Dibromidobis­(4-hydr­oxy-1,5-dimethyl-2-phenyl-3-pyrazolone)zinc(II)

Lemoine, P.; Viossat, B.; Brion, J.D.; Bekaert, A.

doi:10.1107/S1600536808016838

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 64| Part 7| July 2008| Pages m891-m892

doi:10.1107/S1600536808016838

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Dibromidobis(4-hydroxy-1,5-dimethyl-2-phenyl-3-pyrazolone)zinc(II)

Pascale Lemoine,^a ^* Bernard Viossat,^a Jean Daniel Brion ^b and Alain Bekaert ^b

^aLaboratoire de Cristallographie et RMN biologiques, UMR 8015 CNRS, Faculté des Sciences Pharmaceutiques et Biologiques de Paris Descartes, 4 avenue de l'Observatoire, 75270 Paris Cedex 06, France, and ^bUniversité de Paris XI, Faculté des Sciences Pharmaceutiques et Biologiques, Laboratoire de Chimie Thérapeutique BioCIS, UPRES-A 8076 CNRS, 5 rue J. B. Clément, 92296 Châtenay-Malabry Cedex, France
^*Correspondence e-mail: lemoine@pharmacie.univ-paris5.fr

(Received 14 May 2008; accepted 3 June 2008; online 7 June 2008)

In the title compound, [ZnBr₂(C₁₁H₁₂N₂O₂)₂], the Zn(II) ion is coordinated by two Br atoms and two O atoms from two 4-hydroxyantipyrine molecules via the carbonyl O atoms, which act as monodentate ligands, giving rise to a distorted tetrahedral 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 intramolecular 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) interactions.

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_r = 633.64
Tetragonal, P 4₁
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[F² > 2σ(F²)] = 0.035
wR(F²) = 0.093
S = 0.90
7354 reflections
304 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.30 e Å⁻³
Absolute structure: Flack (1983 ), 3602 Friedel pairs
Flack parameter: −0.015 (9)

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) x+1, y, z; (ii) $[-y+1, x-1, z+{\script{1\over 4}}]$ .

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) 1+y, 1-x, $[-{\script{1\over 4}} + z]$ . Cg1 is the centroid of atoms Cl/N2/N3/C4/C5.

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 ).

Supporting information

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

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

checkCIF report

Comment top

Metals like Zn are expected to be involved in neurodegenerative diseases such as Alzheimer or Parkinson leading to neurofibrillary tangles degeneration and tau protein accumulation (Filiz et al.,2008; Tougu et al.,2008). These amyloi¨d plaques in the cortical brain are the sign of cerebral aging and associated with a neuronic a high level of metals. Much work (Melov et al., 1998) is now devoted to theses diseases since no real drug is available up to date. As researchers postulate that soft chelating drugs could interfere with free metal accumulation and neuronal collapsus, our idea was that phenazone (antipyrine), a well known antipyretic brain available drug, could become a soft chelating molecule upon hydroxylation in the 4-hydroxy derivative. For this reason and our knowledge in metal amide complexes, (Bekaert et al., 2007; Lemoine et al., 2007) we have prepared a new cristalline complex including Zn and 4-hydroxy-1,5-dimethyl-2-phenyl-3-pyrazolone (4-hydroxyantipyrine) which is of considerable interest as a antipyrine primary metabolite and which is the object of many biological studies the latter years, by example in the evaluation of the influence of diabete mellitus on antipyrine metabolism (Matzke et al., 2000). The hydroxyamide structure which is close to lactamide let us to test it as a metal pinch. Following our work concerning lactamide and zinc(II) complex (Bekaert et al., 2003), we now report a new zinc complex with 4-hydroxyantipyrine.

The title compound contains one monomeric tetrahedral zinc complex, [Zn(C₂₂H₂₄N₄O₄)Br₂]. The Zn atom is surrounded by two monodentate 4-hydroxyantipyrine ligands via the carbonyl O atom O4 (or O24) in the sp² lone-pair direction and two Br ligands (Fig. 1). The complex exhibits a distorted tetrahedral geometry around the zincII atom. The degree of deviation from an ideal tetrahedron is appreciable with the angles around Zn atom ranging from 99.4 (1) to 113.2 (1) °. The Zn—O and Zn—Br distances in the coordination polyhedron are 1.961 (3)/2.015 (3) Å and 2.351 (1)/2.379 (1)Å, respectively, in good agreement with those found in similar Zn^IItetrahedral coordination (Bekaert et al., 2003). The difference between the two Zn—O (or the two Zn—Br) bond lengths can be explained by the presence of the O5—H5···O24 (or O25—H25···Br1) intramolecular hydrogen bond (Table 1) which causes the stretching of the Zn—O24 (or Zn—Br1) bond. Each hydroxyantipyrine ligand consists of a pyrazole P1 (Cl/N2—N3/C4—C5) [or P3 (C2l/N22—N23/C24—C25)] and a phenyl ring P2 (C8—C13) [or P4 (C28—C33)] which are planar with maximum deviation of 0.017 (3) Å for N2 (first ligand) and 0.021 (3) Å for N23 (second ligand). The dihedral angles are 65.2 (2)° between P1 and P2 and 81.6 (2)° for P3 and P4, these values are significantly different from those reported in 4-hydroxyantipyrine [42.5 (1)°] (Panneerselvam et al.,1996).

The crystal packing is governed by weak C—H···O and Zn—Br···Cg1( centroid of the P1 plane) interactions (Tables1 and 2).

Related literature top

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 top

The title compound, dibromido-bis[4-hydroxyantipyrine]zinc(II), was prepared by mixing 1.02 g (5 mmole) of 4-hydroxyantipyrine dissolved in hot acetic acid (10 ml, 353 K) and 10 ml of a solution of ZnBr2 (0.496 g, 2 mmole) in boiling acetic acid. Upon slow cooling, crystal suitable for X-ray diffraction were recovered.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf Nonius, 1994); 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, 20087); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-32 for Windows (Farrugia, 1997).

Figures top

Fig. 1. Molecular view of the complex with the atom-labelling scheme. Ellipsoids are drawn at the 50% probability level. Hydrogen bonds are shown as dashed lines. H atoms are represented as small spheres of arbitrary radii.

Dibromidobis(4-hydroxy-1,5-dimethyl-2-phenyl-3-pyrazolone)zinc(II) top

Crystal data top

[ZnBr₂(C₁₁H₁₂N₂O₂)₂]	D_x = 1.670 Mg m⁻³
M_r = 633.64	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4₁	Cell parameters from 25 reflections
Hall symbol: P4w	θ = 2.2–7.0°
a = 9.824 (3) Å	µ = 4.18 mm⁻¹
c = 26.120 (3) Å	T = 293 K
V = 2521 (1) Å³	Parallelepiped, colourless
Z = 4	0.18 × 0.16 × 0.15 mm
F(000) = 1264

Data collection top

Enraf-Nonius CAD-4 diffractometer	R_int = 0.091
Radiation source: fine-focus sealed tube	θ_max = 30.1°, θ_min = 2.2°
Graphite monochromator	h = −13→13
ω – 2θ scans	k = 0→13
15417 measured reflections	l = −36→36
7354 independent reflections	3 standard reflections every 60 min
3152 reflections with I > 2σ(I)	intensity decay: none

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.035	H-atom parameters constrained
wR(F²) = 0.093	w = 1/[σ²(F_o²) + (0.0396P)²] where P = (F_o² + 2F_c²)/3
S = 0.90	(Δ/σ)_max = 0.023
7354 reflections	Δρ_max = 0.36 e Å⁻³
304 parameters	Δρ_min = −0.30 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 3602 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.015 (9)

Crystal data top

[ZnBr₂(C₁₁H₁₂N₂O₂)₂]	Z = 4
M_r = 633.64	Mo Kα radiation
Tetragonal, P4₁	µ = 4.18 mm⁻¹
a = 9.824 (3) Å	T = 293 K
c = 26.120 (3) Å	0.18 × 0.16 × 0.15 mm
V = 2521 (1) Å³

Data collection top

Enraf-Nonius CAD-4 diffractometer	R_int = 0.091
15417 measured reflections	3 standard reflections every 60 min
7354 independent reflections	intensity decay: none
3152 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.035	H-atom parameters constrained
wR(F²) = 0.093	Δρ_max = 0.36 e Å⁻³
S = 0.90	Δρ_min = −0.30 e Å⁻³
7354 reflections	Absolute structure: Flack (1983), 3602 Friedel pairs
304 parameters	Absolute structure parameter: −0.015 (9)
1 restraint

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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

Hydrogen-bond geometry (Å, º) top

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) x+1, y, z; (ii) −y+1, x−1, z+1/4.

Experimental details

Crystal data
Chemical formula	[ZnBr₂(C₁₁H₁₂N₂O₂)₂]
M_r	633.64
Crystal system, space group	Tetragonal, P4₁
Temperature (K)	293
a, c (Å)	9.824 (3), 26.120 (3)
V (Å³)	2521 (1)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.18
Crystal size (mm)	0.18 × 0.16 × 0.15

Data collection
Diffractometer	Enraf-Nonius CAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	15417, 7354, 3152
R_int	0.091
(sin θ/λ)_max (Å⁻¹)	0.705

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.093, 0.90
No. of reflections	7354
No. of parameters	304
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.30
Absolute structure	Flack (1983), 3602 Friedel pairs
Absolute structure parameter	−0.015 (9)

Computer programs: CAD-4 EXPRESS (Enraf Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 20087), ORTEPIII (Burnett & Johnson, 1996) and ORTEP-32 for Windows (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···O24	0.82	1.94	2.734 (5)	163.9
O25—H25···Br1	0.82	2.40	3.212 (4)	169.1
C10—H10···O5ⁱ	0.93	2.47	3.378 (8)	165.1
C27—H27C···Br2ⁱⁱ	0.96	2.81	3.686 (7)	151.4

Symmetry codes: (i) x+1, y, z; (ii) −y+1, x−1, z+1/4.

Zn—Br···Cg(π-ring) interaction top

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)

Symmetry code: (i) 1+y, 1-x, -1/4 + z. Cg1 is the centroid of atoms Cl/N2/N3/C4/C5.

References

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