Three 9-[(E)-2-(4-halogenophen­yl)vin­yl]-9H-carbazoles

The crystal structures of 9-[(E)-2-(4-fluoro­phen­yl)vin­yl]-9H-carbazole, C₂₀H₁₄FN, (I), 9-[(E)-2-(4-chloro­phen­yl)vin­yl]-9H-carbazole, C₂₀H₁₄ClN, (II), and 9-[(E)-2-(4-bromo­phen­yl)vin­yl]-9H-carbazole, C₂₀H₁₄BrN, (III), are determined mainly by van der Waals forces. The chloro and bromo derivatives are highly isomorphous, while the fluoro derivative has a different packing mode. Weak C—H...X inter­actions are also involved in the crystal packing. The mol­ecular structures of the three compounds are similar, with relatively large twist angles of ca 55° between the carbazole and benzene planes.

S1. Comment

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.

Related literature

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).

S2. Experimental

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.

S3. Refinement

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 1.2U_eq of the carrier atoms in (II) and (III).

Computing details

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).

Figures

	Fig. 1. An anisotropic ellipsoid representation of (I), together with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are depicted as spheres with arbitrary radii.
	Fig. 2. An anisotropic ellipsoid representation of (II), together with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are depicted as spheres with arbitrary radii.
	Fig. 3. An anisotropic ellipsoid representation of (III), together with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are depicted as spheres with arbitrary radii.
	Fig. 4. The crystal packing of (a) (II) and (b) (III), as seen along the b axis. The C—H···X contacts are depicted as dashed lines.
	Fig. 5. The crystal packing of (I), as seen along the b axis.

(I) 9-[(E)-2-(4-fluorophenyl)vinyl]-9H-carbazole

Crystal data

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) Å^3	0.3 × 0.15 × 0.15 mm
Z = 4

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.060	All H-atom parameters refined
S = 1.01	w = 1/[σ^2(Fo^2) + (0.018P)^2] where P = (Fo^2 + 2Fc^2)/3
3593 reflections	(Δ/σ)max = 0.001
255 parameters	Δρmax = 0.19 e Å^−3
0 restraints	Δρmin = −0.21 e Å^−3

Special details

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 (Ų)

	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)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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)

(II) 9-[(E)-2-(4-chlorophenyl)vinyl]-9H-carbazole

Crystal data

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) Å^3	0.45 × 0.15 × 0.08 mm
Z = 4

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.080	Only H-atom coordinates refined
S = 1.02	w = 1/[σ^2(Fo^2) + (0.040P)^2] where P = (Fo^2 + 2Fc^2)/3
3382 reflections	(Δ/σ)max = 0.003
241 parameters	Δρmax = 0.27 e Å^−3
0 restraints	Δρmin = −0.29 e Å^−3

Special details

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 (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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)

(III) 9-[(E)-2-(4-bromophenyl)vinyl]-9H-carbazole

Crystal data

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) Å^3	0.3 × 0.12 × 0.1 mm
Z = 4

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.066	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.031P)^2] where P = (Fo^2 + 2Fc^2)/3
3714 reflections	(Δ/σ)max = 0.001
199 parameters	Δρmax = 0.56 e Å^−3
0 restraints	Δρmin = −0.57 e Å^−3

Special details

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 (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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)