(2,2′-Bi­pyridine-κ²N)­bis­[N-(2-pyridyl-κN)-p-toluene­sulfon­amido-κN]zinc(II)

The structure of the title compound, [Zn(C₁₂­H₁₁­N₂­O₂S)₂(C₁₀H₈N₂)], consists of monomeric mol­ecules in which the central ZnN₂N′N′′ unit has a distorted tetrahedral geometry, with bond lengths ranging from 2.020 (3) to 2.109 (3) Å. The anionic ligands are potential bidentate donors and thus there are two secondary Zn—N interactions. The shorter of these is 2.317 (3) Å and completes at the Zn atom an irregular five-coordinated geometry, which can be described as a square pyramid showing 30% distortion towards the trigonal bipyramid; the other Zn—N contact is much longer at 2.549 (3) Å.

S1. Comment

The coordination chemistry of sulfonamide ligands has been the subject of some recent investigation (Otter et al., 1998). The electron-withdrawing nature of the sulfonyl group causes important changes both in the neutral ligand and in its complexes. Free ligands, such as tosylsulfonyl-imino-1H-pyridine, are expected to exist as sulfonamides; however, crystallographic and spectroscopic data show that the most stable form bears the acidic hydrogen at the pyridine nitrogen (Cabaleiro et al., 1999a). Therefore, its metal complexes could be easily obtained by its electrochemical deprotonation (Cabaleiro et al., 1999a,b) following an electrochemical procedure similar to that described by Oldham & Tuck (1982).

The title compound, (I), was obtained (see Experimental) by electrolysis of a solution of [(4-methylphenyl)sulfonyl]-imino-1H-pyridine and 2,2'-bipyridine in a mixture of acetonitrile and dichloromethane, using a zinc plate as the anode. The value of the electrochemical efficiency, defined as the amount of zinc dissolved per number of Faradays, was close to 0.5 mol F^-1. This fact and the formation of hydrogen gas at the cathode are compatible with a reaction mechanism involving the anodic oxidation to zinc(II) and the deprotonation of the ligand at the cathode. \sch

The molecule consists of monomeric units where the zinc atom is coordinated to two anionic ligands and to one neutral bipyridine ligand resulting in a highly distorted tetrahedral environment, ZnN₄; the disposition of the anionic ligands around the metal corresponds approximately to non-crystallographic twofold point symmetry. The distortion is, in part, due to the small bite of the 2,2'-bipyridine, N31—Zn—N32 77.86 (10)°, which also leads to non-ideal values for the other N—Zn—N angles, 99.32 (10)–134.82 (10)°. The Zn—N bond lengths, between 2.020 (3) and 2.109 (3) Å, are slightly longer than in other tetracoordinated complexes with tosylamide ligands such as bis{N-[(2-pyrrolyl)methylene]-N'-tosylbenzene-1,2-diaminato}-zinc(II) with values between 1.962 (3) and 2.049 (4) Å (Romero et al., 1997). Nevertheless, the Zn—N_bipy bond distances, 2.106 (3) and 2.110 (3) Å, are similar to those observed in another complexes containing tetrahedral zinc and bipyridine, e.g. [Zn(S-2,4,6-Pri₃C₆H₂)₂bipy] (Corwin & Koch, 1988) or 2,2'-bipyridine bis(benzothiazole-2-thionato)zinc(II) (Castro et al., 1993).

The Zn—N_py bond lengths, 2.020 (3) and 2.082 (3) Å are as expected for tetrahedral pyridine complexes of zinc(II) (Steffen & Palenik, 1977; Xiong et al., 1997; Xu et al., 1998) but they are also consistent with values for pentacoordinated zinc(II), e.g. the cation [µ²-(4-nitrophenyl)phosphato-O,O']-bis[tris(2-pyridylmethyl)amine-N,N',N"] zinc(II) showed values in the range 2.034–2.082 Å (Adams et al., 1995).

In the title compound further Zn—N contacts are provided by the second nitrogen atoms of the potentially bidentate amide ligands. One such nitrogen, N22, is located 2.317 (3) Å from the zinc atom, whereas N12 is appreciably more distant at 2.549 (3) Å. We consider the latter as a contact rather than a bond. However, the former is close to the sum of the covalent radii (0.19 Å larger), and could thus be considered as a bond. Similar Zn—N distances of of 2.330 (6), 2.362 (4), 2.345 (3) or 2.437 (3) Å have been found in various pentacoordinated zinc complexes with N-donors (Alcock et al., 1988; Shionoya et al., 1994; Bhattacharyya et al., 1996; Meyer & Rutsch, 1998), and also interpreted as corresponding to bonds. Accordingly, the coordination polyhedron in the title compound could be described as a square pyramid showing 30% distortion towards a trigonal bipyramid (τ = 0.3) (Addison et al., 1984). The N—Zn—N angle of the four-membered chelate ring is 60.44 (10)°, slightly smaller than those found in other four-membered chelate rings, 63.58 and 63.21° (Engelhardt et al., 1991).

Both tosyl ligands are similar, but with different dihedral angles between the pyridine ring and the benzene ring, 79.30 (11) and 89.86 (12)°, the former corresponding to the bidentate ligand. This angle is smaller than that in the free ligand [83.7 (3) and 87.6 (1)°] (Cabaleiro et al., 1999a) probably due to the coordination.

Although the hydrogen atoms have been included in their idealized positions, some of them are situated close to sulfonyl O atoms, providing evidence for CH···O hydrogen bonds (Taylor & Kennard, 1982) (Table 2). The intramolecular interactions might be due to geometrical constraints, but intermolecular ones may be assumed to play a significant role in the packing arrangement.

In the bipyridyl ligand, the pyridine rings are essentially coplanar, with a dihedral angle of 6.9 (2)°.

S2. Experimental

The electrochemical oxidation of a zinc anode in an acetonitrile/dichloromethane solution (25 + 25 ml) containing the free ligand HL (198.7 mg, 0.8 mmol), 2,2'-bipyridine (62.5 mg, 0.4 mmol) and tetramethylammonium perchlorate (ca 10 mg) for 2 h at 12.5 V and 10 mA, resulted in a loss of 28.5 mg of zinc from the anode and the formation of a colourless solution, which after concentration gave a well crystallized solid. This solid was identified as [Zn(C₁₂H₁₁N₂SO₂)₂(C₁₀H₈N₂)]. Found; H 4.5 C 56.8, N 12.1, S 9.0 Calculated for C₃₄H₃₀N₆O₄S₂Zn, H 4.2, C 57.0, N 11.7, S 8.9.

S3. Refinement

Hydrogen atoms were refined using a riding model (HFIX 43 for aromatic H) and rigid methyl groups (HFIX 137).

Computing details

Data collection: CAD-4 EXPRESS (Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: HELENA (Spek, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1998); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. The title molecule, including atomic numbering scheme, drawn using ORTEP-3 (Farrugia, 1998). Hydrogen atoms are represented as circles of arbitrary radius, other atoms as displacement ellipsoids drawn at the 30% probability level.

2,2'-bipyridine bis{[(4-methylphenyl) sulfonyl]-2-pyridyl-amide}zinc(II)

Crystal data

[Zn(C12H11N2O2S)2(C10H8N2)]	F(000) = 1480
Mr = 716.13	Dx = 1.421 Mg m^−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54184 Å
a = 10.8157 (7) Å	Cell parameters from 25 reflections
b = 21.6466 (6) Å	θ = 19.1–45.2°
c = 14.354 (2) Å	µ = 2.58 mm^−1
β = 95.114 (8)°	T = 293 K
V = 3347.3 (5) Å^3	Block, colourless
Z = 4	0.30 × 0.20 × 0.15 mm

Data collection

CAD4 Enraf Nonius diffractometer	4479 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.039
Graphite monochromator	θmax = 75.9°, θmin = 3.7°
ω–θ scans	h = 0→13
Absorption correction: ψ scan (North et al., 1968) and PLATON (Spek, 1998)	k = −27→0
Tmin = 0.610, Tmax = 0.679	l = −18→17
7357 measured reflections	3 standard reflections every 200 reflections
6986 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.044	H-atom parameters constrained
wR(F^2) = 0.137	Calculated w = 1/[σ^2(Fo^2) + (0.0693P)^2 + 0.9056P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.001
6986 reflections	Δρmax = 0.48 e Å^−3
427 parameters	Δρmin = −0.38 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00124 (11)

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
Zn	0.86020 (4)	0.63768 (2)	0.31084 (3)	0.04617 (14)
S1	1.06592 (8)	0.77267 (4)	0.21262 (6)	0.0564 (2)
O11	1.1379 (3)	0.82034 (12)	0.2620 (2)	0.0786 (8)
O12	0.9607 (2)	0.79283 (14)	0.15122 (19)	0.0785 (8)
S2	1.01866 (8)	0.48652 (4)	0.28286 (7)	0.0576 (2)
O21	1.0251 (3)	0.47998 (15)	0.38255 (19)	0.0855 (9)
O22	0.9826 (3)	0.43263 (11)	0.2285 (2)	0.0865 (9)
N11	1.0121 (2)	0.65668 (11)	0.39838 (17)	0.0440 (6)
N12	1.0152 (2)	0.72193 (12)	0.27819 (17)	0.0487 (6)
C11	1.0559 (4)	0.63081 (17)	0.4793 (2)	0.0588 (9)
H11	1.0101	0.5995	0.5042	0.071*
C12	1.1649 (4)	0.6485 (2)	0.5266 (3)	0.0701 (11)
H12	1.1945	0.6291	0.5820	0.084*
C13	1.2305 (4)	0.6964 (2)	0.4896 (3)	0.0673 (10)
H13	1.3043	0.7102	0.5210	0.081*
C14	1.1869 (3)	0.72348 (16)	0.4071 (2)	0.0552 (8)
H14	1.2310	0.7554	0.3822	0.066*
C15	1.0759 (3)	0.70291 (14)	0.3606 (2)	0.0427 (7)
C16	1.1673 (3)	0.73517 (18)	0.1400 (2)	0.0586 (9)
C17	1.1277 (4)	0.6833 (2)	0.0908 (3)	0.0766 (12)
H17	1.0496	0.6669	0.0978	0.092*
C18	1.2043 (5)	0.6554 (2)	0.0309 (3)	0.0932 (14)
H18	1.1766	0.6202	−0.0019	0.112*
C19	1.3208 (5)	0.6784 (3)	0.0184 (3)	0.0912 (15)
C110	1.3574 (4)	0.7297 (3)	0.0676 (4)	0.0959 (16)
H110	1.4357	0.7459	0.0606	0.115*
C111	1.2830 (4)	0.7591 (2)	0.1280 (3)	0.0806 (12)
H111	1.3109	0.7945	0.1600	0.097*
C112	1.4026 (6)	0.6466 (3)	−0.0470 (4)	0.138 (3)
H11A	1.4496	0.6769	−0.0775	0.207*
H11B	1.3518	0.6236	−0.0932	0.207*
H11C	1.4583	0.6189	−0.0119	0.207*
N21	0.8292 (2)	0.61491 (12)	0.16982 (17)	0.0450 (6)
N22	0.9325 (3)	0.54432 (12)	0.25828 (18)	0.0504 (6)
C21	0.7752 (3)	0.63849 (17)	0.0899 (2)	0.0592 (9)
H21	0.7359	0.6766	0.0916	0.071*
C22	0.7759 (4)	0.6088 (2)	0.0066 (3)	0.0776 (12)
H22	0.7377	0.6261	−0.0480	0.093*
C23	0.8348 (4)	0.5523 (2)	0.0052 (3)	0.0874 (14)
H23	0.8372	0.5313	−0.0511	0.105*
C24	0.8896 (4)	0.5271 (2)	0.0856 (3)	0.0716 (11)
H24	0.9287	0.4889	0.0845	0.086*
C25	0.8862 (3)	0.55931 (15)	0.1693 (2)	0.0484 (7)
C26	1.1695 (3)	0.50495 (15)	0.2542 (2)	0.0483 (7)
C27	1.2504 (3)	0.45805 (17)	0.2356 (2)	0.0549 (8)
H27	1.2243	0.4171	0.2359	0.066*
C28	1.3692 (3)	0.4721 (2)	0.2169 (2)	0.0641 (10)
H28	1.4228	0.4402	0.2042	0.077*
C29	1.4117 (4)	0.5325 (2)	0.2162 (3)	0.0677 (10)
C210	1.3304 (4)	0.5786 (2)	0.2365 (3)	0.0748 (11)
H210	1.3572	0.6194	0.2374	0.090*
C211	1.2103 (4)	0.56568 (17)	0.2553 (3)	0.0657 (10)
H211	1.1569	0.5975	0.2686	0.079*
C212	1.5429 (4)	0.5466 (3)	0.1943 (4)	0.1020 (17)
H21A	1.5534	0.5905	0.1894	0.153*
H21B	1.5583	0.5274	0.1361	0.153*
H21C	1.6004	0.5307	0.2434	0.153*
N31	0.7220 (2)	0.70561 (12)	0.31843 (18)	0.0486 (6)
N32	0.7424 (2)	0.59677 (12)	0.40280 (18)	0.0483 (6)
C31	0.7137 (4)	0.75811 (17)	0.2697 (3)	0.0618 (9)
H31	0.7755	0.7673	0.2307	0.074*
C32	0.6178 (4)	0.79907 (19)	0.2747 (3)	0.0770 (12)
H32	0.6142	0.8352	0.2394	0.092*
C33	0.5276 (4)	0.7857 (2)	0.3327 (3)	0.0881 (14)
H33	0.4617	0.8128	0.3375	0.106*
C34	0.5353 (4)	0.73187 (19)	0.3839 (3)	0.0746 (12)
H34	0.4750	0.7223	0.4238	0.090*
C35	0.5743 (3)	0.61491 (19)	0.4954 (2)	0.0606 (9)
H35	0.5108	0.6405	0.5120	0.073*
C36	0.5956 (4)	0.55891 (19)	0.5385 (2)	0.0653 (10)
H36	0.5460	0.5460	0.5845	0.078*
C37	0.6898 (4)	0.52225 (19)	0.5137 (3)	0.0663 (10)
H37	0.7048	0.4841	0.5424	0.080*
C38	0.7620 (3)	0.54237 (17)	0.4460 (2)	0.0599 (9)
H38	0.8267	0.5175	0.4296	0.072*
C39	0.6495 (3)	0.63294 (15)	0.4259 (2)	0.0479 (7)
C310	0.6341 (3)	0.69209 (15)	0.3753 (2)	0.0498 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn	0.0440 (2)	0.0516 (3)	0.0436 (2)	0.00204 (19)	0.00753 (16)	−0.00034 (19)
S1	0.0548 (5)	0.0567 (5)	0.0582 (5)	−0.0068 (4)	0.0075 (4)	0.0169 (4)
O11	0.095 (2)	0.0531 (15)	0.089 (2)	−0.0250 (15)	0.0133 (16)	0.0048 (14)
O12	0.0586 (16)	0.102 (2)	0.0757 (17)	0.0103 (15)	0.0084 (13)	0.0426 (16)
S2	0.0565 (5)	0.0494 (5)	0.0687 (6)	0.0025 (4)	0.0154 (4)	0.0154 (4)
O21	0.0732 (18)	0.114 (2)	0.0730 (17)	0.0265 (17)	0.0280 (14)	0.0503 (17)
O22	0.0753 (19)	0.0416 (14)	0.142 (3)	−0.0106 (13)	0.0084 (19)	−0.0008 (15)
N11	0.0493 (14)	0.0421 (13)	0.0417 (13)	−0.0006 (11)	0.0099 (11)	0.0044 (10)
N12	0.0483 (15)	0.0559 (16)	0.0416 (14)	−0.0081 (13)	0.0022 (11)	0.0074 (12)
C11	0.065 (2)	0.062 (2)	0.0507 (18)	0.0076 (18)	0.0084 (16)	0.0133 (16)
C12	0.074 (3)	0.089 (3)	0.0469 (19)	0.019 (2)	0.0021 (18)	0.0081 (19)
C13	0.058 (2)	0.090 (3)	0.052 (2)	0.004 (2)	−0.0069 (17)	−0.012 (2)
C14	0.0506 (19)	0.059 (2)	0.0550 (19)	−0.0099 (16)	0.0000 (15)	−0.0039 (16)
C15	0.0460 (17)	0.0408 (15)	0.0420 (16)	−0.0017 (13)	0.0072 (13)	−0.0036 (12)
C16	0.053 (2)	0.070 (2)	0.0530 (19)	−0.0063 (17)	0.0079 (15)	0.0170 (17)
C17	0.072 (3)	0.082 (3)	0.078 (3)	−0.013 (2)	0.024 (2)	0.004 (2)
C18	0.108 (4)	0.089 (3)	0.086 (3)	0.002 (3)	0.024 (3)	−0.002 (3)
C19	0.090 (4)	0.108 (4)	0.081 (3)	0.017 (3)	0.035 (3)	0.025 (3)
C110	0.066 (3)	0.118 (4)	0.109 (4)	0.002 (3)	0.039 (3)	0.026 (3)
C111	0.063 (2)	0.091 (3)	0.089 (3)	−0.018 (2)	0.015 (2)	0.015 (3)
C112	0.139 (5)	0.166 (6)	0.119 (5)	0.059 (5)	0.069 (4)	0.025 (4)
N21	0.0425 (14)	0.0459 (14)	0.0473 (14)	−0.0011 (11)	0.0083 (11)	0.0003 (11)
N22	0.0545 (16)	0.0510 (15)	0.0465 (14)	0.0070 (13)	0.0095 (12)	0.0009 (12)
C21	0.059 (2)	0.061 (2)	0.058 (2)	0.0075 (18)	0.0053 (16)	0.0087 (17)
C22	0.081 (3)	0.100 (3)	0.051 (2)	0.017 (3)	0.0006 (19)	0.005 (2)
C23	0.101 (3)	0.109 (4)	0.051 (2)	0.027 (3)	−0.003 (2)	−0.023 (2)
C24	0.077 (3)	0.075 (3)	0.062 (2)	0.019 (2)	0.003 (2)	−0.019 (2)
C25	0.0454 (17)	0.0494 (18)	0.0512 (18)	−0.0033 (14)	0.0093 (14)	−0.0044 (14)
C26	0.060 (2)	0.0448 (17)	0.0413 (16)	0.0015 (15)	0.0103 (14)	0.0042 (13)
C27	0.061 (2)	0.0514 (19)	0.0524 (19)	0.0090 (16)	0.0055 (16)	−0.0049 (15)
C28	0.056 (2)	0.080 (3)	0.057 (2)	0.015 (2)	0.0079 (17)	−0.0042 (19)
C29	0.059 (2)	0.093 (3)	0.052 (2)	−0.008 (2)	0.0090 (17)	0.003 (2)
C210	0.071 (3)	0.060 (2)	0.097 (3)	−0.013 (2)	0.025 (2)	0.003 (2)
C211	0.073 (3)	0.0446 (19)	0.083 (3)	0.0013 (18)	0.024 (2)	0.0018 (18)
C212	0.062 (3)	0.144 (5)	0.102 (4)	−0.021 (3)	0.024 (2)	−0.002 (3)
N31	0.0480 (15)	0.0497 (15)	0.0493 (15)	0.0004 (12)	0.0111 (12)	−0.0009 (12)
N32	0.0453 (14)	0.0518 (15)	0.0489 (14)	−0.0004 (12)	0.0102 (12)	0.0032 (12)
C31	0.067 (2)	0.055 (2)	0.066 (2)	0.0086 (18)	0.0173 (18)	0.0109 (17)
C32	0.089 (3)	0.060 (2)	0.086 (3)	0.021 (2)	0.024 (2)	0.016 (2)
C33	0.082 (3)	0.073 (3)	0.113 (4)	0.034 (2)	0.033 (3)	0.012 (3)
C34	0.069 (3)	0.067 (2)	0.093 (3)	0.016 (2)	0.036 (2)	0.009 (2)
C35	0.058 (2)	0.076 (2)	0.0503 (19)	−0.0033 (18)	0.0181 (16)	−0.0031 (17)
C36	0.065 (2)	0.084 (3)	0.0482 (19)	−0.011 (2)	0.0130 (17)	0.0106 (19)
C37	0.066 (2)	0.073 (2)	0.060 (2)	−0.004 (2)	0.0034 (18)	0.0218 (19)
C38	0.059 (2)	0.059 (2)	0.063 (2)	0.0029 (17)	0.0092 (17)	0.0147 (17)
C39	0.0451 (16)	0.0551 (19)	0.0442 (16)	−0.0043 (15)	0.0077 (13)	−0.0082 (14)
C310	0.0485 (18)	0.0503 (18)	0.0523 (18)	0.0011 (15)	0.0127 (14)	−0.0044 (14)

Geometric parameters (Å, º)

Zn—N11	2.020 (3)	C21—H21	0.9300
Zn—N21	2.082 (3)	C22—C23	1.381 (6)
Zn—N31	2.106 (3)	C22—H22	0.9300
Zn—N32	2.109 (3)	C23—C24	1.364 (6)
Zn—N22	2.317 (3)	C23—H23	0.9300
Zn—N12	2.549 (3)	C24—C25	1.393 (5)
S1—O11	1.440 (3)	C24—H24	0.9300
S1—O12	1.443 (3)	C26—C27	1.381 (5)
S1—N12	1.576 (3)	C26—C211	1.386 (5)
S1—C16	1.775 (4)	C27—C28	1.371 (5)
S2—O21	1.434 (3)	C27—H27	0.9300
S2—O22	1.438 (3)	C28—C29	1.387 (6)
S2—N22	1.581 (3)	C28—H28	0.9300
S2—C26	1.763 (3)	C29—C210	1.377 (6)
N11—C11	1.337 (4)	C29—C212	1.512 (5)
N11—C15	1.356 (4)	C210—C211	1.379 (5)
N12—C15	1.364 (4)	C210—H210	0.9300
C11—C12	1.362 (5)	C211—H211	0.9300
C11—H11	0.9300	C212—H21A	0.9600
C12—C13	1.389 (6)	C212—H21B	0.9600
C12—H12	0.9300	C212—H21C	0.9600
C13—C14	1.366 (5)	N31—C31	1.333 (4)
C13—H13	0.9300	N31—C310	1.340 (4)
C14—C15	1.394 (4)	N32—C38	1.339 (4)
C14—H14	0.9300	N32—C39	1.339 (4)
C16—C17	1.375 (6)	C31—C32	1.371 (5)
C16—C111	1.379 (5)	C31—H31	0.9300
C17—C18	1.386 (6)	C32—C33	1.369 (6)
C17—H17	0.9300	C32—H32	0.9300
C18—C19	1.381 (7)	C33—C34	1.376 (6)
C18—H18	0.9300	C33—H33	0.9300
C19—C110	1.355 (7)	C34—C310	1.386 (5)
C19—C112	1.513 (6)	C34—H34	0.9300
C110—C111	1.388 (6)	C35—C36	1.371 (5)
C110—H110	0.9300	C35—C39	1.397 (4)
C111—H111	0.9300	C35—H35	0.9300
C112—H11A	0.9600	C36—C37	1.363 (5)
C112—H11B	0.9600	C36—H36	0.9300
C112—H11C	0.9600	C37—C38	1.372 (5)
N21—C21	1.341 (4)	C37—H37	0.9300
N21—C25	1.353 (4)	C38—H38	0.9300
N22—C25	1.369 (4)	C39—C310	1.474 (5)
C21—C22	1.358 (5)
N11—Zn—N21	134.82 (10)	S2—N22—Zn	145.77 (16)
N11—Zn—N31	111.56 (10)	N21—C21—C22	122.5 (4)
N21—Zn—N31	99.32 (10)	N21—C21—H21	118.7
N11—Zn—N32	101.51 (10)	C22—C21—H21	118.7
N21—Zn—N32	117.07 (10)	C21—C22—C23	118.1 (4)
N31—Zn—N32	77.86 (10)	C21—C22—H22	121.0
N11—Zn—N22	95.78 (10)	C23—C22—H22	121.0
N21—Zn—N22	60.44 (10)	C24—C23—C22	120.6 (4)
N31—Zn—N22	152.52 (10)	C24—C23—H23	119.7
N32—Zn—N22	94.46 (10)	C22—C23—H23	119.7
N11—Zn—N12	57.09 (9)	C23—C24—C25	119.1 (4)
N21—Zn—N12	92.43 (9)	C23—C24—H24	120.4
N31—Zn—N12	89.52 (10)	C25—C24—H24	120.4
N32—Zn—N12	149.25 (9)	N21—C25—N22	109.6 (3)
N22—Zn—N12	108.51 (9)	N21—C25—C24	119.8 (3)
O11—S1—O12	116.48 (19)	N22—C25—C24	130.6 (3)
O11—S1—N12	114.02 (15)	C27—C26—C211	119.5 (3)
O12—S1—N12	106.15 (15)	C27—C26—S2	119.6 (3)
O11—S1—C16	106.34 (18)	C211—C26—S2	120.8 (3)
O12—S1—C16	105.92 (17)	C28—C27—C26	119.7 (3)
N12—S1—C16	107.32 (16)	C28—C27—H27	120.1
O21—S2—O22	116.7 (2)	C26—C27—H27	120.1
O21—S2—N22	106.02 (16)	C27—C28—C29	121.9 (4)
O22—S2—N22	113.25 (16)	C27—C28—H28	119.1
O21—S2—C26	106.93 (16)	C29—C28—H28	119.1
O22—S2—C26	105.61 (16)	C210—C29—C28	117.6 (4)
N22—S2—C26	107.95 (15)	C210—C29—C212	121.8 (4)
C11—N11—C15	120.2 (3)	C28—C29—C212	120.6 (4)
C11—N11—Zn	131.3 (2)	C29—C210—C211	121.7 (4)
C15—N11—Zn	108.43 (19)	C29—C210—H210	119.2
C15—N12—S1	124.2 (2)	C211—C210—H210	119.2
C15—N12—Zn	84.16 (17)	C210—C211—C26	119.6 (4)
S1—N12—Zn	151.38 (15)	C210—C211—H211	120.2
N11—C11—C12	122.7 (3)	C26—C211—H211	120.2
N11—C11—H11	118.7	C29—C212—H21A	109.5
C12—C11—H11	118.7	C29—C212—H21B	109.5
C11—C12—C13	117.9 (3)	H21A—C212—H21B	109.5
C11—C12—H12	121.1	C29—C212—H21C	109.5
C13—C12—H12	121.1	H21A—C212—H21C	109.5
C14—C13—C12	120.2 (4)	H21B—C212—H21C	109.5
C14—C13—H13	119.9	C31—N31—C310	119.2 (3)
C12—C13—H13	119.9	C31—N31—Zn	125.6 (2)
C13—C14—C15	119.6 (3)	C310—N31—Zn	115.1 (2)
C13—C14—H14	120.2	C38—N32—C39	119.4 (3)
C15—C14—H14	120.2	C38—N32—Zn	125.4 (2)
N11—C15—N12	110.3 (3)	C39—N32—Zn	114.7 (2)
N11—C15—C14	119.4 (3)	N31—C31—C32	122.6 (3)
N12—C15—C14	130.3 (3)	N31—C31—H31	118.7
C17—C16—C111	119.1 (4)	C32—C31—H31	118.7
C17—C16—S1	119.6 (3)	C33—C32—C31	118.6 (4)
C111—C16—S1	121.1 (3)	C33—C32—H32	120.7
C16—C17—C18	119.9 (4)	C31—C32—H32	120.7
C16—C17—H17	120.0	C32—C33—C34	119.4 (4)
C18—C17—H17	120.0	C32—C33—H33	120.3
C19—C18—C17	121.7 (5)	C34—C33—H33	120.3
C19—C18—H18	119.1	C33—C34—C310	119.3 (4)
C17—C18—H18	119.1	C33—C34—H34	120.4
C110—C19—C18	117.1 (5)	C310—C34—H34	120.4
C110—C19—C112	122.5 (5)	C36—C35—C39	119.0 (4)
C18—C19—C112	120.4 (6)	C36—C35—H35	120.5
C19—C110—C111	122.8 (5)	C39—C35—H35	120.5
C19—C110—H110	118.6	C37—C36—C35	119.7 (3)
C111—C110—H110	118.6	C37—C36—H36	120.1
C16—C111—C110	119.3 (5)	C35—C36—H36	120.1
C16—C111—H111	120.4	C36—C37—C38	119.1 (4)
C110—C111—H111	120.4	C36—C37—H37	120.5
C19—C112—H11A	109.5	C38—C37—H37	120.5
C19—C112—H11B	109.5	N32—C38—C37	122.1 (4)
H11A—C112—H11B	109.5	N32—C38—H38	119.0
C19—C112—H11C	109.5	C37—C38—H38	119.0
H11A—C112—H11C	109.5	N32—C39—C35	120.7 (3)
H11B—C112—H11C	109.5	N32—C39—C310	116.1 (3)
C21—N21—C25	119.9 (3)	C35—C39—C310	123.2 (3)
C21—N21—Zn	139.7 (2)	N31—C310—C34	120.9 (3)
C25—N21—Zn	100.5 (2)	N31—C310—C39	115.8 (3)
C25—N22—S2	123.7 (2)	C34—C310—C39	123.4 (3)
C25—N22—Zn	89.49 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···O21^i	0.93	2.42	3.281 (4)	154
C13—H13···O12^ii	0.93	2.41	3.257 (5)	152
C14—H14···O11	0.93	2.38	2.970 (5)	121
C111—H111···O11	0.93	2.54	2.908 (6)	104
C24—H24···O22	0.93	2.42	3.005 (5)	121
C27—H27···O11^iii	0.93	2.57	3.216 (4)	127
C27—H27···O22	0.93	2.63	2.941 (5)	100
C28—H28···O11^iii	0.93	2.73	3.301 (5)	120
C31—H31···O12	0.93	2.46	3.377 (5)	171
C32—H32···O22^iv	0.93	2.42	3.087 (5)	129
C33—H33···O22^iv	0.93	2.84	3.298 (5)	111
C35—H35···O12^v	0.93	2.56	3.316 (4)	139
C38—H38···O21	0.93	2.44	3.348 (5)	164

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