4-{[(1E)-(3,5-Dibromo-2-hydroxy­phen­yl)methyl­ene]­amino}-1,5-dimethyl-2-phenyl-1,2-dihydro-3H-pyrazol-3-one

The crystal structure of the title compound, C₁₈H₁₅Br₂N₃O₂, shows a strong intra­molecular O—H...N hydrogen bond [N...O = 2.609 (4) Å, O—H = 0.90 Å, H...N = 1.80 Å and O—H...N = 148°], which leads to the existence of a phenol–imine tautomer.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.032
• wR factor = 0.078
• Data-to-parameter ratio = 13.4

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT431_ALERT_2_B Short Inter HL..A Contact  Br1    ..  O2      ..       2.98 Ang.

Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT164_ALERT_4_C Nr. of Refined C-H H-Atoms in Heavy-At Struct...          3
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: SMART (Bruker 2002); cell refinement: SAINT (Bruker 2002); data reduction: SAINT and SHELXTL (Bruker 2002); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

'4-{[(1E)-(3,5-dibromo-2-hydroxyphenyl)methylene]amino} -1,5-dimethyl-2-phenyl-1,2-dihydro-3H-pyrazol-3-one'

Crystal data

C18H15Br2N3O2	Dx = 1.737 Mg m^−3
Mr = 465.15	Melting point: 501-502 K K
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.092 (5) Å	Cell parameters from 3452 reflections
b = 8.231 (5) Å	θ = 2.6–25.3°
c = 30.49 (2) Å	µ = 4.57 mm^−1
β = 91.725 (12)°	T = 293 K
V = 1779 (2) Å^3	Block, orange
Z = 4	0.24 × 0.19 × 0.12 mm
F(000) = 920

Data collection

Siemens SMART CCD area detector diffractometer	3224 independent reflections
Radiation source: fine-focus sealed tube	2631 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
Detector resolution: 7.32 pixels mm^-1	θmax = 25.3°, θmin = 2.6°
ω and φ scans	h = −8→8
Absorption correction: multi-scan (SADABS; Bruker 2002)	k = −9→9
Tmin = 0.367, Tmax = 0.578	l = −33→36
9143 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.078	w = 1/[σ^2(Fo^2) + (0.035P)^2 + 0.3014P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
3207 reflections	Δρmax = 0.41 e Å^−3
239 parameters	Δρmin = −0.34 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0018 (4)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Br1	1.06352 (4)	0.03039 (4)	0.590757 (10)	0.04738 (13)
Br2	0.41203 (5)	0.36835 (5)	0.640272 (10)	0.05478 (14)
O1	0.3302 (3)	0.3650 (3)	0.54230 (7)	0.0459 (6)
H1A	0.3099	0.3580	0.5132	0.070*
O2	0.5981 (3)	0.1603 (3)	0.37960 (7)	0.0490 (6)
N1	0.3894 (3)	0.2885 (3)	0.46084 (7)	0.0367 (6)
N2	0.1681 (3)	0.3457 (3)	0.35547 (8)	0.0376 (6)
N3	0.3248 (3)	0.2511 (3)	0.34344 (7)	0.0370 (6)
C1	0.6023 (4)	0.2147 (4)	0.51982 (9)	0.0357 (7)
C2	0.7709 (4)	0.1374 (4)	0.53182 (10)	0.0413 (8)
H2A	0.8437	0.0899	0.5104	0.050*
C3	0.8300 (4)	0.1309 (4)	0.57502 (10)	0.0379 (7)
C4	0.7228 (4)	0.1983 (4)	0.60739 (9)	0.0392 (7)
H4A	0.7626	0.1922	0.6367	0.047*
C5	0.5559 (4)	0.2750 (4)	0.59562 (9)	0.0371 (7)
C6	0.4920 (4)	0.2867 (4)	0.55238 (9)	0.0349 (7)
C7	0.5433 (4)	0.2178 (4)	0.47414 (10)	0.0413 (7)
H7A	0.6183	0.1673	0.4537	0.050*
C8	0.3358 (4)	0.2878 (4)	0.41651 (9)	0.0339 (7)
C9	0.1744 (4)	0.3540 (4)	0.40016 (9)	0.0359 (7)
C10	0.4415 (4)	0.2235 (4)	0.38093 (9)	0.0358 (7)
C11	0.0163 (5)	0.4285 (5)	0.42436 (13)	0.0497 (9)
C12	−0.0105 (4)	0.3141 (4)	0.33117 (10)	0.0466 (8)
H12A	−0.1069	0.3843	0.3419	0.070*
H12B	−0.0467	0.2029	0.3352	0.070*
H12C	0.0056	0.3347	0.3005	0.070*
C13	0.3982 (4)	0.2686 (4)	0.30074 (9)	0.0358 (7)
C14	0.3486 (5)	0.3989 (4)	0.27411 (10)	0.0445 (8)
H14A	0.2660	0.4779	0.2839	0.053*
C15	0.4230 (5)	0.4103 (5)	0.23299 (11)	0.0590 (10)
H15A	0.3865	0.4952	0.2145	0.071*
C16	0.5509 (5)	0.2971 (5)	0.21902 (11)	0.0607 (10)
H16A	0.6029	0.3074	0.1915	0.073*
C17	0.6013 (5)	0.1695 (5)	0.24556 (11)	0.0565 (10)
H17A	0.6885	0.0937	0.2362	0.068*
C18	0.5235 (4)	0.1527 (4)	0.28618 (10)	0.0454 (8)
H18A	0.5549	0.0639	0.3038	0.054*
H11A	−0.016 (6)	0.535 (5)	0.4164 (13)	0.080 (14)*
H11B	0.050 (6)	0.435 (5)	0.4519 (14)	0.071 (13)*
H11C	−0.100 (8)	0.366 (6)	0.4222 (15)	0.121 (19)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0386 (2)	0.0548 (2)	0.0482 (2)	0.01202 (15)	−0.00702 (14)	0.00193 (15)
Br2	0.0487 (2)	0.0744 (3)	0.0417 (2)	0.00746 (17)	0.00967 (15)	−0.01245 (17)
O1	0.0359 (12)	0.0591 (15)	0.0427 (12)	0.0166 (11)	0.0024 (9)	0.0001 (10)
O2	0.0338 (13)	0.0727 (16)	0.0405 (12)	0.0226 (11)	0.0010 (9)	0.0024 (11)
N1	0.0317 (14)	0.0442 (15)	0.0342 (13)	0.0037 (12)	0.0028 (10)	0.0015 (11)
N2	0.0241 (13)	0.0491 (16)	0.0395 (14)	0.0095 (11)	−0.0005 (10)	0.0035 (12)
N3	0.0269 (13)	0.0510 (16)	0.0332 (13)	0.0113 (11)	0.0021 (10)	0.0044 (11)
C1	0.0347 (17)	0.0395 (18)	0.0330 (15)	0.0067 (14)	0.0033 (12)	0.0005 (13)
C2	0.0378 (18)	0.047 (2)	0.0390 (17)	0.0112 (15)	0.0059 (13)	−0.0022 (14)
C3	0.0360 (17)	0.0375 (18)	0.0401 (17)	0.0034 (14)	−0.0032 (13)	0.0032 (14)
C4	0.0414 (18)	0.0425 (19)	0.0333 (16)	0.0005 (15)	−0.0039 (13)	0.0008 (14)
C5	0.0386 (18)	0.0375 (17)	0.0355 (16)	0.0021 (14)	0.0064 (13)	−0.0043 (13)
C6	0.0297 (16)	0.0376 (17)	0.0374 (16)	0.0031 (13)	0.0034 (12)	0.0011 (13)
C7	0.0350 (18)	0.054 (2)	0.0348 (16)	0.0084 (15)	0.0056 (13)	−0.0030 (15)
C8	0.0287 (16)	0.0422 (18)	0.0308 (15)	0.0030 (13)	0.0021 (12)	0.0029 (13)
C9	0.0297 (16)	0.0392 (18)	0.0389 (17)	0.0024 (13)	0.0048 (13)	0.0036 (13)
C10	0.0306 (17)	0.0415 (18)	0.0354 (16)	0.0048 (14)	0.0020 (12)	0.0035 (13)
C11	0.040 (2)	0.061 (3)	0.048 (2)	0.0155 (19)	0.0048 (17)	0.0003 (19)
C12	0.0308 (17)	0.066 (2)	0.0429 (18)	0.0081 (16)	−0.0054 (14)	0.0056 (16)
C13	0.0293 (16)	0.0456 (18)	0.0324 (15)	0.0012 (14)	−0.0018 (12)	−0.0028 (13)
C14	0.0433 (19)	0.051 (2)	0.0390 (18)	0.0032 (15)	0.0023 (14)	0.0014 (15)
C15	0.063 (3)	0.071 (3)	0.0425 (19)	0.002 (2)	0.0061 (17)	0.0111 (18)
C16	0.053 (2)	0.091 (3)	0.0384 (19)	0.004 (2)	0.0112 (16)	−0.004 (2)
C17	0.043 (2)	0.082 (3)	0.044 (2)	0.0077 (19)	0.0074 (15)	−0.0185 (19)
C18	0.0391 (19)	0.057 (2)	0.0398 (18)	0.0069 (16)	−0.0046 (14)	−0.0076 (15)

Geometric parameters (Å, º)

Br1—C3	1.900 (3)	C7—H7A	0.9300
Br2—C5	1.889 (3)	C8—C9	1.350 (4)
O1—C6	1.344 (3)	C8—C10	1.438 (4)
O1—H1A	0.8975	C9—C11	1.492 (5)
O2—C10	1.228 (3)	C11—H11A	0.93 (4)
N1—C7	1.292 (4)	C11—H11B	0.87 (4)
N1—C8	1.393 (4)	C11—H11C	0.97 (5)
N2—C9	1.363 (4)	C12—H12A	0.9600
N2—N3	1.414 (3)	C12—H12B	0.9600
N2—C12	1.471 (4)	C12—H12C	0.9600
N3—C10	1.409 (3)	C13—C14	1.385 (4)
N3—C13	1.424 (4)	C13—C18	1.386 (4)
C1—C2	1.394 (4)	C14—C15	1.378 (5)
C1—C6	1.413 (4)	C14—H14A	0.9300
C1—C7	1.442 (4)	C15—C16	1.377 (5)
C2—C3	1.371 (4)	C15—H15A	0.9300
C2—H2A	0.9300	C16—C17	1.366 (5)
C3—C4	1.380 (4)	C16—H16A	0.9300
C4—C5	1.380 (4)	C17—C18	1.378 (5)
C4—H4A	0.9300	C17—H17A	0.9300
C5—C6	1.384 (4)	C18—H18A	0.9300
C6—O1—H1A	107.8	N2—C9—C11	120.8 (3)
C7—N1—C8	120.4 (3)	O2—C10—N3	123.5 (3)
C9—N2—N3	106.5 (2)	O2—C10—C8	132.3 (3)
C9—N2—C12	120.9 (2)	N3—C10—C8	104.2 (2)
N3—N2—C12	116.3 (2)	C9—C11—H11A	116 (3)
C10—N3—N2	109.0 (2)	C9—C11—H11B	108 (3)
C10—N3—C13	122.4 (2)	H11A—C11—H11B	105 (4)
N2—N3—C13	119.6 (2)	C9—C11—H11C	113 (3)
C2—C1—C6	119.7 (3)	H11A—C11—H11C	106 (4)
C2—C1—C7	118.9 (3)	H11B—C11—H11C	108 (4)
C6—C1—C7	121.4 (3)	N2—C12—H12A	109.5
C3—C2—C1	120.3 (3)	N2—C12—H12B	109.5
C3—C2—H2A	119.8	H12A—C12—H12B	109.5
C1—C2—H2A	119.8	N2—C12—H12C	109.5
C2—C3—C4	120.8 (3)	H12A—C12—H12C	109.5
C2—C3—Br1	119.9 (2)	H12B—C12—H12C	109.5
C4—C3—Br1	119.3 (2)	C14—C13—C18	120.0 (3)
C5—C4—C3	119.0 (3)	C14—C13—N3	121.4 (3)
C5—C4—H4A	120.5	C18—C13—N3	118.6 (3)
C3—C4—H4A	120.5	C15—C14—C13	119.3 (3)
C4—C5—C6	122.2 (3)	C15—C14—H14A	120.4
C4—C5—Br2	118.5 (2)	C13—C14—H14A	120.4
C6—C5—Br2	119.3 (2)	C16—C15—C14	120.6 (4)
O1—C6—C5	120.3 (3)	C16—C15—H15A	119.7
O1—C6—C1	121.9 (2)	C14—C15—H15A	119.7
C5—C6—C1	117.9 (3)	C17—C16—C15	120.0 (3)
N1—C7—C1	121.9 (3)	C17—C16—H16A	120.0
N1—C7—H7A	119.0	C15—C16—H16A	120.0
C1—C7—H7A	119.0	C16—C17—C18	120.3 (3)
C9—C8—N1	124.1 (3)	C16—C17—H17A	119.8
C9—C8—C10	109.0 (2)	C18—C17—H17A	119.8
N1—C8—C10	126.9 (3)	C17—C18—C13	119.8 (3)
C8—C9—N2	110.5 (3)	C17—C18—H18A	120.1
C8—C9—C11	128.7 (3)	C13—C18—H18A	120.1

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N1	0.90	1.80	2.609 (4)	148
C7—H7A···O2	0.93	2.26	2.958 (4)	131
C18—H18A···O2	0.93	2.46	2.882 (4)	108