070 (4) | 0.0078 (4) |
C12B | 0.0220 (4) | 0.0204 (4) | 0.0219 (4) | −0.0027 (3) | 0.0057 (3) | −0.0005 (3) |
C13B | 0.0238 (4) | 0.0205 (4) | 0.0198 (4) | −0.0019 (3) | 0.0050 (3) | 0.0002 (3) |
C14B | 0.0224 (4) | 0.0235 (4) | 0.0204 (4) | −0.0007 (3) | 0.0050 (3) | 0.0002 (3) |
C15B | 0.0242 (4) | 0.0229 (4) | 0.0206 (4) | −0.0007 (4) | 0.0051 (3) | −0.0001 (3) |
C16B | 0.0237 (4) | 0.0231 (4) | 0.0203 (4) | 0.0009 (4) | 0.0049 (3) | 0.0003 (3) |
C17B | 0.0250 (5) | 0.0228 (4) | 0.0211 (4) | 0.0015 (4) | 0.0050 (4) | 0.0005 (3) |
C18B | 0.0225 (4) | 0.0219 (4) | 0.0209 (4) | 0.0016 (3) | 0.0042 (3) | 0.0002 (3) |
Geometric parameters (Å, º) top
N2A—C2A | 1.1435 (13) | N2B—C2B | 1.1473 (13) |
N3A—C3A | 1.1497 (13) | N3B—C3B | 1.1494 (13) |
N4A—C4A | 1.3750 (12) | N4B—C4B | 1.3683 (12) |
N4A—C10A | 1.4492 (13) | N4B—C10B | 1.4495 (14) |
N4A—C11A | 1.4538 (14) | N4B—C11B | 1.4505 (14) |
C1A—C12A | 1.3668 (13) | C1B—C12B | 1.3714 (13) |
C1A—C3A | 1.4298 (13) | C1B—C3B | 1.4307 (14) |
C1A—C2A | 1.4366 (13) | C1B—C2B | 1.4344 (13) |
C4A—C5A | 1.4101 (14) | C4B—C5B | 1.4089 (14) |
C4A—C9A | 1.4154 (13) | C4B—C9B | 1.4161 (13) |
C5A—C6A | 1.3827 (13) | C5B—C6B | 1.3845 (13) |
C5A—H5A | 0.9500 | C5B—H5B | 0.9500 |
C6A—C7A | 1.4053 (13) | C6B—C7B | 1.4033 (13) |
C6A—H6A | 0.9500 | C6B—H6B | 0.9500 |
C7A—C8A | 1.4045 (13) | C7B—C8B | 1.4041 (14) |
C7A—C18A | 1.4486 (12) | C7B—C18B | 1.4489 (13) |
C8A—C9A | 1.3817 (13) | C8B—C9B | 1.3803 (13) |
C8A—H8A | 0.9500 | C8B—H8B | 0.9500 |
C9A—H9A | 0.9500 | C9B—H9B | 0.9500 |
C10A—H10D | 0.9800 | C10B—H10A | 0.9800 |
C10A—H10E | 0.9800 | C10B—H10B | 0.9800 |
C10A—H10F | 0.9800 | C10B—H10C | 0.9800 |
C11A—H11D | 0.9800 | C11B—H11A | 0.9800 |
C11A—H11E | 0.9800 | C11B—H11B | 0.9800 |
C11A—H11F | 0.9800 | C11B—H11C | 0.9800 |
C12A—C13A | 1.4206 (13) | C12B—C13B | 1.4173 (13) |
C12A—H12A | 0.9500 | C12B—H12B | 0.9500 |
C13A—C14A | 1.3625 (13) | C13B—C14B | 1.3667 (13) |
C13A—H13A | 0.9500 | C13B—H13B | 0.9500 |
C14A—C15A | 1.4250 (13) | C14B—C15B | 1.4218 (13) |
C14A—H14A | 0.9500 | C14B—H14B | 0.9500 |
C15A—C16A | 1.3598 (13) | C15B—C16B | 1.3605 (13) |
C15A—H15A | 0.9500 | C15B—H15B | 0.9500 |
C16A—C17A | 1.4305 (13) | C16B—C17B | 1.4278 (13) |
C16A—H16A | 0.9500 | C16B—H16B | 0.9500 |
C17A—C18A | 1.3551 (13) | C17B—C18B | 1.3559 (13) |
C17A—H17A | 0.9500 | C17B—H17B | 0.9500 |
C18A—H18A | 0.9500 | C18B—H18B | 0.9500 |
| | | |
C4A—N4A—C10A | 120.24 (9) | C4B—N4B—C10B | 120.25 (9) |
C4A—N4A—C11A | 119.61 (9) | C4B—N4B—C11B | 120.48 (9) |
C10A—N4A—C11A | 118.30 (9) | C10B—N4B—C11B | 118.66 (9) |
C12A—C1A—C3A | 123.21 (9) | C12B—C1B—C3B | 122.32 (9) |
C12A—C1A—C2A | 120.85 (9) | C12B—C1B—C2B | 121.55 (9) |
C3A—C1A—C2A | 115.94 (8) | C3B—C1B—C2B | 116.09 (8) |
N2A—C2A—C1A | 178.90 (11) | N2B—C2B—C1B | 179.17 (11) |
N3A—C3A—C1A | 178.58 (10) | N3B—C3B—C1B | 179.14 (10) |
N4A—C4A—C5A | 121.52 (9) | N4B—C4B—C5B | 121.31 (9) |
N4A—C4A—C9A | 121.08 (9) | N4B—C4B—C9B | 121.38 (9) |
C5A—C4A—C9A | 117.39 (8) | C5B—C4B—C9B | 117.31 (9) |
C6A—C5A—C4A | 120.55 (9) | C6B—C5B—C4B | 120.72 (9) |
C6A—C5A—H5A | 119.7 | C6B—C5B—H5B | 119.6 |
C4A—C5A—H5A | 119.7 | C4B—C5B—H5B | 119.6 |
C5A—C6A—C7A | 122.44 (9) | C5B—C6B—C7B | 122.29 (9) |
C5A—C6A—H6A | 118.8 | C5B—C6B—H6B | 118.9 |
C7A—C6A—H6A | 118.8 | C7B—C6B—H6B | 118.9 |
C8A—C7A—C6A | 116.71 (8) | C6B—C7B—C8B | 116.67 (9) |
C8A—C7A—C18A | 123.79 (8) | C6B—C7B—C18B | 119.39 (9) |
C6A—C7A—C18A | 119.50 (8) | C8B—C7B—C18B | 123.91 (9) |
C9A—C8A—C7A | 121.78 (9) | C9B—C8B—C7B | 122.01 (9) |
C9A—C8A—H8A | 119.1 | C9B—C8B—H8B | 119.0 |
C7A—C8A—H8A | 119.1 | C7B—C8B—H8B | 119.0 |
C8A—C9A—C4A | 121.14 (9) | C8B—C9B—C4B | 121.00 (9) |
C8A—C9A—H9A | 119.4 | C8B—C9B—H9B | 119.5 |
C4A—C9A—H9A | 119.4 | C4B—C9B—H9B | 119.5 |
N4A—C10A—H10D | 109.5 | N4B—C10B—H10A | 109.5 |
N4A—C10A—H10E | 109.5 | N4B—C10B—H10B | 109.5 |
H10D—C10A—H10E | 109.5 | H10A—C10B—H10B | 109.5 |
N4A—C10A—H10F | 109.5 | N4B—C10B—H10C | 109.5 |
H10D—C10A—H10F | 109.5 | H10A—C10B—H10C | 109.5 |
H10E—C10A—H10F | 109.5 | H10B—C10B—H10C | 109.5 |
N4A—C11A—H11D | 109.5 | N4B—C11B—H11A | 109.5 |
N4A—C11A—H11E | 109.5 | N4B—C11B—H11B | 109.5 |
H11D—C11A—H11E | 109.5 | H11A—C11B—H11B | 109.5 |
N4A—C11A—H11F | 109.5 | N4B—C11B—H11C | 109.5 |
H11D—C11A—H11F | 109.5 | H11A—C11B—H11C | 109.5 |
H11E—C11A—H11F | 109.5 | H11B—C11B—H11C | 109.5 |
C1A—C12A—C13A | 126.47 (9) | C1B—C12B—C13B | 125.31 (9) |
C1A—C12A—H12A | 116.8 | C1B—C12B—H12B | 117.3 |
C13A—C12A—H12A | 116.8 | C13B—C12B—H12B | 117.3 |
C14A—C13A—C12A | 119.65 (9) | C14B—C13B—C12B | 120.74 (9) |
C14A—C13A—H13A | 120.2 | C14B—C13B—H13B | 119.6 |
C12A—C13A—H13A | 120.2 | C12B—C13B—H13B | 119.6 |
C13A—C14A—C15A | 125.96 (9) | C13B—C14B—C15B | 124.70 (9) |
C13A—C14A—H14A | 117.0 | C13B—C14B—H14B | 117.6 |
C15A—C14A—H14A | 117.0 | C15B—C14B—H14B | 117.6 |
C16A—C15A—C14A | 121.52 (9) | C16B—C15B—C14B | 122.49 (9) |
C16A—C15A—H15A | 119.2 | C16B—C15B—H15B | 118.8 |
C14A—C15A—H15A | 119.2 | C14B—C15B—H15B | 118.8 |
C15A—C16A—C17A | 125.53 (9) | C15B—C16B—C17B | 125.46 (9) |
C15A—C16A—H16A | 117.2 | C15B—C16B—H16B | 117.3 |
C17A—C16A—H16A | 117.2 | C17B—C16B—H16B | 117.3 |
C18A—C17A—C16A | 122.11 (9) | C18B—C17B—C16B | 122.03 (9) |
C18A—C17A—H17A | 118.9 | C18B—C17B—H17B | 119.0 |
C16A—C17A—H17A | 118.9 | C16B—C17B—H17B | 119.0 |
C17A—C18A—C7A | 127.81 (9) | C17B—C18B—C7B | 128.03 (9) |
C17A—C18A—H18A | 116.1 | C17B—C18B—H18B | 116.0 |
C7A—C18A—H18A | 116.1 | C7B—C18B—H18B | 116.0 |
| | | |
C10A—N4A—C4A—C5A | 5.39 (15) | C10B—N4B—C4B—C5B | −9.73 (15) |
C11A—N4A—C4A—C5A | 169.65 (9) | C11B—N4B—C4B—C5B | 179.36 (10) |
C10A—N4A—C4A—C9A | −175.46 (9) | C10B—N4B—C4B—C9B | 170.44 (10) |
C11A—N4A—C4A—C9A | −11.20 (15) | C11B—N4B—C4B—C9B | −0.47 (15) |
N4A—C4A—C5A—C6A | 178.91 (9) | N4B—C4B—C5B—C6B | 179.97 (9) |
C9A—C4A—C5A—C6A | −0.28 (14) | C9B—C4B—C5B—C6B | −0.19 (14) |
C4A—C5A—C6A—C7A | 0.00 (14) | C4B—C5B—C6B—C7B | −0.35 (15) |
C5A—C6A—C7A—C8A | −0.08 (14) | C5B—C6B—C7B—C8B | 0.53 (14) |
C5A—C6A—C7A—C18A | 179.01 (9) | C5B—C6B—C7B—C18B | −177.57 (9) |
C6A—C7A—C8A—C9A | 0.46 (14) | C6B—C7B—C8B—C9B | −0.16 (14) |
C18A—C7A—C8A—C9A | −178.59 (9) | C18B—C7B—C8B—C9B | 177.84 (9) |
C7A—C8A—C9A—C4A | −0.77 (15) | C7B—C8B—C9B—C4B | −0.38 (15) |
N4A—C4A—C9A—C8A | −178.53 (9) | N4B—C4B—C9B—C8B | −179.62 (9) |
C5A—C4A—C9A—C8A | 0.66 (14) | C5B—C4B—C9B—C8B | 0.55 (14) |
C3A—C1A—C12A—C13A | 1.60 (15) | C3B—C1B—C12B—C13B | 4.19 (15) |
C2A—C1A—C12A—C13A | −178.12 (9) | C2B—C1B—C12B—C13B | −178.19 (9) |
C1A—C12A—C13A—C14A | −179.71 (9) | C1B—C12B—C13B—C14B | −175.83 (9) |
C12A—C13A—C14A—C15A | 179.02 (9) | C12B—C13B—C14B—C15B | −176.96 (9) |
C13A—C14A—C15A—C16A | −178.61 (9) | C13B—C14B—C15B—C16B | −172.94 (10) |
C14A—C15A—C16A—C17A | 179.10 (9) | C14B—C15B—C16B—C17B | −177.55 (9) |
C15A—C16A—C17A—C18A | 178.97 (9) | C15B—C16B—C17B—C18B | −175.53 (10) |
C16A—C17A—C18A—C7A | 179.02 (9) | C16B—C17B—C18B—C7B | −175.60 (9) |
C8A—C7A—C18A—C17A | −5.31 (16) | C6B—C7B—C18B—C17B | −173.07 (10) |
C6A—C7A—C18A—C17A | 175.67 (9) | C8B—C7B—C18B—C17B | 8.98 (16) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C11A—H11D···N3Ai | 0.98 | 2.63 | 3.5479 (15) | 157 |
C11A—H11E···N2Bii | 0.98 | 2.54 | 3.4880 (14) | 164 |
Symmetry codes: (i) −x, −y, −z; (ii) −x+1, y−1/2, −z+3/2. |
Dihedral angles (°) between planar fragments and selected bond lengths (Å)
in molecules of DCV[3] and DCV[4] top | DCV[3] (molecules A/B) | DCV[4] (molecules A/B) |
Deviation | 0.112/0.092 | 0.034/0.083 |
Dihedral angle A/B | 55.57 (2) | 14.77 (2) |
Dihedral angle acceptor/bridge | 6.41 (16)/2.59 (16) | 2.19 (7)/16.68 (6) |
Dihedral angle donor/bridge | 7.40 (11)/7.84 (13) | 7.37 (6)/17.63 (3) |
C1—C12 | 1.3631 (15)/1.3637 (15) | 1.3668 (13)/1.3714 (13) |
C12—C13 | 1.4146 (14)/1.4213 (14) | 1.4206 (13)/1.4173 (13) |
C13—C14 | 1.3603 (15)/1.3609 (15) | 1.3625 (13)/1.3667 (13) |
C14—C15 | 1.4260 (14)/1.4287 (14) | 1.4250 (13)/1.4218 (13) |
C15—C16 | 1.3543 (15)/1.3528 (15) | 1.3598 (13)/1.3605 (13) |
C16—C7/C16—C17 | 1.4453 (14)/1.4487 (14) | 1.4305 (13)/1.4278 (13) |
C17—C18 | - | 1.3551 (13)/1.3559 (13) |
C18—C7 | - | 1.4486 (12)/1.4489 (13) |
C7—C6 | 1.4044 (14)/1.4014 (15) | 1.4053 (13)/1.4033 (13) |
C6—C5 | 1.3785 (14)/1.3775 (15) | 1.3827 (13)/1.3845 (13) |
C5—C4 | 1.4140 (14)/1.4124 (15) | 1.4101 (14)/1.4089 (14) |
C4—N4 | 1.3673 (13)/1.3663 (14) | 1.3750 (12)/1.3683 (12) |
C7—C8 | 1.4099 (15)/1.4087 (15) | 1.4045 (13)/1.4041 (14) |
C4—C9 | 1.4195 (14)/1.4189 (15) | 1.4154 (13)/1.4161 (13) |
C8—C9 | 1.3786 (14)/1.3789 (15) | 1.3817 (13)/1.3803 (13) |