Buy article online - an online subscription or single-article purchase is required to access this article.
In the title compounds, C
17H
15N
3 and C
20H
22N
4, the methyl derivative crystallizes with two molecules in the asymmetric unit, while the
N,
N-diethylamino derivative crystallizes with one molecule per asymmetric unit. The biphenyl twist angle for both molecular structures is approximately 45°. The molecular packing is stabilized by N—H
N hydrogen bonds.
Supporting information
CCDC references: 166980; 166981
The title compounds were synthesized as follows: a mixture of
5-(4-methylphenyl)-pent-4-en-3-one (1.0 g, 5.74 mmol), malononitrile (0.76 g,
11.51 mmol) and catalytic amount of pyrrolidine in ethanol (20 ml) for comound
I and a mixture of 5-(4-diethylaminophenyl)-pent-4-en-3-one (1.0 g, 4.6 mmol),
malononitrile (0.29 g, 4.39 mmol) and catalytic amount of pyrrolidine in
ethanol (20 ml) for compound (II), respectively, were taken as starting
materials. The mixtures were heated under reflux for 7 h, concentrated under
reduced pressure and purified by column chromatography over silica gel.
Elution with a mixture of petroleum ether-benzene (1:5) gave the product as a
yellow solid. The compounds were dissolved in ethyl acetate with few drops of
hexane. Slow evaporation of the solvent at room temperature produced crystals
from which experimental samples were obtained.
For both compounds, data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ZORTEP (Zsolnai, 1997); software used to prepare material for publication: SHELXL97 and PARST (Nardelli, 1995).
(I) 3-amino-2,4 dicyano-5-ethyl-4'- methyl Biphenyl
top
Crystal data top
C17H15N3 | F(000) = 664 |
Mr = 261.32 | Dx = 1.216 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.8579 (1) Å | Cell parameters from 8192 reflections |
b = 23.7627 (5) Å | θ = 1.5–28.3° |
c = 15.3423 (2) Å | µ = 0.07 mm−1 |
β = 94.765 (1)° | T = 293 K |
V = 2854.89 (8) Å3 | Rectangular, pale yellow |
Z = 8 | 0.30 × 0.24 × 0.14 mm |
Data collection top
Siemens SMART CCD area detector diffractometer | 6961 independent reflections |
Radiation source: fine-focus sealed tube | 3077 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.090 |
Detector resolution: 8.33 pixels mm-1 | θmax = 28.3°, θmin = 1.6° |
ω scans | h = −10→10 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −31→31 |
Tmin = 0.978, Tmax = 0.990 | l = −10→20 |
19861 measured reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.067 | H-atom parameters constrained |
wR(F2) = 0.173 | w = 1/[σ2(Fo2) + (0.0504P)2 + 0.0465P] where P = (Fo2 + 2Fc2)/3 |
S = 0.97 | (Δ/σ)max = 0.001 |
6961 reflections | Δρmax = 0.32 e Å−3 |
365 parameters | Δρmin = −0.30 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997) |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: none |
Crystal data top
C17H15N3 | V = 2854.89 (8) Å3 |
Mr = 261.32 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.8579 (1) Å | µ = 0.07 mm−1 |
b = 23.7627 (5) Å | T = 293 K |
c = 15.3423 (2) Å | 0.30 × 0.24 × 0.14 mm |
β = 94.765 (1)° | |
Data collection top
Siemens SMART CCD area detector diffractometer | 6961 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 3077 reflections with I > 2σ(I) |
Tmin = 0.978, Tmax = 0.990 | Rint = 0.090 |
19861 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.067 | 0 restraints |
wR(F2) = 0.173 | H-atom parameters constrained |
S = 0.97 | Δρmax = 0.32 e Å−3 |
6961 reflections | Δρmin = −0.30 e Å−3 |
365 parameters | |
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 | |
N1A | 0.1068 (3) | 0.60919 (8) | 0.46133 (13) | 0.0537 (6) | |
H1A1 | 0.0857 | 0.5737 | 0.4591 | 0.064* | |
H1A2 | 0.0840 | 0.6298 | 0.4158 | 0.064* | |
N2A | 0.1276 (3) | 0.74519 (9) | 0.40063 (14) | 0.0564 (6) | |
N3A | 0.1427 (3) | 0.49363 (9) | 0.60111 (15) | 0.0701 (7) | |
C1A' | 0.3287 (3) | 0.77552 (9) | 0.62858 (15) | 0.0362 (6) | |
C2A' | 0.4072 (3) | 0.80462 (9) | 0.56434 (16) | 0.0403 (6) | |
H2A' | 0.4315 | 0.7863 | 0.5133 | 0.048* | |
C3A' | 0.4492 (3) | 0.86090 (10) | 0.57616 (17) | 0.0462 (6) | |
H3A' | 0.5024 | 0.8797 | 0.5328 | 0.055* | |
C4A' | 0.4142 (3) | 0.88966 (10) | 0.6507 (2) | 0.0510 (7) | |
C5A' | 0.3381 (3) | 0.86051 (11) | 0.71425 (19) | 0.0540 (7) | |
H5A' | 0.3147 | 0.8789 | 0.7654 | 0.065* | |
C6A' | 0.2957 (3) | 0.80439 (10) | 0.70374 (16) | 0.0452 (6) | |
H6A' | 0.2442 | 0.7857 | 0.7479 | 0.054* | |
C1A | 0.2871 (3) | 0.71471 (9) | 0.62019 (14) | 0.0351 (5) | |
C2A | 0.2159 (3) | 0.69041 (9) | 0.54184 (14) | 0.0334 (5) | |
C3A | 0.1760 (3) | 0.63275 (9) | 0.53688 (15) | 0.0368 (6) | |
C4A | 0.2138 (3) | 0.59952 (9) | 0.61184 (16) | 0.0401 (6) | |
C5A | 0.2864 (3) | 0.62302 (10) | 0.69014 (16) | 0.0456 (6) | |
C6A | 0.3203 (3) | 0.67982 (9) | 0.69284 (15) | 0.0430 (6) | |
H6A | 0.3671 | 0.6955 | 0.7449 | 0.052* | |
C7A | 0.1699 (3) | 0.72288 (9) | 0.46506 (16) | 0.0392 (6) | |
C8A | 0.1736 (3) | 0.54050 (11) | 0.60650 (16) | 0.0488 (7) | |
C9A | 0.3286 (5) | 0.58558 (11) | 0.76820 (18) | 0.0751 (10) | |
H9A1 | 0.2537 | 0.5531 | 0.7622 | 0.090* | |
H9A2 | 0.4443 | 0.5719 | 0.7650 | 0.090* | |
C10A | 0.3181 (9) | 0.60692 (17) | 0.8489 (2) | 0.181 (3) | |
H10A | 0.4159 | 0.6302 | 0.8643 | 0.271* | |
H10B | 0.3148 | 0.5767 | 0.8903 | 0.271* | |
H10C | 0.2160 | 0.6291 | 0.8497 | 0.271* | |
C11A | 0.4596 (4) | 0.95143 (11) | 0.6617 (2) | 0.0815 (10) | |
H11A | 0.5397 | 0.9561 | 0.7120 | 0.122* | |
H11B | 0.3581 | 0.9727 | 0.6697 | 0.122* | |
H11C | 0.5097 | 0.9646 | 0.6105 | 0.122* | |
N1B | 0.1944 (3) | 0.37256 (9) | 0.68535 (13) | 0.0560 (6) | |
H1B1 | 0.1666 | 0.4074 | 0.6789 | 0.067* | |
H1B2 | 0.2350 | 0.3545 | 0.6432 | 0.067* | |
N2B | 0.3510 (3) | 0.24409 (10) | 0.64279 (15) | 0.0637 (7) | |
N3B | 0.0110 (4) | 0.47704 (10) | 0.80857 (17) | 0.0784 (8) | |
C1B' | 0.2250 (3) | 0.19896 (9) | 0.86189 (15) | 0.0385 (6) | |
C2B' | 0.1694 (3) | 0.16080 (10) | 0.79714 (17) | 0.0483 (7) | |
H2B' | 0.1092 | 0.1736 | 0.7463 | 0.058* | |
C3B' | 0.2025 (3) | 0.10379 (10) | 0.80748 (18) | 0.0527 (7) | |
H3B' | 0.1646 | 0.0790 | 0.7632 | 0.063* | |
C4B' | 0.2906 (3) | 0.08320 (10) | 0.88208 (17) | 0.0483 (7) | |
C5B' | 0.3420 (3) | 0.12094 (11) | 0.94698 (17) | 0.0509 (7) | |
H5B' | 0.4001 | 0.1078 | 0.9982 | 0.061* | |
C6B' | 0.3096 (3) | 0.17788 (10) | 0.93815 (15) | 0.0446 (6) | |
H6B' | 0.3447 | 0.2023 | 0.9835 | 0.054* | |
C1B | 0.1905 (3) | 0.26010 (9) | 0.85158 (16) | 0.0382 (6) | |
C2B | 0.2149 (3) | 0.28828 (9) | 0.77364 (15) | 0.0374 (6) | |
C3B | 0.1739 (3) | 0.34595 (10) | 0.76246 (16) | 0.0403 (6) | |
C4B | 0.1081 (3) | 0.37396 (10) | 0.83261 (17) | 0.0420 (6) | |
C5B | 0.0889 (3) | 0.34729 (10) | 0.91243 (16) | 0.0421 (6) | |
C6B | 0.1330 (3) | 0.29067 (10) | 0.92039 (16) | 0.0424 (6) | |
H6B | 0.1236 | 0.2727 | 0.9736 | 0.051* | |
C7B | 0.2900 (3) | 0.26140 (10) | 0.70208 (17) | 0.0441 (6) | |
C8B | 0.0544 (3) | 0.43156 (12) | 0.82023 (18) | 0.0536 (7) | |
C9B | 0.0220 (4) | 0.37831 (11) | 0.98761 (18) | 0.0581 (7) | |
H9B1 | −0.0292 | 0.3514 | 1.0252 | 0.070* | |
H9B2 | −0.0670 | 0.4040 | 0.9650 | 0.070* | |
C10B | 0.1573 (5) | 0.41131 (15) | 1.0417 (2) | 0.1059 (13) | |
H10D | 0.2464 | 0.3863 | 1.0640 | 0.159* | |
H10E | 0.1071 | 0.4291 | 1.0895 | 0.159* | |
H10F | 0.2042 | 0.4395 | 1.0058 | 0.159* | |
C11B | 0.3303 (4) | 0.02109 (10) | 0.8916 (2) | 0.0704 (9) | |
H11D | 0.2470 | −0.0002 | 0.8561 | 0.106* | |
H11E | 0.3274 | 0.0102 | 0.9517 | 0.106* | |
H11F | 0.4419 | 0.0138 | 0.8730 | 0.106* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1A | 0.0831 (17) | 0.0316 (11) | 0.0438 (13) | −0.0042 (11) | −0.0103 (11) | −0.0059 (10) |
N2A | 0.0791 (17) | 0.0526 (14) | 0.0362 (13) | 0.0033 (12) | −0.0027 (12) | 0.0036 (11) |
N3A | 0.112 (2) | 0.0334 (13) | 0.0649 (16) | −0.0128 (13) | 0.0044 (14) | 0.0010 (12) |
C1A' | 0.0378 (13) | 0.0340 (13) | 0.0355 (14) | −0.0009 (10) | −0.0041 (11) | 0.0000 (11) |
C2A' | 0.0447 (14) | 0.0350 (14) | 0.0405 (14) | −0.0007 (11) | −0.0009 (11) | −0.0011 (11) |
C3A' | 0.0469 (15) | 0.0360 (14) | 0.0544 (17) | −0.0055 (11) | −0.0029 (12) | 0.0096 (13) |
C4A' | 0.0491 (16) | 0.0308 (14) | 0.071 (2) | −0.0031 (12) | −0.0065 (14) | −0.0052 (14) |
C5A' | 0.0574 (17) | 0.0427 (16) | 0.0614 (19) | 0.0005 (13) | 0.0015 (14) | −0.0199 (14) |
C6A' | 0.0510 (16) | 0.0422 (15) | 0.0423 (15) | −0.0031 (12) | 0.0029 (12) | −0.0053 (12) |
C1A | 0.0408 (13) | 0.0296 (12) | 0.0347 (13) | −0.0032 (10) | 0.0020 (11) | −0.0020 (11) |
C2A | 0.0395 (13) | 0.0295 (12) | 0.0312 (13) | 0.0000 (10) | 0.0018 (10) | 0.0007 (10) |
C3A | 0.0441 (14) | 0.0295 (12) | 0.0363 (14) | −0.0018 (10) | 0.0004 (11) | −0.0025 (11) |
C4A | 0.0523 (15) | 0.0261 (13) | 0.0417 (15) | −0.0035 (11) | 0.0036 (12) | 0.0006 (11) |
C5A | 0.0633 (17) | 0.0349 (14) | 0.0387 (15) | −0.0039 (12) | 0.0043 (12) | 0.0056 (12) |
C6A | 0.0609 (17) | 0.0345 (14) | 0.0321 (13) | −0.0067 (12) | −0.0063 (12) | −0.0002 (11) |
C7A | 0.0515 (15) | 0.0292 (13) | 0.0366 (14) | 0.0012 (11) | 0.0013 (12) | −0.0076 (11) |
C8A | 0.0679 (18) | 0.0359 (16) | 0.0424 (15) | −0.0046 (13) | 0.0041 (13) | 0.0027 (12) |
C9A | 0.133 (3) | 0.0477 (17) | 0.0431 (18) | 0.0021 (18) | −0.0010 (18) | 0.0136 (15) |
C10A | 0.405 (9) | 0.090 (3) | 0.044 (2) | 0.055 (4) | 0.001 (4) | 0.012 (2) |
C11A | 0.085 (2) | 0.0386 (17) | 0.119 (3) | −0.0115 (15) | −0.003 (2) | −0.0138 (17) |
N1B | 0.0836 (17) | 0.0418 (12) | 0.0423 (13) | 0.0087 (11) | 0.0035 (12) | 0.0097 (10) |
N2B | 0.0831 (18) | 0.0686 (17) | 0.0399 (14) | 0.0123 (13) | 0.0077 (13) | 0.0009 (12) |
N3B | 0.096 (2) | 0.0473 (16) | 0.093 (2) | 0.0137 (14) | 0.0162 (16) | 0.0062 (15) |
C1B' | 0.0430 (14) | 0.0363 (13) | 0.0364 (14) | −0.0042 (11) | 0.0035 (11) | 0.0037 (11) |
C2B' | 0.0557 (17) | 0.0434 (16) | 0.0445 (15) | −0.0035 (12) | −0.0031 (13) | 0.0047 (12) |
C3B' | 0.0676 (19) | 0.0388 (15) | 0.0510 (17) | −0.0082 (13) | 0.0010 (14) | −0.0040 (13) |
C4B' | 0.0595 (17) | 0.0365 (14) | 0.0506 (17) | −0.0023 (12) | 0.0151 (14) | 0.0055 (13) |
C5B' | 0.0647 (18) | 0.0458 (16) | 0.0422 (16) | 0.0013 (13) | 0.0045 (13) | 0.0144 (13) |
C6B' | 0.0574 (16) | 0.0409 (15) | 0.0356 (14) | −0.0044 (12) | 0.0036 (12) | 0.0025 (12) |
C1B | 0.0385 (13) | 0.0368 (13) | 0.0385 (14) | −0.0033 (11) | −0.0025 (11) | −0.0001 (12) |
C2B | 0.0416 (14) | 0.0361 (13) | 0.0336 (14) | −0.0014 (11) | −0.0016 (11) | −0.0006 (11) |
C3B | 0.0425 (14) | 0.0383 (14) | 0.0387 (15) | −0.0025 (11) | −0.0045 (11) | 0.0051 (12) |
C4B | 0.0408 (14) | 0.0335 (13) | 0.0509 (16) | −0.0013 (11) | −0.0006 (12) | −0.0004 (12) |
C5B | 0.0390 (14) | 0.0407 (14) | 0.0468 (15) | −0.0049 (11) | 0.0050 (12) | −0.0048 (12) |
C6B | 0.0461 (15) | 0.0443 (15) | 0.0369 (14) | −0.0051 (12) | 0.0045 (11) | 0.0017 (12) |
C7B | 0.0551 (16) | 0.0423 (15) | 0.0342 (15) | 0.0023 (12) | −0.0011 (12) | 0.0070 (12) |
C8B | 0.0556 (17) | 0.0441 (17) | 0.0607 (19) | 0.0019 (13) | 0.0035 (14) | −0.0001 (14) |
C9B | 0.0662 (19) | 0.0519 (17) | 0.0583 (18) | 0.0047 (14) | 0.0187 (15) | −0.0092 (14) |
C10B | 0.099 (3) | 0.136 (3) | 0.083 (3) | −0.005 (2) | 0.015 (2) | −0.064 (2) |
C11B | 0.094 (2) | 0.0434 (17) | 0.076 (2) | 0.0088 (15) | 0.0193 (18) | 0.0100 (15) |
Geometric parameters (Å, º) top
N1A—C3A | 1.360 (3) | N1B—C3B | 1.363 (3) |
N1A—H1A1 | 0.8600 | N1B—H1B1 | 0.8600 |
N1A—H1A2 | 0.8600 | N1B—H1B2 | 0.8600 |
N2A—C7A | 1.146 (3) | N2B—C7B | 1.140 (3) |
N3A—C8A | 1.141 (3) | N3B—C8B | 1.143 (3) |
C1A'—C2A' | 1.390 (3) | C1B'—C6B' | 1.390 (3) |
C1A'—C6A' | 1.385 (3) | C1B'—C2B' | 1.389 (3) |
C1A'—C1A | 1.485 (3) | C1B'—C1B | 1.484 (3) |
C2A'—C3A' | 1.386 (3) | C2B'—C3B' | 1.386 (3) |
C2A'—H2A' | 0.9300 | C2B'—H2B' | 0.9300 |
C3A'—C4A' | 1.379 (4) | C3B'—C4B' | 1.377 (4) |
C3A'—H3A' | 0.9300 | C3B'—H3B' | 0.9300 |
C4A'—C5A' | 1.373 (4) | C4B'—C5B' | 1.376 (3) |
C4A'—C11A | 1.517 (3) | C4B'—C11B | 1.513 (3) |
C5A'—C6A' | 1.381 (3) | C5B'—C6B' | 1.381 (3) |
C5A'—H5A' | 0.9300 | C5B'—H5B' | 0.9300 |
C6A'—H6A' | 0.9300 | C6B'—H6B' | 0.9300 |
C1A—C6A | 1.396 (3) | C1B—C6B | 1.388 (3) |
C1A—C2A | 1.407 (3) | C1B—C2B | 1.398 (3) |
C2A—C3A | 1.406 (3) | C2B—C3B | 1.415 (3) |
C2A—C7A | 1.429 (3) | C2B—C7B | 1.438 (3) |
C3A—C4A | 1.406 (3) | C3B—C4B | 1.400 (3) |
C4A—C5A | 1.402 (3) | C4B—C5B | 1.398 (3) |
C4A—C8A | 1.438 (3) | C4B—C8B | 1.440 (4) |
C5A—C6A | 1.376 (3) | C5B—C6B | 1.392 (3) |
C5A—C9A | 1.507 (3) | C5B—C9B | 1.500 (3) |
C6A—H6A | 0.9300 | C6B—H6B | 0.9300 |
C9A—C10A | 1.347 (4) | C9B—C10B | 1.512 (4) |
C9A—H9A1 | 0.9700 | C9B—H9B1 | 0.9700 |
C9A—H9A2 | 0.9700 | C9B—H9B2 | 0.9700 |
C10A—H10A | 0.9600 | C10B—H10D | 0.9600 |
C10A—H10B | 0.9600 | C10B—H10E | 0.9600 |
C10A—H10C | 0.9600 | C10B—H10F | 0.9600 |
C11A—H11A | 0.9600 | C11B—H11D | 0.9600 |
C11A—H11B | 0.9600 | C11B—H11E | 0.9600 |
C11A—H11C | 0.9600 | C11B—H11F | 0.9600 |
| | | |
C3A—N1A—H1A1 | 120.0 | C3B—N1B—H1B1 | 120.0 |
C3A—N1A—H1A2 | 120.0 | C3B—N1B—H1B2 | 120.0 |
H1A1—N1A—H1A2 | 120.0 | H1B1—N1B—H1B2 | 120.0 |
C2A'—C1A'—C6A' | 118.0 (2) | C6B'—C1B'—C2B' | 117.8 (2) |
C2A'—C1A'—C1A | 122.0 (2) | C6B'—C1B'—C1B | 120.9 (2) |
C6A'—C1A'—C1A | 120.0 (2) | C2B'—C1B'—C1B | 121.3 (2) |
C1A'—C2A'—C3A' | 120.2 (2) | C3B'—C2B'—C1B' | 120.8 (2) |
C1A'—C2A'—H2A' | 119.9 | C3B'—C2B'—H2B' | 119.6 |
C3A'—C2A'—H2A' | 119.9 | C1B'—C2B'—H2B' | 119.6 |
C4A'—C3A'—C2A' | 121.7 (2) | C4B'—C3B'—C2B' | 121.3 (2) |
C4A'—C3A'—H3A' | 119.2 | C4B'—C3B'—H3B' | 119.4 |
C2A'—C3A'—H3A' | 119.2 | C2B'—C3B'—H3B' | 119.4 |
C3A'—C4A'—C5A' | 117.9 (2) | C3B'—C4B'—C5B' | 117.8 (2) |
C3A'—C4A'—C11A | 120.7 (3) | C3B'—C4B'—C11B | 120.8 (2) |
C5A'—C4A'—C11A | 121.4 (3) | C5B'—C4B'—C11B | 121.3 (2) |
C6A'—C5A'—C4A' | 121.3 (2) | C4B'—C5B'—C6B' | 121.8 (2) |
C6A'—C5A'—H5A' | 119.4 | C4B'—C5B'—H5B' | 119.1 |
C4A'—C5A'—H5A' | 119.4 | C6B'—C5B'—H5B' | 119.1 |
C5A'—C6A'—C1A' | 121.1 (2) | C5B'—C6B'—C1B' | 120.5 (2) |
C5A'—C6A'—H6A' | 119.5 | C5B'—C6B'—H6B' | 119.8 |
C1A'—C6A'—H6A' | 119.5 | C1B'—C6B'—H6B' | 119.8 |
C6A—C1A—C2A | 118.2 (2) | C6B—C1B—C2B | 118.5 (2) |
C6A—C1A—C1A' | 118.9 (2) | C6B—C1B—C1B' | 120.0 (2) |
C2A—C1A—C1A' | 122.85 (19) | C2B—C1B—C1B' | 121.6 (2) |
C1A—C2A—C3A | 121.1 (2) | C1B—C2B—C3B | 121.4 (2) |
C1A—C2A—C7A | 122.55 (19) | C1B—C2B—C7B | 122.3 (2) |
C3A—C2A—C7A | 116.2 (2) | C3B—C2B—C7B | 116.2 (2) |
N1A—C3A—C4A | 120.6 (2) | C4B—C3B—N1B | 121.6 (2) |
N1A—C3A—C2A | 121.3 (2) | C4B—C3B—C2B | 117.5 (2) |
C4A—C3A—C2A | 118.2 (2) | N1B—C3B—C2B | 120.9 (2) |
C3A—C4A—C5A | 121.3 (2) | C3B—C4B—C5B | 122.1 (2) |
C3A—C4A—C8A | 118.1 (2) | C3B—C4B—C8B | 118.2 (2) |
C5A—C4A—C8A | 120.6 (2) | C5B—C4B—C8B | 119.6 (2) |
C6A—C5A—C4A | 118.7 (2) | C4B—C5B—C6B | 118.1 (2) |
C6A—C5A—C9A | 121.7 (2) | C4B—C5B—C9B | 121.4 (2) |
C4A—C5A—C9A | 119.5 (2) | C6B—C5B—C9B | 120.5 (2) |
C5A—C6A—C1A | 122.4 (2) | C1B—C6B—C5B | 122.2 (2) |
C5A—C6A—H6A | 118.8 | C1B—C6B—H6B | 118.9 |
C1A—C6A—H6A | 118.8 | C5B—C6B—H6B | 118.9 |
N2A—C7A—C2A | 174.7 (2) | N2B—C7B—C2B | 174.8 (3) |
N3A—C8A—C4A | 179.0 (3) | N3B—C8B—C4B | 178.6 (3) |
C10A—C9A—C5A | 118.8 (3) | C5B—C9B—C10B | 113.7 (2) |
C10A—C9A—H9A1 | 107.6 | C5B—C9B—H9B1 | 108.8 |
C5A—C9A—H9A1 | 107.6 | C10B—C9B—H9B1 | 108.8 |
C10A—C9A—H9A2 | 107.6 | C5B—C9B—H9B2 | 108.8 |
C5A—C9A—H9A2 | 107.6 | C10B—C9B—H9B2 | 108.8 |
H9A1—C9A—H9A2 | 107.0 | H9B1—C9B—H9B2 | 107.7 |
C9A—C10A—H10A | 109.5 | C9B—C10B—H10D | 109.5 |
C9A—C10A—H10B | 109.5 | C9B—C10B—H10E | 109.5 |
H10A—C10A—H10B | 109.5 | H10D—C10B—H10E | 109.5 |
C9A—C10A—H10C | 109.5 | C9B—C10B—H10F | 109.5 |
H10A—C10A—H10C | 109.5 | H10D—C10B—H10F | 109.5 |
H10B—C10A—H10C | 109.5 | H10E—C10B—H10F | 109.5 |
C4A'—C11A—H11A | 109.5 | C4B'—C11B—H11D | 109.5 |
C4A'—C11A—H11B | 109.5 | C4B'—C11B—H11E | 109.5 |
H11A—C11A—H11B | 109.5 | H11D—C11B—H11E | 109.5 |
C4A'—C11A—H11C | 109.5 | C4B'—C11B—H11F | 109.5 |
H11A—C11A—H11C | 109.5 | H11D—C11B—H11F | 109.5 |
H11B—C11A—H11C | 109.5 | H11E—C11B—H11F | 109.5 |
| | | |
C6A'—C1A'—C2A'—C3A' | −0.4 (3) | C6B'—C1B'—C2B'—C3B' | −2.1 (4) |
C1A—C1A'—C2A'—C3A' | −177.7 (2) | C1B—C1B'—C2B'—C3B' | 180.0 (2) |
C1A'—C2A'—C3A'—C4A' | −0.4 (3) | C1B'—C2B'—C3B'—C4B' | 0.3 (4) |
C2A'—C3A'—C4A'—C5A' | 1.0 (4) | C2B'—C3B'—C4B'—C5B' | 1.2 (4) |
C2A'—C3A'—C4A'—C11A | −179.3 (2) | C2B'—C3B'—C4B'—C11B | −178.3 (3) |
C3A'—C4A'—C5A'—C6A' | −0.8 (4) | C3B'—C4B'—C5B'—C6B' | −0.9 (4) |
C11A—C4A'—C5A'—C6A' | 179.5 (2) | C11B—C4B'—C5B'—C6B' | 178.5 (2) |
C4A'—C5A'—C6A'—C1A' | 0.0 (4) | C4B'—C5B'—C6B'—C1B' | −0.9 (4) |
C2A'—C1A'—C6A'—C5A' | 0.6 (3) | C2B'—C1B'—C6B'—C5B' | 2.3 (4) |
C1A—C1A'—C6A'—C5A' | 178.0 (2) | C1B—C1B'—C6B'—C5B' | −179.7 (2) |
C2A'—C1A'—C1A—C6A | 136.7 (2) | C6B'—C1B'—C1B—C6B | −42.9 (3) |
C6A'—C1A'—C1A—C6A | −40.5 (3) | C2B'—C1B'—C1B—C6B | 135.0 (2) |
C2A'—C1A'—C1A—C2A | −43.0 (3) | C6B'—C1B'—C1B—C2B | 136.9 (2) |
C6A'—C1A'—C1A—C2A | 139.8 (2) | C2B'—C1B'—C1B—C2B | −45.2 (3) |
C6A—C1A—C2A—C3A | 1.2 (3) | C6B—C1B—C2B—C3B | −3.4 (3) |
C1A'—C1A—C2A—C3A | −179.1 (2) | C1B'—C1B—C2B—C3B | 176.8 (2) |
C6A—C1A—C2A—C7A | 177.0 (2) | C6B—C1B—C2B—C7B | 173.7 (2) |
C1A'—C1A—C2A—C7A | −3.2 (4) | C1B'—C1B—C2B—C7B | −6.1 (3) |
C1A—C2A—C3A—N1A | 179.8 (2) | C1B—C2B—C3B—C4B | 0.2 (3) |
C7A—C2A—C3A—N1A | 3.7 (3) | C7B—C2B—C3B—C4B | −177.1 (2) |
C1A—C2A—C3A—C4A | −1.8 (3) | C1B—C2B—C3B—N1B | −178.3 (2) |
C7A—C2A—C3A—C4A | −177.9 (2) | C7B—C2B—C3B—N1B | 4.4 (3) |
N1A—C3A—C4A—C5A | 179.5 (2) | N1B—C3B—C4B—C5B | −179.1 (2) |
C2A—C3A—C4A—C5A | 1.1 (4) | C2B—C3B—C4B—C5B | 2.5 (3) |
N1A—C3A—C4A—C8A | −1.3 (4) | N1B—C3B—C4B—C8B | 2.8 (3) |
C2A—C3A—C4A—C8A | −179.7 (2) | C2B—C3B—C4B—C8B | −175.7 (2) |
C3A—C4A—C5A—C6A | 0.1 (4) | C3B—C4B—C5B—C6B | −1.8 (3) |
C8A—C4A—C5A—C6A | −179.0 (2) | C8B—C4B—C5B—C6B | 176.4 (2) |
C3A—C4A—C5A—C9A | −178.5 (3) | C3B—C4B—C5B—C9B | 178.5 (2) |
C8A—C4A—C5A—C9A | 2.4 (4) | C8B—C4B—C5B—C9B | −3.3 (3) |
C4A—C5A—C6A—C1A | −0.8 (4) | C2B—C1B—C6B—C5B | 4.2 (3) |
C9A—C5A—C6A—C1A | 177.8 (3) | C1B'—C1B—C6B—C5B | −176.0 (2) |
C2A—C1A—C6A—C5A | 0.1 (4) | C4B—C5B—C6B—C1B | −1.7 (3) |
C1A'—C1A—C6A—C5A | −179.6 (2) | C9B—C5B—C6B—C1B | 178.0 (2) |
C1A—C2A—C7A—N2A | −173 (3) | C1B—C2B—C7B—N2B | −166 (3) |
C3A—C2A—C7A—N2A | 3 (3) | C3B—C2B—C7B—N2B | 12 (3) |
C3A—C4A—C8A—N3A | 46 (17) | C3B—C4B—C8B—N3B | 28 (12) |
C5A—C4A—C8A—N3A | −135 (17) | C5B—C4B—C8B—N3B | −150 (12) |
C6A—C5A—C9A—C10A | 33.2 (6) | C4B—C5B—C9B—C10B | −83.7 (3) |
C4A—C5A—C9A—C10A | −148.2 (4) | C6B—C5B—C9B—C10B | 96.6 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1B—H1B1···N3A | 0.86 | 2.37 | 3.166 (3) | 154 |
N1A—H1A1···N3Ai | 0.86 | 2.52 | 3.228 (3) | 140 |
N1A—H1A2···N1Bi | 0.86 | 2.58 | 3.157 (3) | 126 |
Symmetry code: (i) −x, −y+1, −z+1. |
(II) 3-amino-2,4 dicyano-5-ethyl-4'- N,
N diethyl amino Biphenyl
top
Crystal data top
C20H22N4 | F(000) = 680 |
Mr = 318.42 | Dx = 1.156 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 10.8918 (2) Å | Cell parameters from 5488 reflections |
b = 10.3458 (2) Å | θ = 1.8–28.6° |
c = 16.5707 (2) Å | µ = 0.07 mm−1 |
β = 101.496 (1)° | T = 293 K |
V = 1829.80 (5) Å3 | Rectangular, pale yellow |
Z = 4 | 0.40 × 0.26 × 0.14 mm |
Data collection top
Siemens SMART CCD area detector diffractometer | 4478 independent reflections |
Radiation source: fine-focus sealed tube | 2122 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.079 |
Detector resolution: 8.33 pixels mm-1 | θmax = 28.4°, θmin = 1.9° |
ω scans | h = −14→12 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −7→13 |
Tmin = 0.972, Tmax = 0.990 | l = −21→22 |
12556 measured reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.061 | H-atom parameters constrained |
wR(F2) = 0.145 | w = 1/[σ2(Fo2) + (0.043P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max < 0.001 |
4478 reflections | Δρmax = 0.23 e Å−3 |
221 parameters | Δρmin = −0.23 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0115 (15) |
Crystal data top
C20H22N4 | V = 1829.80 (5) Å3 |
Mr = 318.42 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.8918 (2) Å | µ = 0.07 mm−1 |
b = 10.3458 (2) Å | T = 293 K |
c = 16.5707 (2) Å | 0.40 × 0.26 × 0.14 mm |
β = 101.496 (1)° | |
Data collection top
Siemens SMART CCD area detector diffractometer | 4478 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 2122 reflections with I > 2σ(I) |
Tmin = 0.972, Tmax = 0.990 | Rint = 0.079 |
12556 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.061 | 0 restraints |
wR(F2) = 0.145 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.23 e Å−3 |
4478 reflections | Δρmin = −0.23 e Å−3 |
221 parameters | |
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 | |
N1 | 0.96593 (15) | 0.08450 (16) | 0.20255 (10) | 0.0481 (5) | |
H1A | 1.0043 | 0.1505 | 0.2272 | 0.058* | |
H1B | 0.9603 | 0.0145 | 0.2296 | 0.058* | |
N2 | 0.86240 (19) | −0.22716 (19) | 0.16255 (12) | 0.0619 (6) | |
N3 | 1.02809 (18) | 0.40045 (18) | 0.15633 (11) | 0.0540 (5) | |
N4 | 0.51316 (17) | −0.41009 (19) | −0.19047 (11) | 0.0582 (5) | |
C1' | 0.72722 (17) | −0.11851 (19) | −0.05016 (11) | 0.0370 (5) | |
C2' | 0.63425 (19) | −0.1841 (2) | −0.02130 (12) | 0.0489 (6) | |
H2' | 0.6193 | −0.1637 | 0.0305 | 0.059* | |
C3' | 0.5630 (2) | −0.2786 (2) | −0.06669 (13) | 0.0498 (6) | |
H3' | 0.5003 | −0.3193 | −0.0453 | 0.060* | |
C4' | 0.58311 (18) | −0.3149 (2) | −0.14436 (12) | 0.0414 (5) | |
C5' | 0.67786 (17) | −0.25020 (19) | −0.17304 (11) | 0.0384 (5) | |
H5' | 0.6955 | −0.2727 | −0.2239 | 0.046* | |
C6' | 0.74603 (17) | −0.15358 (19) | −0.12764 (12) | 0.0373 (5) | |
H6' | 0.8067 | −0.1104 | −0.1496 | 0.045* | |
C1 | 0.79815 (17) | −0.00936 (19) | −0.00555 (11) | 0.0380 (5) | |
C2 | 0.85218 (17) | −0.01611 (18) | 0.07884 (11) | 0.0352 (5) | |
C3 | 0.91466 (17) | 0.09071 (18) | 0.12149 (11) | 0.0334 (5) | |
C4 | 0.92264 (17) | 0.20465 (18) | 0.07565 (11) | 0.0342 (5) | |
C5 | 0.87361 (18) | 0.2107 (2) | −0.00893 (12) | 0.0394 (5) | |
C6 | 0.81276 (19) | 0.1047 (2) | −0.04730 (12) | 0.0445 (5) | |
H6 | 0.7799 | 0.1092 | −0.1035 | 0.053* | |
C7 | 0.85451 (19) | −0.1355 (2) | 0.12362 (12) | 0.0418 (5) | |
C8 | 0.98159 (18) | 0.3146 (2) | 0.11921 (12) | 0.0391 (5) | |
C9 | 0.8801 (2) | 0.3355 (2) | −0.05525 (13) | 0.0503 (6) | |
H9A | 0.8740 | 0.3162 | −0.1132 | 0.060* | |
H9B | 0.9607 | 0.3760 | −0.0352 | 0.060* | |
C10 | 0.5292 (2) | −0.4405 (3) | −0.27370 (15) | 0.0678 (8) | |
H10A | 0.5497 | −0.3618 | −0.3000 | 0.081* | |
H10B | 0.4505 | −0.4729 | −0.3053 | 0.081* | |
C11 | 0.6291 (3) | −0.5381 (3) | −0.27568 (18) | 0.0918 (10) | |
H11A | 0.7073 | −0.5070 | −0.2444 | 0.138* | |
H11B | 0.6371 | −0.5525 | −0.3316 | 0.138* | |
H11C | 0.6074 | −0.6178 | −0.2523 | 0.138* | |
C12 | 0.4215 (2) | −0.4881 (3) | −0.15801 (16) | 0.0769 (9) | |
H12A | 0.4487 | −0.4969 | −0.0989 | 0.092* | |
H12B | 0.4180 | −0.5740 | −0.1819 | 0.092* | |
C13 | 0.2958 (3) | −0.4305 (3) | −0.17613 (19) | 0.1041 (11) | |
H13A | 0.2983 | −0.3467 | −0.1509 | 0.156* | |
H13B | 0.2386 | −0.4850 | −0.1547 | 0.156* | |
H13C | 0.2684 | −0.4219 | −0.2346 | 0.156* | |
C14 | 0.7786 (3) | 0.4282 (3) | −0.04611 (19) | 0.0931 (10) | |
H14A | 0.6985 | 0.3909 | −0.0692 | 0.140* | |
H14B | 0.7890 | 0.5071 | −0.0745 | 0.140* | |
H14C | 0.7829 | 0.4462 | 0.0112 | 0.140* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0723 (12) | 0.0351 (10) | 0.0300 (9) | −0.0146 (9) | −0.0060 (8) | 0.0034 (7) |
N2 | 0.0935 (15) | 0.0351 (12) | 0.0516 (12) | −0.0044 (11) | 0.0009 (10) | 0.0074 (10) |
N3 | 0.0763 (13) | 0.0345 (11) | 0.0491 (12) | −0.0095 (10) | 0.0073 (10) | −0.0062 (9) |
N4 | 0.0584 (11) | 0.0613 (13) | 0.0565 (13) | −0.0270 (11) | 0.0155 (10) | −0.0232 (10) |
C1' | 0.0418 (11) | 0.0341 (12) | 0.0323 (11) | −0.0041 (10) | 0.0010 (9) | 0.0014 (9) |
C2' | 0.0587 (13) | 0.0536 (15) | 0.0345 (12) | −0.0125 (12) | 0.0099 (10) | −0.0083 (10) |
C3' | 0.0534 (12) | 0.0523 (15) | 0.0451 (13) | −0.0203 (12) | 0.0131 (10) | −0.0064 (11) |
C4' | 0.0401 (11) | 0.0383 (13) | 0.0442 (13) | −0.0047 (10) | 0.0046 (10) | −0.0056 (10) |
C5' | 0.0424 (11) | 0.0361 (13) | 0.0352 (11) | 0.0024 (10) | 0.0044 (9) | −0.0032 (9) |
C6' | 0.0378 (10) | 0.0330 (12) | 0.0404 (12) | −0.0017 (9) | 0.0056 (9) | 0.0035 (9) |
C1 | 0.0442 (11) | 0.0313 (12) | 0.0360 (12) | −0.0044 (10) | 0.0020 (9) | −0.0010 (9) |
C2 | 0.0429 (10) | 0.0263 (11) | 0.0352 (11) | −0.0015 (9) | 0.0053 (9) | 0.0023 (9) |
C3 | 0.0378 (10) | 0.0280 (11) | 0.0331 (11) | −0.0015 (9) | 0.0038 (8) | −0.0002 (9) |
C4 | 0.0419 (11) | 0.0253 (11) | 0.0342 (11) | −0.0044 (9) | 0.0046 (9) | −0.0005 (8) |
C5 | 0.0460 (11) | 0.0330 (12) | 0.0373 (12) | −0.0009 (10) | 0.0037 (9) | 0.0020 (9) |
C6 | 0.0597 (13) | 0.0378 (13) | 0.0314 (11) | −0.0057 (11) | −0.0022 (10) | 0.0033 (9) |
C7 | 0.0540 (13) | 0.0322 (13) | 0.0359 (12) | −0.0021 (11) | 0.0012 (10) | −0.0023 (10) |
C8 | 0.0473 (12) | 0.0308 (12) | 0.0380 (12) | 0.0002 (10) | 0.0058 (9) | 0.0044 (10) |
C9 | 0.0713 (15) | 0.0351 (13) | 0.0418 (13) | −0.0010 (12) | 0.0043 (11) | 0.0104 (10) |
C10 | 0.0685 (16) | 0.073 (2) | 0.0603 (17) | −0.0258 (15) | 0.0092 (13) | −0.0262 (14) |
C11 | 0.097 (2) | 0.078 (2) | 0.108 (2) | −0.0193 (19) | 0.0389 (19) | −0.0321 (18) |
C12 | 0.0730 (18) | 0.079 (2) | 0.081 (2) | −0.0307 (16) | 0.0205 (15) | −0.0359 (15) |
C13 | 0.082 (2) | 0.138 (3) | 0.096 (2) | −0.018 (2) | 0.0248 (18) | −0.035 (2) |
C14 | 0.112 (2) | 0.065 (2) | 0.106 (2) | 0.0348 (19) | 0.0313 (19) | 0.0401 (17) |
Geometric parameters (Å, º) top
N1—C3 | 1.349 (2) | C4—C5 | 1.398 (2) |
N1—H1A | 0.8600 | C4—C8 | 1.429 (3) |
N1—H1B | 0.8600 | C5—C6 | 1.370 (3) |
N2—C7 | 1.141 (2) | C5—C9 | 1.511 (3) |
N3—C8 | 1.140 (2) | C6—H6 | 0.9300 |
N4—C4' | 1.379 (2) | C9—C14 | 1.494 (3) |
N4—C12 | 1.467 (3) | C9—H9A | 0.9700 |
N4—C10 | 1.459 (3) | C9—H9B | 0.9700 |
C1'—C6' | 1.388 (3) | C10—C11 | 1.490 (4) |
C1'—C2' | 1.381 (3) | C10—H10A | 0.9700 |
C1'—C1 | 1.480 (3) | C10—H10B | 0.9700 |
C2'—C3' | 1.375 (3) | C11—H11A | 0.9600 |
C2'—H2' | 0.9300 | C11—H11B | 0.9600 |
C3'—C4' | 1.399 (3) | C11—H11C | 0.9600 |
C3'—H3' | 0.9300 | C12—C13 | 1.469 (4) |
C4'—C5' | 1.391 (3) | C12—H12A | 0.9700 |
C5'—C6' | 1.376 (3) | C12—H12B | 0.9700 |
C5'—H5' | 0.9300 | C13—H13A | 0.9600 |
C6'—H6' | 0.9300 | C13—H13B | 0.9600 |
C1—C6 | 1.393 (3) | C13—H13C | 0.9600 |
C1—C2 | 1.407 (2) | C14—H14A | 0.9600 |
C2—C3 | 1.412 (3) | C14—H14B | 0.9600 |
C2—C7 | 1.438 (3) | C14—H14C | 0.9600 |
C3—C4 | 1.414 (2) | | |
| | | |
C3—N1—H1A | 120.0 | C5—C6—H6 | 118.7 |
C3—N1—H1B | 120.0 | C1—C6—H6 | 118.7 |
H1A—N1—H1B | 120.0 | N2—C7—C2 | 175.8 (2) |
C4'—N4—C12 | 122.08 (18) | N3—C8—C4 | 177.7 (2) |
C4'—N4—C10 | 121.39 (18) | C5—C9—C14 | 112.74 (19) |
C12—N4—C10 | 116.51 (18) | C5—C9—H9A | 109.0 |
C6'—C1'—C2' | 116.45 (18) | C14—C9—H9A | 109.0 |
C6'—C1'—C1 | 120.19 (18) | C5—C9—H9B | 109.0 |
C2'—C1'—C1 | 123.20 (18) | C14—C9—H9B | 109.0 |
C3'—C2'—C1' | 122.2 (2) | H9A—C9—H9B | 107.8 |
C3'—C2'—H2' | 118.9 | N4—C10—C11 | 113.1 (2) |
C1'—C2'—H2' | 118.9 | N4—C10—H10A | 109.0 |
C2'—C3'—C4' | 121.3 (2) | C11—C10—H10A | 109.0 |
C2'—C3'—H3' | 119.4 | N4—C10—H10B | 109.0 |
C4'—C3'—H3' | 119.4 | C11—C10—H10B | 109.0 |
N4—C4'—C5' | 121.32 (18) | H10A—C10—H10B | 107.8 |
N4—C4'—C3' | 122.05 (19) | C10—C11—H11A | 109.5 |
C5'—C4'—C3' | 116.63 (18) | C10—C11—H11B | 109.5 |
C4'—C5'—C6' | 121.26 (18) | H11A—C11—H11B | 109.5 |
C4'—C5'—H5' | 119.4 | C10—C11—H11C | 109.5 |
C6'—C5'—H5' | 119.4 | H11A—C11—H11C | 109.5 |
C1'—C6'—C5' | 122.17 (18) | H11B—C11—H11C | 109.5 |
C1'—C6'—H6' | 118.9 | N4—C12—C13 | 112.1 (3) |
C5'—C6'—H6' | 118.9 | N4—C12—H12A | 109.2 |
C6—C1—C2 | 117.98 (17) | C13—C12—H12A | 109.2 |
C6—C1—C1' | 119.89 (17) | N4—C12—H12B | 109.2 |
C2—C1—C1' | 122.13 (17) | C13—C12—H12B | 109.2 |
C1—C2—C3 | 121.56 (17) | H12A—C12—H12B | 107.9 |
C1—C2—C7 | 121.10 (17) | C12—C13—H13A | 109.5 |
C3—C2—C7 | 117.17 (17) | C12—C13—H13B | 109.5 |
N1—C3—C4 | 121.11 (17) | H13A—C13—H13B | 109.5 |
N1—C3—C2 | 121.58 (17) | C12—C13—H13C | 109.5 |
C4—C3—C2 | 117.30 (17) | H13A—C13—H13C | 109.5 |
C5—C4—C3 | 121.57 (17) | H13B—C13—H13C | 109.5 |
C5—C4—C8 | 120.94 (18) | C9—C14—H14A | 109.5 |
C3—C4—C8 | 117.48 (17) | C9—C14—H14B | 109.5 |
C6—C5—C4 | 118.82 (18) | H14A—C14—H14B | 109.5 |
C6—C5—C9 | 121.02 (18) | C9—C14—H14C | 109.5 |
C4—C5—C9 | 120.01 (18) | H14A—C14—H14C | 109.5 |
C5—C6—C1 | 122.68 (18) | H14B—C14—H14C | 109.5 |
| | | |
C6'—C1'—C2'—C3' | −0.4 (3) | C1—C2—C3—C4 | −1.0 (3) |
C1—C1'—C2'—C3' | 174.9 (2) | C7—C2—C3—C4 | 174.24 (17) |
C1'—C2'—C3'—C4' | 1.2 (3) | N1—C3—C4—C5 | 177.77 (17) |
C12—N4—C4'—C5' | 173.8 (2) | C2—C3—C4—C5 | −1.6 (3) |
C10—N4—C4'—C5' | −4.6 (3) | N1—C3—C4—C8 | −3.0 (3) |
C12—N4—C4'—C3' | −6.0 (3) | C2—C3—C4—C8 | 177.67 (17) |
C10—N4—C4'—C3' | 175.6 (2) | C3—C4—C5—C6 | 2.3 (3) |
C2'—C3'—C4'—N4 | 179.5 (2) | C8—C4—C5—C6 | −176.98 (18) |
C2'—C3'—C4'—C5' | −0.3 (3) | C3—C4—C5—C9 | 177.95 (18) |
N4—C4'—C5'—C6' | 178.78 (19) | C8—C4—C5—C9 | −1.3 (3) |
C3'—C4'—C5'—C6' | −1.4 (3) | C4—C5—C6—C1 | −0.3 (3) |
C2'—C1'—C6'—C5' | −1.3 (3) | C9—C5—C6—C1 | −175.95 (19) |
C1—C1'—C6'—C5' | −176.76 (17) | C2—C1—C6—C5 | −2.2 (3) |
C4'—C5'—C6'—C1' | 2.2 (3) | C1'—C1—C6—C5 | 177.71 (19) |
C6'—C1'—C1—C6 | 43.8 (3) | C1—C2—C7—N2 | 157 (3) |
C2'—C1'—C1—C6 | −131.4 (2) | C3—C2—C7—N2 | −18 (3) |
C6'—C1'—C1—C2 | −136.3 (2) | C5—C4—C8—N3 | 161 (5) |
C2'—C1'—C1—C2 | 48.5 (3) | C3—C4—C8—N3 | −18 (6) |
C6—C1—C2—C3 | 2.8 (3) | C6—C5—C9—C14 | 94.5 (3) |
C1'—C1—C2—C3 | −177.06 (18) | C4—C5—C9—C14 | −81.1 (3) |
C6—C1—C2—C7 | −172.22 (19) | C4'—N4—C10—C11 | 87.6 (3) |
C1'—C1—C2—C7 | 7.9 (3) | C12—N4—C10—C11 | −90.9 (3) |
C1—C2—C3—N1 | 179.64 (18) | C4'—N4—C12—C13 | 90.9 (3) |
C7—C2—C3—N1 | −5.1 (3) | C10—N4—C12—C13 | −90.6 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···N2i | 0.86 | 2.45 | 3.259 (2) | 158 |
N1—H1B···N3ii | 0.86 | 2.21 | 3.006 (2) | 154 |
Symmetry codes: (i) −x+2, y+1/2, −z+1/2; (ii) −x+2, y−1/2, −z+1/2. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C17H15N3 | C20H22N4 |
Mr | 261.32 | 318.42 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 7.8579 (1), 23.7627 (5), 15.3423 (2) | 10.8918 (2), 10.3458 (2), 16.5707 (2) |
β (°) | 94.765 (1) | 101.496 (1) |
V (Å3) | 2854.89 (8) | 1829.80 (5) |
Z | 8 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.07 | 0.07 |
Crystal size (mm) | 0.30 × 0.24 × 0.14 | 0.40 × 0.26 × 0.14 |
|
Data collection |
Diffractometer | Siemens SMART CCD area detector diffractometer | Siemens SMART CCD area detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.978, 0.990 | 0.972, 0.990 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19861, 6961, 3077 | 12556, 4478, 2122 |
Rint | 0.090 | 0.079 |
(sin θ/λ)max (Å−1) | 0.667 | 0.668 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.067, 0.173, 0.97 | 0.061, 0.145, 1.00 |
No. of reflections | 6961 | 4478 |
No. of parameters | 365 | 221 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.32, −0.30 | 0.23, −0.23 |
Selected geometric parameters (Å, º) for (I) topN1A—C3A | 1.360 (3) | N1B—C3B | 1.363 (3) |
N2A—C7A | 1.146 (3) | N2B—C7B | 1.140 (3) |
N3A—C8A | 1.141 (3) | N3B—C8B | 1.143 (3) |
C1A'—C1A | 1.485 (3) | C1B'—C1B | 1.484 (3) |
| | | |
N2A—C7A—C2A | 174.7 (2) | N2B—C7B—C2B | 174.8 (3) |
N3A—C8A—C4A | 179.0 (3) | N3B—C8B—C4B | 178.6 (3) |
| | | |
C2A'—C1A'—C1A—C6A | 136.7 (2) | C6B'—C1B'—C1B—C6B | −42.9 (3) |
C6A'—C1A'—C1A—C6A | −40.5 (3) | C2B'—C1B'—C1B—C6B | 135.0 (2) |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1B—H1B1···N3A | 0.86 | 2.37 | 3.166 (3) | 154 |
N1A—H1A1···N3Ai | 0.86 | 2.52 | 3.228 (3) | 140 |
N1A—H1A2···N1Bi | 0.86 | 2.58 | 3.157 (3) | 126 |
Symmetry code: (i) −x, −y+1, −z+1. |
Selected geometric parameters (Å, º) for (II) topN1—C3 | 1.349 (2) | N4—C12 | 1.467 (3) |
N2—C7 | 1.141 (2) | N4—C10 | 1.459 (3) |
N3—C8 | 1.140 (2) | C1'—C1 | 1.480 (3) |
N4—C4' | 1.379 (2) | | |
| | | |
C4'—N4—C12 | 122.08 (18) | N2—C7—C2 | 175.8 (2) |
C4'—N4—C10 | 121.39 (18) | N3—C8—C4 | 177.7 (2) |
C12—N4—C10 | 116.51 (18) | | |
| | | |
C6'—C1'—C1—C6 | 43.8 (3) | C2'—C1'—C1—C6 | −131.4 (2) |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···N2i | 0.86 | 2.45 | 3.259 (2) | 158 |
N1—H1B···N3ii | 0.86 | 2.21 | 3.006 (2) | 154 |
Symmetry codes: (i) −x+2, y+1/2, −z+1/2; (ii) −x+2, y−1/2, −z+1/2. |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
If you have already registered and are using a computer listed in your registration details, please email
support@iucr.org for assistance.
Biphenyl derivatives have been extensively studied in the past because of the difference found in the torsion angle between aromatic rings which determines the photophysical, biological and laser activities (Shukla et al., 1985; Nieger et al., 1998). The laser activity of the biphenyl compound can be enhanced by bulkier substitutions on the phenyl rings which cause deviations from coplanarity. The π electron delocalization along the biphenyl unit will be the maximum in the coplanar arrangement of the biphenyls (Nieger et al., 1998). Apart from the photophysical properties, biphenyl compounds are of great importance due to the activity of these molecules on the central nervous system (Reboul et al., 1993). Certain fluoro-substituted biphenyl derivatives have greater affinities to certain receptor proteins (Mckinney & Singh, 1988). The present study is a part of a series of investigations on the crystal structures of biphenyl derivatives. \sch
Compound (I) contains two molecules in the asymmetric unit, designated (Ia) and (Ib). Figure 1 shows the displacement ellipsoids and atom labelling scheme for (Ia) and (Ib). Compound (II) contains one molecule per asymmetric unit, and Figure 2 shows the displacement ellipsoids and atom labelling for (II). The dihedral angles between phenyl rings A and B are 44.1 (1) and 46.7 (1)°, respectively. In (II), the dihedral angle between the phenyl rings is 42.1 (1)°. The twisting of these rings can also be described using the following inter-ring torsion angles: C6A—C1A—C1A'-C6A' = -40.5 (3)° and C6B—C1B—C1B'-C6B' = -42.9 (3)° for (I); C6—C1—C1'-C6' = 43.8 (3)° for (II). The values of the torsion angles C2'-C1A'-C1A—C6A [136.7 (2)°], C2B'-C1B'-C1B—C6B [135.0 (2)°] in (I) and C2'-C1'-C1—C6 [-131.4 (2)°] in (II) indicate that the conformation of both molecules (Ia) and (Ib) is +anticlinal and that of (II) is -anticlinal. The carbon atom C7 significantly deviates from the mean plane of ring A by -0.050 (2) Å in (Ia) and -0.105 (3) Å in (Ib) and 0.158 (2) Å in compound (II). The bond lengths and bond angles for compounds (I) and (II) are listed in Tables 1 and 3, respectively. The triple bond distances N3—C8 and C7—N2 agree with the literature values [1.138 (7) Å] (Allen et al., 1986). The bond angles around C8 and C7 satisfy the triple-bond character of C8—N3 and C7—N2 (sp hybridization). The ring-ring bond distances which connect the two phenyl rings A and B are comparable with the reported values [1.487 (7) Å] (Allen et al., 1986). The ethyl substituent on the A ring in (I) and (II) are twisted out of the plane of the ring as evidenced by the C6—C5—C9—C10 torsion angle. This angle has values of 33.2 (6)° and 96.6 (3)° for (Ia) and (Ib), respectively, and 94.5 (3)° for (II). The diethyl substituent in (II) attached to the phenyl ring B is completely staggered. The sum of the angles around N4 in compound (II) is 360° and is an indicative of the sp2 hybridization.
The inter-ring bond distance in unsubstituted biphenyl is found to be 1.507 Å (Trotter, 1961). The inter-ring bond distances [C1A—C1A', C1B—C1B' in (I) and C1—C1' in (II)] are 1.485 (3), 1.484 (3) and 1.480 (3) Å, respectively. These values agree well with those of related structures found in polychlorinated biphenyl [1.485 (6) Å; Mackinney & Singh, 1981], 2-Fluorobiphenyl [1.483 (4) Å; Rajnikant et al., 1995] and the theoretically calculated value of 1.488 Å between two sp2-hybridized carbon atoms (Dewar & Schmeizing, 1968).
Apart from the normal van der Waals interaction, the packing of the crystal is stabilized by intermolecular N—H···N hydrogen bonds. The hydrogen-bonding geometries for (I) and (II) are given in Tables 2 and 4, respectively. In both structures, the nitrogen atom of the cyano group participates in the hydrogen-bonded interaction as an acceptor atom. All N—H···N interactions have distances less than the sum of their van der Waals radii (Bondi, 1964). The molecular packing arrangement in compound (I) down the a axis is characterized by an intermolecular N—H···N hydrogen bond between (Ia) and (Ib), with N1B···N3A distance of 3.166 (3) Å, and two N—H···N intermolecular interactions with the molecules related by inversion, having donar-acceptor distances of 3.228 (3) and 3.157 (3) Å. It is a layered structure, with the layers parallel to bc plane. In structure (II), the crystal packing is stabilized by two intermolecular hydrogen bonds.: N1···N2i = 3.259 (2) Å and N1···N3ii = 3.006 (2) Å·[Symmetry codes: (i) 2 - x, 1/2 + y, 1/2 - z; (ii) 2 - x, -1/2 + y, 1/2 - z.] Each molecule mutually donates and accepts two protons with symmetry-related molecules.