Poly[[[bis­(N,N'-dimethyl­formamide)­zinc(II)]-[mu]₃-5-hydroxy­benzene-1,3-dicarboxyl­ato] toluene solvate]

The title compound, {[Zn(C₈H₄O₅)(C₃H₇NO)₂]·0.5C₇H₈}_n, is a one-dimensional coordination polymer in which the Zn atoms are linked by bridging 5-hydroxy­benzene-1,3-dicarboxyl­ate ligands. These polymeric chains form two-dimensional sheets via interchain hydrogen bonds, and these sheets, in turn, are stacked tightly with solvent toluene mol­ecules in the inter­layer space. The N,N'-dimethyl­formamide ligands, coordinated axially to the Zn atoms, form van der Waals contacts with ligands in neighboring sheets, and enclose the guest mol­ecules.

S1. Comment

Metal-organic frameworks (MOFs) are crystalline extended structures that are self-assembled from transition metal ions and bridging organic ligands (Rowsell & Yaghi, 2004). As they have potential applications in gas storage, separation, catalysis, optoelectronics and sensors (Evans & Lin, 2001; Kitagawa et al., 2004), research interest has been increasingly directed at producing new desired structural types of MOFs (Yaghi et al., 2003). Among known MOFs, Zn as metal nodes with bridging ligands as aromatic carboxylates have been extensively studied (Kim et al., 2001; Eddaoudi et al., 2000). This is because Zn has the ability to form well defined metal clusters, such as paddle-wheel, trinuclear and basic zinc acetate units, under reaction conditions. Once the reaction conditions for forming the target Zn clusters, called inorganic secondary building units (SBUs), are established, it is possible to predict the structural types of the resulting MOFs when they are combined with suitable organic building blocks (Eddaoudi et al., 2002; Chun et al., 2005). Nevertheless, new assembly rules are still to be discovered for the building blocks for the design and synthesis of MOFs that will be useful for certain applications.

One of the design strategies of MOFs is utilizing both the coordination and the hydrogen-bonding properties of the building blocks to produce extended framework structures (Wang et al., 2006; Du et al., 2005; Cui et al., 2003; Noveron et al., 2002; MacDonald et al., 2000). For this purpose, we have tried to prepare new MOFs by using zinc(II) ions and 5-hydroxybenzene-1,3-dicarboxylate of which hydroxyl group has a possibility to form hydrogen bonds between the frameworks. Although there are many examples using the ligand to Zn for the frameworks construction, most cases contain secondary organic ligands such as bipyridyls (Cao et al., 2004; Plater et al., 2001).

We report here the crystal structure of the title compound, (I), which contains Zn–organic chains that interact with neighboring chains via hydrogen bonds between the peripheral hydroxyl groups and uncoordinated O atoms of the carboxylates. Zn atoms have trigonal-bipyramidal coordination geometry with two axial dimethylformamide O atoms (O6 and O7) and three equatorial carboxylate O atoms (O3, O4, and O5) as shown in Fig. 1. The distances and angles related to Zn (listed in Table 1) match well with those of similar coordination complexes (Evans et al., 2000; Grewe et al., 1982).

Toluene, the included solvent molecule, sits on an inversion center and is disordered over two sites. Of the two carboxylate groups of the organic linker, one links two Zn atoms in a bis-monodentate fashion via O4 and O5, and the other is coordinated to the next Zn atom through one of the carboxylate O atoms, O3. The one-dimensional ladder-like chain running along the b axis and parallel to the bc plane is depicted in Fig. 2. The remaining uncoordinated O atom of the carboxylate group, O2, is engaged in a hydrogen bond with the hydroxyl group of a neighboring metal-organic chain. The O1—H···O2 hydrogen-bond geometry is shown in Table 2. These hydrogen bonds between peripheral hydroxyl groups and the neighboring carboxylates link the one-dimensional chains to form a layer.

The chains are stacked along the a axis, with the protruding dimethylformamide ligands arranged in a herringbone fashion and forming van der Waals contacts, as shown in Fig.3(a). This packing of the chains leaves no voids. However, between these stacks there is a room for the guest molecules, the toluene molecules being surrounded by six dimethylformamide molecules, as shown in Fig. 3(b). Therefore, the title compound has chains formed by coordination bonds between carboxylate groups and Zn atoms, which in turn form tight stacks along the a axis and form hydrogen bonds to neighboring stacks, between which is provided a pore for the guest molecules.

S2. Experimental

1-Hydroxybenzene-3,5-dicarboxylic acid (99%, Aldrich, 18 mg, 0.10 mmol) and Zn(NO₃)₂·6H₂O (30 mg, 0.13 mmol) were dissolved in a mixture of N,N'-dimethylformamide (0.5 ml) and toluene (2 ml) in a 4 ml vial. The vial was placed in a larger vial containing a mixture of toluene (1 ml) and triethylamine (0.05 ml). The larger vial was capped tightly, and left to stand at room temperature for 5 d, yielding crystals suitable for X-ray crystallographic study.

S3. Refinement

The included toluene molecule was disordered around an inversion center at (1, 1/2, 1) and hence one-half was unique in the asymmetric unit. The site occupation factors of C1T, C2T, C3T, C4T and C5T were allocated the fixed values of 1.0, 1/2, 1.0, 0.5 and 1/2, respectively. Eight H atoms of the disordered toluene molecule were generated and incorporated into the structural model with reasonable geometry and fixed site occupation factors of 0.5. Their positions were not allowed to move during the refinement processes. Most H atoms attached to other C atoms could be found in difference Fourier maps, and were then placed in calculated positions and refined by applying a riding model [for phenyl ring H atoms, C–H = 0.95 Å and U_iso(H) = 1.2U_eq(C); for H atoms of –CH₃ in dimethylformamide ligands, C–H = 0.98 Å and U_iso(H) = 1.5U_eq(C)]. The hydroxyl H atom was located in difference Fourier maps and its position and displacement parameter were refined with distance restraints of O–H = 0.85 (2) Å. Friedel equivalents were merged before the final refinement.

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL and MS Modeling 4.0 (Accelrys, 2005).

Figures

	Fig. 1. A fragment of the structure of (I) and the toluene molecule are shown with the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Toluene is disordered over two sites with equal probabilities. C1T and C1T^iv are assigned as methyl C atoms in the fused toluene models. H atoms of the disordered toluene molecule have been omitted for clarity. [Symmetry codes: (i) 1 – x, 1 – y, 1 – z; (ii) x, 1 + y, z; (iii) x, −1 + y, z; (iv) 2 – x, 1 –y, 2 – z.]
	Fig. 2. The three chains formed via hydrogen bonding (dotted lines) are depicted with ball-and-stick models. Donor atoms are O1 and acceptors are O2. Hydroxyl H atoms attached to O1s are represented as small balls. Dimethylformamide and toluene molecules have beeen omitted for simplicity. H atoms in benzene rings have also been omitted.
	Fig. 3. The packing structure of (I) with guest toluene molecules are represented as top (a) and side (b) views. Among the total six chains for the presentation two chains are highlighted in yellow and blue. In addition toluene molecules are drawn in pink. In order to show the molecular contacts some of the toluene and dimethylformamide molecules are shown as CPK models using a full van der Waals scale·COLOUR?

Poly[[[bis(dimethylformamide)zinc(II)]-µ₃-5-hydroxybenzene-1,3-dicarboxylato] toluene solvate]

Crystal data

[Zn(C8H4O5)(C3H7NO)]·0.5C7H8	Z = 2
Mr = 437.74	F(000) = 454
Triclinic, P1	Dx = 1.509 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.9582 (6) Å	Cell parameters from 3464 reflections
b = 9.8360 (6) Å	θ = 2.6–28.3°
c = 11.9183 (7) Å	µ = 1.32 mm^−1
α = 79.294 (1)°	T = 173 K
β = 81.822 (1)°	Plate, colourless
γ = 69.526 (1)°	0.25 × 0.10 × 0.07 mm
V = 963.28 (10) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	3337 independent reflections
Radiation source: fine-focus sealed tube	2921 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
ϕ and ω scans	θmax = 25.0°, θmin = 2.4°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −10→9
Tmin = 0.734, Tmax = 0.914	k = −11→11
4875 measured reflections	l = −13→14

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.075	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	w = 1/[σ^2(Fo^2) + (0.0369P)^2 + 0.5366P] where P = (Fo^2 + 2Fc^2)/3
3337 reflections	(Δ/σ)max = 0.001
270 parameters	Δρmax = 0.35 e Å^−3
1 restraint	Δρmin = −0.37 e Å^−3

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	Occ. (<1)
Zn1	0.55082 (3)	0.81704 (3)	0.59456 (2)	0.01531 (10)
O1	0.6057 (2)	0.13572 (19)	1.04610 (15)	0.0294 (4)
H1	0.578 (4)	0.200 (3)	1.087 (2)	0.043 (10)*
O2	0.5163 (3)	0.6476 (2)	0.82496 (16)	0.0472 (6)
O3	0.5547 (2)	0.61232 (17)	0.64387 (14)	0.0223 (4)
O4	0.4657 (2)	0.16334 (18)	0.57083 (14)	0.0263 (4)
O5	0.5813 (2)	−0.04533 (17)	0.68421 (14)	0.0211 (4)
O6	0.2971 (2)	0.89865 (19)	0.62338 (16)	0.0290 (4)
O7	0.8083 (2)	0.73733 (19)	0.55981 (16)	0.0292 (4)
N1	0.0696 (3)	1.0166 (3)	0.7253 (2)	0.0322 (5)
N2	1.0490 (3)	0.5816 (3)	0.6150 (2)	0.0385 (6)
C1	0.5844 (3)	0.2012 (3)	0.9356 (2)	0.0193 (5)
C2	0.5727 (3)	0.3474 (2)	0.8999 (2)	0.0180 (5)
H2	0.5779	0.4050	0.9540	0.022*
C3	0.5534 (3)	0.4098 (2)	0.7862 (2)	0.0170 (5)
C4	0.5441 (3)	0.3259 (2)	0.7065 (2)	0.0157 (5)
H4	0.5312	0.3678	0.6285	0.019*
C5	0.5539 (3)	0.1799 (2)	0.74281 (19)	0.0154 (5)
C6	0.5745 (3)	0.1174 (2)	0.8562 (2)	0.0176 (5)
H6	0.5818	0.0177	0.8798	0.021*
C7	0.5341 (3)	0.0928 (2)	0.65844 (19)	0.0164 (5)
C8	0.5390 (3)	0.5687 (2)	0.7502 (2)	0.0199 (5)
C9	0.2254 (3)	0.9749 (3)	0.6990 (2)	0.0281 (6)
H9	0.2873	1.0056	0.7412	0.034*
C10	−0.0339 (4)	0.9720 (4)	0.6661 (3)	0.0476 (8)
H10A	−0.1119	1.0594	0.6277	0.071*
H10B	−0.0904	0.9163	0.7218	0.071*
H10C	0.0310	0.9105	0.6091	0.071*
C11	−0.0057 (4)	1.1082 (4)	0.8141 (3)	0.0535 (9)
H11A	0.0760	1.1311	0.8463	0.080*
H11B	−0.0597	1.0558	0.8749	0.080*
H11C	−0.0841	1.1994	0.7811	0.080*
C12	0.8924 (3)	0.6400 (3)	0.6279 (3)	0.0309 (6)
H12	0.8393	0.6040	0.6954	0.037*
C13	1.1377 (4)	0.4642 (5)	0.6998 (4)	0.0739 (13)
H13A	1.0628	0.4414	0.7627	0.111*
H13B	1.2142	0.4960	0.7300	0.111*
H13C	1.1953	0.3765	0.6636	0.111*
C14	1.1428 (4)	0.6296 (4)	0.5169 (3)	0.0514 (9)
H14A	1.0713	0.6964	0.4603	0.077*
H14B	1.2146	0.5443	0.4825	0.077*
H14C	1.2062	0.6808	0.5413	0.077*
C1T	0.8804 (9)	0.7255 (8)	0.9465 (5)	0.118 (2)
H1TA	0.7708	0.7481	0.9421	0.141*	0.50
H1TB	0.9372	0.7483	0.8724	0.141*	0.50
H1TC	0.9007	0.7819	1.0017	0.141*	0.50
H1TD	0.7958	0.8483	0.9288	0.141*	0.50
C2T	0.9351 (11)	0.5901 (9)	0.9849 (6)	0.0525 (18)	0.50
C3T	0.8785 (7)	0.4765 (7)	0.9980 (4)	0.0774 (13)
H3TA	0.7711	0.5089	0.9850	0.093*	0.50
H3TB	0.8738	0.3759	1.0171	0.093*	0.50
C4T	0.8308 (11)	0.6016 (15)	0.9602 (9)	0.079 (3)	0.50
H4TA	0.7159	0.6398	0.9434	0.095*	0.50
C5T	0.9346 (10)	0.3426 (9)	1.0354 (9)	0.070 (2)	0.50
H5TA	0.9054	0.2576	1.0492	0.083*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.02025 (16)	0.01038 (14)	0.01694 (15)	−0.00493 (11)	−0.00480 (10)	−0.00385 (10)
O1	0.0551 (13)	0.0183 (9)	0.0164 (9)	−0.0119 (9)	−0.0092 (9)	−0.0025 (7)
O2	0.102 (2)	0.0197 (9)	0.0250 (11)	−0.0236 (11)	−0.0101 (11)	−0.0065 (8)
O3	0.0309 (10)	0.0137 (8)	0.0204 (9)	−0.0072 (7)	0.0011 (7)	−0.0010 (7)
O4	0.0396 (11)	0.0220 (9)	0.0194 (9)	−0.0094 (8)	−0.0100 (8)	−0.0044 (7)
O5	0.0270 (9)	0.0135 (8)	0.0262 (9)	−0.0067 (7)	−0.0070 (7)	−0.0078 (7)
O6	0.0210 (10)	0.0270 (10)	0.0395 (11)	−0.0052 (8)	−0.0028 (8)	−0.0116 (9)
O7	0.0231 (10)	0.0256 (9)	0.0395 (11)	−0.0062 (8)	−0.0014 (8)	−0.0106 (8)
N1	0.0244 (12)	0.0351 (13)	0.0397 (14)	−0.0109 (10)	0.0035 (10)	−0.0147 (11)
N2	0.0196 (12)	0.0468 (15)	0.0504 (16)	−0.0047 (11)	−0.0036 (11)	−0.0220 (12)
C1	0.0227 (13)	0.0174 (11)	0.0178 (12)	−0.0065 (10)	−0.0029 (10)	−0.0024 (9)
C2	0.0219 (13)	0.0167 (11)	0.0196 (12)	−0.0094 (10)	−0.0018 (10)	−0.0072 (9)
C3	0.0172 (12)	0.0123 (11)	0.0222 (12)	−0.0054 (9)	−0.0018 (9)	−0.0031 (9)
C4	0.0156 (11)	0.0152 (11)	0.0161 (11)	−0.0048 (9)	−0.0017 (9)	−0.0020 (9)
C5	0.0138 (11)	0.0146 (11)	0.0192 (12)	−0.0051 (9)	−0.0013 (9)	−0.0049 (9)
C6	0.0209 (12)	0.0109 (11)	0.0225 (13)	−0.0065 (10)	−0.0030 (10)	−0.0026 (9)
C7	0.0151 (11)	0.0187 (12)	0.0166 (12)	−0.0067 (10)	0.0016 (9)	−0.0057 (9)
C8	0.0212 (13)	0.0161 (12)	0.0251 (14)	−0.0081 (10)	−0.0051 (10)	−0.0037 (10)
C9	0.0249 (14)	0.0257 (13)	0.0349 (15)	−0.0085 (12)	−0.0014 (12)	−0.0078 (12)
C10	0.0265 (16)	0.060 (2)	0.064 (2)	−0.0169 (15)	−0.0004 (15)	−0.0260 (18)
C11	0.0371 (19)	0.067 (2)	0.065 (2)	−0.0208 (17)	0.0165 (16)	−0.040 (2)
C12	0.0220 (14)	0.0356 (15)	0.0384 (16)	−0.0083 (12)	−0.0016 (12)	−0.0166 (13)
C13	0.031 (2)	0.095 (3)	0.072 (3)	0.012 (2)	−0.0178 (18)	−0.011 (2)
C14	0.0305 (17)	0.057 (2)	0.076 (3)	−0.0179 (16)	0.0141 (16)	−0.0394 (19)
C1T	0.165 (7)	0.127 (5)	0.084 (4)	−0.075 (5)	−0.026 (4)	−0.007 (4)
C2T	0.059 (5)	0.060 (5)	0.049 (4)	−0.027 (4)	−0.008 (4)	−0.015 (4)
C3T	0.087 (4)	0.098 (4)	0.071 (3)	−0.055 (3)	−0.008 (3)	−0.019 (3)
C4T	0.035 (5)	0.128 (10)	0.071 (6)	−0.012 (6)	−0.003 (4)	−0.039 (7)
C5T	0.044 (5)	0.050 (5)	0.107 (7)	−0.001 (4)	−0.004 (4)	−0.024 (5)

Geometric parameters (Å, º)

Zn1—O4^i	1.9662 (17)	C10—H10A	0.9800
Zn1—O3	1.9795 (16)	C10—H10B	0.9800
Zn1—O5^ii	1.9820 (15)	C10—H10C	0.9800
Zn1—O6	2.1286 (18)	C11—H11A	0.9800
Zn1—O7	2.1661 (18)	C11—H11B	0.9800
O1—C1	1.362 (3)	C11—H11C	0.9800
O1—H1	0.825 (18)	C12—H12	0.9500
O2—C8	1.238 (3)	C13—H13A	0.9800
O3—C8	1.265 (3)	C13—H13B	0.9800
O4—C7	1.250 (3)	C13—H13C	0.9800
O4—Zn1^i	1.9662 (17)	C14—H14A	0.9800
O5—C7	1.265 (3)	C14—H14B	0.9800
O5—Zn1^iii	1.9820 (15)	C14—H14C	0.9800
O6—C9	1.240 (3)	C1T—C2T	1.267 (10)
O7—C12	1.234 (3)	C1T—C4T	1.412 (14)
N1—C9	1.318 (4)	C1T—C5T^iv	1.586 (10)
N1—C11	1.454 (4)	C1T—H1TA	0.934 (8)
N1—C10	1.461 (4)	C1T—H1TB	0.984 (7)
N2—C12	1.315 (4)	C1T—H1TC	1.006 (6)
N2—C14	1.446 (4)	C1T—H1TD	1.178 (7)
N2—C13	1.462 (4)	C2T—C3T	1.356 (9)
C1—C2	1.392 (3)	C2T—C3T^iv	1.594 (9)
C1—C6	1.397 (3)	C3T—C4T	1.175 (12)
C2—C3	1.388 (3)	C3T—C5T	1.252 (9)
C2—H2	0.9500	C3T—C2T^iv	1.594 (9)
C3—C4	1.397 (3)	C3T—H3TA	0.928 (6)
C3—C8	1.506 (3)	C3T—H3TB	0.987 (5)
C4—C5	1.396 (3)	C4T—H1TA	1.337 (13)
C4—H4	0.9500	C4T—H3TA	1.183 (14)
C5—C6	1.386 (3)	C4T—H4TA	1.000 (9)
C5—C7	1.502 (3)	C5T—C1T^iv	1.586 (10)
C6—H6	0.9500	C5T—H3TB	0.578 (8)
C9—H9	0.9500	C5T—H5TA	0.940 (9)
O4^i—Zn1—O3	100.50 (7)	N2—C13—H13A	109.5
O4^i—Zn1—O5^ii	129.78 (7)	N2—C13—H13B	109.5
O3—Zn1—O5^ii	129.36 (7)	H13A—C13—H13B	109.5
O4^i—Zn1—O6	90.45 (7)	N2—C13—H13C	109.5
O3—Zn1—O6	91.53 (7)	H13A—C13—H13C	109.5
O5^ii—Zn1—O6	93.44 (7)	H13B—C13—H13C	109.5
O4^i—Zn1—O7	87.92 (8)	N2—C14—H14A	109.5
O3—Zn1—O7	89.45 (7)	N2—C14—H14B	109.5
O5^ii—Zn1—O7	87.08 (7)	H14A—C14—H14B	109.5
O6—Zn1—O7	178.23 (7)	N2—C14—H14C	109.5
C1—O1—H1	108 (2)	H14A—C14—H14C	109.5
C8—O3—Zn1	117.90 (15)	H14B—C14—H14C	109.5
C7—O4—Zn1^i	149.05 (17)	C2T—C1T—C5T^iv	62.5 (6)
C7—O5—Zn1^iii	125.10 (15)	C4T—C1T—C5T^iv	103.7 (7)
C9—O6—Zn1	123.43 (17)	C2T—C1T—H1TA	106.7 (7)
C12—O7—Zn1	120.35 (19)	C4T—C1T—H1TA	65.8 (6)
C9—N1—C11	121.4 (2)	C5T^iv—C1T—H1TA	169.2 (7)
C9—N1—C10	121.1 (2)	C2T—C1T—H1TB	110.8 (8)
C11—N1—C10	117.5 (2)	C4T—C1T—H1TB	116.5 (7)
C12—N2—C14	122.0 (3)	C5T^iv—C1T—H1TB	73.6 (6)
C12—N2—C13	121.5 (3)	H1TA—C1T—H1TB	113.0 (6)
C14—N2—C13	116.4 (3)	C2T—C1T—H1TC	108.1 (7)
O1—C1—C2	122.4 (2)	C4T—C1T—H1TC	133.8 (7)
O1—C1—C6	118.2 (2)	C5T^iv—C1T—H1TC	73.6 (5)
C2—C1—C6	119.4 (2)	H1TA—C1T—H1TC	111.0 (7)
C3—C2—C1	120.8 (2)	H1TB—C1T—H1TC	107.0 (6)
C3—C2—H2	119.6	C2T—C1T—H1TD	162.8 (8)
C1—C2—H2	119.6	C4T—C1T—H1TD	125.0 (8)
C2—C3—C4	119.8 (2)	C5T^iv—C1T—H1TD	131.2 (6)
C2—C3—C8	119.7 (2)	H1TA—C1T—H1TD	59.2 (4)
C4—C3—C8	120.5 (2)	H1TB—C1T—H1TD	85.0 (5)
C5—C4—C3	119.2 (2)	H1TC—C1T—H1TD	71.7 (4)
C5—C4—H4	120.4	C1T—C2T—C3T	134.4 (9)
C3—C4—H4	120.4	C1T—C2T—C3T^iv	116.8 (8)
C6—C5—C4	120.8 (2)	C3T—C2T—C3T^iv	107.7 (6)
C6—C5—C7	120.0 (2)	C4T—C3T—C5T	177.6 (9)
C4—C5—C7	119.1 (2)	C4T—C3T—C2T	45.0 (6)
C5—C6—C1	119.8 (2)	C5T—C3T—C2T	133.6 (8)
C5—C6—H6	120.1	C4T—C3T—C2T^iv	115.7 (7)
C1—C6—H6	120.1	C5T—C3T—C2T^iv	62.4 (6)
O4—C7—O5	125.4 (2)	C2T—C3T—C2T^iv	72.3 (6)
O4—C7—C5	117.1 (2)	C4T—C3T—H3TA	67.3 (7)
O5—C7—C5	117.4 (2)	C5T—C3T—H3TA	114.5 (6)
O2—C8—O3	123.9 (2)	C2T—C3T—H3TA	111.3 (7)
O2—C8—C3	119.0 (2)	C2T^iv—C3T—H3TA	175.4 (6)
O3—C8—C3	117.0 (2)	C4T—C3T—H3TB	154.6 (9)
O6—C9—N1	124.8 (2)	C2T—C3T—H3TB	160.3 (8)
O6—C9—H9	117.6	C2T^iv—C3T—H3TB	88.4 (5)
N1—C9—H9	117.6	H3TA—C3T—H3TB	88.2 (4)
N1—C10—H10A	109.5	C3T—C4T—C1T	138.1 (10)
N1—C10—H10B	109.5	C3T—C4T—H1TA	167.0 (9)
H10A—C10—H10B	109.5	C3T—C4T—H3TA	46.3 (6)
N1—C10—H10C	109.5	C1T—C4T—H3TA	169.1 (9)
H10A—C10—H10C	109.5	H1TA—C4T—H3TA	133.0 (8)
H10B—C10—H10C	109.5	C3T—C4T—H4TA	114.9 (13)
N1—C11—H11A	109.5	C1T—C4T—H4TA	106.1 (11)
N1—C11—H11B	109.5	H1TA—C4T—H4TA	66.8 (7)
H11A—C11—H11B	109.5	H3TA—C4T—H4TA	68.5 (7)
N1—C11—H11C	109.5	C3T—C5T—C1T^iv	118.3 (7)
H11A—C11—H11C	109.5	C3T—C5T—H3TB	50.2 (7)
H11B—C11—H11C	109.5	C1T^iv—C5T—H3TB	163.7 (14)
O7—C12—N2	125.7 (3)	C3T—C5T—H5TA	140.0 (9)
O7—C12—H12	117.1	C1T^iv—C5T—H5TA	101.0 (7)
N2—C12—H12	117.1	H3TB—C5T—H5TA	89.9 (10)
O4^i—Zn1—O3—C8	−168.84 (17)	C4—C5—C7—O5	163.1 (2)
O5^ii—Zn1—O3—C8	17.6 (2)	Zn1—O3—C8—O2	2.4 (3)
O6—Zn1—O3—C8	−78.10 (17)	Zn1—O3—C8—C3	−175.98 (15)
O7—Zn1—O3—C8	103.37 (17)	C2—C3—C8—O2	−12.6 (4)
O4^i—Zn1—O6—C9	−146.2 (2)	C4—C3—C8—O2	166.0 (2)
O3—Zn1—O6—C9	113.3 (2)	C2—C3—C8—O3	165.9 (2)
O5^ii—Zn1—O6—C9	−16.3 (2)	C4—C3—C8—O3	−15.5 (3)
O4^i—Zn1—O7—C12	−143.7 (2)	Zn1—O6—C9—N1	−174.0 (2)
O3—Zn1—O7—C12	−43.21 (19)	C11—N1—C9—O6	−179.0 (3)
O5^ii—Zn1—O7—C12	86.25 (19)	C10—N1—C9—O6	1.1 (4)
O1—C1—C2—C3	179.0 (2)	Zn1—O7—C12—N2	178.9 (2)
C6—C1—C2—C3	−0.9 (4)	C14—N2—C12—O7	1.3 (4)
C1—C2—C3—C4	0.6 (4)	C13—N2—C12—O7	−178.7 (3)
C1—C2—C3—C8	179.2 (2)	C4T—C1T—C2T—C3T	−1.9 (9)
C2—C3—C4—C5	0.2 (4)	C5T^iv—C1T—C2T—C3T	−166.3 (11)
C8—C3—C4—C5	−178.4 (2)	C4T—C1T—C2T—C3T^iv	164.2 (11)
C3—C4—C5—C6	−0.7 (4)	C5T^iv—C1T—C2T—C3T^iv	−0.2 (6)
C3—C4—C5—C7	176.4 (2)	C1T—C2T—C3T—C4T	2.2 (10)
C4—C5—C6—C1	0.5 (4)	C3T^iv—C2T—C3T—C4T	−164.8 (10)
C7—C5—C6—C1	−176.6 (2)	C1T—C2T—C3T—C5T	179.4 (10)
O1—C1—C6—C5	−179.6 (2)	C3T^iv—C2T—C3T—C5T	12.4 (10)
C2—C1—C6—C5	0.3 (4)	C1T—C2T—C3T—C2T^iv	167.0 (13)
Zn1^i—O4—C7—O5	−41.0 (5)	C3T^iv—C2T—C3T—C2T^iv	0.0
Zn1^i—O4—C7—C5	142.3 (3)	C2T—C3T—C4T—C1T	−2.1 (10)
Zn1^iii—O5—C7—O4	−2.5 (3)	C2T^iv—C3T—C4T—C1T	−18.1 (16)
Zn1^iii—O5—C7—C5	174.18 (15)	C2T—C1T—C4T—C3T	2.3 (11)
C6—C5—C7—O4	157.2 (2)	C5T^iv—C1T—C4T—C3T	16.5 (15)
C4—C5—C7—O4	−20.0 (3)	C2T—C3T—C5T—C1T^iv	−13.2 (14)
C6—C5—C7—O5	−19.7 (3)	C2T^iv—C3T—C5T—C1T^iv	0.2 (6)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y+1, z; (iii) x, y−1, z; (iv) −x+2, −y+1, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2^v	0.83 (2)	1.87 (2)	2.685 (3)	171 (3)

Symmetry code: (v) −x+1, −y+1, −z+2.