2-(5-Bromo-pyridin-3-yl)-5-[3-(4,5,6,7-tetra-hydro-thieno[3,2-c]pyridine-5-ylsulfon-yl)thio-phen-2-yl]-1,3,4-oxa-diazole.

In the title compound, C(18)H(13)BrN(4)O(3)S(3), the tetra-hydro-pyridine ring adopts a half-chair conformation with the central methyl-ene-C atom of the NCH(2)CH(2) unit at the flap. The dihedral angles between the tetra-hydro-pyridine ring and the pyridine and two thio-phene rings are 69.34 (13) 5.66 (13) and 68.63 (13)°, respectively, while the dihedral angle between the 1,3,4-oxadiazole and tetra-hydro-pyridine rings is 54.76 (13)°. The mol-ecule is stabilized by an intra-molecular C-H⋯N inter-action. In the crystal, adjacent mol-ecules are connected via bifurcated C-H⋯(N,O) hydrogen bonds, forming a chain along the b axis.

Related literature

For applications of 4,5,6,7-tetra­hydro­thieno[3,2-c]pyridine derivatives, see: Lopez-Rodriguez et al. (2001 ▶); Roth et al. (1994 ▶); Ying & Rusak (1997 ▶). For ring conformational analysis, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C18H13BrN4O3S3

M = 509.41

Monoclinic,

a = 7.0327 (14) Å

b = 7.6488 (15) Å

c = 36.939 (7) Å

β = 91.315 (5)°

V = 1986.5 (7) Å3

Z = 4

Mo Kα radiation

μ = 2.41 mm−1

T = 296 K

0.35 × 0.13 × 0.05 mm

Data collection

Bruker APEXII DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.482, T max = 0.885

22958 measured reflections

7230 independent reflections

4160 reflections with I > 2σ(I)

R int = 0.051

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.123

S = 1.02

7230 reflections

262 parameters

H-atom parameters constrained

Δρmax = 0.76 e Å−3

Δρmin = −0.73 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811038529/tk2791sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811038529/tk2791Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811038529/tk2791Isup3.cml

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

C18H13BrN4O3S3	F(000) = 1024
Mr = 509.41	Dx = 1.703 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3605 reflections
a = 7.0327 (14) Å	θ = 2.7–25.9°
b = 7.6488 (15) Å	µ = 2.41 mm−1
c = 36.939 (7) Å	T = 296 K
β = 91.315 (5)°	Plate, colourless
V = 1986.5 (7) Å3	0.35 × 0.13 × 0.05 mm
Z = 4

Bruker APEXII DUO CCD area-detector diffractometer	7230 independent reflections
Radiation source: fine-focus sealed tube	4160 reflections with I > 2σ(I)
graphite	Rint = 0.051
φ and ω scans	θmax = 32.7°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −10→8
Tmin = 0.482, Tmax = 0.885	k = −11→11
22958 measured reflections	l = −55→52

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.123	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0445P)2 + 0.8759P] where P = (Fo2 + 2Fc2)/3
7230 reflections	(Δ/σ)max < 0.001
262 parameters	Δρmax = 0.76 e Å−3
0 restraints	Δρmin = −0.73 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	0.93996 (10)	0.96690 (8)	0.10025 (2)	0.04559 (16)
S2	1.36853 (8)	0.62674 (8)	0.146401 (17)	0.03714 (14)
S3	1.17503 (12)	0.51687 (12)	0.30392 (2)	0.0593 (2)
Br1	0.24445 (4)	−0.00049 (4)	0.017218 (10)	0.06497 (12)
O1	0.7735 (2)	0.6343 (2)	0.07860 (4)	0.0371 (4)
O2	1.5532 (2)	0.7035 (3)	0.14769 (5)	0.0505 (5)
O3	1.3410 (3)	0.4632 (2)	0.12866 (5)	0.0464 (4)
N1	0.7985 (3)	0.3595 (3)	0.09508 (7)	0.0503 (6)
N2	0.9456 (3)	0.4530 (3)	0.11199 (7)	0.0513 (6)
N3	1.3043 (3)	0.6029 (3)	0.18809 (5)	0.0358 (4)
N4	0.2436 (3)	0.5346 (4)	0.02560 (8)	0.0582 (6)
C1	1.3498 (4)	0.7466 (3)	0.21341 (7)	0.0443 (6)
H1A	1.2736	0.8485	0.2073	0.053*
H1B	1.4829	0.7781	0.2117	0.053*
C2	1.3091 (3)	0.6885 (3)	0.25127 (7)	0.0397 (5)
C3	1.3612 (4)	0.7808 (4)	0.28326 (8)	0.0555 (7)
H3A	1.4313	0.8839	0.2833	0.067*
C4	1.2989 (4)	0.7039 (5)	0.31349 (9)	0.0619 (8)
H4A	1.3206	0.7472	0.3368	0.074*
C5	1.2078 (3)	0.5430 (4)	0.25829 (7)	0.0426 (5)
C6	1.1309 (4)	0.4206 (4)	0.22997 (8)	0.0515 (7)
H6A	1.0054	0.3804	0.2365	0.062*
H6B	1.2134	0.3195	0.2281	0.062*
C7	1.1199 (4)	0.5162 (4)	0.19417 (8)	0.0453 (6)
H7A	1.0920	0.4343	0.1747	0.054*
H7B	1.0190	0.6026	0.1945	0.054*
C8	1.2147 (3)	0.7874 (3)	0.12720 (7)	0.0367 (5)
C9	1.2684 (4)	0.9644 (3)	0.13041 (8)	0.0443 (6)
H9A	1.3834	1.0013	0.1407	0.053*
C10	1.1341 (4)	1.0751 (3)	0.11683 (8)	0.0486 (6)
H10A	1.1467	1.1961	0.1166	0.058*
C11	1.0374 (3)	0.7667 (3)	0.11097 (6)	0.0366 (5)
C12	0.9260 (3)	0.6133 (3)	0.10159 (6)	0.0359 (5)
C13	0.7017 (3)	0.4705 (3)	0.07619 (7)	0.0367 (5)
C14	0.5288 (3)	0.4345 (3)	0.05505 (6)	0.0374 (5)
C15	0.4063 (4)	0.5660 (4)	0.04346 (8)	0.0492 (6)
H15A	0.4393	0.6814	0.0484	0.059*
C16	0.1984 (4)	0.3691 (4)	0.01865 (8)	0.0541 (7)
H16A	0.0842	0.3453	0.0064	0.065*
C17	0.3143 (3)	0.2309 (4)	0.02888 (7)	0.0442 (6)
C18	0.4814 (3)	0.2626 (3)	0.04777 (7)	0.0415 (5)
H18A	0.5600	0.1713	0.0554	0.050*

	U11	U22	U33	U12	U13	U23
S1	0.0598 (4)	0.0272 (3)	0.0493 (4)	0.0054 (2)	−0.0094 (3)	0.0027 (3)
S2	0.0358 (3)	0.0367 (3)	0.0390 (3)	0.0038 (2)	0.0026 (2)	−0.0008 (2)
S3	0.0600 (4)	0.0788 (5)	0.0392 (4)	0.0036 (4)	0.0025 (3)	0.0054 (4)
Br1	0.04669 (17)	0.0620 (2)	0.0854 (3)	−0.00962 (13)	−0.01522 (15)	−0.01519 (17)
O1	0.0451 (9)	0.0303 (7)	0.0356 (9)	0.0030 (6)	−0.0073 (7)	0.0014 (7)
O2	0.0351 (9)	0.0595 (12)	0.0571 (12)	−0.0017 (8)	0.0089 (8)	0.0006 (9)
O3	0.0534 (11)	0.0408 (9)	0.0449 (11)	0.0115 (8)	0.0011 (8)	−0.0084 (8)
N1	0.0554 (13)	0.0304 (10)	0.0638 (15)	−0.0004 (9)	−0.0274 (11)	0.0006 (10)
N2	0.0576 (13)	0.0280 (9)	0.0671 (16)	−0.0017 (9)	−0.0277 (12)	−0.0001 (10)
N3	0.0317 (9)	0.0376 (10)	0.0379 (11)	−0.0042 (7)	−0.0015 (8)	−0.0015 (8)
N4	0.0522 (14)	0.0607 (15)	0.0610 (16)	0.0138 (11)	−0.0163 (12)	0.0063 (12)
C1	0.0475 (14)	0.0396 (12)	0.0459 (15)	−0.0084 (10)	0.0007 (11)	−0.0064 (11)
C2	0.0303 (11)	0.0482 (13)	0.0404 (14)	0.0004 (9)	−0.0031 (10)	−0.0065 (11)
C3	0.0443 (14)	0.0685 (19)	0.0534 (18)	−0.0038 (13)	−0.0043 (13)	−0.0197 (15)
C4	0.0549 (16)	0.087 (2)	0.0439 (17)	0.0084 (15)	−0.0062 (13)	−0.0193 (16)
C5	0.0370 (12)	0.0512 (14)	0.0395 (14)	0.0016 (10)	−0.0015 (10)	0.0004 (11)
C6	0.0537 (15)	0.0537 (15)	0.0471 (16)	−0.0187 (12)	0.0028 (12)	0.0018 (13)
C7	0.0367 (12)	0.0570 (16)	0.0420 (14)	−0.0119 (11)	−0.0036 (10)	−0.0012 (12)
C8	0.0431 (12)	0.0300 (10)	0.0369 (13)	0.0003 (9)	0.0010 (10)	0.0013 (9)
C9	0.0537 (15)	0.0346 (11)	0.0445 (15)	−0.0070 (10)	−0.0015 (12)	−0.0003 (11)
C10	0.0658 (17)	0.0285 (11)	0.0512 (16)	−0.0034 (11)	−0.0048 (13)	0.0019 (11)
C11	0.0484 (13)	0.0253 (9)	0.0358 (13)	0.0025 (9)	−0.0029 (10)	0.0002 (9)
C12	0.0454 (12)	0.0281 (10)	0.0338 (12)	0.0029 (9)	−0.0075 (10)	−0.0024 (9)
C13	0.0427 (12)	0.0313 (10)	0.0357 (12)	0.0030 (9)	−0.0055 (10)	−0.0023 (9)
C14	0.0410 (12)	0.0401 (12)	0.0308 (12)	0.0033 (10)	−0.0042 (9)	0.0000 (10)
C15	0.0543 (15)	0.0456 (14)	0.0475 (16)	0.0079 (12)	−0.0071 (12)	0.0021 (12)
C16	0.0401 (13)	0.0674 (19)	0.0542 (17)	0.0042 (13)	−0.0107 (12)	0.0033 (15)
C17	0.0385 (12)	0.0524 (14)	0.0415 (14)	0.0002 (11)	−0.0056 (11)	−0.0016 (12)
C18	0.0373 (12)	0.0436 (12)	0.0432 (14)	0.0049 (10)	−0.0076 (10)	−0.0003 (11)

S1—C10	1.698 (3)	C3—C4	1.345 (4)
S1—C11	1.720 (2)	C3—H3A	0.9300
S2—O3	1.4233 (19)	C4—H4A	0.9300
S2—O2	1.4248 (18)	C5—C6	1.496 (4)
S2—N3	1.625 (2)	C6—C7	1.512 (4)
S2—C8	1.774 (2)	C6—H6A	0.9700
S3—C4	1.707 (4)	C6—H6B	0.9700
S3—C5	1.718 (3)	C7—H7A	0.9700
Br1—C17	1.884 (3)	C7—H7B	0.9700
O1—C13	1.353 (3)	C8—C11	1.381 (3)
O1—C12	1.362 (3)	C8—C9	1.410 (3)
N1—C13	1.284 (3)	C9—C10	1.356 (4)
N1—N2	1.394 (3)	C9—H9A	0.9300
N2—C12	1.291 (3)	C10—H10A	0.9300
N3—C1	1.473 (3)	C11—C12	1.448 (3)
N3—C7	1.479 (3)	C13—C14	1.456 (3)
N4—C15	1.329 (4)	C14—C18	1.381 (3)
N4—C16	1.329 (4)	C14—C15	1.386 (4)
C1—C2	1.501 (4)	C15—H15A	0.9300
C1—H1A	0.9700	C16—C17	1.382 (4)
C1—H1B	0.9700	C16—H16A	0.9300
C2—C5	1.349 (4)	C17—C18	1.375 (3)
C2—C3	1.417 (4)	C18—H18A	0.9300
C10—S1—C11	92.19 (12)	N3—C7—C6	108.8 (2)
O3—S2—O2	119.45 (11)	N3—C7—H7A	109.9
O3—S2—N3	107.45 (11)	C6—C7—H7A	109.9
O2—S2—N3	106.69 (11)	N3—C7—H7B	109.9
O3—S2—C8	110.45 (11)	C6—C7—H7B	109.9
O2—S2—C8	105.95 (11)	H7A—C7—H7B	108.3
N3—S2—C8	106.06 (11)	C11—C8—C9	112.6 (2)
C4—S3—C5	91.51 (15)	C11—C8—S2	129.09 (17)
C13—O1—C12	102.63 (17)	C9—C8—S2	118.17 (19)
C13—N1—N2	106.4 (2)	C10—C9—C8	112.7 (2)
C12—N2—N1	106.31 (19)	C10—C9—H9A	123.7
C1—N3—C7	114.6 (2)	C8—C9—H9A	123.7
C1—N3—S2	117.19 (16)	C9—C10—S1	112.13 (19)
C7—N3—S2	117.26 (16)	C9—C10—H10A	123.9
C15—N4—C16	117.9 (2)	S1—C10—H10A	123.9
N3—C1—C2	109.1 (2)	C8—C11—C12	132.5 (2)
N3—C1—H1A	109.9	C8—C11—S1	110.41 (17)
C2—C1—H1A	109.9	C12—C11—S1	117.10 (17)
N3—C1—H1B	109.9	N2—C12—O1	112.0 (2)
C2—C1—H1B	109.9	N2—C12—C11	130.1 (2)
H1A—C1—H1B	108.3	O1—C12—C11	117.87 (19)
C5—C2—C3	112.2 (3)	N1—C13—O1	112.6 (2)
C5—C2—C1	122.4 (2)	N1—C13—C14	126.3 (2)
C3—C2—C1	125.3 (2)	O1—C13—C14	121.0 (2)
C4—C3—C2	113.0 (3)	C18—C14—C15	119.0 (2)
C4—C3—H3A	123.5	C18—C14—C13	118.6 (2)
C2—C3—H3A	123.5	C15—C14—C13	122.3 (2)
C3—C4—S3	111.7 (2)	N4—C15—C14	123.0 (3)
C3—C4—H4A	124.2	N4—C15—H15A	118.5
S3—C4—H4A	124.2	C14—C15—H15A	118.5
C2—C5—C6	124.5 (2)	N4—C16—C17	122.6 (3)
C2—C5—S3	111.6 (2)	N4—C16—H16A	118.7
C6—C5—S3	124.0 (2)	C17—C16—H16A	118.7
C5—C6—C7	108.6 (2)	C18—C17—C16	119.7 (3)
C5—C6—H6A	110.0	C18—C17—Br1	119.8 (2)
C7—C6—H6A	110.0	C16—C17—Br1	120.4 (2)
C5—C6—H6B	110.0	C17—C18—C14	117.8 (2)
C7—C6—H6B	110.0	C17—C18—H18A	121.1
H6A—C6—H6B	108.3	C14—C18—H18A	121.1
C13—N1—N2—C12	−0.5 (3)	C8—C9—C10—S1	0.5 (3)
O3—S2—N3—C1	170.10 (17)	C11—S1—C10—C9	−0.6 (2)
O2—S2—N3—C1	40.9 (2)	C9—C8—C11—C12	179.0 (3)
C8—S2—N3—C1	−71.75 (19)	S2—C8—C11—C12	−5.7 (4)
O3—S2—N3—C7	−47.6 (2)	C9—C8—C11—S1	−0.3 (3)
O2—S2—N3—C7	−176.79 (18)	S2—C8—C11—S1	174.96 (15)
C8—S2—N3—C7	70.6 (2)	C10—S1—C11—C8	0.5 (2)
C7—N3—C1—C2	45.9 (3)	C10—S1—C11—C12	−178.9 (2)
S2—N3—C1—C2	−170.77 (16)	N1—N2—C12—O1	0.1 (3)
N3—C1—C2—C5	−13.3 (3)	N1—N2—C12—C11	179.3 (3)
N3—C1—C2—C3	170.1 (2)	C13—O1—C12—N2	0.3 (3)
C5—C2—C3—C4	0.0 (4)	C13—O1—C12—C11	−179.0 (2)
C1—C2—C3—C4	176.9 (3)	C8—C11—C12—N2	15.1 (5)
C2—C3—C4—S3	0.0 (3)	S1—C11—C12—N2	−165.6 (2)
C5—S3—C4—C3	0.0 (2)	C8—C11—C12—O1	−165.8 (2)
C3—C2—C5—C6	179.2 (3)	S1—C11—C12—O1	13.5 (3)
C1—C2—C5—C6	2.2 (4)	N2—N1—C13—O1	0.7 (3)
C3—C2—C5—S3	0.0 (3)	N2—N1—C13—C14	−177.0 (2)
C1—C2—C5—S3	−177.00 (19)	C12—O1—C13—N1	−0.6 (3)
C4—S3—C5—C2	0.0 (2)	C12—O1—C13—C14	177.3 (2)
C4—S3—C5—C6	−179.2 (2)	N1—C13—C14—C18	−14.6 (4)
C2—C5—C6—C7	−20.7 (4)	O1—C13—C14—C18	167.9 (2)
S3—C5—C6—C7	158.4 (2)	N1—C13—C14—C15	162.4 (3)
C1—N3—C7—C6	−67.1 (3)	O1—C13—C14—C15	−15.1 (4)
S2—N3—C7—C6	149.6 (2)	C16—N4—C15—C14	−0.2 (4)
C5—C6—C7—N3	49.6 (3)	C18—C14—C15—N4	0.2 (4)
O3—S2—C8—C11	29.5 (3)	C13—C14—C15—N4	−176.8 (3)
O2—S2—C8—C11	160.2 (2)	C15—N4—C16—C17	−0.7 (5)
N3—S2—C8—C11	−86.6 (2)	N4—C16—C17—C18	1.6 (4)
O3—S2—C8—C9	−155.4 (2)	N4—C16—C17—Br1	−178.6 (2)
O2—S2—C8—C9	−24.7 (2)	C16—C17—C18—C14	−1.5 (4)
N3—S2—C8—C9	88.4 (2)	Br1—C17—C18—C14	178.66 (19)
C11—C8—C9—C10	−0.1 (3)	C15—C14—C18—C17	0.7 (4)
S2—C8—C9—C10	−175.9 (2)	C13—C14—C18—C17	177.8 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7A···N2	0.97	2.52	3.283 (4)	136
C10—H10A···O3i	0.93	2.49	3.330 (3)	150
C10—H10A···N2i	0.93	2.42	3.183 (3)	139

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7A⋯N2	0.97	2.52	3.283 (4)	136
C10—H10A⋯O3i	0.93	2.49	3.330 (3)	150
C10—H10A⋯N2i	0.93	2.42	3.183 (3)	139

Symmetry code: (i) .