Ethyl 4-(1,3-benzodioxol-5-yl)-6-methyl-2-sulfanylidene-1,2,3,4-tetra-hydro-pyrimidine-5-carboxyl-ate.

In the title compound, C(15)H(16)N(2)O(4)S, the dihedral angles between the planes of the benzodioxole and ester groups and the plane of the six-membered tetra-hydro-pyrimidine ring are 89.5 (1) and 20.2 (1)°, respectively. Inter-molecular N-H⋯S hydrogen bonds assemble the mol-ecules into dimers, which are further connected via N-H⋯O inter-actions into chains parallel to [010]. Weak C-H⋯S and C-H⋯π inter-actions enhance the stability of the crystal structure.

Related literature

For background to the applications of multi-functionalized dihydro­pyrimidines, see: Jauk et al. (2000 ▶); Kappe (2000 ▶); Mayer et al. (1999 ▶). For similar structures, see: Nayak et al. (2009 ▶, 2010 ▶, 2011 ▶).

Experimental

Crystal data

C15H16N2O4S

M = 320.37

Monoclinic,

a = 12.5102 (9) Å

b = 7.2054 (4) Å

c = 17.0881 (12) Å

β = 107.178 (8)°

V = 1471.62 (17) Å3

Z = 4

Mo Kα radiation

μ = 0.24 mm−1

T = 120 K

0.28 × 0.22 × 0.19 mm

Data collection

Oxford Diffraction Xcalibur E diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T min = 0.936, T max = 0.956

18163 measured reflections

2883 independent reflections

2349 reflections with I > 2σ(I)

R int = 0.067

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.103

S = 1.09

2883 reflections

263 parameters

All H-atom parameters refined

Δρmax = 0.33 e Å−3

Δρmin = −0.30 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and CAMERON (Watkin et al., 1993 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶) and PARST (Nardelli, 1995 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811043649/gk2420sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811043649/gk2420Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811043649/gk2420Isup3.cml

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

C15H16N2O4S	F(000) = 672
Mr = 320.37	Dx = 1.446 Mg m−3
Monoclinic, P21/c	Melting point: 447(2) K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 12.5102 (9) Å	Cell parameters from 430 reflections
b = 7.2054 (4) Å	θ = 1.0–27.9°
c = 17.0881 (12) Å	µ = 0.24 mm−1
β = 107.178 (8)°	T = 120 K
V = 1471.62 (17) Å3	Block, colorless
Z = 4	0.28 × 0.22 × 0.19 mm

Oxford Diffraction Xcalibur E diffractometer	2883 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2349 reflections with I > 2σ(I)
graphite	Rint = 0.067
Detector resolution: 16.0839 pixels mm-1	θmax = 26.0°, θmin = 2.5°
ω scans	h = −15→15
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −8→8
Tmin = 0.936, Tmax = 0.956	l = −21→21
18163 measured reflections

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) = 0.103	All H-atom parameters refined
S = 1.09	w = 1/[σ2(Fo2) + (0.044P)2 + 0.4413P] where P = (Fo2 + 2Fc2)/3
2883 reflections	(Δ/σ)max < 0.001
263 parameters	Δρmax = 0.33 e Å−3
0 restraints	Δρmin = −0.30 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
S1	0.03990 (4)	0.22578 (6)	0.06240 (3)	0.02136 (16)
O2	0.21637 (11)	0.77438 (16)	0.39149 (7)	0.0190 (3)
C4	0.14810 (16)	0.7167 (2)	0.17046 (11)	0.0167 (4)
O1	0.14472 (12)	0.97853 (17)	0.29048 (8)	0.0246 (3)
C9	0.26335 (16)	0.7523 (2)	0.16168 (10)	0.0164 (4)
N1	0.12326 (13)	0.3507 (2)	0.21437 (9)	0.0178 (4)
N2	0.08802 (14)	0.5707 (2)	0.11385 (10)	0.0179 (4)
C2	0.14299 (15)	0.4837 (2)	0.27642 (11)	0.0161 (4)
C5	0.16897 (15)	0.8200 (2)	0.31311 (11)	0.0164 (4)
C3	0.15224 (15)	0.6627 (2)	0.25676 (10)	0.0157 (4)
C8	0.14782 (18)	0.4050 (3)	0.35838 (12)	0.0194 (4)
C1	0.08656 (15)	0.3933 (2)	0.13312 (11)	0.0173 (4)
C6	0.23338 (18)	0.9229 (3)	0.45154 (12)	0.0214 (4)
C12	0.47322 (16)	0.8166 (3)	0.14736 (12)	0.0242 (4)
C10	0.28717 (17)	0.9248 (3)	0.13323 (12)	0.0240 (4)
O5	0.57092 (12)	0.8812 (2)	0.13570 (10)	0.0348 (4)
C14	0.34567 (17)	0.6153 (3)	0.18099 (12)	0.0236 (4)
C13	0.45264 (18)	0.6459 (3)	0.17449 (13)	0.0268 (5)
O3	0.43410 (14)	1.1070 (2)	0.09967 (13)	0.0551 (6)
C11	0.39210 (18)	0.9510 (3)	0.12682 (13)	0.0267 (5)
C7	0.3423 (2)	1.0191 (3)	0.46053 (15)	0.0316 (5)
C15	0.54868 (19)	1.0701 (3)	0.10926 (16)	0.0341 (5)
H8A	0.1201 (17)	0.491 (3)	0.3892 (13)	0.022 (5)*
H6B	0.1710 (17)	1.006 (3)	0.4352 (12)	0.017 (5)*
H10	0.2310 (19)	1.017 (3)	0.1214 (13)	0.030 (6)*
H8B	0.1075 (18)	0.292 (3)	0.3532 (12)	0.022 (5)*
H13	0.5136 (19)	0.551 (3)	0.1892 (13)	0.030 (6)*
H2N	0.0633 (19)	0.599 (3)	0.0693 (14)	0.023 (6)*
H1N	0.122 (2)	0.240 (3)	0.2286 (14)	0.031 (7)*
H4	0.1015 (16)	0.829 (3)	0.1527 (11)	0.015 (5)*
H6A	0.2297 (16)	0.861 (3)	0.5017 (12)	0.016 (5)*
H14	0.326 (2)	0.496 (3)	0.2002 (14)	0.042 (7)*
H7A	0.408 (2)	0.932 (4)	0.4772 (16)	0.050 (7)*
H7B	0.3470 (19)	1.077 (3)	0.4079 (14)	0.033 (6)*
H8C	0.222 (2)	0.379 (3)	0.3889 (15)	0.038 (7)*
H15A	0.593 (2)	1.155 (4)	0.1543 (16)	0.048 (7)*
H7C	0.349 (2)	1.111 (4)	0.5042 (16)	0.051 (8)*
H15B	0.556 (2)	1.086 (4)	0.0541 (17)	0.053 (8)*

	U11	U22	U33	U12	U13	U23
S1	0.0238 (3)	0.0142 (3)	0.0213 (3)	0.00006 (18)	−0.0006 (2)	−0.00166 (17)
O2	0.0258 (8)	0.0137 (7)	0.0154 (6)	−0.0003 (5)	0.0032 (6)	−0.0012 (5)
C4	0.0206 (10)	0.0107 (9)	0.0162 (9)	0.0004 (7)	0.0014 (7)	−0.0004 (7)
O1	0.0350 (8)	0.0129 (7)	0.0225 (7)	0.0038 (6)	0.0033 (6)	0.0012 (5)
C9	0.0188 (10)	0.0162 (9)	0.0129 (8)	−0.0021 (7)	0.0023 (7)	−0.0014 (7)
N1	0.0230 (9)	0.0095 (8)	0.0194 (8)	0.0010 (6)	0.0040 (7)	0.0005 (6)
N2	0.0211 (9)	0.0136 (8)	0.0157 (9)	−0.0001 (6)	0.0004 (7)	0.0027 (6)
C2	0.0143 (9)	0.0145 (9)	0.0188 (9)	0.0018 (7)	0.0037 (7)	0.0009 (7)
C5	0.0159 (9)	0.0144 (9)	0.0194 (9)	0.0008 (7)	0.0060 (7)	−0.0001 (7)
C3	0.0159 (9)	0.0139 (9)	0.0162 (9)	0.0008 (7)	0.0033 (7)	0.0003 (7)
C8	0.0258 (12)	0.0126 (10)	0.0199 (10)	0.0005 (8)	0.0067 (9)	0.0011 (7)
C1	0.0127 (9)	0.0169 (10)	0.0205 (9)	0.0017 (7)	0.0020 (7)	−0.0002 (7)
C6	0.0301 (12)	0.0165 (10)	0.0164 (9)	−0.0008 (8)	0.0050 (8)	−0.0028 (7)
C12	0.0177 (10)	0.0290 (11)	0.0262 (10)	−0.0032 (8)	0.0070 (8)	−0.0042 (8)
C10	0.0209 (11)	0.0165 (10)	0.0321 (11)	0.0008 (8)	0.0040 (9)	0.0037 (8)
O5	0.0236 (8)	0.0302 (9)	0.0538 (10)	−0.0040 (6)	0.0162 (7)	0.0021 (7)
C14	0.0266 (11)	0.0175 (10)	0.0283 (10)	0.0020 (8)	0.0102 (9)	0.0049 (8)
C13	0.0232 (11)	0.0219 (11)	0.0360 (11)	0.0047 (8)	0.0099 (9)	0.0034 (9)
O3	0.0303 (10)	0.0329 (10)	0.1070 (16)	−0.0001 (7)	0.0281 (10)	0.0314 (10)
C11	0.0264 (11)	0.0187 (10)	0.0345 (11)	−0.0037 (8)	0.0083 (9)	0.0061 (8)
C7	0.0301 (13)	0.0261 (12)	0.0348 (13)	−0.0056 (10)	0.0036 (10)	−0.0075 (10)
C15	0.0274 (13)	0.0331 (13)	0.0427 (14)	−0.0071 (9)	0.0117 (11)	0.0052 (10)

S1—C1	1.6854 (18)	C8—H8C	0.94 (3)
O2—C5	1.336 (2)	C6—C7	1.496 (3)
O2—C6	1.454 (2)	C6—H6B	0.96 (2)
C4—N2	1.476 (2)	C6—H6A	0.98 (2)
C4—C3	1.511 (2)	C12—C13	1.365 (3)
C4—C9	1.515 (3)	C12—C11	1.372 (3)
C4—H4	0.99 (2)	C12—O5	1.376 (2)
O1—C5	1.215 (2)	C10—C11	1.362 (3)
C9—C14	1.394 (3)	C10—H10	0.94 (2)
C9—C10	1.398 (3)	O5—C15	1.435 (3)
N1—C1	1.362 (2)	C14—C13	1.393 (3)
N1—C2	1.396 (2)	C14—H14	0.97 (2)
N1—H1N	0.84 (2)	C13—H13	1.00 (2)
N2—C1	1.322 (2)	O3—C11	1.378 (2)
N2—H2N	0.76 (2)	O3—C15	1.419 (3)
C2—C3	1.346 (2)	C7—H7A	1.01 (3)
C2—C8	1.495 (3)	C7—H7B	1.01 (2)
C5—C3	1.462 (2)	C7—H7C	0.98 (3)
C8—H8A	0.94 (2)	C15—H15A	1.01 (3)
C8—H8B	0.95 (2)	C15—H15B	0.98 (3)
C5—O2—C6	117.10 (14)	O2—C6—H6B	108.5 (12)
N2—C4—C3	108.68 (15)	C7—C6—H6B	112.3 (12)
N2—C4—C9	111.78 (15)	O2—C6—H6A	104.3 (11)
C3—C4—C9	112.39 (15)	C7—C6—H6A	113.5 (11)
N2—C4—H4	104.0 (11)	H6B—C6—H6A	107.2 (17)
C3—C4—H4	110.9 (11)	C13—C12—C11	121.57 (19)
C9—C4—H4	108.7 (11)	C13—C12—O5	128.22 (19)
C14—C9—C10	119.55 (18)	C11—C12—O5	110.21 (18)
C14—C9—C4	120.99 (17)	C11—C10—C9	117.43 (18)
C10—C9—C4	119.46 (16)	C11—C10—H10	124.0 (14)
C1—N1—C2	123.39 (16)	C9—C10—H10	118.6 (14)
C1—N1—H1N	118.8 (16)	C12—O5—C15	105.58 (16)
C2—N1—H1N	116.7 (16)	C13—C14—C9	121.93 (19)
C1—N2—C4	124.61 (16)	C13—C14—H14	120.6 (15)
C1—N2—H2N	118.7 (17)	C9—C14—H14	117.4 (15)
C4—N2—H2N	116.1 (17)	C12—C13—C14	116.87 (18)
C3—C2—N1	118.48 (16)	C12—C13—H13	119.6 (13)
C3—C2—C8	127.90 (17)	C14—C13—H13	123.6 (13)
N1—C2—C8	113.59 (15)	C11—O3—C15	106.32 (17)
O1—C5—O2	123.07 (16)	C10—C11—C12	122.62 (19)
O1—C5—C3	123.06 (16)	C10—C11—O3	127.79 (19)
O2—C5—C3	113.85 (15)	C12—C11—O3	109.59 (18)
C2—C3—C5	125.78 (16)	C6—C7—H7A	112.5 (15)
C2—C3—C4	120.63 (16)	C6—C7—H7B	113.0 (13)
C5—C3—C4	113.58 (15)	H7A—C7—H7B	105 (2)
C2—C8—H8A	110.8 (12)	C6—C7—H7C	104.9 (15)
C2—C8—H8B	111.5 (12)	H7A—C7—H7C	109 (2)
H8A—C8—H8B	110.1 (18)	H7B—C7—H7C	112.7 (19)
C2—C8—H8C	110.8 (15)	O3—C15—O5	108.02 (17)
H8A—C8—H8C	106.6 (19)	O3—C15—H15A	106.3 (15)
H8B—C8—H8C	106.9 (19)	O5—C15—H15A	108.9 (15)
N2—C1—N1	116.51 (16)	O3—C15—H15B	104.3 (16)
N2—C1—S1	122.78 (14)	O5—C15—H15B	110.3 (16)
N1—C1—S1	120.71 (14)	H15A—C15—H15B	118 (2)
O2—C6—C7	110.65 (17)
N2—C4—C9—C14	−64.5 (2)	C4—N2—C1—S1	−167.04 (14)
C3—C4—C9—C14	58.0 (2)	C2—N1—C1—N2	11.3 (3)
N2—C4—C9—C10	115.08 (18)	C2—N1—C1—S1	−167.60 (15)
C3—C4—C9—C10	−122.40 (18)	C5—O2—C6—C7	−86.5 (2)
C3—C4—N2—C1	−30.0 (2)	C14—C9—C10—C11	−0.9 (3)
C9—C4—N2—C1	94.6 (2)	C4—C9—C10—C11	179.58 (18)
C1—N1—C2—C3	−16.3 (3)	C13—C12—O5—C15	−178.2 (2)
C1—N1—C2—C8	162.00 (17)	C11—C12—O5—C15	2.3 (2)
C6—O2—C5—O1	3.2 (3)	C10—C9—C14—C13	1.4 (3)
C6—O2—C5—C3	−178.61 (16)	C4—C9—C14—C13	−179.05 (18)
N1—C2—C3—C5	177.79 (17)	C11—C12—C13—C14	−0.5 (3)
C8—C2—C3—C5	−0.2 (3)	O5—C12—C13—C14	179.97 (19)
N1—C2—C3—C4	−3.5 (3)	C9—C14—C13—C12	−0.7 (3)
C8—C2—C3—C4	178.49 (18)	C9—C10—C11—C12	−0.3 (3)
O1—C5—C3—C2	−157.7 (2)	C9—C10—C11—O3	179.2 (2)
O2—C5—C3—C2	24.2 (3)	C13—C12—C11—C10	1.0 (3)
O1—C5—C3—C4	23.5 (3)	O5—C12—C11—C10	−179.37 (19)
O2—C5—C3—C4	−154.60 (16)	C13—C12—C11—O3	−178.55 (19)
N2—C4—C3—C2	23.6 (2)	O5—C12—C11—O3	1.0 (2)
C9—C4—C3—C2	−100.7 (2)	C15—O3—C11—C10	176.5 (2)
N2—C4—C3—C5	−157.57 (15)	C15—O3—C11—C12	−4.0 (3)
C9—C4—C3—C5	78.17 (19)	C11—O3—C15—O5	5.3 (3)
C4—N2—C1—N1	14.1 (3)	C12—O5—C15—O3	−4.7 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1i	0.84 (2)	2.14 (2)	2.9578 (19)	167 (2)
N2—H2N···S1ii	0.76 (2)	2.57 (2)	3.3069 (17)	164 (2)
C10—H10···S1iii	0.95 (2)	2.75 (2)	3.678 (2)	166.9 (18)
C15—H15B···Cg1iv	0.98 (3)	2.95 (3)	3.890 (2)	160 (2)
C6—H6A···Cg2v	0.98 (2)	2.87 (2)	3.691 (2)	142 (2)

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the O3/C11/C12/O5/C15 and C9–C14 rings respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1i	0.84 (2)	2.14 (2)	2.9578 (19)	167 (2)
N2—H2N⋯S1ii	0.76 (2)	2.57 (2)	3.3069 (17)	164 (2)
C10—H10⋯S1iii	0.95 (2)	2.75 (2)	3.678 (2)	166.9 (18)
C15—H15B⋯Cg1iv	0.98 (3)	2.95 (3)	3.890 (2)	160 (2)
C6—H6A⋯Cg2v	0.98 (2)	2.87 (2)	3.691 (2)	142 (2)

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