Tetra-[mu]-benzoato-[kappa]⁸O:O'-bis({1-[(3,4-di­methoxy­phenyl)­methyl]-6,7-di­methoxy­iso­quinoline-[kappa]N}­zinc(II)): the first crystal structure with papaverine as a ligand

The title complex, [Zn₂(C₇H₅O₂)₄(C₂₀H₂₁NO₄)₂], forms dimers of the paddle-wheel cage type located at crystallographic inversion centres. The two Zn atoms [Zn...Zn = 3.0533 (4) Å] are connected by four syn-syn benzoate ligands. The apical positions of the square-pyramidal zinc coordination polyhedra are occupied by the N atoms of the papaverine ligand. Upon coordination, the mutual orientation of the phenyl and iso­quinoline rings in papaverine is changed compared with that in the uncoordinated ligand.

S1. Comment

Papaverine [1-(3,4-Dimethoxyphenyl)methyl-6,7-dimethoxyisoquinoline] is an alkaloid used as a vasodilator in cardiac and kidney surgery (Ali et al., 1997; Zacherl et al., 2002). When applied to human organisms, it can interact with a number of metal ions present in the body. One way to understand these metal–drug interactions is to study structures of metal complexes containing the drug as a ligand. There are a number of examples of such structural studies (Cini, 2000), although reports dealing with properties of metal complexes of papaverine are scarce (e.g. Sabirov et al., 1994; Melník et al., 1996; Györyová et al., 2002; Williams et al., 2003). The crystal structures of papaverine and its hydrochloric salt have already been described (Reynolds et al., 1974; Marek et al., 1996). Moreover, the papaverinium cation as the counter-ion in a cobalt-containing complex has been structurally characterized (Sabirov et al., 1994). However, the Cambridge Structural Database (Allen, 2002) does not contain an entry of a crystal structure with papaverine as a ligand. The present study fills this gap; we describe here the structure of a zinc(II) benzoate complex, (I), of papaverine.

The molecular structure of complex (I) consists of discrete centrosymmetric [Zn₂(C₆H₅COO)₄(C₂₀H₂₁NO₄)₂] dimers of the paddle-wheel cage type, with an inversion centre located at the mid-point of the Zn···Zn vector. This known structural type was first described in 1953 for copper acetate monohydrate (van Nieker & Schoening, 1953) and has since been observed for a variety of transition metals (Mehrotra & Bohra, 1983). In the structure of (I), the pair of Zn^II atoms is bridged by four syn–syn benzoate ligands. The O atoms of these ligands are placed in the basal plane of a tetragonal pyramid around each Zn^II atom (τ = 0.0; Addison et al., 1984), while the apical position is occupied by the N atom of the papaverine molecule. The Zn atom is shifted by 0.412 (1) Å from the basal plane toward the apical position. Among Zn^II carboxylate complexes, a similar coordination type was found in some aliphatic carboxylates, for example, acetate (Singh et al., 1997) and crotonate (Clegg et al., 1986; Clegg et al., 1995).

The average Zn—O bond length [2.048 Å; Table 1] is slightly longer than those observed for structurally characterized paddle-wheel zinc(II) complexes of formula [Zn₂(RCOO)₄L₂], with average values of 2.043 Å (where RCOO is crotonate and L is quinoline; Clegg et al., 1986], 2.037 Å (where RCOO is crotonate and L is 4-cyanopyridine; Clegg et al., 1995), 2.038 and 2.041 Å (where RCOO is acetate and L is pyridine; Singh et al., 1997), and 2.034, 2.039 or 2.042 Å [where RCOO is indomethacin and L is 1-methylpyrrolidinone, pyridine or dimethylacetamide; Zhou et al., 2000). As a consequence, the Zn···Zn separation [3.053 (1) Å] in (I) is longer than those in the above-mentioned complexes, which exhibit Zn···Zn separatios of less than? 3 Å.

The geometric parameters in the papaverine ligand are close to those observed for the free base (Marek et al., 1996). The most remarkable differences were observed in the O5—C31 [1.384 (3) Å] and O6—C32 [1.381 (4) Å] bond lengths, which are shorter than the respective values in free papaverine [1.415 (5) Å (x 2); Marek et al., 1996]. This difference may be due to the strongly anisotropic displacement parameters within this peripheral groups. Moreover, as a result of the coordination of papaverine, a change in the orientation of the phenyl and isochinoline rings is observed. The C25—C26—C27 angle [112.2 (1)°] changes only slightly [115.2 (3)° in the free base, 112.2° in the hydrochloride and 113.8 (8)° in the cobalt complex containing the papaverinium cation]. More important changes were observed in the torsion angles. The C28—C27—C26—C25 torsion angle is −134.1 (2)°, while the angles in free papaverine and papaverine hydrochloride are 117.9 (4) and 80.5°, respectively (Reynolds et al., 1974; Marek et al., 1996). The value of this torsion angle in the cobalt complex containing the papaverinium cation is 63 (1)° (Sabirov et al., 1994). Similarly, a difference was observed in the C27—C26—C25—N1 torsion angle [−106.6 (2)°, c.f 112.7 (3)° in the free base, 84.8° in the hydrochloric salt and −112.8 (9)° in the cation in the cobalt complex. This change of the mutual orientation of both rings may be a result of both steric hindrance of benzoate ligands and non-bonding interactions.

From the composition of complex (I), it is obvious that no conventional hydrogen bonds can be expected in the structure. The molecules are held together only by C—H···O and van der Waals interactions. The most important C—H···O intermolecular contacts shorter than the sum of the van der Waals radii are shown in Fig. 2 and listed in Table 2. These C—H···O intermolecular interactions connect the dimers into sheets parallel to the bc plane.

S2. Experimental

In a typical procedure, papaverine hydrochloride (5 g, 13.30 mmol) was dissolved in water (150 cm³). To this solution an equimolar amount of sodium hydroxide (0.532 g) dissolved in water (25 cm³) was added dropwise under vigorous stirring. White precipitated papaverine powder was filtered off, washed with water and dried. The prepared papaverine was used in the next step of the synthesis. Sodium benzoate (5 g, 3.47 mmol) dissolved in absolute ethanol (25 cm³) was mixed with an ethanol solution (25 cm³) of zinc chloride (0.236 g; 1.73 mmol). After stirring for 30 min, the solution was filtered and then an ethanol solution (30 cm³) of papaverine (1.178 g; 3.47 mmol) was added to the filtrate. The reaction mixture was stirred for 1 h, and then filtered and left to stand at room temperature. Within a week colourless crystals appeared. Recrystallization from ethanol gave crystals suitable for X-ray diffraction.

S3. Refinement

155 reflections are missing from the dataset [up to sin(θ)/λ=0.6] as a result of the use of an IPDS one-circle imaging-plate diffractometer system. All H atoms were found in a difference map and then treated as riding, with U_iso(H) values equal to 1.2U_eq(C) [1.5U_eq(C) for the methyl groups].

Computing details

Data collection: ?EXPOSE (Stoe, 1997); cell refinement: CELL (Stoe, 1997); data reduction: INTEGRATE (Stoe, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2000); software used to prepare material for publication: SHELXL97 and enCIFer (Smith & Johnson, 2002).

Figures

	Fig. 1. The centrosymmetric dimer [Zn2(C6H5COO)4(C20H21NO4)2], with the atom labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as spheres of arbitrary radii.
	Fig. 2. A view along the a axis, showing the intermolecular C—H···O contacts (dashed lines) in the planes parallel to bc. One such planes is displayed fully. From the adjacent? plane only the dimeric cages (grey) are shown for the sake of clarity. Benzoate ligands not involved in the contacts have also been omitted.

Tetra-µ-benzoato-κ²O,O'-bis{1-[(3,4-dimethoxyphenyl)methyl]-6,7- dimethoxyisoquinoline-κN)zinc(II)}

Crystal data

[Zn2(C7H5O2)4(C20H21NO4)2]	F(000) = 1344
Mr = 1293.98	Dx = 1.382 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 8002 reflections
a = 14.1780 (9) Å	θ = 3.0–30.3°
b = 14.4118 (6) Å	µ = 0.84 mm^−1
c = 15.5442 (11) Å	T = 193 K
β = 101.799 (8)°	Block, colourless
V = 3109.0 (3) Å^3	0.60 × 0.45 × 0.38 mm
Z = 2

Data collection

IPDS Stoe diffractometer	8890 independent reflections
Radiation source: fine-focus sealed tube	5836 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.057
Detector resolution: 150 pixels mm^-1	θmax = 30.4°, θmin = 3.0°
D=50mm, Φ 0–250°, ΔΦ 1.0°, 1 min/rec scans	h = −20→20
Absorption correction: multi-scan (XPREP in SHELXTL; Sheldrick, 1996)	k = −19→18
Tmin = 0.659, Tmax = 0.737	l = −22→22
45411 measured reflections

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)] = 0.036	Hydrogen site location: difference Fourier map
wR(F^2) = 0.088	H-atom parameters constrained
S = 0.91	w = 1/[σ^2(Fo^2) + (0.05P)^2] where P = (Fo^2 + 2Fc^2)/3
8890 reflections	(Δ/σ)max < 0.001
402 parameters	Δρmax = 0.60 e Å^−3
0 restraints	Δρmin = −0.69 e Å^−3

Special details

Experimental. 155 reflections are missing from the dataset up to sin(θ)/λ=0.6. This is due to IPDS 1-circle imaging plate diffractometer system used. The missing cusp of data could be measured only after remounting the crystal in a different orientation which was not done in the experiment. Sufficient overdetermination (data/parameter ratio 22.1) has been achieved by measuring to θ = 30.4 °.

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.

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

	x	y	z	Uiso*/Ueq
Zn	0.005948 (14)	0.101252 (15)	0.029481 (13)	0.01757 (6)
N1	−0.00881 (10)	0.24306 (11)	0.04829 (9)	0.0194 (3)
O1A	−0.05128 (11)	0.10760 (11)	−0.10242 (8)	0.0349 (3)
O1B	−0.06363 (11)	−0.03956 (10)	−0.14728 (8)	0.0304 (3)
O2A	0.13705 (9)	0.08380 (10)	−0.00323 (10)	0.0317 (3)
O2B	0.12702 (10)	−0.06288 (11)	−0.05091 (11)	0.0363 (4)
O3	−0.05522 (10)	0.66294 (10)	0.16615 (10)	0.0340 (3)
O4	0.09650 (9)	0.59486 (11)	0.26264 (10)	0.0326 (3)
O5	0.05331 (13)	0.17342 (16)	0.50858 (11)	0.0580 (6)
O6	−0.07495 (13)	0.13233 (14)	0.36958 (12)	0.0528 (5)
C1	−0.07010 (12)	0.04628 (13)	−0.16090 (11)	0.0202 (4)
C2	−0.10022 (12)	0.07893 (13)	−0.25421 (11)	0.0198 (4)
C3	−0.08910 (13)	0.17170 (14)	−0.27507 (12)	0.0249 (4)
H3	−0.0677	0.2154	−0.2295	0.030*
C4	−0.10913 (14)	0.20095 (15)	−0.36217 (13)	0.0294 (4)
H4	−0.1005	0.2642	−0.3759	0.035*
C5	−0.14153 (14)	0.13805 (16)	−0.42880 (12)	0.0298 (4)
H5	−0.1543	0.1579	−0.4883	0.036*
C6	−0.15544 (15)	0.04598 (16)	−0.40873 (13)	0.0300 (4)
H6	−0.1795	0.0032	−0.4544	0.036*
C7	−0.13431 (13)	0.01627 (15)	−0.32188 (11)	0.0248 (4)
H7	−0.1431	−0.0471	−0.3085	0.030*
C8	0.16849 (12)	0.01396 (14)	−0.03693 (11)	0.0226 (4)
C9	0.26473 (13)	0.02500 (15)	−0.06287 (12)	0.0262 (4)
C10	0.31428 (14)	0.10844 (17)	−0.04770 (15)	0.0359 (5)
H10	0.2877	0.1584	−0.0206	0.043*
C11	0.40300 (18)	0.1191 (2)	−0.0721 (2)	0.0577 (8)
H11	0.4369	0.1762	−0.0613	0.069*
C12	0.4411 (2)	0.0478 (3)	−0.1115 (2)	0.0714 (10)
H12	0.5012	0.0558	−0.1285	0.086*
C13	0.3934 (2)	−0.0356 (3)	−0.1268 (2)	0.0668 (9)
H13	0.4206	−0.0850	−0.1542	0.080*
C14	0.30491 (16)	−0.0476 (2)	−0.10207 (17)	0.0439 (6)
H14	0.2721	−0.1053	−0.1120	0.053*
C15	−0.08722 (12)	0.28195 (14)	−0.00696 (12)	0.0229 (4)
H15	−0.1232	0.2446	−0.0525	0.027*
C16	−0.11559 (13)	0.37122 (14)	0.00050 (12)	0.0245 (4)
H16	−0.1708	0.3946	−0.0388	0.029*
C17	−0.06315 (12)	0.42921 (13)	0.06655 (11)	0.0199 (3)
C18	−0.09046 (13)	0.52194 (14)	0.08014 (12)	0.0234 (4)
H18	−0.1462	0.5477	0.0436	0.028*
C19	−0.03652 (13)	0.57450 (13)	0.14606 (13)	0.0233 (4)
C20	−0.13711 (15)	0.70835 (16)	0.11416 (16)	0.0368 (5)
H20A	−0.1323	0.7067	0.0522	0.055*
H20B	−0.1390	0.7730	0.1333	0.055*
H20C	−0.1960	0.6765	0.1214	0.055*
C21	0.18346 (14)	0.56093 (17)	0.31685 (15)	0.0351 (5)
H21A	0.1689	0.5067	0.3499	0.053*
H21B	0.2122	0.6096	0.3580	0.053*
H21C	0.2288	0.5433	0.2799	0.053*
C22	0.04915 (13)	0.53623 (14)	0.20043 (12)	0.0235 (4)
C23	0.07644 (12)	0.44758 (13)	0.18754 (12)	0.0219 (4)
H23	0.1336	0.4233	0.2231	0.026*
C24	0.02012 (11)	0.39104 (13)	0.12137 (11)	0.0188 (3)
C25	0.04411 (11)	0.29682 (13)	0.10992 (11)	0.0175 (3)
C26	0.12889 (12)	0.25288 (13)	0.17104 (11)	0.0200 (3)
H26B	0.1861	0.2932	0.1747	0.024*
H26A	0.1434	0.1924	0.1465	0.024*
C27	0.10990 (12)	0.23810 (14)	0.26276 (12)	0.0227 (4)
C28	0.17714 (14)	0.26173 (16)	0.33709 (13)	0.0311 (4)
H28	0.2354	0.2914	0.3314	0.037*
C29	0.15971 (16)	0.24215 (18)	0.42079 (14)	0.0386 (5)
H29	0.2060	0.2593	0.4715	0.048 (7)*
C30	0.07611 (15)	0.19829 (18)	0.43013 (13)	0.0363 (5)
C31	0.1233 (2)	0.1793 (3)	0.58484 (17)	0.0767 (11)
H31A	0.1821	0.1482	0.5760	0.115*
H31B	0.1000	0.1493	0.6331	0.115*
H31C	0.1374	0.2447	0.5994	0.115*
C32	−0.1370 (2)	0.0952 (3)	0.2976 (2)	0.0832 (12)
H32A	−0.1665	0.1455	0.2588	0.125*
H32B	−0.1875	0.0596	0.3174	0.125*
H32C	−0.1010	0.0543	0.2656	0.125*
C33	0.00667 (15)	0.17600 (16)	0.35513 (14)	0.0330 (5)
C34	0.02320 (13)	0.19656 (15)	0.27280 (12)	0.0266 (4)
H34	−0.0247	0.1824	0.2222	0.032*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn	0.02110 (9)	0.01342 (11)	0.01778 (9)	−0.00049 (8)	0.00302 (6)	−0.00289 (8)
N1	0.0192 (7)	0.0169 (9)	0.0212 (7)	−0.0001 (5)	0.0021 (5)	−0.0028 (6)
O1A	0.0590 (9)	0.0233 (9)	0.0170 (6)	0.0057 (7)	−0.0049 (6)	−0.0062 (6)
O1B	0.0489 (8)	0.0199 (9)	0.0191 (6)	−0.0020 (6)	−0.0005 (6)	0.0021 (5)
O2A	0.0279 (7)	0.0288 (9)	0.0422 (8)	−0.0002 (5)	0.0158 (6)	−0.0049 (6)
O2B	0.0268 (7)	0.0302 (9)	0.0554 (10)	−0.0091 (6)	0.0165 (7)	−0.0085 (7)
O3	0.0361 (7)	0.0141 (8)	0.0470 (9)	0.0047 (6)	−0.0029 (6)	−0.0070 (6)
O4	0.0305 (7)	0.0211 (8)	0.0406 (8)	−0.0010 (6)	−0.0058 (6)	−0.0139 (6)
O5	0.0507 (10)	0.0994 (17)	0.0270 (8)	0.0160 (10)	0.0150 (7)	0.0113 (9)
O6	0.0552 (10)	0.0660 (14)	0.0456 (10)	−0.0160 (9)	0.0302 (8)	−0.0084 (9)
C1	0.0201 (8)	0.0201 (11)	0.0200 (8)	0.0013 (6)	0.0035 (6)	−0.0009 (7)
C2	0.0208 (7)	0.0201 (11)	0.0185 (8)	0.0010 (6)	0.0038 (6)	−0.0020 (6)
C3	0.0303 (9)	0.0188 (11)	0.0244 (9)	−0.0003 (7)	0.0027 (7)	−0.0011 (7)
C4	0.0396 (11)	0.0214 (12)	0.0273 (10)	0.0001 (8)	0.0068 (8)	0.0048 (8)
C5	0.0363 (10)	0.0323 (13)	0.0203 (9)	0.0036 (8)	0.0049 (8)	0.0051 (8)
C6	0.0376 (10)	0.0293 (13)	0.0212 (9)	−0.0016 (8)	0.0017 (8)	−0.0058 (8)
C7	0.0331 (9)	0.0199 (11)	0.0198 (8)	−0.0020 (7)	0.0018 (7)	−0.0014 (7)
C8	0.0220 (8)	0.0250 (11)	0.0206 (8)	−0.0007 (7)	0.0040 (6)	0.0024 (7)
C9	0.0246 (9)	0.0294 (12)	0.0253 (9)	−0.0014 (7)	0.0071 (7)	0.0021 (8)
C10	0.0315 (10)	0.0340 (14)	0.0442 (12)	−0.0064 (9)	0.0120 (8)	0.0045 (10)
C11	0.0396 (13)	0.065 (2)	0.0733 (19)	−0.0193 (12)	0.0228 (13)	0.0077 (15)
C12	0.0384 (14)	0.102 (3)	0.085 (2)	−0.0120 (16)	0.0388 (15)	−0.001 (2)
C13	0.0486 (15)	0.084 (3)	0.078 (2)	0.0057 (15)	0.0372 (15)	−0.0181 (18)
C14	0.0380 (12)	0.0464 (17)	0.0520 (14)	−0.0006 (10)	0.0204 (11)	−0.0121 (11)
C15	0.0222 (8)	0.0192 (11)	0.0238 (9)	0.0007 (7)	−0.0035 (6)	−0.0060 (7)
C16	0.0229 (8)	0.0218 (11)	0.0253 (9)	0.0022 (7)	−0.0033 (7)	−0.0022 (7)
C17	0.0211 (8)	0.0156 (10)	0.0225 (8)	−0.0010 (6)	0.0033 (6)	−0.0009 (6)
C18	0.0231 (8)	0.0171 (10)	0.0280 (9)	0.0024 (7)	0.0002 (7)	0.0002 (7)
C19	0.0274 (9)	0.0121 (10)	0.0302 (9)	0.0010 (6)	0.0051 (7)	−0.0019 (7)
C20	0.0372 (11)	0.0200 (13)	0.0509 (13)	0.0086 (8)	0.0031 (9)	0.0003 (9)
C21	0.0292 (10)	0.0341 (14)	0.0379 (11)	−0.0024 (8)	−0.0032 (8)	−0.0152 (9)
C22	0.0250 (8)	0.0165 (11)	0.0270 (9)	−0.0034 (7)	0.0006 (7)	−0.0055 (7)
C23	0.0218 (8)	0.0180 (11)	0.0241 (9)	−0.0006 (7)	0.0005 (6)	−0.0025 (7)
C24	0.0209 (7)	0.0149 (10)	0.0202 (7)	−0.0018 (6)	0.0034 (6)	−0.0015 (7)
C25	0.0182 (7)	0.0152 (10)	0.0191 (8)	−0.0013 (6)	0.0039 (6)	−0.0034 (6)
C26	0.0198 (8)	0.0160 (10)	0.0236 (8)	0.0018 (6)	0.0026 (6)	−0.0030 (7)
C27	0.0240 (8)	0.0186 (11)	0.0242 (9)	0.0071 (7)	0.0022 (7)	−0.0013 (7)
C28	0.0253 (9)	0.0388 (14)	0.0265 (10)	0.0070 (8)	−0.0010 (7)	−0.0007 (8)
C29	0.0354 (11)	0.0548 (17)	0.0218 (10)	0.0149 (10)	−0.0031 (8)	−0.0039 (9)
C30	0.0393 (11)	0.0470 (16)	0.0248 (10)	0.0160 (10)	0.0118 (8)	0.0033 (9)
C31	0.0652 (18)	0.135 (4)	0.0298 (13)	0.022 (2)	0.0093 (13)	0.0179 (17)
C32	0.070 (2)	0.110 (3)	0.081 (2)	−0.050 (2)	0.0434 (18)	−0.040 (2)
C33	0.0366 (10)	0.0330 (13)	0.0329 (11)	0.0039 (9)	0.0157 (9)	−0.0025 (9)
C34	0.0297 (9)	0.0247 (12)	0.0253 (9)	0.0024 (7)	0.0054 (7)	−0.0050 (7)

Geometric parameters (Å, º)

Zn—O2A	2.0404 (12)	C12—H12	0.9500
Zn—O1A	2.0470 (13)	C13—C14	1.396 (3)
Zn—O1B^i	2.0494 (14)	C13—H13	0.9500
Zn—O2B^i	2.0562 (13)	C14—H14	0.9500
Zn—N1	2.0812 (16)	C15—C16	1.360 (3)
Zn—Zn^i	3.0533 (4)	C15—H15	0.9500
N1—C25	1.337 (2)	C16—C17	1.412 (3)
N1—C15	1.377 (2)	C16—H16	0.9500
O1A—C1	1.257 (2)	C17—C24	1.418 (2)
O1B—C1	1.255 (2)	C17—C18	1.419 (3)
O1B—Zn^i	2.0494 (14)	C18—C19	1.374 (3)
O2A—C8	1.258 (2)	C18—H18	0.9500
O2B—C8	1.252 (2)	C19—C22	1.440 (3)
O2B—Zn^i	2.0561 (13)	C20—H20A	0.9800
O3—C19	1.351 (2)	C20—H20B	0.9800
O3—C20	1.430 (2)	C20—H20C	0.9800
O4—C22	1.354 (2)	C21—H21A	0.9800
O4—C21	1.430 (2)	C21—H21B	0.9800
O5—C30	1.372 (2)	C21—H21C	0.9800
O5—C31	1.384 (3)	C22—C23	1.361 (3)
O6—C33	1.376 (3)	C23—C24	1.422 (2)
O6—C32	1.381 (4)	C23—H23	0.9500
C1—C2	1.501 (2)	C24—C25	1.420 (3)
C2—C3	1.392 (3)	C25—C26	1.510 (2)
C2—C7	1.396 (2)	C26—C27	1.519 (2)
C3—C4	1.391 (3)	C26—H26B	0.9900
C3—H3	0.9500	C26—H26A	0.9900
C4—C5	1.382 (3)	C27—C28	1.382 (3)
C4—H4	0.9500	C27—C34	1.404 (3)
C5—C6	1.386 (3)	C28—C29	1.402 (3)
C5—H5	0.9500	C28—H28	0.9500
C6—C7	1.389 (3)	C29—C30	1.377 (3)
C6—H6	0.9500	C29—H29	0.9500
C7—H7	0.9500	C30—C33	1.401 (3)
C8—C9	1.508 (2)	C31—H31A	0.9800
C9—C10	1.388 (3)	C31—H31B	0.9800
C9—C14	1.390 (3)	C31—H31C	0.9800
C10—C11	1.395 (3)	C32—H32A	0.9800
C10—H10	0.9500	C32—H32B	0.9800
C11—C12	1.363 (5)	C32—H32C	0.9800
C11—H11	0.9500	C33—C34	1.380 (3)
C12—C13	1.377 (5)	C34—H34	0.9500
O2A—Zn—O1A	87.17 (6)	C15—C16—H16	120.0
O2A—Zn—O1B^i	87.24 (6)	C17—C16—H16	120.0
O1A—Zn—O1B^i	156.69 (6)	C16—C17—C24	117.22 (17)
O2A—Zn—O2B^i	156.84 (6)	C16—C17—C18	123.13 (17)
O1A—Zn—O2B^i	89.17 (7)	C24—C17—C18	119.65 (16)
O1B^i—Zn—O2B^i	87.14 (6)	C19—C18—C17	120.20 (17)
O2A—Zn—N1	106.20 (6)	C19—C18—H18	119.9
O1A—Zn—N1	93.79 (6)	C17—C18—H18	119.9
O1B^i—Zn—N1	109.50 (6)	O3—C19—C18	125.93 (17)
O2B^i—Zn—N1	96.86 (6)	O3—C19—C22	114.04 (17)
O2A—Zn—Zn^i	78.73 (4)	C18—C19—C22	120.03 (17)
O1A—Zn—Zn^i	75.87 (4)	O3—C20—H20A	109.5
O1B^i—Zn—Zn^i	80.85 (4)	O3—C20—H20B	109.5
O2B^i—Zn—Zn^i	78.19 (4)	H20A—C20—H20B	109.5
N1—Zn—Zn^i	168.48 (4)	O3—C20—H20C	109.5
C25—N1—C15	118.31 (16)	H20A—C20—H20C	109.5
C25—N1—Zn	127.73 (12)	H20B—C20—H20C	109.5
C15—N1—Zn	113.80 (12)	O4—C21—H21A	109.5
C1—O1A—Zn	132.46 (14)	O4—C21—H21B	109.5
C1—O1B—Zn^i	125.47 (12)	H21A—C21—H21B	109.5
C8—O2A—Zn	128.39 (12)	O4—C21—H21C	109.5
C8—O2B—Zn^i	128.57 (13)	H21A—C21—H21C	109.5
C19—O3—C20	118.42 (16)	H21B—C21—H21C	109.5
C22—O4—C21	116.69 (16)	O4—C22—C23	125.19 (17)
C30—O5—C31	119.2 (2)	O4—C22—C19	114.55 (17)
C33—O6—C32	117.54 (19)	C23—C22—C19	120.26 (17)
O1B—C1—O1A	125.01 (17)	C22—C23—C24	120.63 (17)
O1B—C1—C2	117.92 (16)	C22—C23—H23	119.7
O1A—C1—C2	117.04 (17)	C24—C23—H23	119.7
C3—C2—C7	118.95 (17)	C17—C24—C25	119.14 (15)
C3—C2—C1	120.17 (16)	C17—C24—C23	119.18 (17)
C7—C2—C1	120.77 (17)	C25—C24—C23	121.67 (16)
C4—C3—C2	120.50 (19)	N1—C25—C24	122.03 (16)
C4—C3—H3	119.8	N1—C25—C26	117.76 (16)
C2—C3—H3	119.8	C24—C25—C26	120.15 (15)
C5—C4—C3	120.1 (2)	C25—C26—C27	112.22 (13)
C5—C4—H4	120.0	C25—C26—H26B	109.2
C3—C4—H4	120.0	C27—C26—H26B	109.2
C4—C5—C6	119.99 (18)	C25—C26—H26A	109.2
C4—C5—H5	120.0	C27—C26—H26A	109.2
C6—C5—H5	120.0	H26B—C26—H26A	107.9
C5—C6—C7	120.09 (19)	C28—C27—C34	118.82 (17)
C5—C6—H6	120.0	C28—C27—C26	121.72 (17)
C7—C6—H6	120.0	C34—C27—C26	119.42 (16)
C6—C7—C2	120.37 (19)	C27—C28—C29	120.3 (2)
C6—C7—H7	119.8	C27—C28—H28	119.9
C2—C7—H7	119.8	C29—C28—H28	119.9
O2B—C8—O2A	125.90 (16)	C30—C29—C28	120.6 (2)
O2B—C8—C9	117.73 (17)	C30—C29—H29	119.7
O2A—C8—C9	116.36 (17)	C28—C29—H29	119.7
C10—C9—C14	119.18 (19)	O5—C30—C29	125.3 (2)
C10—C9—C8	120.01 (18)	O5—C30—C33	115.3 (2)
C14—C9—C8	120.81 (19)	C29—C30—C33	119.42 (18)
C9—C10—C11	120.2 (2)	O5—C31—H31A	109.5
C9—C10—H10	119.9	O5—C31—H31B	109.5
C11—C10—H10	119.9	H31A—C31—H31B	109.5
C12—C11—C10	120.1 (3)	O5—C31—H31C	109.5
C12—C11—H11	120.0	H31A—C31—H31C	109.5
C10—C11—H11	120.0	H31B—C31—H31C	109.5
C11—C12—C13	120.7 (2)	O6—C32—H32A	109.5
C11—C12—H12	119.6	O6—C32—H32B	109.5
C13—C12—H12	119.6	H32A—C32—H32B	109.5
C12—C13—C14	119.8 (3)	O6—C32—H32C	109.5
C12—C13—H13	120.1	H32A—C32—H32C	109.5
C14—C13—H13	120.1	H32B—C32—H32C	109.5
C9—C14—C13	120.0 (3)	O6—C33—C34	123.9 (2)
C9—C14—H14	120.0	O6—C33—C30	116.14 (18)
C13—C14—H14	120.0	C34—C33—C30	119.93 (19)
C16—C15—N1	123.15 (16)	C33—C34—C27	120.88 (19)
C16—C15—H15	118.4	C33—C34—H34	119.6
N1—C15—H15	118.4	C27—C34—H34	119.6
C15—C16—C17	120.07 (17)

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O3^ii	0.95	2.53	3.364 (2)	147
C4—H4···O4^ii	0.95	2.68	3.312 (2)	125
C5—H5···O6^iii	0.95	2.70	3.454 (2)	137

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