6-Amino-8-(2-bromo-phen-yl)-1,7,8,8a-tetrahydro-3H-isothio-chromene-5,7,7-tricarbonitrile dimethyl-formamide solvate.

In the title compound, C(18)H(13)BrN(4)S·C(3)H(7)NO, the thio-pyran ring and the adjacent six-numbered ring adopt distorted boat conformations. The mol-ecules, lying about inversion centers, form hydrogen-bonded dimers involving one of the H atoms on the amino group with the N atom of a cyano group of an adjacent mol-ecule, resulting in a 12-membered ring system [R(2) (2)(12) ring motif]. The other H atom of the amino group forms an inter-molecular hydrogen bond with the O atom of the dimethyl-formamide (DMF) mol-ecule. Another lone pair of electrons on the same carbonyl O atom of DMF mol-ecule forms a non-classical C-H⋯O inter-molecular hydrogen bond, resulting in a chain of mol-ecules.

Related literature

For the biological activity of related compounds, see: Karsten & Krisztina (2007 ▶); Wang et al. (1998 ▶, 2006 ▶); Zhang et al. (2008 ▶). For a related structure, see: (Mereiter et al. 2000 ▶). For graph-set notation, see: Bernstein et al. (1994 ▶).

Experimental

Crystal data

C18H13BrN4S·C3H7NO

M = 470.39

Monoclinic,

a = 14.7733 (4) Å

b = 9.1710 (3) Å

c = 15.7897 (4) Å

β = 92.478 (2)°

V = 2137.28 (11) Å3

Z = 4

Mo Kα radiation

μ = 2.04 mm−1

T = 296 K

0.44 × 0.36 × 0.05 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.422, T max = 0.900

13894 measured reflections

3841 independent reflections

2723 reflections with I > 2σ(I)

R int = 0.032

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.098

S = 1.04

3841 reflections

270 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.32 e Å−3

Δρmin = −0.23 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809039105/pv2211sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809039105/pv2211Isup2.hkl

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

C18H13BrN4S·C3H7NO	F(000) = 960
Mr = 470.39	Dx = 1.462 Mg m−3
Monoclinic, P21/c	Melting point = 530–532 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 14.7733 (4) Å	Cell parameters from 4434 reflections
b = 9.1710 (3) Å	θ = 2.6–22.6°
c = 15.7897 (4) Å	µ = 2.04 mm−1
β = 92.478 (2)°	T = 296 K
V = 2137.28 (11) Å3	Plate, colourless
Z = 4	0.44 × 0.36 × 0.05 mm

Bruker SMART CCD area-detector diffractometer	3841 independent reflections
Radiation source: fine-focus sealed tube	2723 reflections with I > 2σ(I)
graphite	Rint = 0.032
φ and ω scans	θmax = 25.2°, θmin = 1.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→17
Tmin = 0.422, Tmax = 0.900	k = −9→10
13894 measured reflections	l = −18→16

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0486P)2 + 0.4516P] where P = (Fo2 + 2Fc2)/3
3841 reflections	(Δ/σ)max = 0.001
270 parameters	Δρmax = 0.32 e Å−3
0 restraints	Δρmin = −0.23 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
Br1	0.26620 (2)	0.56202 (4)	0.85086 (2)	0.06278 (16)
S1	−0.08662 (5)	0.75087 (9)	0.66332 (5)	0.0568 (2)
C9	−0.08406 (19)	0.4522 (3)	0.65402 (18)	0.0437 (7)
H9A	−0.1163	0.3654	0.6481	0.052*
C1	0.15871 (17)	0.5338 (3)	0.66735 (17)	0.0353 (6)
H1A	0.1505	0.4901	0.7231	0.042*
C5	0.00049 (18)	0.4509 (3)	0.62871 (16)	0.0347 (6)
C6	0.06373 (18)	0.5807 (3)	0.63235 (17)	0.0361 (6)
H6A	0.0694	0.6179	0.5746	0.043*
C4	0.03938 (18)	0.3190 (3)	0.59218 (15)	0.0341 (6)
N3	0.1653 (2)	0.1753 (3)	0.54913 (17)	0.0465 (7)
C2	0.19932 (18)	0.4123 (3)	0.61042 (17)	0.0347 (6)
C10	−0.02003 (18)	0.2040 (3)	0.56411 (17)	0.0400 (7)
C3	0.12949 (18)	0.2955 (3)	0.58223 (16)	0.0351 (6)
C11	0.2753 (2)	0.3418 (3)	0.66002 (19)	0.0447 (7)
N4	−0.06658 (17)	0.1117 (3)	0.53989 (18)	0.0582 (7)
C12	0.2385 (2)	0.4739 (3)	0.5331 (2)	0.0428 (7)
C13	0.22316 (18)	0.6621 (3)	0.68104 (17)	0.0379 (6)
C18	0.27173 (19)	0.6886 (3)	0.75675 (17)	0.0431 (7)
C7	0.02957 (19)	0.7038 (3)	0.6874 (2)	0.0506 (8)
H7A	0.0670	0.7893	0.6799	0.061*
H7B	0.0361	0.6749	0.7465	0.061*
N1	0.2686 (2)	0.5194 (3)	0.47443 (19)	0.0646 (8)
N2	0.3323 (2)	0.2913 (3)	0.69975 (19)	0.0716 (8)
C14	0.2323 (2)	0.7653 (3)	0.6164 (2)	0.0489 (8)
H14A	0.2002	0.7527	0.5650	0.059*
C8	−0.1330 (2)	0.5780 (3)	0.6909 (2)	0.0555 (8)
H8A	−0.1309	0.5687	0.7522	0.067*
H8B	−0.1961	0.5745	0.6713	0.067*
C15	0.2877 (2)	0.8846 (3)	0.6273 (2)	0.0628 (9)
H15A	0.2939	0.9498	0.5829	0.075*
C17	0.3260 (2)	0.8109 (4)	0.7679 (2)	0.0633 (9)
H17A	0.3570	0.8270	0.8196	0.076*
C16	0.3338 (3)	0.9082 (4)	0.7027 (3)	0.0738 (11)
H16A	0.3704	0.9901	0.7099	0.089*
O1	0.65268 (16)	0.8365 (3)	0.50459 (17)	0.0758 (7)
N5	0.53153 (19)	0.7245 (3)	0.55611 (19)	0.0675 (8)
C19	0.6160 (2)	0.7654 (4)	0.5584 (3)	0.0671 (10)
H19A	0.6517	0.7376	0.6056	0.081*
C20	0.4938 (3)	0.6366 (6)	0.6229 (3)	0.1171 (17)
H20A	0.5399	0.6179	0.6662	0.176*
H20B	0.4721	0.5458	0.5995	0.176*
H20C	0.4445	0.6882	0.6469	0.176*
C21	0.4730 (3)	0.7652 (6)	0.4850 (3)	0.1229 (18)
H21A	0.5064	0.8220	0.4460	0.184*
H21B	0.4233	0.8218	0.5044	0.184*
H21C	0.4501	0.6790	0.4571	0.184*
H3A	0.131 (2)	0.119 (3)	0.5268 (18)	0.042 (9)*
H3B	0.222 (3)	0.169 (4)	0.533 (2)	0.074 (12)*

	U11	U22	U33	U12	U13	U23
Br1	0.0733 (3)	0.0739 (3)	0.0399 (2)	−0.01304 (18)	−0.01097 (16)	0.00090 (16)
S1	0.0557 (5)	0.0529 (5)	0.0613 (5)	0.0176 (4)	−0.0045 (4)	−0.0084 (4)
C9	0.0404 (18)	0.0459 (17)	0.0447 (17)	−0.0014 (14)	0.0006 (14)	−0.0004 (13)
C1	0.0387 (15)	0.0341 (15)	0.0329 (15)	−0.0012 (12)	−0.0014 (12)	0.0010 (12)
C5	0.0372 (16)	0.0374 (16)	0.0289 (14)	0.0018 (12)	−0.0060 (12)	0.0021 (11)
C6	0.0403 (16)	0.0359 (16)	0.0317 (15)	0.0042 (12)	−0.0025 (12)	−0.0003 (12)
C4	0.0368 (16)	0.0320 (14)	0.0333 (14)	−0.0021 (12)	−0.0014 (12)	0.0026 (12)
N3	0.0385 (16)	0.0382 (16)	0.0624 (18)	−0.0015 (13)	−0.0031 (14)	−0.0120 (13)
C2	0.0353 (15)	0.0323 (15)	0.0359 (15)	0.0021 (12)	−0.0037 (12)	0.0026 (12)
C10	0.0356 (16)	0.0396 (17)	0.0450 (17)	0.0027 (14)	0.0039 (13)	0.0003 (13)
C3	0.0416 (17)	0.0286 (15)	0.0343 (15)	0.0002 (12)	−0.0055 (12)	0.0018 (12)
C11	0.0474 (18)	0.0373 (17)	0.0487 (18)	0.0025 (14)	−0.0066 (14)	−0.0090 (14)
N4	0.0469 (16)	0.0502 (16)	0.077 (2)	−0.0109 (14)	0.0022 (14)	−0.0160 (14)
C12	0.0422 (17)	0.0393 (17)	0.0467 (19)	−0.0041 (13)	−0.0005 (15)	−0.0043 (14)
C13	0.0391 (16)	0.0300 (15)	0.0444 (16)	0.0005 (12)	−0.0024 (13)	−0.0013 (13)
C18	0.0443 (17)	0.0378 (16)	0.0468 (17)	−0.0017 (13)	−0.0022 (14)	−0.0030 (13)
C7	0.0465 (18)	0.0455 (17)	0.059 (2)	0.0053 (14)	−0.0028 (15)	−0.0130 (15)
N1	0.075 (2)	0.0656 (19)	0.0541 (18)	−0.0172 (15)	0.0148 (16)	−0.0007 (15)
N2	0.070 (2)	0.0647 (19)	0.077 (2)	0.0193 (16)	−0.0305 (16)	−0.0106 (16)
C14	0.0499 (19)	0.0363 (17)	0.0597 (19)	−0.0021 (14)	−0.0066 (15)	0.0070 (15)
C8	0.0440 (18)	0.066 (2)	0.057 (2)	0.0067 (15)	0.0035 (15)	−0.0056 (16)
C15	0.063 (2)	0.0366 (18)	0.089 (3)	0.0007 (17)	0.005 (2)	0.0175 (18)
C17	0.060 (2)	0.053 (2)	0.076 (2)	−0.0118 (17)	−0.0147 (18)	−0.0157 (19)
C16	0.071 (3)	0.040 (2)	0.109 (3)	−0.0164 (17)	−0.012 (2)	−0.004 (2)
O1	0.0585 (16)	0.0812 (18)	0.0890 (19)	−0.0077 (13)	0.0197 (14)	−0.0008 (15)
N5	0.0437 (17)	0.084 (2)	0.075 (2)	0.0016 (15)	0.0046 (15)	0.0082 (17)
C19	0.054 (2)	0.074 (3)	0.073 (3)	0.0110 (19)	−0.0049 (19)	−0.013 (2)
C20	0.099 (4)	0.121 (4)	0.135 (4)	0.020 (3)	0.041 (3)	0.047 (3)
C21	0.074 (3)	0.190 (5)	0.103 (4)	−0.014 (3)	−0.022 (3)	0.025 (4)

Br1—C18	1.890 (3)	C13—C18	1.389 (4)
S1—C8	1.788 (3)	C13—C14	1.402 (4)
S1—C7	1.795 (3)	C18—C17	1.385 (4)
C9—C5	1.328 (4)	C7—H7A	0.9700
C9—C8	1.494 (4)	C7—H7B	0.9700
C9—H9A	0.9300	C14—C15	1.372 (4)
C1—C13	1.523 (4)	C14—H14A	0.9300
C1—C6	1.546 (4)	C8—H8A	0.9700
C1—C2	1.568 (4)	C8—H8B	0.9700
C1—H1A	0.9800	C15—C16	1.363 (5)
C5—C4	1.468 (4)	C15—H15A	0.9300
C5—C6	1.512 (4)	C17—C16	1.371 (5)
C6—C7	1.525 (4)	C17—H17A	0.9300
C6—H6A	0.9800	C16—H16A	0.9300
C4—C3	1.364 (4)	O1—C19	1.216 (4)
C4—C10	1.431 (4)	N5—C19	1.302 (4)
N3—C3	1.339 (4)	N5—C21	1.436 (5)
N3—H3A	0.79 (3)	N5—C20	1.457 (5)
N3—H3B	0.89 (4)	C19—H19A	0.9300
C2—C12	1.485 (4)	C20—H20A	0.9600
C2—C11	1.488 (4)	C20—H20B	0.9600
C2—C3	1.539 (4)	C20—H20C	0.9600
C10—N4	1.145 (3)	C21—H21A	0.9600
C11—N2	1.128 (4)	C21—H21B	0.9600
C12—N1	1.126 (4)	C21—H21C	0.9600
C8—S1—C7	96.21 (14)	C6—C7—S1	113.2 (2)
C5—C9—C8	127.0 (3)	C6—C7—H7A	108.9
C5—C9—H9A	116.5	S1—C7—H7A	108.9
C8—C9—H9A	116.5	C6—C7—H7B	108.9
C13—C1—C6	112.8 (2)	S1—C7—H7B	108.9
C13—C1—C2	112.2 (2)	H7A—C7—H7B	107.7
C6—C1—C2	110.9 (2)	C15—C14—C13	121.5 (3)
C13—C1—H1A	106.8	C15—C14—H14A	119.2
C6—C1—H1A	106.8	C13—C14—H14A	119.2
C2—C1—H1A	106.8	C9—C8—S1	113.1 (2)
C9—C5—C4	121.0 (2)	C9—C8—H8A	109.0
C9—C5—C6	124.7 (2)	S1—C8—H8A	109.0
C4—C5—C6	114.3 (2)	C9—C8—H8B	109.0
C5—C6—C7	112.7 (2)	S1—C8—H8B	109.0
C5—C6—C1	110.2 (2)	H8A—C8—H8B	107.8
C7—C6—C1	108.6 (2)	C16—C15—C14	120.6 (3)
C5—C6—H6A	108.4	C16—C15—H15A	119.7
C7—C6—H6A	108.4	C14—C15—H15A	119.7
C1—C6—H6A	108.4	C16—C17—C18	119.9 (3)
C3—C4—C10	115.9 (2)	C16—C17—H17A	120.1
C3—C4—C5	125.2 (2)	C18—C17—H17A	120.1
C10—C4—C5	119.0 (2)	C15—C16—C17	119.8 (3)
C3—N3—H3A	117 (2)	C15—C16—H16A	120.1
C3—N3—H3B	124 (2)	C17—C16—H16A	120.1
H3A—N3—H3B	115 (3)	C19—N5—C21	119.4 (3)
C12—C2—C11	106.6 (2)	C19—N5—C20	122.4 (4)
C12—C2—C3	107.9 (2)	C21—N5—C20	118.2 (3)
C11—C2—C3	109.3 (2)	O1—C19—N5	126.2 (4)
C12—C2—C1	111.9 (2)	O1—C19—H19A	116.9
C11—C2—C1	107.8 (2)	N5—C19—H19A	116.9
C3—C2—C1	113.1 (2)	N5—C20—H20A	109.5
N4—C10—C4	178.4 (3)	N5—C20—H20B	109.5
N3—C3—C4	125.4 (3)	H20A—C20—H20B	109.5
N3—C3—C2	114.5 (2)	N5—C20—H20C	109.5
C4—C3—C2	120.1 (2)	H20A—C20—H20C	109.5
N2—C11—C2	177.7 (3)	H20B—C20—H20C	109.5
N1—C12—C2	179.4 (3)	N5—C21—H21A	109.5
C18—C13—C14	116.4 (2)	N5—C21—H21B	109.5
C18—C13—C1	123.6 (2)	H21A—C21—H21B	109.5
C14—C13—C1	119.9 (2)	N5—C21—H21C	109.5
C17—C18—C13	121.7 (3)	H21A—C21—H21C	109.5
C17—C18—Br1	116.2 (2)	H21B—C21—H21C	109.5
C13—C18—Br1	122.1 (2)
C8—C9—C5—C4	−179.0 (3)	C11—C2—C3—C4	133.3 (3)
C8—C9—C5—C6	−0.4 (5)	C1—C2—C3—C4	13.2 (3)
C9—C5—C6—C7	13.9 (4)	C12—C2—C11—N2	121 (9)
C4—C5—C6—C7	−167.4 (2)	C3—C2—C11—N2	−123 (9)
C9—C5—C6—C1	135.4 (3)	C1—C2—C11—N2	1(9)
C4—C5—C6—C1	−46.0 (3)	C11—C2—C12—N1	40 (33)
C13—C1—C6—C5	−174.2 (2)	C3—C2—C12—N1	−77 (33)
C2—C1—C6—C5	58.9 (3)	C1—C2—C12—N1	158 (100)
C13—C1—C6—C7	−50.4 (3)	C6—C1—C13—C18	127.9 (3)
C2—C1—C6—C7	−177.3 (2)	C2—C1—C13—C18	−106.0 (3)
C9—C5—C4—C3	−164.3 (3)	C6—C1—C13—C14	−48.9 (3)
C6—C5—C4—C3	17.0 (4)	C2—C1—C13—C14	77.3 (3)
C9—C5—C4—C10	15.7 (4)	C14—C13—C18—C17	0.3 (4)
C6—C5—C4—C10	−163.0 (2)	C1—C13—C18—C17	−176.5 (3)
C13—C1—C2—C12	−47.4 (3)	C14—C13—C18—Br1	179.3 (2)
C6—C1—C2—C12	79.8 (3)	C1—C13—C18—Br1	2.4 (4)
C13—C1—C2—C11	69.6 (3)	C5—C6—C7—S1	−49.2 (3)
C6—C1—C2—C11	−163.2 (2)	C1—C6—C7—S1	−171.53 (19)
C13—C1—C2—C3	−169.4 (2)	C8—S1—C7—C6	62.6 (2)
C6—C1—C2—C3	−42.2 (3)	C18—C13—C14—C15	1.1 (4)
C3—C4—C10—N4	−48 (11)	C1—C13—C14—C15	178.1 (3)
C5—C4—C10—N4	131 (11)	C5—C9—C8—S1	22.8 (4)
C10—C4—C3—N3	−0.2 (4)	C7—S1—C8—C9	−47.3 (3)
C5—C4—C3—N3	179.8 (3)	C13—C14—C15—C16	−1.8 (5)
C10—C4—C3—C2	−179.9 (2)	C13—C18—C17—C16	−1.1 (5)
C5—C4—C3—C2	0.1 (4)	Br1—C18—C17—C16	179.9 (3)
C12—C2—C3—N3	69.1 (3)	C14—C15—C16—C17	1.0 (5)
C11—C2—C3—N3	−46.5 (3)	C18—C17—C16—C15	0.4 (5)
C1—C2—C3—N3	−166.6 (2)	C21—N5—C19—O1	−0.4 (6)
C12—C2—C3—C4	−111.2 (3)	C20—N5—C19—O1	178.7 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···O1i	0.89 (4)	1.96 (4)	2.856 (4)	178 (3)
N3—H3A···N4ii	0.79 (3)	2.54 (3)	3.294 (4)	162 (3)
C15—H15A···O1iii	0.93	2.54	3.438 (4)	162

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3B⋯O1i	0.89 (4)	1.96 (4)	2.856 (4)	178 (3)
N3—H3A⋯N4ii	0.79 (3)	2.54 (3)	3.294 (4)	162 (3)
C15—H15A⋯O1iii	0.93	2.54	3.438 (4)	162

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