6-(4-Fluoro-pheneth-yl)-7-imino-3-phenyl-2,3,6,7-tetra-hydro-1,3-thia-zolo[4,5-d]pyrimidine-2-thione.

In the title compound, C(19)H(15)FN(4)S(2), the mean plane of the thia-zolopyrimidine makes a dihedral angle of 77.6 (1)° with the attached phenyl ring. The crystal packing is stabilized by inter-molecular C-H⋯N hydrogen bonds and weak C-H-π stacking inter-actions.

Related literature

For the biological activity of thia­zolo[4,5-d]pyrimidine deriv­atives, see: Balkan et al. (2002 ▶); Bekhit et al. (2003 ▶); Danel et al. (1998 ▶); Fahmy et al. (2003 ▶). For the synthesis of thia­zolo [4,5-d]pyrimidines via tandem aza-Wittig and cyclization reactions of imino­phospho­rane and alkyl­amines, see: Liang et al. (2007 ▶). For C—H⋯π inter­actions, see: Janiak (2000 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C19H15FN4S2

M = 382.47

Monoclinic,

a = 8.6449 (13) Å

b = 12.3780 (19) Å

c = 16.546 (3) Å

β = 91.531 (3)°

V = 1769.9 (5) Å3

Z = 4

Mo Kα radiation

μ = 0.32 mm−1

T = 298 K

0.30 × 0.20 × 0.20 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ▶) T min = 0.910, T max = 0.939

13207 measured reflections

4047 independent reflections

3442 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.119

S = 1.05

4047 reflections

238 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.31 e Å−3

Δρmin = −0.24 e Å−3

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809047576/jh2113sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809047576/jh2113Isup2.hkl

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

C19H15FN4S2	F(000) = 792
Mr = 382.47	Dx = 1.435 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.6449 (13) Å	Cell parameters from 5242 reflections
b = 12.3780 (19) Å	θ = 2.5–27.9°
c = 16.546 (3) Å	µ = 0.32 mm−1
β = 91.531 (3)°	T = 298 K
V = 1769.9 (5) Å3	Block, colorless
Z = 4	0.30 × 0.20 × 0.20 mm

Bruker SMART APEX CCD area-detector diffractometer	4047 independent reflections
Radiation source: fine-focus sealed tube	3442 reflections with I > 2σ(I)
graphite	Rint = 0.023
φ and ω scans	θmax = 27.5°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −11→11
Tmin = 0.910, Tmax = 0.939	k = −15→16
13207 measured reflections	l = −20→21

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.063P)2 + 0.3948P] where P = (Fo2 + 2Fc2)/3
4047 reflections	(Δ/σ)max = 0.001
238 parameters	Δρmax = 0.31 e Å−3
0 restraints	Δρmin = −0.24 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	0.4958 (2)	1.34258 (14)	0.58804 (13)	0.0535 (5)
C2	0.4537 (2)	1.33892 (14)	0.50835 (13)	0.0542 (5)
H2	0.4863	1.3917	0.4726	0.065*
C3	0.3607 (2)	1.25414 (15)	0.48189 (11)	0.0502 (4)
H3	0.3306	1.2503	0.4276	0.060*
C4	0.31153 (19)	1.17484 (13)	0.53462 (11)	0.0429 (4)
C5	0.3617 (2)	1.18055 (15)	0.61453 (11)	0.0504 (4)
H5	0.3335	1.1265	0.6503	0.060*
C6	0.4530 (2)	1.26536 (16)	0.64208 (12)	0.0572 (5)
H6	0.4846	1.2697	0.6961	0.069*
C7	0.2083 (2)	1.08369 (14)	0.50454 (11)	0.0482 (4)
H7A	0.1203	1.1133	0.4745	0.058*
H7B	0.1696	1.0439	0.5503	0.058*
C8	0.29661 (19)	1.00780 (14)	0.45073 (12)	0.0467 (4)
H8A	0.3450	1.0496	0.4087	0.056*
H8B	0.3782	0.9732	0.4827	0.056*
C9	0.10871 (19)	0.95138 (14)	0.34270 (10)	0.0422 (4)
C10	0.03504 (19)	0.85689 (13)	0.30865 (10)	0.0411 (4)
C11	0.04789 (18)	0.75959 (13)	0.34560 (9)	0.0379 (3)
C12	0.1989 (2)	0.82329 (14)	0.44484 (11)	0.0458 (4)
H12	0.2567	0.8135	0.4925	0.055*
C13	−0.0990 (2)	0.70793 (14)	0.23294 (10)	0.0445 (4)
C14	−0.02508 (18)	0.56612 (13)	0.33171 (10)	0.0402 (4)
C15	0.0719 (3)	0.49373 (17)	0.29640 (13)	0.0621 (5)
H15	0.1341	0.5146	0.2541	0.075*
C16	0.0753 (3)	0.38912 (19)	0.32496 (16)	0.0780 (7)
H16	0.1398	0.3386	0.3014	0.094*
C17	−0.0147 (3)	0.35897 (17)	0.38718 (18)	0.0776 (8)
H17	−0.0116	0.2881	0.4058	0.093*
C18	−0.1101 (3)	0.4326 (2)	0.42259 (16)	0.0739 (7)
H18	−0.1711	0.4117	0.4653	0.089*
C19	−0.1156 (2)	0.53768 (16)	0.39494 (12)	0.0554 (5)
H19	−0.1796	0.5882	0.4188	0.066*
N1	0.19862 (15)	0.92398 (11)	0.41267 (8)	0.0411 (3)
N2	0.12708 (17)	0.73932 (11)	0.41615 (9)	0.0459 (3)
N3	0.1072 (2)	1.04959 (13)	0.31970 (11)	0.0605 (4)
H3A	0.052 (3)	1.0564 (19)	0.2764 (15)	0.073*
N4	−0.02702 (16)	0.67676 (11)	0.30352 (8)	0.0397 (3)
F1	0.58230 (17)	1.42773 (10)	0.61527 (9)	0.0823 (4)
S1	−0.07386 (6)	0.84673 (4)	0.21932 (3)	0.05356 (16)
S2	−0.19713 (7)	0.63041 (4)	0.16868 (3)	0.06299 (18)

	U11	U22	U33	U12	U13	U23
C1	0.0557 (10)	0.0390 (9)	0.0653 (12)	−0.0015 (7)	−0.0051 (9)	−0.0124 (8)
C2	0.0649 (11)	0.0400 (9)	0.0579 (12)	−0.0030 (8)	0.0053 (9)	0.0022 (8)
C3	0.0616 (11)	0.0468 (10)	0.0418 (9)	0.0013 (8)	−0.0036 (8)	−0.0013 (7)
C4	0.0455 (9)	0.0374 (8)	0.0457 (9)	0.0022 (7)	0.0017 (7)	−0.0069 (7)
C5	0.0657 (11)	0.0424 (9)	0.0431 (10)	0.0013 (8)	0.0027 (8)	−0.0003 (7)
C6	0.0738 (13)	0.0516 (11)	0.0456 (10)	0.0017 (9)	−0.0113 (9)	−0.0088 (8)
C7	0.0463 (9)	0.0461 (9)	0.0523 (10)	−0.0049 (7)	0.0040 (8)	−0.0077 (8)
C8	0.0384 (8)	0.0437 (9)	0.0576 (11)	−0.0028 (7)	−0.0038 (7)	−0.0108 (8)
C9	0.0456 (9)	0.0420 (9)	0.0391 (8)	−0.0044 (7)	0.0005 (7)	0.0010 (7)
C10	0.0478 (9)	0.0415 (8)	0.0337 (8)	−0.0036 (7)	−0.0048 (7)	0.0028 (6)
C11	0.0403 (8)	0.0388 (8)	0.0344 (8)	−0.0022 (6)	−0.0019 (6)	−0.0006 (6)
C12	0.0493 (9)	0.0426 (9)	0.0448 (10)	0.0028 (7)	−0.0131 (7)	−0.0014 (7)
C13	0.0541 (10)	0.0429 (9)	0.0361 (8)	−0.0027 (7)	−0.0056 (7)	0.0005 (7)
C14	0.0455 (8)	0.0356 (8)	0.0390 (8)	−0.0024 (6)	−0.0096 (7)	−0.0015 (6)
C15	0.0763 (14)	0.0584 (12)	0.0516 (11)	0.0159 (10)	0.0021 (10)	−0.0024 (9)
C16	0.1057 (19)	0.0501 (12)	0.0772 (16)	0.0275 (12)	−0.0187 (14)	−0.0099 (11)
C17	0.0875 (16)	0.0422 (11)	0.101 (2)	−0.0070 (11)	−0.0404 (15)	0.0170 (11)
C18	0.0622 (12)	0.0699 (15)	0.0891 (17)	−0.0130 (11)	−0.0077 (11)	0.0346 (13)
C19	0.0493 (10)	0.0549 (11)	0.0621 (12)	0.0020 (8)	0.0031 (8)	0.0128 (9)
N1	0.0389 (7)	0.0388 (7)	0.0453 (8)	−0.0018 (5)	−0.0053 (6)	−0.0052 (6)
N2	0.0560 (8)	0.0401 (7)	0.0409 (8)	−0.0006 (6)	−0.0147 (6)	0.0024 (6)
N3	0.0840 (12)	0.0420 (8)	0.0547 (10)	−0.0113 (8)	−0.0114 (9)	0.0082 (7)
N4	0.0479 (7)	0.0373 (7)	0.0335 (7)	−0.0034 (5)	−0.0060 (5)	0.0010 (5)
F1	0.0964 (10)	0.0541 (7)	0.0954 (10)	−0.0209 (7)	−0.0147 (8)	−0.0206 (7)
S1	0.0767 (3)	0.0453 (3)	0.0377 (3)	−0.0082 (2)	−0.0170 (2)	0.00820 (18)
S2	0.0860 (4)	0.0531 (3)	0.0483 (3)	−0.0078 (2)	−0.0276 (3)	−0.0050 (2)

C1—C2	1.359 (3)	C10—S1	1.7356 (16)
C1—F1	1.362 (2)	C11—N2	1.361 (2)
C1—C6	1.367 (3)	C11—N4	1.390 (2)
C2—C3	1.386 (3)	C12—N2	1.294 (2)
C2—H2	0.9300	C12—N1	1.355 (2)
C3—C4	1.387 (3)	C12—H12	0.9300
C3—H3	0.9300	C13—N4	1.364 (2)
C4—C5	1.382 (2)	C13—S2	1.6501 (17)
C4—C7	1.515 (2)	C13—S1	1.7472 (18)
C5—C6	1.384 (3)	C14—C15	1.369 (3)
C5—H5	0.9300	C14—C19	1.369 (3)
C6—H6	0.9300	C14—N4	1.447 (2)
C7—C8	1.515 (2)	C15—C16	1.378 (3)
C7—H7A	0.9700	C15—H15	0.9300
C7—H7B	0.9700	C16—C17	1.359 (4)
C8—N1	1.470 (2)	C16—H16	0.9300
C8—H8A	0.9700	C17—C18	1.371 (4)
C8—H8B	0.9700	C17—H17	0.9300
C9—N3	1.274 (2)	C18—C19	1.379 (3)
C9—N1	1.418 (2)	C18—H18	0.9300
C9—C10	1.439 (2)	C19—H19	0.9300
C10—C11	1.354 (2)	N3—H3A	0.86 (2)
C2—C1—F1	118.50 (18)	C10—C11—N2	125.78 (15)
C2—C1—C6	122.77 (17)	C10—C11—N4	113.49 (14)
F1—C1—C6	118.72 (18)	N2—C11—N4	120.72 (14)
C1—C2—C3	118.01 (18)	N2—C12—N1	126.76 (15)
C1—C2—H2	121.0	N2—C12—H12	116.6
C3—C2—H2	121.0	N1—C12—H12	116.6
C2—C3—C4	121.47 (17)	N4—C13—S2	127.02 (13)
C2—C3—H3	119.3	N4—C13—S1	109.46 (12)
C4—C3—H3	119.3	S2—C13—S1	123.52 (10)
C5—C4—C3	118.15 (16)	C15—C14—C19	121.81 (18)
C5—C4—C7	121.30 (16)	C15—C14—N4	118.95 (17)
C3—C4—C7	120.54 (16)	C19—C14—N4	119.19 (15)
C4—C5—C6	121.04 (18)	C14—C15—C16	118.4 (2)
C4—C5—H5	119.5	C14—C15—H15	120.8
C6—C5—H5	119.5	C16—C15—H15	120.8
C1—C6—C5	118.50 (18)	C17—C16—C15	120.7 (2)
C1—C6—H6	120.7	C17—C16—H16	119.7
C5—C6—H6	120.7	C15—C16—H16	119.7
C4—C7—C8	110.67 (14)	C16—C17—C18	120.3 (2)
C4—C7—H7A	109.5	C16—C17—H17	119.9
C8—C7—H7A	109.5	C18—C17—H17	119.9
C4—C7—H7B	109.5	C17—C18—C19	120.1 (2)
C8—C7—H7B	109.5	C17—C18—H18	120.0
H7A—C7—H7B	108.1	C19—C18—H18	120.0
N1—C8—C7	113.30 (14)	C14—C19—C18	118.7 (2)
N1—C8—H8A	108.9	C14—C19—H19	120.6
C7—C8—H8A	108.9	C18—C19—H19	120.6
N1—C8—H8B	108.9	C12—N1—C9	122.40 (13)
C7—C8—H8B	108.9	C12—N1—C8	119.05 (14)
H8A—C8—H8B	107.7	C9—N1—C8	118.54 (14)
N3—C9—N1	118.24 (15)	C12—N2—C11	113.08 (14)
N3—C9—C10	131.12 (16)	C9—N3—H3A	110.2 (16)
N1—C9—C10	110.63 (14)	C13—N4—C11	114.58 (13)
C11—C10—C9	121.06 (15)	C13—N4—C14	123.01 (13)
C11—C10—S1	110.87 (12)	C11—N4—C14	122.39 (12)
C9—C10—S1	128.06 (12)	C10—S1—C13	91.60 (8)
F1—C1—C2—C3	−177.55 (17)	C17—C18—C19—C14	0.3 (3)
C6—C1—C2—C3	1.4 (3)	N2—C12—N1—C9	3.5 (3)
C1—C2—C3—C4	−0.1 (3)	N2—C12—N1—C8	−175.59 (17)
C2—C3—C4—C5	−1.9 (3)	N3—C9—N1—C12	175.35 (18)
C2—C3—C4—C7	179.23 (16)	C10—C9—N1—C12	−5.8 (2)
C3—C4—C5—C6	2.7 (3)	N3—C9—N1—C8	−5.6 (2)
C7—C4—C5—C6	−178.48 (17)	C10—C9—N1—C8	173.26 (14)
C2—C1—C6—C5	−0.7 (3)	C7—C8—N1—C12	−100.26 (19)
F1—C1—C6—C5	178.28 (18)	C7—C8—N1—C9	80.6 (2)
C4—C5—C6—C1	−1.4 (3)	N1—C12—N2—C11	1.3 (3)
C5—C4—C7—C8	−109.01 (19)	C10—C11—N2—C12	−3.2 (3)
C3—C4—C7—C8	69.8 (2)	N4—C11—N2—C12	175.53 (15)
C4—C7—C8—N1	−173.93 (15)	S2—C13—N4—C11	179.73 (13)
N3—C9—C10—C11	−177.3 (2)	S1—C13—N4—C11	−0.73 (19)
N1—C9—C10—C11	4.0 (2)	S2—C13—N4—C14	1.2 (3)
N3—C9—C10—S1	4.0 (3)	S1—C13—N4—C14	−179.28 (13)
N1—C9—C10—S1	−174.59 (13)	C10—C11—N4—C13	0.2 (2)
C9—C10—C11—N2	0.3 (3)	N2—C11—N4—C13	−178.63 (15)
S1—C10—C11—N2	179.18 (14)	C10—C11—N4—C14	178.81 (15)
C9—C10—C11—N4	−178.47 (15)	N2—C11—N4—C14	−0.1 (2)
S1—C10—C11—N4	0.37 (19)	C15—C14—N4—C13	76.3 (2)
C19—C14—C15—C16	1.2 (3)	C19—C14—N4—C13	−106.2 (2)
N4—C14—C15—C16	178.58 (18)	C15—C14—N4—C11	−102.1 (2)
C14—C15—C16—C17	−0.5 (4)	C19—C14—N4—C11	75.4 (2)
C15—C16—C17—C18	−0.2 (4)	C11—C10—S1—C13	−0.66 (14)
C16—C17—C18—C19	0.3 (4)	C9—C10—S1—C13	178.08 (17)
C15—C14—C19—C18	−1.1 (3)	N4—C13—S1—C10	0.78 (14)
N4—C14—C19—C18	−178.46 (17)	S2—C13—S1—C10	−179.66 (13)

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15···N3i	0.93	2.61	3.486 (3)	156
C19—H19···Cg3ii	0.93	2.74	3.637 (2)	161

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C15—H15⋯N3i	0.93	2.61	3.486 (3)	156
C19—H19⋯Cg3ii	0.93	2.74	3.637 (2)	161

Symmetry codes: (i) ; (ii) . Cg3 is the centroid of the C1–C6 ring.