4-Imino-2,7-dimethyl-5,6,7,8-tetra-hydro-4H-1-benzothieno[2,3-d]pyrimidin-3-amine.

In the title compound, C(12)H(16)N(4)S, the fused benzothio-phene and the pyrimidine rings are coplanar [dihedral angle = 1.61 (6)°]. Three C atoms of the cyclohexene ring (at positions 3, 6 and 7) are disordered over two sites with an occupancy ratio of 0.702 (8):0.298 (8). The cyclo-hexene ring in both the major and minor components adopts a half-chair conformation. The crystal structure is stabilized by N-H⋯N and C-H⋯N inter-actions, resulting in the formation of inversion dimers with R(2) (2)(10) and R(2) (2)(12) graph-set motifs.

Related literature

For the biological activity of thio­phenes, benzothio­phenes and pyrimidines, see: Pathak et al. (1991 ▶); Shishoo & Jain (1992 ▶). For a related crystal structure, see: Panchamukhi et al. (2011 ▶). For graph-set notations, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C12H16N4S

M = 248.35

Triclinic,

a = 6.7514 (5) Å

b = 8.7139 (6) Å

c = 11.8309 (9) Å

α = 97.221 (4)°

β = 102.820 (4)°

γ = 112.482 (3)°

V = 609.73 (8) Å3

Z = 2

Mo Kα radiation

μ = 0.25 mm−1

T = 296 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 = 0.957, T max = 0.961

11883 measured reflections

2641 independent reflections

2378 reflections with I > 2σ(I)

R int = 0.018

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.112

S = 1.08

2641 reflections

184 parameters

H-atom parameters constrained

Δρmax = 0.23 e Å−3

Δρmin = −0.31 e Å−3

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT-Plus (Bruker, 1998 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) 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/S1600536812031893/pv2567sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812031893/pv2567Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812031893/pv2567Isup3.cml

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

C12H16N4S	Z = 2
Mr = 248.35	F(000) = 264
Triclinic, P1	Dx = 1.353 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.7514 (5) Å	Cell parameters from 2641 reflections
b = 8.7139 (6) Å	θ = 1.8–27.0°
c = 11.8309 (9) Å	µ = 0.25 mm−1
α = 97.221 (4)°	T = 296 K
β = 102.820 (4)°	Block, yellow
γ = 112.482 (3)°	0.18 × 0.16 × 0.16 mm
V = 609.73 (8) Å3

Bruker SMART APEX CCD detector diffractometer	2641 independent reflections
Radiation source: fine-focus sealed tube	2378 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
ω scans	θmax = 27.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −8→8
Tmin = 0.957, Tmax = 0.961	k = −11→11
11883 measured reflections	l = −15→15

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.112	H-atom parameters constrained
S = 1.08	w = 1/[σ2(Fo2) + (0.0684P)2 + 0.0963P] where P = (Fo2 + 2Fc2)/3
2641 reflections	(Δ/σ)max < 0.001
184 parameters	Δρmax = 0.23 e Å−3
0 restraints	Δρmin = −0.31 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	1.01003 (6)	0.58317 (4)	0.33947 (3)	0.04948 (15)
N1	0.6333 (2)	0.59256 (15)	0.20955 (11)	0.0467 (3)
N2	0.33573 (19)	0.33614 (14)	0.09087 (10)	0.0423 (3)
N3	0.1200 (2)	0.26296 (17)	0.00579 (13)	0.0562 (4)
H3A	0.0589	0.3371	0.0081	0.084*	0.667
H3B	0.0330	0.1680	0.0228	0.084*	0.667
H3C	0.1328	0.2380	−0.0667	0.084*	0.667
N4	0.3265 (2)	0.06821 (16)	0.06949 (12)	0.0537 (3)
H4	0.3922	0.0196	0.0911	0.064*
C1	0.2976 (3)	0.6054 (2)	0.09622 (16)	0.0554 (4)
H1A	0.3829	0.7246	0.1342	0.083*
H1B	0.1612	0.5628	0.1181	0.083*
H1C	0.2624	0.5908	0.0113	0.083*
C2	0.4318 (2)	0.50924 (17)	0.13533 (13)	0.0424 (3)
C4	0.4389 (2)	0.22735 (17)	0.12130 (12)	0.0396 (3)
C5	0.7837 (3)	0.07178 (18)	0.24560 (14)	0.0497 (4)
H5A	0.6800	0.0160	0.2872	0.060*
H5B	0.7192	0.0146	0.1627	0.060*
C3	1.3585 (14)	0.1498 (15)	0.4674 (10)	0.0689 (15)	0.702 (8)
H3D	1.3159	0.0309	0.4658	0.103*	0.702 (8)
H3E	1.4308	0.2156	0.5482	0.103*	0.702 (8)
H3F	1.4600	0.1856	0.4206	0.103*	0.702 (8)
C6	1.0074 (5)	0.0565 (3)	0.2941 (3)	0.0509 (8)	0.702 (8)
H6A	0.9744	−0.0599	0.3010	0.061*	0.702 (8)
H6B	1.0937	0.0813	0.2379	0.061*	0.702 (8)
C7	1.1470 (4)	0.1779 (3)	0.4152 (3)	0.0477 (8)	0.702 (8)
H7A	1.0552	0.1574	0.4701	0.057*	0.702 (8)
C3'	1.355 (4)	0.150 (4)	0.435 (2)	0.093 (8)	0.298 (8)
H3AA	1.5012	0.2346	0.4410	0.140*	0.298 (8)
H3AB	1.3436	0.0386	0.4057	0.140*	0.298 (8)
H3AC	1.3323	0.1576	0.5127	0.140*	0.298 (8)
C6'	0.9513 (13)	0.0591 (8)	0.3484 (8)	0.057 (2)	0.298 (8)
H6AA	0.9204	0.0873	0.4226	0.068*	0.298 (8)
H6AB	0.9393	−0.0567	0.3371	0.068*	0.298 (8)
C7'	1.1840 (11)	0.1812 (8)	0.3536 (8)	0.0525 (18)	0.298 (8)
H7AA	1.2031	0.1697	0.2737	0.063*	0.298 (8)
C8	1.2128 (2)	0.3636 (2)	0.40058 (14)	0.0492 (3)
H8A	1.3251	0.3925	0.3595	0.059*
H8B	1.2756	0.4402	0.4780	0.059*
C9	0.7411 (2)	0.49320 (17)	0.24249 (12)	0.0405 (3)
C10	0.6592 (2)	0.31806 (16)	0.20678 (11)	0.0384 (3)
C11	0.8178 (2)	0.25520 (17)	0.25982 (12)	0.0392 (3)
C12	1.0128 (2)	0.38438 (18)	0.33207 (12)	0.0422 (3)

	U11	U22	U33	U12	U13	U23
S1	0.0383 (2)	0.0365 (2)	0.0568 (2)	0.01117 (15)	−0.00373 (15)	0.00092 (15)
N1	0.0416 (6)	0.0355 (6)	0.0558 (7)	0.0156 (5)	0.0042 (5)	0.0066 (5)
N2	0.0323 (6)	0.0381 (6)	0.0484 (6)	0.0129 (5)	0.0015 (5)	0.0078 (5)
N3	0.0367 (7)	0.0479 (7)	0.0693 (8)	0.0171 (6)	−0.0077 (6)	0.0087 (6)
N4	0.0418 (7)	0.0370 (6)	0.0655 (8)	0.0139 (5)	−0.0062 (6)	0.0039 (5)
C1	0.0487 (9)	0.0457 (8)	0.0701 (10)	0.0244 (7)	0.0065 (7)	0.0138 (7)
C2	0.0394 (7)	0.0385 (7)	0.0481 (7)	0.0165 (6)	0.0100 (6)	0.0113 (6)
C4	0.0341 (6)	0.0369 (6)	0.0422 (6)	0.0131 (5)	0.0046 (5)	0.0085 (5)
C5	0.0458 (8)	0.0382 (7)	0.0546 (8)	0.0165 (6)	−0.0012 (6)	0.0078 (6)
C3	0.045 (2)	0.067 (3)	0.088 (4)	0.0301 (18)	−0.0069 (19)	0.022 (2)
C6	0.0469 (13)	0.0476 (12)	0.0571 (18)	0.0251 (11)	0.0064 (11)	0.0077 (11)
C7	0.0400 (12)	0.0492 (12)	0.0517 (17)	0.0210 (9)	0.0043 (10)	0.0140 (11)
C3'	0.078 (8)	0.068 (7)	0.115 (17)	0.028 (6)	−0.012 (8)	0.037 (9)
C6'	0.058 (4)	0.053 (3)	0.058 (4)	0.026 (3)	0.006 (3)	0.021 (3)
C7'	0.051 (3)	0.057 (3)	0.055 (4)	0.031 (3)	0.010 (3)	0.016 (3)
C8	0.0351 (7)	0.0485 (8)	0.0543 (8)	0.0154 (6)	0.0010 (6)	0.0085 (6)
C9	0.0356 (7)	0.0367 (6)	0.0418 (6)	0.0129 (5)	0.0041 (5)	0.0056 (5)
C10	0.0352 (7)	0.0359 (7)	0.0383 (6)	0.0127 (5)	0.0053 (5)	0.0071 (5)
C11	0.0365 (6)	0.0384 (7)	0.0380 (6)	0.0147 (5)	0.0051 (5)	0.0076 (5)
C12	0.0358 (7)	0.0413 (7)	0.0436 (7)	0.0149 (6)	0.0046 (5)	0.0077 (5)

S1—C9	1.7288 (14)	C3—H3D	0.9600
S1—C12	1.7308 (14)	C3—H3E	0.9600
N1—C2	1.3051 (18)	C3—H3F	0.9600
N1—C9	1.3682 (18)	C6—C7	1.523 (5)
N2—C2	1.3688 (18)	C6—H6A	0.9700
N2—C4	1.4118 (17)	C6—H6B	0.9700
N2—N3	1.4211 (16)	C7—C8	1.549 (3)
N3—H3A	0.8900	C7—H7A	0.9800
N3—H3B	0.8900	C3'—C7'	1.47 (2)
N3—H3C	0.8900	C3'—H3AA	0.9600
N4—C4	1.2844 (18)	C3'—H3AB	0.9600
N4—H4	0.7500	C3'—H3AC	0.9600
C1—C2	1.4933 (19)	C6'—C7'	1.506 (13)
C1—H1A	0.9600	C6'—H6AA	0.9700
C1—H1B	0.9600	C6'—H6AB	0.9700
C1—H1C	0.9600	C7'—C8	1.538 (6)
C4—C10	1.4465 (17)	C7'—H7AA	0.9800
C5—C11	1.5067 (19)	C8—C12	1.5008 (19)
C5—C6'	1.513 (6)	C8—H8A	0.9599
C5—C6	1.554 (3)	C8—H8B	0.9600
C5—H5A	0.9600	C9—C10	1.3793 (19)
C5—H5B	0.9601	C10—C11	1.4410 (18)
C3—C7	1.548 (8)	C11—C12	1.3624 (19)
C9—S1—C12	91.18 (6)	C6—C7—H7A	108.7
C2—N1—C9	114.93 (12)	C3—C7—H7A	108.7
C2—N2—C4	124.49 (12)	C8—C7—H7A	108.7
C2—N2—N3	117.21 (11)	C7'—C3'—H3AA	109.5
C4—N2—N3	118.27 (11)	C7'—C3'—H3AB	109.5
N2—N3—H3A	109.5	H3AA—C3'—H3AB	109.5
N2—N3—H3B	109.5	C7'—C3'—H3AC	109.5
H3A—N3—H3B	109.5	H3AA—C3'—H3AC	109.5
N2—N3—H3C	109.5	H3AB—C3'—H3AC	109.5
H3A—N3—H3C	109.5	C7'—C6'—C5	109.0 (7)
H3B—N3—H3C	109.5	C7'—C6'—H6AA	109.9
C4—N4—H4	109.5	C5—C6'—H6AA	109.9
C2—C1—H1A	109.5	C7'—C6'—H6AB	109.9
C2—C1—H1B	109.5	C5—C6'—H6AB	109.9
H1A—C1—H1B	109.5	H6AA—C6'—H6AB	108.3
C2—C1—H1C	109.5	C3'—C7'—C6'	111.2 (13)
H1A—C1—H1C	109.5	C3'—C7'—C8	108.3 (13)
H1B—C1—H1C	109.5	C6'—C7'—C8	108.0 (7)
N1—C2—N2	123.07 (13)	C3'—C7'—H7AA	109.8
N1—C2—C1	119.13 (13)	C6'—C7'—H7AA	109.8
N2—C2—C1	117.80 (13)	C8—C7'—H7AA	109.8
N4—C4—N2	116.33 (12)	C12—C8—C7'	108.5 (2)
N4—C4—C10	130.93 (12)	C12—C8—C7	111.03 (14)
N2—C4—C10	112.74 (11)	C12—C8—H8A	109.5
C11—C5—C6'	108.9 (3)	C7'—C8—H8A	82.4
C11—C5—C6	112.04 (14)	C7—C8—H8A	109.6
C11—C5—H5A	109.1	C12—C8—H8B	109.5
C6'—C5—H5A	82.6	C7'—C8—H8B	133.9
C6—C5—H5A	109.5	C7—C8—H8B	109.2
C11—C5—H5B	109.2	H8A—C8—H8B	108.1
C6'—C5—H5B	133.9	N1—C9—C10	127.20 (13)
C6—C5—H5B	109.0	N1—C9—S1	120.97 (10)
H5A—C5—H5B	108.0	C10—C9—S1	111.83 (10)
C7—C6—C5	112.0 (3)	C9—C10—C11	112.38 (12)
C7—C6—H6A	109.2	C9—C10—C4	117.49 (12)
C5—C6—H6A	109.2	C11—C10—C4	130.08 (12)
C7—C6—H6B	109.2	C12—C11—C10	111.76 (12)
C5—C6—H6B	109.2	C12—C11—C5	120.89 (13)
H6A—C6—H6B	107.9	C10—C11—C5	127.32 (12)
C6—C7—C3	111.4 (5)	C11—C12—C8	125.54 (13)
C6—C7—C8	108.5 (3)	C11—C12—S1	112.85 (11)
C3—C7—C8	110.7 (5)	C8—C12—S1	121.60 (11)
C9—N1—C2—N2	−1.5 (2)	C12—S1—C9—N1	179.87 (12)
C9—N1—C2—C1	178.47 (13)	C12—S1—C9—C10	0.01 (11)
C4—N2—C2—N1	1.5 (2)	N1—C9—C10—C11	−179.52 (13)
N3—N2—C2—N1	−176.67 (13)	S1—C9—C10—C11	0.34 (15)
C4—N2—C2—C1	−178.53 (13)	N1—C9—C10—C4	2.7 (2)
N3—N2—C2—C1	3.3 (2)	S1—C9—C10—C4	−177.40 (10)
C2—N2—C4—N4	−178.75 (14)	N4—C4—C10—C9	176.81 (15)
N3—N2—C4—N4	−0.62 (19)	N2—C4—C10—C9	−2.54 (18)
C2—N2—C4—C10	0.71 (19)	N4—C4—C10—C11	−0.5 (3)
N3—N2—C4—C10	178.83 (12)	N2—C4—C10—C11	−179.81 (13)
C11—C5—C6—C7	45.4 (4)	C9—C10—C11—C12	−0.62 (17)
C6'—C5—C6—C7	−45.0 (5)	C4—C10—C11—C12	176.76 (13)
C5—C6—C7—C3	174.9 (5)	C9—C10—C11—C5	177.34 (13)
C5—C6—C7—C8	−63.1 (4)	C4—C10—C11—C5	−5.3 (2)
C11—C5—C6'—C7'	−55.1 (9)	C6'—C5—C11—C12	18.5 (5)
C6—C5—C6'—C7'	46.4 (7)	C6—C5—C11—C12	−14.3 (3)
C5—C6'—C7'—C3'	−168.6 (14)	C6'—C5—C11—C10	−159.3 (5)
C5—C6'—C7'—C8	72.8 (10)	C6—C5—C11—C10	167.9 (2)
C3'—C7'—C8—C12	−169.0 (12)	C10—C11—C12—C8	−179.79 (13)
C6'—C7'—C8—C12	−48.4 (8)	C5—C11—C12—C8	2.1 (2)
C3'—C7'—C8—C7	−68.8 (13)	C10—C11—C12—S1	0.63 (16)
C6'—C7'—C8—C7	51.8 (7)	C5—C11—C12—S1	−177.49 (11)
C6—C7—C8—C12	48.3 (3)	C7'—C8—C12—C11	13.1 (5)
C3—C7—C8—C12	170.8 (5)	C7—C8—C12—C11	−19.6 (3)
C6—C7—C8—C7'	−42.9 (5)	C7'—C8—C12—S1	−167.3 (4)
C3—C7—C8—C7'	79.6 (7)	C7—C8—C12—S1	159.94 (19)
C2—N1—C9—C10	−0.6 (2)	C9—S1—C12—C11	−0.37 (11)
C2—N1—C9—S1	179.55 (10)	C9—S1—C12—C8	−179.97 (13)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···N4i	0.89	2.40	3.117 (2)	137
C5—H5B···N4ii	0.96	2.67	3.587 (2)	160

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3B⋯N4i	0.89	2.40	3.117 (2)	137
C5—H5B⋯N4ii	0.96	2.67	3.587 (2)	160

Symmetry codes: (i) ; (ii) .