7-Methyl-5,6,7,8-tetra-hydro-1-benzo-thieno[2,3-d]pyrimidin-4-amine.

In the title compound, C(11)H(13)N(3)S, two of the C atoms of the cyclo-hexene ring and the methyl group attached to it are disordered over two sets of sites in a 0.544 (2):0.456 (2) ratio. The benzothiene and pyrimidine rings are almost coplanar with an angular tilt of 2.371 (9)° between them. The thio-phene ring is essentially planar (r.m.s. deviation 0.05 Å), while the cyclo-hexene ring in both the major- and minor-occupancy conformers adopts a half-chair conformation. In the crystal structure, pairs of intermolecular N-H⋯N hydrogen bonds involving the amino groups result in centrosymmetric head-to-head dimers about inversion centres, corresponding to an R(2) (2)(8) graph-set motif. Further, N-H⋯N hydrogen bonding generates a two-dimensional hydrogen-bonded network perpendicular to the ac plane and running along the diagonal of the ac plane.

Related literature

For the preparation of the title compound, see: Shetty et al. (2009 ▶). For medicinal background, see: Brown (1983 ▶); Heildelberg & Arafield (1963 ▶); De Clercq (1986a ▶,b ▶); Sishoo et al. (1983 ▶). For related structures, see: Akkurt et al. (2008 ▶); Harrison et al. (2006 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C11H13N3S

M = 219.30

Monoclinic,

a = 10.395 (4) Å

b = 8.422 (3) Å

c = 13.155 (5) Å

β = 110.015 (6)°

V = 1082.0 (7) Å3

Z = 4

Mo Kα radiation

μ = 0.27 mm−1

T = 123 K

0.18 × 0.16 × 0.16 mm

Data collection

Bruker SMART APEX CCD detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1998 ▶) T min = 0.953, T max = 0.958

6268 measured reflections

2347 independent reflections

1917 reflections with I > 2σ(I)

R int = 0.044

Refinement

R[F 2 > 2σ(F 2)] = 0.053

wR(F 2) = 0.169

S = 0.84

2347 reflections

168 parameters

H-atom parameters constrained

Δρmax = 0.71 e Å−3

Δρmin = −0.41 e Å−3

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SMART; data reduction: SAINT (Bruker, 1998 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1999 ▶) and CAMERON (Watkin et al., 1996 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811021155/ds2116sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811021155/ds2116Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811021155/ds2116Isup3.cml

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

C11H13N3S	F(000) = 464
Mr = 219.30	Dx = 1.346 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2347 reflections
a = 10.395 (4) Å	θ = 2.2–27.0°
b = 8.422 (3) Å	µ = 0.27 mm−1
c = 13.155 (5) Å	T = 123 K
β = 110.015 (6)°	Block, yellow
V = 1082.0 (7) Å3	0.18 × 0.16 × 0.16 mm
Z = 4

Bruker SMART APEX CCD detector diffractometer	2347 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1917 reflections with I > 2σ(I)
graphite	Rint = 0.044
ω scans	θmax = 27.0°, θmin = 2.2°
Absorption correction: multi-scan (SMART; Bruker, 1998) [is this correct?]	h = −11→13
Tmin = 0.953, Tmax = 0.958	k = −10→10
6268 measured reflections	l = −16→6

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.169	H-atom parameters constrained
S = 0.84	w = 1/[σ2(Fo2) + (0.0936P)2 + 3.4562P] where P = (Fo2 + 2Fc2)/3
2347 reflections	(Δ/σ)max < 0.001
168 parameters	Δρmax = 0.71 e Å−3
0 restraints	Δρmin = −0.41 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)
C1	0.3496 (3)	0.4303 (3)	0.0551 (2)	0.0240 (6)
C2	0.3466 (3)	0.6871 (3)	0.1469 (2)	0.0227 (6)
C3	0.2341 (3)	0.6672 (3)	0.0522 (2)	0.0221 (5)
C4	0.1409 (3)	0.7972 (3)	0.0259 (2)	0.0225 (5)
C5	0.1329 (3)	0.4538 (3)	−0.1015 (2)	0.0307 (7)
H5A	0.0422	0.4744	−0.0991	0.037*
H5B	0.1411	0.5100	−0.1633	0.037*
C6A	0.1477 (10)	0.2803 (11)	−0.1164 (9)	0.036 (3)	0.465 (19)
H6A1	0.0699	0.2298	−0.1050	0.043*	0.465 (19)
H6A2	0.1358	0.2654	−0.1922	0.043*	0.465 (19)
C7A	0.2648 (6)	0.1894 (7)	−0.0569 (5)	0.0224 (17)	0.544 (16)
H7A	0.2274	0.1383	−0.0061	0.027*	0.544 (16)
C11A	0.3087 (17)	0.037 (2)	−0.1037 (13)	0.029 (3)	0.50 (5)
H11A	0.2289	−0.0152	−0.1514	0.044*	0.50 (5)
H11B	0.3565	−0.0329	−0.0455	0.044*	0.50 (5)
H11C	0.3679	0.0661	−0.1429	0.044*	0.50 (5)
C6B	0.1995 (8)	0.3109 (6)	−0.1466 (5)	0.021 (2)	0.535 (19)
H6B1	0.1271	0.2331	−0.1743	0.025*	0.535 (19)
H6B2	0.2169	0.3534	−0.2092	0.025*	0.535 (19)
C7B	0.2932 (8)	0.2411 (11)	−0.1011 (8)	0.035 (3)	0.456 (16)
H7B	0.3552	0.2922	−0.1329	0.042*	0.456 (16)
C11B	0.3192 (18)	0.072 (3)	−0.127 (2)	0.042 (4)	0.50 (5)
H11D	0.2934	0.0007	−0.0809	0.063*	0.50 (5)
H11E	0.4147	0.0589	−0.1166	0.063*	0.50 (5)
H11F	0.2661	0.0496	−0.2015	0.063*	0.50 (5)
C8	0.3857 (3)	0.2702 (3)	0.0241 (2)	0.0298 (6)
H8A	0.4201	0.2045	0.0883	0.036*
H8B	0.4580	0.2812	−0.0063	0.036*
C9	0.2746 (3)	0.9236 (3)	0.1821 (2)	0.0258 (6)
H9	0.2863	1.0124	0.2263	0.031*
C10	0.2379 (3)	0.5173 (3)	0.0000 (2)	0.0231 (6)
N1	0.0301 (2)	0.8031 (3)	−0.06281 (18)	0.0273 (5)
H1A	−0.0235	0.8840	−0.0745	0.033*
H1B	0.0121	0.7260	−0.1084	0.033*
N2	0.1624 (2)	0.9225 (3)	0.09383 (18)	0.0244 (5)
N3	0.3714 (2)	0.8140 (3)	0.21457 (18)	0.0250 (5)
S1	0.45432 (7)	0.52481 (9)	0.17184 (5)	0.0273 (2)

	U11	U22	U33	U12	U13	U23
C1	0.0243 (13)	0.0236 (13)	0.0217 (13)	0.0006 (10)	0.0046 (10)	0.0007 (10)
C2	0.0237 (12)	0.0205 (13)	0.0204 (12)	0.0013 (10)	0.0028 (10)	0.0030 (10)
C3	0.0232 (13)	0.0226 (13)	0.0174 (12)	−0.0003 (10)	0.0032 (10)	0.0014 (10)
C4	0.0237 (12)	0.0210 (13)	0.0189 (12)	0.0002 (10)	0.0022 (10)	0.0024 (10)
C5	0.0312 (15)	0.0245 (14)	0.0254 (14)	0.0031 (11)	−0.0043 (12)	−0.0028 (11)
C6A	0.030 (4)	0.036 (4)	0.039 (5)	−0.004 (3)	0.008 (4)	−0.017 (3)
C7A	0.023 (3)	0.019 (3)	0.024 (3)	0.003 (2)	0.006 (2)	0.005 (2)
C11A	0.022 (4)	0.017 (5)	0.046 (6)	0.000 (3)	0.009 (3)	0.001 (4)
C6B	0.021 (4)	0.016 (2)	0.020 (3)	0.001 (2)	0.000 (2)	−0.0016 (19)
C7B	0.035 (4)	0.028 (4)	0.037 (5)	0.003 (3)	0.006 (3)	−0.010 (4)
C11B	0.035 (5)	0.025 (7)	0.068 (10)	−0.010 (5)	0.020 (6)	−0.022 (6)
C8	0.0293 (14)	0.0243 (14)	0.0320 (15)	0.0063 (11)	0.0055 (12)	0.0006 (11)
C9	0.0258 (13)	0.0258 (14)	0.0213 (13)	0.0017 (11)	0.0022 (11)	−0.0025 (10)
C10	0.0251 (13)	0.0213 (13)	0.0187 (12)	−0.0004 (10)	0.0020 (10)	0.0010 (10)
N1	0.0279 (12)	0.0219 (12)	0.0223 (11)	0.0073 (9)	−0.0043 (9)	−0.0025 (9)
N2	0.0245 (11)	0.0215 (11)	0.0213 (11)	0.0035 (9)	0.0000 (9)	−0.0008 (9)
N3	0.0247 (11)	0.0251 (12)	0.0188 (11)	0.0003 (9)	−0.0008 (9)	−0.0020 (9)
S1	0.0239 (4)	0.0254 (4)	0.0245 (4)	0.0053 (3)	−0.0022 (3)	0.0000 (3)

C1—C10	1.354 (4)	C7A—H7A	0.9800
C1—C8	1.493 (4)	C11A—H11A	0.9600
C1—S1	1.741 (3)	C11A—H11B	0.9600
C2—N3	1.358 (3)	C11A—H11C	0.9600
C2—C3	1.397 (4)	C6B—C7B	1.120 (9)
C2—S1	1.725 (3)	C6B—H6B1	0.9700
C3—C4	1.424 (4)	C6B—H6B2	0.9700
C3—C10	1.443 (4)	C7B—C11B	1.51 (2)
C4—N1	1.331 (3)	C7B—C8	1.616 (9)
C4—N2	1.351 (3)	C7B—H7B	0.9800
C5—C6A	1.489 (8)	C11B—H11D	0.9600
C5—C10	1.504 (4)	C11B—H11E	0.9600
C5—C6B	1.601 (7)	C11B—H11F	0.9600
C5—H5A	0.9700	C8—H8A	0.9700
C5—H5B	0.9700	C8—H8B	0.9700
C6A—C7A	1.424 (9)	C9—N3	1.323 (3)
C6A—H6A1	0.9700	C9—N2	1.335 (3)
C6A—H6A2	0.9700	C9—H9	0.9300
C7A—C8	1.503 (6)	N1—H1A	0.8600
C7A—C11A	1.556 (19)	N1—H1B	0.8600
C10—C1—C8	126.3 (2)	C7B—C6B—H6B2	105.5
C10—C1—S1	112.8 (2)	C5—C6B—H6B2	105.5
C8—C1—S1	120.9 (2)	H6B1—C6B—H6B2	106.1
N3—C2—C3	126.3 (2)	C6B—C7B—C11B	124.3 (10)
N3—C2—S1	122.3 (2)	C6B—C7B—C8	124.8 (6)
C3—C2—S1	111.4 (2)	C11B—C7B—C8	106.6 (11)
C2—C3—C4	114.6 (2)	C6B—C7B—H7B	96.9
C2—C3—C10	112.2 (2)	C11B—C7B—H7B	96.9
C4—C3—C10	133.2 (2)	C8—C7B—H7B	96.9
N1—C4—N2	116.6 (2)	C7B—C11B—H11D	109.5
N1—C4—C3	123.6 (2)	C7B—C11B—H11E	109.5
N2—C4—C3	119.7 (2)	H11D—C11B—H11E	109.5
C6A—C5—C10	112.9 (4)	C7B—C11B—H11F	109.5
C6A—C5—C6B	30.2 (4)	H11D—C11B—H11F	109.5
C10—C5—C6B	108.8 (3)	H11E—C11B—H11F	109.5
C6A—C5—H5A	109.0	C1—C8—C7A	112.0 (3)
C10—C5—H5A	109.0	C1—C8—C7B	107.3 (3)
C6B—C5—H5A	134.1	C7A—C8—C7B	31.6 (3)
C6A—C5—H5B	109.0	C1—C8—H8A	109.2
C10—C5—H5B	109.0	C7A—C8—H8A	109.2
C6B—C5—H5B	83.3	C7B—C8—H8A	135.6
H5A—C5—H5B	107.8	C1—C8—H8B	109.2
C7A—C6A—C5	124.2 (6)	C7A—C8—H8B	109.2
C7A—C6A—H6A1	106.3	C7B—C8—H8B	82.5
C5—C6A—H6A1	106.3	H8A—C8—H8B	107.9
C7A—C6A—H6A2	106.3	N3—C9—N2	128.1 (3)
C5—C6A—H6A2	106.3	N3—C9—H9	115.9
H6A1—C6A—H6A2	106.4	N2—C9—H9	115.9
C6A—C7A—C8	119.7 (5)	C1—C10—C3	112.1 (2)
C6A—C7A—C11A	122.4 (7)	C1—C10—C5	120.7 (2)
C8—C7A—C11A	111.5 (7)	C3—C10—C5	127.1 (2)
C6A—C7A—H7A	98.4	C4—N1—H1A	120.0
C8—C7A—H7A	98.4	C4—N1—H1B	120.0
C11A—C7A—H7A	98.4	H1A—N1—H1B	120.0
C7B—C6B—C5	127.1 (6)	C9—N2—C4	118.6 (2)
C7B—C6B—H6B1	105.5	C9—N3—C2	112.6 (2)
C5—C6B—H6B1	105.5	C2—S1—C1	91.45 (13)
N3—C2—C3—C4	1.6 (4)	C11B—C7B—C8—C1	−173.8 (11)
S1—C2—C3—C4	−179.64 (19)	C6B—C7B—C8—C7A	87.6 (14)
N3—C2—C3—C10	−179.1 (3)	C11B—C7B—C8—C7A	−69.8 (12)
S1—C2—C3—C10	−0.3 (3)	C8—C1—C10—C3	−179.9 (3)
C2—C3—C4—N1	177.7 (3)	S1—C1—C10—C3	0.1 (3)
C10—C3—C4—N1	−1.5 (5)	C8—C1—C10—C5	1.8 (5)
C2—C3—C4—N2	−3.1 (4)	S1—C1—C10—C5	−178.3 (2)
C10—C3—C4—N2	177.8 (3)	C2—C3—C10—C1	0.1 (3)
C10—C5—C6A—C7A	−13.7 (15)	C4—C3—C10—C1	179.3 (3)
C6B—C5—C6A—C7A	74.5 (12)	C2—C3—C10—C5	178.4 (3)
C5—C6A—C7A—C8	−2.4 (17)	C4—C3—C10—C5	−2.5 (5)
C5—C6A—C7A—C11A	−152.0 (12)	C6A—C5—C10—C1	14.0 (8)
C6A—C5—C6B—C7B	−85.2 (13)	C6B—C5—C10—C1	−18.1 (5)
C10—C5—C6B—C7B	18.3 (13)	C6A—C5—C10—C3	−164.1 (7)
C5—C6B—C7B—C11B	153.1 (15)	C6B—C5—C10—C3	163.8 (4)
C5—C6B—C7B—C8	−0.4 (19)	N3—C9—N2—C4	−0.7 (4)
C10—C1—C8—C7A	−17.7 (5)	N1—C4—N2—C9	−178.0 (3)
S1—C1—C8—C7A	162.3 (4)	C3—C4—N2—C9	2.7 (4)
C10—C1—C8—C7B	15.5 (6)	N2—C9—N3—C2	−0.8 (4)
S1—C1—C8—C7B	−164.5 (5)	C3—C2—N3—C9	0.3 (4)
C6A—C7A—C8—C1	17.3 (10)	S1—C2—N3—C9	−178.4 (2)
C11A—C7A—C8—C1	169.9 (8)	N3—C2—S1—C1	179.2 (2)
C6A—C7A—C8—C7B	−70.1 (10)	C3—C2—S1—C1	0.3 (2)
C11A—C7A—C8—C7B	82.5 (10)	C10—C1—S1—C2	−0.2 (2)
C6B—C7B—C8—C1	−16.5 (14)	C8—C1—S1—C2	179.7 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N2i	0.86	2.13	2.992 (3)	175
C7A—H7A···N2ii	0.98 (1)	2.47 (1)	3.400 (7)	158
C7B—H7B···S1iii	0.98 (1)	2.69 (1)	3.649 (1)	165

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯N2i	0.86	2.13	2.992 (3)	175
C7A—H7A⋯N2ii	0.98 (1)	2.47 (1)	3.400 (7)	158
C7B—H7B⋯S1iii	0.98 (1)	2.69 (1)	3.649 (1)	165

Symmetry codes: (i) ; (ii) ; (iii) .