Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107054571/av3120sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107054571/av3120Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107054571/av3120IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107054571/av3120IIIsup4.hkl |
CCDC references: 672563; 672564; 672565
For related literature, see: Chan et al. (2006); Chopra & Guru Row (2005); Desiraju & Steiner (1999); Domenicano (1988); Friend et al. (1999); Ito et al. (1991, 2006); Itoigawa et al. (2000); Kálmán et al. (1991); Kubicki & Szafrański (1998); Kubicki et al. (2007); Lommerse et al. (1996); Nakahara et al. (2002); Pan et al. (2005); Prukała et al. (2007); Ramsewak et al. (1999); Tachibana et al. (2001); Valerio et al. (2000); Zhang et al. (2006).
The syntheses of the title compounds were described elsewhere (Prukała et al., 2007). Crystals suitable for X-ray analysis were obtained by slow evaporation from methanol solutions.
The positions of H atoms in the structures of (I) and (II) were found in difference Fourier maps, and their positional and – in the case of (I) – isotropic displacement parameters were refined. For (III), H atoms were placed in ideal positions and refined as riding. The displacement parameters were set at 1.2Ueq of the carrier atoms in (II) and (III).
For all 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).
C20H14FN | F(000) = 600 |
Mr = 287.32 | Dx = 1.332 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3035 reflections |
a = 10.6715 (5) Å | θ = 2.4–29.4° |
b = 5.9502 (3) Å | µ = 0.09 mm−1 |
c = 22.9870 (11) Å | T = 100 K |
β = 100.953 (5)° | Block, colourless |
V = 1433.03 (12) Å3 | 0.3 × 0.15 × 0.15 mm |
Z = 4 |
Kuma KM-4 CCD four-circle diffractometer | 3593 independent reflections |
Radiation source: fine-focus sealed tube | 1963 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.040 |
Detector resolution: 8.1929 pixels mm-1 | θmax = 29.5°, θmin = 2.9° |
ω scan | h = −14→14 |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006) | k = −5→8 |
Tmin = 0.89, Tmax = 0.98 | l = −29→31 |
9484 measured reflections |
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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.060 | All H-atom parameters refined |
S = 1.01 | w = 1/[σ2(Fo2) + (0.018P)2] where P = (Fo2 + 2Fc2)/3 |
3593 reflections | (Δ/σ)max = 0.001 |
255 parameters | Δρmax = 0.19 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
C20H14FN | V = 1433.03 (12) Å3 |
Mr = 287.32 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.6715 (5) Å | µ = 0.09 mm−1 |
b = 5.9502 (3) Å | T = 100 K |
c = 22.9870 (11) Å | 0.3 × 0.15 × 0.15 mm |
β = 100.953 (5)° |
Kuma KM-4 CCD four-circle diffractometer | 3593 independent reflections |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006) | 1963 reflections with I > 2σ(I) |
Tmin = 0.89, Tmax = 0.98 | Rint = 0.040 |
9484 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.060 | All H-atom parameters refined |
S = 1.01 | Δρmax = 0.19 e Å−3 |
3593 reflections | Δρmin = −0.21 e Å−3 |
255 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 | ||
C1 | 0.35874 (12) | 0.0862 (2) | 0.58145 (5) | 0.0251 (3) | |
H1 | 0.3265 (10) | −0.0553 (18) | 0.5632 (4) | 0.021 (3)* | |
C2 | 0.43819 (13) | 0.2227 (2) | 0.55620 (6) | 0.0278 (3) | |
H2 | 0.4591 (11) | 0.1740 (18) | 0.5193 (5) | 0.032 (4)* | |
C3 | 0.48874 (13) | 0.4210 (2) | 0.58281 (6) | 0.0285 (3) | |
H3 | 0.5460 (11) | 0.518 (2) | 0.5643 (5) | 0.032 (4)* | |
C4 | 0.46118 (12) | 0.4868 (2) | 0.63668 (6) | 0.0254 (3) | |
H4 | 0.4954 (11) | 0.6212 (19) | 0.6565 (5) | 0.027 (3)* | |
C5 | 0.38248 (11) | 0.3508 (2) | 0.66349 (5) | 0.0202 (3) | |
C6 | 0.34288 (11) | 0.36184 (19) | 0.72057 (5) | 0.0206 (3) | |
C7 | 0.36399 (12) | 0.5165 (2) | 0.76690 (5) | 0.0246 (3) | |
H7 | 0.4139 (11) | 0.6532 (18) | 0.7635 (5) | 0.024 (3)* | |
C8 | 0.31127 (12) | 0.4752 (2) | 0.81633 (6) | 0.0277 (3) | |
H8 | 0.3259 (11) | 0.5816 (19) | 0.8491 (5) | 0.033 (4)* | |
C9 | 0.23703 (13) | 0.2845 (2) | 0.81938 (6) | 0.0272 (3) | |
H9 | 0.2012 (11) | 0.2563 (18) | 0.8537 (5) | 0.030 (4)* | |
C10 | 0.21406 (12) | 0.1297 (2) | 0.77383 (5) | 0.0250 (3) | |
H10 | 0.1608 (11) | −0.007 (2) | 0.7768 (4) | 0.025 (3)* | |
C11 | 0.26898 (11) | 0.1690 (2) | 0.72473 (5) | 0.0218 (3) | |
N12 | 0.26027 (9) | 0.04211 (16) | 0.67258 (4) | 0.0226 (3) | |
C13 | 0.33080 (11) | 0.1533 (2) | 0.63549 (5) | 0.0219 (3) | |
C14 | 0.17437 (11) | −0.1369 (2) | 0.65848 (5) | 0.0228 (3) | |
H14 | 0.1633 (10) | −0.2333 (17) | 0.6922 (5) | 0.021 (3)* | |
C15 | 0.10788 (12) | −0.1806 (2) | 0.60484 (5) | 0.0238 (3) | |
H15 | 0.1137 (10) | −0.0788 (18) | 0.5721 (5) | 0.027 (3)* | |
C16 | 0.01508 (11) | −0.3629 (2) | 0.59106 (5) | 0.0211 (3) | |
C17 | −0.08124 (12) | −0.3482 (2) | 0.54044 (5) | 0.0244 (3) | |
H17 | −0.0844 (10) | −0.2117 (18) | 0.5155 (5) | 0.026 (3)* | |
C18 | −0.17277 (12) | −0.5132 (2) | 0.52629 (5) | 0.0259 (3) | |
H18 | −0.2389 (11) | −0.5127 (18) | 0.4894 (5) | 0.036 (4)* | |
C19 | −0.16668 (12) | −0.6942 (2) | 0.56326 (5) | 0.0245 (3) | |
F19 | −0.25577 (7) | −0.86206 (11) | 0.54919 (3) | 0.0354 (2) | |
C20 | −0.07454 (12) | −0.7187 (2) | 0.61346 (6) | 0.0253 (3) | |
H20 | −0.0760 (11) | −0.8490 (19) | 0.6387 (5) | 0.034 (4)* | |
C21 | 0.01673 (12) | −0.5523 (2) | 0.62692 (5) | 0.0236 (3) | |
H21 | 0.0822 (11) | −0.5666 (18) | 0.6636 (5) | 0.033 (3)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0247 (8) | 0.0267 (8) | 0.0234 (7) | 0.0024 (7) | 0.0035 (6) | 0.0010 (6) |
C2 | 0.0250 (8) | 0.0362 (9) | 0.0234 (7) | 0.0068 (7) | 0.0077 (6) | 0.0032 (7) |
C3 | 0.0232 (8) | 0.0341 (9) | 0.0287 (8) | 0.0013 (7) | 0.0060 (6) | 0.0091 (7) |
C4 | 0.0212 (7) | 0.0249 (8) | 0.0287 (8) | 0.0004 (6) | 0.0006 (6) | 0.0020 (7) |
C5 | 0.0171 (7) | 0.0202 (7) | 0.0228 (7) | 0.0020 (6) | 0.0025 (5) | 0.0037 (6) |
C6 | 0.0160 (7) | 0.0215 (7) | 0.0234 (7) | 0.0025 (6) | 0.0018 (5) | 0.0017 (6) |
C7 | 0.0195 (7) | 0.0244 (8) | 0.0284 (7) | −0.0001 (6) | 0.0007 (6) | −0.0020 (6) |
C8 | 0.0247 (8) | 0.0326 (9) | 0.0248 (8) | 0.0023 (7) | 0.0022 (6) | −0.0081 (7) |
C9 | 0.0247 (8) | 0.0364 (9) | 0.0219 (7) | 0.0026 (7) | 0.0079 (6) | −0.0002 (7) |
C10 | 0.0239 (7) | 0.0276 (8) | 0.0239 (7) | −0.0015 (7) | 0.0053 (6) | 0.0008 (6) |
C11 | 0.0204 (7) | 0.0244 (8) | 0.0202 (6) | 0.0031 (6) | 0.0029 (6) | 0.0000 (6) |
N12 | 0.0254 (6) | 0.0219 (6) | 0.0206 (6) | −0.0021 (5) | 0.0052 (5) | −0.0008 (5) |
C13 | 0.0191 (7) | 0.0238 (7) | 0.0222 (7) | 0.0017 (6) | 0.0027 (6) | 0.0043 (6) |
C14 | 0.0236 (7) | 0.0205 (7) | 0.0250 (7) | 0.0021 (6) | 0.0066 (6) | 0.0016 (6) |
C15 | 0.0246 (7) | 0.0244 (8) | 0.0231 (7) | 0.0029 (6) | 0.0059 (6) | 0.0024 (6) |
C16 | 0.0196 (7) | 0.0233 (7) | 0.0213 (6) | 0.0021 (6) | 0.0062 (5) | −0.0036 (6) |
C17 | 0.0261 (7) | 0.0270 (8) | 0.0206 (7) | 0.0050 (7) | 0.0055 (6) | 0.0017 (6) |
C18 | 0.0213 (8) | 0.0338 (9) | 0.0229 (7) | 0.0025 (7) | 0.0048 (6) | −0.0042 (7) |
C19 | 0.0181 (7) | 0.0282 (8) | 0.0285 (7) | −0.0045 (6) | 0.0081 (6) | −0.0090 (6) |
F19 | 0.0288 (4) | 0.0407 (5) | 0.0363 (4) | −0.0096 (4) | 0.0052 (3) | −0.0081 (4) |
C20 | 0.0248 (8) | 0.0237 (8) | 0.0280 (8) | 0.0015 (6) | 0.0061 (6) | 0.0015 (6) |
C21 | 0.0207 (7) | 0.0252 (8) | 0.0236 (7) | 0.0034 (6) | 0.0010 (6) | 0.0000 (6) |
C1—C2 | 1.3793 (17) | C10—H10 | 1.002 (12) |
C1—C13 | 1.3901 (17) | C11—N12 | 1.4050 (14) |
C1—H1 | 0.974 (11) | N12—C14 | 1.4026 (15) |
C2—C3 | 1.3902 (18) | N12—C13 | 1.4054 (15) |
C2—H2 | 0.963 (11) | C14—C15 | 1.3261 (15) |
C3—C4 | 1.3826 (17) | C14—H14 | 0.988 (11) |
C3—H3 | 0.992 (12) | C15—C16 | 1.4625 (17) |
C4—C5 | 1.3914 (17) | C15—H15 | 0.978 (11) |
C4—H4 | 0.958 (11) | C16—C21 | 1.3943 (16) |
C5—C13 | 1.4018 (15) | C16—C17 | 1.4013 (16) |
C5—C6 | 1.4543 (16) | C17—C18 | 1.3792 (17) |
C6—C7 | 1.3932 (16) | C17—H17 | 0.992 (10) |
C6—C11 | 1.4055 (16) | C18—C19 | 1.3659 (16) |
C7—C8 | 1.3825 (17) | C18—H18 | 0.995 (11) |
C7—H7 | 0.983 (11) | C19—C20 | 1.3743 (16) |
C8—C9 | 1.3931 (18) | C19—F19 | 1.3744 (13) |
C8—H8 | 0.974 (11) | C20—C21 | 1.3822 (17) |
C9—C10 | 1.3813 (17) | C20—H20 | 0.970 (11) |
C9—H9 | 0.954 (12) | C21—H21 | 0.991 (11) |
C10—C11 | 1.3870 (17) | ||
C2—C1—C13 | 117.40 (12) | N12—C11—C6 | 109.13 (10) |
C2—C1—H1 | 121.5 (6) | C14—N12—C11 | 122.68 (10) |
C13—C1—H1 | 121.0 (6) | C14—N12—C13 | 128.26 (10) |
C1—C2—C3 | 122.20 (13) | C11—N12—C13 | 107.96 (9) |
C1—C2—H2 | 117.3 (7) | C1—C13—C5 | 121.25 (12) |
C3—C2—H2 | 120.5 (7) | C1—C13—N12 | 129.60 (11) |
C4—C3—C2 | 120.23 (13) | C5—C13—N12 | 108.99 (10) |
C4—C3—H3 | 118.3 (7) | C15—C14—N12 | 125.06 (12) |
C2—C3—H3 | 121.5 (7) | C15—C14—H14 | 119.5 (6) |
C3—C4—C5 | 118.77 (13) | N12—C14—H14 | 115.5 (6) |
C3—C4—H4 | 122.4 (7) | C14—C15—C16 | 124.57 (12) |
C5—C4—H4 | 118.8 (7) | C14—C15—H15 | 119.6 (7) |
C4—C5—C13 | 120.12 (11) | C16—C15—H15 | 115.6 (7) |
C4—C5—C6 | 132.59 (11) | C21—C16—C17 | 117.78 (12) |
C13—C5—C6 | 107.20 (10) | C21—C16—C15 | 122.64 (11) |
C7—C6—C11 | 119.90 (11) | C17—C16—C15 | 119.57 (11) |
C7—C6—C5 | 133.38 (12) | C18—C17—C16 | 121.76 (12) |
C11—C6—C5 | 106.72 (10) | C18—C17—H17 | 120.1 (6) |
C8—C7—C6 | 118.61 (13) | C16—C17—H17 | 118.1 (6) |
C8—C7—H7 | 121.6 (6) | C19—C18—C17 | 117.82 (12) |
C6—C7—H7 | 119.8 (6) | C19—C18—H18 | 118.4 (7) |
C7—C8—C9 | 120.69 (13) | C17—C18—H18 | 123.7 (7) |
C7—C8—H8 | 119.3 (7) | C18—C19—C20 | 123.23 (12) |
C9—C8—H8 | 120.0 (7) | C18—C19—F19 | 118.53 (11) |
C10—C9—C8 | 121.73 (13) | C20—C19—F19 | 118.23 (11) |
C10—C9—H9 | 117.9 (7) | C19—C20—C21 | 118.24 (12) |
C8—C9—H9 | 120.4 (7) | C19—C20—H20 | 119.8 (7) |
C9—C10—C11 | 117.55 (13) | C21—C20—H20 | 122.0 (7) |
C9—C10—H10 | 120.8 (6) | C20—C21—C16 | 121.16 (12) |
C11—C10—H10 | 121.6 (6) | C20—C21—H21 | 118.8 (7) |
C10—C11—N12 | 129.33 (12) | C16—C21—H21 | 120.0 (7) |
C10—C11—C6 | 121.51 (11) | ||
C13—C1—C2—C3 | −0.40 (19) | C2—C1—C13—N12 | −175.61 (11) |
C1—C2—C3—C4 | 0.7 (2) | C4—C5—C13—C1 | 1.43 (18) |
C2—C3—C4—C5 | 0.09 (19) | C6—C5—C13—C1 | −175.55 (11) |
C3—C4—C5—C13 | −1.12 (18) | C4—C5—C13—N12 | 177.32 (11) |
C3—C4—C5—C6 | 174.96 (12) | C6—C5—C13—N12 | 0.35 (13) |
C4—C5—C6—C7 | 3.9 (2) | C14—N12—C13—C1 | −17.3 (2) |
C13—C5—C6—C7 | −179.68 (12) | C11—N12—C13—C1 | 174.66 (12) |
C4—C5—C6—C11 | −176.23 (12) | C14—N12—C13—C5 | 167.27 (11) |
C13—C5—C6—C11 | 0.22 (13) | C11—N12—C13—C5 | −0.79 (13) |
C11—C6—C7—C8 | 0.17 (18) | C11—N12—C14—C15 | 139.70 (13) |
C5—C6—C7—C8 | −179.94 (13) | C13—N12—C14—C15 | −26.78 (19) |
C6—C7—C8—C9 | −0.93 (19) | N12—C14—C15—C16 | −177.64 (12) |
C7—C8—C9—C10 | 0.5 (2) | C14—C15—C16—C21 | −22.22 (19) |
C8—C9—C10—C11 | 0.71 (19) | C14—C15—C16—C17 | 156.80 (12) |
C9—C10—C11—N12 | −179.22 (12) | C21—C16—C17—C18 | 0.63 (18) |
C9—C10—C11—C6 | −1.49 (18) | C15—C16—C17—C18 | −178.44 (12) |
C7—C6—C11—C10 | 1.07 (18) | C16—C17—C18—C19 | −0.30 (19) |
C5—C6—C11—C10 | −178.85 (11) | C17—C18—C19—C20 | 0.16 (19) |
C7—C6—C11—N12 | 179.21 (10) | C17—C18—C19—F19 | −178.81 (10) |
C5—C6—C11—N12 | −0.71 (13) | C18—C19—C20—C21 | −0.37 (19) |
C10—C11—N12—C14 | 10.01 (19) | F19—C19—C20—C21 | 178.61 (11) |
C6—C11—N12—C14 | −167.94 (10) | C19—C20—C21—C16 | 0.71 (19) |
C10—C11—N12—C13 | 178.88 (12) | C17—C16—C21—C20 | −0.84 (18) |
C6—C11—N12—C13 | 0.93 (13) | C15—C16—C21—C20 | 178.20 (12) |
C2—C1—C13—C5 | −0.65 (18) |
C20H14ClN | F(000) = 632 |
Mr = 303.77 | Dx = 1.362 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 5665 reflections |
a = 14.3190 (11) Å | θ = 2.4–29.9° |
b = 5.6943 (5) Å | µ = 0.25 mm−1 |
c = 18.6247 (18) Å | T = 100 K |
β = 102.730 (7)° | Block, colourless |
V = 1481.3 (2) Å3 | 0.45 × 0.15 × 0.08 mm |
Z = 4 |
Kuma KM-4 CCD four-circle diffractometer | 3382 independent reflections |
Radiation source: fine-focus sealed tube | 2241 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.039 |
ω scans | θmax = 27.5°, θmin = 2.9° |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006) | h = −18→18 |
Tmin = 0.85, Tmax = 0.98 | k = −5→7 |
12780 measured reflections | l = −23→24 |
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)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.080 | Only H-atom coordinates refined |
S = 1.02 | w = 1/[σ2(Fo2) + (0.040P)2] where P = (Fo2 + 2Fc2)/3 |
3382 reflections | (Δ/σ)max = 0.003 |
241 parameters | Δρmax = 0.27 e Å−3 |
0 restraints | Δρmin = −0.29 e Å−3 |
C20H14ClN | V = 1481.3 (2) Å3 |
Mr = 303.77 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 14.3190 (11) Å | µ = 0.25 mm−1 |
b = 5.6943 (5) Å | T = 100 K |
c = 18.6247 (18) Å | 0.45 × 0.15 × 0.08 mm |
β = 102.730 (7)° |
Kuma KM-4 CCD four-circle diffractometer | 3382 independent reflections |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006) | 2241 reflections with I > 2σ(I) |
Tmin = 0.85, Tmax = 0.98 | Rint = 0.039 |
12780 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.080 | Only H-atom coordinates refined |
S = 1.02 | Δρmax = 0.27 e Å−3 |
3382 reflections | Δρmin = −0.29 e Å−3 |
241 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 | ||
C1 | 0.06071 (11) | 0.7169 (3) | 0.08097 (9) | 0.0220 (3) | |
H1 | 0.0282 (10) | 0.576 (3) | 0.0618 (8) | 0.024* | |
C2 | 0.09982 (11) | 0.8623 (3) | 0.03547 (10) | 0.0258 (4) | |
H2 | 0.0876 (11) | 0.819 (3) | −0.0143 (9) | 0.031* | |
C3 | 0.14861 (11) | 1.0680 (3) | 0.06184 (10) | 0.0268 (4) | |
H3 | 0.1750 (11) | 1.164 (3) | 0.0270 (9) | 0.032* | |
C4 | 0.16037 (11) | 1.1320 (3) | 0.13475 (9) | 0.0240 (4) | |
H4 | 0.1940 (11) | 1.270 (3) | 0.1544 (8) | 0.029* | |
C5 | 0.12167 (10) | 0.9885 (2) | 0.18185 (8) | 0.0200 (3) | |
C6 | 0.12583 (10) | 0.9950 (2) | 0.26021 (8) | 0.0197 (3) | |
C7 | 0.16602 (11) | 1.1519 (3) | 0.31622 (9) | 0.0237 (4) | |
H7 | 0.1983 (11) | 1.291 (3) | 0.3037 (8) | 0.024* | |
C8 | 0.15803 (11) | 1.1040 (3) | 0.38746 (9) | 0.0257 (4) | |
H8 | 0.1865 (11) | 1.210 (3) | 0.4273 (9) | 0.031* | |
C9 | 0.11018 (11) | 0.9026 (3) | 0.40359 (9) | 0.0249 (4) | |
H9 | 0.1075 (11) | 0.874 (3) | 0.4558 (9) | 0.030* | |
C10 | 0.06864 (11) | 0.7459 (3) | 0.34907 (8) | 0.0210 (3) | |
H10 | 0.0376 (11) | 0.616 (3) | 0.3614 (8) | 0.025* | |
C11 | 0.07787 (10) | 0.7923 (2) | 0.27766 (8) | 0.0194 (3) | |
N12 | 0.04314 (9) | 0.6646 (2) | 0.21250 (7) | 0.0196 (3) | |
C13 | 0.07097 (10) | 0.7825 (2) | 0.15426 (8) | 0.0197 (3) | |
C14 | −0.02501 (11) | 0.4834 (2) | 0.20733 (9) | 0.0198 (3) | |
H14 | −0.0159 (10) | 0.384 (3) | 0.2517 (8) | 0.024* | |
C15 | −0.09655 (11) | 0.4494 (2) | 0.14920 (9) | 0.0201 (3) | |
H15 | −0.1036 (11) | 0.556 (2) | 0.1092 (8) | 0.024* | |
C16 | −0.17044 (10) | 0.2663 (2) | 0.14205 (8) | 0.0188 (3) | |
C17 | −0.25505 (11) | 0.2971 (3) | 0.08903 (9) | 0.0226 (4) | |
H17 | −0.2595 (11) | 0.431 (3) | 0.0572 (9) | 0.027* | |
C18 | −0.32980 (12) | 0.1378 (3) | 0.08031 (9) | 0.0249 (4) | |
H18 | −0.3940 (11) | 0.154 (3) | 0.0401 (9) | 0.030* | |
C19 | −0.31942 (11) | −0.0586 (3) | 0.12567 (9) | 0.0228 (4) | |
Cl19 | −0.41367 (3) | −0.26053 (7) | 0.11498 (2) | 0.02892 (13) | |
C20 | −0.23636 (11) | −0.0970 (3) | 0.17828 (9) | 0.0242 (4) | |
H20 | −0.2302 (11) | −0.233 (3) | 0.2079 (9) | 0.029* | |
C21 | −0.16189 (11) | 0.0642 (3) | 0.18604 (9) | 0.0215 (4) | |
H21 | −0.1045 (11) | 0.033 (2) | 0.2237 (8) | 0.026* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0181 (8) | 0.0227 (8) | 0.0250 (9) | 0.0007 (7) | 0.0046 (7) | −0.0025 (7) |
C2 | 0.0209 (9) | 0.0322 (9) | 0.0247 (9) | 0.0051 (7) | 0.0061 (8) | 0.0016 (8) |
C3 | 0.0209 (9) | 0.0284 (9) | 0.0324 (11) | 0.0028 (7) | 0.0089 (8) | 0.0083 (8) |
C4 | 0.0185 (8) | 0.0195 (8) | 0.0342 (10) | −0.0001 (7) | 0.0059 (7) | 0.0025 (7) |
C5 | 0.0153 (8) | 0.0178 (7) | 0.0263 (9) | 0.0029 (6) | 0.0033 (7) | 0.0010 (6) |
C6 | 0.0127 (7) | 0.0192 (8) | 0.0268 (9) | 0.0023 (6) | 0.0033 (7) | 0.0008 (6) |
C7 | 0.0176 (8) | 0.0191 (8) | 0.0335 (10) | 0.0005 (7) | 0.0035 (7) | −0.0029 (7) |
C8 | 0.0202 (9) | 0.0269 (9) | 0.0281 (10) | 0.0011 (7) | 0.0010 (7) | −0.0088 (7) |
C9 | 0.0203 (8) | 0.0307 (9) | 0.0232 (9) | 0.0050 (7) | 0.0036 (7) | −0.0012 (7) |
C10 | 0.0180 (7) | 0.0219 (8) | 0.0235 (8) | −0.0003 (7) | 0.0051 (6) | 0.0016 (7) |
C11 | 0.0125 (7) | 0.0202 (8) | 0.0244 (9) | 0.0020 (6) | 0.0013 (6) | −0.0024 (6) |
N12 | 0.0178 (7) | 0.0187 (6) | 0.0222 (7) | −0.0012 (5) | 0.0041 (6) | −0.0007 (5) |
C13 | 0.0146 (7) | 0.0193 (7) | 0.0250 (9) | 0.0034 (6) | 0.0040 (7) | 0.0022 (6) |
C14 | 0.0180 (8) | 0.0172 (8) | 0.0252 (9) | 0.0005 (6) | 0.0071 (7) | −0.0002 (6) |
C15 | 0.0208 (8) | 0.0174 (7) | 0.0235 (9) | 0.0022 (6) | 0.0079 (7) | 0.0016 (6) |
C16 | 0.0183 (7) | 0.0191 (7) | 0.0209 (8) | 0.0000 (6) | 0.0086 (6) | −0.0039 (6) |
C17 | 0.0221 (8) | 0.0240 (8) | 0.0225 (9) | −0.0007 (7) | 0.0065 (7) | 0.0010 (7) |
C18 | 0.0207 (9) | 0.0281 (8) | 0.0263 (9) | −0.0010 (7) | 0.0058 (7) | −0.0021 (7) |
C19 | 0.0193 (8) | 0.0221 (8) | 0.0301 (10) | −0.0040 (6) | 0.0119 (7) | −0.0073 (7) |
Cl19 | 0.0235 (2) | 0.0258 (2) | 0.0403 (3) | −0.00755 (17) | 0.01306 (18) | −0.00714 (18) |
C20 | 0.0253 (9) | 0.0192 (8) | 0.0299 (10) | 0.0010 (7) | 0.0100 (8) | −0.0002 (7) |
C21 | 0.0186 (8) | 0.0202 (8) | 0.0257 (9) | 0.0026 (6) | 0.0045 (7) | −0.0015 (7) |
C1—C2 | 1.388 (2) | C10—H10 | 0.916 (16) |
C1—C13 | 1.391 (2) | C11—N12 | 1.4081 (18) |
C1—H1 | 0.958 (15) | N12—C13 | 1.4060 (19) |
C2—C3 | 1.396 (2) | N12—C14 | 1.4085 (18) |
C2—H2 | 0.937 (16) | C14—C15 | 1.330 (2) |
C3—C4 | 1.380 (2) | C14—H14 | 0.985 (15) |
C3—H3 | 0.986 (16) | C15—C16 | 1.470 (2) |
C4—C5 | 1.400 (2) | C15—H15 | 0.949 (15) |
C4—H4 | 0.952 (16) | C16—C17 | 1.395 (2) |
C5—C13 | 1.4154 (19) | C16—C21 | 1.402 (2) |
C5—C6 | 1.448 (2) | C17—C18 | 1.385 (2) |
C6—C7 | 1.397 (2) | C17—H17 | 0.960 (15) |
C6—C11 | 1.417 (2) | C18—C19 | 1.390 (2) |
C7—C8 | 1.384 (2) | C18—H18 | 1.053 (16) |
C7—H7 | 0.971 (15) | C19—C20 | 1.382 (2) |
C8—C9 | 1.402 (2) | C19—Cl19 | 1.7506 (15) |
C8—H8 | 0.974 (16) | C20—C21 | 1.390 (2) |
C9—C10 | 1.384 (2) | C20—H20 | 0.946 (15) |
C9—H9 | 0.996 (16) | C21—H21 | 0.972 (15) |
C10—C11 | 1.391 (2) | ||
C2—C1—C13 | 118.01 (15) | N12—C11—C6 | 108.66 (13) |
C2—C1—H1 | 120.1 (9) | C13—N12—C14 | 127.35 (13) |
C13—C1—H1 | 121.9 (9) | C13—N12—C11 | 108.19 (12) |
C1—C2—C3 | 121.55 (16) | C14—N12—C11 | 123.01 (13) |
C1—C2—H2 | 115.8 (10) | C1—C13—N12 | 129.97 (13) |
C3—C2—H2 | 122.5 (10) | C1—C13—C5 | 120.88 (14) |
C4—C3—C2 | 120.73 (16) | N12—C13—C5 | 109.00 (13) |
C4—C3—H3 | 121.3 (9) | C15—C14—N12 | 124.04 (14) |
C2—C3—H3 | 117.9 (9) | C15—C14—H14 | 122.4 (9) |
C3—C4—C5 | 118.88 (15) | N12—C14—H14 | 113.6 (9) |
C3—C4—H4 | 122.6 (9) | C14—C15—C16 | 125.91 (14) |
C5—C4—H4 | 118.5 (9) | C14—C15—H15 | 118.4 (9) |
C4—C5—C13 | 119.92 (14) | C16—C15—H15 | 115.6 (9) |
C4—C5—C6 | 133.06 (14) | C17—C16—C21 | 117.85 (14) |
C13—C5—C6 | 106.91 (13) | C17—C16—C15 | 118.06 (13) |
C7—C6—C11 | 119.35 (14) | C21—C16—C15 | 124.09 (13) |
C7—C6—C5 | 133.43 (14) | C18—C17—C16 | 121.93 (15) |
C11—C6—C5 | 107.22 (12) | C18—C17—H17 | 120.2 (9) |
C8—C7—C6 | 118.85 (15) | C16—C17—H17 | 117.8 (9) |
C8—C7—H7 | 122.3 (9) | C17—C18—C19 | 118.65 (15) |
C6—C7—H7 | 118.8 (9) | C17—C18—H18 | 124.0 (8) |
C7—C8—C9 | 120.94 (15) | C19—C18—H18 | 117.4 (8) |
C7—C8—H8 | 120.0 (9) | C20—C19—C18 | 121.22 (14) |
C9—C8—H8 | 119.1 (9) | C20—C19—Cl19 | 119.90 (12) |
C10—C9—C8 | 121.44 (16) | C18—C19—Cl19 | 118.88 (12) |
C10—C9—H9 | 120.4 (9) | C19—C20—C21 | 119.35 (15) |
C8—C9—H9 | 118.1 (9) | C19—C20—H20 | 119.9 (10) |
C9—C10—C11 | 117.59 (15) | C21—C20—H20 | 120.7 (10) |
C9—C10—H10 | 119.3 (10) | C20—C21—C16 | 120.99 (15) |
C11—C10—H10 | 123.1 (10) | C20—C21—H21 | 117.4 (9) |
C10—C11—N12 | 129.51 (13) | C16—C21—H21 | 121.6 (9) |
C10—C11—C6 | 121.81 (14) | ||
C13—C1—C2—C3 | 0.3 (2) | C2—C1—C13—C5 | −1.4 (2) |
C1—C2—C3—C4 | 0.7 (2) | C14—N12—C13—C1 | −19.3 (2) |
C2—C3—C4—C5 | −0.7 (2) | C11—N12—C13—C1 | 174.23 (14) |
C3—C4—C5—C13 | −0.4 (2) | C14—N12—C13—C5 | 165.16 (13) |
C3—C4—C5—C6 | 175.43 (15) | C11—N12—C13—C5 | −1.30 (16) |
C4—C5—C6—C7 | 3.5 (3) | C4—C5—C13—C1 | 1.5 (2) |
C13—C5—C6—C7 | 179.71 (15) | C6—C5—C13—C1 | −175.36 (13) |
C4—C5—C6—C11 | −176.00 (16) | C4—C5—C13—N12 | 177.48 (13) |
C13—C5—C6—C11 | 0.23 (15) | C6—C5—C13—N12 | 0.66 (16) |
C11—C6—C7—C8 | 0.2 (2) | C13—N12—C14—C15 | −24.4 (2) |
C5—C6—C7—C8 | −179.22 (15) | C11—N12—C14—C15 | 140.21 (15) |
C6—C7—C8—C9 | −0.3 (2) | N12—C14—C15—C16 | −178.56 (13) |
C7—C8—C9—C10 | −0.5 (2) | C14—C15—C16—C17 | 160.69 (15) |
C8—C9—C10—C11 | 1.4 (2) | C14—C15—C16—C21 | −18.2 (2) |
C9—C10—C11—N12 | −179.90 (14) | C21—C16—C17—C18 | 1.3 (2) |
C9—C10—C11—C6 | −1.5 (2) | C15—C16—C17—C18 | −177.63 (14) |
C7—C6—C11—C10 | 0.7 (2) | C16—C17—C18—C19 | −0.3 (2) |
C5—C6—C11—C10 | −179.71 (13) | C17—C18—C19—C20 | −0.4 (2) |
C7—C6—C11—N12 | 179.40 (12) | C17—C18—C19—Cl19 | 179.95 (12) |
C5—C6—C11—N12 | −1.03 (15) | C18—C19—C20—C21 | 0.1 (2) |
C10—C11—N12—C13 | 179.99 (15) | Cl19—C19—C20—C21 | 179.75 (12) |
C6—C11—N12—C13 | 1.45 (15) | C19—C20—C21—C16 | 0.9 (2) |
C10—C11—N12—C14 | 12.8 (2) | C17—C16—C21—C20 | −1.6 (2) |
C6—C11—N12—C14 | −165.73 (13) | C15—C16—C21—C20 | 177.27 (14) |
C2—C1—C13—N12 | −176.48 (14) |
C20H14BrN | F(000) = 704 |
Mr = 348.23 | Dx = 1.542 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2826 reflections |
a = 14.5152 (5) Å | θ = 2.8–29.2° |
b = 5.6485 (2) Å | µ = 2.74 mm−1 |
c = 18.8260 (6) Å | T = 100 K |
β = 103.605 (3)° | Block, colourless |
V = 1500.22 (9) Å3 | 0.3 × 0.12 × 0.1 mm |
Z = 4 |
Kuma KM-4 CCD four-circle diffractometer | 3714 independent reflections |
Radiation source: fine-focus sealed tube | 2839 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
Detector resolution: 8.1929 pixels mm-1 | θmax = 29.0°, θmin = 2.9° |
ω scan | h = −18→19 |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006) | k = −7→6 |
Tmin = 0.44, Tmax = 0.77 | l = −24→20 |
9787 measured reflections |
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)] = 0.029 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.066 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.031P)2] where P = (Fo2 + 2Fc2)/3 |
3714 reflections | (Δ/σ)max = 0.001 |
199 parameters | Δρmax = 0.56 e Å−3 |
0 restraints | Δρmin = −0.57 e Å−3 |
C20H14BrN | V = 1500.22 (9) Å3 |
Mr = 348.23 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 14.5152 (5) Å | µ = 2.74 mm−1 |
b = 5.6485 (2) Å | T = 100 K |
c = 18.8260 (6) Å | 0.3 × 0.12 × 0.1 mm |
β = 103.605 (3)° |
Kuma KM-4 CCD four-circle diffractometer | 3714 independent reflections |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006) | 2839 reflections with I > 2σ(I) |
Tmin = 0.44, Tmax = 0.77 | Rint = 0.030 |
9787 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.066 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.56 e Å−3 |
3714 reflections | Δρmin = −0.57 e Å−3 |
199 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 | Occ. (<1) | |
C1 | 0.05920 (14) | 0.7145 (3) | 0.08078 (11) | 0.0191 (4) | |
H1 | 0.0261 | 0.5737 | 0.0627 | 0.023* | |
C2 | 0.09773 (14) | 0.8590 (4) | 0.03575 (11) | 0.0213 (4) | |
H2 | 0.0904 | 0.8167 | −0.0141 | 0.026* | |
C3 | 0.14720 (14) | 1.0660 (3) | 0.06207 (11) | 0.0235 (5) | |
H3 | 0.1725 | 1.1623 | 0.0299 | 0.028* | |
C4 | 0.15959 (13) | 1.1315 (3) | 0.13433 (10) | 0.0199 (4) | |
H4 | 0.1933 | 1.2718 | 0.1522 | 0.024* | |
C5 | 0.12176 (13) | 0.9880 (3) | 0.18066 (10) | 0.0167 (4) | |
X1 | 0.10952 (13) | 0.9168 (3) | 0.10834 (10) | 0.020* | 0.00 |
X2 | 0.08631 (13) | 0.8487 (3) | 0.21419 (10) | 0.020* | 0.00 |
X3 | 0.11896 (13) | 0.9556 (3) | 0.32800 (10) | 0.020* | 0.00 |
C6 | 0.12728 (13) | 0.9944 (3) | 0.25859 (10) | 0.0168 (4) | |
C7 | 0.16865 (13) | 1.1515 (3) | 0.31410 (11) | 0.0202 (4) | |
H7 | 0.2007 | 1.2889 | 0.3035 | 0.024* | |
C8 | 0.16222 (14) | 1.1040 (3) | 0.38472 (11) | 0.0220 (4) | |
H8 | 0.1901 | 1.2098 | 0.4230 | 0.026* | |
C9 | 0.11512 (14) | 0.9020 (3) | 0.40060 (11) | 0.0211 (4) | |
H9 | 0.1124 | 0.8717 | 0.4497 | 0.025* | |
C10 | 0.07213 (13) | 0.7446 (3) | 0.34608 (10) | 0.0191 (4) | |
H10 | 0.0390 | 0.6093 | 0.3568 | 0.023* | |
C11 | 0.07947 (13) | 0.7928 (3) | 0.27533 (10) | 0.0161 (4) | |
N12 | 0.04381 (11) | 0.6642 (3) | 0.21092 (8) | 0.0161 (3) | |
C13 | 0.07051 (13) | 0.7824 (3) | 0.15321 (10) | 0.0159 (4) | |
C14 | −0.02351 (13) | 0.4834 (3) | 0.20561 (10) | 0.0162 (4) | |
H14 | −0.0180 | 0.3795 | 0.2461 | 0.019* | |
C15 | −0.09497 (14) | 0.4475 (3) | 0.14735 (10) | 0.0172 (4) | |
H15 | −0.0986 | 0.5502 | 0.1068 | 0.021* | |
C16 | −0.16824 (13) | 0.2646 (3) | 0.13998 (10) | 0.0168 (4) | |
X4 | −0.24202 (13) | 0.1007 (3) | 0.13133 (10) | 0.020* | 0.00 |
C17 | −0.25092 (14) | 0.2920 (3) | 0.08539 (10) | 0.0213 (4) | |
H17 | −0.2565 | 0.4246 | 0.0536 | 0.026* | |
C18 | −0.32524 (14) | 0.1326 (4) | 0.07583 (11) | 0.0228 (4) | |
H18 | −0.3809 | 0.1543 | 0.0381 | 0.027* | |
C19 | −0.31630 (14) | −0.0591 (3) | 0.12261 (11) | 0.0196 (4) | |
Br19 | −0.419658 (14) | −0.27550 (3) | 0.111363 (11) | 0.02423 (7) | |
C20 | −0.23509 (14) | −0.0956 (3) | 0.17672 (11) | 0.0225 (4) | |
H20 | −0.2301 | −0.2291 | 0.2081 | 0.027* | |
C21 | −0.16088 (14) | 0.0643 (3) | 0.18495 (10) | 0.0188 (4) | |
H21 | −0.1044 | 0.0379 | 0.2215 | 0.023* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0155 (10) | 0.0188 (9) | 0.0214 (10) | 0.0011 (8) | 0.0011 (8) | −0.0033 (8) |
C2 | 0.0191 (11) | 0.0272 (10) | 0.0180 (10) | 0.0044 (8) | 0.0050 (8) | 0.0005 (8) |
C3 | 0.0179 (11) | 0.0253 (11) | 0.0279 (11) | 0.0023 (8) | 0.0067 (9) | 0.0099 (9) |
C4 | 0.0153 (11) | 0.0153 (9) | 0.0275 (11) | 0.0000 (7) | 0.0015 (8) | 0.0032 (8) |
C5 | 0.0134 (10) | 0.0140 (9) | 0.0214 (10) | 0.0025 (7) | 0.0015 (8) | 0.0004 (8) |
C6 | 0.0127 (10) | 0.0160 (9) | 0.0204 (10) | 0.0029 (7) | 0.0011 (8) | 0.0006 (8) |
C7 | 0.0146 (10) | 0.0168 (9) | 0.0269 (11) | 0.0006 (7) | 0.0005 (8) | −0.0027 (8) |
C8 | 0.0157 (10) | 0.0229 (10) | 0.0241 (11) | 0.0006 (8) | −0.0015 (8) | −0.0078 (8) |
C9 | 0.0181 (11) | 0.0253 (11) | 0.0184 (10) | 0.0050 (8) | 0.0014 (8) | −0.0020 (8) |
C10 | 0.0167 (10) | 0.0199 (10) | 0.0203 (10) | 0.0007 (8) | 0.0033 (8) | 0.0008 (8) |
C11 | 0.0120 (9) | 0.0152 (9) | 0.0189 (9) | 0.0028 (7) | −0.0007 (7) | −0.0021 (7) |
N12 | 0.0165 (9) | 0.0152 (8) | 0.0155 (8) | −0.0021 (6) | 0.0014 (6) | −0.0004 (6) |
C13 | 0.0119 (9) | 0.0154 (9) | 0.0200 (9) | 0.0018 (7) | 0.0027 (7) | 0.0015 (8) |
C14 | 0.0161 (10) | 0.0128 (9) | 0.0207 (10) | 0.0013 (7) | 0.0066 (8) | 0.0000 (7) |
C15 | 0.0179 (10) | 0.0143 (9) | 0.0194 (10) | −0.0004 (7) | 0.0047 (8) | 0.0001 (7) |
C16 | 0.0161 (9) | 0.0171 (10) | 0.0179 (9) | −0.0006 (7) | 0.0052 (7) | −0.0045 (7) |
C17 | 0.0224 (11) | 0.0213 (10) | 0.0193 (10) | −0.0013 (8) | 0.0028 (8) | 0.0038 (8) |
C18 | 0.0183 (11) | 0.0262 (10) | 0.0229 (11) | −0.0015 (8) | 0.0031 (8) | −0.0011 (9) |
C19 | 0.0175 (10) | 0.0189 (10) | 0.0245 (11) | −0.0034 (7) | 0.0091 (8) | −0.0069 (8) |
Br19 | 0.02019 (11) | 0.02325 (11) | 0.03118 (12) | −0.00704 (9) | 0.00994 (8) | −0.00681 (9) |
C20 | 0.0240 (11) | 0.0202 (10) | 0.0240 (11) | 0.0007 (8) | 0.0070 (9) | 0.0015 (8) |
C21 | 0.0169 (10) | 0.0177 (10) | 0.0209 (10) | 0.0021 (7) | 0.0024 (8) | −0.0012 (8) |
C1—C2 | 1.386 (3) | C10—H10 | 0.9500 |
C1—C13 | 1.388 (3) | C11—N12 | 1.404 (2) |
C1—H1 | 0.9500 | N12—C14 | 1.401 (2) |
C2—C3 | 1.400 (3) | N12—C13 | 1.405 (2) |
C2—H2 | 0.9500 | C14—C15 | 1.336 (2) |
C3—C4 | 1.380 (3) | C14—H14 | 0.9500 |
C3—H3 | 0.9500 | C15—C16 | 1.465 (2) |
C4—C5 | 1.395 (3) | C15—H15 | 0.9500 |
C4—H4 | 0.9500 | C16—C17 | 1.393 (3) |
C5—C13 | 1.410 (2) | C16—C21 | 1.402 (2) |
C5—C6 | 1.451 (3) | C17—C18 | 1.384 (3) |
C6—C7 | 1.394 (3) | C17—H17 | 0.9500 |
C6—C11 | 1.408 (3) | C18—C19 | 1.382 (3) |
C7—C8 | 1.381 (3) | C18—H18 | 0.9500 |
C7—H7 | 0.9500 | C19—C20 | 1.380 (3) |
C8—C9 | 1.398 (3) | C19—Br19 | 1.9079 (19) |
C8—H8 | 0.9500 | C20—C21 | 1.386 (3) |
C9—C10 | 1.390 (3) | C20—H20 | 0.9500 |
C9—H9 | 0.9500 | C21—H21 | 0.9500 |
C10—C11 | 1.388 (3) | ||
C2—C1—C13 | 117.82 (18) | N12—C11—C6 | 109.03 (16) |
C2—C1—H1 | 121.1 | C14—N12—C11 | 123.23 (16) |
C13—C1—H1 | 121.1 | C14—N12—C13 | 127.30 (15) |
C1—C2—C3 | 121.49 (18) | C11—N12—C13 | 108.03 (14) |
C1—C2—H2 | 119.3 | C1—C13—N12 | 129.63 (17) |
C3—C2—H2 | 119.3 | C1—C13—C5 | 121.17 (17) |
C4—C3—C2 | 120.65 (18) | N12—C13—C5 | 109.01 (16) |
C4—C3—H3 | 119.7 | C15—C14—N12 | 124.28 (17) |
C2—C3—H3 | 119.7 | C15—C14—H14 | 117.9 |
C3—C4—C5 | 118.79 (18) | N12—C14—H14 | 117.9 |
C3—C4—H4 | 120.6 | C14—C15—C16 | 126.21 (17) |
C5—C4—H4 | 120.6 | C14—C15—H15 | 116.9 |
C4—C5—C13 | 120.06 (17) | C16—C15—H15 | 116.9 |
C4—C5—C6 | 132.99 (17) | C17—C16—C21 | 117.72 (17) |
C13—C5—C6 | 106.86 (16) | C17—C16—C15 | 118.14 (16) |
C7—C6—C11 | 119.67 (18) | C21—C16—C15 | 124.13 (17) |
C7—C6—C5 | 133.27 (18) | C18—C17—C16 | 122.25 (18) |
C11—C6—C5 | 107.06 (16) | C18—C17—H17 | 118.9 |
C8—C7—C6 | 118.91 (18) | C16—C17—H17 | 118.9 |
C8—C7—H7 | 120.5 | C19—C18—C17 | 118.25 (18) |
C6—C7—H7 | 120.5 | C19—C18—H18 | 120.9 |
C7—C8—C9 | 120.77 (18) | C17—C18—H18 | 120.9 |
C7—C8—H8 | 119.6 | C20—C19—C18 | 121.53 (18) |
C9—C8—H8 | 119.6 | C20—C19—Br19 | 119.94 (15) |
C10—C9—C8 | 121.42 (19) | C18—C19—Br19 | 118.53 (15) |
C10—C9—H9 | 119.3 | C19—C20—C21 | 119.45 (18) |
C8—C9—H9 | 119.3 | C19—C20—H20 | 120.3 |
C11—C10—C9 | 117.44 (18) | C21—C20—H20 | 120.3 |
C11—C10—H10 | 121.3 | C20—C21—C16 | 120.76 (18) |
C9—C10—H10 | 121.3 | C20—C21—H21 | 119.6 |
C10—C11—N12 | 129.19 (17) | C16—C21—H21 | 119.6 |
C10—C11—C6 | 121.78 (17) | ||
C13—C1—C2—C3 | 0.5 (3) | C2—C1—C13—C5 | −1.7 (3) |
C1—C2—C3—C4 | 0.4 (3) | C14—N12—C13—C1 | −19.6 (3) |
C2—C3—C4—C5 | −0.1 (3) | C11—N12—C13—C1 | 173.86 (19) |
C3—C4—C5—C13 | −1.1 (3) | C14—N12—C13—C5 | 165.56 (17) |
C3—C4—C5—C6 | 174.84 (19) | C11—N12—C13—C5 | −1.0 (2) |
C4—C5—C6—C7 | 3.4 (4) | C4—C5—C13—C1 | 2.1 (3) |
C13—C5—C6—C7 | 179.68 (19) | C6—C5—C13—C1 | −174.82 (17) |
C4—C5—C6—C11 | −176.2 (2) | C4—C5—C13—N12 | 177.40 (16) |
C13—C5—C6—C11 | 0.1 (2) | C6—C5—C13—N12 | 0.5 (2) |
C11—C6—C7—C8 | 0.5 (3) | C11—N12—C14—C15 | 140.91 (19) |
C5—C6—C7—C8 | −179.05 (19) | C13—N12—C14—C15 | −23.7 (3) |
C6—C7—C8—C9 | 0.0 (3) | N12—C14—C15—C16 | −178.47 (17) |
C7—C8—C9—C10 | −1.0 (3) | C14—C15—C16—C17 | 162.37 (19) |
C8—C9—C10—C11 | 1.4 (3) | C14—C15—C16—C21 | −17.0 (3) |
C9—C10—C11—N12 | 179.51 (18) | C21—C16—C17—C18 | 1.5 (3) |
C9—C10—C11—C6 | −0.9 (3) | C15—C16—C17—C18 | −177.85 (18) |
C7—C6—C11—C10 | 0.0 (3) | C16—C17—C18—C19 | 0.2 (3) |
C5—C6—C11—C10 | 179.61 (17) | C17—C18—C19—C20 | −1.3 (3) |
C7—C6—C11—N12 | 179.66 (16) | C17—C18—C19—Br19 | 178.47 (15) |
C5—C6—C11—N12 | −0.7 (2) | C18—C19—C20—C21 | 0.5 (3) |
C10—C11—N12—C14 | 13.5 (3) | Br19—C19—C20—C21 | −179.23 (15) |
C6—C11—N12—C14 | −166.16 (16) | C19—C20—C21—C16 | 1.3 (3) |
C10—C11—N12—C13 | −179.31 (18) | C17—C16—C21—C20 | −2.3 (3) |
C6—C11—N12—C13 | 1.0 (2) | C15—C16—C21—C20 | 177.04 (18) |
C2—C1—C13—N12 | −176.00 (19) |
Experimental details
(I) | (II) | (III) | |
Crystal data | |||
Chemical formula | C20H14FN | C20H14ClN | C20H14BrN |
Mr | 287.32 | 303.77 | 348.23 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/n | Monoclinic, P21/n |
Temperature (K) | 100 | 100 | 100 |
a, b, c (Å) | 10.6715 (5), 5.9502 (3), 22.9870 (11) | 14.3190 (11), 5.6943 (5), 18.6247 (18) | 14.5152 (5), 5.6485 (2), 18.8260 (6) |
β (°) | 100.953 (5) | 102.730 (7) | 103.605 (3) |
V (Å3) | 1433.03 (12) | 1481.3 (2) | 1500.22 (9) |
Z | 4 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.09 | 0.25 | 2.74 |
Crystal size (mm) | 0.3 × 0.15 × 0.15 | 0.45 × 0.15 × 0.08 | 0.3 × 0.12 × 0.1 |
Data collection | |||
Diffractometer | Kuma KM-4 CCD four-circle diffractometer | Kuma KM-4 CCD four-circle diffractometer | Kuma KM-4 CCD four-circle diffractometer |
Absorption correction | Multi-scan (CrysAlis RED; Oxford Diffraction, 2006) | Multi-scan (CrysAlis RED; Oxford Diffraction, 2006) | Multi-scan (CrysAlis RED; Oxford Diffraction, 2006) |
Tmin, Tmax | 0.89, 0.98 | 0.85, 0.98 | 0.44, 0.77 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9484, 3593, 1963 | 12780, 3382, 2241 | 9787, 3714, 2839 |
Rint | 0.040 | 0.039 | 0.030 |
(sin θ/λ)max (Å−1) | 0.692 | 0.650 | 0.682 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.060, 1.01 | 0.035, 0.080, 1.02 | 0.029, 0.066, 1.08 |
No. of reflections | 3593 | 3382 | 3714 |
No. of parameters | 255 | 241 | 199 |
H-atom treatment | All H-atom parameters refined | Only H-atom coordinates refined | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.19, −0.21 | 0.27, −0.29 | 0.56, −0.57 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP (Siemens, 1989).
angle | 1(exp) | 1(calc) | 2(exp) | 2(calc) | 3(exp) | 3(calc) |
C21—C16—C17 | 117.8 (1) | 117.8 | 117.8 (1) | 118.0 | 117.7 (2) | 117.9 |
C16—C17—C18 | 121.8 (1) | 121.3 | 121.9 (2) | 121.4 | 122.3 (2) | 121.4 |
C17—C18—C19 | 117.8 (1) | 118.3 | 118.7 (2) | 118.9 | 118.3 (2) | 119.3 |
C18—C19—C20 | 123.2 (1) | 123.0 | 121.2 (1) | 121.5 | 121.5 (2) | 120.7 |
C19—C20—C21 | 118.2 (1) | 118.3 | 119.4 (2) | 118.9 | 119.5 (2) | 119.3 |
C20—C21—C16 | 121.2 (1) | 121.3 | 121.0 (2) | 121.4 | 120.8 (2) | 121.4 |
1 | 2 | 3 | |
C13—N12—C14—C15 | -26.8 (2) | -24.4 (2) | -23.8 (3) |
N12—C14—C15—C16 | -177.6 (1) | -178.6 (1) | -178.4 (2) |
C14—C15—C16—C17 | 156.8 (1) | 160.7 (1) | 162.3 (2) |
A/B | 58.28 (3) | 53.57 (4) | 54.04 (6) |
A/C | 36.36 (9) | 35.46 (8) | 34.62 (10) |
B/C | 22.22 (13) | 18.5 (2) | 16.9 (3) |
D | H | A | D-H | H···A | D···A | D-H···A |
Compound 1 | ||||||
C1 | H1 | F19i | 0.974 (11) | 2.597 (10) | 3.2788 (14) | 127.2 (8) |
C8 | H8 | F19ii | 0.974 (11) | 2.608 (11) | 3.3970 (15) | 138.2 (9) |
C4 | H4 | Cg3iii | 0.958 (11) | 2.839 (16) | 3.671 (12) | 145.8 (9) |
C9 | H9 | Cg4iv | 0.954 (12) | 2.834 (16) | 3.698 (11) | 151.0 (9) |
Compound 2 | ||||||
C10 | H10 | Cl19v | 0.916 (16) | 2.879 (16) | 3.7871 (16) | 171.1 (12) |
C14 | H14 | Cl19v | 0.985 (15) | 2.995 (15) | 3.8644 (17) | 147.9 (11) |
C4 | H4 | Cg3vi | 0.952 (16) | 2.870 (16) | 3.624 (2) | 136.9 (12) |
Compound 3 | ||||||
C10 | H10 | Br19v | 0.95 | 2.93 | 3.8738 (19) | 174 |
C14 | H14 | Br19v | 0.95 | 3.15 | 4.0036 (19) | 150 |
C4 | H4 | Cg3vi | 0.95 | 2.86 | 3.621 (3) | 138 |
Symmetry codes: (i) -x, -y-1, -z+1; (ii) -x, y+3/2, -z+3/2; (iii) -x+1, y+1/2, -z+3/2; (iv) -x, y+1/2, -z+3/2; (v) -x-1/2, y+1/2, -z+1/2; (vi) x, y-1, z. |
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Carbazole and its derivatives have become quite attractive compounds owing to their applications in pharmacy and molecular electronics. Some carbazole alkaloids have been isolated from Murraya euchrestifolia (Ito et al., 1991), Murraya koenigii (e.g. Ito et al., 2006, and references therein) and Micromelum minutum (Nakahara et al., 2002). It has been reported that carbazole derivatives possess various biological activities, such as antitumor (Itoigawa et al., 2000), anti-oxidative (Tachibana et al., 2001), anti-inflammatory and antimutagenic (Ramsewak et al., 1999). On the other hand, carbazole and its derivatives are very attractive compounds because of their electroactivity and luminescence properties and are also considered to be potential candidates for electronic devices, such as colour displays, organic semiconductor lasers and solar cells (Friend et al., 1999, and references therein). This molecule with a π-conjugated system is widely used as a good hole-transporting material in polymeric light-emitting diodes (PLEDs) (e.g. Zhang et al., 2006) or as an organic light-emitting diode (OLED) (Pan et al., 2005). Carbazole derivatives with N-halogenostyryl- substituents have important applications in photochemistry, possess an extended π-conjugated double-bond system and can easy undergo further modification (Prukała et al., 2007).
We report here the crystal and molecular structures of three N-halogenostyryl-carbazoles: 9-[(E)-2-(4-fluorophenyl)vinyl]-9H-carbazole, (I), 9-[(E)-2-(4-chlorophenyl)vinyl]-9H-carbazole, (II), and 9-[(E)-2-(4-bromophenyl)vinyl]-9H-carbazole, (III). Comparison of these structures is interesting also from the point of view of crystal engineering; it has been shown that in this aspect (intermolecular interactions) fluorine has different properties from the other halogens.
The bond angles within the phenyl ring are influenced by the presence of substituents (cf. Domenicano, 1988), and the final bond-angles patterns are close to additive combinations of their effects (Table 1); we have observed a similar influence in two nitrovinylcarbazoles (Kubicki et al., 2007).
The conformation of the molecules (Figs. 1–3) can be described by the dihedral angles between three approximately planar fragments, viz. the carbazole system, the bridging vinyl group and the phenyl ring (Table 2). The maximum deviations from the least-squares planes do not exceed 0.070 (2) Å for the carbazole ring system and 0.012 (1) Å for the benzene ring. In contrast to the m- and p-nitro derivatives (Kubicki et al., 2007), in which these angles are small, in halogen derivatives the twist is significant, up to almost 60° between the carbazole and phenyl ring planes. A similarly large value, 64.29 (4)°, was observed in the structure of 9-[(E)-2-(4-methoxyphenyl)vinyl]-9H-carbazole (Prukała et al., 2007).
In the crystal structures, van der Waals forces and some weak C—H···π and C—H···X interactions (Table 3) seem to be the most important factors determining the packing. Interestingly, contrary to the nitro-derivatives, there are no short π–π stacking interactions between the phenyl and carbazole ring systems.
The crystal structures of (II) and (III) are highly isomorphous; they crystallize in the same space group, and the unit cells and the packing modes are similar (Fig. 4). To obtain some insight into the degree of isomorphism, we have used the descriptors introduced by Kálmán et al. (1991). The unit-cell similarity index, Π, defined as the difference between unity and the ratio of the sums of the orthogonalized unit-cell parameters, is almost ideal (0.01). The isostructurality index, which shows how close are the positions of the atoms in the unit cells, is defined by the sum of the differences between the positions of the analogous atoms. In the case of (II) and (III) the value of this index is also close to the ideal value (99.5%). Kubicki & Szafrański (1998) proposed a modification of this latter parameter, which takes into account the point-group symmetry and gives a more absolute measure of the degree of isostructurality (it should be 1 for ideally isomorphous compounds and 0 for randomly distributed atoms). The value of this modified index is 98.5%.
In all three structures the crystal packing is determined mainly by van der Waals forces, weak C—H···π interactions and some C—H···X interactions. The role of relatively short and directional C—H···X contacts in the crystal packing can be important in the absence of other stronger interactions (cf. Desiraju & Steiner, 1999). In isomorphous (II) and (III), C—H···Cl and C—H···Br hydrogen bonds (Table 3) connect the molecules into infinite chains of 21 screw-related molecules along the [010] direction.
In (I), there are also chains of molecules along [010] – it can be stressed that the unit-cell b parameters are very similar in all three structures. Additionally, in (I), C—H···F interactions close centrosymmetric dimers (Table 3; cf. Chopra & Guru Row, 2005; Chan et al., 2006). The uniqueness of fluorine among the halogenes in crystal engineering has often been stressed (e.g. Lommerse et al., 1996; Valerio et al., 2000); the differences in the crystal packing of closely related structures described here are just another proof of this phenomenon.