N-(4-Chloro-phen-yl)-5-(4,5-dihydro-1H-imidazol-2-yl)thieno[2,3-b]pyridin-4-amine.

In the title compound, C(16)H(13)ClN(4)S, the thienopyridine fused-ring system is nearly planar (r.m.s. deviation = 0.0333 Å) and forms a dihedral angle of 4.4 (3)° with the attached dihydro-imidazole ring (r.m.s. deviation = 0.0429 Å) allowing for the formation of an intra-molecular (exocyclic amine)N-H⋯N(imine) hydrogen bond. The benzene rings of the disordered (50:50) -N(H)-C(6)H(4)Cl residue form dihedral angles of 59.1 (3) and 50.59 (15)° with the fused ring system. In the crystal, (imidazole amine)N-H⋯N(pyridine) hydrogen bonds lead to a supra-molecular helical chain along the b axis. The chains assemble into layers (ab plane) with inter-digitation of the chloro-benzene rings which results in weak C-H⋯Cl inter-actions in the c-axis direction.

Related literature

For the synthesis and biological activity of thienopyridine derivatives, see: Kaigorodova et al. (2000 ▶); Moloney (2001 ▶); Bernardino et al. (2004 ▶, 2006 ▶); Leal et al. (2008 ▶); Pinheiro et al. (2008a ▶); El-Kashef et al. (2010 ▶); Testa et al. (2010 ▶); Panchamukhi et al. (2011 ▶). For the anti-leishmanial activity of 5-(4,5-dihydro-1H-imidazol-2-yl)-4-(aryl­amino)­thieno[2,3-b]pyridine, see: Pinheiro et al. (2012 ▶).

Experimental

Crystal data

C16H13ClN4S

M = 328.81

Monoclinic,

a = 17.784 (3) Å

b = 6.2264 (4) Å

c = 13.6226 (18) Å

β = 102.700 (4)°

V = 1471.5 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.40 mm−1

T = 120 K

0.25 × 0.15 × 0.03 mm

Data collection

Bruker–Nonius Roper CCD camera on κ-goniostat diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2007 ▶) T min = 0.639, T max = 1.000

9375 measured reflections

2591 independent reflections

1106 reflections with I > 2σ(I)

R int = 0.138

Refinement

R[F 2 > 2σ(F 2)] = 0.079

wR(F 2) = 0.217

S = 0.99

2591 reflections

191 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.22 e Å−3

Δρmin = −0.42 e Å−3

Data collection: COLLECT (Hooft, 1998 ▶); cell refinement: DENZO (Otwinowski & Minor, 1997 ▶) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows(Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681202658X/xu5563sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681202658X/xu5563Isup2.hkl

Supplementary material file. DOI: 10.1107/S160053681202658X/xu5563Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C16H13ClN4S	F(000) = 680
Mr = 328.81	Dx = 1.484 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5430 reflections
a = 17.784 (3) Å	θ = 1.0–26.4°
b = 6.2264 (4) Å	µ = 0.40 mm−1
c = 13.6226 (18) Å	T = 120 K
β = 102.700 (4)°	Plate, colourless
V = 1471.5 (3) Å3	0.25 × 0.15 × 0.03 mm
Z = 4

Bruker–Nonius Roper CCD camera on κ-goniostat diffractometer	2591 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	1106 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.138
Detector resolution: 9.091 pixels mm-1	θmax = 25.0°, θmin = 3.4°
φ & ω scans	h = −21→21
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	k = −7→7
Tmin = 0.639, Tmax = 1.000	l = −16→16
9375 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)] = 0.079	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.217	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	w = 1/[σ2(Fo2) + (0.088P)2 + 1.3236P] where P = (Fo2 + 2Fc2)/3
2591 reflections	(Δ/σ)max < 0.001
191 parameters	Δρmax = 0.22 e Å−3
2 restraints	Δρmin = −0.42 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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)
S1	0.12641 (12)	0.5151 (2)	0.60112 (15)	0.0763 (7)
N1	0.0697 (3)	0.2115 (6)	0.7026 (4)	0.0512 (13)
N3	0.2209 (3)	−0.3570 (7)	0.8955 (4)	0.0739 (18)
N4	0.0959 (3)	−0.3191 (7)	0.8940 (4)	0.0549 (14)
H4N	0.0473 (11)	−0.288 (8)	0.869 (4)	0.066*
C1	0.0829 (3)	0.0361 (8)	0.7610 (4)	0.0462 (14)
H1	0.0394	−0.0312	0.7777	0.055*
C2	0.1545 (3)	−0.0563 (7)	0.7995 (4)	0.0464 (15)
C3	0.2210 (3)	0.0395 (8)	0.7765 (5)	0.0601 (18)
C4	0.2088 (4)	0.2238 (8)	0.7136 (5)	0.0592 (18)
C5	0.2606 (4)	0.3478 (10)	0.6675 (6)	0.081 (2)
H5	0.3144	0.3211	0.6777	0.097*
C6	0.2236 (5)	0.5055 (10)	0.6084 (6)	0.087 (2)
H6	0.2493	0.6035	0.5736	0.104*
C7	0.1334 (4)	0.2970 (8)	0.6822 (5)	0.0526 (16)
Cl1	0.6039 (3)	0.3366 (8)	0.9082 (4)	0.0739 (13)	0.50
N2	0.2952 (7)	−0.067 (3)	0.8204 (17)	0.074 (3)	0.50
H2N	0.292 (7)	−0.200 (8)	0.842 (9)	0.089*	0.50
C8	0.3602 (3)	0.0556 (17)	0.8170 (11)	0.066 (3)	0.50
C9	0.3724 (3)	0.2610 (16)	0.8574 (12)	0.083 (3)	0.50
H9	0.3297	0.3483	0.8629	0.099*	0.50
C10	0.4470 (3)	0.3387 (12)	0.8896 (11)	0.093 (3)	0.50
H10	0.4554	0.4790	0.9172	0.111*	0.50
C11	0.5095 (3)	0.2109 (10)	0.8815 (5)	0.100 (3)	0.50
C12	0.4973 (4)	0.0056 (14)	0.8411 (8)	0.095 (4)	0.50
H12	0.5400	−0.0817	0.8356	0.113*	0.50
C13	0.4227 (4)	−0.0721 (16)	0.8089 (10)	0.071 (4)	0.50
H13	0.4143	−0.2124	0.7813	0.085*	0.50
Cl1'	0.6109 (3)	0.2495 (8)	0.9508 (4)	0.0739 (13)	0.50
N2'	0.2871 (4)	−0.045 (2)	0.8004 (14)	0.074 (3)	0.50
H2N'	0.2828	−0.1058	0.8574	0.089*	0.50
C8'	0.3706 (3)	0.0220 (11)	0.8521 (6)	0.066 (3)	0.50
C9'	0.3835 (4)	0.2370 (11)	0.8780 (8)	0.083 (3)	0.50
H9'	0.3412	0.3287	0.8805	0.099*	0.50
C10'	0.4582 (4)	0.3178 (14)	0.9004 (9)	0.093 (3)	0.50
H10'	0.4670	0.4647	0.9181	0.111*	0.50
C11'	0.5200 (4)	0.1836 (17)	0.8968 (9)	0.100 (3)	0.50
C12'	0.5071 (3)	−0.0313 (16)	0.8709 (9)	0.095 (4)	0.50
H12'	0.5494	−0.1230	0.8685	0.113*	0.50
C13'	0.4325 (3)	−0.1121 (14)	0.8486 (7)	0.071 (4)	0.50
H13'	0.4237	−0.2590	0.8309	0.085*	0.50
C14	0.1587 (2)	−0.2514 (6)	0.8627 (3)	0.0494 (15)
C15	0.2003 (2)	−0.5287 (6)	0.9594 (4)	0.079 (2)
H15A	0.2272	−0.5067	1.0304	0.094*
H15B	0.2153	−0.6706	0.9371	0.094*
C16	0.1138 (3)	−0.5183 (6)	0.9492 (3)	0.0678 (19)
H16A	0.0875	−0.6421	0.9108	0.081*
H16B	0.1000	−0.5117	1.0157	0.081*

	U11	U22	U33	U12	U13	U23
S1	0.1145 (17)	0.0388 (9)	0.0898 (14)	0.0007 (9)	0.0533 (12)	0.0066 (8)
N1	0.051 (3)	0.038 (3)	0.068 (4)	0.004 (2)	0.020 (3)	0.007 (2)
N3	0.048 (3)	0.035 (3)	0.121 (5)	−0.001 (2)	−0.019 (3)	0.006 (3)
N4	0.051 (3)	0.048 (3)	0.060 (4)	0.000 (3)	0.000 (3)	0.011 (2)
C1	0.037 (4)	0.043 (3)	0.059 (4)	−0.007 (3)	0.012 (3)	−0.004 (3)
C2	0.037 (4)	0.032 (3)	0.066 (4)	−0.002 (2)	0.003 (3)	−0.002 (3)
C3	0.035 (4)	0.033 (3)	0.113 (6)	−0.002 (3)	0.018 (4)	−0.016 (3)
C4	0.055 (4)	0.031 (3)	0.100 (5)	−0.007 (3)	0.034 (4)	−0.013 (3)
C5	0.082 (5)	0.050 (4)	0.129 (7)	−0.024 (4)	0.061 (5)	−0.024 (4)
C6	0.129 (7)	0.041 (4)	0.113 (6)	−0.019 (4)	0.077 (5)	−0.011 (4)
C7	0.060 (4)	0.032 (3)	0.071 (5)	0.002 (3)	0.027 (3)	−0.005 (3)
Cl1	0.0423 (14)	0.087 (4)	0.094 (4)	−0.012 (2)	0.019 (2)	−0.012 (2)
N2	0.031 (4)	0.041 (4)	0.144 (8)	0.002 (3)	0.004 (4)	−0.005 (4)
C8	0.022 (4)	0.043 (4)	0.126 (11)	0.008 (3)	−0.004 (5)	−0.012 (5)
C9	0.036 (4)	0.048 (4)	0.166 (9)	−0.002 (3)	0.028 (5)	−0.035 (5)
C10	0.038 (5)	0.083 (5)	0.162 (8)	−0.011 (4)	0.029 (5)	−0.061 (5)
C11	0.034 (5)	0.112 (6)	0.154 (8)	−0.021 (5)	0.022 (5)	−0.075 (6)
C12	0.022 (4)	0.102 (7)	0.147 (11)	0.013 (4)	−0.009 (5)	−0.057 (7)
C13	0.040 (5)	0.059 (5)	0.097 (12)	0.020 (4)	−0.020 (6)	−0.024 (7)
Cl1'	0.0423 (14)	0.087 (4)	0.094 (4)	−0.012 (2)	0.019 (2)	−0.012 (2)
N2'	0.031 (4)	0.041 (4)	0.144 (8)	0.002 (3)	0.004 (4)	−0.005 (4)
C8'	0.022 (4)	0.043 (4)	0.126 (11)	0.008 (3)	−0.004 (5)	−0.012 (5)
C9'	0.036 (4)	0.048 (4)	0.166 (9)	−0.002 (3)	0.028 (5)	−0.035 (5)
C10'	0.038 (5)	0.083 (5)	0.162 (8)	−0.011 (4)	0.029 (5)	−0.061 (5)
C11'	0.034 (5)	0.112 (6)	0.154 (8)	−0.021 (5)	0.022 (5)	−0.075 (6)
C12'	0.022 (4)	0.102 (7)	0.147 (11)	0.013 (4)	−0.009 (5)	−0.057 (7)
C13'	0.040 (5)	0.059 (5)	0.097 (12)	0.020 (4)	−0.020 (6)	−0.024 (7)
C14	0.045 (4)	0.035 (3)	0.061 (4)	−0.009 (3)	−0.003 (3)	−0.011 (3)
C15	0.091 (6)	0.042 (4)	0.082 (5)	0.002 (3)	−0.026 (4)	−0.001 (3)
C16	0.077 (5)	0.044 (3)	0.068 (5)	−0.007 (3)	−0.015 (4)	0.010 (3)

S1—C6	1.710 (8)	C9—C10	1.3900
S1—C7	1.738 (6)	C9—H9	0.9500
N1—C7	1.336 (7)	C10—C11	1.3900
N1—C1	1.341 (6)	C10—H10	0.9500
N3—C14	1.281 (6)	C11—C12	1.3900
N3—C15	1.474 (6)	C12—C13	1.3900
N4—C14	1.348 (6)	C12—H12	0.9500
N4—C16	1.449 (6)	C13—H13	0.9500
N4—H4N	0.877 (10)	Cl1'—C11'	1.674 (10)
C1—C2	1.390 (7)	N2'—C8'	1.556 (10)
C1—H1	0.9500	N2'—H2N'	0.88 (1)
C2—C3	1.421 (8)	C8'—C9'	1.3900
C2—C14	1.481 (6)	C8'—C13'	1.3900
C3—N2'	1.263 (12)	C9'—C10'	1.3900
C3—C4	1.420 (8)	C9'—H9'	0.9500
C3—N2	1.479 (16)	C10'—C11'	1.3900
C4—C7	1.391 (8)	C10'—H10'	0.9500
C4—C5	1.447 (8)	C11'—C12'	1.3900
C5—C6	1.347 (10)	C12'—C13'	1.3900
C5—H5	0.9500	C12'—H12'	0.9500
C6—H6	0.9500	C13'—H13'	0.9500
Cl1—C11	1.815 (9)	C15—C16	1.5151
N2—C8	1.394 (17)	C15—H15A	0.9900
N2—H2N	0.88 (1)	C15—H15B	0.9900
C8—C9	1.3900	C16—H16A	0.9900
C8—C13	1.3900	C16—H16B	0.9900
C6—S1—C7	90.3 (3)	C13—C12—C11	120.0
C7—N1—C1	113.7 (5)	C13—C12—H12	120.0
C14—N3—C15	105.7 (4)	C11—C12—H12	120.0
C14—N4—C16	109.2 (4)	C12—C13—C8	120.0
C14—N4—H4N	128 (4)	C12—C13—H13	120.0
C16—N4—H4N	119 (4)	C8—C13—H13	120.0
N1—C1—C2	126.0 (5)	C3—N2'—C8'	138.2 (13)
N1—C1—H1	117.0	C3—N2'—H2N	118 (6)
C2—C1—H1	117.0	C8'—N2'—H2N	92 (6)
C1—C2—C3	118.8 (5)	C3—N2'—H2N'	98.6
C1—C2—C14	118.9 (5)	C8'—N2'—H2N'	88.6
C3—C2—C14	122.3 (5)	C9'—C8'—C13'	120.0
N2'—C3—C4	120.3 (8)	C9'—C8'—N2'	117.5 (7)
N2'—C3—C2	122.7 (8)	C13'—C8'—N2'	120.4 (8)
C4—C3—C2	116.6 (5)	C8'—C9'—C10'	120.0
C4—C3—N2	127.6 (8)	C8'—C9'—H9'	120.0
C2—C3—N2	115.8 (8)	C10'—C9'—H9'	120.0
C7—C4—C3	117.4 (5)	C11'—C10'—C9'	120.0
C7—C4—C5	110.8 (6)	C11'—C10'—H10'	120.0
C3—C4—C5	131.6 (6)	C9'—C10'—H10'	120.0
C6—C5—C4	111.9 (7)	C10'—C11'—C12'	120.0
C6—C5—H5	124.0	C10'—C11'—Cl1'	122.2 (6)
C4—C5—H5	124.0	C12'—C11'—Cl1'	115.9 (6)
C5—C6—S1	114.6 (5)	C13'—C12'—C11'	120.0
C5—C6—H6	122.7	C13'—C12'—H12'	120.0
S1—C6—H6	122.7	C11'—C12'—H12'	120.0
N1—C7—C4	127.6 (5)	C12'—C13'—C8'	120.0
N1—C7—S1	119.9 (5)	C12'—C13'—H13'	120.0
C4—C7—S1	112.4 (4)	C8'—C13'—H13'	120.0
C8—N2—C3	114.5 (16)	N3—C14—N4	116.2 (4)
C8—N2—H2N	129 (8)	N3—C14—C2	123.6 (4)
C3—N2—H2N	116 (8)	N4—C14—C2	120.1 (4)
C3—N2—H2N'	93.2	N3—C15—C16	107.1 (2)
C9—C8—C13	120.0	N3—C15—H15A	110.3
C9—C8—N2	123.2 (15)	C16—C15—H15A	110.3
C13—C8—N2	111.9 (13)	N3—C15—H15B	110.3
C10—C9—C8	120.0	C16—C15—H15B	110.3
C10—C9—H9	120.0	H15A—C15—H15B	108.6
C8—C9—H9	120.0	N4—C16—C15	100.8 (2)
C11—C10—C9	120.0	N4—C16—H16A	111.6
C11—C10—H10	120.0	C15—C16—H16A	111.6
C9—C10—H10	120.0	N4—C16—H16B	111.6
C10—C11—C12	120.0	C15—C16—H16B	111.6
C10—C11—Cl1	117.2 (4)	H16A—C16—H16B	109.4
C12—C11—Cl1	122.2 (4)
C7—N1—C1—C2	0.1 (8)	C8—C9—C10—C11	0.0
N1—C1—C2—C3	0.1 (8)	C9—C10—C11—C12	0.0
N1—C1—C2—C14	−179.7 (5)	C9—C10—C11—Cl1	171.4 (3)
C1—C2—C3—N2'	−173.2 (10)	C10—C11—C12—C13	0.0
C14—C2—C3—N2'	6.6 (13)	Cl1—C11—C12—C13	−170.9 (3)
C1—C2—C3—C4	−0.9 (8)	C11—C12—C13—C8	0.0
C14—C2—C3—C4	178.9 (5)	C9—C8—C13—C12	0.0
C1—C2—C3—N2	179.7 (10)	N2—C8—C13—C12	−156.1 (17)
C14—C2—C3—N2	−0.5 (11)	C4—C3—N2'—C8'	57 (3)
N2'—C3—C4—C7	174.0 (10)	C2—C3—N2'—C8'	−131.2 (19)
C2—C3—C4—C7	1.5 (8)	N2—C3—N2'—C8'	−87 (7)
N2—C3—C4—C7	−179.2 (11)	C3—N2'—C8'—C9'	−4 (3)
N2'—C3—C4—C5	−0.7 (13)	C3—N2'—C8'—C13'	−168.0 (18)
C2—C3—C4—C5	−173.2 (6)	C13'—C8'—C9'—C10'	0.0
N2—C3—C4—C5	6.1 (15)	N2'—C8'—C9'—C10'	−163.7 (10)
C7—C4—C5—C6	1.7 (8)	C8'—C9'—C10'—C11'	0.0
C3—C4—C5—C6	176.6 (6)	C9'—C10'—C11'—C12'	0.0
C4—C5—C6—S1	−1.2 (8)	C9'—C10'—C11'—Cl1'	−163.6 (6)
C7—S1—C6—C5	0.4 (5)	C10'—C11'—C12'—C13'	0.0
C1—N1—C7—C4	0.6 (8)	Cl1'—C11'—C12'—C13'	164.6 (6)
C1—N1—C7—S1	176.0 (4)	C11'—C12'—C13'—C8'	0.0
C3—C4—C7—N1	−1.5 (9)	C9'—C8'—C13'—C12'	0.0
C5—C4—C7—N1	174.3 (6)	N2'—C8'—C13'—C12'	163.2 (9)
C3—C4—C7—S1	−177.2 (4)	C15—N3—C14—N4	0.7 (6)
C5—C4—C7—S1	−1.4 (6)	C15—N3—C14—C2	176.6 (5)
C6—S1—C7—N1	−175.4 (5)	C16—N4—C14—N3	−7.2 (7)
C6—S1—C7—C4	0.6 (5)	C16—N4—C14—C2	176.7 (4)
N2'—C3—N2—C8	55 (5)	C1—C2—C14—N3	174.8 (5)
C4—C3—N2—C8	15 (3)	C3—C2—C14—N3	−5.0 (8)
C2—C3—N2—C8	−165.7 (17)	C1—C2—C14—N4	−9.4 (8)
C3—N2—C8—C9	55 (2)	C3—C2—C14—N4	170.8 (5)
C3—N2—C8—C13	−149.3 (11)	C14—N3—C15—C16	5.8 (4)
C13—C8—C9—C10	0.0	C14—N4—C16—C15	9.7 (5)
N2—C8—C9—C10	153.3 (17)	N3—C15—C16—N4	−9.2 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2n···N3	0.88 (10)	1.87 (11)	2.578 (18)	136 (10)
N2′—H2n'···N3	0.88 (10)	2.04 (11)	2.740 (15)	135 (7)
N4—H4n···N1i	0.88 (3)	2.10 (3)	2.956 (8)	167 (5)
C6—H6···Cl1′ii	0.95	2.74	3.559 (10)	146

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2n⋯N3	0.88 (10)	1.87 (11)	2.578 (18)	136 (10)
N2′—H2n’⋯N3	0.88 (10)	2.04 (11)	2.740 (15)	135 (7)
N4—H4n⋯N1i	0.88 (3)	2.10 (3)	2.956 (8)	167 (5)
C6—H6⋯Cl1′ii	0.95	2.74	3.559 (10)	146

Symmetry codes: (i) ; (ii) .