Dibromidobis-(4-hydr-oxy-1,5-dimethyl-2-phenyl-3-pyrazolone)zinc(II).

In the title compound, [ZnBr(2)(C(11)H(12)N(2)O(2))(2)], the Zn(II) ion is coordinated by two Br atoms and two O atoms from two 4-hydroxy-anti-pyrine mol-ecules via the carbonyl O atoms, which act as monodentate ligands, giving rise to a distorted tetra-hedral geometry. The values of the bond angles at the Zn atom are in the range 99.4 (1) to 113.2 (1)°. The presence of O-H⋯O and O-H⋯Br intra-molecular hydrogen bonds can explain the difference between the two Zn-O [1.961 (3)/2.015 (3) Å] and the two Zn-Br [2.350 (1)/2.378 (1) Å] bond lengths. The crystal structure is governed by C-H⋯O, C-H⋯Br and Zn-Br⋯Cg(π-ring) inter-actions.

Related literature

For related literature, see: Bekaert et al. (2003 ▶, 2007 ▶); Filiz et al. (2008 ▶); Lemoine et al. (2007 ▶); Matzke et al. (2000 ▶); Melov et al., (1998 ▶); Panneerselvam et al. (1996 ▶); Tougu et al. (2008 ▶).

Experimental

Crystal data

[ZnBr2(C11H12N2O2)2]

M = 633.64

Tetragonal,

a = 9.824 (3) Å

c = 26.120 (3) Å

V = 2521 (1) Å3

Z = 4

Mo Kα radiation

μ = 4.18 mm−1

T = 293 (2) K

0.17 × 0.16 × 0.15 mm

Data collection

Enraf-Nonius CAD-4 diffractometer

Absorption correction: none

15417 measured reflections

7354 independent reflections

3152 reflections with I > 2σ(I)

R int = 0.091

3 standard reflections frequency: 60 min intensity decay: none

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.093

S = 0.90

7354 reflections

304 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.36 e Å−3

Δρmin = −0.30 e Å−3

Absolute structure: Flack (1983 ▶), 3602 Friedel pairs

Flack parameter: −0.015 (9)

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶) and ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808016838/dn2351sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808016838/dn2351Isup2.hkl

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

[ZnBr2(C11H12N2O2)2]	Z = 4
Mr = 633.64	F000 = 1264
Tetragonal, P41	Dx = 1.670 Mg m−3
Hall symbol: P4w	Mo Kα radiation λ = 0.71073 Å
a = 9.824 (3) Å	Cell parameters from 25 reflections
b = 9.824 (3) Å	θ = 2.2–7.0º
c = 26.120 (3) Å	µ = 4.18 mm−1
α = 90º	T = 293 (2) K
β = 90º	Parallelepiped, colourless
γ = 90º	0.18 × 0.16 × 0.15 mm
V = 2521 (1) Å3

Enraf-Nonius CAD-4 diffractometer	Rint = 0.091
Radiation source: fine-focus sealed tube	θmax = 30.1º
Monochromator: graphite	θmin = 2.2º
T = 293(2) K	h = −13→13
ω – 2θ scans	k = 0→13
Absorption correction: none	l = −36→36
15417 measured reflections	3 standard reflections
7354 independent reflections	every 60 min
3152 reflections with I > 2σ(I)	intensity decay: none

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.035	w = 1/[σ2(Fo2) + (0.0396P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.093	(Δ/σ)max = 0.023
S = 0.90	Δρmax = 0.36 e Å−3
7354 reflections	Δρmin = −0.30 e Å−3
304 parameters	Extinction correction: none
1 restraint	Absolute structure: Flack (1983), 3602 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.015 (9)
Secondary atom site location: difference Fourier map

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
Zn1	0.74076 (5)	0.20414 (5)	0.423054 (19)	0.05571 (13)
Br1	0.88194 (6)	0.16046 (6)	0.35092 (2)	0.07972 (17)
Br2	0.57242 (7)	0.36720 (6)	0.40493 (2)	0.0908 (2)
C1	0.6782 (5)	0.2246 (5)	0.6042 (2)	0.0645 (13)
N2	0.8063 (4)	0.2622 (5)	0.61659 (16)	0.0699 (11)
N3	0.8827 (4)	0.2682 (4)	0.57175 (14)	0.0579 (9)
O4	0.8439 (3)	0.2507 (3)	0.48491 (13)	0.0627 (8)
C4	0.7980 (5)	0.2417 (4)	0.53136 (18)	0.0531 (11)
O5	0.5526 (3)	0.1862 (4)	0.52624 (16)	0.0774 (10)
H5	0.5683	0.1309	0.5035	0.116*
C5	0.6701 (4)	0.2140 (4)	0.5522 (2)	0.0574 (12)
C6	0.5746 (6)	0.1951 (7)	0.6436 (2)	0.097 (2)
H6A	0.5993	0.1139	0.6618	0.146*
H6B	0.4877	0.1824	0.6275	0.146*
H6C	0.5694	0.2700	0.6672	0.146*
C7	0.8723 (6)	0.2520 (7)	0.6664 (2)	0.0960 (18)
H7A	0.8082	0.2746	0.6928	0.144*
H7B	0.9477	0.3140	0.6677	0.144*
H7C	0.9045	0.1607	0.6714	0.144*
C8	1.0114 (4)	0.3326 (5)	0.57024 (18)	0.0565 (11)
C9	1.1196 (6)	0.2603 (7)	0.5512 (2)	0.094 (2)
H9	1.1110	0.1706	0.5403	0.113*
C10	1.2471 (7)	0.3318 (13)	0.5490 (3)	0.135 (4)
H10	1.3244	0.2882	0.5367	0.162*
C11	1.2545 (10)	0.4602 (14)	0.5647 (3)	0.140 (4)
H11	1.3380	0.5045	0.5626	0.168*
C12	1.1441 (9)	0.5314 (8)	0.5840 (3)	0.111 (3)
H12	1.1530	0.6205	0.5956	0.133*
C13	1.0223 (6)	0.4661 (6)	0.5853 (2)	0.0779 (15)
H13	0.9453	0.5123	0.5966	0.093*
C21	0.8032 (5)	−0.2887 (4)	0.4583 (2)	0.0630 (12)
N22	0.6796 (4)	−0.3069 (4)	0.47977 (18)	0.0638 (11)
N23	0.6143 (4)	−0.1837 (4)	0.47984 (16)	0.0595 (10)
O24	0.6506 (3)	0.0316 (3)	0.44738 (13)	0.0597 (8)
C24	0.6943 (4)	−0.0888 (4)	0.45531 (17)	0.0487 (10)
O25	0.9281 (3)	−0.1073 (3)	0.41933 (19)	0.0825 (10)
H25	0.9098	−0.0349	0.4053	0.124*
C25	0.8144 (4)	−0.1576 (5)	0.4424 (2)	0.0602 (12)
C26	0.9040 (6)	−0.4025 (5)	0.4535 (3)	0.099 (2)
H26A	0.9660	−0.3830	0.4260	0.148*
H26B	0.8568	−0.4859	0.4465	0.148*
H26C	0.9539	−0.4112	0.4849	0.148*
C27	0.6348 (7)	−0.4141 (5)	0.5139 (3)	0.0872 (18)
H27A	0.6787	−0.4979	0.5047	0.131*
H27B	0.5380	−0.4247	0.5111	0.131*
H27C	0.6581	−0.3907	0.5485	0.131*
C28	0.4741 (5)	−0.1712 (4)	0.49287 (19)	0.0572 (12)
C29	0.4387 (6)	−0.1184 (6)	0.5390 (3)	0.0860 (18)
H29	0.5048	−0.0915	0.5624	0.103*
C30	0.3006 (9)	−0.1055 (7)	0.5503 (3)	0.110 (3)
H30	0.2737	−0.0673	0.5813	0.132*
C31	0.2057 (7)	−0.1483 (7)	0.5167 (4)	0.107 (3)
H31	0.1142	−0.1402	0.5253	0.128*
C32	0.2391 (6)	−0.2030 (8)	0.4702 (3)	0.108 (2)
H32	0.1727	−0.2318	0.4472	0.129*
C33	0.3770 (6)	−0.2138 (6)	0.4589 (3)	0.0827 (16)
H33	0.4037	−0.2506	0.4277	0.099*

	U11	U22	U33	U12	U13	U23
Zn1	0.0566 (3)	0.0519 (3)	0.0587 (3)	−0.0067 (2)	−0.0048 (2)	0.0016 (2)
Br1	0.0845 (4)	0.0840 (4)	0.0706 (4)	0.0026 (3)	0.0170 (3)	0.0095 (3)
Br2	0.0966 (4)	0.0866 (4)	0.0893 (5)	0.0281 (3)	−0.0168 (3)	−0.0011 (3)
C1	0.064 (3)	0.062 (3)	0.068 (4)	−0.011 (2)	0.008 (3)	−0.009 (2)
N2	0.077 (3)	0.077 (3)	0.056 (3)	−0.012 (2)	0.012 (2)	−0.005 (2)
N3	0.053 (2)	0.073 (2)	0.048 (3)	−0.0083 (17)	0.0001 (18)	0.0005 (18)
O4	0.0571 (18)	0.073 (2)	0.058 (2)	−0.0122 (15)	0.0017 (15)	−0.0002 (16)
C4	0.063 (3)	0.043 (2)	0.053 (3)	0.0022 (19)	0.001 (2)	0.000 (2)
O5	0.0492 (19)	0.093 (3)	0.090 (3)	−0.0133 (17)	0.0043 (18)	−0.013 (2)
C5	0.041 (3)	0.051 (3)	0.080 (4)	−0.0038 (19)	0.008 (2)	−0.001 (2)
C6	0.088 (4)	0.109 (4)	0.095 (5)	−0.034 (3)	0.034 (4)	−0.013 (4)
C7	0.101 (4)	0.138 (5)	0.049 (4)	−0.019 (4)	0.007 (3)	0.002 (3)
C8	0.055 (3)	0.062 (3)	0.052 (3)	−0.002 (2)	−0.001 (2)	0.001 (2)
C9	0.067 (4)	0.136 (6)	0.078 (4)	0.027 (4)	−0.004 (3)	−0.034 (4)
C10	0.058 (4)	0.255 (11)	0.092 (6)	0.006 (5)	0.010 (3)	−0.048 (7)
C11	0.113 (7)	0.249 (12)	0.057 (5)	−0.082 (8)	0.006 (4)	0.001 (6)
C12	0.142 (7)	0.107 (5)	0.084 (5)	−0.064 (5)	0.000 (5)	0.000 (4)
C13	0.091 (4)	0.072 (3)	0.071 (4)	−0.023 (3)	−0.002 (3)	0.001 (3)
C21	0.055 (3)	0.050 (3)	0.084 (4)	0.003 (2)	−0.003 (3)	0.003 (2)
N22	0.064 (3)	0.041 (2)	0.086 (3)	0.0001 (18)	0.010 (2)	0.0034 (19)
N23	0.062 (2)	0.044 (2)	0.072 (3)	−0.0030 (17)	0.0102 (19)	−0.0017 (18)
O24	0.0507 (16)	0.0470 (16)	0.081 (2)	−0.0025 (13)	0.0073 (15)	−0.0007 (15)
C24	0.048 (2)	0.044 (2)	0.053 (3)	−0.0052 (19)	−0.0045 (19)	−0.0060 (19)
O25	0.0525 (17)	0.073 (2)	0.122 (3)	0.0007 (15)	0.021 (2)	0.020 (2)
C25	0.052 (3)	0.059 (3)	0.069 (3)	−0.001 (2)	−0.001 (2)	0.001 (2)
C26	0.086 (4)	0.059 (3)	0.150 (7)	0.019 (3)	0.024 (4)	0.020 (4)
C27	0.110 (5)	0.055 (3)	0.097 (5)	0.001 (3)	0.017 (4)	0.009 (3)
C28	0.058 (3)	0.048 (2)	0.066 (3)	−0.006 (2)	0.014 (2)	0.005 (2)
C29	0.086 (4)	0.083 (4)	0.089 (5)	−0.010 (3)	0.024 (3)	−0.017 (3)
C30	0.119 (6)	0.075 (4)	0.136 (7)	0.006 (4)	0.066 (5)	−0.007 (4)
C31	0.068 (4)	0.083 (4)	0.170 (9)	0.002 (3)	0.037 (5)	0.023 (5)
C32	0.069 (4)	0.129 (6)	0.125 (7)	−0.021 (4)	−0.006 (4)	0.044 (5)
C33	0.068 (3)	0.093 (4)	0.088 (5)	−0.017 (3)	0.011 (3)	0.002 (3)

Zn1—O4	1.961 (3)	C12—H12	0.9300
Zn1—O24	2.015 (3)	C13—H13	0.9300
Zn1—Br2	2.3505 (10)	C21—N22	1.349 (6)
Zn1—Br1	2.3786 (8)	C21—C25	1.357 (7)
C1—N2	1.350 (6)	C21—C26	1.498 (7)
C1—C5	1.365 (7)	N22—N23	1.370 (5)
C1—C6	1.477 (7)	N22—C27	1.448 (7)
N2—N3	1.392 (5)	N23—C24	1.378 (5)
N2—C7	1.457 (7)	N23—C28	1.424 (6)
N3—C4	1.369 (6)	O24—C24	1.275 (5)
N3—C8	1.415 (6)	C24—C25	1.400 (6)
O4—C4	1.297 (5)	O25—C25	1.363 (6)
C4—C5	1.396 (7)	O25—H25	0.8200
O5—C5	1.366 (6)	C26—H26A	0.9600
O5—H5	0.8200	C26—H26B	0.9600
C6—H6A	0.9600	C26—H26C	0.9600
C6—H6B	0.9600	C27—H27A	0.9600
C6—H6C	0.9600	C27—H27B	0.9600
C7—H7A	0.9600	C27—H27C	0.9600
C7—H7B	0.9600	C28—C29	1.356 (7)
C7—H7C	0.9600	C28—C33	1.368 (8)
C8—C9	1.372 (7)	C29—C30	1.395 (9)
C8—C13	1.373 (7)	C29—H29	0.9300
C9—C10	1.437 (11)	C30—C31	1.349 (12)
C9—H9	0.9300	C30—H30	0.9300
C10—C11	1.328 (14)	C31—C32	1.368 (11)
C10—H10	0.9300	C31—H31	0.9300
C11—C12	1.386 (13)	C32—C33	1.390 (9)
C11—H11	0.9300	C32—H32	0.9300
C12—C13	1.358 (9)	C33—H33	0.9300
O4—Zn1—O24	99.41 (13)	C12—C13—C8	120.9 (6)
O4—Zn1—Br2	111.74 (10)	C12—C13—H13	119.6
O24—Zn1—Br2	109.12 (8)	C8—C13—H13	119.6
O4—Zn1—Br1	113.16 (10)	N22—C21—C25	109.0 (4)
O24—Zn1—Br1	110.75 (9)	N22—C21—C26	122.0 (4)
Br2—Zn1—Br1	111.94 (3)	C25—C21—C26	129.0 (5)
N2—C1—C5	108.3 (4)	C21—N22—N23	107.8 (3)
N2—C1—C6	121.9 (5)	C21—N22—C27	128.8 (4)
C5—C1—C6	129.7 (5)	N23—N22—C27	119.9 (4)
C1—N2—N3	108.2 (4)	N22—N23—C24	109.2 (3)
C1—N2—C7	127.6 (4)	N22—N23—C28	122.0 (4)
N3—N2—C7	120.9 (4)	C24—N23—C28	127.2 (4)
C4—N3—N2	108.2 (4)	C24—O24—Zn1	133.1 (3)
C4—N3—C8	127.4 (4)	O24—C24—N23	120.7 (4)
N2—N3—C8	121.6 (4)	O24—C24—C25	133.8 (4)
C4—O4—Zn1	125.1 (3)	N23—C24—C25	105.4 (4)
O4—C4—N3	119.8 (4)	C25—O25—H25	109.5
O4—C4—C5	133.7 (4)	C21—C25—O25	123.1 (4)
N3—C4—C5	106.5 (4)	C21—C25—C24	108.5 (4)
C5—O5—H5	109.5	O25—C25—C24	128.4 (4)
C1—C5—O5	123.9 (4)	C21—C26—H26A	109.5
C1—C5—C4	108.7 (4)	C21—C26—H26B	109.5
O5—C5—C4	127.3 (5)	H26A—C26—H26B	109.5
C1—C6—H6A	109.5	C21—C26—H26C	109.5
C1—C6—H6B	109.5	H26A—C26—H26C	109.5
H6A—C6—H6B	109.5	H26B—C26—H26C	109.5
C1—C6—H6C	109.5	N22—C27—H27A	109.5
H6A—C6—H6C	109.5	N22—C27—H27B	109.5
H6B—C6—H6C	109.5	H27A—C27—H27B	109.5
N2—C7—H7A	109.5	N22—C27—H27C	109.5
N2—C7—H7B	109.5	H27A—C27—H27C	109.5
H7A—C7—H7B	109.5	H27B—C27—H27C	109.5
N2—C7—H7C	109.5	C29—C28—C33	120.9 (5)
H7A—C7—H7C	109.5	C29—C28—N23	119.6 (5)
H7B—C7—H7C	109.5	C33—C28—N23	119.5 (4)
C9—C8—C13	122.5 (5)	C28—C29—C30	118.2 (7)
C9—C8—N3	118.1 (5)	C28—C29—H29	120.9
C13—C8—N3	119.2 (4)	C30—C29—H29	120.9
C8—C9—C10	115.8 (7)	C31—C30—C29	120.4 (7)
C8—C9—H9	122.1	C31—C30—H30	119.8
C10—C9—H9	122.1	C29—C30—H30	119.8
C11—C10—C9	120.0 (7)	C30—C31—C32	122.4 (6)
C11—C10—H10	120.0	C30—C31—H31	118.8
C9—C10—H10	120.0	C32—C31—H31	118.8
C10—C11—C12	123.3 (7)	C31—C32—C33	116.9 (7)
C10—C11—H11	118.4	C31—C32—H32	121.6
C12—C11—H11	118.4	C33—C32—H32	121.6
C13—C12—C11	117.4 (7)	C28—C33—C32	121.2 (7)
C13—C12—H12	121.3	C28—C33—H33	119.4
C11—C12—H12	121.3	C32—C33—H33	119.4

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···O24	0.82	1.94	2.734 (5)	164
O25—H25···Br1	0.82	2.40	3.212 (4)	169
C10—H10···O5i	0.93	2.47	3.378 (8)	165
C27—H27C···Br2ii	0.96	2.81	3.686 (7)	151

Y—X(I)···Cg(J)	X···Cg	X-Perp	Gamma	Y—X···Cg
Zn1—Br1···Cg1i	3.671 (2)	3.646	6.76	132.21 (4)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5⋯O24	0.82	1.94	2.734 (5)	164
O25—H25⋯Br1	0.82	2.40	3.212 (4)	169
C10—H10⋯O5i	0.93	2.47	3.378 (8)	165
C27—H27C⋯Br2ii	0.96	2.81	3.686 (7)	151

Symmetry codes: (i) ; (ii) .

Table 2

Zn—Br⋯Cg(π-ring) interaction

y—X(I)⋯Cg(J)	X⋯Cg	X-Perp	γ	Y—X⋯Cg
Zn1—Br1⋯Cg1i	3.671 (2)	3.646	6.76	132.21 (4)

Symmetry code: (i) , , . Cg1 is the centroid of atoms Cl/N2/N3/C4/C5.