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Three
N-ethylcarbazole derivatives have been synthesized and tested for non-linear optical (NLO) properties. The compounds are 2-(9-ethyl-9
H-carbazol-3-ylmethylene)malononitrile, C
18H
13N
3, (III
a), 2-cyano-3-(9-ethyl-9
H-carbazol-3-yl)thioacrylamide, C
18H
15N
3S, (III
b), and 3-(9-ethyl-9
H-carbazol-3-yl)-2-(4-phenyl-1,3-thiazol-2-yl)acrylonitrile, C
26H
19N
3S, (V). It was found that the molecules of (III
a) and (V) are nearly planar, while non-planarity is more pronounced for (III
b). Molecules of (III
a) and (V) exhibit herring-bone packing motifs. In (III
b), the molecules form layers coplanar with (
01), within which they form centrosymmetric dimers
via N—H
S hydrogen bonds.
Supporting information
CCDC references: 182017; 182018; 182019
The title compounds (IIIa) and (IIIb) were obtained by the reaction of
N-ethyl-3-carbazolealdehyde, (I) (1.115 g, 0.005 mol), with
malononitrile, (IIa) (0.330 g, 0.005 mol), or 2-cyanothioacetamide, (IIb)
(0.500 g, 0.005 mol), respectively, in the presence of a catalytic amount of
morpholine in ethanol (20 ml) at room temperature. The precipitates which
separated from the solutions were recrystallized from ethanol (30 ml) and
acetonitrile (30 ml), respectively [m.p. 431 K, yield 1.018 g (75%) for
(IIIa); m.p. 490 K, yield 1.176 g (77%) for (IIIb)]. Compound (V) was obtained
by the reaction of (IIIb) (1.527 g, 0.005 mol) with 2-bromoacetophenone, (IV)
(0.995 g, 0.005 mol), in dimethylformamide (20 ml) at room temperature. The
precipitate which separated from the solution was recrystallized from
acetonitrile (30 ml) [m.p. 428 K; yield 1.521 g (75%)]. Crystals were obtained
by isothermal evaporation from ethanolic solutions of (IIIa) or (IIIb), or
from a solution of (V) in acetonitrile.
Molecular mechanics calculations were carried out using MM3 (Allinger
et al., 1989; Lii & Allinger, 1989). EFISH measurements of
hyperpolarizability of the three compounds in solution were performed using
the methods described by Sanghadasa et al. (1996) and Antipin et
al. (1997). H atoms were placed geometrically; for (IIIa) and (V), those
attached to sp2, methyl and methylene C atoms were set at 0.95, 0.98
and 0.99 Å, respectively. For (IIIb), the corresponding distances were 0.93,
0.96 and 0.97 Å. For methyl H atoms, Uiso(H) = 1.5Ueq(C),
for all others Uiso(H) = 1.2Ueq(C).
Data collection: CAD-4 Software (Enraf-Nonius, 1989) for (IIIa), (IIIb); P3 (Siemens, 1989) for (V). Cell refinement: CAD-4 Software for (IIIa), (IIIb); P3 for (V). For all compounds, data reduction: SHELXTL-Plus (Sheldrick, 1994); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus; software used to prepare material for publication: SHELXL97.
(IIIa) 2-(9-ethyl-9
H-carbazol-3-ylmethylene)malononitrile
top
Crystal data top
C18H13N3 | F(000) = 568 |
Mr = 271.31 | Dx = 1.269 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 12.731 (3) Å | Cell parameters from 24 reflections |
b = 4.2160 (8) Å | θ = 11–12° |
c = 26.640 (5) Å | µ = 0.08 mm−1 |
β = 96.87 (3)° | T = 298 K |
V = 1419.6 (5) Å3 | Needle, yellow |
Z = 4 | 0.5 × 0.1 × 0.1 mm |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.024 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 1.5° |
Graphite monochromator | h = 0→15 |
θ/2θ scans | k = 0→5 |
2575 measured reflections | l = −31→31 |
2458 independent reflections | 3 standard reflections every 97 reflections |
1280 reflections with I > 2σ(I) | intensity decay: 3% |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.062 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.156 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.062P)2] where P = (Fo2 + 2Fc2)/3 |
2458 reflections | (Δ/σ)max = 0.001 |
191 parameters | Δρmax = 0.17 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
Crystal data top
C18H13N3 | V = 1419.6 (5) Å3 |
Mr = 271.31 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.731 (3) Å | µ = 0.08 mm−1 |
b = 4.2160 (8) Å | T = 298 K |
c = 26.640 (5) Å | 0.5 × 0.1 × 0.1 mm |
β = 96.87 (3)° | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.024 |
2575 measured reflections | 3 standard reflections every 97 reflections |
2458 independent reflections | intensity decay: 3% |
1280 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.062 | 0 restraints |
wR(F2) = 0.156 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.17 e Å−3 |
2458 reflections | Δρmin = −0.21 e Å−3 |
191 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 0.24263 (18) | 0.2665 (6) | 0.12782 (9) | 0.0432 (7) | |
N2 | 0.7266 (3) | 0.2384 (9) | 0.01848 (13) | 0.0812 (11) | |
N3 | 0.9166 (2) | −0.3603 (10) | 0.12600 (12) | 0.0877 (12) | |
C1 | 0.4002 (2) | 0.2588 (8) | 0.08033 (12) | 0.0487 (9) | |
H1A | 0.3686 | 0.3770 | 0.0521 | 0.058* | |
C2 | 0.5028 (2) | 0.1540 (8) | 0.08266 (11) | 0.0502 (9) | |
H2A | 0.5425 | 0.2047 | 0.0557 | 0.060* | |
C3 | 0.5512 (2) | −0.0260 (8) | 0.12358 (11) | 0.0447 (8) | |
C4 | 0.4921 (2) | −0.1046 (8) | 0.16329 (11) | 0.0452 (9) | |
H4A | 0.5230 | −0.2311 | 0.1907 | 0.054* | |
C5 | 0.3892 (2) | 0.0020 (8) | 0.16249 (10) | 0.0418 (8) | |
C6 | 0.3086 (2) | −0.0295 (8) | 0.19616 (11) | 0.0416 (8) | |
C7 | 0.3045 (2) | −0.1738 (8) | 0.24234 (12) | 0.0497 (9) | |
H7A | 0.3637 | −0.2884 | 0.2581 | 0.060* | |
C8 | 0.2135 (3) | −0.1496 (9) | 0.26530 (12) | 0.0559 (9) | |
H8A | 0.2103 | −0.2450 | 0.2974 | 0.067* | |
C9 | 0.1260 (3) | 0.0143 (9) | 0.24167 (13) | 0.0565 (10) | |
H9A | 0.0635 | 0.0243 | 0.2579 | 0.068* | |
C10 | 0.1272 (2) | 0.1612 (8) | 0.19584 (12) | 0.0495 (9) | |
H10A | 0.0674 | 0.2727 | 0.1800 | 0.059* | |
C11 | 0.2202 (2) | 0.1390 (8) | 0.17366 (11) | 0.0416 (8) | |
C12 | 0.1706 (2) | 0.4617 (9) | 0.09390 (12) | 0.0533 (9) | |
H12A | 0.2127 | 0.6077 | 0.0751 | 0.064* | |
H12B | 0.1269 | 0.5921 | 0.1143 | 0.064* | |
C13 | 0.0992 (3) | 0.2686 (10) | 0.05679 (13) | 0.0719 (12) | |
H13A | 0.0530 | 0.4105 | 0.0349 | 0.108* | |
H13B | 0.0559 | 0.1276 | 0.0751 | 0.108* | |
H13C | 0.1420 | 0.1416 | 0.0361 | 0.108* | |
C14 | 0.3439 (2) | 0.1862 (8) | 0.12072 (11) | 0.0415 (8) | |
C15 | 0.6578 (2) | −0.1410 (8) | 0.12851 (12) | 0.0513 (9) | |
H15A | 0.6763 | −0.2702 | 0.1574 | 0.062* | |
C16 | 0.7369 (2) | −0.0986 (8) | 0.09939 (11) | 0.0466 (9) | |
C17 | 0.7297 (2) | 0.0886 (10) | 0.05432 (14) | 0.0563 (10) | |
C18 | 0.8373 (3) | −0.2418 (10) | 0.11382 (13) | 0.0595 (10) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0349 (14) | 0.0495 (18) | 0.0444 (15) | 0.0088 (13) | 0.0006 (11) | 0.0012 (14) |
N2 | 0.076 (2) | 0.101 (3) | 0.069 (2) | 0.019 (2) | 0.0201 (18) | 0.015 (2) |
N3 | 0.0536 (19) | 0.124 (3) | 0.088 (2) | 0.028 (2) | 0.0153 (17) | 0.017 (2) |
C1 | 0.0421 (19) | 0.059 (2) | 0.0440 (18) | 0.0069 (17) | 0.0025 (14) | 0.0087 (18) |
C2 | 0.0402 (18) | 0.063 (2) | 0.0472 (19) | 0.0058 (19) | 0.0053 (14) | 0.0010 (19) |
C3 | 0.0355 (17) | 0.052 (2) | 0.0460 (18) | 0.0026 (17) | 0.0033 (14) | −0.0014 (17) |
C4 | 0.0433 (19) | 0.048 (2) | 0.0413 (18) | 0.0024 (17) | −0.0054 (14) | 0.0005 (16) |
C5 | 0.0359 (17) | 0.045 (2) | 0.0429 (18) | 0.0005 (16) | −0.0008 (13) | −0.0013 (17) |
C6 | 0.0392 (18) | 0.045 (2) | 0.0390 (17) | 0.0020 (16) | −0.0007 (14) | −0.0013 (16) |
C7 | 0.050 (2) | 0.049 (2) | 0.049 (2) | 0.0031 (18) | 0.0030 (15) | 0.0026 (18) |
C8 | 0.056 (2) | 0.066 (3) | 0.0459 (19) | −0.004 (2) | 0.0076 (16) | 0.0047 (19) |
C9 | 0.047 (2) | 0.068 (3) | 0.057 (2) | −0.006 (2) | 0.0145 (16) | −0.007 (2) |
C10 | 0.0415 (18) | 0.053 (2) | 0.054 (2) | 0.0055 (17) | 0.0042 (15) | −0.0012 (18) |
C11 | 0.0400 (17) | 0.045 (2) | 0.0394 (18) | 0.0051 (16) | 0.0040 (14) | −0.0034 (16) |
C12 | 0.0494 (19) | 0.057 (2) | 0.0526 (19) | 0.0165 (19) | 0.0040 (15) | 0.0107 (19) |
C13 | 0.068 (2) | 0.078 (3) | 0.064 (2) | 0.025 (2) | −0.0192 (19) | −0.001 (2) |
C14 | 0.0347 (17) | 0.045 (2) | 0.0439 (18) | 0.0042 (16) | −0.0014 (13) | −0.0045 (16) |
C15 | 0.0411 (18) | 0.063 (2) | 0.0493 (19) | 0.0054 (18) | 0.0018 (15) | −0.0008 (18) |
C16 | 0.0395 (18) | 0.055 (2) | 0.0452 (19) | 0.0041 (17) | 0.0038 (14) | −0.0072 (18) |
C17 | 0.044 (2) | 0.072 (3) | 0.054 (2) | 0.0055 (19) | 0.0118 (17) | −0.002 (2) |
C18 | 0.043 (2) | 0.078 (3) | 0.059 (2) | 0.010 (2) | 0.0114 (17) | 0.007 (2) |
Geometric parameters (Å, º) top
N1—C11 | 1.395 (4) | C7—C8 | 1.377 (4) |
N1—C12 | 1.461 (4) | C7—H7A | 0.9500 |
N1—C14 | 1.368 (3) | C8—C9 | 1.396 (4) |
N2—C17 | 1.142 (4) | C8—H8A | 0.9500 |
N3—C18 | 1.138 (4) | C9—C10 | 1.371 (4) |
C1—C2 | 1.372 (4) | C9—H9A | 0.9500 |
C1—C14 | 1.396 (4) | C10—C11 | 1.387 (4) |
C1—H1A | 0.9500 | C10—H10A | 0.9500 |
C2—C3 | 1.408 (4) | C12—C13 | 1.501 (4) |
C2—H2A | 0.9500 | C12—H12A | 0.9900 |
C3—C4 | 1.409 (4) | C12—H12B | 0.9900 |
C3—C15 | 1.432 (4) | C13—H13A | 0.9800 |
C4—C5 | 1.383 (4) | C13—H13B | 0.9800 |
C4—H4A | 0.9500 | C13—H13C | 0.9800 |
C5—C14 | 1.421 (4) | C15—C16 | 1.355 (4) |
C5—C6 | 1.448 (4) | C15—H15A | 0.9500 |
C6—C7 | 1.379 (4) | C16—C18 | 1.424 (5) |
C6—C11 | 1.403 (4) | C16—C17 | 1.431 (5) |
| | | |
C14—N1—C11 | 108.7 (2) | C9—C10—C11 | 116.8 (3) |
C14—N1—C12 | 125.8 (3) | C9—C10—H10A | 121.6 |
C11—N1—C12 | 125.4 (2) | C11—C10—H10A | 121.6 |
C2—C1—C14 | 117.9 (3) | C10—C11—N1 | 128.4 (3) |
C2—C1—H1A | 121.1 | C10—C11—C6 | 122.2 (3) |
C14—C1—H1A | 121.1 | N1—C11—C6 | 109.3 (3) |
C1—C2—C3 | 122.3 (3) | N1—C12—C13 | 112.8 (3) |
C1—C2—H2A | 118.9 | N1—C12—H12A | 109.0 |
C3—C2—H2A | 118.9 | C13—C12—H12A | 109.0 |
C2—C3—C4 | 119.0 (3) | N1—C12—H12B | 109.0 |
C2—C3—C15 | 125.1 (3) | C13—C12—H12B | 109.0 |
C4—C3—C15 | 115.9 (3) | H12A—C12—H12B | 107.8 |
C5—C4—C3 | 120.1 (3) | C12—C13—H13A | 109.5 |
C5—C4—H4A | 119.9 | C12—C13—H13B | 109.5 |
C3—C4—H4A | 119.9 | H13A—C13—H13B | 109.5 |
C4—C5—C14 | 119.0 (3) | C12—C13—H13C | 109.5 |
C4—C5—C6 | 134.5 (3) | H13A—C13—H13C | 109.5 |
C14—C5—C6 | 106.5 (2) | H13B—C13—H13C | 109.5 |
C7—C6—C11 | 119.4 (3) | N1—C14—C1 | 129.2 (3) |
C7—C6—C5 | 134.3 (3) | N1—C14—C5 | 109.1 (3) |
C11—C6—C5 | 106.3 (3) | C1—C14—C5 | 121.7 (3) |
C8—C7—C6 | 119.1 (3) | C16—C15—C3 | 131.6 (3) |
C8—C7—H7A | 120.4 | C16—C15—H15A | 114.2 |
C6—C7—H7A | 120.4 | C3—C15—H15A | 114.2 |
C7—C8—C9 | 120.4 (3) | C15—C16—C18 | 119.6 (3) |
C7—C8—H8A | 119.8 | C15—C16—C17 | 125.2 (3) |
C9—C8—H8A | 119.8 | C18—C16—C17 | 115.2 (3) |
C10—C9—C8 | 122.1 (3) | N2—C17—C16 | 178.3 (4) |
C10—C9—H9A | 119.0 | N3—C18—C16 | 178.6 (4) |
C8—C9—H9A | 119.0 | | |
| | | |
C14—C1—C2—C3 | 1.1 (5) | C12—N1—C11—C6 | −178.9 (3) |
C1—C2—C3—C4 | 0.7 (5) | C7—C6—C11—C10 | −1.3 (5) |
C1—C2—C3—C15 | −179.6 (3) | C5—C6—C11—C10 | −179.7 (3) |
C2—C3—C4—C5 | −1.8 (5) | C7—C6—C11—N1 | 179.3 (3) |
C15—C3—C4—C5 | 178.5 (3) | C5—C6—C11—N1 | 0.9 (4) |
C3—C4—C5—C14 | 1.1 (5) | C14—N1—C12—C13 | 94.2 (4) |
C3—C4—C5—C6 | −179.2 (3) | C11—N1—C12—C13 | −87.8 (4) |
C4—C5—C6—C7 | 1.3 (7) | C11—N1—C14—C1 | 179.6 (3) |
C14—C5—C6—C7 | −178.9 (4) | C12—N1—C14—C1 | −2.2 (5) |
C4—C5—C6—C11 | 179.4 (4) | C11—N1—C14—C5 | 0.1 (3) |
C14—C5—C6—C11 | −0.8 (3) | C12—N1—C14—C5 | 178.4 (3) |
C11—C6—C7—C8 | 0.1 (5) | C2—C1—C14—N1 | 178.8 (3) |
C5—C6—C7—C8 | 178.0 (3) | C2—C1—C14—C5 | −1.8 (5) |
C6—C7—C8—C9 | 1.1 (5) | C4—C5—C14—N1 | −179.8 (3) |
C7—C8—C9—C10 | −1.3 (5) | C6—C5—C14—N1 | 0.4 (3) |
C8—C9—C10—C11 | 0.2 (5) | C4—C5—C14—C1 | 0.8 (5) |
C9—C10—C11—N1 | −179.6 (3) | C6—C5—C14—C1 | −179.1 (3) |
C9—C10—C11—C6 | 1.1 (5) | C2—C3—C15—C16 | 3.9 (6) |
C14—N1—C11—C10 | −180.0 (3) | C4—C3—C15—C16 | −176.5 (3) |
C12—N1—C11—C10 | 1.7 (5) | C3—C15—C16—C18 | 179.5 (4) |
C14—N1—C11—C6 | −0.7 (4) | C3—C15—C16—C17 | 0.9 (6) |
(IIIb) 2-cyano-3-(9-ethyl-9
H-carbazol-3-yl)thioacrylamide
top
Crystal data top
C18H15N3S | Z = 2 |
Mr = 305.39 | F(000) = 320 |
Triclinic, P1 | Dx = 1.284 Mg m−3 |
a = 8.4370 (17) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.7500 (17) Å | Cell parameters from 24 reflections |
c = 12.300 (3) Å | θ = 11–12° |
α = 79.82 (3)° | µ = 0.20 mm−1 |
β = 76.82 (3)° | T = 298 K |
γ = 63.76 (3)° | Parallelepiped prism, orange |
V = 790.0 (3) Å3 | 0.50 × 0.35 × 0.30 mm |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.013 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 1.7° |
Graphite monochromator | h = 0→10 |
θ/2θ scans | k = −9→10 |
2971 measured reflections | l = −14→14 |
2762 independent reflections | 3 standard reflections every 97 reflections |
2257 reflections with I > 2σ(I) | intensity decay: 3% |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.114 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.06P)2 + 0.24P] where P = (Fo2 + 2Fc2)/3 |
2762 reflections | (Δ/σ)max = 0.001 |
200 parameters | Δρmax = 0.33 e Å−3 |
0 restraints | Δρmin = −0.19 e Å−3 |
Crystal data top
C18H15N3S | γ = 63.76 (3)° |
Mr = 305.39 | V = 790.0 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.4370 (17) Å | Mo Kα radiation |
b = 8.7500 (17) Å | µ = 0.20 mm−1 |
c = 12.300 (3) Å | T = 298 K |
α = 79.82 (3)° | 0.50 × 0.35 × 0.30 mm |
β = 76.82 (3)° | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.013 |
2971 measured reflections | 3 standard reflections every 97 reflections |
2762 independent reflections | intensity decay: 3% |
2257 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.114 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.33 e Å−3 |
2762 reflections | Δρmin = −0.19 e Å−3 |
200 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 0.41428 (8) | 0.37861 (7) | 0.89386 (4) | 0.0599 (2) | |
N1 | 0.0770 (2) | 0.5525 (2) | 0.26053 (12) | 0.0453 (4) | |
N2 | 0.2878 (3) | 0.9276 (3) | 0.64142 (18) | 0.0721 (6) | |
N3 | 0.4516 (2) | 0.6662 (2) | 0.85720 (13) | 0.0565 (5) | |
H3A | 0.4438 | 0.7603 | 0.8181 | 0.068* | |
H3B | 0.4880 | 0.6413 | 0.9206 | 0.068* | |
C1 | 0.1080 (3) | 0.7126 (2) | 0.39735 (15) | 0.0482 (4) | |
H1A | 0.0477 | 0.8207 | 0.3629 | 0.058* | |
C2 | 0.1753 (3) | 0.6928 (2) | 0.49317 (15) | 0.0475 (4) | |
H2A | 0.1617 | 0.7895 | 0.5226 | 0.057* | |
C3 | 0.2644 (2) | 0.5304 (2) | 0.54832 (13) | 0.0409 (4) | |
C4 | 0.2851 (2) | 0.3853 (2) | 0.50360 (14) | 0.0414 (4) | |
H4A | 0.3405 | 0.2775 | 0.5400 | 0.050* | |
C5 | 0.2230 (2) | 0.4016 (2) | 0.40500 (13) | 0.0385 (4) | |
C6 | 0.2251 (2) | 0.2815 (2) | 0.33690 (14) | 0.0420 (4) | |
C7 | 0.2969 (3) | 0.1045 (3) | 0.34141 (18) | 0.0565 (5) | |
H7A | 0.3554 | 0.0374 | 0.4001 | 0.068* | |
C8 | 0.2804 (4) | 0.0297 (3) | 0.2577 (2) | 0.0702 (6) | |
H8A | 0.3288 | −0.0889 | 0.2597 | 0.084* | |
C9 | 0.1920 (4) | 0.1294 (3) | 0.1701 (2) | 0.0707 (7) | |
H9A | 0.1837 | 0.0755 | 0.1142 | 0.085* | |
C10 | 0.1163 (3) | 0.3055 (3) | 0.16378 (17) | 0.0561 (5) | |
H10A | 0.0557 | 0.3713 | 0.1057 | 0.067* | |
C11 | 0.1346 (2) | 0.3806 (2) | 0.24809 (14) | 0.0427 (4) | |
C12 | −0.0334 (3) | 0.6954 (3) | 0.19076 (17) | 0.0569 (5) | |
H12A | −0.1117 | 0.7893 | 0.2364 | 0.068* | |
H12B | −0.1081 | 0.6606 | 0.1608 | 0.068* | |
C13 | 0.0772 (4) | 0.7543 (4) | 0.0971 (2) | 0.0844 (8) | |
H13A | 0.0004 | 0.8491 | 0.0535 | 0.127* | |
H13B | 0.1522 | 0.6625 | 0.0505 | 0.127* | |
H13C | 0.1508 | 0.7894 | 0.1265 | 0.127* | |
C14 | 0.1327 (2) | 0.5660 (2) | 0.35335 (14) | 0.0402 (4) | |
C15 | 0.3292 (2) | 0.5051 (2) | 0.65209 (14) | 0.0431 (4) | |
H15A | 0.3658 | 0.3937 | 0.6856 | 0.052* | |
C16 | 0.3463 (2) | 0.6140 (2) | 0.70918 (14) | 0.0426 (4) | |
C17 | 0.3106 (3) | 0.7882 (3) | 0.66844 (16) | 0.0502 (5) | |
C18 | 0.4077 (2) | 0.5594 (3) | 0.81966 (14) | 0.0445 (4) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0807 (4) | 0.0756 (4) | 0.0394 (3) | −0.0425 (3) | −0.0283 (2) | 0.0058 (2) |
N1 | 0.0520 (9) | 0.0510 (9) | 0.0372 (8) | −0.0203 (7) | −0.0196 (7) | −0.0021 (6) |
N2 | 0.0845 (14) | 0.0540 (12) | 0.0779 (13) | −0.0146 (10) | −0.0425 (11) | −0.0081 (9) |
N3 | 0.0723 (11) | 0.0784 (12) | 0.0355 (8) | −0.0440 (10) | −0.0190 (8) | 0.0010 (8) |
C1 | 0.0533 (11) | 0.0451 (10) | 0.0448 (10) | −0.0132 (8) | −0.0228 (8) | −0.0019 (8) |
C2 | 0.0527 (11) | 0.0491 (10) | 0.0427 (10) | −0.0161 (9) | −0.0188 (8) | −0.0089 (8) |
C3 | 0.0401 (9) | 0.0528 (10) | 0.0296 (8) | −0.0185 (8) | −0.0083 (7) | −0.0031 (7) |
C4 | 0.0452 (10) | 0.0479 (10) | 0.0308 (8) | −0.0198 (8) | −0.0092 (7) | 0.0015 (7) |
C5 | 0.0400 (9) | 0.0472 (10) | 0.0300 (8) | −0.0203 (8) | −0.0066 (7) | −0.0015 (7) |
C6 | 0.0470 (10) | 0.0510 (10) | 0.0333 (9) | −0.0258 (8) | −0.0068 (7) | −0.0023 (7) |
C7 | 0.0732 (14) | 0.0504 (12) | 0.0528 (11) | −0.0301 (10) | −0.0191 (10) | 0.0013 (9) |
C8 | 0.0951 (18) | 0.0534 (13) | 0.0728 (15) | −0.0348 (13) | −0.0231 (13) | −0.0099 (11) |
C9 | 0.0991 (18) | 0.0702 (15) | 0.0619 (13) | −0.0448 (14) | −0.0225 (13) | −0.0156 (11) |
C10 | 0.0708 (13) | 0.0679 (13) | 0.0434 (10) | −0.0363 (11) | −0.0200 (9) | −0.0052 (9) |
C11 | 0.0461 (10) | 0.0529 (11) | 0.0351 (9) | −0.0252 (8) | −0.0083 (7) | −0.0048 (7) |
C12 | 0.0641 (13) | 0.0597 (12) | 0.0519 (11) | −0.0215 (10) | −0.0300 (10) | −0.0026 (9) |
C13 | 0.102 (2) | 0.0909 (19) | 0.0746 (17) | −0.0514 (17) | −0.0369 (15) | 0.0167 (14) |
C14 | 0.0398 (9) | 0.0497 (10) | 0.0326 (8) | −0.0181 (8) | −0.0117 (7) | −0.0019 (7) |
C15 | 0.0424 (9) | 0.0554 (11) | 0.0306 (8) | −0.0189 (8) | −0.0088 (7) | −0.0026 (7) |
C16 | 0.0372 (9) | 0.0550 (11) | 0.0321 (8) | −0.0147 (8) | −0.0077 (7) | −0.0056 (7) |
C17 | 0.0480 (11) | 0.0588 (13) | 0.0422 (10) | −0.0128 (9) | −0.0179 (8) | −0.0135 (9) |
C18 | 0.0384 (9) | 0.0653 (12) | 0.0315 (9) | −0.0212 (9) | −0.0064 (7) | −0.0094 (8) |
Geometric parameters (Å, º) top
S1—C18 | 1.665 (2) | C6—C11 | 1.410 (3) |
N1—C11 | 1.387 (2) | C7—C8 | 1.375 (3) |
N1—C12 | 1.457 (2) | C7—H7A | 0.9300 |
N1—C14 | 1.371 (2) | C8—C9 | 1.392 (3) |
N2—C17 | 1.146 (3) | C8—H8A | 0.9300 |
N3—C18 | 1.327 (2) | C9—C10 | 1.378 (3) |
N3—H3A | 0.8600 | C9—H9A | 0.9300 |
N3—H3B | 0.8600 | C10—C11 | 1.391 (3) |
C1—C2 | 1.374 (2) | C10—H10A | 0.9300 |
C1—C14 | 1.393 (3) | C12—C13 | 1.480 (3) |
C1—H1A | 0.9300 | C12—H12A | 0.9700 |
C2—C3 | 1.411 (3) | C12—H12B | 0.9700 |
C2—H2A | 0.9300 | C13—H13A | 0.9600 |
C3—C4 | 1.397 (3) | C13—H13B | 0.9600 |
C3—C15 | 1.445 (2) | C13—H13C | 0.9600 |
C4—C5 | 1.388 (2) | C15—C16 | 1.351 (3) |
C4—H4A | 0.9300 | C15—H15A | 0.9300 |
C5—C14 | 1.408 (2) | C16—C17 | 1.435 (3) |
C5—C6 | 1.447 (2) | C16—C18 | 1.488 (2) |
C6—C7 | 1.387 (3) | | |
| | | |
C14—N1—C11 | 108.64 (15) | C8—C9—H9A | 119.0 |
C14—N1—C12 | 125.48 (16) | C9—C10—C11 | 117.1 (2) |
C11—N1—C12 | 125.79 (15) | C9—C10—H10A | 121.4 |
C18—N3—H3A | 120.0 | C11—C10—H10A | 121.4 |
C18—N3—H3B | 120.0 | N1—C11—C10 | 129.15 (18) |
H3A—N3—H3B | 120.0 | N1—C11—C6 | 109.16 (15) |
C2—C1—C14 | 118.06 (17) | C10—C11—C6 | 121.68 (18) |
C2—C1—H1A | 121.0 | N1—C12—C13 | 111.69 (19) |
C14—C1—H1A | 121.0 | N1—C12—H12A | 109.3 |
C1—C2—C3 | 122.13 (17) | C13—C12—H12A | 109.3 |
C1—C2—H2A | 118.9 | N1—C12—H12B | 109.3 |
C3—C2—H2A | 118.9 | C13—C12—H12B | 109.3 |
C4—C3—C2 | 118.78 (15) | H12A—C12—H12B | 107.9 |
C4—C3—C15 | 117.50 (16) | C12—C13—H13A | 109.5 |
C2—C3—C15 | 123.66 (17) | C12—C13—H13B | 109.5 |
C5—C4—C3 | 120.19 (16) | H13A—C13—H13B | 109.5 |
C5—C4—H4A | 119.9 | C12—C13—H13C | 109.5 |
C3—C4—H4A | 119.9 | H13A—C13—H13C | 109.5 |
C4—C5—C14 | 119.26 (16) | H13B—C13—H13C | 109.5 |
C4—C5—C6 | 134.19 (17) | N1—C14—C1 | 128.98 (17) |
C14—C5—C6 | 106.53 (15) | N1—C14—C5 | 109.49 (15) |
C7—C6—C11 | 119.55 (17) | C1—C14—C5 | 121.53 (15) |
C7—C6—C5 | 134.28 (17) | C16—C15—C3 | 131.64 (18) |
C11—C6—C5 | 106.15 (16) | C16—C15—H15A | 114.2 |
C8—C7—C6 | 118.9 (2) | C3—C15—H15A | 114.2 |
C8—C7—H7A | 120.5 | C15—C16—C17 | 123.41 (16) |
C6—C7—H7A | 120.5 | C15—C16—C18 | 121.76 (17) |
C7—C8—C9 | 120.8 (2) | C17—C16—C18 | 114.82 (16) |
C7—C8—H8A | 119.6 | N2—C17—C16 | 175.4 (2) |
C9—C8—H8A | 119.6 | N3—C18—C16 | 115.93 (17) |
C10—C9—C8 | 121.9 (2) | N3—C18—S1 | 121.89 (14) |
C10—C9—H9A | 119.0 | C16—C18—S1 | 122.14 (14) |
| | | |
C14—C1—C2—C3 | −1.2 (3) | C5—C6—C11—N1 | −0.78 (19) |
C1—C2—C3—C4 | 0.2 (3) | C7—C6—C11—C10 | −0.5 (3) |
C1—C2—C3—C15 | −176.91 (18) | C5—C6—C11—C10 | 177.96 (17) |
C2—C3—C4—C5 | 1.7 (3) | C14—N1—C12—C13 | 90.9 (2) |
C15—C3—C4—C5 | 179.03 (15) | C11—N1—C12—C13 | −93.0 (2) |
C3—C4—C5—C14 | −2.6 (3) | C11—N1—C14—C1 | 179.08 (18) |
C3—C4—C5—C6 | 178.88 (17) | C12—N1—C14—C1 | −4.3 (3) |
C4—C5—C6—C7 | −3.6 (4) | C11—N1—C14—C5 | −1.9 (2) |
C14—C5—C6—C7 | 177.8 (2) | C12—N1—C14—C5 | 174.73 (17) |
C4—C5—C6—C11 | 178.26 (19) | C2—C1—C14—N1 | 179.17 (18) |
C14—C5—C6—C11 | −0.37 (19) | C2—C1—C14—C5 | 0.3 (3) |
C11—C6—C7—C8 | 1.0 (3) | C4—C5—C14—N1 | −177.47 (15) |
C5—C6—C7—C8 | −176.9 (2) | C6—C5—C14—N1 | 1.41 (19) |
C6—C7—C8—C9 | −0.5 (4) | C4—C5—C14—C1 | 1.6 (3) |
C7—C8—C9—C10 | −0.6 (4) | C6—C5—C14—C1 | −179.51 (16) |
C8—C9—C10—C11 | 1.1 (4) | C4—C3—C15—C16 | 172.01 (18) |
C14—N1—C11—C10 | −176.94 (19) | C2—C3—C15—C16 | −10.9 (3) |
C12—N1—C11—C10 | 6.4 (3) | C3—C15—C16—C17 | −4.8 (3) |
C14—N1—C11—C6 | 1.7 (2) | C3—C15—C16—C18 | 176.30 (17) |
C12—N1—C11—C6 | −174.96 (17) | C15—C16—C18—N3 | 167.64 (17) |
C9—C10—C11—N1 | 177.9 (2) | C17—C16—C18—N3 | −11.3 (2) |
C9—C10—C11—C6 | −0.5 (3) | C15—C16—C18—S1 | −14.4 (2) |
C7—C6—C11—N1 | −179.26 (17) | C17—C16—C18—S1 | 166.67 (14) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3B···S1i | 0.86 | 2.55 | 3.402 (2) | 170 |
Symmetry code: (i) −x+1, −y+1, −z+2. |
(V) 3-(9-ethyl-9
H-carbazol-3-yl)-2-(4-phenyl-1,3-thiazol-2-yl)acrylonitrile
top
Crystal data top
C26H19N3S | F(000) = 848 |
Mr = 405.50 | Dx = 1.299 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 19.384 (5) Å | Cell parameters from 24 reflections |
b = 16.456 (4) Å | θ = 10–11° |
c = 6.5323 (17) Å | µ = 0.17 mm−1 |
β = 95.637 (19)° | T = 155 K |
V = 2073.6 (9) Å3 | Parallelepiped prism, yellow |
Z = 4 | 0.45 × 0.30 × 0.25 mm |
Data collection top
Syntex P21 diffractometer | Rint = 0.037 |
Radiation source: fine-focus sealed tube | θmax = 27.1°, θmin = 1.6° |
Graphite monochromator | h = −24→24 |
θ/2θ scans | k = −21→1 |
4942 measured reflections | l = 0→8 |
4540 independent reflections | 2 standard reflections every 98 reflections |
3066 reflections with I > 2σ(I) | intensity decay: 3% |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.112 | H-atom parameters constrained |
S = 0.92 | w = 1/[σ2(Fo2) + (0.068P)2] where P = (Fo2 + 2Fc2)/3 |
4540 reflections | (Δ/σ)max = 0.001 |
272 parameters | Δρmax = 0.30 e Å−3 |
0 restraints | Δρmin = −0.32 e Å−3 |
Crystal data top
C26H19N3S | V = 2073.6 (9) Å3 |
Mr = 405.50 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 19.384 (5) Å | µ = 0.17 mm−1 |
b = 16.456 (4) Å | T = 155 K |
c = 6.5323 (17) Å | 0.45 × 0.30 × 0.25 mm |
β = 95.637 (19)° | |
Data collection top
Syntex P21 diffractometer | Rint = 0.037 |
4942 measured reflections | 2 standard reflections every 98 reflections |
4540 independent reflections | intensity decay: 3% |
3066 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.112 | H-atom parameters constrained |
S = 0.92 | Δρmax = 0.30 e Å−3 |
4540 reflections | Δρmin = −0.32 e Å−3 |
272 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 0.20194 (3) | 0.31806 (3) | 0.05188 (7) | 0.02802 (13) | |
N1 | 0.12528 (8) | 0.61215 (9) | 1.2467 (2) | 0.0254 (3) | |
N2 | 0.06157 (9) | 0.38222 (11) | 0.3266 (3) | 0.0384 (4) | |
N3 | 0.30257 (8) | 0.38962 (9) | 0.2654 (2) | 0.0248 (3) | |
C1 | 0.09224 (10) | 0.53882 (11) | 0.9157 (3) | 0.0263 (4) | |
H1A | 0.0436 | 0.5443 | 0.9202 | 0.032* | |
C2 | 0.11898 (9) | 0.49900 (11) | 0.7554 (3) | 0.0250 (4) | |
H2A | 0.0879 | 0.4766 | 0.6487 | 0.030* | |
C3 | 0.19116 (9) | 0.49047 (10) | 0.7449 (3) | 0.0233 (4) | |
C4 | 0.23698 (9) | 0.52376 (10) | 0.9019 (3) | 0.0222 (4) | |
H4A | 0.2856 | 0.5190 | 0.8964 | 0.027* | |
C5 | 0.21125 (9) | 0.56379 (10) | 1.0661 (3) | 0.0216 (4) | |
C6 | 0.24330 (9) | 0.60339 (10) | 1.2497 (3) | 0.0229 (4) | |
C7 | 0.31150 (10) | 0.61490 (11) | 1.3325 (3) | 0.0276 (4) | |
H7A | 0.3489 | 0.5938 | 1.2653 | 0.033* | |
C8 | 0.32373 (10) | 0.65775 (11) | 1.5147 (3) | 0.0313 (4) | |
H8A | 0.3700 | 0.6662 | 1.5730 | 0.038* | |
C9 | 0.26847 (11) | 0.68879 (11) | 1.6141 (3) | 0.0311 (4) | |
H9A | 0.2782 | 0.7187 | 1.7380 | 0.037* | |
C10 | 0.20072 (11) | 0.67714 (11) | 1.5376 (3) | 0.0289 (4) | |
H10A | 0.1637 | 0.6980 | 1.6070 | 0.035* | |
C11 | 0.18801 (9) | 0.63357 (10) | 1.3541 (3) | 0.0242 (4) | |
C12 | 0.05616 (9) | 0.62479 (11) | 1.3134 (3) | 0.0281 (4) | |
H12A | 0.0607 | 0.6353 | 1.4633 | 0.034* | |
H12B | 0.0288 | 0.5744 | 1.2884 | 0.034* | |
C13 | 0.01729 (12) | 0.69442 (14) | 1.2049 (3) | 0.0428 (5) | |
H13A | −0.0286 | 0.6993 | 1.2548 | 0.064* | |
H13B | 0.0120 | 0.6842 | 1.0564 | 0.064* | |
H13C | 0.0432 | 0.7450 | 1.2329 | 0.064* | |
C14 | 0.13916 (9) | 0.57089 (10) | 1.0716 (3) | 0.0235 (4) | |
C15 | 0.22154 (9) | 0.45043 (10) | 0.5780 (3) | 0.0230 (4) | |
H15A | 0.2707 | 0.4538 | 0.5862 | 0.028* | |
C16 | 0.19238 (9) | 0.40897 (10) | 0.4118 (3) | 0.0231 (4) | |
C17 | 0.11940 (10) | 0.39494 (11) | 0.3680 (3) | 0.0267 (4) | |
C18 | 0.23587 (9) | 0.37656 (10) | 0.2586 (3) | 0.0235 (4) | |
C19 | 0.28324 (10) | 0.31182 (11) | −0.0283 (3) | 0.0294 (4) | |
H19A | 0.2941 | 0.2833 | −0.1474 | 0.035* | |
C20 | 0.33026 (10) | 0.35307 (11) | 0.1013 (3) | 0.0262 (4) | |
C21 | 0.40495 (10) | 0.36253 (12) | 0.0813 (3) | 0.0305 (4) | |
C22 | 0.43695 (12) | 0.32309 (16) | −0.0731 (4) | 0.0494 (6) | |
H22A | 0.4100 | 0.2901 | −0.1699 | 0.059* | |
C23 | 0.50706 (13) | 0.33114 (18) | −0.0876 (4) | 0.0596 (7) | |
H23A | 0.5279 | 0.3037 | −0.1938 | 0.072* | |
C24 | 0.54709 (12) | 0.37859 (17) | 0.0506 (4) | 0.0522 (6) | |
H24A | 0.5956 | 0.3833 | 0.0416 | 0.063* | |
C25 | 0.51646 (12) | 0.41932 (16) | 0.2021 (4) | 0.0509 (6) | |
H25A | 0.5437 | 0.4533 | 0.2958 | 0.061* | |
C26 | 0.44613 (11) | 0.41086 (13) | 0.2182 (3) | 0.0400 (5) | |
H26A | 0.4257 | 0.4386 | 0.3246 | 0.048* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0328 (3) | 0.0242 (2) | 0.0271 (2) | −0.00163 (19) | 0.00313 (18) | −0.00433 (19) |
N1 | 0.0276 (8) | 0.0254 (8) | 0.0243 (8) | 0.0004 (6) | 0.0084 (6) | −0.0026 (6) |
N2 | 0.0320 (10) | 0.0438 (10) | 0.0395 (10) | −0.0056 (8) | 0.0040 (8) | −0.0111 (8) |
N3 | 0.0303 (8) | 0.0197 (7) | 0.0250 (8) | 0.0020 (6) | 0.0050 (6) | −0.0011 (6) |
C1 | 0.0243 (9) | 0.0279 (9) | 0.0271 (9) | −0.0015 (7) | 0.0050 (7) | −0.0005 (8) |
C2 | 0.0251 (9) | 0.0256 (9) | 0.0241 (9) | −0.0017 (7) | 0.0012 (7) | −0.0008 (7) |
C3 | 0.0271 (10) | 0.0182 (8) | 0.0250 (9) | −0.0005 (7) | 0.0057 (7) | 0.0026 (7) |
C4 | 0.0222 (9) | 0.0186 (8) | 0.0263 (9) | 0.0002 (7) | 0.0054 (7) | 0.0041 (7) |
C5 | 0.0252 (9) | 0.0168 (8) | 0.0228 (9) | −0.0010 (7) | 0.0028 (7) | 0.0027 (7) |
C6 | 0.0312 (10) | 0.0154 (8) | 0.0231 (9) | −0.0001 (7) | 0.0067 (7) | 0.0021 (7) |
C7 | 0.0299 (10) | 0.0220 (9) | 0.0314 (10) | 0.0004 (8) | 0.0054 (8) | 0.0012 (8) |
C8 | 0.0339 (10) | 0.0261 (10) | 0.0326 (11) | −0.0029 (8) | −0.0031 (8) | 0.0015 (8) |
C9 | 0.0447 (12) | 0.0213 (9) | 0.0266 (10) | −0.0040 (8) | 0.0006 (8) | −0.0010 (8) |
C10 | 0.0408 (11) | 0.0214 (9) | 0.0257 (9) | 0.0006 (8) | 0.0084 (8) | −0.0013 (8) |
C11 | 0.0302 (10) | 0.0171 (8) | 0.0261 (9) | −0.0002 (7) | 0.0062 (8) | 0.0034 (7) |
C12 | 0.0281 (10) | 0.0287 (9) | 0.0287 (10) | 0.0000 (8) | 0.0094 (8) | −0.0008 (8) |
C13 | 0.0451 (13) | 0.0471 (13) | 0.0376 (12) | 0.0191 (10) | 0.0115 (9) | 0.0045 (10) |
C14 | 0.0294 (10) | 0.0185 (8) | 0.0230 (9) | 0.0007 (7) | 0.0054 (7) | 0.0007 (7) |
C15 | 0.0238 (9) | 0.0199 (8) | 0.0259 (9) | −0.0003 (7) | 0.0048 (7) | 0.0026 (7) |
C16 | 0.0279 (9) | 0.0190 (8) | 0.0231 (9) | 0.0004 (7) | 0.0059 (7) | 0.0022 (7) |
C17 | 0.0330 (11) | 0.0229 (9) | 0.0252 (10) | −0.0008 (8) | 0.0075 (8) | −0.0045 (7) |
C18 | 0.0310 (10) | 0.0152 (8) | 0.0245 (9) | 0.0003 (7) | 0.0040 (7) | −0.0008 (7) |
C19 | 0.0381 (11) | 0.0246 (9) | 0.0266 (10) | 0.0023 (8) | 0.0079 (8) | −0.0033 (8) |
C20 | 0.0311 (10) | 0.0202 (8) | 0.0283 (10) | 0.0031 (7) | 0.0076 (8) | 0.0012 (7) |
C21 | 0.0339 (10) | 0.0289 (10) | 0.0298 (10) | 0.0056 (8) | 0.0090 (8) | 0.0021 (8) |
C22 | 0.0428 (13) | 0.0622 (16) | 0.0456 (13) | −0.0008 (11) | 0.0165 (11) | −0.0182 (12) |
C23 | 0.0471 (15) | 0.089 (2) | 0.0461 (15) | 0.0132 (14) | 0.0202 (12) | −0.0094 (14) |
C24 | 0.0348 (12) | 0.0761 (18) | 0.0477 (14) | 0.0025 (12) | 0.0135 (11) | 0.0098 (13) |
C25 | 0.0322 (12) | 0.0656 (16) | 0.0549 (15) | −0.0057 (11) | 0.0033 (10) | −0.0062 (13) |
C26 | 0.0366 (12) | 0.0434 (12) | 0.0406 (12) | 0.0007 (9) | 0.0069 (9) | −0.0078 (10) |
Geometric parameters (Å, º) top
S1—C18 | 1.7342 (18) | C10—C11 | 1.398 (3) |
S1—C19 | 1.712 (2) | C10—H10A | 0.9500 |
N1—C11 | 1.388 (2) | C12—C13 | 1.509 (3) |
N1—C12 | 1.464 (2) | C12—H12A | 0.9900 |
N1—C14 | 1.379 (2) | C12—H12B | 0.9900 |
N2—C17 | 1.146 (2) | C13—H13A | 0.9800 |
N3—C18 | 1.307 (2) | C13—H13B | 0.9800 |
N3—C20 | 1.383 (2) | C13—H13C | 0.9800 |
C1—C2 | 1.379 (3) | C15—C16 | 1.358 (2) |
C1—C14 | 1.401 (3) | C15—H15A | 0.9500 |
C1—H1A | 0.9500 | C16—C17 | 1.434 (3) |
C2—C3 | 1.415 (2) | C16—C18 | 1.471 (2) |
C2—H2A | 0.9500 | C19—C20 | 1.362 (3) |
C3—C4 | 1.401 (3) | C19—H19A | 0.9500 |
C3—C15 | 1.448 (2) | C20—C21 | 1.475 (3) |
C4—C5 | 1.392 (2) | C21—C26 | 1.389 (3) |
C4—H4A | 0.9500 | C21—C22 | 1.395 (3) |
C5—C14 | 1.406 (2) | C22—C23 | 1.378 (3) |
C5—C6 | 1.450 (2) | C22—H22A | 0.9500 |
C6—C7 | 1.391 (3) | C23—C24 | 1.374 (4) |
C6—C11 | 1.415 (2) | C23—H23A | 0.9500 |
C7—C8 | 1.384 (3) | C24—C25 | 1.377 (3) |
C7—H7A | 0.9500 | C24—H24A | 0.9500 |
C8—C9 | 1.403 (3) | C25—C26 | 1.385 (3) |
C8—H8A | 0.9500 | C25—H25A | 0.9500 |
C9—C10 | 1.372 (3) | C26—H26A | 0.9500 |
C9—H9A | 0.9500 | | |
| | | |
C18—S1—C19 | 88.93 (9) | C12—C13—H13A | 109.5 |
C11—N1—C12 | 126.54 (15) | C12—C13—H13B | 109.5 |
C11—N1—C14 | 108.14 (14) | H13A—C13—H13B | 109.5 |
C12—N1—C14 | 125.15 (15) | C12—C13—H13C | 109.5 |
C18—N3—C20 | 111.08 (15) | H13A—C13—H13C | 109.5 |
C2—C1—C14 | 117.76 (17) | H13B—C13—H13C | 109.5 |
C2—C1—H1A | 121.1 | N1—C14—C1 | 128.54 (17) |
C14—C1—H1A | 121.1 | N1—C14—C5 | 109.72 (15) |
C1—C2—C3 | 122.11 (17) | C1—C14—C5 | 121.74 (16) |
C1—C2—H2A | 118.9 | C16—C15—C3 | 131.52 (17) |
C3—C2—H2A | 118.9 | C16—C15—H15A | 114.2 |
C4—C3—C2 | 118.98 (16) | C3—C15—H15A | 114.2 |
C4—C3—C15 | 117.00 (16) | C15—C16—C17 | 124.43 (16) |
C2—C3—C15 | 124.00 (16) | C15—C16—C18 | 120.34 (16) |
C5—C4—C3 | 119.99 (16) | C17—C16—C18 | 115.21 (16) |
C5—C4—H4A | 120.0 | N2—C17—C16 | 177.5 (2) |
C3—C4—H4A | 120.0 | N3—C18—C16 | 123.25 (16) |
C4—C5—C14 | 119.41 (16) | N3—C18—S1 | 114.59 (13) |
C4—C5—C6 | 133.87 (16) | C16—C18—S1 | 122.16 (14) |
C14—C5—C6 | 106.72 (15) | C20—C19—S1 | 111.09 (14) |
C7—C6—C11 | 120.04 (17) | C20—C19—H19A | 124.5 |
C7—C6—C5 | 134.13 (17) | S1—C19—H19A | 124.5 |
C11—C6—C5 | 105.83 (16) | C19—C20—N3 | 114.30 (17) |
C8—C7—C6 | 118.66 (17) | C19—C20—C21 | 126.89 (17) |
C8—C7—H7A | 120.7 | N3—C20—C21 | 118.81 (17) |
C6—C7—H7A | 120.7 | C26—C21—C22 | 117.6 (2) |
C7—C8—C9 | 120.66 (18) | C26—C21—C20 | 120.70 (18) |
C7—C8—H8A | 119.7 | C22—C21—C20 | 121.67 (19) |
C9—C8—H8A | 119.7 | C23—C22—C21 | 121.1 (2) |
C10—C9—C8 | 121.84 (18) | C23—C22—H22A | 119.4 |
C10—C9—H9A | 119.1 | C21—C22—H22A | 119.4 |
C8—C9—H9A | 119.1 | C24—C23—C22 | 120.4 (2) |
C9—C10—C11 | 117.78 (18) | C24—C23—H23A | 119.8 |
C9—C10—H10A | 121.1 | C22—C23—H23A | 119.8 |
C11—C10—H10A | 121.1 | C23—C24—C25 | 119.5 (2) |
N1—C11—C10 | 129.45 (17) | C23—C24—H24A | 120.2 |
N1—C11—C6 | 109.55 (15) | C25—C24—H24A | 120.2 |
C10—C11—C6 | 121.00 (17) | C24—C25—C26 | 120.2 (2) |
N1—C12—C13 | 113.41 (16) | C24—C25—H25A | 119.9 |
N1—C12—H12A | 108.9 | C26—C25—H25A | 119.9 |
C13—C12—H12A | 108.9 | C25—C26—C21 | 121.1 (2) |
N1—C12—H12B | 108.9 | C25—C26—H26A | 119.5 |
C13—C12—H12B | 108.9 | C21—C26—H26A | 119.5 |
H12A—C12—H12B | 107.7 | | |
| | | |
C14—C1—C2—C3 | −0.4 (3) | C4—C5—C14—N1 | 179.80 (15) |
C1—C2—C3—C4 | −0.2 (3) | C6—C5—C14—N1 | −0.06 (19) |
C1—C2—C3—C15 | −178.89 (17) | C4—C5—C14—C1 | −0.1 (2) |
C2—C3—C4—C5 | 0.6 (2) | C6—C5—C14—C1 | −179.98 (16) |
C15—C3—C4—C5 | 179.40 (15) | C4—C3—C15—C16 | 175.92 (18) |
C3—C4—C5—C14 | −0.5 (2) | C2—C3—C15—C16 | −5.4 (3) |
C3—C4—C5—C6 | 179.34 (17) | C3—C15—C16—C17 | −0.9 (3) |
C4—C5—C6—C7 | −1.5 (3) | C3—C15—C16—C18 | 177.52 (17) |
C14—C5—C6—C7 | 178.36 (19) | C20—N3—C18—C16 | −179.18 (16) |
C4—C5—C6—C11 | 179.14 (18) | C20—N3—C18—S1 | 0.39 (19) |
C14—C5—C6—C11 | −1.03 (18) | C15—C16—C18—N3 | −4.4 (3) |
C11—C6—C7—C8 | −1.5 (3) | C17—C16—C18—N3 | 174.18 (16) |
C5—C6—C7—C8 | 179.18 (18) | C15—C16—C18—S1 | 176.07 (13) |
C6—C7—C8—C9 | 0.1 (3) | C17—C16—C18—S1 | −5.4 (2) |
C7—C8—C9—C10 | 1.0 (3) | C19—S1—C18—N3 | −0.20 (14) |
C8—C9—C10—C11 | −0.6 (3) | C19—S1—C18—C16 | 179.38 (15) |
C14—N1—C11—C10 | 178.64 (17) | C18—S1—C19—C20 | −0.06 (15) |
C12—N1—C11—C10 | −5.9 (3) | S1—C19—C20—N3 | 0.3 (2) |
C14—N1—C11—C6 | −1.84 (19) | S1—C19—C20—C21 | −178.99 (15) |
C12—N1—C11—C6 | 173.61 (16) | C18—N3—C20—C19 | −0.4 (2) |
C9—C10—C11—N1 | 178.72 (17) | C18—N3—C20—C21 | 178.91 (16) |
C9—C10—C11—C6 | −0.8 (3) | C19—C20—C21—C26 | 175.8 (2) |
C7—C6—C11—N1 | −177.73 (15) | N3—C20—C21—C26 | −3.4 (3) |
C5—C6—C11—N1 | 1.76 (19) | C19—C20—C21—C22 | −4.8 (3) |
C7—C6—C11—C10 | 1.8 (3) | N3—C20—C21—C22 | 175.92 (19) |
C5—C6—C11—C10 | −178.67 (15) | C26—C21—C22—C23 | 0.7 (4) |
C14—N1—C12—C13 | −81.2 (2) | C20—C21—C22—C23 | −178.7 (2) |
C11—N1—C12—C13 | 104.1 (2) | C21—C22—C23—C24 | −0.1 (4) |
C11—N1—C14—C1 | −178.92 (17) | C22—C23—C24—C25 | −1.1 (4) |
C12—N1—C14—C1 | 5.6 (3) | C23—C24—C25—C26 | 1.6 (4) |
C11—N1—C14—C5 | 1.16 (19) | C24—C25—C26—C21 | −1.0 (4) |
C12—N1—C14—C5 | −174.36 (15) | C22—C21—C26—C25 | −0.2 (3) |
C2—C1—C14—N1 | −179.38 (17) | C20—C21—C26—C25 | 179.2 (2) |
C2—C1—C14—C5 | 0.5 (3) | | |
Experimental details
| (IIIa) | (IIIb) | (V) |
Crystal data |
Chemical formula | C18H13N3 | C18H15N3S | C26H19N3S |
Mr | 271.31 | 305.39 | 405.50 |
Crystal system, space group | Monoclinic, P21/c | Triclinic, P1 | Monoclinic, P21/c |
Temperature (K) | 298 | 298 | 155 |
a, b, c (Å) | 12.731 (3), 4.2160 (8), 26.640 (5) | 8.4370 (17), 8.7500 (17), 12.300 (3) | 19.384 (5), 16.456 (4), 6.5323 (17) |
α, β, γ (°) | 90, 96.87 (3), 90 | 79.82 (3), 76.82 (3), 63.76 (3) | 90, 95.637 (19), 90 |
V (Å3) | 1419.6 (5) | 790.0 (3) | 2073.6 (9) |
Z | 4 | 2 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.08 | 0.20 | 0.17 |
Crystal size (mm) | 0.5 × 0.1 × 0.1 | 0.50 × 0.35 × 0.30 | 0.45 × 0.30 × 0.25 |
|
Data collection |
Diffractometer | Enraf-Nonius CAD-4 diffractometer | Enraf-Nonius CAD-4 diffractometer | Syntex P21 diffractometer |
Absorption correction | – | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2575, 2458, 1280 | 2971, 2762, 2257 | 4942, 4540, 3066 |
Rint | 0.024 | 0.013 | 0.037 |
(sin θ/λ)max (Å−1) | 0.594 | 0.594 | 0.640 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.062, 0.156, 1.00 | 0.039, 0.114, 1.05 | 0.043, 0.112, 0.92 |
No. of reflections | 2458 | 2762 | 4540 |
No. of parameters | 191 | 200 | 272 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.17, −0.21 | 0.33, −0.19 | 0.30, −0.32 |
Selected geometric parameters (Å, º) for (IIIa) topN2—C17 | 1.142 (4) | C15—C16 | 1.355 (4) |
N3—C18 | 1.138 (4) | C16—C18 | 1.424 (5) |
C3—C15 | 1.432 (4) | C16—C17 | 1.431 (5) |
| | | |
C2—C3—C15 | 125.1 (3) | C18—C16—C17 | 115.2 (3) |
C16—C15—C3 | 131.6 (3) | N2—C17—C16 | 178.3 (4) |
C15—C16—C18 | 119.6 (3) | N3—C18—C16 | 178.6 (4) |
C15—C16—C17 | 125.2 (3) | | |
| | | |
C11—N1—C12—C13 | −87.8 (4) | | |
Selected geometric parameters (Å, º) for (IIIb) topS1—C18 | 1.665 (2) | C15—C16 | 1.351 (3) |
N2—C17 | 1.146 (3) | C16—C17 | 1.435 (3) |
N3—C18 | 1.327 (2) | C16—C18 | 1.488 (2) |
C3—C15 | 1.445 (2) | | |
| | | |
C2—C3—C15 | 123.66 (17) | N2—C17—C16 | 175.4 (2) |
C16—C15—C3 | 131.64 (18) | N3—C18—C16 | 115.93 (17) |
C15—C16—C17 | 123.41 (16) | N3—C18—S1 | 121.89 (14) |
C15—C16—C18 | 121.76 (17) | C16—C18—S1 | 122.14 (14) |
C17—C16—C18 | 114.82 (16) | | |
| | | |
C11—N1—C12—C13 | −93.0 (2) | | |
Hydrogen-bond geometry (Å, º) for (IIIb) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3B···S1i | 0.86 | 2.55 | 3.402 (2) | 170 |
Symmetry code: (i) −x+1, −y+1, −z+2. |
Selected geometric parameters (Å, º) for (V) topS1—C18 | 1.7342 (18) | C3—C15 | 1.448 (2) |
S1—C19 | 1.712 (2) | C15—C16 | 1.358 (2) |
N2—C17 | 1.146 (2) | C16—C17 | 1.434 (3) |
N3—C18 | 1.307 (2) | C16—C18 | 1.471 (2) |
N3—C20 | 1.383 (2) | C19—C20 | 1.362 (3) |
| | | |
C18—S1—C19 | 88.93 (9) | N3—C18—C16 | 123.25 (16) |
C18—N3—C20 | 111.08 (15) | N3—C18—S1 | 114.59 (13) |
C2—C3—C15 | 124.00 (16) | C16—C18—S1 | 122.16 (14) |
C16—C15—C3 | 131.52 (17) | C20—C19—S1 | 111.09 (14) |
C15—C16—C17 | 124.43 (16) | C19—C20—N3 | 114.30 (17) |
C15—C16—C18 | 120.34 (16) | C19—C20—C21 | 126.89 (17) |
C17—C16—C18 | 115.21 (16) | N3—C20—C21 | 118.81 (17) |
N2—C17—C16 | 177.5 (2) | | |
| | | |
C11—N1—C12—C13 | 104.1 (2) | N3—C20—C21—C26 | −3.4 (3) |
C15—C16—C18—N3 | −4.4 (3) | | |
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Polar organic molecules as components of NLO, electro-optical, photorefractive and optical-limiting materials have been under intensive investigation for the last two decades (e.g. Zyss, 1994; Nalwa & Miyata, 1997; Kuzyk & Dirk, 1998). Structural data, along with theoretical calculations and experimental measurements, help to reveal the nature of the relevant structure-property relationships. The present investigation is a continuation of our project which includes synthesis, structural studies and evaluation of properties of organic compounds for potential optical applications (Antipin et al., 1997, 1998, 2001; Timofeeva et al., 2000; Nesterov et al., 2000). To our knowledge, no structural information on NLO carbazole derivatives has previously been available. Recently, we have synthesized and characterized a series of N-ethylcarbazole derivatives, (IIIa), (IIIb) and (V), shown in the synthetic scheme below. \sch
In this paper we present the results of structural investigations and the evaluation of second-harmonic generation (SGH) in solution for compounds (IIIa), (IIIb) and (V). Recently, we investigated another polar N-ethylcarbazole derivative, namely (E)-4-(9-ethyl-9H-carbazol-3-ylvinyl)-N-methylpyridinium iodide, (VI) (Wang et al., 2001), and we will compare the molecular geometry parameters for all four of these compounds.
The polar molecules under investigation can be formally divided into three planar fragments: a donor part, D, comprising the N-ethylcarbazole moiety less the ethyl group, a bridging part, B [–CH═C< in (IIIa), (IIIb) and (V), but –CH═CH– in (VI)], and an acceptor part, A, which differs in each molecule. The geometric parameters for N-ethylcarbazole in (IIIa), (IIIb), (V) and in the two symmetrically independent molecules of (VI) are very similar and do not vary from the standard values for corresponding heterocyclic systems (Allen et al., 1987). The orientation of the N-ethyl substituents in all the molecules is almost perpendicular to the carbazole plane (Tables 1, 2 and 4). In all the molecules, the bridging part B has a C═C bond which is slightly longer than the standard value (Allen et al., 1987). As the attached single bonds are slightly shorter (Tables 1, 2 and 4), this is evidence of some delocalization in the bridging units of these molecules.
The geometric parameters of the dicyanovinyl acceptor fragment in molecule (IIIa) (Fig. 1) are standard (Timofeeva et al., 2000). Molecule (IIIa) is almost planar, the dihedral angle between the least-squares mean planes of the donor part D Is this change OK? and the dicyanovinyl group is 5.1 (1)°. This does not differ significantly from the results for the other dicyanovinylaromatic molecules (Timofeeva et al., 2000). Molecules of (IIIa) adopt a herring-bone packing motif.
The Cambridge Structural Database (CSD, Version?; Allen & Kennard, 1993) contains only one compound, namely trans,trans-2-cyano-5-(4-methoxyphenyl)penta-2,4-dienethioamide (Nesterov et al., 2000), which has mutually trans CN and S substituents and is suitable for direct comparison with the cyanovinylthioamide fragment found in (IIIb) (Fig. 2). In the other two known structures containing such fragments, the cyano and thio substituents are mutually cis (Brunskill at al., 1984; Nesterov et al., 1991).
The different relative orientations of the substituents do not significantly influence the bond lengths and angles in this fragment, and their values are very similar in all these molecules. Molecule (IIIb) is less planar than (IIIa); the dihedral angle between the D and B fragments is 15.5 (1)°, and between B and A it is 12.0 (2)°. The molecules pack in layers coplanar with (201). Within these layers, (IIIb) forms centrosymmetric dimers via N3—H3B···S1i hydrogen bonds [Table 3; symmetry code: (i) 1 - x, 1 - y, 2 - z].
In molecule (V) (Fig. 3), the values for the molecular geometry parameters of the phenylthiazole (Ph—T) substituents are similar to the other examples found in the CSD. The dihedral angles between planar fragments in (V) are D/B 6.3 (1), B/T 5.0 (1) and T/Ph 4.2 (1)°. Molecule (V) has a `bent' conformation and a mutually trans orientation of the S atom and C═C bridge (Fig. 3). We used molecular mechanics calculations to compare the relative energies of `bent' and `stretched' molecules of (V) having cis orientations of S and the double bond. Please explain `bent' and `stretched'. We found that the `stretched' conformation is favoured (the energy difference is 2.1 kcal mol-1; 1kcal mol-1 = 4.184 kJ mol-1), and this suggests that under other circumstances (e.g. in solution or in other polymorph), molecule (V) might adopt a different conformation. Molecules of (V) exhibit a herring-bone pattern in their packing.
All crystalline samples investigated are centrosymmetric, so they cannot manifest SHG in their crystalline phases. X-ray powder diffraction has shown that for both (IIIb) and (V), the crystalline phase present in the powder samples and in single crystals is the same. In contrast, the powder diffraction pattern for compound (IIIa) shows the presence of another crystalline phase. Unfortunately, we have not been able to obtain single crystals of the second phase of (IIIa) by conventional methods, and we are currently investigating other approaches to growing single crystals suitable for X-ray investigation.
SHG in solution can be measured after orientation of the molecules by an electric field. Electric field-induced second harmonic generation (EFISH) measurements of hyperpolarizability β(ω) in solution give values of 42.5, 60.2 and 65.2 × 10-30 esu for molecules (IIIa), (IIIb) and (V), respectively. These results suggest that materials incorporating molecules of (IIIb) or (V) might be as efficient as traditional cyanovinyl derivatives (Antipin et al., 1997), but their melting point and thermal stability would both be higher because of the presence of the N-ethylcarbazole moiety.