1-[5-(4-Bromo-phen-yl)-3-(4-fluoro-phen-yl)-4,5-dihydro-1H-pyrazol-1-yl]butan-1-one.

In the title compound, C(19)H(18)BrFN(2)O, the benzene rings form dihedral angles of 5.38 (7) and 85.48 (7)° with the mean plane of the 4,5-dihydro-1H-pyrazole ring (r.m.s. deviation = 0.0849 Å), which approximates to an envelope conformation with the -CH(2)- group as the flap. The dihedral angle between the benzene rings is 82.86 (7)°. In the crystal, C-H⋯F and C-H⋯O hydrogen bonds link the mol-ecules to form inversion dimers and together these generate chains along [011]. The crystal packing also features C-H⋯π inter-actions.

Related literature

For background to pyrazoline derivatives, see: Fun et al. (2010 ▶); Samshuddin et al. (2011 ▶). For related structures, see: Fun, Quah et al. (2012 ▶); Fun, Loh et al. (2012 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C19H18BrFN2O

M = 389.26

Triclinic,

a = 6.7502 (3) Å

b = 10.1253 (5) Å

c = 13.7792 (8) Å

α = 105.354 (1)°

β = 98.976 (1)°

γ = 107.369 (1)°

V = 838.01 (7) Å3

Z = 2

Mo Kα radiation

μ = 2.47 mm−1

T = 100 K

0.28 × 0.23 × 0.08 mm

Data collection

Bruker SMART APEXII DUO CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.546, T max = 0.823

17838 measured reflections

4816 independent reflections

4458 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.025

wR(F 2) = 0.066

S = 1.06

4816 reflections

218 parameters

H-atom parameters constrained

Δρmax = 0.49 e Å−3

Δρmin = −0.63 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/S1600536812034368/hb6918sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812034368/hb6918Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812034368/hb6918Isup3.cml

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

C19H18BrFN2O	Z = 2
Mr = 389.26	F(000) = 396
Triclinic, P1	Dx = 1.543 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.7502 (3) Å	Cell parameters from 9994 reflections
b = 10.1253 (5) Å	θ = 3.1–33.0°
c = 13.7792 (8) Å	µ = 2.47 mm−1
α = 105.354 (1)°	T = 100 K
β = 98.976 (1)°	Plate, colourless
γ = 107.369 (1)°	0.28 × 0.23 × 0.08 mm
V = 838.01 (7) Å3

Bruker SMART APEXII DUO CCD diffractometer	4816 independent reflections
Radiation source: fine-focus sealed tube	4458 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
φ and ω scans	θmax = 30.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −9→9
Tmin = 0.546, Tmax = 0.823	k = −14→14
17838 measured reflections	l = −19→19

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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.066	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0342P)2 + 0.3618P] where P = (Fo2 + 2Fc2)/3
4816 reflections	(Δ/σ)max = 0.001
218 parameters	Δρmax = 0.49 e Å−3
0 restraints	Δρmin = −0.63 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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	0.29346 (2)	1.105034 (15)	0.629792 (11)	0.02435 (5)
F1	1.22640 (16)	0.30984 (10)	0.49188 (7)	0.02653 (19)
O1	0.44837 (15)	0.73712 (10)	0.95847 (7)	0.01715 (18)
N1	0.69619 (17)	0.56573 (11)	0.78382 (8)	0.01292 (18)
N2	0.65164 (17)	0.67234 (11)	0.85431 (8)	0.01310 (19)
C1	0.8653 (2)	0.39253 (14)	0.64641 (10)	0.0171 (2)
H1A	0.7351	0.3438	0.6608	0.020*
C2	0.9522 (2)	0.31297 (15)	0.57824 (11)	0.0201 (2)
H2A	0.8834	0.2100	0.5457	0.024*
C3	1.1414 (2)	0.38745 (16)	0.55897 (10)	0.0184 (2)
C4	1.2486 (2)	0.53618 (15)	0.60412 (10)	0.0175 (2)
H4A	1.3788	0.5836	0.5892	0.021*
C5	1.1603 (2)	0.61528 (14)	0.67260 (10)	0.0150 (2)
H5A	1.2310	0.7182	0.7049	0.018*
C6	0.96862 (19)	0.54438 (13)	0.69403 (9)	0.0133 (2)
C7	0.87764 (19)	0.62814 (13)	0.76656 (9)	0.0127 (2)
C8	0.98525 (19)	0.78883 (13)	0.83134 (10)	0.0149 (2)
H8A	1.0376	0.8493	0.7883	0.018*
H8B	1.1065	0.8046	0.8891	0.018*
C9	0.80040 (19)	0.82300 (13)	0.87232 (9)	0.0131 (2)
H9A	0.8511	0.8801	0.9484	0.016*
C10	0.68978 (19)	0.89988 (13)	0.81387 (9)	0.0129 (2)
C11	0.6768 (2)	0.87756 (14)	0.70818 (10)	0.0165 (2)
H11A	0.7482	0.8192	0.6735	0.020*
C12	0.5613 (2)	0.93907 (14)	0.65294 (10)	0.0183 (2)
H12A	0.5527	0.9229	0.5810	0.022*
C13	0.4586 (2)	1.02469 (14)	0.70504 (10)	0.0167 (2)
C14	0.4748 (2)	1.05360 (13)	0.81074 (10)	0.0158 (2)
H14A	0.4084	1.1155	0.8458	0.019*
C15	0.59010 (19)	0.99012 (13)	0.86442 (9)	0.0143 (2)
H15A	0.6012	1.0085	0.9367	0.017*
C16	0.48284 (19)	0.63837 (13)	0.89729 (9)	0.0128 (2)
C17	0.34922 (19)	0.47749 (13)	0.86741 (9)	0.0137 (2)
H17A	0.4423	0.4249	0.8877	0.016*
H17B	0.2912	0.4363	0.7909	0.016*
C18	0.1640 (2)	0.45162 (14)	0.91894 (10)	0.0157 (2)
H18A	0.0674	0.5007	0.8965	0.019*
H18B	0.2213	0.4959	0.9954	0.019*
C19	0.0363 (2)	0.28890 (16)	0.89136 (11)	0.0226 (3)
H19A	−0.0778	0.2765	0.9279	0.034*
H19B	0.1321	0.2396	0.9123	0.034*
H19C	−0.0274	0.2459	0.8161	0.034*

	U11	U22	U33	U12	U13	U23
Br1	0.02830 (8)	0.02231 (8)	0.02494 (8)	0.01276 (6)	0.00379 (5)	0.00926 (5)
F1	0.0359 (5)	0.0316 (5)	0.0200 (4)	0.0222 (4)	0.0148 (4)	0.0051 (3)
O1	0.0176 (4)	0.0163 (4)	0.0177 (4)	0.0058 (3)	0.0095 (3)	0.0033 (3)
N1	0.0128 (4)	0.0133 (4)	0.0136 (4)	0.0056 (4)	0.0056 (4)	0.0037 (4)
N2	0.0127 (4)	0.0109 (4)	0.0156 (5)	0.0035 (4)	0.0068 (4)	0.0030 (4)
C1	0.0156 (5)	0.0162 (5)	0.0185 (6)	0.0053 (4)	0.0053 (5)	0.0042 (5)
C2	0.0235 (6)	0.0180 (6)	0.0174 (6)	0.0097 (5)	0.0041 (5)	0.0018 (5)
C3	0.0242 (6)	0.0247 (6)	0.0122 (5)	0.0163 (5)	0.0071 (5)	0.0054 (5)
C4	0.0169 (6)	0.0244 (6)	0.0167 (5)	0.0108 (5)	0.0085 (5)	0.0092 (5)
C5	0.0142 (5)	0.0174 (5)	0.0153 (5)	0.0070 (4)	0.0058 (4)	0.0058 (4)
C6	0.0128 (5)	0.0162 (5)	0.0123 (5)	0.0069 (4)	0.0041 (4)	0.0047 (4)
C7	0.0110 (5)	0.0134 (5)	0.0137 (5)	0.0047 (4)	0.0036 (4)	0.0040 (4)
C8	0.0110 (5)	0.0142 (5)	0.0187 (5)	0.0032 (4)	0.0066 (4)	0.0037 (4)
C9	0.0117 (5)	0.0120 (5)	0.0147 (5)	0.0026 (4)	0.0059 (4)	0.0032 (4)
C10	0.0126 (5)	0.0115 (5)	0.0134 (5)	0.0027 (4)	0.0057 (4)	0.0027 (4)
C11	0.0190 (6)	0.0170 (5)	0.0154 (5)	0.0077 (5)	0.0096 (5)	0.0041 (4)
C12	0.0224 (6)	0.0186 (6)	0.0151 (5)	0.0072 (5)	0.0083 (5)	0.0054 (5)
C13	0.0168 (5)	0.0142 (5)	0.0194 (6)	0.0050 (4)	0.0054 (5)	0.0063 (4)
C14	0.0151 (5)	0.0131 (5)	0.0193 (6)	0.0046 (4)	0.0078 (4)	0.0036 (4)
C15	0.0145 (5)	0.0132 (5)	0.0142 (5)	0.0034 (4)	0.0072 (4)	0.0026 (4)
C16	0.0113 (5)	0.0154 (5)	0.0124 (5)	0.0046 (4)	0.0041 (4)	0.0052 (4)
C17	0.0123 (5)	0.0140 (5)	0.0146 (5)	0.0035 (4)	0.0048 (4)	0.0048 (4)
C18	0.0127 (5)	0.0191 (5)	0.0165 (5)	0.0039 (4)	0.0063 (4)	0.0080 (4)
C19	0.0180 (6)	0.0216 (6)	0.0240 (7)	−0.0006 (5)	0.0067 (5)	0.0087 (5)

Br1—C13	1.8991 (13)	C9—C10	1.5177 (17)
F1—C3	1.3606 (14)	C9—H9A	1.0000
O1—C16	1.2322 (15)	C10—C15	1.3960 (16)
N1—C7	1.2901 (16)	C10—C11	1.3978 (17)
N1—N2	1.3888 (13)	C11—C12	1.3894 (19)
N2—C16	1.3608 (15)	C11—H11A	0.9500
N2—C9	1.4846 (15)	C12—C13	1.3902 (17)
C1—C2	1.3891 (17)	C12—H12A	0.9500
C1—C6	1.4013 (17)	C13—C14	1.3872 (18)
C1—H1A	0.9500	C14—C15	1.3918 (18)
C2—C3	1.381 (2)	C14—H14A	0.9500
C2—H2A	0.9500	C15—H15A	0.9500
C3—C4	1.375 (2)	C16—C17	1.5127 (17)
C4—C5	1.3957 (16)	C17—C18	1.5219 (16)
C4—H4A	0.9500	C17—H17A	0.9900
C5—C6	1.3975 (17)	C17—H17B	0.9900
C5—H5A	0.9500	C18—C19	1.5232 (19)
C6—C7	1.4660 (16)	C18—H18A	0.9900
C7—C8	1.5148 (17)	C18—H18B	0.9900
C8—C9	1.5394 (16)	C19—H19A	0.9800
C8—H8A	0.9900	C19—H19B	0.9800
C8—H8B	0.9900	C19—H19C	0.9800
C7—N1—N2	107.76 (10)	C15—C10—C9	120.04 (11)
C16—N2—N1	122.03 (10)	C11—C10—C9	121.35 (10)
C16—N2—C9	125.22 (10)	C12—C11—C10	121.24 (11)
N1—N2—C9	112.69 (9)	C12—C11—H11A	119.4
C2—C1—C6	120.32 (12)	C10—C11—H11A	119.4
C2—C1—H1A	119.8	C11—C12—C13	118.64 (12)
C6—C1—H1A	119.8	C11—C12—H12A	120.7
C3—C2—C1	118.28 (12)	C13—C12—H12A	120.7
C3—C2—H2A	120.9	C14—C13—C12	121.63 (12)
C1—C2—H2A	120.9	C14—C13—Br1	119.20 (9)
F1—C3—C4	118.22 (12)	C12—C13—Br1	119.17 (10)
F1—C3—C2	118.38 (12)	C13—C14—C15	118.73 (11)
C4—C3—C2	123.40 (12)	C13—C14—H14A	120.6
C3—C4—C5	117.96 (12)	C15—C14—H14A	120.6
C3—C4—H4A	121.0	C14—C15—C10	121.14 (11)
C5—C4—H4A	121.0	C14—C15—H15A	119.4
C4—C5—C6	120.54 (12)	C10—C15—H15A	119.4
C4—C5—H5A	119.7	O1—C16—N2	119.59 (11)
C6—C5—H5A	119.7	O1—C16—C17	123.68 (11)
C5—C6—C1	119.50 (11)	N2—C16—C17	116.72 (10)
C5—C6—C7	120.20 (11)	C16—C17—C18	112.50 (10)
C1—C6—C7	120.30 (11)	C16—C17—H17A	109.1
N1—C7—C6	121.06 (11)	C18—C17—H17A	109.1
N1—C7—C8	113.62 (10)	C16—C17—H17B	109.1
C6—C7—C8	125.25 (10)	C18—C17—H17B	109.1
C7—C8—C9	101.79 (9)	H17A—C17—H17B	107.8
C7—C8—H8A	111.4	C17—C18—C19	111.82 (11)
C9—C8—H8A	111.4	C17—C18—H18A	109.3
C7—C8—H8B	111.4	C19—C18—H18A	109.3
C9—C8—H8B	111.4	C17—C18—H18B	109.3
H8A—C8—H8B	109.3	C19—C18—H18B	109.3
N2—C9—C10	110.08 (10)	H18A—C18—H18B	107.9
N2—C9—C8	100.37 (9)	C18—C19—H19A	109.5
C10—C9—C8	114.80 (10)	C18—C19—H19B	109.5
N2—C9—H9A	110.4	H19A—C19—H19B	109.5
C10—C9—H9A	110.4	C18—C19—H19C	109.5
C8—C9—H9A	110.4	H19A—C19—H19C	109.5
C15—C10—C11	118.55 (11)	H19B—C19—H19C	109.5
C7—N1—N2—C16	−172.51 (11)	C7—C8—C9—N2	17.81 (11)
C7—N1—N2—C9	10.01 (13)	C7—C8—C9—C10	−100.16 (11)
C6—C1—C2—C3	−0.1 (2)	N2—C9—C10—C15	94.86 (13)
C1—C2—C3—F1	−179.72 (12)	C8—C9—C10—C15	−152.80 (11)
C1—C2—C3—C4	0.3 (2)	N2—C9—C10—C11	−82.31 (14)
F1—C3—C4—C5	179.79 (11)	C8—C9—C10—C11	30.03 (16)
C2—C3—C4—C5	−0.2 (2)	C15—C10—C11—C12	−2.23 (19)
C3—C4—C5—C6	−0.02 (19)	C9—C10—C11—C12	174.98 (12)
C4—C5—C6—C1	0.20 (19)	C10—C11—C12—C13	0.3 (2)
C4—C5—C6—C7	179.61 (11)	C11—C12—C13—C14	2.1 (2)
C2—C1—C6—C5	−0.13 (19)	C11—C12—C13—Br1	−178.25 (10)
C2—C1—C6—C7	−179.54 (12)	C12—C13—C14—C15	−2.6 (2)
N2—N1—C7—C6	−179.32 (10)	Br1—C13—C14—C15	177.84 (9)
N2—N1—C7—C8	3.50 (14)	C13—C14—C15—C10	0.53 (19)
C5—C6—C7—N1	176.94 (12)	C11—C10—C15—C14	1.81 (18)
C1—C6—C7—N1	−3.66 (18)	C9—C10—C15—C14	−175.44 (11)
C5—C6—C7—C8	−6.23 (18)	N1—N2—C16—O1	−179.08 (11)
C1—C6—C7—C8	173.18 (12)	C9—N2—C16—O1	−1.92 (18)
N1—C7—C8—C9	−14.48 (14)	N1—N2—C16—C17	2.02 (16)
C6—C7—C8—C9	168.48 (11)	C9—N2—C16—C17	179.18 (11)
C16—N2—C9—C10	−74.12 (14)	O1—C16—C17—C18	1.59 (17)
N1—N2—C9—C10	103.27 (11)	N2—C16—C17—C18	−179.55 (10)
C16—N2—C9—C8	164.49 (11)	C16—C17—C18—C19	−177.81 (11)
N1—N2—C9—C8	−18.12 (12)

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11A···F1i	0.95	2.37	3.1873 (17)	144
C14—H14A···O1ii	0.95	2.57	3.1832 (16)	122
C5—H5A···Cg2iii	0.95	2.68	3.5453 (15)	152
C17—H17B···Cg1iv	0.99	2.70	3.5488 (14)	144

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C1–C5 and C10–C15 benzene rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11A⋯F1i	0.95	2.37	3.1873 (17)	144
C14—H14A⋯O1ii	0.95	2.57	3.1832 (16)	122
C5—H5A⋯Cg2iii	0.95	2.68	3.5453 (15)	152
C17—H17B⋯Cg1iv	0.99	2.70	3.5488 (14)	144

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