1-(9-Methyl-11-sulfanyl­idene-8-oxa-10,12-diaza­tricyclo­[7.3.1.02,7]trideca-2,4,6-trien-13-yl)ethanone

Kurbanova, M.M.; Maharramov, A.M.; Novruzova, A.B.; Gurbanov, A.V.; Ng, S.W.

doi:10.1107/S1600536811013699

organic compounds

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doi:10.1107/S1600536811013699

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

Malahat M. Kurbanova,^a Abel M. Maharramov,^a Aysel B. Novruzova,^a Atash V. Gurbanov ^a and Seik Weng Ng ^b ^*

^aDepartment of Organic Chemistry, Baku State University, Baku, Azerbaijan, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 11 April 2011; accepted 12 April 2011; online 16 April 2011)

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, P 2₁ /n
a = 8.2382 (5) Å
b = 19.1223 (12) Å
c = 9.2209 (6) Å
β = 114.623 (1)°
V = 1320.51 (14) Å³
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[F² > 2σ(F²)] = 0.079
wR(F²) = 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

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) -x+1, -y+1, -z+1; (ii) -x+2, -y+1, -z+1.

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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811013699/xu5193sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811013699/xu5193Isup2.hkl

checkCIF report

Comment top

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).

Related literature top

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

Experimental top

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%.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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).

Figures top

	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.

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

Crystal data top

C₁₃H₁₄N₂O₂S	F(000) = 552
M_r = 262.32	D_x = 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 top

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

Refinement top

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(F_o²) + (0.1282P)²] where P = (F_o² + 2F_c²)/3
2292 reflections	(Δ/σ)_max = 0.001
164 parameters	Δρ_max = 0.65 e Å⁻³
0 restraints	Δρ_min = −0.41 e Å⁻³

Crystal data top

C₁₃H₁₄N₂O₂S	V = 1320.51 (14) Å³
M_r = 262.32	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.2382 (5) Å	µ = 0.24 mm⁻¹
b = 19.1223 (12) Å	T = 296 K
c = 9.2209 (6) Å	0.40 × 0.30 × 0.20 mm
β = 114.623 (1)°

Data collection top

Bruker APEXII diffractometer	2292 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1523 reflections with I > 2σ(I)
T_min = 0.589, T_max = 1.000	R_int = 0.119
8830 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.079	0 restraints
wR(F²) = 0.211	H-atom parameters constrained
S = 0.99	Δρ_max = 0.65 e Å⁻³
2292 reflections	Δρ_min = −0.41 e Å⁻³
164 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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, º) top

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, º) top

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.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₄N₂O₂S
M_r	262.32
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	8.2382 (5), 19.1223 (12), 9.2209 (6)
β (°)	114.623 (1)
V (Å³)	1320.51 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.24
Crystal size (mm)	0.40 × 0.30 × 0.20

Data collection
Diffractometer	Bruker APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.589, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	8830, 2292, 1523
R_int	0.119
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.079, 0.211, 0.99
No. of reflections	2292
No. of parameters	164
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.65, −0.41

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

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.

Acknowledgements

We thank Baku State University and the University of Malaya for supporting this study.

References

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

1-(9-Methyl-11-sulfanyl­­idene-8-oxa-10,12-di­aza­tri­cyclo­[7.3.1.02,7]trideca-2,4,6-trien-13-yl)ethanone

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

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