Crystal structure of 2-(2-bromo-phen-yl)-4-(1H-indol-3-yl)-6-(thio-phen-2-yl)pyridine-3-carbo-nitrile.

In the title compound, C24H14BrN3S, the dihedral angles between the planes of the pyridine ring and the pendant thio-phene ring, the indole ring system (r.m.s. deviation = 0.022 Å) and the bromo-benzene ring are 9.37 (17), 21.90 (12) and 69.01 (15)°, respectively. The approximate coplanarity of the central ring and the indole ring system is supported by two intra-molecular C-H⋯N inter-actions. In the crystal, inversion dimers linked by pairs of N-H⋯N hydrogen bonds generate R 2 (2)(16) loops and the dimers are linked by C-H⋯π and aromatic π-π stacking [shortest centroid-centroid separation = 3.729 (3) Å] into a three-dimensional network.

Related literature

For the biological activity of pyridine-3-carbo­nitrile derivatives, see: Kim et al. (2005 ▶); Ji et al. (2007 ▶); Brandt et al. (2010 ▶); El-Sayed et al. (2011 ▶).

Experimental

Crystal data

C24H14BrN3S

M = 456.35

Monoclinic,

a = 10.470 (5) Å

b = 21.353 (5) Å

c = 9.292 (5) Å

β = 107.710 (5)°

V = 1978.9 (15) Å3

Z = 4

Mo Kα radiation

μ = 2.20 mm−1

T = 293 K

0.52 × 0.23 × 0.17 mm

Data collection

Bruker Kappa APEXII diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.958, T max = 0.986

17079 measured reflections

4305 independent reflections

2837 reflections with I > 2σ(I)

R int = 0.041

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.121

S = 1.02

4305 reflections

262 parameters

H-atom parameters constrained

Δρmax = 0.48 e Å−3

Δρmin = −0.35 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814017188/hb7260sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814017188/hb7260Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814017188/hb7260Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S1600536814017188/hb7260fig1.tif

The mol­ecular structure of compound showing 30% probability displacement ellipsoids.

Click here for additional data file.

x y z . DOI: 10.1107/S1600536814017188/hb7260fig2.tif

Partial packing view of the compound showing mol­ecules inter­connected through a C—H⋯π stacking inter­action (dotted lines; symmetry code: (i)  − x,  + y,  − z)

CCDC reference: 1015962

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

C24H14BrN3S	F(000) = 920
Mr = 456.35	Dx = 1.532 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2000 reflections
a = 10.470 (5) Å	θ = 2–27°
b = 21.353 (5) Å	µ = 2.20 mm−1
c = 9.292 (5) Å	T = 293 K
β = 107.710 (5)°	Block, colourless
V = 1978.9 (15) Å3	0.52 × 0.23 × 0.17 mm
Z = 4

Bruker Kappa APEXII diffractometer	4305 independent reflections
Radiation source: fine-focus sealed tube	2837 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
Detector resolution: 0 pixels mm-1	θmax = 27.0°, θmin = 1.9°
ω and φ scans	h = −12→13
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −27→27
Tmin = 0.958, Tmax = 0.986	l = −11→11
17079 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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.121	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0618P)2 + 0.4334P] where P = (Fo2 + 2Fc2)/3
4305 reflections	(Δ/σ)max < 0.001
262 parameters	Δρmax = 0.48 e Å−3
0 restraints	Δρmin = −0.35 e Å−3

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	0.2640 (3)	0.50193 (12)	0.7417 (3)	0.0386 (7)
C2	0.3077 (3)	0.44165 (13)	0.7289 (3)	0.0425 (7)
H2	0.3543	0.4194	0.8149	0.051*
C3	0.2818 (3)	0.41458 (12)	0.5880 (3)	0.0390 (7)
C4	0.2078 (3)	0.45002 (12)	0.4630 (3)	0.0368 (6)
C5	0.1664 (3)	0.51133 (12)	0.4822 (3)	0.0371 (6)
C11	0.2890 (3)	0.53182 (14)	0.8898 (3)	0.0432 (7)
C12	0.3376 (3)	0.50426 (15)	1.0315 (3)	0.0481 (8)
H12	0.3625	0.4624	1.0484	0.058*
C13	0.3439 (4)	0.54874 (19)	1.1471 (3)	0.0622 (9)
H13	0.3745	0.5393	1.2496	0.075*
C14	0.3011 (4)	0.60608 (18)	1.0930 (4)	0.0651 (10)
H14	0.2995	0.6405	1.1538	0.078*
C31	0.3330 (3)	0.35097 (13)	0.5742 (3)	0.0402 (7)
C32	0.2810 (4)	0.30034 (14)	0.6331 (3)	0.0555 (8)
H32	0.2108	0.3068	0.6733	0.067*
C33	0.3322 (4)	0.24105 (16)	0.6326 (4)	0.0697 (11)
H33	0.2958	0.2078	0.6716	0.084*
C34	0.4351 (5)	0.23060 (17)	0.5759 (4)	0.0736 (11)
H34	0.4695	0.1904	0.5774	0.088*
C35	0.4892 (4)	0.27918 (16)	0.5159 (4)	0.0650 (10)
H35	0.5597	0.2721	0.4766	0.078*
C36	0.4366 (3)	0.33884 (13)	0.5151 (3)	0.0466 (7)
C41	0.1792 (3)	0.42163 (13)	0.3172 (3)	0.0451 (7)
C51	0.0943 (3)	0.55225 (13)	0.3593 (3)	0.0380 (6)
C52	0.0877 (3)	0.61968 (13)	0.3648 (3)	0.0404 (7)
C53	0.1419 (3)	0.66595 (14)	0.4726 (3)	0.0497 (8)
H53	0.1932	0.6550	0.5699	0.060*
C54	0.1186 (4)	0.72736 (15)	0.4329 (4)	0.0614 (9)
H54	0.1561	0.7581	0.5041	0.074*
C55	0.0405 (4)	0.74537 (17)	0.2892 (4)	0.0657 (10)
H55	0.0253	0.7877	0.2669	0.079*
C56	−0.0136 (4)	0.70208 (16)	0.1814 (4)	0.0581 (9)
H56	−0.0650	0.7140	0.0849	0.070*
C57	0.0104 (3)	0.63913 (14)	0.2198 (3)	0.0451 (7)
C58	0.0214 (3)	0.53562 (14)	0.2152 (3)	0.0452 (7)
H58	0.0082	0.4948	0.1791	0.054*
N1	0.1961 (2)	0.53636 (10)	0.6215 (2)	0.0386 (6)
N2	0.1568 (3)	0.39821 (12)	0.2015 (3)	0.0630 (8)
N3	−0.0283 (3)	0.58711 (12)	0.1335 (3)	0.0500 (7)
H3	−0.0773	0.5870	0.0405	0.060*
S	0.25060 (12)	0.60852 (4)	0.90204 (10)	0.0706 (3)
Br	0.51614 (4)	0.404354 (16)	0.43368 (4)	0.06285 (16)

	U11	U22	U33	U12	U13	U23
C1	0.0378 (18)	0.0460 (16)	0.0330 (14)	−0.0027 (13)	0.0123 (13)	0.0018 (13)
C2	0.049 (2)	0.0473 (17)	0.0288 (14)	0.0025 (14)	0.0084 (13)	0.0054 (12)
C3	0.0397 (18)	0.0415 (15)	0.0365 (15)	−0.0016 (13)	0.0128 (13)	0.0067 (12)
C4	0.0403 (18)	0.0393 (14)	0.0298 (14)	−0.0037 (13)	0.0094 (12)	0.0000 (12)
C5	0.0362 (17)	0.0420 (15)	0.0330 (14)	−0.0041 (13)	0.0103 (12)	0.0019 (12)
C11	0.0382 (18)	0.0517 (17)	0.0380 (16)	−0.0058 (14)	0.0093 (13)	−0.0024 (13)
C12	0.054 (2)	0.0600 (18)	0.0271 (14)	−0.0014 (15)	0.0083 (14)	−0.0045 (14)
C13	0.059 (2)	0.088 (3)	0.0347 (17)	−0.005 (2)	0.0078 (16)	−0.0043 (17)
C14	0.076 (3)	0.075 (2)	0.0419 (18)	−0.001 (2)	0.0139 (18)	−0.0232 (17)
C31	0.0467 (19)	0.0402 (15)	0.0285 (14)	0.0000 (13)	0.0038 (13)	0.0009 (12)
C32	0.062 (2)	0.0500 (19)	0.0537 (19)	−0.0032 (16)	0.0163 (17)	0.0094 (15)
C33	0.087 (3)	0.0421 (19)	0.071 (2)	−0.0048 (19)	0.012 (2)	0.0172 (17)
C34	0.086 (3)	0.046 (2)	0.080 (3)	0.011 (2)	0.013 (2)	0.0019 (18)
C35	0.070 (3)	0.057 (2)	0.066 (2)	0.0158 (18)	0.0176 (19)	−0.0031 (18)
C36	0.051 (2)	0.0464 (17)	0.0392 (16)	−0.0005 (15)	0.0082 (15)	0.0002 (13)
C41	0.054 (2)	0.0375 (15)	0.0383 (17)	0.0044 (14)	0.0051 (14)	0.0058 (14)
C51	0.0384 (18)	0.0446 (15)	0.0318 (14)	−0.0001 (13)	0.0119 (13)	0.0035 (12)
C52	0.0407 (18)	0.0457 (15)	0.0389 (16)	0.0046 (14)	0.0182 (14)	0.0090 (13)
C53	0.056 (2)	0.0463 (17)	0.0477 (18)	0.0001 (15)	0.0179 (16)	0.0005 (14)
C54	0.072 (3)	0.0451 (18)	0.073 (2)	−0.0003 (17)	0.031 (2)	0.0008 (17)
C55	0.076 (3)	0.0490 (19)	0.078 (3)	0.0099 (18)	0.032 (2)	0.0204 (19)
C56	0.057 (2)	0.061 (2)	0.058 (2)	0.0113 (18)	0.0199 (17)	0.0262 (18)
C57	0.0436 (19)	0.0540 (18)	0.0409 (16)	0.0052 (15)	0.0177 (14)	0.0119 (14)
C58	0.045 (2)	0.0494 (17)	0.0402 (16)	0.0037 (14)	0.0111 (14)	0.0024 (14)
N1	0.0424 (15)	0.0416 (13)	0.0316 (12)	−0.0021 (11)	0.0107 (11)	0.0006 (10)
N2	0.089 (2)	0.0508 (16)	0.0405 (15)	0.0127 (14)	0.0065 (15)	−0.0049 (12)
N3	0.0488 (18)	0.0617 (17)	0.0330 (13)	0.0058 (13)	0.0024 (12)	0.0085 (12)
S	0.0982 (9)	0.0602 (5)	0.0497 (5)	0.0089 (5)	0.0167 (5)	−0.0073 (4)
Br	0.0616 (3)	0.0661 (3)	0.0687 (3)	−0.00767 (17)	0.0314 (2)	0.00167 (16)

C1—N1	1.345 (3)	C33—H33	0.9300
C1—C2	1.383 (4)	C34—C35	1.378 (5)
C1—C11	1.466 (4)	C34—H34	0.9300
C2—C3	1.380 (4)	C35—C36	1.387 (4)
C2—H2	0.9300	C35—H35	0.9300
C3—C4	1.405 (4)	C36—Br	1.899 (3)
C3—C31	1.480 (4)	C41—N2	1.143 (4)
C4—C5	1.408 (4)	C51—C58	1.371 (4)
C4—C41	1.431 (4)	C51—C52	1.443 (4)
C5—N1	1.346 (3)	C52—C53	1.399 (4)
C5—C51	1.454 (4)	C52—C57	1.407 (4)
C11—C12	1.390 (4)	C53—C54	1.364 (4)
C11—S	1.698 (3)	C53—H53	0.9300
C12—C13	1.420 (4)	C54—C55	1.391 (5)
C12—H12	0.9300	C54—H54	0.9300
C13—C14	1.347 (5)	C55—C56	1.354 (5)
C13—H13	0.9300	C55—H55	0.9300
C14—S	1.691 (4)	C56—C57	1.394 (4)
C14—H14	0.9300	C56—H56	0.9300
C31—C36	1.381 (4)	C57—N3	1.358 (4)
C31—C32	1.395 (4)	C58—N3	1.347 (4)
C32—C33	1.376 (5)	C58—H58	0.9300
C32—H32	0.9300	N3—H3	0.8600
C33—C34	1.354 (6)
N1—C1—C2	122.8 (2)	C35—C34—H34	119.8
N1—C1—C11	116.1 (2)	C34—C35—C36	118.8 (4)
C2—C1—C11	121.1 (2)	C34—C35—H35	120.6
C3—C2—C1	119.8 (3)	C36—C35—H35	120.6
C3—C2—H2	120.1	C31—C36—C35	121.9 (3)
C1—C2—H2	120.1	C31—C36—Br	120.9 (2)
C2—C3—C4	117.3 (3)	C35—C36—Br	117.2 (3)
C2—C3—C31	119.7 (2)	N2—C41—C4	179.1 (3)
C4—C3—C31	123.1 (2)	C58—C51—C52	105.9 (2)
C3—C4—C5	120.6 (2)	C58—C51—C5	127.8 (3)
C3—C4—C41	117.3 (2)	C52—C51—C5	126.2 (2)
C5—C4—C41	122.0 (2)	C53—C52—C57	117.9 (3)
N1—C5—C4	120.1 (2)	C53—C52—C51	135.8 (3)
N1—C5—C51	115.4 (2)	C57—C52—C51	106.3 (2)
C4—C5—C51	124.5 (2)	C54—C53—C52	119.0 (3)
C12—C11—C1	127.9 (3)	C54—C53—H53	120.5
C12—C11—S	111.8 (2)	C52—C53—H53	120.5
C1—C11—S	120.3 (2)	C53—C54—C55	122.0 (3)
C11—C12—C13	110.6 (3)	C53—C54—H54	119.0
C11—C12—H12	124.7	C55—C54—H54	119.0
C13—C12—H12	124.7	C56—C55—C54	120.9 (3)
C14—C13—C12	113.1 (3)	C56—C55—H55	119.6
C14—C13—H13	123.5	C54—C55—H55	119.6
C12—C13—H13	123.5	C55—C56—C57	117.8 (3)
C13—C14—S	112.5 (3)	C55—C56—H56	121.1
C13—C14—H14	123.8	C57—C56—H56	121.1
S—C14—H14	123.8	N3—C57—C56	129.7 (3)
C36—C31—C32	117.3 (3)	N3—C57—C52	107.8 (3)
C36—C31—C3	123.8 (3)	C56—C57—C52	122.4 (3)
C32—C31—C3	118.8 (3)	N3—C58—C51	110.1 (3)
C33—C32—C31	120.8 (3)	N3—C58—H58	124.9
C33—C32—H32	119.6	C51—C58—H58	124.9
C31—C32—H32	119.6	C1—N1—C5	119.4 (2)
C34—C33—C32	120.7 (3)	C58—N3—C57	109.9 (3)
C34—C33—H33	119.7	C58—N3—H3	125.1
C32—C33—H33	119.7	C57—N3—H3	125.1
C33—C34—C35	120.5 (3)	C14—S—C11	92.04 (16)
C33—C34—H34	119.8
N1—C1—C2—C3	0.0 (5)	C34—C35—C36—C31	0.8 (5)
C11—C1—C2—C3	179.6 (3)	C34—C35—C36—Br	179.2 (3)
C1—C2—C3—C4	−1.7 (4)	N1—C5—C51—C58	−161.3 (3)
C1—C2—C3—C31	177.8 (3)	C4—C5—C51—C58	20.3 (5)
C2—C3—C4—C5	2.1 (4)	N1—C5—C51—C52	20.1 (4)
C31—C3—C4—C5	−177.3 (3)	C4—C5—C51—C52	−158.3 (3)
C2—C3—C4—C41	−179.0 (3)	C58—C51—C52—C53	−177.4 (3)
C31—C3—C4—C41	1.6 (4)	C5—C51—C52—C53	1.5 (5)
C3—C4—C5—N1	−0.8 (4)	C58—C51—C52—C57	−0.4 (3)
C41—C4—C5—N1	−179.7 (3)	C5—C51—C52—C57	178.4 (3)
C3—C4—C5—C51	177.5 (3)	C57—C52—C53—C54	−0.4 (4)
C41—C4—C5—C51	−1.4 (4)	C51—C52—C53—C54	176.3 (3)
N1—C1—C11—C12	169.4 (3)	C52—C53—C54—C55	1.2 (5)
C2—C1—C11—C12	−10.2 (5)	C53—C54—C55—C56	−1.3 (5)
N1—C1—C11—S	−7.5 (4)	C54—C55—C56—C57	0.7 (5)
C2—C1—C11—S	172.9 (2)	C55—C56—C57—N3	−178.0 (3)
C1—C11—C12—C13	−178.3 (3)	C55—C56—C57—C52	0.0 (5)
S—C11—C12—C13	−1.2 (4)	C53—C52—C57—N3	178.3 (3)
C11—C12—C13—C14	0.5 (4)	C51—C52—C57—N3	0.7 (3)
C12—C13—C14—S	0.5 (4)	C53—C52—C57—C56	−0.2 (4)
C2—C3—C31—C36	−108.6 (3)	C51—C52—C57—C56	−177.8 (3)
C4—C3—C31—C36	70.8 (4)	C52—C51—C58—N3	0.1 (3)
C2—C3—C31—C32	66.9 (4)	C5—C51—C58—N3	−178.8 (3)
C4—C3—C31—C32	−113.7 (3)	C2—C1—N1—C5	1.3 (4)
C36—C31—C32—C33	0.4 (5)	C11—C1—N1—C5	−178.3 (2)
C3—C31—C32—C33	−175.3 (3)	C4—C5—N1—C1	−0.9 (4)
C31—C32—C33—C34	0.5 (5)	C51—C5—N1—C1	−179.3 (2)
C32—C33—C34—C35	−0.8 (6)	C51—C58—N3—C57	0.4 (4)
C33—C34—C35—C36	0.2 (6)	C56—C57—N3—C58	177.6 (3)
C32—C31—C36—C35	−1.1 (4)	C52—C57—N3—C58	−0.6 (4)
C3—C31—C36—C35	174.4 (3)	C13—C14—S—C11	−1.0 (3)
C32—C31—C36—Br	−179.4 (2)	C12—C11—S—C14	1.3 (3)
C3—C31—C36—Br	−3.9 (4)	C1—C11—S—C14	178.6 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C53—H53···N1	0.93	2.58	3.069 (4)	114
C58—H58···N2	0.93	2.55	3.278 (4)	135
N3—H3···N2i	0.86	2.17	3.008 (4)	165
C32—H32···Cg1ii	0.93	2.89	3.761 (4)	157

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the benzene ring of the indole moiety.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C53—H53⋯N1	0.93	2.58	3.069 (4)	114
C58—H58⋯N2	0.93	2.55	3.278 (4)	135
N3—H3⋯N2i	0.86	2.17	3.008 (4)	165
C32—H32⋯Cg1ii	0.93	2.89	3.761 (4)	157

Symmetry codes: (i) ; (ii) .