1-(3-Fluoro-phen-yl)-4,4,6-trimethyl-3,4-dihydro-pyrimidine-2(1H)-thione.

In the title compound, C(13)H(15)FN(2)S, the dihydro-pyrimidine ring is essentially planar, with a maximum deviation of 0.086 (3) Å from the mean plane of the rest of the ring for the dimethyl-ated C atom. The benzene ring is almost perpendicular to the dihydro-pyrimidine ring, with a dihedral angle of 83.97 (14)°. The crystal packing is characterized by centrosymmetric dimers resulting from pairs of inter-molecular N-H⋯S hydrogen bonds. There are also C-H⋯π inter-actions.

Related literature

For the biological properties of related compounds, see: Rovnyak et al. (1995 ▶); Kappe (2000 ▶); Alam et al. (2005 ▶); Sriram et al. (2006 ▶); Leite et al. (2006 ▶). For related structures, see: Yamin et al. (2005 ▶); Ismail et al. (2007 ▶); Saeed et al. (2010 ▶); Yamin & Salem (2011 ▶). For standard bond lengths, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C13H15FN2S

M = 250.33

Monoclinic,

a = 8.814 (3) Å

b = 14.997 (5) Å

c = 10.215 (3) Å

β = 95.711 (6)°

V = 1343.6 (7) Å3

Z = 4

Mo Kα radiation

μ = 0.23 mm−1

T = 298 K

0.50 × 0.29 × 0.20 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.892, T max = 0.954

7116 measured reflections

2497 independent reflections

1764 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.059

wR(F 2) = 0.153

S = 1.06

2497 reflections

157 parameters

H-atom parameters constrained

Δρmax = 0.37 e Å−3

Δρmin = −0.17 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, PARST (Nardelli, 1995 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811023671/ld2016sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811023671/ld2016Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811023671/ld2016Isup3.cml

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

C13H15FN2S	F(000) = 528
Mr = 250.33	Dx = 1.238 Mg m−3
Monoclinic, P21/c	Melting point = 458.9–456.8 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 8.814 (3) Å	Cell parameters from 2497 reflections
b = 14.997 (5) Å	θ = 2.3–25.5°
c = 10.215 (3) Å	µ = 0.23 mm−1
β = 95.711 (6)°	T = 298 K
V = 1343.6 (7) Å3	Block, colourless
Z = 4	0.50 × 0.29 × 0.20 mm

Bruker SMART APEX CCD area-detector diffractometer	2497 independent reflections
Radiation source: fine-focus sealed tube	1764 reflections with I > 2σ(I)
graphite	Rint = 0.034
ω scans	θmax = 25.5°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −10→10
Tmin = 0.892, Tmax = 0.954	k = −16→18
7116 measured reflections	l = −12→11

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.153	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0666P)2 + 0.4935P] where P = (Fo2 + 2Fc2)/3
2497 reflections	(Δ/σ)max = 0.001
157 parameters	Δρmax = 0.37 e Å−3
0 restraints	Δρmin = −0.17 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
F1	0.9699 (2)	0.40143 (14)	0.6648 (2)	0.0938 (7)
S1	0.65807 (8)	0.11011 (5)	0.47356 (8)	0.0623 (3)
N1	0.3831 (3)	0.11471 (16)	0.5539 (2)	0.0620 (7)
H1A	0.3939	0.0577	0.5561	0.074*
N2	0.4991 (2)	0.25140 (15)	0.5427 (2)	0.0519 (6)
C1	0.5038 (3)	0.1608 (2)	0.5251 (3)	0.0506 (7)
C2	0.3725 (3)	0.2932 (2)	0.5938 (3)	0.0601 (8)
C3	0.2523 (4)	0.2442 (2)	0.6138 (4)	0.0780 (10)
H3A	0.1727	0.2723	0.6507	0.094*
C4	0.2343 (3)	0.1480 (2)	0.5824 (3)	0.0644 (8)
C5	0.3852 (4)	0.3902 (2)	0.6208 (4)	0.0895 (12)
H5A	0.2904	0.4120	0.6471	0.134*
H5B	0.4085	0.4209	0.5428	0.134*
H5C	0.4650	0.4006	0.6902	0.134*
C6	0.1856 (5)	0.0964 (3)	0.6999 (5)	0.1206 (18)
H6A	0.2611	0.1035	0.7736	0.181*
H6B	0.1757	0.0343	0.6777	0.181*
H6C	0.0895	0.1188	0.7222	0.181*
C7	0.1209 (5)	0.1335 (3)	0.4636 (5)	0.1154 (16)
H7A	0.1512	0.1673	0.3908	0.173*
H7B	0.0217	0.1525	0.4832	0.173*
H7C	0.1177	0.0713	0.4412	0.173*
C8	0.6272 (3)	0.30394 (18)	0.5099 (3)	0.0493 (7)
C9	0.6358 (4)	0.3306 (2)	0.3822 (3)	0.0653 (8)
H9A	0.5581	0.3160	0.3174	0.078*
C10	0.7597 (5)	0.3789 (2)	0.3506 (4)	0.0802 (11)
H10A	0.7663	0.3960	0.2638	0.096*
C11	0.8726 (4)	0.4018 (2)	0.4449 (4)	0.0747 (10)
H11A	0.9569	0.4341	0.4238	0.090*
C12	0.8593 (3)	0.3763 (2)	0.5706 (3)	0.0606 (8)
C13	0.7392 (3)	0.32727 (19)	0.6068 (3)	0.0538 (7)
H13A	0.7338	0.3104	0.6938	0.065*

	U11	U22	U33	U12	U13	U23
F1	0.0710 (13)	0.0981 (17)	0.1111 (16)	−0.0189 (11)	0.0028 (12)	−0.0109 (12)
S1	0.0536 (4)	0.0493 (5)	0.0878 (6)	−0.0031 (3)	0.0263 (4)	−0.0071 (4)
N1	0.0512 (14)	0.0491 (15)	0.0893 (18)	−0.0086 (11)	0.0249 (13)	−0.0059 (13)
N2	0.0487 (12)	0.0461 (14)	0.0630 (14)	−0.0021 (11)	0.0151 (11)	−0.0044 (11)
C1	0.0491 (15)	0.0509 (18)	0.0527 (16)	−0.0045 (13)	0.0093 (13)	−0.0007 (13)
C2	0.0531 (17)	0.0572 (19)	0.0717 (19)	0.0065 (14)	0.0151 (15)	−0.0071 (16)
C3	0.0562 (18)	0.072 (2)	0.110 (3)	0.0044 (17)	0.0322 (19)	−0.011 (2)
C4	0.0487 (16)	0.066 (2)	0.082 (2)	−0.0057 (15)	0.0223 (16)	−0.0062 (17)
C5	0.073 (2)	0.063 (2)	0.137 (3)	0.0071 (17)	0.032 (2)	−0.021 (2)
C6	0.125 (4)	0.109 (4)	0.142 (4)	0.007 (3)	0.086 (3)	0.021 (3)
C7	0.071 (3)	0.134 (4)	0.137 (4)	−0.004 (2)	−0.010 (3)	−0.038 (3)
C8	0.0523 (16)	0.0392 (16)	0.0582 (17)	−0.0004 (12)	0.0142 (14)	−0.0044 (13)
C9	0.079 (2)	0.060 (2)	0.0577 (18)	−0.0084 (17)	0.0093 (16)	−0.0043 (15)
C10	0.116 (3)	0.059 (2)	0.071 (2)	−0.019 (2)	0.034 (2)	0.0013 (17)
C11	0.090 (2)	0.053 (2)	0.088 (3)	−0.0223 (17)	0.042 (2)	−0.0133 (18)
C12	0.0552 (17)	0.0483 (18)	0.079 (2)	−0.0063 (14)	0.0102 (16)	−0.0146 (15)
C13	0.0556 (16)	0.0470 (17)	0.0605 (17)	−0.0005 (13)	0.0138 (14)	0.0029 (14)

F1—C12	1.353 (3)	C6—H6A	0.9600
S1—C1	1.687 (3)	C6—H6B	0.9600
N1—C1	1.326 (3)	C6—H6C	0.9600
N1—C4	1.460 (4)	C7—H7A	0.9600
N1—H1A	0.8600	C7—H7B	0.9600
N2—C1	1.372 (4)	C7—H7C	0.9600
N2—C2	1.423 (3)	C8—C13	1.372 (4)
N2—C8	1.443 (3)	C8—C9	1.374 (4)
C2—C3	1.321 (4)	C9—C10	1.376 (5)
C2—C5	1.483 (4)	C9—H9A	0.9300
C3—C4	1.483 (5)	C10—C11	1.359 (5)
C3—H3A	0.9300	C10—H10A	0.9300
C4—C7	1.509 (5)	C11—C12	1.356 (5)
C4—C6	1.526 (5)	C11—H11A	0.9300
C5—H5A	0.9600	C12—C13	1.369 (4)
C5—H5B	0.9600	C13—H13A	0.9300
C5—H5C	0.9600
C1—N1—C4	128.5 (3)	H6A—C6—H6B	109.5
C1—N1—H1A	115.7	C4—C6—H6C	109.5
C4—N1—H1A	115.7	H6A—C6—H6C	109.5
C1—N2—C2	121.3 (2)	H6B—C6—H6C	109.5
C1—N2—C8	118.4 (2)	C4—C7—H7A	109.5
C2—N2—C8	120.3 (2)	C4—C7—H7B	109.5
N1—C1—N2	116.8 (2)	H7A—C7—H7B	109.5
N1—C1—S1	121.6 (2)	C4—C7—H7C	109.5
N2—C1—S1	121.5 (2)	H7A—C7—H7C	109.5
C3—C2—N2	118.8 (3)	H7B—C7—H7C	109.5
C3—C2—C5	124.3 (3)	C13—C8—C9	120.5 (3)
N2—C2—C5	116.9 (3)	C13—C8—N2	119.7 (2)
C2—C3—C4	125.3 (3)	C9—C8—N2	119.8 (3)
C2—C3—H3A	117.4	C8—C9—C10	119.8 (3)
C4—C3—H3A	117.4	C8—C9—H9A	120.1
N1—C4—C3	107.3 (2)	C10—C9—H9A	120.1
N1—C4—C7	109.1 (3)	C11—C10—C9	120.6 (3)
C3—C4—C7	111.3 (3)	C11—C10—H10A	119.7
N1—C4—C6	108.1 (3)	C9—C10—H10A	119.7
C3—C4—C6	110.9 (3)	C12—C11—C10	118.3 (3)
C7—C4—C6	110.1 (3)	C12—C11—H11A	120.9
C2—C5—H5A	109.5	C10—C11—H11A	120.9
C2—C5—H5B	109.5	F1—C12—C11	118.0 (3)
H5A—C5—H5B	109.5	F1—C12—C13	118.7 (3)
C2—C5—H5C	109.5	C11—C12—C13	123.3 (3)
H5A—C5—H5C	109.5	C12—C13—C8	117.5 (3)
H5B—C5—H5C	109.5	C12—C13—H13A	121.2
C4—C6—H6A	109.5	C8—C13—H13A	121.2
C4—C6—H6B	109.5
C4—N1—C1—N2	10.7 (4)	C2—C3—C4—C7	−107.0 (4)
C4—N1—C1—S1	−171.0 (2)	C2—C3—C4—C6	130.1 (4)
C2—N2—C1—N1	2.1 (4)	C1—N2—C8—C13	−96.2 (3)
C8—N2—C1—N1	−178.8 (2)	C2—N2—C8—C13	82.9 (3)
C2—N2—C1—S1	−176.1 (2)	C1—N2—C8—C9	84.1 (3)
C8—N2—C1—S1	2.9 (3)	C2—N2—C8—C9	−96.8 (3)
C1—N2—C2—C3	−5.8 (4)	C13—C8—C9—C10	1.8 (5)
C8—N2—C2—C3	175.2 (3)	N2—C8—C9—C10	−178.5 (3)
C1—N2—C2—C5	174.3 (3)	C8—C9—C10—C11	−1.1 (5)
C8—N2—C2—C5	−4.7 (4)	C9—C10—C11—C12	−0.4 (5)
N2—C2—C3—C4	−2.6 (5)	C10—C11—C12—F1	−178.1 (3)
C5—C2—C3—C4	177.3 (4)	C10—C11—C12—C13	1.2 (5)
C1—N1—C4—C3	−16.9 (4)	F1—C12—C13—C8	178.9 (2)
C1—N1—C4—C7	103.7 (4)	C11—C12—C13—C8	−0.5 (5)
C1—N1—C4—C6	−136.5 (3)	C9—C8—C13—C12	−1.0 (4)
C2—C3—C4—N1	12.2 (5)	N2—C8—C13—C12	179.3 (2)

Cg1 is the centroid of the N1/N2/C1–C4 pyrimidine ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···S1i	0.86	2.57	3.400 (3)	162
C9—H9A···Cg1ii	0.93	2.89	3.788 (4)	163

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the N1/N2/C1–C4 pyrimidine ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯S1i	0.86	2.57	3.400 (3)	162
C9—H9A⋯Cg1ii	0.93	2.89	3.788 (4)	163

Symmetry codes: (i) ; (ii) .