3,6-Di-chloro-9-(prop-2-yn-1-yl)-9H-carbazole.

The tricyclic aromatic ring system of the title compound, C15H9Cl2N, is essentially planar (r.m.s. deviation = 0.002 Å). The two Cl atoms lie slightly out of the plane of the carbazole ring system, with the C-Cl bonds forming angles of 1.23 (8) and 1.14 (8)° with the plane. The acetylene group has a syn orientation with respect to the ring system. In the crystal, no weak hydrogen bonds nor any π-π stacking inter-actions are observed.

Related literature

For industrial applications of carbazole-containing compounds, see: Zhang et al. (1998 ▶). For pharmaceutical properties of carbazoles, see: Liu & Larock (2007 ▶); Hussain et al. (2011 ▶); Zhang et al. (2010 ▶); Conchon et al. (2006 ▶). For a related structure, see: Xie et al. (2012 ▶).

Experimental

Crystal data

C15H9Cl2N

M = 274.13

Orthorhombic,

a = 3.9825 (1) Å

b = 11.1705 (4) Å

c = 27.4417 (9) Å

V = 1220.79 (7) Å3

Z = 4

Cu Kα radiation

μ = 4.59 mm−1

T = 100 K

0.18 × 0.05 × 0.02 mm

Data collection

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2013 ▶) T min = 0.74, T max = 0.91

10712 measured reflections

2224 independent reflections

2160 reflections with I > 2σ(I)

R int = 0.088

Refinement

R[F 2 > 2σ(F 2)] = 0.026

wR(F 2) = 0.068

S = 1.05

2224 reflections

163 parameters

H-atom parameters constrained

Δρmax = 0.22 e Å−3

Δρmin = −0.18 e Å−3

Absolute structure: Flack parameter determined using 817 quotients [(I +)−(I −)]/[(I +)+(I −)] (Parsons et al., 2013 ▶)

Absolute structure parameter: −0.002 (12)

Data collection: APEX2 (Bruker, 2013 ▶); cell refinement: SAINT (Bruker, 2013 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXT (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813032777/lh5674sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813032777/lh5674Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536813032777/lh5674Isup3.cml

Additional supporting information: crystallographic information; 3D view; checkCIF report

C15H9Cl2N	F(000) = 560
Mr = 274.13	Dx = 1.492 Mg m−3
Orthorhombic, P212121	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2ac 2ab	Cell parameters from 9151 reflections
a = 3.9825 (1) Å	θ = 4.3–68.0°
b = 11.1705 (4) Å	µ = 4.59 mm−1
c = 27.4417 (9) Å	T = 100 K
V = 1220.79 (7) Å3	Column, colourless
Z = 4	0.18 × 0.05 × 0.02 mm

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	2224 independent reflections
Radiation source: INCOATEC IµS micro–focus source	2160 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.088
Detector resolution: 10.4167 pixels mm-1	θmax = 68.1°, θmin = 3.2°
ω scans	h = −4→4
Absorption correction: multi-scan (SADABS; Bruker, 2013)	k = −13→13
Tmin = 0.74, Tmax = 0.91	l = −32→33
10712 measured reflections

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.026	W = 1/[Σ2(FO2) + (0.0351P)2 + 0.195P] where P = (FO2 + 2FC2)/3
wR(F2) = 0.068	(Δ/σ)max < 0.001
S = 1.05	Δρmax = 0.22 e Å−3
2224 reflections	Δρmin = −0.18 e Å−3
163 parameters	Absolute structure: Flack parameter determined using 817 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
0 restraints	Absolute structure parameter: −0.002 (12)

Experimental. 1H-NMR (300 MHz, CDCl3): d 3.31 (s, 1H, C—CH), 5.34 (d, 2H, J=2.4 Hz, CH2—C), 7.54 (m, 2H, Ar—H), 7.74 (m, 2H, Ar—H), 8.34 (s, 2H, Ar—H). 13 C-NMR (75 MHz, CDCl3): d 32.2 (CH2), 74.8 (C—CH), 78.5 (C—CH), 111.4, 120.5, (4CH-Ar), 122.9, 124.2 (4 C-Ar), 126.4 (2CH-Ar), 138.6 (2 C-Ar). MS: (EI) m/z (%): 275 (M+2, 70), 274 (M+1, 74), 273 (M+, 100), 247 (10), 233 (44), 201 (4), 174 (2), 164 (14), 150 (2), 122 (2), 98 (2), 75 (4). Anal. for C15H9Cl2N: calcd. C, 65.72; H, 3.31; Cl, 25.86; N, 5.11. Found: C, 65.38; H, 3.11; N, 4.95%.

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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
Cl1	0.52328 (16)	0.39290 (5)	−0.06840 (2)	0.0240 (2)
Cl2	0.52780 (15)	0.15240 (5)	0.22392 (2)	0.0252 (2)
N1	0.0291 (5)	0.57255 (17)	0.11884 (6)	0.0190 (5)
C1	0.1356 (6)	0.5462 (2)	0.07181 (8)	0.0180 (6)
C2	0.0865 (6)	0.6107 (2)	0.02874 (8)	0.0218 (7)
C3	0.2076 (6)	0.5615 (2)	−0.01405 (8)	0.0214 (7)
C4	0.3762 (6)	0.4513 (2)	−0.01335 (8)	0.0197 (6)
C5	0.4309 (6)	0.3879 (2)	0.02890 (8)	0.0190 (6)
C6	0.3072 (6)	0.4360 (2)	0.07226 (8)	0.0175 (6)
C7	0.3067 (6)	0.3947 (2)	0.12215 (8)	0.0177 (6)
C8	0.4327 (6)	0.2920 (2)	0.14472 (8)	0.0188 (6)
C9	0.3751 (6)	0.2800 (2)	0.19418 (8)	0.0208 (7)
C10	0.2040 (6)	0.3660 (2)	0.22166 (8)	0.0217 (7)
C11	0.0803 (6)	0.4677 (2)	0.19960 (8)	0.0213 (7)
C12	0.1317 (6)	0.4812 (2)	0.14950 (8)	0.0183 (6)
C13	−0.1714 (6)	0.6755 (2)	0.13263 (9)	0.0219 (7)
C14	0.0264 (6)	0.7838 (2)	0.14305 (8)	0.0216 (6)
C15	0.1835 (7)	0.8710 (2)	0.15139 (10)	0.0284 (7)
H2	−0.02610	0.68560	0.02880	0.0260*
H3	0.17640	0.60250	−0.04400	0.0260*
H5	0.54890	0.31400	0.02860	0.0230*
H8	0.55280	0.23300	0.12690	0.0230*
H10	0.17270	0.35420	0.25560	0.0260*
H11	−0.03610	0.52690	0.21790	0.0260*
H13A	−0.30450	0.65470	0.16190	0.0260*
H13B	−0.33110	0.69340	0.10600	0.0260*
H15	0.31000	0.94120	0.15810	0.0340*

	U11	U22	U33	U12	U13	U23
Cl1	0.0287 (3)	0.0266 (3)	0.0167 (2)	−0.0027 (3)	0.0020 (2)	−0.0015 (2)
Cl2	0.0256 (3)	0.0274 (3)	0.0226 (3)	−0.0015 (3)	−0.0015 (2)	0.0073 (2)
N1	0.0184 (9)	0.0176 (9)	0.0209 (9)	−0.0002 (9)	0.0008 (8)	−0.0031 (7)
C1	0.0165 (11)	0.0170 (11)	0.0206 (11)	−0.0036 (9)	−0.0012 (9)	−0.0023 (9)
C2	0.0201 (11)	0.0185 (11)	0.0269 (12)	−0.0009 (10)	−0.0024 (9)	0.0002 (9)
C3	0.0221 (11)	0.0228 (12)	0.0192 (11)	−0.0057 (10)	−0.0024 (9)	0.0016 (10)
C4	0.0191 (11)	0.0212 (11)	0.0189 (11)	−0.0052 (9)	0.0009 (9)	−0.0023 (9)
C5	0.0186 (11)	0.0180 (11)	0.0204 (10)	−0.0036 (10)	0.0004 (9)	−0.0017 (9)
C6	0.0157 (10)	0.0174 (11)	0.0195 (11)	−0.0028 (9)	−0.0017 (9)	−0.0014 (9)
C7	0.0155 (10)	0.0188 (11)	0.0188 (11)	−0.0045 (9)	0.0006 (8)	−0.0018 (9)
C8	0.0168 (11)	0.0201 (10)	0.0194 (10)	−0.0028 (9)	−0.0008 (9)	−0.0028 (9)
C9	0.0178 (12)	0.0235 (12)	0.0211 (11)	−0.0056 (10)	−0.0038 (9)	0.0031 (10)
C10	0.0194 (11)	0.0291 (13)	0.0167 (10)	−0.0066 (10)	0.0015 (9)	−0.0024 (10)
C11	0.0193 (12)	0.0238 (12)	0.0207 (11)	−0.0041 (10)	0.0017 (9)	−0.0064 (9)
C12	0.0143 (11)	0.0188 (11)	0.0219 (11)	−0.0034 (9)	−0.0008 (9)	−0.0031 (9)
C13	0.0173 (11)	0.0208 (12)	0.0276 (12)	0.0012 (10)	0.0005 (9)	−0.0043 (10)
C14	0.0212 (12)	0.0219 (11)	0.0217 (10)	0.0062 (11)	0.0028 (10)	−0.0018 (9)
C15	0.0276 (12)	0.0206 (12)	0.0369 (14)	0.0005 (11)	0.0004 (11)	−0.0031 (11)

Cl1—C4	1.747 (2)	C9—C10	1.399 (3)
Cl2—C9	1.751 (2)	C10—C11	1.378 (3)
N1—C1	1.390 (3)	C11—C12	1.398 (3)
N1—C12	1.384 (3)	C13—C14	1.472 (3)
N1—C13	1.450 (3)	C14—C15	1.180 (3)
C1—C2	1.398 (3)	C2—H2	0.9500
C1—C6	1.408 (3)	C3—H3	0.9500
C2—C3	1.383 (3)	C5—H5	0.9500
C3—C4	1.402 (3)	C8—H8	0.9500
C4—C5	1.376 (3)	C10—H10	0.9500
C5—C6	1.395 (3)	C11—H11	0.9500
C6—C7	1.445 (3)	C13—H13A	0.9900
C7—C8	1.397 (3)	C13—H13B	0.9900
C7—C12	1.408 (3)	C15—H15	0.9500
C8—C9	1.383 (3)
C1—N1—C12	108.55 (18)	N1—C12—C7	109.15 (19)
C1—N1—C13	125.32 (19)	N1—C12—C11	129.3 (2)
C12—N1—C13	126.05 (18)	C7—C12—C11	121.5 (2)
N1—C1—C2	129.3 (2)	N1—C13—C14	114.1 (2)
N1—C1—C6	108.97 (19)	C13—C14—C15	179.7 (3)
C2—C1—C6	121.7 (2)	C1—C2—H2	121.00
C1—C2—C3	117.7 (2)	C3—C2—H2	121.00
C2—C3—C4	120.3 (2)	C2—C3—H3	120.00
Cl1—C4—C3	118.46 (17)	C4—C3—H3	120.00
Cl1—C4—C5	118.91 (17)	C4—C5—H5	121.00
C3—C4—C5	122.6 (2)	C6—C5—H5	121.00
C4—C5—C6	117.7 (2)	C7—C8—H8	121.00
C1—C6—C5	120.0 (2)	C9—C8—H8	121.00
C1—C6—C7	106.67 (19)	C9—C10—H10	120.00
C5—C6—C7	133.3 (2)	C11—C10—H10	120.00
C6—C7—C8	133.0 (2)	C10—C11—H11	121.00
C6—C7—C12	106.66 (19)	C12—C11—H11	121.00
C8—C7—C12	120.3 (2)	N1—C13—H13A	109.00
C7—C8—C9	117.1 (2)	N1—C13—H13B	109.00
Cl2—C9—C8	118.59 (17)	C14—C13—H13A	109.00
Cl2—C9—C10	118.49 (17)	C14—C13—H13B	109.00
C8—C9—C10	122.9 (2)	H13A—C13—H13B	108.00
C9—C10—C11	120.2 (2)	C14—C15—H15	180.00
C10—C11—C12	117.9 (2)
C12—N1—C1—C2	178.9 (2)	C3—C4—C5—C6	1.0 (4)
C12—N1—C1—C6	0.4 (3)	C4—C5—C6—C1	−0.5 (3)
C13—N1—C1—C2	1.9 (4)	C4—C5—C6—C7	177.8 (2)
C13—N1—C1—C6	−176.6 (2)	C1—C6—C7—C8	179.0 (3)
C1—N1—C12—C7	0.0 (3)	C1—C6—C7—C12	0.6 (3)
C1—N1—C12—C11	−179.3 (2)	C5—C6—C7—C8	0.6 (5)
C13—N1—C12—C7	177.0 (2)	C5—C6—C7—C12	−177.8 (3)
C13—N1—C12—C11	−2.4 (4)	C6—C7—C8—C9	−177.8 (2)
C1—N1—C13—C14	−86.6 (3)	C12—C7—C8—C9	0.4 (3)
C12—N1—C13—C14	97.0 (3)	C6—C7—C12—N1	−0.4 (3)
N1—C1—C2—C3	−177.2 (2)	C6—C7—C12—C11	179.0 (2)
C6—C1—C2—C3	1.1 (4)	C8—C7—C12—N1	−179.1 (2)
N1—C1—C6—C5	178.1 (2)	C8—C7—C12—C11	0.3 (4)
N1—C1—C6—C7	−0.6 (3)	C7—C8—C9—Cl2	179.84 (17)
C2—C1—C6—C5	−0.6 (4)	C7—C8—C9—C10	−1.0 (4)
C2—C1—C6—C7	−179.3 (2)	Cl2—C9—C10—C11	179.94 (18)
C1—C2—C3—C4	−0.7 (3)	C8—C9—C10—C11	0.8 (4)
C2—C3—C4—Cl1	179.85 (18)	C9—C10—C11—C12	0.0 (3)
C2—C3—C4—C5	−0.4 (4)	C10—C11—C12—N1	178.7 (2)
Cl1—C4—C5—C6	−179.26 (18)	C10—C11—C12—C7	−0.6 (4)