3-Phenyl-2-(pyrrolidin-1-yl)-5,6-dihydro-8H-thio-pyrano[4',3':4,5]thieno[2,3-d]pyrimidin-4(3H)-one.

In the title compound, C(19)H(19)N(3)OS(2), the thio-pyran ring adopts a twist-chair conformation and the pyrimidinone unit is essentially planar, with a mean deviation of 0.0497 Å. The thio-phene ring is essentially planar with a maximum deviation of 0.024 (2) Å, while the pyrrolidine ring exhibits an envelope conformation. The pyrimidinone and thio-phene rings are almost coplanar, forming a dihedral angle of 6.31 (15)°, while the dihedral angle between the mean planes of the phenyl ring and the pyrimidinone ring is 68.13 (10)°. In the crystal structure, adjacent mol-ecules are linked by C-H⋯O hydrogen bonds, forming a two-dimensional network in the ac plane.

Related literature

For the applications of pyrimidine derivatives as pesticides and pharmaceutical agents, see: Condon et al. (1993 ▶) and as anti­viral agents, see; Gilchrist (1997 ▶). For a related structure, see: Xie et al. (2008 ▶).

Experimental

Crystal data

C19H19N3OS2

M = 369.49

Triclinic,

a = 8.1484 (8) Å

b = 9.3455 (9) Å

c = 12.1834 (12) Å

α = 73.668 (1)°

β = 88.629 (1)°

γ = 79.568 (1)°

V = 875.26 (15) Å3

Z = 2

Mo Kα radiation

μ = 0.32 mm−1

T = 298 K

0.30 × 0.23 × 0.18 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2000 ▶) T min = 0.911, T max = 0.945

4828 measured reflections

3349 independent reflections

2709 reflections with I > 2σ(I)

R int = 0.016

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.119

S = 1.06

3349 reflections

226 parameters

H-atom parameters constrained

Δρmax = 0.50 e Å−3

Δρmin = −0.44 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/PC (Sheldrick, 2008 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810032794/pv2315sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810032794/pv2315Isup2.hkl

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

C19H19N3OS2	Z = 2
Mr = 369.49	F(000) = 388
Triclinic, P1	Dx = 1.402 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.1484 (8) Å	Cell parameters from 2113 reflections
b = 9.3455 (9) Å	θ = 0.9–0.8°
c = 12.1834 (12) Å	µ = 0.32 mm−1
α = 73.668 (1)°	T = 298 K
β = 88.629 (1)°	Block, yellow
γ = 79.568 (1)°	0.30 × 0.23 × 0.18 mm
V = 875.26 (15) Å3

Bruker SMART CCD area-detector diffractometer	3349 independent reflections
Radiation source: fine-focus sealed tube	2709 reflections with I > 2σ(I)
graphite	Rint = 0.016
ω scans	θmax = 26.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	h = −10→7
Tmin = 0.911, Tmax = 0.945	k = −11→11
4828 measured reflections	l = −15→14

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.119	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0534P)2 + 0.3774P] where P = (Fo2 + 2Fc2)/3
3349 reflections	(Δ/σ)max < 0.001
226 parameters	Δρmax = 0.50 e Å−3
0 restraints	Δρmin = −0.44 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
S1	0.47598 (8)	0.15501 (7)	0.76959 (5)	0.04843 (19)
S2	0.06845 (11)	−0.09908 (9)	0.87874 (6)	0.0725 (3)
N1	0.5900 (2)	0.2755 (2)	0.55975 (14)	0.0395 (4)
N3	0.4362 (2)	0.27799 (19)	0.39525 (13)	0.0364 (4)
N2	0.6791 (2)	0.3883 (2)	0.38313 (14)	0.0370 (4)
O1	0.2152 (2)	0.1535 (2)	0.40870 (14)	0.0604 (5)
C7	0.3484 (3)	0.1486 (2)	0.58029 (17)	0.0374 (5)
C5	0.4765 (3)	0.1994 (2)	0.62133 (17)	0.0383 (5)
C13	0.8080 (3)	0.4343 (3)	0.44164 (18)	0.0409 (5)
H13A	0.8767	0.3469	0.4935	0.049*
H13B	0.7579	0.5036	0.4844	0.049*
C9	0.5685 (3)	0.3119 (2)	0.44757 (16)	0.0346 (4)
C10	0.7206 (3)	0.4014 (3)	0.26241 (17)	0.0419 (5)
H10A	0.6474	0.4861	0.2112	0.050*
H10B	0.7122	0.3092	0.2429	0.050*
C14	0.3260 (3)	0.5119 (2)	0.24945 (17)	0.0400 (5)
H14	0.3266	0.5642	0.3041	0.048*
C15	0.3794 (3)	0.2783 (3)	0.1980 (2)	0.0505 (6)
H15	0.4169	0.1740	0.2178	0.061*
C6	0.2442 (3)	0.0770 (2)	0.66839 (18)	0.0407 (5)
C8	0.3242 (3)	0.1861 (2)	0.45921 (18)	0.0404 (5)
C3	0.0878 (3)	0.0243 (3)	0.6458 (2)	0.0483 (6)
H3A	0.1178	−0.0747	0.6326	0.058*
H3B	0.0316	0.0940	0.5769	0.058*
C4	0.2990 (3)	0.0722 (3)	0.77344 (19)	0.0460 (5)
C11	0.8993 (3)	0.4273 (3)	0.25634 (19)	0.0491 (6)
H11A	0.9223	0.4878	0.1807	0.059*
H11B	0.9775	0.3318	0.2752	0.059*
C12	0.9097 (3)	0.5119 (3)	0.34500 (19)	0.0479 (6)
H12A	1.0244	0.5019	0.3700	0.057*
H12B	0.8620	0.6186	0.3150	0.057*
C18	0.2692 (3)	0.5888 (3)	0.13848 (19)	0.0523 (6)
H18	0.2326	0.6933	0.1183	0.063*
C1	−0.0312 (3)	0.0142 (3)	0.7442 (2)	0.0656 (7)
H1A	−0.1244	−0.0294	0.7287	0.079*
H1B	−0.0750	0.1156	0.7496	0.079*
C17	0.2670 (4)	0.5117 (4)	0.0587 (2)	0.0652 (8)
H17	0.2289	0.5640	−0.0157	0.078*
C2	0.2226 (4)	0.0138 (3)	0.8875 (2)	0.0639 (7)
H2A	0.1707	0.0990	0.9146	0.077*
H2B	0.3099	−0.0470	0.9425	0.077*
C16	0.3206 (4)	0.3571 (4)	0.0874 (2)	0.0660 (8)
H16	0.3174	0.3053	0.0328	0.079*
C19	0.3813 (2)	0.3578 (2)	0.27804 (16)	0.0362 (5)

	U11	U22	U33	U12	U13	U23
S1	0.0565 (4)	0.0596 (4)	0.0322 (3)	−0.0235 (3)	0.0016 (2)	−0.0098 (2)
S2	0.0983 (6)	0.0831 (5)	0.0519 (4)	−0.0533 (5)	0.0301 (4)	−0.0233 (4)
N1	0.0401 (10)	0.0474 (10)	0.0320 (9)	−0.0142 (8)	−0.0005 (7)	−0.0089 (8)
N3	0.0368 (9)	0.0427 (9)	0.0302 (8)	−0.0127 (8)	−0.0029 (7)	−0.0073 (7)
N2	0.0354 (9)	0.0487 (10)	0.0308 (8)	−0.0153 (8)	0.0017 (7)	−0.0128 (7)
O1	0.0633 (11)	0.0780 (12)	0.0444 (9)	−0.0425 (10)	−0.0097 (8)	−0.0050 (8)
C7	0.0400 (11)	0.0339 (10)	0.0361 (11)	−0.0085 (9)	−0.0015 (9)	−0.0053 (8)
C5	0.0420 (11)	0.0402 (11)	0.0322 (10)	−0.0102 (9)	0.0008 (9)	−0.0078 (9)
C13	0.0378 (11)	0.0512 (13)	0.0377 (11)	−0.0149 (10)	−0.0038 (9)	−0.0143 (10)
C9	0.0350 (10)	0.0375 (10)	0.0321 (10)	−0.0082 (9)	−0.0006 (8)	−0.0102 (8)
C10	0.0371 (11)	0.0597 (14)	0.0324 (11)	−0.0131 (10)	0.0027 (9)	−0.0158 (10)
C14	0.0365 (11)	0.0520 (13)	0.0324 (10)	−0.0137 (10)	0.0018 (8)	−0.0100 (9)
C15	0.0524 (14)	0.0603 (15)	0.0471 (13)	−0.0160 (12)	0.0031 (11)	−0.0249 (11)
C6	0.0433 (12)	0.0350 (11)	0.0416 (12)	−0.0100 (9)	0.0012 (9)	−0.0055 (9)
C8	0.0412 (12)	0.0398 (11)	0.0405 (11)	−0.0130 (10)	−0.0034 (9)	−0.0080 (9)
C3	0.0481 (13)	0.0464 (13)	0.0484 (13)	−0.0182 (11)	0.0020 (10)	−0.0042 (10)
C4	0.0514 (13)	0.0464 (12)	0.0414 (12)	−0.0172 (11)	0.0070 (10)	−0.0097 (10)
C11	0.0388 (12)	0.0715 (16)	0.0441 (12)	−0.0180 (11)	0.0081 (10)	−0.0235 (12)
C12	0.0403 (12)	0.0599 (14)	0.0498 (13)	−0.0198 (11)	0.0049 (10)	−0.0189 (11)
C18	0.0510 (14)	0.0613 (15)	0.0376 (12)	−0.0139 (12)	−0.0022 (10)	−0.0002 (11)
C1	0.0525 (15)	0.0728 (18)	0.083 (2)	−0.0252 (14)	0.0168 (14)	−0.0334 (16)
C17	0.0686 (18)	0.095 (2)	0.0297 (12)	−0.0255 (16)	−0.0049 (11)	−0.0070 (13)
C2	0.0761 (19)	0.0790 (18)	0.0458 (14)	−0.0381 (16)	0.0188 (13)	−0.0187 (13)
C16	0.0736 (19)	0.099 (2)	0.0394 (13)	−0.0287 (17)	0.0014 (12)	−0.0347 (14)
C19	0.0317 (10)	0.0490 (12)	0.0298 (10)	−0.0128 (9)	−0.0002 (8)	−0.0107 (9)

S1—C5	1.736 (2)	C14—H14	0.9300
S1—C4	1.750 (2)	C15—C19	1.385 (3)
S2—C1	1.801 (3)	C15—C16	1.390 (4)
S2—C2	1.803 (3)	C15—H15	0.9300
N1—C9	1.320 (3)	C6—C4	1.352 (3)
N1—C5	1.352 (3)	C6—C3	1.504 (3)
N3—C9	1.392 (3)	C3—C1	1.517 (3)
N3—C8	1.432 (3)	C3—H3A	0.9700
N3—C19	1.451 (2)	C3—H3B	0.9700
N2—C9	1.350 (3)	C4—C2	1.507 (3)
N2—C13	1.473 (2)	C11—C12	1.519 (3)
N2—C10	1.477 (2)	C11—H11A	0.9700
O1—C8	1.220 (3)	C11—H11B	0.9700
C7—C5	1.379 (3)	C12—H12A	0.9700
C7—C8	1.427 (3)	C12—H12B	0.9700
C7—C6	1.442 (3)	C18—C17	1.366 (4)
C13—C12	1.513 (3)	C18—H18	0.9300
C13—H13A	0.9700	C1—H1A	0.9700
C13—H13B	0.9700	C1—H1B	0.9700
C10—C11	1.516 (3)	C17—C16	1.377 (4)
C10—H10A	0.9700	C17—H17	0.9300
C10—H10B	0.9700	C2—H2A	0.9700
C14—C19	1.375 (3)	C2—H2B	0.9700
C14—C18	1.386 (3)	C16—H16	0.9300
C5—S1—C4	91.1 (1)	C1—C3—H3A	109.1
C1—S2—C2	98.8 (1)	C6—C3—H3B	109.1
C9—N1—C5	115.5 (2)	C1—C3—H3B	109.1
C9—N3—C8	122.0 (2)	H3A—C3—H3B	107.9
C9—N3—C19	122.1 (2)	C6—C4—C2	128.5 (2)
C8—N3—C19	114.7 (2)	C6—C4—S1	113.0 (2)
C9—N2—C13	118.4 (2)	C2—C4—S1	118.5 (2)
C9—N2—C10	128.8 (2)	C10—C11—C12	103.6 (2)
C13—N2—C10	110.9 (2)	C10—C11—H11A	111.0
C5—C7—C8	117.7 (2)	C12—C11—H11A	111.0
C5—C7—C6	113.8 (2)	C10—C11—H11B	111.0
C8—C7—C6	128.2 (2)	C12—C11—H11B	111.0
N1—C5—C7	127.4 (2)	H11A—C11—H11B	109.0
N1—C5—S1	121.8 (2)	C13—C12—C11	103.2 (2)
C7—C5—S1	110.8 (2)	C13—C12—H12A	111.1
N2—C13—C12	103.8 (2)	C11—C12—H12A	111.1
N2—C13—H13A	111.0	C13—C12—H12B	111.1
C12—C13—H13A	111.0	C11—C12—H12B	111.1
N2—C13—H13B	111.0	H12A—C12—H12B	109.1
C12—C13—H13B	111.0	C17—C18—C14	120.2 (2)
H13A—C13—H13B	109.0	C17—C18—H18	119.9
N1—C9—N2	117.2 (2)	C14—C18—H18	119.9
N1—C9—N3	122.8 (2)	C3—C1—S2	112.3 (2)
N2—C9—N3	120.0 (2)	C3—C1—H1A	109.2
N2—C10—C11	103.5 (2)	S2—C1—H1A	109.2
N2—C10—H10A	111.1	C3—C1—H1B	109.2
C11—C10—H10A	111.1	S2—C1—H1B	109.2
N2—C10—H10B	111.1	H1A—C1—H1B	107.9
C11—C10—H10B	111.1	C18—C17—C16	120.5 (2)
H10A—C10—H10B	109.0	C18—C17—H17	119.7
C19—C14—C18	119.4 (2)	C16—C17—H17	119.7
C19—C14—H14	120.3	C4—C2—S2	111.9 (2)
C18—C14—H14	120.3	C4—C2—H2A	109.2
C19—C15—C16	118.8 (2)	S2—C2—H2A	109.2
C19—C15—H15	120.6	C4—C2—H2B	109.2
C16—C15—H15	120.6	S2—C2—H2B	109.2
C4—C6—C7	111.3 (2)	H2A—C2—H2B	107.9
C4—C6—C3	124.3 (2)	C17—C16—C15	120.1 (2)
C7—C6—C3	124.3 (2)	C17—C16—H16	119.9
O1—C8—C7	126.3 (2)	C15—C16—H16	119.9
O1—C8—N3	119.5 (2)	C14—C19—C15	121.0 (2)
C7—C8—N3	114.1 (2)	C14—C19—N3	118.9 (2)
C6—C3—C1	112.4 (2)	C15—C19—N3	120.1 (2)
C6—C3—H3A	109.1
C9—N1—C5—C7	4.1 (3)	C19—N3—C8—O1	16.0 (3)
C9—N1—C5—S1	−175.1 (2)	C9—N3—C8—C7	7.0 (3)
C8—C7—C5—N1	−3.7 (3)	C19—N3—C8—C7	−160.6 (2)
C6—C7—C5—N1	−177.4 (2)	C4—C6—C3—C1	19.0 (3)
C8—C7—C5—S1	175.5 (2)	C7—C6—C3—C1	−156.5 (2)
C6—C7—C5—S1	1.9 (2)	C7—C6—C4—C2	177.0 (2)
C4—S1—C5—N1	178.0 (2)	C3—C6—C4—C2	1.0 (4)
C4—S1—C5—C7	−1.3 (2)	C7—C6—C4—S1	0.6 (3)
C9—N2—C13—C12	178.6 (2)	C3—C6—C4—S1	−175.5 (2)
C10—N2—C13—C12	13.1 (2)	C5—S1—C4—C6	0.4 (2)
C5—N1—C9—N2	179.8 (2)	C5—S1—C4—C2	−176.4 (2)
C5—N1—C9—N3	1.5 (3)	N2—C10—C11—C12	−30.9 (2)
C13—N2—C9—N1	−4.0 (3)	N2—C13—C12—C11	−31.9 (2)
C10—N2—C9—N1	158.6 (2)	C10—C11—C12—C13	39.2 (2)
C13—N2—C9—N3	174.4 (2)	C19—C14—C18—C17	0.6 (3)
C10—N2—C9—N3	−23.0 (3)	C6—C3—C1—S2	−53.3 (3)
C8—N3—C9—N1	−7.1 (3)	C2—S2—C1—C3	62.2 (2)
C19—N3—C9—N1	159.5 (2)	C14—C18—C17—C16	0.1 (4)
C8—N3—C9—N2	174.5 (2)	C6—C4—C2—S2	14.9 (4)
C19—N3—C9—N2	−18.8 (3)	S1—C4—C2—S2	−168.8 (2)
C9—N2—C10—C11	−152.5 (2)	C1—S2—C2—C4	−40.8 (2)
C13—N2—C10—C11	11.2 (2)	C18—C17—C16—C15	−0.7 (4)
C5—C7—C6—C4	−1.6 (3)	C19—C15—C16—C17	0.7 (4)
C8—C7—C6—C4	−174.4 (2)	C18—C14—C19—C15	−0.7 (3)
C5—C7—C6—C3	174.4 (2)	C18—C14—C19—N3	−178.4 (2)
C8—C7—C6—C3	1.6 (4)	C16—C15—C19—C14	0.1 (3)
C5—C7—C8—O1	−178.3 (2)	C16—C15—C19—N3	177.7 (2)
C6—C7—C8—O1	−5.7 (4)	C9—N3—C19—C14	−60.2 (3)
C5—C7—C8—N3	−1.9 (3)	C8—N3—C19—C14	107.4 (2)
C6—C7—C8—N3	170.6 (2)	C9—N3—C19—C15	122.1 (2)
C9—N3—C8—O1	−176.4 (2)	C8—N3—C19—C15	−70.3 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11B···O1i	0.97	2.58	3.434 (3)	148.
C1—H1A···O1ii	0.97	2.48	3.287 (3)	140.
C3—H3B···O1	0.97	2.50	3.038 (3)	115.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11B⋯O1i	0.97	2.58	3.434 (3)	148
C1—H1A⋯O1ii	0.97	2.48	3.287 (3)	140

Symmetry codes: (i) ; (ii) .