First-row transition metal–pyridine (py)–sulfate [(py)_xM](SO₄) complexes (M = Ni, Cu and Zn): crystal field theory in action

The crystal structures of three first-row transition metal–pyridine–sulfate com­plexes, namely catena-poly[[tetra­kis­(pyridine-κN)nickel(II)]-μ-sulfato-κ²O:O′], [Ni(SO₄)(C₅H₅N)₄]_n, (1), di-μ-sulfato-κ⁴O:O-bis­[tris­(pyridine-κN)cop­per(II)], [Cu₂(SO₄)₂(C₅H₅N)₆], (2), and catena-poly[[tetra­kis­(pyridine-κN)zinc(II)]-μ-sulfato-κ²O:O′-[bis­(pyridine-κN)zinc(II)]-μ-sulfato-κ²O:O′], [Zn₂(SO₄)₂(C₅H₅N)₆]_n, (3), are reported. Ni compound (1) displays a polymeric crystal structure, with infinite chains of Ni^II atoms adopting an octa­hedral N₄O₂ coordination environment that involves four pyridine ligands and two bridging sulfate ligands. Cu compound (2) features a dimeric molecular structure, with the Cu^II atoms possessing square-pyramidal N₃O₂ coordination environments that contain three pyridine ligands and two bridging sulfate ligands. Zn compound (3) exhibits a polymeric crystal structure of infinite chains, with two alternating zinc coordination environments, i.e. octa­hedral N₄O₂ coordination involving four pyridine ligands and two bridging sulfate ligands, and tetra­hedral N₂O₂ coordination containing two pyridine ligands and two bridging sulfate ligands. The observed coordination environments are consistent with those predicted by crystal field theory.

Computing details

Data collection: APEX3 (Bruker, 2016) for UMD1285_a, UMD1296; APEX2 (Bruker, 2016) for UMD1091_a. For all structures, cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

catena-Poly[[tetrakis(pyridine-κN)nickel(II)]-µ-sulfato-κ²O:O'] (UMD1285_a)

Crystal data

[Ni(SO4)(C5H5N)4]	F(000) = 976
Mr = 471.17	Dx = 1.533 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.6370 (9) Å	Cell parameters from 9889 reflections
b = 18.0065 (18) Å	θ = 2.9–25.4°
c = 12.4723 (13) Å	µ = 1.09 mm^−1
β = 109.396 (3)°	T = 200 K
V = 2041.5 (4) Å^3	Block, green
Z = 4	0.2 × 0.14 × 0.12 mm

Data collection

Bruker APEXIII CMOS diffractometer	3279 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.047
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θmax = 25.4°, θmin = 3.2°
Tmin = 0.215, Tmax = 0.259	h = −11→11
72344 measured reflections	k = −21→21
3743 independent reflections	l = −15→15

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.035	H-atom parameters constrained
wR(F^2) = 0.093	w = 1/[σ^2(Fo^2) + (0.0225P)^2 + 5.8638P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max < 0.001
3743 reflections	Δρmax = 0.49 e Å^−3
271 parameters	Δρmin = −0.39 e Å^−3
0 restraints

Special details

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.

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

	x	y	z	Uiso*/Ueq
Ni1	0.26956 (4)	0.26345 (2)	0.45601 (3)	0.01793 (11)
S1	0.29287 (8)	0.32844 (4)	0.72492 (6)	0.02024 (16)
O1	0.2542 (3)	0.30017 (14)	0.60842 (18)	0.0348 (5)
O2	0.1988 (4)	0.39076 (16)	0.7252 (3)	0.0624 (9)
O3	0.4477 (3)	0.34843 (17)	0.7677 (2)	0.0521 (8)
O4	0.2661 (2)	0.26674 (12)	0.79449 (17)	0.0279 (5)
N1	0.0612 (3)	0.21403 (14)	0.4261 (2)	0.0260 (6)
N2	0.3731 (3)	0.16598 (14)	0.5388 (2)	0.0236 (5)
N3	0.1622 (3)	0.36269 (14)	0.3767 (2)	0.0213 (5)
N4	0.4713 (3)	0.31862 (13)	0.4862 (2)	0.0214 (5)
C1	0.0255 (4)	0.1842 (2)	0.5115 (3)	0.0387 (9)
H1A	0.0951	0.1862	0.5862	0.046*
C2	−0.1086 (4)	0.1505 (2)	0.4954 (4)	0.0542 (12)
H2A	−0.1296	0.1287	0.5576	0.065*
C3	−0.2116 (4)	0.1490 (2)	0.3879 (4)	0.0499 (11)
H3A	−0.3048	0.1264	0.3750	0.060*
C4	−0.1771 (4)	0.1805 (2)	0.3006 (4)	0.0442 (10)
H4A	−0.2472	0.1813	0.2262	0.053*
C5	−0.0392 (4)	0.21147 (19)	0.3214 (3)	0.0334 (8)
H5A	−0.0147	0.2316	0.2596	0.040*
C6	0.4830 (4)	0.1687 (2)	0.6388 (3)	0.0354 (8)
H6A	0.5176	0.2158	0.6708	0.042*
C7	0.5475 (5)	0.1056 (2)	0.6968 (3)	0.0535 (11)
H7A	0.6276	0.1097	0.7659	0.064*
C8	0.4956 (5)	0.0369 (2)	0.6545 (4)	0.0546 (12)
H8A	0.5377	−0.0071	0.6942	0.066*
C9	0.3813 (5)	0.0334 (2)	0.5534 (3)	0.0434 (9)
H9A	0.3416	−0.0132	0.5223	0.052*
C10	0.3249 (4)	0.09875 (18)	0.4974 (3)	0.0292 (7)
H10A	0.2483	0.0957	0.4261	0.035*
C11	0.0596 (3)	0.39587 (18)	0.4104 (3)	0.0280 (7)
H11A	0.0385	0.3764	0.4741	0.034*
C12	−0.0170 (4)	0.45771 (18)	0.3556 (3)	0.0320 (7)
H12A	−0.0906	0.4796	0.3806	0.038*
C13	0.0147 (4)	0.48711 (18)	0.2643 (3)	0.0328 (8)
H13A	−0.0367	0.5295	0.2254	0.039*
C14	0.1223 (4)	0.45399 (19)	0.2304 (3)	0.0335 (7)
H14A	0.1476	0.4736	0.1687	0.040*
C15	0.1929 (3)	0.39138 (16)	0.2885 (2)	0.0243 (6)
H15A	0.2660	0.3681	0.2644	0.029*
C16	0.4936 (3)	0.38521 (17)	0.5364 (3)	0.0254 (6)
H16A	0.4171	0.4066	0.5585	0.030*
C17	0.6236 (4)	0.42406 (18)	0.5575 (3)	0.0325 (7)
H17A	0.6358	0.4715	0.5928	0.039*
C18	0.7350 (4)	0.3932 (2)	0.5265 (3)	0.0379 (8)
H18A	0.8256	0.4187	0.5404	0.045*
C19	0.7128 (4)	0.3245 (2)	0.4749 (3)	0.0369 (8)
H19A	0.7882	0.3018	0.4530	0.044*
C20	0.5794 (3)	0.28913 (19)	0.4554 (3)	0.0289 (7)
H20A	0.5641	0.2421	0.4187	0.035*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.01880 (19)	0.01861 (19)	0.01523 (18)	−0.00063 (14)	0.00411 (14)	0.00002 (14)
S1	0.0260 (4)	0.0184 (3)	0.0160 (3)	0.0026 (3)	0.0066 (3)	0.0009 (3)
O1	0.0431 (14)	0.0470 (14)	0.0162 (11)	−0.0034 (11)	0.0126 (10)	−0.0032 (10)
O2	0.101 (3)	0.0413 (16)	0.0538 (18)	0.0445 (17)	0.0369 (18)	0.0113 (14)
O3	0.0381 (15)	0.0672 (19)	0.0368 (15)	−0.0282 (14)	−0.0065 (12)	0.0153 (13)
O4	0.0370 (12)	0.0287 (12)	0.0176 (10)	−0.0058 (10)	0.0084 (9)	0.0046 (9)
N1	0.0202 (13)	0.0265 (14)	0.0286 (14)	−0.0009 (10)	0.0044 (11)	0.0028 (11)
N2	0.0286 (13)	0.0232 (13)	0.0204 (13)	0.0010 (11)	0.0098 (11)	0.0014 (10)
N3	0.0208 (12)	0.0229 (13)	0.0185 (12)	0.0011 (10)	0.0042 (10)	−0.0017 (10)
N4	0.0231 (13)	0.0224 (13)	0.0179 (12)	−0.0015 (10)	0.0057 (10)	0.0011 (10)
C1	0.0264 (17)	0.043 (2)	0.043 (2)	−0.0011 (15)	0.0064 (15)	0.0189 (17)
C2	0.032 (2)	0.051 (2)	0.079 (3)	−0.0017 (18)	0.019 (2)	0.032 (2)
C3	0.0231 (18)	0.0309 (19)	0.090 (3)	−0.0023 (15)	0.012 (2)	0.000 (2)
C4	0.0277 (18)	0.044 (2)	0.049 (2)	−0.0011 (16)	−0.0029 (16)	−0.0178 (18)
C5	0.0285 (17)	0.0376 (19)	0.0285 (17)	0.0011 (14)	0.0021 (14)	−0.0081 (14)
C6	0.0376 (19)	0.0387 (19)	0.0242 (17)	0.0105 (15)	0.0028 (14)	0.0006 (14)
C7	0.060 (3)	0.059 (3)	0.032 (2)	0.028 (2)	0.0030 (19)	0.0065 (19)
C8	0.085 (3)	0.043 (2)	0.046 (2)	0.035 (2)	0.034 (2)	0.0220 (19)
C9	0.067 (3)	0.0248 (18)	0.049 (2)	0.0078 (17)	0.034 (2)	0.0058 (16)
C10	0.0370 (18)	0.0257 (16)	0.0284 (17)	0.0000 (14)	0.0155 (14)	0.0017 (13)
C11	0.0276 (16)	0.0291 (17)	0.0303 (17)	0.0011 (13)	0.0136 (14)	−0.0014 (13)
C12	0.0294 (17)	0.0302 (17)	0.0353 (18)	0.0077 (14)	0.0095 (14)	−0.0051 (14)
C13	0.0370 (18)	0.0257 (17)	0.0286 (18)	0.0096 (14)	0.0016 (14)	0.0022 (13)
C14	0.043 (2)	0.0301 (17)	0.0270 (17)	0.0027 (15)	0.0105 (15)	0.0027 (14)
C15	0.0292 (16)	0.0229 (15)	0.0209 (15)	0.0016 (12)	0.0087 (13)	−0.0014 (12)
C16	0.0300 (16)	0.0229 (15)	0.0217 (15)	−0.0007 (13)	0.0065 (13)	0.0000 (12)
C17	0.0383 (19)	0.0250 (16)	0.0308 (18)	−0.0090 (14)	0.0069 (15)	−0.0032 (13)
C18	0.0330 (18)	0.043 (2)	0.037 (2)	−0.0167 (16)	0.0109 (15)	−0.0050 (16)
C19	0.0294 (17)	0.046 (2)	0.040 (2)	−0.0081 (16)	0.0176 (15)	−0.0108 (16)
C20	0.0266 (16)	0.0329 (17)	0.0272 (16)	−0.0022 (13)	0.0090 (13)	−0.0077 (14)

Geometric parameters (Å, º)

Ni1—O1	2.064 (2)	C6—H6A	0.9500
Ni1—O4^i	2.076 (2)	C6—C7	1.379 (5)
Ni1—N1	2.113 (3)	C7—H7A	0.9500
Ni1—N2	2.111 (3)	C7—C8	1.373 (6)
Ni1—N3	2.136 (2)	C8—H8A	0.9500
Ni1—N4	2.103 (2)	C8—C9	1.373 (6)
S1—O1	1.466 (2)	C9—H9A	0.9500
S1—O2	1.443 (3)	C9—C10	1.385 (5)
S1—O3	1.454 (3)	C10—H10A	0.9500
S1—O4	1.484 (2)	C11—H11A	0.9500
O4—Ni1^ii	2.076 (2)	C11—C12	1.385 (5)
N1—C1	1.337 (4)	C12—H12A	0.9500
N1—C5	1.342 (4)	C12—C13	1.378 (5)
N2—C6	1.343 (4)	C13—H13A	0.9500
N2—C10	1.337 (4)	C13—C14	1.378 (5)
N3—C11	1.337 (4)	C14—H14A	0.9500
N3—C15	1.335 (4)	C14—C15	1.389 (4)
N4—C16	1.337 (4)	C15—H15A	0.9500
N4—C20	1.334 (4)	C16—H16A	0.9500
C1—H1A	0.9500	C16—C17	1.382 (4)
C1—C2	1.380 (5)	C17—H17A	0.9500
C2—H2A	0.9500	C17—C18	1.373 (5)
C2—C3	1.378 (6)	C18—H18A	0.9500
C3—H3A	0.9500	C18—C19	1.377 (5)
C3—C4	1.364 (6)	C19—H19A	0.9500
C4—H4A	0.9500	C19—C20	1.382 (5)
C4—C5	1.384 (5)	C20—H20A	0.9500
C5—H5A	0.9500
O1—Ni1—O4^i	174.06 (9)	N1—C5—H5A	118.9
O1—Ni1—N1	86.73 (10)	C4—C5—H5A	118.9
O1—Ni1—N2	89.02 (10)	N2—C6—H6A	118.8
O1—Ni1—N3	89.21 (10)	N2—C6—C7	122.4 (4)
O1—Ni1—N4	91.65 (10)	C7—C6—H6A	118.8
O4^i—Ni1—N1	90.57 (10)	C6—C7—H7A	120.1
O4^i—Ni1—N2	96.28 (9)	C8—C7—C6	119.9 (4)
O4^i—Ni1—N3	85.45 (9)	C8—C7—H7A	120.1
O4^i—Ni1—N4	90.76 (9)	C7—C8—H8A	120.9
N1—Ni1—N3	89.12 (10)	C7—C8—C9	118.2 (3)
N2—Ni1—N1	90.19 (10)	C9—C8—H8A	120.9
N2—Ni1—N3	178.14 (9)	C8—C9—H9A	120.5
N4—Ni1—N1	176.69 (10)	C8—C9—C10	119.0 (4)
N4—Ni1—N2	92.68 (10)	C10—C9—H9A	120.5
N4—Ni1—N3	87.96 (9)	N2—C10—C9	123.2 (3)
O1—S1—O4	106.45 (13)	N2—C10—H10A	118.4
O2—S1—O1	108.63 (16)	C9—C10—H10A	118.4
O2—S1—O3	112.1 (2)	N3—C11—H11A	118.9
O2—S1—O4	110.42 (16)	N3—C11—C12	122.2 (3)
O3—S1—O1	110.01 (16)	C12—C11—H11A	118.9
O3—S1—O4	109.11 (14)	C11—C12—H12A	120.4
S1—O1—Ni1	162.09 (16)	C13—C12—C11	119.3 (3)
S1—O4—Ni1^ii	144.43 (14)	C13—C12—H12A	120.4
C1—N1—Ni1	120.6 (2)	C12—C13—H13A	120.6
C1—N1—C5	117.9 (3)	C12—C13—C14	118.8 (3)
C5—N1—Ni1	121.5 (2)	C14—C13—H13A	120.6
C6—N2—Ni1	121.5 (2)	C13—C14—H14A	120.7
C10—N2—Ni1	121.1 (2)	C13—C14—C15	118.7 (3)
C10—N2—C6	117.2 (3)	C15—C14—H14A	120.7
C11—N3—Ni1	121.6 (2)	N3—C15—C14	122.6 (3)
C15—N3—Ni1	120.0 (2)	N3—C15—H15A	118.7
C15—N3—C11	118.4 (3)	C14—C15—H15A	118.7
C16—N4—Ni1	120.2 (2)	N4—C16—H16A	118.8
C20—N4—Ni1	121.6 (2)	N4—C16—C17	122.5 (3)
C20—N4—C16	118.2 (3)	C17—C16—H16A	118.8
N1—C1—H1A	118.8	C16—C17—H17A	120.5
N1—C1—C2	122.4 (4)	C18—C17—C16	119.1 (3)
C2—C1—H1A	118.8	C18—C17—H17A	120.5
C1—C2—H2A	120.4	C17—C18—H18A	120.7
C3—C2—C1	119.2 (4)	C17—C18—C19	118.7 (3)
C3—C2—H2A	120.4	C19—C18—H18A	120.7
C2—C3—H3A	120.7	C18—C19—H19A	120.4
C4—C3—C2	118.7 (3)	C18—C19—C20	119.2 (3)
C4—C3—H3A	120.7	C20—C19—H19A	120.4
C3—C4—H4A	120.3	N4—C20—C19	122.3 (3)
C3—C4—C5	119.5 (4)	N4—C20—H20A	118.8
C5—C4—H4A	120.3	C19—C20—H20A	118.8
N1—C5—C4	122.2 (3)
Ni1—N1—C1—C2	−179.1 (3)	C1—C2—C3—C4	0.4 (6)
Ni1—N1—C5—C4	−178.8 (3)	C2—C3—C4—C5	1.6 (6)
Ni1—N2—C6—C7	176.9 (3)	C3—C4—C5—N1	−2.5 (6)
Ni1—N2—C10—C9	−174.5 (3)	C5—N1—C1—C2	0.8 (5)
Ni1—N3—C11—C12	−176.1 (2)	C6—N2—C10—C9	1.0 (5)
Ni1—N3—C15—C14	177.3 (2)	C6—C7—C8—C9	1.1 (6)
Ni1—N4—C16—C17	−179.5 (2)	C7—C8—C9—C10	1.1 (6)
Ni1—N4—C20—C19	−179.8 (3)	C8—C9—C10—N2	−2.3 (5)
O1—S1—O4—Ni1^ii	−177.4 (2)	C10—N2—C6—C7	1.4 (5)
O2—S1—O1—Ni1	129.4 (5)	C11—N3—C15—C14	−0.2 (4)
O2—S1—O4—Ni1^ii	−59.7 (3)	C11—C12—C13—C14	−0.1 (5)
O3—S1—O1—Ni1	6.4 (6)	C12—C13—C14—C15	1.1 (5)
O3—S1—O4—Ni1^ii	63.9 (3)	C13—C14—C15—N3	−1.0 (5)
O4—S1—O1—Ni1	−111.7 (5)	C15—N3—C11—C12	1.3 (5)
N1—C1—C2—C3	−1.6 (6)	C16—N4—C20—C19	0.8 (5)
N2—C6—C7—C8	−2.5 (6)	C16—C17—C18—C19	0.3 (5)
N3—C11—C12—C13	−1.1 (5)	C17—C18—C19—C20	0.3 (5)
N4—C16—C17—C18	−0.5 (5)	C18—C19—C20—N4	−0.9 (5)
C1—N1—C5—C4	1.2 (5)	C20—N4—C16—C17	−0.1 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O1	0.95	2.52	2.985 (4)	110
C5—H5A···O4^i	0.95	2.59	3.095 (4)	113
C10—H10A···S1^i	0.95	3.01	3.559 (3)	118
C10—H10A···O2^i	0.95	2.40	3.208 (5)	143
C11—H11A···O1	0.95	2.59	3.083 (4)	113
C15—H15A···O4^i	0.95	2.46	2.928 (4)	111
C20—H20A···O3^i	0.95	2.46	3.354 (4)	157

Symmetry code: (i) x, −y+1/2, z−1/2.

Di-µ-sulfato-κ⁴O:O-bis[tris(pyridine-κN)copper(II)] (UMD1091_a)

Crystal data

[Cu2(SO4)2(C5H5N)6]	F(000) = 812
Mr = 793.80	Dx = 1.723 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.0147 (4) Å	Cell parameters from 9132 reflections
b = 18.5456 (7) Å	θ = 2.9–25.7°
c = 9.6355 (4) Å	µ = 1.59 mm^−1
β = 108.191 (1)°	T = 200 K
V = 1530.38 (11) Å^3	Block, blue
Z = 2	0.24 × 0.2 × 0.2 mm

Data collection

Bruker CMOS diffractometer	2614 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.041
Absorption correction: multi-scan (SADABS; Bruker, 2014)	θmax = 25.7°, θmin = 3.1°
Tmin = 0.226, Tmax = 0.259	h = −10→11
37745 measured reflections	k = −22→22
2904 independent reflections	l = −11→11

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.022	w = 1/[σ^2(Fo^2) + (0.0215P)^2 + 1.4607P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.055	(Δ/σ)max = 0.001
S = 1.06	Δρmax = 0.28 e Å^−3
2904 reflections	Δρmin = −0.31 e Å^−3
218 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0123 (6)
Primary atom site location: structure-invariant direct methods

Special details

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.

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

	x	y	z	Uiso*/Ueq
Cu1	0.33166 (2)	0.54421 (2)	0.46286 (2)	0.01329 (9)
S1	0.30845 (5)	0.41053 (2)	0.62080 (5)	0.01411 (11)
O1	0.42399 (14)	0.45307 (6)	0.56285 (13)	0.0148 (3)
O2	0.38792 (16)	0.39592 (8)	0.77495 (14)	0.0263 (3)
O3	0.17338 (15)	0.45837 (7)	0.59806 (16)	0.0246 (3)
O4	0.26653 (16)	0.34418 (7)	0.53642 (15)	0.0229 (3)
N1	0.23407 (18)	0.49026 (8)	0.27389 (16)	0.0162 (3)
N2	0.22025 (17)	0.63296 (8)	0.35850 (16)	0.0154 (3)
N3	0.40156 (18)	0.60213 (8)	0.65143 (16)	0.0153 (3)
C1	0.2987 (2)	0.49312 (10)	0.1657 (2)	0.0186 (4)
H1A	0.3905	0.5211	0.1796	0.022*
C2	0.2366 (3)	0.45686 (11)	0.0349 (2)	0.0246 (4)
H2A	0.2846	0.4598	−0.0399	0.030*
C3	0.1027 (3)	0.41615 (11)	0.0155 (2)	0.0301 (5)
H3A	0.0574	0.3906	−0.0730	0.036*
C4	0.0359 (3)	0.41311 (11)	0.1261 (2)	0.0287 (5)
H4A	−0.0557	0.3854	0.1147	0.034*
C5	0.1040 (2)	0.45093 (10)	0.2535 (2)	0.0220 (4)
H5A	0.0572	0.4491	0.3292	0.026*
C6	0.2702 (2)	0.67040 (10)	0.2625 (2)	0.0198 (4)
H6A	0.3674	0.6580	0.2499	0.024*
C7	0.1843 (2)	0.72651 (11)	0.1815 (2)	0.0242 (4)
H7A	0.2222	0.7519	0.1138	0.029*
C8	0.0431 (2)	0.74542 (10)	0.1995 (2)	0.0237 (4)
H8A	−0.0179	0.7835	0.1443	0.028*
C9	−0.0072 (2)	0.70735 (11)	0.3002 (2)	0.0241 (4)
H9A	−0.1028	0.7196	0.3164	0.029*
C10	0.0832 (2)	0.65144 (10)	0.3767 (2)	0.0195 (4)
H10A	0.0473	0.6251	0.4445	0.023*
C11	0.3486 (2)	0.58962 (10)	0.7653 (2)	0.0197 (4)
H11A	0.2717	0.5534	0.7564	0.024*
C12	0.4023 (3)	0.62778 (11)	0.8945 (2)	0.0251 (4)
H12A	0.3646	0.6170	0.9739	0.030*
C13	0.5113 (2)	0.68172 (11)	0.9072 (2)	0.0265 (5)
H13A	0.5503	0.7083	0.9954	0.032*
C14	0.5625 (2)	0.69626 (11)	0.7891 (2)	0.0242 (4)
H14A	0.6350	0.7341	0.7938	0.029*
C15	0.5071 (2)	0.65515 (10)	0.6645 (2)	0.0196 (4)
H15A	0.5448	0.6646	0.5846	0.023*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.01582 (13)	0.01228 (12)	0.01069 (12)	−0.00011 (8)	0.00257 (8)	−0.00006 (8)
S1	0.0143 (2)	0.0142 (2)	0.0144 (2)	−0.00128 (16)	0.00522 (17)	0.00127 (17)
O1	0.0149 (6)	0.0144 (6)	0.0155 (6)	−0.0020 (5)	0.0051 (5)	0.0022 (5)
O2	0.0269 (8)	0.0370 (8)	0.0152 (7)	−0.0020 (6)	0.0070 (6)	0.0073 (6)
O3	0.0155 (7)	0.0217 (7)	0.0359 (8)	0.0012 (6)	0.0071 (6)	−0.0030 (6)
O4	0.0280 (8)	0.0155 (7)	0.0275 (8)	−0.0065 (6)	0.0121 (6)	−0.0031 (6)
N1	0.0174 (8)	0.0146 (7)	0.0137 (8)	0.0013 (6)	0.0008 (6)	0.0007 (6)
N2	0.0163 (8)	0.0151 (7)	0.0129 (7)	−0.0021 (6)	0.0020 (6)	−0.0020 (6)
N3	0.0174 (8)	0.0133 (7)	0.0146 (8)	0.0022 (6)	0.0040 (6)	0.0007 (6)
C1	0.0185 (9)	0.0176 (9)	0.0177 (9)	0.0030 (8)	0.0027 (8)	0.0024 (8)
C2	0.0315 (11)	0.0243 (10)	0.0164 (10)	0.0081 (9)	0.0050 (8)	0.0008 (8)
C3	0.0382 (12)	0.0219 (10)	0.0209 (11)	−0.0004 (9)	−0.0041 (9)	−0.0065 (9)
C4	0.0263 (11)	0.0229 (10)	0.0287 (11)	−0.0067 (9)	−0.0033 (9)	−0.0008 (9)
C5	0.0206 (10)	0.0212 (10)	0.0217 (10)	−0.0017 (8)	0.0032 (8)	0.0040 (8)
C6	0.0175 (9)	0.0201 (9)	0.0223 (10)	−0.0001 (8)	0.0068 (8)	0.0014 (8)
C7	0.0249 (10)	0.0221 (10)	0.0251 (11)	−0.0021 (8)	0.0069 (8)	0.0071 (8)
C8	0.0233 (10)	0.0157 (9)	0.0267 (11)	0.0022 (8)	−0.0003 (8)	0.0004 (8)
C9	0.0178 (10)	0.0260 (10)	0.0276 (11)	0.0037 (8)	0.0058 (8)	−0.0038 (8)
C10	0.0192 (10)	0.0217 (10)	0.0182 (9)	−0.0027 (8)	0.0066 (8)	−0.0017 (8)
C11	0.0227 (10)	0.0188 (9)	0.0182 (10)	0.0013 (8)	0.0074 (8)	0.0016 (8)
C12	0.0339 (12)	0.0261 (11)	0.0170 (10)	0.0051 (9)	0.0103 (9)	0.0001 (8)
C13	0.0318 (11)	0.0237 (10)	0.0183 (10)	0.0050 (9)	−0.0003 (9)	−0.0085 (8)
C14	0.0214 (10)	0.0180 (10)	0.0296 (11)	−0.0025 (8)	0.0030 (9)	−0.0058 (8)
C15	0.0211 (10)	0.0166 (9)	0.0220 (10)	0.0006 (7)	0.0083 (8)	0.0003 (8)

Geometric parameters (Å, º)

Cu1—O1	1.9943 (12)	C4—H4A	0.9500
Cu1—O1^i	2.2927 (12)	C4—C5	1.381 (3)
Cu1—N1	2.0224 (15)	C5—H5A	0.9500
Cu1—N2	2.0244 (15)	C6—H6A	0.9500
Cu1—N3	2.0341 (15)	C6—C7	1.384 (3)
S1—O1	1.5434 (13)	C7—H7A	0.9500
S1—O2	1.4589 (14)	C7—C8	1.383 (3)
S1—O3	1.4668 (14)	C8—H8A	0.9500
S1—O4	1.4581 (14)	C8—C9	1.385 (3)
O1—Cu1^i	2.2927 (12)	C9—H9A	0.9500
N1—C1	1.345 (2)	C9—C10	1.381 (3)
N1—C5	1.342 (2)	C10—H10A	0.9500
N2—C6	1.342 (2)	C11—H11A	0.9500
N2—C10	1.345 (2)	C11—C12	1.382 (3)
N3—C11	1.346 (2)	C12—H12A	0.9500
N3—C15	1.346 (2)	C12—C13	1.381 (3)
C1—H1A	0.9500	C13—H13A	0.9500
C1—C2	1.383 (3)	C13—C14	1.381 (3)
C2—H2A	0.9500	C14—H14A	0.9500
C2—C3	1.386 (3)	C14—C15	1.378 (3)
C3—H3A	0.9500	C15—H15A	0.9500
C3—C4	1.379 (3)
O1—Cu1—O1^i	78.51 (5)	C3—C4—H4A	120.4
O1—Cu1—N1	90.82 (6)	C3—C4—C5	119.1 (2)
O1—Cu1—N2	175.23 (6)	C5—C4—H4A	120.4
O1—Cu1—N3	92.86 (5)	N1—C5—C4	122.10 (19)
N1—Cu1—O1^i	94.37 (5)	N1—C5—H5A	119.0
N1—Cu1—N2	86.91 (6)	C4—C5—H5A	119.0
N1—Cu1—N3	172.68 (6)	N2—C6—H6A	119.0
N2—Cu1—O1^i	105.83 (5)	N2—C6—C7	121.93 (18)
N2—Cu1—N3	88.95 (6)	C7—C6—H6A	119.0
N3—Cu1—O1^i	92.56 (5)	C6—C7—H7A	120.2
O2—S1—O1	106.91 (8)	C8—C7—C6	119.67 (19)
O2—S1—O3	112.66 (9)	C8—C7—H7A	120.2
O3—S1—O1	105.02 (8)	C7—C8—H8A	120.9
O4—S1—O1	108.45 (7)	C7—C8—C9	118.29 (18)
O4—S1—O2	111.74 (9)	C9—C8—H8A	120.9
O4—S1—O3	111.64 (8)	C8—C9—H9A	120.4
Cu1—O1—Cu1^i	101.49 (5)	C10—C9—C8	119.28 (18)
S1—O1—Cu1^i	146.09 (7)	C10—C9—H9A	120.4
S1—O1—Cu1	112.40 (7)	N2—C10—C9	122.30 (18)
C1—N1—Cu1	120.43 (13)	N2—C10—H10A	118.9
C5—N1—Cu1	121.00 (13)	C9—C10—H10A	118.9
C5—N1—C1	118.57 (16)	N3—C11—H11A	118.9
C6—N2—Cu1	122.81 (13)	N3—C11—C12	122.17 (18)
C6—N2—C10	118.52 (16)	C12—C11—H11A	118.9
C10—N2—Cu1	118.41 (13)	C11—C12—H12A	120.3
C11—N3—Cu1	123.16 (13)	C13—C12—C11	119.34 (19)
C11—N3—C15	118.01 (16)	C13—C12—H12A	120.3
C15—N3—Cu1	118.83 (12)	C12—C13—H13A	120.6
N1—C1—H1A	118.7	C12—C13—C14	118.72 (18)
N1—C1—C2	122.50 (18)	C14—C13—H13A	120.6
C2—C1—H1A	118.7	C13—C14—H14A	120.5
C1—C2—H2A	120.8	C15—C14—C13	119.08 (19)
C1—C2—C3	118.3 (2)	C15—C14—H14A	120.5
C3—C2—H2A	120.8	N3—C15—C14	122.63 (18)
C2—C3—H3A	120.3	N3—C15—H15A	118.7
C4—C3—C2	119.38 (19)	C14—C15—H15A	118.7
C4—C3—H3A	120.3
Cu1—N1—C1—C2	179.67 (14)	C1—N1—C5—C4	0.6 (3)
Cu1—N1—C5—C4	−179.41 (15)	C1—C2—C3—C4	0.1 (3)
Cu1—N2—C6—C7	173.42 (15)	C2—C3—C4—C5	0.1 (3)
Cu1—N2—C10—C9	−174.34 (15)	C3—C4—C5—N1	−0.5 (3)
Cu1—N3—C11—C12	177.39 (14)	C5—N1—C1—C2	−0.3 (3)
Cu1—N3—C15—C14	−178.99 (15)	C6—N2—C10—C9	0.0 (3)
O2—S1—O1—Cu1^i	54.46 (15)	C6—C7—C8—C9	0.5 (3)
O2—S1—O1—Cu1	−127.34 (8)	C7—C8—C9—C10	−1.1 (3)
O3—S1—O1—Cu1^i	174.36 (12)	C8—C9—C10—N2	0.9 (3)
O3—S1—O1—Cu1	−7.45 (10)	C10—N2—C6—C7	−0.7 (3)
O4—S1—O1—Cu1^i	−66.17 (15)	C11—N3—C15—C14	0.3 (3)
O4—S1—O1—Cu1	112.02 (8)	C11—C12—C13—C14	0.5 (3)
N1—C1—C2—C3	0.0 (3)	C12—C13—C14—C15	−2.0 (3)
N2—C6—C7—C8	0.4 (3)	C13—C14—C15—N3	1.6 (3)
N3—C11—C12—C13	1.5 (3)	C15—N3—C11—C12	−1.9 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O1^i	0.95	2.57	3.163 (2)	121
C1—H1A···O2^i	0.95	2.45	3.396 (2)	174
C2—H2A···O2^ii	0.95	2.55	3.397 (3)	149
C5—H5A···O3	0.95	2.48	3.183 (3)	131
C6—H6A···O2^i	0.95	2.50	3.440 (2)	170
C9—H9A···O4^iii	0.95	2.63	3.340 (2)	132
C10—H10A···O3^iii	0.95	2.45	3.147 (2)	130
C11—H11A···S1	0.95	3.02	3.576 (2)	119
C11—H11A···O3	0.95	2.32	3.070 (2)	136
C14—H14A···O4^iv	0.95	2.59	3.333 (2)	135
C15—H15A···O4^i	0.95	2.35	3.222 (2)	153

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

catena-Poly[[tetrakis(pyridine-κN)zinc(II)]-µ-sulfato-κ²O:O'-[bis(pyridine-κN)zinc(II)]-µ-sulfato-κ²O:O'] (UMD1296)

Crystal data

[Zn2(SO4)2(C5H5N)6]	Dx = 1.580 Mg m^−3
Mr = 797.46	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P3121	Cell parameters from 9863 reflections
a = 10.5383 (10) Å	θ = 3.2–25.6°
c = 26.135 (3) Å	µ = 1.61 mm^−1
V = 2513.5 (5) Å^3	T = 200 K
Z = 3	Block, colourless
F(000) = 1224	0.34 × 0.15 × 0.14 mm

Data collection

Bruker APEX-III CMOS diffractometer	3039 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.036
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θmax = 25.7°, θmin = 3.2°
Tmin = 0.598, Tmax = 0.754	h = −12→12
68074 measured reflections	k = −12→12
3183 independent reflections	l = −31→31

Refinement

Refinement on F^2	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0267P)^2 + 0.6802P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.018	(Δ/σ)max = 0.001
wR(F^2) = 0.045	Δρmax = 0.21 e Å^−3
S = 1.00	Δρmin = −0.18 e Å^−3
3183 reflections	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
219 parameters	Extinction coefficient: 0.0037 (6)
0 restraints	Absolute structure: Flack x determined using 1240 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.004 (3)
Hydrogen site location: inferred from neighbouring sites

Special details

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.

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

	x	y	z	Uiso*/Ueq
Zn1	1.0000	1.01827 (3)	0.1667	0.02079 (11)
Zn2	0.70511 (4)	0.70511 (4)	0.0000	0.02290 (12)
S1	0.70074 (7)	0.90587 (6)	0.08225 (2)	0.02090 (14)
O1	0.8125 (2)	0.9323 (2)	0.12076 (7)	0.0360 (5)
O2	0.6788 (3)	1.0302 (2)	0.07833 (8)	0.0418 (5)
O3	0.5669 (2)	0.7690 (2)	0.09268 (8)	0.0392 (5)
O4	0.7620 (2)	0.8909 (2)	0.03187 (6)	0.0340 (4)
N1	1.0933 (2)	1.2137 (2)	0.11751 (8)	0.0262 (4)
N2	1.1140 (2)	0.9269 (2)	0.12359 (7)	0.0239 (4)
N3	0.6647 (2)	0.5299 (2)	0.04345 (8)	0.0259 (5)
C1	1.0711 (3)	1.2026 (3)	0.06682 (10)	0.0341 (6)
H1A	1.0172	1.1077	0.0521	0.041*
C2	1.1231 (4)	1.3230 (3)	0.03504 (11)	0.0440 (8)
H2A	1.1077	1.3111	−0.0009	0.053*
C3	1.1976 (4)	1.4603 (4)	0.05634 (12)	0.0488 (8)
H3A	1.2321	1.5451	0.0355	0.059*
C4	1.2217 (4)	1.4735 (3)	0.10865 (12)	0.0452 (7)
H4A	1.2740	1.5672	0.1243	0.054*
C5	1.1684 (3)	1.3479 (3)	0.13745 (10)	0.0317 (6)
H5A	1.1860	1.3571	0.1733	0.038*
C6	1.0686 (3)	0.8642 (3)	0.07773 (10)	0.0321 (6)
H6A	0.9795	0.8526	0.0645	0.039*
C7	1.1451 (3)	0.8156 (3)	0.04872 (10)	0.0367 (7)
H7A	1.1096	0.7723	0.0161	0.044*
C8	1.2737 (3)	0.8306 (3)	0.06768 (10)	0.0341 (6)
H8A	1.3288	0.7987	0.0483	0.041*
C9	1.3211 (3)	0.8928 (3)	0.11522 (11)	0.0360 (7)
H9A	1.4092	0.9041	0.1294	0.043*
C10	1.2382 (3)	0.9381 (3)	0.14183 (11)	0.0346 (7)
H10A	1.2706	0.9796	0.1748	0.042*
C11	0.5465 (3)	0.4616 (3)	0.07328 (11)	0.0389 (7)
H11A	0.4831	0.5011	0.0761	0.047*
C12	0.5128 (4)	0.3360 (3)	0.10020 (12)	0.0458 (8)
H12A	0.4276	0.2900	0.1211	0.055*
C13	0.6033 (4)	0.2786 (3)	0.09647 (12)	0.0429 (7)
H13A	0.5811	0.1911	0.1141	0.052*
C14	0.7278 (4)	0.3497 (3)	0.06660 (11)	0.0431 (7)
H14A	0.7935	0.3130	0.0640	0.052*
C15	0.7552 (3)	0.4744 (3)	0.04071 (10)	0.0334 (6)
H15A	0.8408	0.5231	0.0202	0.040*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0203 (2)	0.01975 (16)	0.02253 (19)	0.01013 (10)	0.00147 (15)	0.00074 (8)
Zn2	0.02289 (17)	0.02289 (17)	0.0266 (2)	0.01424 (18)	−0.00146 (8)	0.00146 (8)
S1	0.0219 (3)	0.0200 (3)	0.0246 (3)	0.0133 (3)	−0.0017 (2)	0.0000 (2)
O1	0.0302 (10)	0.0353 (11)	0.0328 (9)	0.0091 (9)	−0.0110 (8)	0.0057 (8)
O2	0.0542 (14)	0.0363 (12)	0.0524 (12)	0.0359 (11)	0.0089 (11)	0.0083 (10)
O3	0.0236 (10)	0.0303 (11)	0.0557 (12)	0.0075 (9)	0.0017 (8)	0.0039 (9)
O4	0.0487 (12)	0.0295 (10)	0.0264 (8)	0.0213 (9)	0.0051 (8)	−0.0007 (8)
N1	0.0229 (11)	0.0254 (11)	0.0287 (10)	0.0109 (10)	0.0016 (10)	0.0016 (9)
N2	0.0232 (11)	0.0237 (12)	0.0261 (10)	0.0127 (9)	−0.0004 (9)	−0.0016 (9)
N3	0.0315 (12)	0.0235 (11)	0.0269 (11)	0.0169 (10)	−0.0037 (9)	−0.0007 (9)
C1	0.0327 (16)	0.0318 (15)	0.0298 (13)	0.0101 (13)	0.0017 (12)	0.0015 (11)
C2	0.0425 (18)	0.0429 (18)	0.0325 (15)	0.0108 (15)	0.0018 (13)	0.0103 (13)
C3	0.056 (2)	0.0365 (17)	0.0439 (16)	0.0150 (17)	0.0067 (15)	0.0199 (14)
C4	0.0502 (19)	0.0225 (14)	0.0515 (17)	0.0097 (15)	0.0027 (15)	0.0026 (13)
C5	0.0337 (15)	0.0262 (13)	0.0331 (13)	0.0132 (13)	0.0002 (12)	0.0012 (11)
C6	0.0299 (14)	0.0391 (17)	0.0324 (13)	0.0211 (13)	−0.0058 (11)	−0.0068 (12)
C7	0.0425 (18)	0.0456 (18)	0.0298 (13)	0.0279 (15)	−0.0061 (12)	−0.0119 (13)
C8	0.0361 (16)	0.0351 (15)	0.0378 (15)	0.0227 (14)	0.0059 (13)	−0.0028 (12)
C9	0.0302 (15)	0.0426 (17)	0.0441 (16)	0.0247 (14)	−0.0050 (12)	−0.0063 (13)
C10	0.0361 (16)	0.0416 (17)	0.0341 (14)	0.0254 (14)	−0.0098 (12)	−0.0113 (12)
C11	0.0362 (16)	0.0328 (16)	0.0523 (17)	0.0206 (13)	0.0049 (14)	0.0071 (14)
C12	0.0441 (19)	0.0350 (16)	0.0533 (18)	0.0160 (15)	0.0081 (16)	0.0134 (14)
C13	0.057 (2)	0.0286 (15)	0.0456 (16)	0.0228 (15)	−0.0049 (15)	0.0087 (13)
C14	0.058 (2)	0.0416 (18)	0.0477 (17)	0.0379 (17)	−0.0027 (15)	0.0028 (14)
C15	0.0391 (17)	0.0333 (15)	0.0368 (15)	0.0249 (14)	−0.0005 (12)	0.0013 (11)

Geometric parameters (Å, º)

Zn1—O1^i	2.0913 (18)	C3—H3A	0.9500
Zn1—O1	2.0913 (18)	C3—C4	1.385 (4)
Zn1—N1^i	2.199 (2)	C4—H4A	0.9500
Zn1—N1	2.199 (2)	C4—C5	1.375 (4)
Zn1—N2	2.190 (2)	C5—H5A	0.9500
Zn1—N2^i	2.190 (2)	C6—H6A	0.9500
Zn2—O4	1.9273 (18)	C6—C7	1.379 (4)
Zn2—O4^ii	1.9273 (18)	C7—H7A	0.9500
Zn2—N3^ii	2.023 (2)	C7—C8	1.375 (4)
Zn2—N3	2.023 (2)	C8—H8A	0.9500
S1—O1	1.4663 (18)	C8—C9	1.377 (4)
S1—O2	1.4428 (19)	C9—H9A	0.9500
S1—O3	1.452 (2)	C9—C10	1.376 (4)
S1—O4	1.5088 (18)	C10—H10A	0.9500
N1—C1	1.340 (3)	C11—H11A	0.9500
N1—C5	1.334 (3)	C11—C12	1.380 (4)
N2—C6	1.336 (3)	C12—H12A	0.9500
N2—C10	1.341 (3)	C12—C13	1.364 (5)
N3—C11	1.334 (4)	C13—H13A	0.9500
N3—C15	1.347 (3)	C13—C14	1.382 (5)
C1—H1A	0.9500	C14—H14A	0.9500
C1—C2	1.380 (4)	C14—C15	1.374 (4)
C2—H2A	0.9500	C15—H15A	0.9500
C2—C3	1.373 (5)
O1^i—Zn1—O1	175.52 (12)	C3—C2—C1	118.7 (3)
O1^i—Zn1—N1	89.46 (9)	C3—C2—H2A	120.7
O1^i—Zn1—N1^i	87.35 (7)	C2—C3—H3A	120.5
O1—Zn1—N1^i	89.46 (9)	C2—C3—C4	119.0 (3)
O1—Zn1—N1	87.35 (7)	C4—C3—H3A	120.5
O1^i—Zn1—N2	86.23 (8)	C3—C4—H4A	120.7
O1—Zn1—N2	96.98 (8)	C5—C4—C3	118.6 (3)
O1^i—Zn1—N2^i	96.98 (8)	C5—C4—H4A	120.7
O1—Zn1—N2^i	86.23 (8)	N1—C5—C4	123.2 (2)
N1—Zn1—N1^i	89.02 (11)	N1—C5—H5A	118.4
N2^i—Zn1—N1^i	91.42 (8)	C4—C5—H5A	118.4
N2^i—Zn1—N1	173.55 (8)	N2—C6—H6A	118.5
N2—Zn1—N1	91.43 (8)	N2—C6—C7	123.1 (3)
N2—Zn1—N1^i	173.55 (8)	C7—C6—H6A	118.5
N2—Zn1—N2^i	88.86 (11)	C6—C7—H7A	120.5
O4—Zn2—O4^ii	96.86 (12)	C8—C7—C6	119.0 (3)
O4—Zn2—N3	120.09 (8)	C8—C7—H7A	120.5
O4^ii—Zn2—N3^ii	120.08 (8)	C7—C8—H8A	120.6
O4—Zn2—N3^ii	104.12 (8)	C7—C8—C9	118.8 (3)
O4^ii—Zn2—N3	104.12 (8)	C9—C8—H8A	120.6
N3—Zn2—N3^ii	111.67 (13)	C8—C9—H9A	120.7
O1—S1—O4	105.90 (12)	C10—C9—C8	118.6 (3)
O2—S1—O1	110.76 (13)	C10—C9—H9A	120.7
O2—S1—O3	113.46 (13)	N2—C10—C9	123.4 (2)
O2—S1—O4	107.67 (12)	N2—C10—H10A	118.3
O3—S1—O1	110.42 (12)	C9—C10—H10A	118.3
O3—S1—O4	108.29 (12)	N3—C11—H11A	118.7
S1—O1—Zn1	166.23 (13)	N3—C11—C12	122.6 (3)
S1—O4—Zn2	123.45 (11)	C12—C11—H11A	118.7
C1—N1—Zn1	121.29 (18)	C11—C12—H12A	120.4
C5—N1—Zn1	121.01 (16)	C13—C12—C11	119.1 (3)
C5—N1—C1	117.6 (2)	C13—C12—H12A	120.4
C6—N2—Zn1	122.62 (17)	C12—C13—H13A	120.5
C6—N2—C10	117.1 (2)	C12—C13—C14	119.0 (3)
C10—N2—Zn1	120.26 (17)	C14—C13—H13A	120.5
C11—N3—Zn2	122.29 (18)	C13—C14—H14A	120.5
C11—N3—C15	118.0 (2)	C15—C14—C13	119.0 (3)
C15—N3—Zn2	119.64 (18)	C15—C14—H14A	120.5
N1—C1—H1A	118.5	N3—C15—C14	122.2 (3)
N1—C1—C2	122.9 (3)	N3—C15—H15A	118.9
C2—C1—H1A	118.5	C14—C15—H15A	118.9
C1—C2—H2A	120.7
Zn1—N1—C1—C2	177.4 (2)	C1—N1—C5—C4	0.8 (4)
Zn1—N1—C5—C4	−176.2 (2)	C1—C2—C3—C4	1.9 (5)
Zn1—N2—C6—C7	175.3 (2)	C2—C3—C4—C5	−0.8 (5)
Zn1—N2—C10—C9	−175.2 (2)	C3—C4—C5—N1	−0.6 (5)
Zn2—N3—C11—C12	175.3 (2)	C5—N1—C1—C2	0.4 (4)
Zn2—N3—C15—C14	−175.4 (2)	C6—N2—C10—C9	1.9 (4)
O1—S1—O4—Zn2	100.82 (15)	C6—C7—C8—C9	0.5 (4)
O2—S1—O1—Zn1	−47.1 (6)	C7—C8—C9—C10	−0.3 (4)
O2—S1—O4—Zn2	−140.65 (14)	C8—C9—C10—N2	−0.9 (5)
O3—S1—O1—Zn1	−173.6 (6)	C10—N2—C6—C7	−1.7 (4)
O3—S1—O4—Zn2	−17.61 (17)	C11—N3—C15—C14	1.3 (4)
O4—S1—O1—Zn1	69.4 (6)	C11—C12—C13—C14	1.3 (5)
N1—C1—C2—C3	−1.7 (5)	C12—C13—C14—C15	−1.3 (5)
N2—C6—C7—C8	0.5 (5)	C13—C14—C15—N3	0.0 (5)
N3—C11—C12—C13	0.1 (5)	C15—N3—C11—C12	−1.4 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···S1	0.95	3.03	3.602 (3)	120
C1—H1A···O4	0.95	2.57	3.397 (3)	146
C5—H5A···O2^i	0.95	2.59	3.460 (3)	153
C6—H6A···O4	0.95	2.66	3.587 (3)	166
C7—H7A···O2^ii	0.95	2.63	3.581 (3)	174
C7—H7A···O4^ii	0.95	2.58	3.228 (3)	126
C10—H10A···S1^i	0.95	3.00	3.830 (3)	147
C10—H10A···O1^i	0.95	2.28	2.896 (3)	122
C11—H11A···O3	0.95	2.54	3.178 (4)	125
C14—H14A···O2^iii	0.95	2.62	3.157 (4)	116

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