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The crystal structures of 9-[(
E)-(4-nitrophenyl)vinyl]-9
H-carbazole and 9-[(
E)-(3-nitrophenyl)vinyl]-9
H-carbazole, both C
20H
14N
2O
2, are determined mainly by van der Waals forces and
-
interactions between the carbazole and benzene systems. However, the packing modes are different. In the 4-nitro derivative, the molecules in the weakly bound stack are related by a unit-cell translation, while in the 3-nitro derivative there are centrosymmetric pairs of molecules joined by
-
interactions and also pairs of molecules, related by another centre of symmetry, connected by eight relatively short C-H
O interactions.
Supporting information
CCDC references: 672535; 672536
The syntheses of the title compounds have been described elsewhere (Prukała
et al., 2007). Crystals appropriate for X-ray diffraction experiments
were obtained by slow evaporation from methanol solutions.
The positions of the H atoms were found in difference Fourier maps, and their
positional parameters were then refined. In the case of (I), their isotropic
dispacement parameters were also refined. After convergence, the positional
parameters were kept as a `riding model' [Range of C—H distances?], while
the displacement parameters were fixed at the refined values in (I) and set at
1.2Ueq(parent) in (II). In (I), some weak constraints on the
Uij tensor components of selected atoms were applied.
For both compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1989); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
(I) 9-[(
E)-(4-nitrophenyl)vinyl]-9
H-carbazole
top
Crystal data top
C20H14N2O2 | F(000) = 656 |
Mr = 314.33 | Dx = 1.380 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 3233 reflections |
a = 6.2627 (9) Å | θ = 4–22° |
b = 8.6572 (8) Å | µ = 0.09 mm−1 |
c = 27.943 (2) Å | T = 295 K |
β = 92.578 (10)° | Prism, colourless |
V = 1513.5 (3) Å3 | 0.35 × 0.2 × 0.15 mm |
Z = 4 | |
Data collection top
Kuma KM-4 CCD area-detector diffractometer | 1873 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.027 |
Graphite monochromator | θmax = 28.0°, θmin = 2.8° |
ω scans | h = −5→8 |
12049 measured reflections | k = −11→11 |
3634 independent reflections | l = −36→36 |
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)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.106 | Only H-atom displacement parameters refined |
S = 1.01 | w = 1/[σ2(Fo2) + (0.05P)2] where P = (Fo2 + 2Fc2)/3 |
3634 reflections | (Δ/σ)max = 0.001 |
231 parameters | Δρmax = 0.31 e Å−3 |
8 restraints | Δρmin = −0.24 e Å−3 |
Crystal data top
C20H14N2O2 | V = 1513.5 (3) Å3 |
Mr = 314.33 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 6.2627 (9) Å | µ = 0.09 mm−1 |
b = 8.6572 (8) Å | T = 295 K |
c = 27.943 (2) Å | 0.35 × 0.2 × 0.15 mm |
β = 92.578 (10)° | |
Data collection top
Kuma KM-4 CCD area-detector diffractometer | 1873 reflections with I > 2σ(I) |
12049 measured reflections | Rint = 0.027 |
3634 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.044 | 8 restraints |
wR(F2) = 0.106 | Only H-atom displacement parameters refined |
S = 1.01 | Δρmax = 0.31 e Å−3 |
3634 reflections | Δρmin = −0.24 e Å−3 |
231 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. Weak restraints to the Uij components were applied (DELU) due to the
relatively large values of Hirshfeld differences for some pairs of atoms. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.2771 (3) | 0.23323 (18) | 0.92256 (6) | 0.0478 (4) | |
H1 | 0.4069 | 0.2600 | 0.9378 | 0.053 (5)* | |
C2 | 0.1324 (3) | 0.1413 (2) | 0.94503 (6) | 0.0535 (5) | |
H2 | 0.1647 | 0.1074 | 0.9761 | 0.064 (5)* | |
C3 | −0.0603 (3) | 0.0982 (2) | 0.92257 (6) | 0.0516 (4) | |
H3 | −0.1550 | 0.0365 | 0.9387 | 0.054 (5)* | |
C4 | −0.1122 (3) | 0.14587 (17) | 0.87673 (6) | 0.0453 (4) | |
H4 | −0.2411 | 0.1160 | 0.8616 | 0.046 (4)* | |
C5 | 0.0290 (2) | 0.23886 (17) | 0.85309 (5) | 0.0371 (4) | |
C6 | 0.0220 (2) | 0.30748 (16) | 0.80580 (5) | 0.0371 (4) | |
C7 | −0.1282 (3) | 0.30712 (18) | 0.76771 (6) | 0.0456 (4) | |
H7 | −0.2542 | 0.2511 | 0.7696 | 0.047 (5)* | |
C8 | −0.0885 (3) | 0.3905 (2) | 0.72712 (6) | 0.0542 (5) | |
H8 | −0.1885 | 0.3908 | 0.7015 | 0.053 (5)* | |
C9 | 0.0992 (3) | 0.4740 (2) | 0.72413 (6) | 0.0568 (5) | |
H9 | 0.1233 | 0.5294 | 0.6964 | 0.060 (5)* | |
C10 | 0.2508 (3) | 0.47656 (19) | 0.76132 (6) | 0.0498 (4) | |
H10 | 0.3760 | 0.5335 | 0.7592 | 0.046 (4)* | |
C11 | 0.2113 (2) | 0.39208 (17) | 0.80199 (5) | 0.0385 (4) | |
N12 | 0.33454 (18) | 0.37887 (14) | 0.84508 (4) | 0.0411 (3) | |
C13 | 0.2231 (2) | 0.28458 (17) | 0.87650 (5) | 0.0383 (4) | |
C14 | 0.5227 (2) | 0.46500 (18) | 0.85405 (6) | 0.0473 (4) | |
H14 | 0.5833 | 0.5060 | 0.8270 | 0.069 (6)* | |
C15 | 0.6234 (3) | 0.4956 (2) | 0.89453 (7) | 0.0530 (4) | |
H15 | 0.5645 | 0.4576 | 0.9221 | 0.112 (8)* | |
C16 | 0.8226 (2) | 0.58482 (18) | 0.90043 (6) | 0.0445 (4) | |
C17 | 0.9088 (3) | 0.6095 (2) | 0.94609 (6) | 0.0559 (5) | |
H17 | 0.8376 | 0.5721 | 0.9722 | 0.074 (6)* | |
C18 | 1.0962 (3) | 0.6873 (2) | 0.95383 (6) | 0.0545 (5) | |
H18 | 1.1530 | 0.7016 | 0.9848 | 0.064 (5)* | |
C19 | 1.2005 (2) | 0.74447 (17) | 0.91558 (6) | 0.0410 (4) | |
C20 | 1.1197 (2) | 0.72733 (18) | 0.86951 (6) | 0.0455 (4) | |
H20 | 1.1902 | 0.7690 | 0.8439 | 0.045 (5)* | |
C21 | 0.9294 (2) | 0.64616 (18) | 0.86192 (6) | 0.0453 (4) | |
H21 | 0.8727 | 0.6324 | 0.8309 | 0.065 (5)* | |
N22 | 1.4031 (2) | 0.82691 (17) | 0.92450 (6) | 0.0534 (4) | |
O23 | 1.4798 (2) | 0.83148 (18) | 0.96520 (5) | 0.0823 (5) | |
O24 | 1.4852 (2) | 0.88750 (16) | 0.89045 (5) | 0.0737 (4) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0451 (10) | 0.0504 (10) | 0.0473 (10) | −0.0017 (8) | −0.0058 (8) | −0.0012 (8) |
C2 | 0.0635 (12) | 0.0531 (10) | 0.0435 (10) | 0.0001 (9) | −0.0009 (9) | 0.0053 (8) |
C3 | 0.0512 (11) | 0.0511 (10) | 0.0528 (11) | −0.0070 (9) | 0.0055 (9) | 0.0061 (9) |
C4 | 0.0433 (10) | 0.0428 (9) | 0.0496 (10) | −0.0046 (8) | 0.0012 (8) | −0.0035 (8) |
C5 | 0.0361 (9) | 0.0350 (8) | 0.0402 (9) | 0.0022 (7) | 0.0014 (7) | −0.0055 (7) |
C6 | 0.0367 (9) | 0.0377 (8) | 0.0369 (9) | −0.0002 (7) | 0.0002 (7) | −0.0064 (7) |
C7 | 0.0428 (10) | 0.0420 (9) | 0.0515 (11) | −0.0057 (8) | −0.0046 (8) | −0.0029 (8) |
C8 | 0.0586 (11) | 0.0559 (11) | 0.0467 (11) | −0.0037 (9) | −0.0135 (9) | 0.0000 (9) |
C9 | 0.0681 (12) | 0.0585 (11) | 0.0436 (11) | −0.0116 (10) | −0.0004 (9) | 0.0076 (9) |
C10 | 0.0463 (10) | 0.0567 (11) | 0.0466 (11) | −0.0113 (9) | 0.0026 (9) | 0.0015 (8) |
C11 | 0.0365 (9) | 0.0415 (9) | 0.0373 (9) | −0.0001 (7) | −0.0001 (7) | −0.0039 (7) |
N12 | 0.0340 (7) | 0.0460 (8) | 0.0433 (8) | −0.0013 (6) | 0.0001 (6) | −0.0011 (6) |
C13 | 0.0374 (9) | 0.0373 (9) | 0.0401 (9) | 0.0036 (7) | 0.0013 (7) | −0.0025 (7) |
C14 | 0.0328 (8) | 0.0507 (10) | 0.0582 (10) | 0.0021 (7) | 0.0002 (7) | −0.0070 (8) |
C15 | 0.0446 (9) | 0.0563 (11) | 0.0578 (10) | −0.0046 (7) | −0.0031 (7) | −0.0054 (8) |
C16 | 0.0336 (8) | 0.0407 (9) | 0.0590 (10) | 0.0037 (6) | 0.0012 (7) | −0.0034 (7) |
C17 | 0.0488 (11) | 0.0661 (12) | 0.0530 (11) | −0.0060 (9) | 0.0036 (9) | 0.0013 (9) |
C18 | 0.0495 (11) | 0.0652 (12) | 0.0480 (11) | −0.0012 (10) | −0.0051 (9) | −0.0012 (9) |
C19 | 0.0334 (8) | 0.0424 (9) | 0.0467 (10) | 0.0020 (6) | −0.0025 (7) | −0.0059 (7) |
C20 | 0.0418 (10) | 0.0477 (10) | 0.0469 (11) | −0.0008 (8) | 0.0006 (8) | −0.0018 (8) |
C21 | 0.0436 (9) | 0.0482 (10) | 0.0434 (9) | 0.0039 (7) | −0.0075 (7) | −0.0067 (7) |
N22 | 0.0407 (8) | 0.0564 (9) | 0.0624 (10) | −0.0032 (7) | −0.0047 (8) | −0.0109 (8) |
O23 | 0.0612 (9) | 0.1133 (12) | 0.0699 (10) | −0.0123 (8) | −0.0248 (8) | −0.0153 (8) |
O24 | 0.0579 (8) | 0.0792 (9) | 0.0845 (10) | −0.0234 (7) | 0.0090 (7) | −0.0003 (8) |
Geometric parameters (Å, º) top
C1—C2 | 1.378 (2) | C11—N12 | 1.4053 (18) |
C1—C13 | 1.389 (2) | N12—C13 | 1.4069 (19) |
C1—H1 | 0.9300 | N12—C14 | 1.4076 (19) |
C2—C3 | 1.386 (2) | C14—C15 | 1.297 (2) |
C2—H2 | 0.9300 | C14—H14 | 0.9300 |
C3—C4 | 1.371 (2) | C15—C16 | 1.470 (2) |
C3—H3 | 0.9300 | C15—H15 | 0.9300 |
C4—C5 | 1.386 (2) | C16—C17 | 1.380 (2) |
C4—H4 | 0.9300 | C16—C21 | 1.397 (2) |
C5—C13 | 1.411 (2) | C17—C18 | 1.362 (2) |
C5—C6 | 1.448 (2) | C17—H17 | 0.9300 |
C6—C7 | 1.389 (2) | C18—C19 | 1.370 (2) |
C6—C11 | 1.401 (2) | C18—H18 | 0.9300 |
C7—C8 | 1.376 (2) | C19—C20 | 1.370 (2) |
C7—H7 | 0.9300 | C19—N22 | 1.467 (2) |
C8—C9 | 1.386 (2) | C20—C21 | 1.391 (2) |
C8—H8 | 0.9300 | C20—H20 | 0.9300 |
C9—C10 | 1.376 (2) | C21—H21 | 0.9300 |
C9—H9 | 0.9300 | N22—O23 | 1.2153 (17) |
C10—C11 | 1.383 (2) | N22—O24 | 1.2202 (18) |
C10—H10 | 0.9300 | | |
| | | |
C2—C1—C13 | 118.00 (16) | C11—N12—C13 | 108.26 (12) |
C2—C1—H1 | 121.0 | C11—N12—C14 | 122.19 (13) |
C13—C1—H1 | 121.0 | C13—N12—C14 | 129.12 (13) |
C1—C2—C3 | 121.74 (16) | C1—C13—N12 | 131.09 (14) |
C1—C2—H2 | 119.2 | C1—C13—C5 | 120.56 (14) |
C3—C2—H2 | 119.1 | N12—C13—C5 | 108.33 (12) |
C4—C3—C2 | 120.48 (16) | C15—C14—N12 | 129.31 (18) |
C4—C3—H3 | 119.8 | C15—C14—H14 | 115.4 |
C2—C3—H3 | 119.8 | N12—C14—H14 | 115.3 |
C3—C4—C5 | 119.37 (15) | C14—C15—C16 | 125.57 (18) |
C3—C4—H4 | 120.3 | C14—C15—H15 | 117.1 |
C5—C4—H4 | 120.3 | C16—C15—H15 | 117.3 |
C4—C5—C13 | 119.81 (14) | C17—C16—C21 | 118.19 (15) |
C4—C5—C6 | 132.83 (14) | C17—C16—C15 | 118.69 (16) |
C13—C5—C6 | 107.35 (13) | C21—C16—C15 | 123.13 (15) |
C7—C6—C11 | 119.28 (14) | C18—C17—C16 | 121.47 (17) |
C7—C6—C5 | 133.66 (15) | C18—C17—H17 | 119.2 |
C11—C6—C5 | 107.03 (13) | C16—C17—H17 | 119.3 |
C8—C7—C6 | 119.28 (16) | C17—C18—C19 | 119.51 (16) |
C8—C7—H7 | 120.4 | C17—C18—H18 | 120.3 |
C6—C7—H7 | 120.3 | C19—C18—H18 | 120.2 |
C7—C8—C9 | 120.55 (16) | C18—C19—C20 | 121.67 (15) |
C7—C8—H8 | 119.7 | C18—C19—N22 | 118.83 (15) |
C9—C8—H8 | 119.7 | C20—C19—N22 | 119.50 (15) |
C10—C9—C8 | 121.43 (17) | C19—C20—C21 | 118.40 (16) |
C10—C9—H9 | 119.3 | C19—C20—H20 | 120.8 |
C8—C9—H9 | 119.3 | C21—C20—H20 | 120.8 |
C9—C10—C11 | 117.97 (16) | C20—C21—C16 | 120.73 (15) |
C9—C10—H10 | 121.0 | C20—C21—H21 | 119.7 |
C11—C10—H10 | 121.0 | C16—C21—H21 | 119.6 |
C10—C11—C6 | 121.48 (14) | O23—N22—O24 | 123.59 (15) |
C10—C11—N12 | 129.44 (14) | O23—N22—C19 | 118.50 (16) |
C6—C11—N12 | 109.03 (13) | O24—N22—C19 | 117.91 (14) |
| | | |
C13—C1—C2—C3 | 1.1 (2) | C14—N12—C13—C1 | −9.3 (3) |
C1—C2—C3—C4 | 0.3 (3) | C11—N12—C13—C5 | −0.17 (16) |
C2—C3—C4—C5 | −0.5 (2) | C14—N12—C13—C5 | 172.28 (13) |
C3—C4—C5—C13 | −0.6 (2) | C4—C5—C13—C1 | 2.0 (2) |
C3—C4—C5—C6 | −179.82 (16) | C6—C5—C13—C1 | −178.59 (13) |
C4—C5—C6—C7 | 1.2 (3) | C4—C5—C13—N12 | −179.33 (12) |
C13—C5—C6—C7 | −178.08 (16) | C6—C5—C13—N12 | 0.05 (16) |
C4—C5—C6—C11 | 179.36 (15) | C11—N12—C14—C15 | 161.13 (16) |
C13—C5—C6—C11 | 0.09 (16) | C13—N12—C14—C15 | −10.4 (3) |
C11—C6—C7—C8 | −0.3 (2) | N12—C14—C15—C16 | 178.80 (14) |
C5—C6—C7—C8 | 177.68 (16) | C14—C15—C16—C17 | 179.08 (16) |
C6—C7—C8—C9 | 0.0 (3) | C14—C15—C16—C21 | −0.9 (3) |
C7—C8—C9—C10 | −0.1 (3) | C21—C16—C17—C18 | −1.9 (2) |
C8—C9—C10—C11 | 0.4 (3) | C15—C16—C17—C18 | 178.05 (16) |
C9—C10—C11—C6 | −0.7 (2) | C16—C17—C18—C19 | 0.9 (3) |
C9—C10—C11—N12 | −177.79 (15) | C17—C18—C19—C20 | 0.9 (2) |
C7—C6—C11—C10 | 0.7 (2) | C17—C18—C19—N22 | −179.49 (15) |
C5—C6—C11—C10 | −177.79 (14) | C18—C19—C20—C21 | −1.6 (2) |
C7—C6—C11—N12 | 178.29 (13) | N22—C19—C20—C21 | 178.79 (13) |
C5—C6—C11—N12 | −0.19 (16) | C19—C20—C21—C16 | 0.6 (2) |
C10—C11—N12—C13 | 177.57 (16) | C17—C16—C21—C20 | 1.2 (2) |
C6—C11—N12—C13 | 0.23 (16) | C15—C16—C21—C20 | −178.80 (14) |
C10—C11—N12—C14 | 4.5 (2) | C18—C19—N22—O23 | 5.5 (2) |
C6—C11—N12—C14 | −172.85 (13) | C20—C19—N22—O23 | −174.88 (15) |
C2—C1—C13—N12 | 179.50 (15) | C18—C19—N22—O24 | −174.35 (15) |
C2—C1—C13—C5 | −2.2 (2) | C20—C19—N22—O24 | 5.2 (2) |
C11—N12—C13—C1 | 178.28 (16) | | |
(II) 9-[(
E)-(3-nitrophenyl)vinyl]-9
H-carbazole
top
Crystal data top
C20H14N2O2 | F(000) = 656 |
Mr = 314.33 | Dx = 1.420 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3582 reflections |
a = 8.1085 (16) Å | θ = 3–24° |
b = 7.5179 (11) Å | µ = 0.09 mm−1 |
c = 24.122 (4) Å | T = 100 K |
β = 90.507 (14)° | Prism, colourless |
V = 1470.4 (4) Å3 | 0.3 × 0.15 × 0.15 mm |
Z = 4 | |
Data collection top
Kuma KM-4 CCD area-detector diffractometer | 1278 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.091 |
Graphite monochromator | θmax = 25.0°, θmin = 2.5° |
ω scans | h = −9→9 |
10298 measured reflections | k = −8→5 |
2555 independent reflections | l = −28→28 |
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.092 | H-atom parameters constrained |
S = 0.99 | w = 1/[σ2(Fo2) + (0.02P)2] where P = (Fo2 + 2Fc2)/3 |
2554 reflections | (Δ/σ)max = 0.002 |
217 parameters | Δρmax = 0.21 e Å−3 |
0 restraints | Δρmin = −0.32 e Å−3 |
Crystal data top
C20H14N2O2 | V = 1470.4 (4) Å3 |
Mr = 314.33 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.1085 (16) Å | µ = 0.09 mm−1 |
b = 7.5179 (11) Å | T = 100 K |
c = 24.122 (4) Å | 0.3 × 0.15 × 0.15 mm |
β = 90.507 (14)° | |
Data collection top
Kuma KM-4 CCD area-detector diffractometer | 1278 reflections with I > 2σ(I) |
10298 measured reflections | Rint = 0.091 |
2555 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.092 | H-atom parameters constrained |
S = 0.99 | Δρmax = 0.21 e Å−3 |
2554 reflections | Δρmin = −0.32 e Å−3 |
217 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 | |
C1 | 0.4487 (3) | 0.4476 (3) | 0.84764 (11) | 0.0237 (7) | |
H1 | 0.3531 | 0.4554 | 0.8752 | 0.028* | |
C2 | 0.4330 (4) | 0.5271 (3) | 0.79613 (11) | 0.0279 (7) | |
H2 | 0.3239 | 0.5888 | 0.7900 | 0.034* | |
C3 | 0.5591 (4) | 0.5289 (3) | 0.75777 (11) | 0.0271 (7) | |
H3 | 0.5510 | 0.5919 | 0.7227 | 0.033* | |
C4 | 0.7082 (3) | 0.4451 (3) | 0.76950 (11) | 0.0259 (7) | |
H4 | 0.8015 | 0.4346 | 0.7419 | 0.031* | |
C5 | 0.7271 (3) | 0.3621 (3) | 0.82124 (11) | 0.0215 (6) | |
C6 | 0.8671 (3) | 0.2737 (3) | 0.84613 (11) | 0.0228 (7) | |
C7 | 1.0236 (4) | 0.2277 (3) | 0.82740 (11) | 0.0275 (7) | |
H7 | 1.0580 | 0.2556 | 0.7890 | 0.033* | |
C8 | 1.1323 (3) | 0.1435 (3) | 0.86341 (11) | 0.0268 (7) | |
H8 | 1.2423 | 0.1063 | 0.8483 | 0.032* | |
C9 | 1.0855 (3) | 0.1069 (3) | 0.91765 (11) | 0.0253 (7) | |
H9 | 1.1684 | 0.0517 | 0.9439 | 0.030* | |
C10 | 0.9313 (3) | 0.1503 (3) | 0.93759 (11) | 0.0234 (7) | |
H10 | 0.8994 | 0.1238 | 0.9796 | 0.028* | |
C11 | 0.8212 (3) | 0.2314 (3) | 0.90060 (11) | 0.0218 (7) | |
N12 | 0.6578 (3) | 0.2856 (3) | 0.90930 (8) | 0.0212 (6) | |
C13 | 0.6004 (4) | 0.3677 (3) | 0.86045 (11) | 0.0235 (7) | |
C14 | 0.5805 (3) | 0.2567 (3) | 0.96012 (11) | 0.0222 (7) | |
H14 | 0.6465 | 0.1881 | 0.9847 | 0.027* | |
C15 | 0.4334 (3) | 0.3086 (3) | 0.97653 (10) | 0.0214 (7) | |
H15 | 0.3609 | 0.3793 | 0.9518 | 0.026* | |
C16 | 0.3671 (3) | 0.2699 (3) | 1.03155 (10) | 0.0201 (7) | |
C17 | 0.2047 (3) | 0.3205 (3) | 1.04328 (10) | 0.0190 (7) | |
H17 | 0.1338 | 0.3778 | 1.0149 | 0.023* | |
C18 | 0.1416 (3) | 0.2848 (3) | 1.09534 (11) | 0.0209 (7) | |
C19 | 0.2291 (4) | 0.2014 (3) | 1.13681 (11) | 0.0261 (7) | |
H19 | 0.1808 | 0.1856 | 1.1733 | 0.031* | |
C20 | 0.3884 (3) | 0.1541 (3) | 1.12526 (11) | 0.0256 (7) | |
H20 | 0.4572 | 0.0978 | 1.1528 | 0.031* | |
C21 | 0.4564 (3) | 0.1875 (3) | 1.07385 (11) | 0.0240 (7) | |
H21 | 0.5722 | 0.1567 | 1.0681 | 0.029* | |
N22 | −0.0320 (3) | 0.3347 (3) | 1.10608 (10) | 0.0305 (6) | |
O23 | −0.1178 (2) | 0.3875 (2) | 1.06681 (9) | 0.0387 (6) | |
O24 | −0.0833 (2) | 0.3187 (3) | 1.15389 (8) | 0.0395 (6) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0235 (18) | 0.0257 (15) | 0.0218 (16) | −0.0017 (14) | −0.0002 (14) | −0.0017 (13) |
C2 | 0.0271 (19) | 0.0273 (17) | 0.0293 (17) | 0.0008 (14) | −0.0010 (15) | −0.0014 (14) |
C3 | 0.032 (2) | 0.0301 (17) | 0.0194 (16) | 0.0000 (15) | 0.0001 (15) | −0.0018 (14) |
C4 | 0.0293 (19) | 0.0251 (16) | 0.0234 (17) | −0.0055 (14) | 0.0049 (14) | −0.0065 (13) |
C5 | 0.0194 (16) | 0.0218 (15) | 0.0235 (16) | −0.0010 (13) | 0.0020 (14) | −0.0047 (13) |
C6 | 0.0253 (18) | 0.0170 (15) | 0.0262 (16) | −0.0068 (13) | 0.0023 (15) | −0.0041 (13) |
C7 | 0.0303 (19) | 0.0270 (17) | 0.0253 (17) | −0.0045 (15) | 0.0094 (15) | −0.0043 (13) |
C8 | 0.0231 (18) | 0.0258 (16) | 0.0315 (17) | 0.0000 (14) | 0.0065 (15) | −0.0058 (15) |
C9 | 0.0194 (17) | 0.0249 (16) | 0.0315 (18) | 0.0002 (13) | 0.0023 (15) | −0.0002 (13) |
C10 | 0.0248 (18) | 0.0176 (15) | 0.0279 (17) | −0.0022 (13) | 0.0030 (14) | −0.0001 (13) |
C11 | 0.0166 (16) | 0.0196 (15) | 0.0293 (17) | −0.0047 (13) | 0.0032 (14) | −0.0024 (13) |
N12 | 0.0240 (14) | 0.0214 (12) | 0.0182 (13) | 0.0021 (11) | 0.0070 (12) | 0.0002 (10) |
C13 | 0.0351 (19) | 0.0149 (15) | 0.0205 (16) | −0.0026 (14) | 0.0007 (15) | −0.0003 (13) |
C14 | 0.0231 (18) | 0.0204 (15) | 0.0232 (16) | 0.0006 (13) | −0.0025 (14) | 0.0023 (13) |
C15 | 0.0148 (16) | 0.0285 (17) | 0.0208 (15) | 0.0035 (13) | −0.0042 (13) | −0.0003 (13) |
C16 | 0.0186 (16) | 0.0249 (16) | 0.0166 (15) | −0.0016 (13) | −0.0032 (13) | −0.0040 (13) |
C17 | 0.0183 (16) | 0.0192 (15) | 0.0196 (16) | −0.0009 (13) | 0.0021 (13) | −0.0018 (12) |
C18 | 0.0196 (17) | 0.0173 (15) | 0.0260 (16) | −0.0016 (13) | 0.0055 (14) | −0.0067 (13) |
C19 | 0.036 (2) | 0.0255 (16) | 0.0165 (15) | −0.0033 (14) | 0.0033 (15) | −0.0048 (13) |
C20 | 0.0251 (18) | 0.0250 (16) | 0.0265 (17) | 0.0054 (14) | −0.0063 (15) | 0.0020 (13) |
C21 | 0.0132 (15) | 0.0268 (17) | 0.0319 (18) | 0.0007 (13) | −0.0021 (14) | −0.0041 (14) |
N22 | 0.0334 (17) | 0.0258 (14) | 0.0325 (16) | −0.0025 (12) | 0.0077 (14) | −0.0055 (12) |
O23 | 0.0271 (13) | 0.0502 (13) | 0.0389 (13) | 0.0068 (11) | 0.0016 (11) | 0.0022 (11) |
O24 | 0.0376 (14) | 0.0475 (13) | 0.0337 (13) | 0.0004 (10) | 0.0177 (11) | 0.0013 (10) |
Geometric parameters (Å, º) top
C1—C2 | 1.384 (3) | C11—N12 | 1.404 (3) |
C1—C13 | 1.401 (4) | N12—C14 | 1.399 (3) |
C1—H1 | 1.0265 | N12—C13 | 1.406 (3) |
C2—C3 | 1.385 (4) | C14—C15 | 1.319 (3) |
C2—H2 | 1.0086 | C14—H14 | 0.9476 |
C3—C4 | 1.390 (4) | C15—C16 | 1.465 (3) |
C3—H3 | 0.9724 | C15—H15 | 0.9889 |
C4—C5 | 1.402 (3) | C16—C21 | 1.391 (3) |
C4—H4 | 1.0149 | C16—C17 | 1.402 (3) |
C5—C13 | 1.404 (4) | C17—C18 | 1.386 (3) |
C5—C6 | 1.442 (4) | C17—H17 | 0.9878 |
C6—C7 | 1.395 (4) | C18—C19 | 1.373 (3) |
C6—C11 | 1.405 (3) | C18—N22 | 1.482 (3) |
C7—C8 | 1.385 (3) | C19—C20 | 1.371 (4) |
C7—H7 | 0.9918 | C19—H19 | 0.9744 |
C8—C9 | 1.393 (3) | C20—C21 | 1.385 (3) |
C8—H8 | 1.0061 | C20—H20 | 0.9622 |
C9—C10 | 1.382 (3) | C21—H21 | 0.9784 |
C9—H9 | 1.0089 | N22—O24 | 1.235 (3) |
C10—C11 | 1.397 (3) | N22—O23 | 1.236 (3) |
C10—H10 | 1.0659 | | |
| | | |
C2—C1—C13 | 117.2 (3) | C14—N12—C11 | 121.1 (2) |
C2—C1—H1 | 119.5 | C14—N12—C13 | 130.9 (2) |
C13—C1—H1 | 123.2 | C11—N12—C13 | 107.9 (2) |
C1—C2—C3 | 122.8 (3) | C1—C13—C5 | 120.7 (3) |
C1—C2—H2 | 113.8 | C1—C13—N12 | 131.1 (2) |
C3—C2—H2 | 123.3 | C5—C13—N12 | 108.2 (2) |
C2—C3—C4 | 120.3 (3) | C15—C14—N12 | 129.1 (3) |
C2—C3—H3 | 122.8 | C15—C14—H14 | 118.7 |
C4—C3—H3 | 116.8 | N12—C14—H14 | 112.2 |
C3—C4—C5 | 118.1 (3) | C14—C15—C16 | 123.6 (2) |
C3—C4—H4 | 123.6 | C14—C15—H15 | 120.8 |
C5—C4—H4 | 118.2 | C16—C15—H15 | 115.6 |
C4—C5—C13 | 120.7 (3) | C21—C16—C17 | 117.1 (2) |
C4—C5—C6 | 131.0 (3) | C21—C16—C15 | 124.0 (3) |
C13—C5—C6 | 108.2 (2) | C17—C16—C15 | 118.8 (2) |
C7—C6—C11 | 119.8 (3) | C18—C17—C16 | 119.0 (3) |
C7—C6—C5 | 134.0 (3) | C18—C17—H17 | 119.6 |
C11—C6—C5 | 106.2 (2) | C16—C17—H17 | 121.4 |
C8—C7—C6 | 119.1 (3) | C19—C18—C17 | 123.8 (3) |
C8—C7—H7 | 120.0 | C19—C18—N22 | 118.3 (2) |
C6—C7—H7 | 120.9 | C17—C18—N22 | 117.9 (3) |
C7—C8—C9 | 120.1 (3) | C20—C19—C18 | 116.9 (2) |
C7—C8—H8 | 117.5 | C20—C19—H19 | 122.6 |
C9—C8—H8 | 122.3 | C18—C19—H19 | 120.3 |
C10—C9—C8 | 122.3 (3) | C19—C20—C21 | 121.2 (3) |
C10—C9—H9 | 118.6 | C19—C20—H20 | 121.0 |
C8—C9—H9 | 119.0 | C21—C20—H20 | 117.7 |
C9—C10—C11 | 117.1 (2) | C20—C21—C16 | 121.9 (3) |
C9—C10—H10 | 120.9 | C20—C21—H21 | 118.3 |
C11—C10—H10 | 121.9 | C16—C21—H21 | 119.7 |
C10—C11—N12 | 129.1 (2) | O24—N22—O23 | 123.7 (3) |
C10—C11—C6 | 121.5 (3) | O24—N22—C18 | 117.8 (3) |
N12—C11—C6 | 109.4 (2) | O23—N22—C18 | 118.4 (2) |
| | | |
C13—C1—C2—C3 | 0.4 (4) | C6—C5—C13—C1 | 179.6 (2) |
C1—C2—C3—C4 | 1.6 (4) | C4—C5—C13—N12 | −175.8 (2) |
C2—C3—C4—C5 | −1.0 (4) | C6—C5—C13—N12 | 0.2 (3) |
C3—C4—C5—C13 | −1.6 (4) | C14—N12—C13—C1 | 0.7 (4) |
C3—C4—C5—C6 | −176.6 (3) | C11—N12—C13—C1 | −178.4 (3) |
C4—C5—C6—C7 | −5.7 (5) | C14—N12—C13—C5 | −180.0 (2) |
C13—C5—C6—C7 | 178.8 (3) | C11—N12—C13—C5 | 0.9 (3) |
C4—C5—C6—C11 | 174.2 (3) | C11—N12—C14—C15 | 175.1 (3) |
C13—C5—C6—C11 | −1.2 (3) | C13—N12—C14—C15 | −4.0 (5) |
C11—C6—C7—C8 | −1.0 (4) | N12—C14—C15—C16 | −179.6 (2) |
C5—C6—C7—C8 | 178.9 (3) | C14—C15—C16—C21 | 5.4 (4) |
C6—C7—C8—C9 | −0.5 (4) | C14—C15—C16—C17 | −175.5 (3) |
C7—C8—C9—C10 | 0.6 (4) | C21—C16—C17—C18 | −0.6 (4) |
C8—C9—C10—C11 | 0.9 (4) | C15—C16—C17—C18 | −179.8 (2) |
C9—C10—C11—N12 | 178.6 (2) | C16—C17—C18—C19 | −0.2 (4) |
C9—C10—C11—C6 | −2.5 (4) | C16—C17—C18—N22 | −178.2 (2) |
C7—C6—C11—C10 | 2.6 (4) | C17—C18—C19—C20 | 0.9 (4) |
C5—C6—C11—C10 | −177.4 (2) | N22—C18—C19—C20 | 178.9 (2) |
C7—C6—C11—N12 | −178.2 (2) | C18—C19—C20—C21 | −0.8 (4) |
C5—C6—C11—N12 | 1.8 (3) | C19—C20—C21—C16 | −0.1 (4) |
C10—C11—N12—C14 | −1.9 (4) | C17—C16—C21—C20 | 0.8 (4) |
C6—C11—N12—C14 | 179.1 (2) | C15—C16—C21—C20 | 179.9 (2) |
C10—C11—N12—C13 | 177.4 (3) | C19—C18—N22—O24 | 8.7 (3) |
C6—C11—N12—C13 | −1.7 (3) | C17—C18—N22—O24 | −173.2 (2) |
C2—C1—C13—C5 | −3.0 (4) | C19—C18—N22—O23 | −170.4 (2) |
C2—C1—C13—N12 | 176.3 (2) | C17—C18—N22—O23 | 7.7 (3) |
C4—C5—C13—C1 | 3.6 (4) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···O23i | 1.03 | 2.65 | 3.619 (3) | 157 |
C2—H2···O24i | 1.01 | 2.48 | 3.302 (3) | 138 |
C15—H15···O23i | 0.99 | 2.67 | 3.580 (3) | 153 |
C17—H17···O23i | 0.99 | 2.65 | 3.512 (3) | 146 |
Symmetry code: (i) −x, −y+1, −z+2. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C20H14N2O2 | C20H14N2O2 |
Mr | 314.33 | 314.33 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, P21/c |
Temperature (K) | 295 | 100 |
a, b, c (Å) | 6.2627 (9), 8.6572 (8), 27.943 (2) | 8.1085 (16), 7.5179 (11), 24.122 (4) |
β (°) | 92.578 (10) | 90.507 (14) |
V (Å3) | 1513.5 (3) | 1470.4 (4) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.09 | 0.09 |
Crystal size (mm) | 0.35 × 0.2 × 0.15 | 0.3 × 0.15 × 0.15 |
|
Data collection |
Diffractometer | Kuma KM-4 CCD area-detector diffractometer | Kuma KM-4 CCD area-detector diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12049, 3634, 1873 | 10298, 2555, 1278 |
Rint | 0.027 | 0.091 |
(sin θ/λ)max (Å−1) | 0.661 | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.106, 1.01 | 0.046, 0.092, 0.99 |
No. of reflections | 3634 | 2554 |
No. of parameters | 231 | 217 |
No. of restraints | 8 | 0 |
H-atom treatment | Only H-atom displacement parameters refined | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.31, −0.24 | 0.21, −0.32 |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···O23i | 1.03 | 2.65 | 3.619 (3) | 157 |
C2—H2···O24i | 1.01 | 2.48 | 3.302 (3) | 138 |
C15—H15···O23i | 0.99 | 2.67 | 3.580 (3) | 153 |
C17—H17···O23i | 0.99 | 2.65 | 3.512 (3) | 146 |
Symmetry code: (i) −x, −y+1, −z+2. |
The influence of the substituents on the endocyclic
bond angles in the benzene ring. The `calc' values are taken
from Domenicano (1988) topAngle | (I) (exp) | (I) (calc) | (II) (exp) | (II) (calc) |
C21—C16—C17 | 118.2 (2) | 118.7 | 117.1 (2) | 118.5 |
C16—C17—C18 | 121.5 (2) | 121.2 | 119.0 (3) | 118.9 |
C17—C18—C19 | 119.5 (2) | 118.4 | 123.8 (3) | 123.2 |
C18—C19—C20 | 121.7 (2) | 122.5 | 116.9 (2) | 117.7 |
C19—C20—C21 | 118.4 (2) | 118.4 | 121.2 (3) | 120.6 |
C20—C21—C16 | 120.7 (2) | 121.2 | 121.9 (3) | 121.2 |
Selected torsion angles (°) and the angles between the mean planes of the
planar fragments (°). A is the carbazole ring system, B is the phenyl ring,
and C is the N—C═C—C bridge; s.u.'s in parentheses top | (I) | (II) |
C13—N12—C14—C15 | -10.4 (3) | -4.0 (5) |
N12—C14—C15—C16 | 178.8 (1) | -179.6 (2) |
C14—C15—C16—C17 | 179.1 (2) | -175.5 (3) |
A/B | 17.91 (6) | 1.71 (10) |
A/C | 17.43 (16) | 3.3 (3) |
B/C | 1.92 (15) | 5.0 (4) |
B/(NO2) | 5.6 (3) | 8.3 (3) |
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Over the past few years, vigorous growth has been observed in the chemistry of carbazole derivatives, due to their electroactivity and luminescent properties (Grazulevicius et al., 2003, and references therein; Hyun et al., 2006). These compounds are thermally and photochemically stable, which makes them useful objects for technological applications. For instance, the carbazole ring is easily funtionalized and covalently linked to other molecules (Diaz et al., 2002). This enables its use as a convenient building block for the design and synthesis of molecular glasses, which are widely studied as components of electroactive and photoactive materials (Zhang et al., 2004). The high photoconductivities and hole-transporting properties of many polymeric materials can be greatly improved by incorporating carbazole as a pendant group in the framework. This molecule, with a π-conjugated system, is used as a host material for both small-molecule OLEDs (organic light-emitting diodes) and polymer PLEDs (polymer light-emitting diodes), due to its high triplet energy and good hole-transporting ability (see, for example, Chen et al., 2003). PLEDs can emit white (Paik et al., 2002), pure deep-blue (Lu et al., 2004) or green or red (Zhang et al., 2006) light. Further extension of the π-conjugated double-bond system has been obtained via the synthesis of N-nitrostyryl-substituted carbazole derivatives, which are interesting from the photochemical point of view (Prukała et al., 2007). We report here the crystal and molecular structures of two such derivatives, the p-nitro isomer, 9-[(E)-(4-nitrophenyl)vinyl]-9H-carbazole, (I), and the m-nitro isomer, 9-[(E)-(3-nitrophenyl)vinyl]-9H-carbazole, (II).
The bond angles within the phenyl ring are influenced by the presence of the substituents. The nitro group causes an increase in the angle at the place of substitution and a decrease in the neighbouring angles. The effect of the vinyl group is the reverse (cf. Domenicano, 1988). The final bond-angle pattern is close to an additive combination of these effects (Table 1). It might be noted, however, that other factors (e.g. crystal packing) also influence the bond angles; otherwise, for instance, the bond angles in (I) should be symmetrically distributed.
The conformation of the molecules of (I) and (II) (Figs. 1 and 2, respectively) can be described by the dihedral angles between the approximately planar fragments of the carbazole moiety, the bridging vinyl group, the phenyl ring and the nitro group (Table 2). In (I), the whole nitrostyryl group is close to planarity [maximum dihedral angle 5.6 (3)°], but it is significantly tilted with respect to the carbazole group [17.4 (2)°]. The whole of compound (II) is almost planar, with the largest dihedral angle of 8.3 (3)° being observed between the phenyl and nitro planes. Interestingly, the maximum deviation from the mean plane through all 13 atoms of the carbazole fragment is significantly larger in (II) [0.074 (2) Å] than in (I) [0.028 (1) Å].
In the crystal structures of (I) and (II), van der Waals forces and π–π stacking interactions between the phenyl and carbazole moieties seem to be the most important factors determining the packing. In (I), the mean distance between the phenyl and carbazole planes, which create a stair-like structure along [001] (Fig. 3), is ca 3.45 Å, and the planes are inclined by 17.1°. In (II), the structure is more complicated. There are two kinds of centrosymmetric dimers, one of stacked molecules, with a mean distance between the planes of 3.30 Å, and the other formed by a number of weak C—H···O contacts (Table 3, Fig. 4). These dimers lie on different centres of symmetry and together also create a stair-like structure (Fig. 5).