(2Z)-3-(3-Bromo-anilino)-1-(5-hy-droxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)but-2-en-1-one.

In the title compound, C(20)H(18)BrN(3)O(2), the central carbonyl group forms amine-N-H⋯O and hy-droxy-O-H⋯O hydrogen bonds, which lead to two fused S(6) rings. The N-bound phenyl ring is coplanar with the five-membered ring to which it is attached [dihedral angle = 5.22 (18)°], but the dihedral angle [33.87 (17)°] between the terminal phenyl and bromo-benzene rings indicates an overall twist in the mol-ecule. In the crystal packing, mol-ecules assemble into dimeric aggregates via C-H⋯π inter-actions.

Related literature

For background to the synthesis, see: Gelin et al. (1983 ▶); Bendaas et al. (1999 ▶). For the structures of the 4-chloro and 4-meth­oxy derivatives, see: Asiri, Al-Youbi, Alamry et al. (2011 ▶); Asiri, Al-Youbi, Faidallah et al. (2011 ▶).

Experimental

Crystal data

C20H18BrN3O2

M = 412.28

Monoclinic,

a = 8.7065 (5) Å

b = 11.7982 (8) Å

c = 17.5954 (12) Å

β = 101.536 (6)°

V = 1770.9 (2) Å3

Z = 4

Mo Kα radiation

μ = 2.34 mm−1

T = 100 K

0.25 × 0.10 × 0.05 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T min = 0.592, T max = 0.892

7812 measured reflections

4041 independent reflections

3033 reflections with I > 2σ(I)

R int = 0.048

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.105

S = 1.01

4041 reflections

245 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.58 e Å−3

Δρmin = −0.47 e Å−3

Data collection: CrysAlis PRO (Agilent, 2011 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812006939/sj5199sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812006939/sj5199Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812006939/sj5199Isup3.cml

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

C20H18BrN3O2	F(000) = 840
Mr = 412.28	Dx = 1.546 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1846 reflections
a = 8.7065 (5) Å	θ = 2.4–27.5°
b = 11.7982 (8) Å	µ = 2.34 mm−1
c = 17.5954 (12) Å	T = 100 K
β = 101.536 (6)°	Bead, yellow
V = 1770.9 (2) Å3	0.25 × 0.10 × 0.05 mm
Z = 4

Agilent SuperNova Dual diffractometer with an Atlas detector	4041 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	3033 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.048
Detector resolution: 10.4041 pixels mm-1	θmax = 27.6°, θmin = 2.4°
ω scan	h = −10→11
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −11→14
Tmin = 0.592, Tmax = 0.892	l = −14→22
7812 measured reflections

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.105	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ2(Fo2) + (0.0373P)2] where P = (Fo2 + 2Fc2)/3
4041 reflections	(Δ/σ)max = 0.001
245 parameters	Δρmax = 0.58 e Å−3
2 restraints	Δρmin = −0.47 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.

	x	y	z	Uiso*/Ueq
Br1	−0.18793 (4)	0.67333 (3)	0.911231 (19)	0.01841 (12)
O1	0.4430 (3)	0.3220 (2)	0.53800 (14)	0.0156 (5)
H1	0.409 (7)	0.351 (5)	0.575 (2)	0.11 (2)*
O2	0.3101 (2)	0.44759 (19)	0.61666 (13)	0.0160 (5)
N1	0.3917 (3)	0.3741 (2)	0.40520 (15)	0.0126 (6)
N2	0.3061 (3)	0.4591 (2)	0.35913 (16)	0.0148 (6)
N3	0.1528 (3)	0.5638 (2)	0.70229 (17)	0.0160 (6)
H3	0.218 (3)	0.510 (2)	0.694 (2)	0.034 (12)*
C1	0.4707 (3)	0.2917 (3)	0.36862 (19)	0.0142 (7)
C2	0.4743 (4)	0.3022 (3)	0.2904 (2)	0.0174 (7)
H2	0.4249	0.3651	0.2617	0.021*
C3	0.5495 (4)	0.2218 (3)	0.2542 (2)	0.0205 (8)
H3A	0.5514	0.2293	0.2006	0.025*
C4	0.6222 (4)	0.1298 (3)	0.2955 (2)	0.0190 (8)
H4	0.6733	0.0740	0.2705	0.023*
C5	0.6196 (4)	0.1204 (3)	0.3735 (2)	0.0197 (8)
H5	0.6701	0.0578	0.4019	0.024*
C6	0.5448 (4)	0.2005 (3)	0.4112 (2)	0.0176 (7)
H6	0.5442	0.1932	0.4649	0.021*
C7	0.3772 (3)	0.3860 (3)	0.48029 (19)	0.0131 (7)
C8	0.2809 (3)	0.4804 (3)	0.48482 (19)	0.0129 (7)
C9	0.2418 (3)	0.5222 (3)	0.40686 (18)	0.0130 (7)
C10	0.1464 (4)	0.6231 (3)	0.37541 (19)	0.0184 (7)
H10A	0.1370	0.6263	0.3190	0.028*
H10B	0.1978	0.6922	0.3989	0.028*
H10C	0.0418	0.6172	0.3877	0.028*
C11	0.2435 (3)	0.5109 (3)	0.55732 (19)	0.0155 (7)
C12	0.1439 (3)	0.6012 (3)	0.56902 (19)	0.0154 (7)
H12	0.1024	0.6472	0.5254	0.018*
C13	0.1018 (3)	0.6283 (3)	0.63815 (19)	0.0152 (7)
C14	0.0010 (4)	0.7306 (3)	0.6434 (2)	0.0178 (7)
H14A	0.0427	0.7721	0.6914	0.027*
H14B	−0.1065	0.7062	0.6435	0.027*
H14C	0.0014	0.7801	0.5987	0.027*
C15	0.1320 (4)	0.5704 (3)	0.77953 (19)	0.0165 (7)
C16	0.2537 (4)	0.5276 (3)	0.8356 (2)	0.0242 (8)
H16	0.3453	0.4987	0.8208	0.029*
C17	0.2420 (4)	0.5269 (3)	0.9128 (2)	0.0256 (9)
H17	0.3254	0.4963	0.9504	0.031*
C18	0.1116 (4)	0.5696 (3)	0.9364 (2)	0.0220 (8)
H18	0.1046	0.5707	0.9896	0.026*
C19	−0.0089 (4)	0.6110 (3)	0.87941 (19)	0.0154 (7)
C20	−0.0032 (4)	0.6109 (3)	0.80153 (19)	0.0172 (7)
H20	−0.0893	0.6377	0.7639	0.021*

	U11	U22	U33	U12	U13	U23
Br1	0.01953 (19)	0.0200 (2)	0.01736 (19)	0.00189 (14)	0.00775 (13)	−0.00017 (14)
O1	0.0169 (11)	0.0183 (13)	0.0119 (12)	0.0042 (10)	0.0035 (9)	0.0031 (10)
O2	0.0196 (11)	0.0165 (12)	0.0120 (12)	0.0033 (10)	0.0034 (9)	−0.0002 (10)
N1	0.0147 (13)	0.0130 (14)	0.0110 (14)	0.0010 (11)	0.0043 (10)	0.0009 (11)
N2	0.0159 (13)	0.0132 (14)	0.0150 (15)	0.0020 (12)	0.0024 (11)	0.0021 (12)
N3	0.0175 (14)	0.0164 (16)	0.0154 (15)	0.0035 (13)	0.0069 (11)	0.0011 (13)
C1	0.0119 (15)	0.0175 (17)	0.0134 (17)	−0.0035 (14)	0.0028 (12)	−0.0040 (14)
C2	0.0162 (16)	0.0213 (19)	0.0148 (18)	−0.0002 (15)	0.0032 (13)	−0.0013 (15)
C3	0.0192 (17)	0.027 (2)	0.0165 (19)	−0.0036 (16)	0.0072 (14)	−0.0036 (16)
C4	0.0150 (16)	0.0172 (18)	0.026 (2)	−0.0022 (15)	0.0072 (14)	−0.0088 (15)
C5	0.0193 (17)	0.0179 (19)	0.022 (2)	0.0018 (15)	0.0036 (14)	−0.0020 (16)
C6	0.0152 (16)	0.0216 (19)	0.0167 (18)	−0.0043 (15)	0.0046 (13)	−0.0020 (15)
C7	0.0141 (15)	0.0160 (17)	0.0097 (16)	−0.0028 (14)	0.0034 (12)	0.0004 (14)
C8	0.0117 (15)	0.0145 (17)	0.0121 (17)	−0.0026 (14)	0.0016 (12)	0.0014 (14)
C9	0.0140 (15)	0.0129 (17)	0.0123 (17)	−0.0014 (14)	0.0031 (12)	0.0016 (14)
C10	0.0221 (17)	0.0194 (19)	0.0146 (18)	0.0035 (15)	0.0055 (14)	−0.0007 (15)
C11	0.0127 (15)	0.0188 (18)	0.0150 (18)	−0.0068 (14)	0.0031 (13)	0.0007 (14)
C12	0.0147 (15)	0.0198 (18)	0.0117 (17)	−0.0013 (14)	0.0028 (12)	0.0017 (14)
C13	0.0129 (15)	0.0164 (18)	0.0163 (18)	−0.0049 (14)	0.0026 (13)	0.0000 (14)
C14	0.0201 (17)	0.0186 (19)	0.0151 (18)	−0.0006 (15)	0.0043 (13)	−0.0016 (14)
C15	0.0205 (16)	0.0162 (18)	0.0136 (18)	−0.0024 (15)	0.0051 (13)	−0.0002 (14)
C16	0.0202 (17)	0.033 (2)	0.020 (2)	0.0076 (17)	0.0049 (14)	0.0007 (17)
C17	0.0235 (18)	0.036 (2)	0.0172 (19)	0.0091 (17)	0.0031 (14)	0.0048 (17)
C18	0.0273 (18)	0.026 (2)	0.0129 (18)	−0.0004 (16)	0.0039 (14)	0.0031 (15)
C19	0.0177 (16)	0.0133 (18)	0.0174 (18)	0.0001 (14)	0.0090 (13)	0.0004 (14)
C20	0.0165 (16)	0.0220 (19)	0.0129 (17)	−0.0016 (15)	0.0025 (13)	−0.0009 (15)

Br1—C19	1.906 (3)	C8—C11	1.425 (4)
O1—C7	1.303 (4)	C8—C9	1.433 (4)
O1—H1	0.843 (10)	C9—C10	1.493 (4)
O2—C11	1.320 (4)	C10—H10A	0.9800
N1—C7	1.359 (4)	C10—H10B	0.9800
N1—N2	1.406 (4)	C10—H10C	0.9800
N1—C1	1.417 (4)	C11—C12	1.415 (5)
N2—C9	1.327 (4)	C12—C13	1.376 (4)
N3—C13	1.360 (4)	C12—H12	0.9500
N3—C15	1.409 (4)	C13—C14	1.506 (5)
N3—H3	0.881 (10)	C14—H14A	0.9800
C1—C2	1.389 (4)	C14—H14B	0.9800
C1—C6	1.395 (5)	C14—H14C	0.9800
C2—C3	1.379 (5)	C15—C16	1.391 (4)
C2—H2	0.9500	C15—C20	1.395 (5)
C3—C4	1.386 (5)	C16—C17	1.382 (5)
C3—H3A	0.9500	C16—H16	0.9500
C4—C5	1.381 (5)	C17—C18	1.380 (5)
C4—H4	0.9500	C17—H17	0.9500
C5—C6	1.389 (5)	C18—C19	1.387 (4)
C5—H5	0.9500	C18—H18	0.9500
C6—H6	0.9500	C19—C20	1.381 (4)
C7—C8	1.405 (4)	C20—H20	0.9500
C7—O1—H1	102 (4)	H10A—C10—H10B	109.5
C7—N1—N2	110.2 (3)	C9—C10—H10C	109.5
C7—N1—C1	131.3 (3)	H10A—C10—H10C	109.5
N2—N1—C1	118.5 (3)	H10B—C10—H10C	109.5
C9—N2—N1	106.1 (3)	O2—C11—C12	119.7 (3)
C13—N3—C15	133.3 (3)	O2—C11—C8	115.0 (3)
C13—N3—H3	113 (3)	C12—C11—C8	125.3 (3)
C15—N3—H3	114 (3)	C13—C12—C11	125.6 (3)
C2—C1—C6	120.1 (3)	C13—C12—H12	117.2
C2—C1—N1	119.9 (3)	C11—C12—H12	117.2
C6—C1—N1	120.0 (3)	N3—C13—C12	120.2 (3)
C3—C2—C1	120.2 (3)	N3—C13—C14	119.7 (3)
C3—C2—H2	119.9	C12—C13—C14	120.1 (3)
C1—C2—H2	119.9	C13—C14—H14A	109.5
C2—C3—C4	120.4 (3)	C13—C14—H14B	109.5
C2—C3—H3A	119.8	H14A—C14—H14B	109.5
C4—C3—H3A	119.8	C13—C14—H14C	109.5
C5—C4—C3	119.2 (3)	H14A—C14—H14C	109.5
C5—C4—H4	120.4	H14B—C14—H14C	109.5
C3—C4—H4	120.4	C16—C15—C20	119.5 (3)
C4—C5—C6	121.6 (3)	C16—C15—N3	115.9 (3)
C4—C5—H5	119.2	C20—C15—N3	124.4 (3)
C6—C5—H5	119.2	C17—C16—C15	120.2 (3)
C5—C6—C1	118.6 (3)	C17—C16—H16	119.9
C5—C6—H6	120.7	C15—C16—H16	119.9
C1—C6—H6	120.7	C18—C17—C16	121.4 (3)
O1—C7—N1	125.9 (3)	C18—C17—H17	119.3
O1—C7—C8	126.1 (3)	C16—C17—H17	119.3
N1—C7—C8	108.0 (3)	C17—C18—C19	117.4 (3)
C7—C8—C11	119.8 (3)	C17—C18—H18	121.3
C7—C8—C9	104.4 (3)	C19—C18—H18	121.3
C11—C8—C9	135.8 (3)	C20—C19—C18	123.0 (3)
N2—C9—C8	111.3 (3)	C20—C19—Br1	119.0 (2)
N2—C9—C10	119.1 (3)	C18—C19—Br1	117.9 (3)
C8—C9—C10	129.6 (3)	C19—C20—C15	118.4 (3)
C9—C10—H10A	109.5	C19—C20—H20	120.8
C9—C10—H10B	109.5	C15—C20—H20	120.8
C7—N1—N2—C9	0.6 (3)	C11—C8—C9—N2	−178.1 (3)
C1—N1—N2—C9	178.5 (3)	C7—C8—C9—C10	−178.0 (3)
C7—N1—C1—C2	−176.6 (3)	C11—C8—C9—C10	3.2 (6)
N2—N1—C1—C2	5.9 (4)	C7—C8—C11—O2	2.5 (4)
C7—N1—C1—C6	3.2 (5)	C9—C8—C11—O2	−178.9 (3)
N2—N1—C1—C6	−174.2 (3)	C7—C8—C11—C12	−177.7 (3)
C6—C1—C2—C3	0.9 (5)	C9—C8—C11—C12	1.0 (6)
N1—C1—C2—C3	−179.3 (3)	O2—C11—C12—C13	−3.1 (5)
C1—C2—C3—C4	−0.1 (5)	C8—C11—C12—C13	177.0 (3)
C2—C3—C4—C5	−0.5 (5)	C15—N3—C13—C12	179.1 (3)
C3—C4—C5—C6	0.5 (5)	C15—N3—C13—C14	0.0 (5)
C4—C5—C6—C1	0.3 (5)	C11—C12—C13—N3	−2.1 (5)
C2—C1—C6—C5	−0.9 (5)	C11—C12—C13—C14	176.9 (3)
N1—C1—C6—C5	179.2 (3)	C13—N3—C15—C16	−150.3 (3)
N2—N1—C7—O1	−179.2 (3)	C13—N3—C15—C20	33.1 (5)
C1—N1—C7—O1	3.2 (5)	C20—C15—C16—C17	−1.1 (5)
N2—N1—C7—C8	−0.2 (3)	N3—C15—C16—C17	−177.9 (3)
C1—N1—C7—C8	−177.8 (3)	C15—C16—C17—C18	−0.9 (6)
O1—C7—C8—C11	−2.2 (5)	C16—C17—C18—C19	1.4 (6)
N1—C7—C8—C11	178.7 (3)	C17—C18—C19—C20	0.1 (5)
O1—C7—C8—C9	178.8 (3)	C17—C18—C19—Br1	−178.7 (3)
N1—C7—C8—C9	−0.3 (3)	C18—C19—C20—C15	−2.0 (5)
N1—N2—C9—C8	−0.8 (3)	Br1—C19—C20—C15	176.7 (2)
N1—N2—C9—C10	178.1 (3)	C16—C15—C20—C19	2.5 (5)
C7—C8—C9—N2	0.7 (3)	N3—C15—C20—C19	179.0 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.84 (1)	1.68 (3)	2.468 (3)	154 (6)
N3—H3···O2	0.88 (1)	1.87 (3)	2.617 (4)	142 (4)
C14—H14B···Cg1i	0.98	2.69	3.495 (4)	140

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the N1/N2/C7–C9 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2	0.84 (1)	1.68 (3)	2.468 (3)	154 (6)
N3—H3⋯O2	0.88 (1)	1.87 (3)	2.617 (4)	142 (4)
C14—H14B⋯Cg1i	0.98	2.69	3.495 (4)	140

Symmetry code: (i) .