Crystal structure of 6-amino-4-(3-bromo-4-meth-oxy-phen-yl)-3-methyl-2,4-di-hydro-pyrano[2,3-c]pyrazole-5-carbo-nitrile dimethyl sulfoxide monosolvate.

In the pyrazole mol-ecule of the title solvate, C15H13BrN4O2·C2H6OS, the dihedral angle between the benzene ring and the mean plane of the di-hydro-pyrano[2,3-c]pyrazole ring system [r.m.s deviation = 0.031 (2) Å] is 86.71 (14)°. In the crystal, the pyrazole mol-ecules are linked by N-H⋯N hydrogen bonds, forming a layer parallel to (10-1). The pyrazole and dimethyl sulfoxide mol-ecules are connected by an N-H⋯O hydrogen bond.

Related literature

For the applications and biological activities of pyrazole derivative, see: Balbia et al. (2011 ▸); Insuasty et al. (2010 ▸); Szabó et al. (2008 ▸); Perchellet et al. (2006 ▸); Tanitame et al. (2004 ▸, 2005 ▸); Abadi et al. (2003 ▸). For crystal structures of related compounds, see: Sharma et al. (2014 ▸).

Experimental

Crystal data

C15H13BrN4O2·C2H6OS

M = 439.33

Monoclinic,

a = 13.4982 (6) Å

b = 8.3470 (4) Å

c = 17.7173 (8) Å

β = 101.510 (1)°

V = 1956.05 (16) Å3

Z = 4

Mo Kα radiation

μ = 2.23 mm−1

T = 273 K

0.54 × 0.51 × 0.33 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▸) T min = 0.345, T max = 0.479

9464 measured reflections

3642 independent reflections

2776 reflections with I > 2σ(I)

R int = 0.019

Refinement

R[F 2 > 2σ(F 2)] = 0.052

wR(F 2) = 0.149

S = 1.04

3642 reflections

247 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.15 e Å−3

Δρmin = −0.59 e Å−3

Data collection: SMART (Bruker, 2000 ▸); cell refinement: SAINT (Bruker, 2000 ▸); 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, PARST (Nardelli, 1995 ▸) and PLATON (Spek, 2009 ▸).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015010543/is5403sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015010543/is5403Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015010543/is5403Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015010543/is5403fig1.tif

The mol­ecular structure of the title compound with displacement ellipsoids drawn at 30% probability level. H atoms have been omitted.

Click here for additional data file.

. DOI: 10.1107/S2056989015010543/is5403fig2.tif

A crystal packing view of the title compound. Only H atoms involved in the hydrogen bonds (dashed lines) are shown.

CCDC reference: 1404448

Additional supporting information: crystallographic information; 3D view; checkCIF report

C15H13BrN4O2·C2H6OS	F(000) = 896
Mr = 439.33	Dx = 1.492 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3172 reflections
a = 13.4982 (6) Å	θ = 2.4–25.5°
b = 8.3470 (4) Å	µ = 2.23 mm−1
c = 17.7173 (8) Å	T = 273 K
β = 101.510 (1)°	BLOCK, colorless
V = 1956.05 (16) Å3	0.54 × 0.51 × 0.33 mm
Z = 4

Bruker SMART APEX CCD area-detector diffractometer	3642 independent reflections
Radiation source: fine-focus sealed tube	2776 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
ω scan	θmax = 25.5°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −16→8
Tmin = 0.345, Tmax = 0.479	k = −10→10
9464 measured reflections	l = −16→21

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.149	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0714P)2 + 2.3987P] where P = (Fo2 + 2Fc2)/3
3642 reflections	(Δ/σ)max < 0.001
247 parameters	Δρmax = 1.15 e Å−3
0 restraints	Δρmin = −0.59 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	0.53684 (5)	0.80041 (9)	0.10616 (4)	0.1100 (3)
S2	0.41262 (9)	1.33033 (14)	0.16737 (7)	0.0725 (4)
O1	0.80217 (17)	0.8729 (2)	−0.16690 (11)	0.0408 (5)
C11	0.8828 (2)	0.8290 (3)	−0.03464 (16)	0.0318 (6)
C10	0.8569 (2)	0.7805 (4)	−0.10982 (17)	0.0347 (7)
C7	0.8596 (2)	0.9926 (3)	−0.00378 (16)	0.0328 (6)
H7A	0.9235	1.0499	0.0131	0.039*
N1	0.7159 (2)	1.1133 (3)	−0.19466 (15)	0.0415 (6)
N3	0.8795 (3)	0.6418 (4)	−0.13885 (18)	0.0499 (8)
C12	0.9385 (2)	0.7201 (4)	0.01801 (17)	0.0378 (7)
C8	0.7977 (2)	1.0822 (3)	−0.07006 (16)	0.0328 (6)
C6	0.8067 (2)	0.9806 (4)	0.06440 (16)	0.0348 (7)
N2	0.7048 (2)	1.2445 (3)	−0.15155 (16)	0.0432 (7)
C9	0.7727 (2)	1.0195 (3)	−0.14372 (16)	0.0345 (7)
C2	0.6640 (3)	0.9018 (5)	0.1172 (2)	0.0530 (9)
C13	0.7513 (3)	1.2299 (4)	−0.07755 (18)	0.0388 (7)
C4	0.7998 (3)	1.0387 (5)	0.19660 (19)	0.0527 (9)
H4A	0.8299	1.0837	0.2436	0.063*
N4	0.9847 (3)	0.6326 (4)	0.06142 (17)	0.0545 (8)
C5	0.8497 (3)	1.0446 (4)	0.13548 (18)	0.0458 (8)
H5A	0.9131	1.0925	0.1423	0.055*
O2	0.6509 (2)	0.9565 (4)	0.24480 (16)	0.0713 (8)
C1	0.7129 (3)	0.9085 (4)	0.05641 (18)	0.0439 (8)
H1B	0.6826	0.8641	0.0093	0.053*
C14	0.7477 (3)	1.3584 (4)	−0.0197 (2)	0.0588 (10)
H14A	0.7084	1.4468	−0.0441	0.088*
H14B	0.8151	1.3940	0.0015	0.088*
H14C	0.7171	1.3170	0.0208	0.088*
C15	0.6936 (4)	1.0205 (7)	0.3188 (2)	0.0878 (16)
H15A	0.6470	1.0061	0.3527	0.132*
H15B	0.7068	1.1327	0.3140	0.132*
H15C	0.7557	0.9659	0.3394	0.132*
C3	0.7068 (3)	0.9673 (4)	0.18880 (19)	0.0499 (9)
O3	0.4267 (3)	1.5021 (4)	0.1919 (3)	0.1011 (12)
C16	0.4432 (4)	1.2187 (6)	0.2534 (3)	0.0736 (12)
H16A	0.3899	1.2292	0.2817	0.110*
H16B	0.5052	1.2583	0.2840	0.110*
H16C	0.4511	1.1079	0.2413	0.110*
C17	0.5216 (5)	1.2847 (8)	0.1298 (4)	0.106 (2)
H17A	0.5175	1.3380	0.0812	0.159*
H17B	0.5255	1.1711	0.1226	0.159*
H17C	0.5808	1.3204	0.1652	0.159*
H3A	0.913 (3)	0.572 (5)	−0.110 (2)	0.055 (11)*
H3B	0.850 (3)	0.620 (4)	−0.185 (2)	0.041 (9)*
H2A	0.670 (3)	1.320 (4)	−0.1703 (19)	0.034 (9)*

	U11	U22	U33	U12	U13	U23
Br1	0.0905 (4)	0.1520 (6)	0.1031 (5)	−0.0652 (4)	0.0569 (4)	−0.0322 (4)
S2	0.0579 (6)	0.0701 (7)	0.0833 (8)	0.0025 (5)	−0.0009 (5)	0.0238 (6)
O1	0.0583 (14)	0.0336 (11)	0.0269 (10)	0.0099 (10)	0.0000 (9)	0.0002 (9)
C11	0.0335 (15)	0.0346 (15)	0.0262 (14)	0.0017 (12)	0.0030 (11)	0.0019 (12)
C10	0.0387 (16)	0.0351 (16)	0.0299 (15)	0.0015 (13)	0.0060 (12)	0.0021 (12)
C7	0.0349 (15)	0.0341 (16)	0.0285 (14)	−0.0028 (12)	0.0042 (12)	−0.0005 (12)
N1	0.0535 (16)	0.0364 (14)	0.0329 (13)	0.0044 (12)	0.0042 (12)	0.0039 (11)
N3	0.072 (2)	0.0428 (17)	0.0293 (15)	0.0176 (16)	−0.0038 (14)	−0.0042 (13)
C12	0.0441 (17)	0.0405 (17)	0.0288 (15)	0.0015 (15)	0.0075 (13)	−0.0036 (14)
C8	0.0380 (16)	0.0325 (15)	0.0277 (14)	−0.0033 (12)	0.0063 (12)	0.0010 (12)
C6	0.0414 (17)	0.0341 (16)	0.0286 (15)	0.0038 (13)	0.0064 (12)	0.0007 (12)
N2	0.0552 (18)	0.0322 (15)	0.0413 (16)	0.0082 (13)	0.0077 (13)	0.0058 (12)
C9	0.0425 (17)	0.0305 (15)	0.0302 (15)	−0.0014 (13)	0.0065 (12)	0.0025 (12)
C2	0.056 (2)	0.055 (2)	0.053 (2)	−0.0082 (18)	0.0221 (17)	−0.0011 (17)
C13	0.0484 (18)	0.0331 (16)	0.0360 (16)	−0.0018 (14)	0.0114 (14)	0.0015 (13)
C4	0.066 (2)	0.062 (2)	0.0303 (17)	0.0052 (19)	0.0112 (16)	−0.0061 (16)
N4	0.069 (2)	0.0520 (18)	0.0379 (16)	0.0160 (16)	0.0002 (14)	0.0015 (14)
C5	0.0481 (19)	0.055 (2)	0.0331 (17)	−0.0028 (16)	0.0045 (14)	−0.0050 (15)
O2	0.089 (2)	0.084 (2)	0.0512 (16)	0.0065 (17)	0.0397 (15)	0.0057 (14)
C1	0.0467 (19)	0.0522 (19)	0.0343 (16)	−0.0085 (16)	0.0115 (14)	−0.0051 (14)
C14	0.087 (3)	0.0398 (19)	0.049 (2)	0.0094 (19)	0.014 (2)	−0.0070 (16)
C15	0.105 (4)	0.127 (4)	0.040 (2)	0.034 (3)	0.034 (2)	0.005 (2)
C3	0.066 (2)	0.051 (2)	0.0377 (18)	0.0106 (18)	0.0239 (16)	0.0077 (15)
O3	0.104 (3)	0.0544 (19)	0.151 (4)	0.0290 (18)	0.041 (2)	0.030 (2)
C16	0.070 (3)	0.065 (3)	0.084 (3)	0.003 (2)	0.011 (2)	0.020 (2)
C17	0.119 (5)	0.109 (5)	0.101 (4)	0.031 (4)	0.047 (4)	0.014 (4)

Br1—C2	1.889 (4)	N2—H2A	0.81 (3)
S2—O3	1.499 (4)	C2—C1	1.371 (5)
S2—C16	1.764 (5)	C2—C3	1.397 (5)
S2—C17	1.773 (6)	C13—C14	1.492 (5)
O1—C10	1.365 (4)	C4—C3	1.372 (5)
O1—C9	1.374 (4)	C4—C5	1.385 (5)
C11—C10	1.369 (4)	C4—H4A	0.9300
C11—C12	1.408 (4)	C5—H5A	0.9300
C11—C7	1.527 (4)	O2—C3	1.365 (4)
C10—N3	1.327 (4)	O2—C15	1.426 (6)
C7—C8	1.498 (4)	C1—H1B	0.9300
C7—C6	1.524 (4)	C14—H14A	0.9600
C7—H7A	0.9800	C14—H14B	0.9600
N1—C9	1.319 (4)	C14—H14C	0.9600
N1—N2	1.360 (4)	C15—H15A	0.9600
N3—H3A	0.84 (4)	C15—H15B	0.9600
N3—H3B	0.86 (4)	C15—H15C	0.9600
C12—N4	1.150 (4)	C16—H16A	0.9600
C8—C13	1.377 (4)	C16—H16B	0.9600
C8—C9	1.384 (4)	C16—H16C	0.9600
C6—C1	1.384 (4)	C17—H17A	0.9600
C6—C5	1.385 (4)	C17—H17B	0.9600
N2—C13	1.341 (4)	C17—H17C	0.9600
O3—S2—C16	105.1 (2)	C8—C13—C14	130.9 (3)
O3—S2—C17	104.3 (3)	C3—C4—C5	121.0 (3)
C16—S2—C17	98.2 (3)	C3—C4—H4A	119.5
C10—O1—C9	115.3 (2)	C5—C4—H4A	119.5
C10—C11—C12	116.9 (3)	C6—C5—C4	121.1 (3)
C10—C11—C7	125.6 (3)	C6—C5—H5A	119.5
C12—C11—C7	117.4 (2)	C4—C5—H5A	119.5
N3—C10—O1	109.7 (3)	C3—O2—C15	117.6 (4)
N3—C10—C11	126.9 (3)	C2—C1—C6	120.7 (3)
O1—C10—C11	123.3 (3)	C2—C1—H1B	119.6
C8—C7—C6	112.2 (2)	C6—C1—H1B	119.6
C8—C7—C11	106.7 (2)	C13—C14—H14A	109.5
C6—C7—C11	112.7 (2)	C13—C14—H14B	109.5
C8—C7—H7A	108.3	H14A—C14—H14B	109.5
C6—C7—H7A	108.3	C13—C14—H14C	109.5
C11—C7—H7A	108.3	H14A—C14—H14C	109.5
C9—N1—N2	102.0 (2)	H14B—C14—H14C	109.5
C10—N3—H3A	120 (3)	O2—C15—H15A	109.5
C10—N3—H3B	117 (2)	O2—C15—H15B	109.5
H3A—N3—H3B	122 (4)	H15A—C15—H15B	109.5
N4—C12—C11	179.2 (4)	O2—C15—H15C	109.5
C13—C8—C9	103.1 (3)	H15A—C15—H15C	109.5
C13—C8—C7	133.9 (3)	H15B—C15—H15C	109.5
C9—C8—C7	122.9 (3)	O2—C3—C4	125.7 (3)
C1—C6—C5	118.0 (3)	O2—C3—C2	116.5 (4)
C1—C6—C7	120.8 (3)	C4—C3—C2	117.8 (3)
C5—C6—C7	121.2 (3)	S2—C16—H16A	109.5
C13—N2—N1	113.1 (3)	S2—C16—H16B	109.5
C13—N2—H2A	126 (2)	H16A—C16—H16B	109.5
N1—N2—H2A	121 (2)	S2—C16—H16C	109.5
N1—C9—O1	119.2 (3)	H16A—C16—H16C	109.5
N1—C9—C8	114.8 (3)	H16B—C16—H16C	109.5
O1—C9—C8	126.0 (3)	S2—C17—H17A	109.5
C1—C2—C3	121.4 (3)	S2—C17—H17B	109.5
C1—C2—Br1	120.4 (3)	H17A—C17—H17B	109.5
C3—C2—Br1	118.2 (3)	S2—C17—H17C	109.5
N2—C13—C8	106.9 (3)	H17A—C17—H17C	109.5
N2—C13—C14	122.2 (3)	H17B—C17—H17C	109.5
C9—O1—C10—N3	179.1 (3)	C7—C8—C9—N1	178.5 (3)
C9—O1—C10—C11	−0.9 (4)	C13—C8—C9—O1	179.3 (3)
C12—C11—C10—N3	−0.7 (5)	C7—C8—C9—O1	−1.9 (5)
C7—C11—C10—N3	177.0 (3)	N1—N2—C13—C8	0.9 (4)
C12—C11—C10—O1	179.4 (3)	N1—N2—C13—C14	−179.0 (3)
C7—C11—C10—O1	−2.9 (5)	C9—C8—C13—N2	−0.4 (3)
C10—C11—C7—C8	4.0 (4)	C7—C8—C13—N2	−179.0 (3)
C12—C11—C7—C8	−178.4 (3)	C9—C8—C13—C14	179.6 (4)
C10—C11—C7—C6	127.6 (3)	C7—C8—C13—C14	0.9 (6)
C12—C11—C7—C6	−54.7 (4)	C1—C6—C5—C4	−0.8 (5)
C6—C7—C8—C13	52.8 (4)	C7—C6—C5—C4	177.6 (3)
C11—C7—C8—C13	176.8 (3)	C3—C4—C5—C6	0.8 (6)
C6—C7—C8—C9	−125.6 (3)	C3—C2—C1—C6	0.1 (6)
C11—C7—C8—C9	−1.6 (4)	Br1—C2—C1—C6	−179.1 (3)
C8—C7—C6—C1	58.8 (4)	C5—C6—C1—C2	0.3 (5)
C11—C7—C6—C1	−61.8 (4)	C7—C6—C1—C2	−178.1 (3)
C8—C7—C6—C5	−119.6 (3)	C15—O2—C3—C4	−2.0 (6)
C11—C7—C6—C5	119.8 (3)	C15—O2—C3—C2	179.1 (4)
C9—N1—N2—C13	−1.0 (4)	C5—C4—C3—O2	−179.2 (3)
N2—N1—C9—O1	−178.8 (3)	C5—C4—C3—C2	−0.4 (6)
N2—N1—C9—C8	0.8 (4)	C1—C2—C3—O2	178.8 (3)
C10—O1—C9—N1	−177.1 (3)	Br1—C2—C3—O2	−2.0 (5)
C10—O1—C9—C8	3.4 (4)	C1—C2—C3—C4	−0.1 (6)
C13—C8—C9—N1	−0.3 (4)	Br1—C2—C3—C4	179.1 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O3i	0.82 (3)	1.96 (4)	2.762 (5)	166 (4)
N3—H3A···N4ii	0.84 (4)	2.26 (4)	3.080 (5)	165 (3)
N3—H3B···N1iii	0.86 (3)	2.14 (4)	2.983 (4)	169 (3)

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N2H2AO3i	0.82(3)	1.96(4)	2.762(5)	166(4)
N3H3AN4ii	0.84(4)	2.26(4)	3.080(5)	165(3)
N3H3BN1iii	0.86(3)	2.14(4)	2.983(4)	169(3)

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