Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802001745/ci6096sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802001745/ci6096Isup2.hkl |
CCDC reference: 182596
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.005 Å
- R factor = 0.068
- wR factor = 0.185
- Data-to-parameter ratio = 16.7
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
RINTA_01 Alert C The value of Rint is greater than 0.10 Rint given 0.124 PLAT_371 Alert C Long C(sp2)-C(sp1) Bond C(2) - C(7) = 1.43 Ang. PLAT_371 Alert C Long C(sp2)-C(sp1) Bond C(4) - C(8) = 1.44 Ang. PLAT_420 Alert C D-H Without Acceptor N(1) - H(1B) ?
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
4 Alert Level C = Please check
The title compound was synthesized according to the reaction described by Raghukumar et al., (2001). The crystals of the monoclinic form were grown at room temperature by slow evaporation of a ethyl acetate and hexane (1:1) solution of the compound. In our earlier work, the crystals of the orthorhombic form were grown from a mixture of ethyl acetate and methanol.
Owing to the poor quality of the crystal, the higher angle relections were very weak and only 32% of the reflections were found to be observed with I>2σ(I). This resulted in a high Rint value. The 2θ maximum was limited to 53° because of the large fraction of weak data at higher angles. All H atoms were fixed geometrically and allowed to ride on the corresponding non-H atoms.
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 WinGX (Farrugia, 1999).
Fig. 1. The structure of (I) showing 50% probability displacement ellipsoids and the atom-numbering scheme. |
C19H20N4 | F(000) = 648 |
Mr = 304.39 | Dx = 1.197 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 9.2925 (4) Å | Cell parameters from 3225 reflections |
b = 10.8655 (3) Å | θ = 2.2–28.3° |
c = 16.7229 (5) Å | µ = 0.07 mm−1 |
β = 90.367 (2)° | T = 293 K |
V = 1688.44 (10) Å3 | Slab, yellow |
Z = 4 | 0.26 × 0.14 × 0.10 mm |
Siemens SMART CCD area detector diffractometer | 3496 independent reflections |
Radiation source: fine-focus sealed tube | 1313 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.124 |
Detector resolution: 8.33 pixels mm-1 | θmax = 26.5°, θmin = 2.2° |
ω scans | h = −11→11 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −12→13 |
Tmin = 0.978, Tmax = 0.990 | l = −20→20 |
10442 measured reflections |
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)] = 0.068 | Riding |
wR(F2) = 0.185 | w = 1/[σ2(Fo2) + (0.0674P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.92 | (Δ/σ)max < 0.001 |
3496 reflections | Δρmax = 0.19 e Å−3 |
209 parameters | Δρmin = −0.18 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.010 (2) |
C19H20N4 | V = 1688.44 (10) Å3 |
Mr = 304.39 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.2925 (4) Å | µ = 0.07 mm−1 |
b = 10.8655 (3) Å | T = 293 K |
c = 16.7229 (5) Å | 0.26 × 0.14 × 0.10 mm |
β = 90.367 (2)° |
Siemens SMART CCD area detector diffractometer | 3496 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 1313 reflections with I > 2σ(I) |
Tmin = 0.978, Tmax = 0.990 | Rint = 0.124 |
10442 measured reflections |
R[F2 > 2σ(F2)] = 0.068 | 0 restraints |
wR(F2) = 0.185 | Riding |
S = 0.92 | Δρmax = 0.19 e Å−3 |
3496 reflections | Δρmin = −0.18 e Å−3 |
209 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
N1 | 1.2550 (3) | 0.1435 (2) | −0.04938 (17) | 0.0627 (10) | |
H1A | 1.3355 | 0.1044 | −0.0492 | 0.075* | |
H1B | 1.2323 | 0.1895 | −0.0894 | 0.075* | |
N2 | 0.9802 (4) | 0.3249 (3) | −0.1129 (2) | 0.0769 (11) | |
N3 | 1.4420 (4) | −0.0533 (3) | 0.0832 (2) | 0.0753 (11) | |
N4 | 0.4297 (3) | 0.4792 (3) | 0.10641 (17) | 0.0527 (8) | |
C1' | 0.8075 (3) | 0.2666 (3) | 0.08398 (19) | 0.0429 (9) | |
C2' | 0.8091 (4) | 0.3932 (3) | 0.07514 (19) | 0.0491 (9) | |
H2' | 0.8953 | 0.4320 | 0.0629 | 0.059* | |
C3' | 0.6867 (4) | 0.4634 (3) | 0.08397 (19) | 0.0493 (10) | |
H3' | 0.6927 | 0.5485 | 0.0788 | 0.059* | |
C4' | 0.5531 (3) | 0.4092 (3) | 0.10059 (19) | 0.0432 (9) | |
C5' | 0.5515 (3) | 0.2820 (3) | 0.1093 (2) | 0.0485 (9) | |
H5' | 0.4652 | 0.2423 | 0.1203 | 0.058* | |
C6' | 0.6752 (3) | 0.2137 (3) | 0.10183 (19) | 0.0487 (9) | |
H6' | 0.6702 | 0.1289 | 0.1090 | 0.058* | |
C1 | 0.9396 (3) | 0.1910 (3) | 0.0799 (2) | 0.0422 (9) | |
C2 | 1.0330 (3) | 0.1983 (3) | 0.0147 (2) | 0.0417 (9) | |
C3 | 1.1640 (4) | 0.1325 (3) | 0.0133 (2) | 0.0441 (9) | |
C4 | 1.1961 (3) | 0.0586 (3) | 0.0799 (2) | 0.0460 (9) | |
C5 | 1.1036 (4) | 0.0476 (3) | 0.1446 (2) | 0.0482 (9) | |
C6 | 0.9761 (4) | 0.1141 (3) | 0.1434 (2) | 0.0527 (10) | |
H6 | 0.9132 | 0.1070 | 0.1862 | 0.063* | |
C7 | 0.9996 (3) | 0.2700 (3) | −0.0548 (2) | 0.0519 (10) | |
C8 | 1.3319 (4) | −0.0049 (3) | 0.0824 (2) | 0.0535 (10) | |
C9 | 1.1408 (4) | −0.0327 (3) | 0.2149 (2) | 0.0688 (12) | |
H9A | 1.0646 | −0.0291 | 0.2534 | 0.103* | |
H9B | 1.2287 | −0.0042 | 0.2391 | 0.103* | |
H9C | 1.1529 | −0.1161 | 0.1972 | 0.103* | |
C10 | 0.2906 (4) | 0.4206 (3) | 0.1182 (3) | 0.0723 (12) | |
H10A | 0.2878 | 0.3455 | 0.0869 | 0.087* | |
H10B | 0.2164 | 0.4748 | 0.0973 | 0.087* | |
C11 | 0.2543 (5) | 0.3893 (5) | 0.2031 (3) | 0.1119 (18) | |
H11A | 0.3252 | 0.3335 | 0.2242 | 0.168* | |
H11B | 0.1612 | 0.3512 | 0.2048 | 0.168* | |
H11C | 0.2535 | 0.4631 | 0.2347 | 0.168* | |
C12 | 0.4342 (4) | 0.6127 (3) | 0.1089 (2) | 0.0602 (11) | |
H12A | 0.3396 | 0.6443 | 0.0952 | 0.072* | |
H12B | 0.5008 | 0.6416 | 0.0687 | 0.072* | |
C13 | 0.4785 (6) | 0.6639 (4) | 0.1883 (2) | 0.1050 (18) | |
H13A | 0.4118 | 0.6376 | 0.2284 | 0.157* | |
H13B | 0.4791 | 0.7522 | 0.1857 | 0.157* | |
H13C | 0.5732 | 0.6349 | 0.2018 | 0.157* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0456 (19) | 0.072 (2) | 0.070 (2) | 0.0191 (16) | 0.0188 (17) | 0.0173 (16) |
N2 | 0.075 (3) | 0.082 (3) | 0.074 (3) | 0.022 (2) | 0.003 (2) | 0.018 (2) |
N3 | 0.051 (2) | 0.077 (3) | 0.099 (3) | 0.0224 (19) | 0.013 (2) | 0.0235 (19) |
N4 | 0.0386 (18) | 0.0498 (19) | 0.070 (2) | 0.0088 (16) | 0.0001 (15) | −0.0035 (15) |
C1' | 0.035 (2) | 0.047 (2) | 0.047 (2) | 0.0033 (18) | 0.0029 (16) | −0.0006 (17) |
C2' | 0.040 (2) | 0.056 (2) | 0.052 (2) | 0.0020 (19) | 0.0009 (18) | −0.0031 (18) |
C3' | 0.046 (2) | 0.045 (2) | 0.057 (2) | 0.0056 (19) | −0.0013 (19) | −0.0023 (17) |
C4' | 0.036 (2) | 0.052 (2) | 0.042 (2) | 0.0089 (18) | −0.0029 (16) | −0.0037 (17) |
C5' | 0.032 (2) | 0.052 (2) | 0.061 (2) | 0.0042 (18) | 0.0053 (17) | 0.0035 (18) |
C6' | 0.044 (2) | 0.042 (2) | 0.060 (2) | 0.0067 (19) | 0.0037 (19) | 0.0017 (17) |
C1 | 0.0278 (18) | 0.048 (2) | 0.051 (2) | 0.0044 (17) | 0.0021 (17) | −0.0053 (17) |
C2 | 0.0330 (19) | 0.041 (2) | 0.051 (2) | 0.0076 (16) | −0.0019 (17) | 0.0019 (17) |
C3 | 0.040 (2) | 0.042 (2) | 0.051 (2) | −0.0004 (17) | 0.0045 (18) | −0.0036 (18) |
C4 | 0.0307 (19) | 0.045 (2) | 0.063 (2) | 0.0093 (17) | 0.0026 (18) | −0.0036 (18) |
C5 | 0.036 (2) | 0.053 (2) | 0.056 (2) | 0.0053 (18) | −0.0013 (18) | −0.0008 (19) |
C6 | 0.038 (2) | 0.064 (2) | 0.055 (2) | 0.0067 (19) | 0.0065 (18) | 0.008 (2) |
C7 | 0.033 (2) | 0.057 (2) | 0.066 (3) | 0.0119 (19) | 0.011 (2) | 0.001 (2) |
C8 | 0.048 (2) | 0.049 (2) | 0.063 (3) | 0.002 (2) | 0.008 (2) | 0.0069 (18) |
C9 | 0.053 (3) | 0.088 (3) | 0.065 (3) | 0.015 (2) | −0.001 (2) | 0.022 (2) |
C10 | 0.043 (2) | 0.068 (3) | 0.105 (4) | 0.016 (2) | 0.000 (2) | 0.001 (2) |
C11 | 0.084 (4) | 0.117 (4) | 0.135 (5) | 0.006 (3) | 0.053 (3) | 0.007 (3) |
C12 | 0.058 (3) | 0.054 (2) | 0.068 (3) | 0.015 (2) | −0.012 (2) | −0.005 (2) |
C13 | 0.167 (5) | 0.071 (3) | 0.076 (4) | 0.004 (3) | −0.015 (3) | −0.022 (3) |
N1—C3 | 1.356 (4) | C2—C7 | 1.432 (5) |
N1—H1A | 0.86 | C3—C4 | 1.404 (4) |
N1—H1B | 0.86 | C4—C5 | 1.390 (4) |
N2—C7 | 1.153 (4) | C4—C8 | 1.439 (5) |
N3—C8 | 1.150 (4) | C5—C6 | 1.388 (4) |
N4—C4' | 1.380 (4) | C5—C9 | 1.503 (5) |
N4—C12 | 1.451 (4) | C6—H6 | 0.93 |
N4—C10 | 1.456 (4) | C9—H9A | 0.96 |
C1'—C2' | 1.383 (4) | C9—H9B | 0.96 |
C1'—C6' | 1.392 (4) | C9—H9C | 0.96 |
C1'—C1 | 1.479 (4) | C10—C11 | 1.500 (5) |
C2'—C3' | 1.379 (4) | C10—H10A | 0.97 |
C2'—H2' | 0.93 | C10—H10B | 0.97 |
C3'—C4' | 1.403 (4) | C11—H11A | 0.96 |
C3'—H3' | 0.93 | C11—H11B | 0.96 |
C4'—C5' | 1.390 (4) | C11—H11C | 0.96 |
C5'—C6' | 1.374 (4) | C12—C13 | 1.496 (5) |
C5'—H5' | 0.93 | C12—H12A | 0.97 |
C6'—H6' | 0.93 | C12—H12B | 0.97 |
C1—C6 | 1.391 (4) | C13—H13A | 0.96 |
C1—C2 | 1.400 (4) | C13—H13B | 0.96 |
C2—C3 | 1.411 (4) | C13—H13C | 0.96 |
C3—N1—H1A | 120.0 | C6—C5—C9 | 120.4 (3) |
C3—N1—H1B | 120.0 | C4—C5—C9 | 121.2 (3) |
H1A—N1—H1B | 120.0 | C5—C6—C1 | 121.8 (3) |
C4'—N4—C12 | 122.0 (3) | C5—C6—H6 | 119.1 |
C4'—N4—C10 | 120.5 (3) | C1—C6—H6 | 119.1 |
C12—N4—C10 | 117.3 (3) | N2—C7—C2 | 175.8 (4) |
C2'—C1'—C6' | 116.3 (3) | N3—C8—C4 | 178.3 (4) |
C2'—C1'—C1 | 122.5 (3) | C5—C9—H9A | 109.5 |
C6'—C1'—C1 | 121.0 (3) | C5—C9—H9B | 109.5 |
C3'—C2'—C1' | 122.0 (3) | H9A—C9—H9B | 109.5 |
C3'—C2'—H2' | 119.0 | C5—C9—H9C | 109.5 |
C1'—C2'—H2' | 119.0 | H9A—C9—H9C | 109.5 |
C2'—C3'—C4' | 121.4 (3) | H9B—C9—H9C | 109.5 |
C2'—C3'—H3' | 119.3 | N4—C10—C11 | 115.6 (4) |
C4'—C3'—H3' | 119.3 | N4—C10—H10A | 108.4 |
N4—C4'—C5' | 122.1 (3) | C11—C10—H10A | 108.4 |
N4—C4'—C3' | 121.3 (3) | N4—C10—H10B | 108.4 |
C5'—C4'—C3' | 116.6 (3) | C11—C10—H10B | 108.4 |
C6'—C5'—C4' | 121.2 (3) | H10A—C10—H10B | 107.4 |
C6'—C5'—H5' | 119.4 | C10—C11—H11A | 109.5 |
C4'—C5'—H5' | 119.4 | C10—C11—H11B | 109.5 |
C5'—C6'—C1' | 122.5 (3) | H11A—C11—H11B | 109.5 |
C5'—C6'—H6' | 118.7 | C10—C11—H11C | 109.5 |
C1'—C6'—H6' | 118.7 | H11A—C11—H11C | 109.5 |
C6—C1—C2 | 118.6 (3) | H11B—C11—H11C | 109.5 |
C6—C1—C1' | 119.8 (3) | N4—C12—C13 | 113.9 (3) |
C2—C1—C1' | 121.5 (3) | N4—C12—H12A | 108.8 |
C1—C2—C3 | 121.5 (3) | C13—C12—H12A | 108.8 |
C1—C2—C7 | 122.1 (3) | N4—C12—H12B | 108.8 |
C3—C2—C7 | 116.4 (3) | C13—C12—H12B | 108.8 |
N1—C3—C4 | 122.2 (3) | H12A—C12—H12B | 107.7 |
N1—C3—C2 | 120.7 (3) | C12—C13—H13A | 109.5 |
C4—C3—C2 | 117.1 (3) | C12—C13—H13B | 109.5 |
C5—C4—C3 | 122.5 (3) | H13A—C13—H13B | 109.5 |
C5—C4—C8 | 118.9 (3) | C12—C13—H13C | 109.5 |
C3—C4—C8 | 118.6 (3) | H13A—C13—H13C | 109.5 |
C6—C5—C4 | 118.4 (3) | H13B—C13—H13C | 109.5 |
C6'—C1'—C2'—C3' | 0.4 (5) | C1'—C1—C2—C7 | −6.0 (5) |
C1—C1'—C2'—C3' | −175.9 (3) | C1—C2—C3—N1 | −178.1 (3) |
C1'—C2'—C3'—C4' | −1.5 (5) | C7—C2—C3—N1 | 3.4 (5) |
C12—N4—C4'—C5' | 170.9 (3) | C1—C2—C3—C4 | 0.6 (5) |
C10—N4—C4'—C5' | −3.0 (5) | C7—C2—C3—C4 | −178.0 (3) |
C12—N4—C4'—C3' | −10.3 (5) | N1—C3—C4—C5 | 179.6 (3) |
C10—N4—C4'—C3' | 175.8 (3) | C2—C3—C4—C5 | 1.0 (5) |
C2'—C3'—C4'—N4 | −177.5 (3) | N1—C3—C4—C8 | 1.6 (5) |
C2'—C3'—C4'—C5' | 1.3 (5) | C2—C3—C4—C8 | −177.0 (3) |
N4—C4'—C5'—C6' | 178.8 (3) | C3—C4—C5—C6 | −1.1 (5) |
C3'—C4'—C5'—C6' | 0.0 (5) | C8—C4—C5—C6 | 176.8 (3) |
C4'—C5'—C6'—C1' | −1.2 (5) | C3—C4—C5—C9 | 179.8 (3) |
C2'—C1'—C6'—C5' | 0.9 (5) | C8—C4—C5—C9 | −2.3 (5) |
C1—C1'—C6'—C5' | 177.3 (3) | C4—C5—C6—C1 | −0.3 (5) |
C2'—C1'—C1—C6 | 124.0 (4) | C9—C5—C6—C1 | 178.8 (3) |
C6'—C1'—C1—C6 | −52.1 (5) | C2—C1—C6—C5 | 1.8 (5) |
C2'—C1'—C1—C2 | −53.5 (5) | C1'—C1—C6—C5 | −175.7 (3) |
C6'—C1'—C1—C2 | 130.4 (3) | C4'—N4—C10—C11 | 83.6 (4) |
C6—C1—C2—C3 | −1.9 (5) | C12—N4—C10—C11 | −90.5 (4) |
C1'—C1—C2—C3 | 175.6 (3) | C4'—N4—C12—C13 | −77.3 (4) |
C6—C1—C2—C7 | 176.5 (3) | C10—N4—C12—C13 | 96.8 (4) |
Experimental details
Crystal data | |
Chemical formula | C19H20N4 |
Mr | 304.39 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 9.2925 (4), 10.8655 (3), 16.7229 (5) |
β (°) | 90.367 (2) |
V (Å3) | 1688.44 (10) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.07 |
Crystal size (mm) | 0.26 × 0.14 × 0.10 |
Data collection | |
Diffractometer | Siemens SMART CCD area detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.978, 0.990 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10442, 3496, 1313 |
Rint | 0.124 |
(sin θ/λ)max (Å−1) | 0.628 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.068, 0.185, 0.92 |
No. of reflections | 3496 |
No. of parameters | 209 |
H-atom treatment | Riding |
Δρmax, Δρmin (e Å−3) | 0.19, −0.18 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ZORTEP (Zsolnai, 1997), SHELXL97 and WinGX (Farrugia, 1999).
C12—N4—C4'—C5' | 170.9 (3) | C6'—C1'—C1—C6 | −52.1 (5) |
C10—N4—C4'—C5' | −3.0 (5) | C2'—C1'—C1—C2 | −53.5 (5) |
C12—N4—C4'—C3' | −10.3 (5) | C4'—N4—C10—C11 | 83.6 (4) |
C10—N4—C4'—C3' | 175.8 (3) | C4'—N4—C12—C13 | −77.3 (4) |
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Biphenyl derivatives exhibit a wide spectrum of photophysical, biological and laser activities (Shukla et al., 1985; Nieger et al., 1998). We recently reported the structure of 3-Amino-4'-(N,N-diethylamino)-5-methylbiphenyl-2,4-dicarbonitrile, (I), in the orthorhombic system (Subbiah Pandi et al., 2000). Here we report the structural details of the monoclinic polymorph of (I).
The bond lengths and bond angles observed in the present study agree well with the corresponding values reported for the orthorhombic form. However, the structures of the two polymorphs differ in the conformations of the biphenyl ring system and the diethyl substituent. The dihedral angle between the two phenyl rings is 53.5 (2)° in the monoclinic form, whereas it is 41.4 (1)° in the orthorhombic form. In the monoclinic polymorph, one of the ethyl groups is twisted 9° more about the C4'—N4 bond compared to the orthorhombic form. Even though in both polymorphs the packing of the molecules is stabilized by intermolecular N—H···N hydrogen bonds, the pattern of hydrogen bonding is different. In the monoclinic form, the molecules are linked by N1—H1A···N3i hydrogen bonds into cyclic centrosymmetric dimers denoted by the R22(12) (Bernstein et al., 1995) ring system [H1A···N3 2.22, N1···N3 3.038 (5) Å and N1—H1A···N3 159°; symmetry code (i): 3 - x, -y, -z]. In the orthorhombic form, the molecules are linked by N—H···N hydrogen bonds to form zigzag chains.