Halogeno(triazol­yl)zinc complexes as mol­ecular building blocks for metal–organic frameworks

The isomorphous title complexes, dichlorido[4-(3,5-dimethyl-4H-1,2,4-triazol-4-yl)benzoic acid-κN¹]zinc(II) dihydrate, [ZnCl₂(C₁₁H₁₁N₃O₂)₂]·2H₂O, and dibromido[4-(3,5-dimethyl-4H-1,2,4-triazol-4-yl)benzoic acid-κN¹]zinc(II) dihydrate, [ZnBr₂(C₁₁H₁₁N₃O₂)₂]·2H₂O, were synthesized and crystallized by slow evaporation of the solvent from a solution of the ligand and either zinc chloride or zinc bromide, respectively, in water/ethanol. The Zn^II ions occupy twofold axes in the noncentrosymmetric ortho­rhom­bic space group Fdd2. The metal ion is approximately tetra­hedrally coordinated by two monodentate triazole groups of the ligands and additionally by two halide ions. The water mol­ecules incorporate the complexes into a three-dimensional framework made up by hydrogen bonds. Furthermore, each complex possesses two hydrogen-bond-donor sites represented by the carb­oxy groups and two acceptor sites at the noncoordinating N atoms of the triazoles.

S1. Comment

Typically, metal–organic frameworks (MOFs) consist of inorganic building blocks, e.g. metal ions, or more complex secondary building blocks connected by bridging organic linkers. Knowledge of hydrogen bonding as well as of self-assembly is essential for understanding the underlying processes of MOF formation, and for the design of coordination polymers. The complexes reported herein, [ZnCl₂(C₁₁H₁₁N₃O₂)₂].2H₂O, (I), and [ZnBr₂(C₁₁H₁₁N₃O₂)₂].2H₂O, (II), containing additional noncoordinating water molecules, are excellent examples for investigating these properties.

Lukashuk et al. (2007) and Zou et al. (2005) reported the hydrogen-bonding behaviour of 4-(1,2,4-triazol-4-yl)benzoic acid. Depending on the reaction conditions, varying coordination behaviour of the ligand was observed. We synthesized 3,5-dimethyl-4-(1,2,4-triazol-4-yl)benzoic acid [H(Me₂trzpba)] [ok?], the corresponding dimethylated triazol ligand. The methyl groups lead to a higher torsion angle of 59.44 (4)° between the phenyl ring and the triazole unit in the neat ligand H(Me₂trzpba) in comparison to the unsubstituted 4-(1,2,4-triazol-4-yl)benzoic acid [33.79 (7)°, 20.77 (6)°]. This leads to enhanced solubility due to reduced π–π-stacking interactions (Lässig et al., 2009).

The crystal structures of two isostructural zinc halide complexes incorporating this new ligand are reported here. The synthesis of both complexes was performed by reacting the ligand with the respective zinc halide (chloride or bromide) in a water/ethanol mixture (1:1, v/v). While the pure ligand is only slightly soluble in water/ethanol, the addition of zinc chloride or zinc bromide increases the solubility significantly. A clear solution results, from which single crystals of (I) and (II), respectively, were obtained by slow evaporation of the solvent.

The asymmetric unit is represented by half of the complex where the Zn ions reside on the twofold axis in the achiral noncentrosymmetric orthorhombic space group Fdd2 (No. 43).

The Zn ion is approximately tetrahedrally coordinated by two monodentate triazol units and two halide ions (see scheme). The bond length of the coordinating N atoms to the metal ion is 2.055 (2) Å in (I) which correlates quite well with a typical Zn—N bond, as can be seen from Zn(dmatrz)₂Cl₂ (dmatrz = 3,5-dimethyl-4-amino-1,2,4-triazole) (Du, 2004).

The hydrogen-bonding interactions are discussed for (I). There are three types of hydrogen bonds (Fig. 2), all incorporating the water molecule (O3). As a result, a three-dimensional network (Fig. 3) is formed. A strong hydrogen bond can be found between O1 and O3 with a donor–acceptor distance of 2.605 (3) Å. Furthermore, the water molecule (O3) acts as a donor group in two further hydrogen-bonding interactions. One involves the carbonyl O atom O2 of a neighbouring complex with a distance of 2.788 (3) Å. The second, weaker hydrogen bond is directed to the N atom N2 of the triazole with a distance of 2.971 (3) Å.

The observation that the ligand HMe₂trzpba is soluble in the presence of zinc halides led us to the conclusion that (I) and (II) already exist in solution. This shows impressively the ability of this ligand to competitively replace coordinating water and the dramatic change in solubility due to coordination.

Related literature

For related literature, see: Du (2004); Lässig et al. (2009); Lukashuk et al. (2007); Zou et al. (2005).

S2. Experimental

All chemicals and solvents were commercially available and used without further purification. The ligand H(Me₂trzpba) was synthesized according to Lässig et al. (2009). (I) and (II) were synthesized as follows: in a typical procedure 21.7 mg (0.1 mmol) of the ligand was suspended in 2 ml of ethanol, to which a solution of 0.1 mmol zinc halide, dissolved in 2 ml distilled water, was added and stirred for 5 min at room temperature. Colourless prismatic crystals of (I) and (II) were obtained after 3–4 d by slow evaporation of the solvent under ambient conditions.

For (I): yield 13.3 mg; 22.0 µmol; 44% of th. (based on the ligand). IR (KBr): [cm^-1] 3085m, 2968w, 1679 s, 1610 s, 1548 s, 1513m, 1418 s, 1387m, 1340m, 1313m, 1274 s, 1179m, 1131m, 1066w, 1044m, 1014 s, 871m, 805m, 793m, 770m, 701m, 632w, 558m, 528m.

For (II): yield: 7.5 mg; 10.8 µmol; 22% of th. (based on the ligand). IR (KBr): [cm^-1] 3081m, 2973w, 1698m, 1607m, 1546 s, 1510m, 1416 s, 1381m, 1335m, 1300m, 1259 s, 1173m, 1124m, 1062w, 1037m, 1011 s, 871m, 807m, 788m, 764m, 698m, 629w, 555m, 525m.

S3. Refinement

Methyl H atoms were located in difference syntheses and thereafter refined as part of rigid rotating groups, with C—-H = 0.98Å and U_iso(H) = 1.5U_eq(C). Aromatic H atoms were placed geometrically and refined using a riding model, with C—H = 0.95Å and U_iso(H) = 1.2U_eq(C). In each case, the acidic H1 atom on O1 was located in a difference Fourier map and refined as part of a rigid rotating group, with O—H = 0.84Å and U_iso(H) = 1.5U_eq(O). The H atoms of the water molecule in each structure were located from difference Fourier maps and refined using distance restraints [O—H = 0.84 (2)Å and H···H = 1.33 (2)Å] and with U_iso(H) = 1.5U_eq(O).

Computing details

For both compounds, data collection: X-AREA (Stoe & Cie, 2000); cell refinement: X-AREA (Stoe & Cie, 2000); data reduction: X-AREA, X-RED (Stoe & Cie, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. The molecular structure of (I) including the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. Symmetry code: a: 1 - x, 1 - y, z.
	Fig. 2. Hydrogen bonding between different complexes of (I). Displacement ellipsoids are drawn at the 50% probability level. Symmetry codes: b: -1/2 + x, y, -1.5 + z; c: -1/4 + x, 1.25 - y, -1.25 + z.
	Fig. 3. Packing diagram in [001] showing the hydrogen-bonded three-dimensional network of (I). H atoms are omitted for clarity.

(I) dichlorido[4-(3,5-dimethyl-4H-1,2,4-triazol-4-yl)benzoic acid-κN¹]zinc(II) dihydrate

Crystal data

[ZnCl2(C11H11N3O2)2]·2H2O	F(000) = 2496
Mr = 606.76	Dx = 1.557 Mg m^−3
Orthorhombic, Fdd2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2d	Cell parameters from 10095 reflections
a = 15.893 (3) Å	θ = 1.8–29.7°
b = 44.480 (5) Å	µ = 1.21 mm^−1
c = 7.3582 (10) Å	T = 180 K
V = 5201.7 (14) Å^3	Prism, colourless
Z = 8	0.50 × 0.32 × 0.15 mm

Data collection

Stoe IPDS-2T diffractometer	2189 independent reflections
Radiation source: fine-focus sealed tube	2157 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
Detector resolution: 6.67 pixels mm^-1	θmax = 26.0°, θmin = 1.8°
ω scans	h = −14→19
Absorption correction: numerical (X-RED; Stoe & Cie, 2000)	k = −54→52
Tmin = 0.417, Tmax = 0.583	l = −7→9
3974 measured reflections

Refinement

Refinement on F^2	w = 1/[σ^2(Fo^2) + (0.0497P)^2 + 3.2765P] where P = (Fo^2 + 2Fc^2)/3
Least-squares matrix: full	(Δ/σ)max = 0.001
R[F^2 > 2σ(F^2)] = 0.025	Δρmax = 0.29 e Å^−3
wR(F^2) = 0.068	Δρmin = −0.31 e Å^−3
S = 1.09	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
2189 reflections	Extinction coefficient: 0.00178 (17)
180 parameters	Absolute structure: Flack (1983)
4 restraints	Absolute structure parameter: −0.009 (10)
H atoms treated by a mixture of independent and constrained refinement

Special details

Geometry. All s.u. (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u. are taken into account individually in the estimation of s.u. in distances, angles and torsion angles; correlations between s.u. in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u. is used for estimating s.u. involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
Zn1	0.5	0.5	0.15366 (4)	0.02374 (13)
Cl1	0.38859 (4)	0.516648 (14)	0.00346 (10)	0.04152 (18)
C1	0.75803 (14)	0.58751 (5)	1.2215 (4)	0.0270 (5)
C2	0.71742 (14)	0.57952 (5)	1.0452 (3)	0.0255 (5)
C3	0.76203 (14)	0.56792 (4)	0.8980 (4)	0.0259 (4)
H3	0.8209	0.5647	0.9086	0.031*
C4	0.72149 (15)	0.56110 (4)	0.7366 (3)	0.0263 (4)
H4	0.7525	0.554	0.6348	0.032*
C5	0.63477 (14)	0.56483 (5)	0.7257 (3)	0.0246 (4)
C6	0.58891 (14)	0.57584 (6)	0.8723 (4)	0.0321 (5)
H6	0.5295	0.5778	0.8642	0.039*
C7	0.63062 (15)	0.58390 (6)	1.0300 (3)	0.0305 (5)
H7	0.6001	0.5924	1.1283	0.037*
C8	0.64289 (18)	0.50414 (5)	0.5165 (4)	0.0356 (6)
H8A	0.6227	0.4866	0.4484	0.053*
H8B	0.6388	0.5001	0.6471	0.053*
H8C	0.7017	0.5081	0.4844	0.053*
C9	0.59046 (14)	0.53078 (4)	0.4701 (3)	0.0250 (4)
C10	0.53203 (13)	0.57535 (4)	0.4742 (3)	0.0249 (4)
C11	0.51341 (16)	0.60743 (5)	0.5204 (4)	0.0321 (5)
H11A	0.4682	0.6082	0.6108	0.048*
H11B	0.4958	0.6182	0.4104	0.048*
H11C	0.5641	0.6169	0.5701	0.048*
N1	0.53600 (12)	0.53250 (4)	0.3363 (3)	0.0259 (4)
N2	0.49881 (11)	0.56078 (4)	0.3381 (3)	0.0256 (4)
N3	0.58990 (12)	0.55756 (4)	0.5624 (3)	0.0243 (4)
O1	0.83617 (11)	0.57818 (4)	1.2366 (3)	0.0379 (4)
H1	0.855	0.583	1.3393	0.057*
O2	0.72146 (13)	0.60109 (4)	1.3419 (3)	0.0388 (4)
O3	0.40044 (12)	0.59201 (4)	0.0514 (2)	0.0339 (4)
H3A	0.426 (2)	0.5790 (6)	0.113 (5)	0.054 (10)*
H3B	0.423 (2)	0.6088 (5)	0.068 (5)	0.056 (11)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.02843 (19)	0.02259 (17)	0.02020 (19)	0.00080 (13)	0	0
Cl1	0.0411 (3)	0.0437 (3)	0.0397 (4)	0.0097 (2)	−0.0151 (3)	−0.0036 (3)
C1	0.0324 (12)	0.0250 (10)	0.0235 (13)	−0.0014 (7)	−0.0024 (9)	0.0031 (9)
C2	0.0297 (12)	0.0233 (10)	0.0236 (12)	−0.0021 (8)	−0.0018 (9)	0.0038 (8)
C3	0.0248 (11)	0.0254 (9)	0.0274 (12)	0.0005 (7)	−0.0017 (9)	0.0010 (11)
C4	0.0284 (11)	0.0253 (9)	0.0252 (11)	0.0022 (8)	0.0009 (9)	0.0000 (9)
C5	0.0274 (10)	0.0253 (9)	0.0213 (11)	−0.0018 (8)	−0.0030 (9)	−0.0012 (8)
C6	0.0239 (10)	0.0432 (12)	0.0292 (13)	0.0015 (9)	0.0011 (9)	−0.0017 (10)
C7	0.0278 (11)	0.0396 (11)	0.0242 (12)	0.0026 (9)	0.0006 (9)	−0.0009 (9)
C8	0.0425 (14)	0.0280 (10)	0.0363 (15)	0.0063 (9)	−0.0098 (12)	−0.0036 (10)
C9	0.0294 (11)	0.0225 (9)	0.0233 (11)	−0.0015 (7)	−0.0032 (8)	−0.0015 (8)
C10	0.0251 (10)	0.0242 (9)	0.0255 (11)	0.0003 (8)	−0.0008 (9)	−0.0004 (9)
C11	0.0358 (11)	0.0244 (11)	0.0361 (13)	0.0025 (8)	−0.0021 (10)	−0.0042 (9)
N1	0.0305 (10)	0.0224 (8)	0.0247 (9)	0.0008 (7)	−0.0027 (7)	0.0004 (7)
N2	0.0292 (10)	0.0210 (9)	0.0266 (11)	0.0016 (6)	−0.0021 (7)	0.0005 (7)
N3	0.0259 (9)	0.0229 (8)	0.0240 (10)	−0.0005 (7)	−0.0030 (7)	−0.0008 (7)
O1	0.0323 (9)	0.0528 (10)	0.0286 (9)	0.0053 (7)	−0.0082 (7)	−0.0047 (8)
O2	0.0427 (10)	0.0469 (10)	0.0267 (9)	0.0105 (8)	−0.0068 (8)	−0.0059 (8)
O3	0.0348 (9)	0.0363 (9)	0.0305 (10)	−0.0008 (7)	−0.0092 (7)	0.0010 (7)

Geometric parameters (Å, º)

Zn1—N1	2.0550 (19)	C7—H7	0.95
Zn1—N1^i	2.0550 (19)	C8—C9	1.488 (3)
Zn1—Cl1^i	2.2147 (7)	C8—H8A	0.98
Zn1—Cl1	2.2147 (7)	C8—H8B	0.98
C1—O2	1.220 (3)	C8—H8C	0.98
C1—O1	1.314 (3)	C9—N1	1.313 (3)
C1—C2	1.492 (3)	C9—N3	1.371 (3)
C2—C3	1.393 (3)	C10—N2	1.304 (3)
C2—C7	1.398 (3)	C10—N3	1.376 (3)
C3—C4	1.385 (4)	C10—C11	1.496 (3)
C3—H3	0.95	C11—H11A	0.98
C4—C5	1.390 (3)	C11—H11B	0.98
C4—H4	0.95	C11—H11C	0.98
C5—C6	1.391 (3)	N1—N2	1.390 (3)
C5—N3	1.434 (3)	O1—H1	0.84
C6—C7	1.383 (3)	O3—H3A	0.843 (18)
C6—H6	0.95	O3—H3B	0.840 (18)
N1—Zn1—N1^i	98.31 (11)	C9—C8—H8A	109.5
N1—Zn1—Cl1^i	109.82 (6)	C9—C8—H8B	109.5
N1^i—Zn1—Cl1^i	108.28 (6)	H8A—C8—H8B	109.5
N1—Zn1—Cl1	108.28 (6)	C9—C8—H8C	109.5
N1^i—Zn1—Cl1	109.82 (6)	H8A—C8—H8C	109.5
Cl1^i—Zn1—Cl1	120.13 (4)	H8B—C8—H8C	109.5
O2—C1—O1	123.0 (2)	N1—C9—N3	108.45 (18)
O2—C1—C2	122.9 (2)	N1—C9—C8	126.0 (2)
O1—C1—C2	114.0 (2)	N3—C9—C8	125.6 (2)
C3—C2—C7	119.4 (2)	N2—C10—N3	110.31 (17)
C3—C2—C1	122.9 (2)	N2—C10—C11	124.6 (2)
C7—C2—C1	117.6 (2)	N3—C10—C11	125.0 (2)
C4—C3—C2	120.7 (2)	C10—C11—H11A	109.5
C4—C3—H3	119.6	C10—C11—H11B	109.5
C2—C3—H3	119.6	H11A—C11—H11B	109.5
C3—C4—C5	119.0 (2)	C10—C11—H11C	109.5
C3—C4—H4	120.5	H11A—C11—H11C	109.5
C5—C4—H4	120.5	H11B—C11—H11C	109.5
C6—C5—C4	121.1 (2)	C9—N1—N2	109.00 (18)
C6—C5—N3	117.94 (19)	C9—N1—Zn1	129.27 (15)
C4—C5—N3	120.9 (2)	N2—N1—Zn1	121.64 (15)
C7—C6—C5	119.4 (2)	C10—N2—N1	106.56 (18)
C7—C6—H6	120.3	C9—N3—C10	105.68 (18)
C5—C6—H6	120.3	C9—N3—C5	127.41 (18)
C6—C7—C2	120.3 (2)	C10—N3—C5	126.73 (17)
C6—C7—H7	119.9	C1—O1—H1	109.5
C2—C7—H7	119.9	H3A—O3—H3B	109 (3)

Symmetry code: (i) −x+1, −y+1, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···N2	0.84 (2)	2.17 (2)	2.971 (3)	158 (3)
O3—H3B···O2^ii	0.84 (2)	1.95 (2)	2.787 (3)	176 (4)
O1—H1···O3^iii	0.84	1.77	2.605 (3)	176

Symmetry codes: (ii) x−1/4, −y+5/4, z−5/4; (iii) x+1/2, y, z+3/2.

(II) dibromido[4-(3,5-dimethyl-4H-1,2,4-triazol-4-yl)benzoic acid-κN¹]zinc(II) dihydrate

Crystal data

[ZnBr2(C11H11N3O2)2]·2H2O	F(000) = 2784
Mr = 695.68	Dx = 1.748 Mg m^−3
Orthorhombic, Fdd2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2d	Cell parameters from 10693 reflections
a = 16.1158 (12) Å	θ = 1.8–29.6°
b = 44.425 (4) Å	µ = 4.01 mm^−1
c = 7.3861 (5) Å	T = 180 K
V = 5288.0 (7) Å^3	Prism, colourless
Z = 8	0.34 × 0.25 × 0.11 mm

Data collection

Stoe IPDS-2T diffractometer	3189 independent reflections
Radiation source: fine-focus sealed tube	2987 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.052
Detector resolution: 6.67 pixels mm^-1	θmax = 28°, θmin = 2.7°
ω scans	h = −21→21
Absorption correction: numerical (X-RED; Stoe & Cie, 2000)	k = −58→50
Tmin = 0.396, Tmax = 0.713	l = −9→9
8551 measured reflections

Refinement

Refinement on F^2	w = 1/[σ^2(Fo^2) + (0.0658P)^2] where P = (Fo^2 + 2Fc^2)/3
Least-squares matrix: full	(Δ/σ)max = 0.002
R[F^2 > 2σ(F^2)] = 0.033	Δρmax = 0.62 e Å^−3
wR(F^2) = 0.09	Δρmin = −0.65 e Å^−3
S = 1.01	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
3189 reflections	Extinction coefficient: 0.00096 (10)
179 parameters	Absolute structure: Flack (1983)
4 restraints	Absolute structure parameter: −0.007 (10)
H atoms treated by a mixture of independent and constrained refinement

Special details

Geometry. All s.u. (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u. are taken into account individually in the estimation of s.u. in distances, angles and torsion angles; correlations between s.u. in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u. is used for estimating s.u. involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
Zn1	0.5	0.5	0.15980 (6)	0.02364 (13)
Br1	0.38200 (2)	0.515555 (9)	−0.00035 (5)	0.04164 (13)
C1	0.75146 (17)	0.58742 (8)	1.2218 (5)	0.0277 (6)
C2	0.71176 (19)	0.57958 (7)	1.0464 (4)	0.0253 (6)
C3	0.75579 (18)	0.56818 (7)	0.8990 (5)	0.0265 (6)
H3	0.8138	0.5648	0.9094	0.032*
C4	0.71572 (17)	0.56171 (7)	0.7374 (5)	0.0266 (6)
H4	0.7463	0.5551	0.6349	0.032*
C5	0.62950 (17)	0.56505 (7)	0.7277 (5)	0.0254 (6)
C6	0.58480 (19)	0.57582 (9)	0.8737 (5)	0.0311 (7)
H6	0.5262	0.5779	0.8657	0.037*
C7	0.62594 (18)	0.58361 (9)	1.0319 (4)	0.0301 (7)
H7	0.5957	0.5917	1.1309	0.036*
C8	0.6409 (2)	0.50520 (8)	0.5136 (6)	0.0350 (7)
H8A	0.6195	0.4873	0.4511	0.053*
H8B	0.641	0.5016	0.6445	0.053*
H8C	0.6976	0.5093	0.4726	0.053*
C9	0.58709 (17)	0.53142 (7)	0.4722 (4)	0.0250 (6)
C10	0.52695 (17)	0.57572 (7)	0.4798 (5)	0.0257 (6)
C11	0.5081 (2)	0.60745 (8)	0.5256 (6)	0.0340 (7)
H11A	0.4942	0.6185	0.4149	0.051*
H11B	0.5566	0.6167	0.5832	0.051*
H11C	0.4609	0.6081	0.6092	0.051*
N1	0.53273 (16)	0.53308 (6)	0.3404 (4)	0.0252 (5)
N2	0.49473 (15)	0.56101 (6)	0.3429 (4)	0.0251 (5)
N3	0.58543 (16)	0.55784 (6)	0.5651 (4)	0.0252 (5)
O1	0.83002 (15)	0.57899 (7)	1.2334 (4)	0.0380 (6)
H1	0.8491	0.584	1.3349	0.057*
O2	0.71477 (17)	0.60028 (7)	1.3436 (4)	0.0391 (6)
H3B	0.416 (3)	0.6093 (6)	0.077 (7)	0.047 (14)*
H3A	0.419 (3)	0.5796 (8)	0.119 (6)	0.039 (12)*
O3	0.39598 (16)	0.59261 (6)	0.0495 (4)	0.0351 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0265 (2)	0.0232 (2)	0.0212 (2)	0.00084 (18)	0	0
Br1	0.04058 (19)	0.0433 (2)	0.0411 (2)	0.01080 (15)	−0.01645 (15)	−0.00694 (17)
C1	0.0304 (14)	0.0270 (14)	0.0259 (15)	−0.0011 (11)	−0.0013 (12)	0.0023 (12)
C2	0.0292 (13)	0.0253 (14)	0.0214 (14)	−0.0018 (11)	−0.0021 (11)	0.0032 (11)
C3	0.0244 (12)	0.0260 (12)	0.0291 (15)	0.0034 (11)	−0.0007 (11)	0.0000 (14)
C4	0.0263 (12)	0.0264 (13)	0.0271 (14)	0.0032 (11)	0.0017 (12)	−0.0012 (13)
C5	0.0266 (12)	0.0263 (14)	0.0232 (15)	−0.0018 (10)	−0.0034 (11)	−0.0033 (13)
C6	0.0246 (13)	0.0405 (18)	0.0283 (16)	−0.0012 (13)	0.0024 (12)	−0.0020 (14)
C7	0.0259 (13)	0.0402 (17)	0.0242 (16)	−0.0002 (12)	0.0012 (11)	−0.0018 (14)
C8	0.0405 (17)	0.0298 (16)	0.0347 (17)	0.0103 (14)	−0.0103 (15)	−0.0024 (14)
C9	0.0282 (12)	0.0258 (14)	0.0212 (14)	0.0010 (11)	−0.0001 (11)	−0.0017 (13)
C10	0.0246 (12)	0.0251 (13)	0.0272 (14)	0.0009 (11)	0.0000 (12)	0.0014 (13)
C11	0.0371 (15)	0.0274 (15)	0.0374 (18)	0.0042 (13)	−0.0021 (13)	−0.0059 (14)
N1	0.0290 (12)	0.0211 (12)	0.0253 (12)	0.0009 (9)	−0.0054 (10)	−0.0039 (10)
N2	0.0272 (11)	0.0216 (12)	0.0265 (12)	0.0023 (9)	−0.0011 (10)	−0.0015 (10)
N3	0.0270 (11)	0.0260 (13)	0.0227 (12)	0.0014 (10)	−0.0018 (10)	0.0005 (10)
O1	0.0326 (10)	0.0522 (15)	0.0291 (12)	0.0047 (10)	−0.0048 (10)	−0.0013 (13)
O2	0.0425 (13)	0.0488 (15)	0.0261 (12)	0.0098 (12)	−0.0062 (10)	−0.0071 (12)
O3	0.0387 (12)	0.0326 (13)	0.0339 (14)	−0.0002 (11)	−0.0096 (10)	−0.0007 (11)

Geometric parameters (Å, º)

Zn1—N1	2.054 (3)	C7—H7	0.95
Zn1—N1^i	2.054 (3)	C8—C9	1.484 (4)
Zn1—Br1	2.3438 (4)	C8—H8A	0.98
Zn1—Br1^i	2.3438 (4)	C8—H8B	0.98
C1—O2	1.219 (4)	C8—H8C	0.98
C1—O1	1.323 (4)	C9—N1	1.312 (4)
C1—C2	1.486 (4)	C9—N3	1.360 (4)
C2—C3	1.394 (5)	C10—N2	1.311 (4)
C2—C7	1.399 (4)	C10—N3	1.384 (4)
C3—C4	1.387 (5)	C10—C11	1.482 (5)
C3—H3	0.95	C11—H11A	0.98
C4—C5	1.399 (4)	C11—H11B	0.98
C4—H4	0.95	C11—H11C	0.98
C5—C6	1.382 (5)	N1—N2	1.384 (4)
C5—N3	1.431 (4)	O1—H1	0.84
C6—C7	1.388 (5)	O3—H3B	0.835 (19)
C6—H6	0.95	O3—H3A	0.855 (19)
N1—Zn1—N1^i	98.97 (16)	C9—C8—H8A	109.5
N1—Zn1—Br1	108.98 (7)	C9—C8—H8B	109.5
N1^i—Zn1—Br1	109.29 (7)	H8A—C8—H8B	109.5
N1—Zn1—Br1^i	109.29 (7)	C9—C8—H8C	109.5
N1^i—Zn1—Br1^i	108.98 (7)	H8A—C8—H8C	109.5
Br1—Zn1—Br1^i	119.38 (3)	H8B—C8—H8C	109.5
O2—C1—O1	123.3 (3)	N1—C9—N3	108.2 (3)
O2—C1—C2	123.0 (3)	N1—C9—C8	126.0 (3)
O1—C1—C2	113.7 (3)	N3—C9—C8	125.8 (3)
C3—C2—C7	119.3 (3)	N2—C10—N3	109.6 (3)
C3—C2—C1	123.1 (3)	N2—C10—C11	124.7 (3)
C7—C2—C1	117.5 (3)	N3—C10—C11	125.6 (3)
C4—C3—C2	120.7 (3)	C10—C11—H11A	109.5
C4—C3—H3	119.7	C10—C11—H11B	109.5
C2—C3—H3	119.7	H11A—C11—H11B	109.5
C3—C4—C5	119.0 (3)	C10—C11—H11C	109.5
C3—C4—H4	120.5	H11A—C11—H11C	109.5
C5—C4—H4	120.5	H11B—C11—H11C	109.5
C6—C5—C4	121.0 (3)	C9—N1—N2	109.6 (3)
C6—C5—N3	118.2 (3)	C9—N1—Zn1	127.8 (2)
C4—C5—N3	120.8 (3)	N2—N1—Zn1	122.5 (2)
C5—C6—C7	119.6 (3)	C10—N2—N1	106.4 (2)
C5—C6—H6	120.2	C9—N3—C10	106.2 (3)
C7—C6—H6	120.2	C9—N3—C5	127.4 (3)
C6—C7—C2	120.3 (3)	C10—N3—C5	126.3 (3)
C6—C7—H7	119.8	C1—O1—H1	109.5
C2—C7—H7	119.8	H3B—O3—H3A	107 (4)

Symmetry code: (i) −x+1, −y+1, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···N2	0.86 (2)	2.22 (3)	3.033 (4)	159 (4)
O3—H3B···O2^ii	0.84 (2)	1.96 (2)	2.788 (4)	169 (5)
O1—H1···O3^iii	0.84	1.80	2.636 (4)	176

Symmetry codes: (ii) x−1/4, −y+5/4, z−5/4; (iii) x+1/2, y, z+3/2.