1-(9-Methyl-11-sulfanyl­idene-8-oxa-10,12-diaza­tricyclo­[7.3.1.0^2,7]trideca-2,4,6-trien-13-yl)ethanone

Abstract

The six-membered oxacyclo­hexene ring of the title compound, C₁₃H₁₄N₂O₂S, is fused with the benzene ring and the quarternary C atom lies above the plane of the benzene ring by 0.229 (8) Å, whereas the methine C atom (which bears the acetyl substituent) lies below this plane by 0.595 (8) Å. The oxacyclo­hexene ring is also fused with the sofa-shaped 2,6-diaza­cyclo­hexa­none ring. The methine C atom that belongs to both six-membered rings lies above the mean plane of the other five atoms (r.m.s. deviation = 0.077 Å) by 0.759 (5) Å. In the crystal, N—H⋯S hydrogen bonds link adjacent mol­ecules into a linear chain.

Related literature

For related structures, see: Kettmann & Svetlík (1996 ▶, 1997) ▶; Kurbanova et al. (2009 ▶).

Experimental

Crystal data

• C₁₃H₁₄N₂O₂S

• M _r = 262.32

• Monoclinic,

• a = 8.2382 (5) Å

• b = 19.1223 (12) Å

• c = 9.2209 (6) Å

• β = 114.623 (1)°

• V = 1320.51 (14) ų

• Z = 4

• Mo Kα radiation

• μ = 0.24 mm⁻¹

• T = 296 K

• 0.40 × 0.30 × 0.20 mm

Data collection

• Bruker APEXII diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.589, T _max = 1.000

• 8830 measured reflections

• 2292 independent reflections

• 1523 reflections with I > 2σ(I)

• R _int = 0.119

Refinement

• R[F ² > 2σ(F ²)] = 0.079

• wR(F ²) = 0.211

• S = 0.99

• 2292 reflections

• 164 parameters

• H-atom parameters constrained

• Δρ_max = 0.65 e Å⁻³

• Δρ_min = −0.41 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯S1i	0.88	2.49	3.324 (3)	158
N2—H2⋯S1ii	0.88	2.43	3.259 (3)	158

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Comment

The title compound, C₁₃H₁₄N₂O₂S (Scheme I, Fig. 1), is a conformationally restricted dihydropyrimidine analogue of 1,4-dihydropyridine-type calcium antagonists; the crystal structures of similar compounds have been reported (Kurbanova et al., 2009; Kettmann & Svetlík, 1996; Kettmann & Svetlík, 1997). Tthe six-membered oxacyclohexene ring that is fused with the benzene ring has the quarternary C atom lying above the plane of the benzene ring and the methine C (which bears the acetyl substituent) lying below this plane. The oxacyclohexene ring is also fused with the sofa-shaped diazacyclcohexane ring; the methine C that belongs to both six-membered rings lies above the mean plane of the other five atoms. Hydrogen bonds of the type N–H···S link adjacent molecules to form a linear chain (Fig. 2).

Experimental

In round-bottom flask that was fitted with a reflux condenser and a mechanical stirrer, salicylaldehyde (1.25 mol), acetylacetone (1.50 mol), thiocarbamide (1.25 mol), trichloroacetic acid (25 mg) and ethanol (10 ml) were reacted for 3 h. The solid that formed was collected and recrystallized from ethanol, m.p. 514–515 K; yield 80%.

Refinement

Hydrogen atoms were placed in calculated positions [C–H 0.93 to 0.9 and N–H 0.88 7 Å; U(H) 1.2 to 1.5U(C,N)] and were included in the refinement in the riding model approximation.

Figures

Fig. 1.

Thermal ellipsoid plot (Barbour, 2001) of the hydrogen-bonded dimeric structure of C13H14N2O2 at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

Fig. 2.

Hydrogen-bonded chain structure.

Crystal data

C13H14N2O2S	F(000) = 552
Mr = 262.32	Dx = 1.319 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2832 reflections
a = 8.2382 (5) Å	θ = 2.7–28.3°
b = 19.1223 (12) Å	µ = 0.24 mm−1
c = 9.2209 (6) Å	T = 296 K
β = 114.623 (1)°	Irregular block, colorless
V = 1320.51 (14) Å3	0.40 × 0.30 × 0.20 mm
Z = 4

Data collection

Bruker APEXII diffractometer	2292 independent reflections
Radiation source: fine-focus sealed tube	1523 reflections with I > 2σ(I)
graphite	Rint = 0.119
φ and ω scans	θmax = 25.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.589, Tmax = 1.000	k = −22→21
8830 measured reflections	l = −10→10

Refinement

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)] = 0.079	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.211	H-atom parameters constrained
S = 0.99	w = 1/[σ2(Fo2) + (0.1282P)2] where P = (Fo2 + 2Fc2)/3
2292 reflections	(Δ/σ)max = 0.001
164 parameters	Δρmax = 0.65 e Å−3
0 restraints	Δρmin = −0.41 e Å−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.70755 (12)	0.51631 (6)	0.41553 (12)	0.0471 (4)
O1	0.6767 (4)	0.29345 (19)	0.3421 (3)	0.0690 (10)
O2	0.6966 (4)	0.34703 (14)	0.7965 (3)	0.0491 (8)
N1	0.6447 (4)	0.40871 (16)	0.5610 (3)	0.0381 (8)
H1	0.5416	0.4296	0.5371	0.046*
N2	0.9280 (4)	0.41746 (16)	0.5844 (3)	0.0398 (8)
H2	1.0075	0.4362	0.5556	0.048*
C1	0.7642 (4)	0.4431 (2)	0.5272 (4)	0.0358 (9)
C2	0.8091 (5)	0.2822 (2)	0.4611 (5)	0.0489 (10)
C3	0.9636 (7)	0.2461 (4)	0.4534 (6)	0.0855 (18)
H3A	0.9226	0.2139	0.3655	0.128*
H3B	1.0271	0.2210	0.5510	0.128*
H3C	1.0417	0.2799	0.4388	0.128*
C4	0.4941 (5)	0.3002 (2)	0.5599 (5)	0.0584 (12)
H4A	0.4010	0.3264	0.5719	0.088*
H4B	0.5078	0.2559	0.6126	0.088*
H4C	0.4633	0.2927	0.4486	0.088*
C5	0.6667 (5)	0.3403 (2)	0.6330 (4)	0.0406 (9)
C6	0.8282 (5)	0.3056 (2)	0.6238 (4)	0.0383 (9)
H6	0.8597	0.2647	0.6940	0.046*
C7	0.9783 (5)	0.35889 (19)	0.6938 (4)	0.0405 (9)
H7	1.0902	0.3386	0.7000	0.049*
C8	0.9989 (6)	0.3797 (2)	0.8581 (4)	0.0472 (11)
C9	1.1601 (7)	0.4052 (2)	0.9698 (5)	0.0716 (15)
H9	1.2577	0.4100	0.9445	0.086*
C10	1.1735 (10)	0.4238 (3)	1.1220 (6)	0.094 (2)
H10	1.2805	0.4410	1.1985	0.113*
C11	1.0297 (11)	0.4164 (3)	1.1571 (6)	0.096 (2)
H11	1.0396	0.4288	1.2580	0.115*
C12	0.8736 (8)	0.3917 (2)	1.0492 (5)	0.0747 (16)
H12	0.7766	0.3869	1.0752	0.090*
C13	0.8582 (6)	0.3734 (2)	0.8995 (4)	0.0500 (11)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
S1	0.0296 (6)	0.0510 (7)	0.0610 (7)	0.0056 (4)	0.0192 (5)	0.0222 (5)
O1	0.0578 (18)	0.099 (3)	0.0400 (16)	−0.0015 (17)	0.0104 (14)	−0.0118 (16)
O2	0.0670 (18)	0.0456 (18)	0.0456 (15)	−0.0074 (14)	0.0341 (13)	−0.0029 (12)
N1	0.0286 (15)	0.0385 (19)	0.0522 (18)	0.0001 (13)	0.0218 (13)	0.0067 (14)
N2	0.0265 (16)	0.0402 (19)	0.0509 (18)	0.0005 (13)	0.0144 (13)	0.0105 (14)
C1	0.0246 (18)	0.045 (2)	0.0375 (19)	−0.0003 (16)	0.0130 (14)	−0.0014 (16)
C2	0.051 (2)	0.053 (3)	0.046 (2)	−0.010 (2)	0.0228 (19)	−0.0091 (19)
C3	0.072 (3)	0.122 (5)	0.063 (3)	0.025 (3)	0.029 (2)	−0.022 (3)
C4	0.053 (3)	0.055 (3)	0.074 (3)	−0.018 (2)	0.033 (2)	−0.010 (2)
C5	0.047 (2)	0.037 (2)	0.043 (2)	−0.0050 (17)	0.0232 (17)	−0.0016 (16)
C6	0.043 (2)	0.035 (2)	0.0365 (18)	0.0000 (16)	0.0171 (15)	0.0004 (16)
C7	0.036 (2)	0.036 (2)	0.044 (2)	0.0025 (16)	0.0102 (15)	0.0059 (16)
C8	0.058 (3)	0.029 (2)	0.039 (2)	−0.0001 (18)	0.0048 (18)	0.0003 (16)
C9	0.076 (3)	0.050 (3)	0.055 (3)	−0.008 (2)	−0.007 (2)	0.000 (2)
C10	0.115 (5)	0.065 (4)	0.050 (3)	−0.010 (4)	−0.016 (3)	−0.011 (3)
C11	0.156 (6)	0.061 (4)	0.047 (3)	−0.012 (4)	0.019 (4)	−0.015 (3)
C12	0.127 (5)	0.045 (3)	0.054 (3)	0.003 (3)	0.038 (3)	−0.005 (2)
C13	0.075 (3)	0.029 (2)	0.042 (2)	−0.001 (2)	0.020 (2)	−0.0014 (17)

Geometric parameters (Å, °)

S1—C1	1.685 (4)	C4—H4B	0.9600
O1—C2	1.201 (5)	C4—H4C	0.9600
O2—C13	1.369 (5)	C5—C6	1.520 (5)
O2—C5	1.429 (4)	C6—C7	1.523 (5)
N1—C1	1.324 (5)	C6—H6	0.9800
N1—C5	1.443 (5)	C7—C8	1.505 (6)
N1—H1	0.8800	C7—H7	0.9800
N2—C1	1.322 (4)	C8—C13	1.369 (6)
N2—C7	1.447 (5)	C8—C9	1.387 (6)
N2—H2	0.8800	C9—C10	1.407 (9)
C2—C3	1.475 (6)	C9—H9	0.9300
C2—C6	1.509 (5)	C10—C11	1.359 (10)
C3—H3A	0.9600	C10—H10	0.9300
C3—H3B	0.9600	C11—C12	1.342 (8)
C3—H3C	0.9600	C11—H11	0.9300
C4—C5	1.506 (5)	C12—C13	1.377 (6)
C4—H4A	0.9600	C12—H12	0.9300
C13—O2—C5	117.1 (3)	C2—C6—C5	117.0 (3)
C1—N1—C5	126.5 (3)	C2—C6—C7	110.5 (3)
C1—N1—H1	116.8	C5—C6—C7	105.0 (3)
C5—N1—H1	116.8	C2—C6—H6	108.0
C1—N2—C7	120.9 (3)	C5—C6—H6	108.0
C1—N2—H2	119.5	C7—C6—H6	108.0
C7—N2—H2	119.5	N2—C7—C8	112.1 (3)
N2—C1—N1	117.2 (3)	N2—C7—C6	106.0 (3)
N2—C1—S1	121.9 (3)	C8—C7—C6	109.5 (3)
N1—C1—S1	120.9 (2)	N2—C7—H7	109.7
O1—C2—C3	120.9 (4)	C8—C7—H7	109.7
O1—C2—C6	122.2 (4)	C6—C7—H7	109.7
C3—C2—C6	116.9 (4)	C13—C8—C9	118.9 (4)
C2—C3—H3A	109.5	C13—C8—C7	120.3 (3)
C2—C3—H3B	109.5	C9—C8—C7	120.8 (5)
H3A—C3—H3B	109.5	C8—C9—C10	118.9 (6)
C2—C3—H3C	109.5	C8—C9—H9	120.6
H3A—C3—H3C	109.5	C10—C9—H9	120.6
H3B—C3—H3C	109.5	C11—C10—C9	119.9 (5)
C5—C4—H4A	109.5	C11—C10—H10	120.1
C5—C4—H4B	109.5	C9—C10—H10	120.1
H4A—C4—H4B	109.5	C12—C11—C10	121.3 (6)
C5—C4—H4C	109.5	C12—C11—H11	119.3
H4A—C4—H4C	109.5	C10—C11—H11	119.3
H4B—C4—H4C	109.5	C11—C12—C13	119.5 (6)
O2—C5—N1	109.7 (3)	C11—C12—H12	120.2
O2—C5—C4	103.5 (3)	C13—C12—H12	120.2
N1—C5—C4	110.0 (3)	C8—C13—O2	122.0 (3)
O2—C5—C6	109.2 (3)	C8—C13—C12	121.5 (4)
N1—C5—C6	108.4 (3)	O2—C13—C12	116.5 (5)
C4—C5—C6	116.0 (3)
C7—N2—C1—N1	−6.7 (5)	C2—C6—C7—N2	60.7 (4)
C7—N2—C1—S1	173.4 (3)	C5—C6—C7—N2	−66.3 (4)
C5—N1—C1—N2	−10.3 (5)	C2—C6—C7—C8	−178.1 (3)
C5—N1—C1—S1	169.6 (3)	C5—C6—C7—C8	54.9 (4)
C13—O2—C5—N1	−71.3 (4)	N2—C7—C8—C13	93.0 (4)
C13—O2—C5—C4	171.3 (3)	C6—C7—C8—C13	−24.3 (5)
C13—O2—C5—C6	47.3 (4)	N2—C7—C8—C9	−87.1 (4)
C1—N1—C5—O2	104.1 (4)	C6—C7—C8—C9	155.5 (4)
C1—N1—C5—C4	−142.7 (4)	C13—C8—C9—C10	0.1 (6)
C1—N1—C5—C6	−15.0 (5)	C7—C8—C9—C10	−179.8 (4)
O1—C2—C6—C5	3.9 (6)	C8—C9—C10—C11	0.0 (8)
C3—C2—C6—C5	−177.7 (4)	C9—C10—C11—C12	0.0 (10)
O1—C2—C6—C7	−116.2 (4)	C10—C11—C12—C13	−0.1 (9)
C3—C2—C6—C7	62.3 (5)	C9—C8—C13—O2	−178.5 (4)
O2—C5—C6—C2	169.3 (3)	C7—C8—C13—O2	1.4 (6)
N1—C5—C6—C2	−71.2 (4)	C9—C8—C13—C12	−0.2 (6)
C4—C5—C6—C2	53.0 (5)	C7—C8—C13—C12	179.7 (4)
O2—C5—C6—C7	−67.8 (3)	C5—O2—C13—C8	−13.2 (5)
N1—C5—C6—C7	51.7 (4)	C5—O2—C13—C12	168.4 (4)
C4—C5—C6—C7	175.9 (3)	C11—C12—C13—C8	0.2 (7)
C1—N2—C7—C8	−73.8 (4)	C11—C12—C13—O2	178.6 (4)
C1—N2—C7—C6	45.6 (4)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1i	0.88	2.49	3.324 (3)	158
N2—H2···S1ii	0.88	2.43	3.259 (3)	158

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y+1, −z+1.