More crystal field theory in action: the metal–4-picoline (pic)–sulfate [M(pic)x]SO4 complexes (M = Fe, Co, Ni, Cu, Zn, and Cd)

Pham, D.N.K.; Roy, M.; Kreider-Mueller, A.; Golen, J.A.; Manke, D.R.

doi:10.1107/S2053229619004625

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More crystal field theory in action: the metal–4-picoline (pic)–sulfate [M(pic)_x]SO₄ complexes (M = Fe, Co, Ni, Cu, Zn, and Cd)

D. N. K. Pham, M. Roy, A. Kreider-Mueller, J. A. Golen and D. R. Manke

Seven crystal structures of five first-row (Fe, Co, Ni, Cu, and Zn) and one second-row (Cd) transition metal–4-picoline (pic)–sulfate complexes of the form [M(pic)_x]SO₄ are reported. These complexes are catena-poly[[tetrakis(4-methylpyridine-κN)metal(II)]-μ-sulfato-κ²O:O′], [M(SO₄)(C₆H₇N)₄]_n, where the metal/M is iron, cobalt, nickel, and cadmium, di-μ-sulfato-κ⁴O:O-bis[tris(4-methylpyridine-κN)copper(II)], [Cu₂(SO₄)₂(C₆H₇N)₆], catena-poly[[bis(4-methylpyridine-κN)zinc(II)]-μ-sulfato-κ²O:O′], [Zn(SO₄)(C₆H₇N)₂]_n, and catena-poly[[tris(4-methylpyridine-κN)zinc(II)]-μ-sulfato-κ²O:O′], [Zn(SO₄)(C₆H₇N)₃]_n. The Fe, Co, Ni, and Cd compounds are isomorphous, displaying polymeric crystal structures with infinite chains of M^II ions adopting an octahedral N₄O₂ coordination environment that involves four picoline ligands and two bridging sulfate anions. The Cu compound features a dimeric crystal structure, with the Cu^II ions possessing square-pyramidal N₃O₂ coordination environments that contain three picoline ligands and two bridging sulfate anions. Zinc crystallizes in two forms, one exhibiting a polymeric crystal structure with infinite chains of Zn^II ions adopting a tetrahedral N₂O₂ coordination containing two picoline ligands and two bridging sulfate anions, and the other exhibiting a polymeric crystal structure with infinite chains of Zn^II ions adopting a trigonal bipyramidal N₃O₂ coordination containing three picoline ligands and two bridging sulfate anions. The structures are compared with the analogous pyridine complexes, and the observed coordination environments are examined in relation to crystal field theory.

Keywords: crystal field theory; picoline; sulfate; transition metals; coordination chemistry; one-dimensional coordination polymer; crystal structure; periodic trend.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229619004625/ov3124sup1.cif Contains datablocks umd1308_a, umd1358_a, umd1307, umd1301_a, UMD1448_a, umd1540c_a, umd1375_a, global
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229619004625/ov3124umd1308_asup2.hkl Contains datablock umd1308_a
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229619004625/ov3124umd1358_asup3.hkl Contains datablock umd1358_a
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229619004625/ov3124umd1307sup4.hkl Contains datablock umd1307
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229619004625/ov3124umd1301_asup5.hkl Contains datablock umd1301_a
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229619004625/ov3124UMD1448_asup6.hkl Contains datablock UMD1448_a
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229619004625/ov3124umd1540c_asup7.hkl Contains datablock umd1540c_a
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229619004625/ov3124umd1375_asup8.hkl Contains datablock umd1375_a

CCDC references: 1908116; 1908115; 1908114; 1908113; 1908112; 1908111; 1908110

Computing details top

Data collection: APEX3 (Bruker, 2016) for umd1308_a, umd1358_a, umd1307, umd1301_a, UMD1448_a, umd1375_a; APEX2 (Bruker, 2015) for umd1540c_a. Cell refinement: SAINT (Bruker, 2016) for umd1308_a, umd1358_a, umd1307, umd1301_a, UMD1448_a, umd1375_a; SAINT (Bruker, 2015) for umd1540c_a. Data reduction: SAINT (Bruker, 2016) for umd1308_a, umd1358_a, umd1307, umd1301_a, UMD1448_a, umd1375_a; SAINT (Bruker, 2015) for umd1540c_a. For all structures, 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(4-methylpyridine-κN)iron(II)]-sulfato-κ²O:O'] (umd1308_a) top

Crystal data top

[Fe(SO₄)(C₆H₇N)₄]	F(000) = 2192
M_r = 524.41	D_x = 1.364 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.4472 (13) Å	Cell parameters from 9601 reflections
b = 18.822 (2) Å	θ = 3.1–25.8°
c = 24.010 (3) Å	µ = 0.71 mm⁻¹
β = 99.112 (3)°	T = 297 K
V = 5108.0 (11) Å³	Block, yellow-brown
Z = 8	0.22 × 0.2 × 0.2 mm

Data collection top

Bruker D8 Venture CMOS diffractometer	4320 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.037
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θ_max = 25.8°, θ_min = 2.9°
T_min = 0.306, T_max = 0.332	h = −13→14
80351 measured reflections	k = −22→22
4895 independent reflections	l = −29→29

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.030	w = 1/[σ²(F_o²) + (0.0378P)² + 5.7613P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.083	(Δ/σ)_max = 0.002
S = 1.10	Δρ_max = 0.40 e Å⁻³
4895 reflections	Δρ_min = −0.30 e Å⁻³
314 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
6 restraints	Extinction coefficient: 0.00300 (16)
Primary atom site location: structure-invariant direct methods

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Fe1	0.5000	0.5000	0.5000	0.02613 (11)
Fe2	0.5000	0.47022 (2)	0.7500	0.02408 (11)
S1	0.34329 (4)	0.47876 (3)	0.61286 (2)	0.02862 (12)
O1	0.42874 (11)	0.48685 (8)	0.57272 (5)	0.0355 (3)
O2	0.41429 (12)	0.46837 (8)	0.66946 (5)	0.0397 (3)
O3	0.27471 (15)	0.54311 (10)	0.61302 (7)	0.0601 (5)
O4	0.27080 (14)	0.41670 (10)	0.59876 (6)	0.0541 (4)
N1	0.51167 (14)	0.38214 (9)	0.49376 (6)	0.0368 (4)
N2	0.31868 (13)	0.50168 (8)	0.44867 (6)	0.0317 (3)
N3	0.61876 (13)	0.55408 (8)	0.72335 (6)	0.0309 (3)
N4	0.38082 (13)	0.38122 (8)	0.76966 (6)	0.0319 (3)
C1	0.4357 (2)	0.33786 (12)	0.51286 (10)	0.0503 (5)
H1	0.3763	0.3570	0.5305	0.060*
C2	0.4416 (3)	0.26555 (14)	0.50761 (13)	0.0735 (8)
H2	0.3860	0.2370	0.5211	0.088*
C3	0.5296 (3)	0.23473 (14)	0.48236 (13)	0.0762 (9)
C4	0.6085 (3)	0.28022 (14)	0.46382 (11)	0.0614 (7)
H4	0.6704	0.2622	0.4472	0.074*
C5	0.59684 (19)	0.35242 (12)	0.46958 (9)	0.0448 (5)
H5	0.6510	0.3820	0.4560	0.054*
C6	0.5398 (5)	0.15502 (19)	0.4760 (2)	0.142 (2)
H6A	0.4628	0.1353	0.4633	0.213*
H6B	0.5723	0.1345	0.5116	0.213*
H6C	0.5907	0.1447	0.4488	0.213*
C7	0.21927 (18)	0.47721 (12)	0.46451 (8)	0.0423 (5)
H7	0.2243	0.4555	0.4996	0.051*
C8	0.11013 (18)	0.48259 (14)	0.43148 (9)	0.0480 (6)
H8	0.0438	0.4643	0.4444	0.058*
C9	0.09827 (17)	0.51482 (12)	0.37941 (9)	0.0405 (5)
C10	0.20008 (17)	0.54053 (12)	0.36336 (8)	0.0421 (5)
H10	0.1968	0.5632	0.3287	0.051*
C11	0.30687 (17)	0.53292 (11)	0.39820 (8)	0.0381 (5)
H11	0.3744	0.5505	0.3860	0.046*
C12	−0.0192 (2)	0.52174 (19)	0.34214 (12)	0.0723 (9)
H12A	−0.0736	0.4879	0.3535	0.108*
H12B	−0.0099	0.5128	0.3037	0.108*
H12C	−0.0494	0.5689	0.3453	0.108*
C13	0.58588 (18)	0.59392 (11)	0.67754 (8)	0.0392 (4)
H13	0.5089	0.5894	0.6586	0.047*
C14	0.6601 (2)	0.64131 (12)	0.65696 (9)	0.0486 (5)
H14	0.6325	0.6679	0.6249	0.058*
C15	0.7746 (2)	0.64959 (12)	0.68349 (10)	0.0492 (5)
C16	0.80798 (19)	0.60973 (14)	0.73155 (10)	0.0524 (6)
H16	0.8840	0.6143	0.7517	0.063*
C17	0.72941 (17)	0.56319 (12)	0.74991 (9)	0.0418 (5)
H17	0.7546	0.5368	0.7824	0.050*
C18	0.8597 (3)	0.69965 (17)	0.66174 (15)	0.0827 (9)
H18A	0.9071	0.7231	0.6929	0.124*
H18B	0.8162	0.7344	0.6375	0.124*
H18C	0.9102	0.6733	0.6409	0.124*
C19	0.40919 (17)	0.34134 (11)	0.81595 (8)	0.0376 (4)
H19	0.4811	0.3497	0.8390	0.045*
C20	0.33698 (19)	0.28836 (12)	0.83116 (9)	0.0444 (5)
H20	0.3609	0.2622	0.8638	0.053*
C21	0.22959 (19)	0.27409 (11)	0.79815 (9)	0.0432 (5)
C22	0.20183 (19)	0.31401 (12)	0.74954 (9)	0.0461 (5)
H22	0.1313	0.3058	0.7253	0.055*
C23	0.27806 (17)	0.36581 (11)	0.73682 (8)	0.0388 (4)
H23	0.2572	0.3915	0.7037	0.047*
C24	0.1458 (2)	0.21870 (14)	0.81395 (11)	0.0631 (7)
H24A	0.1063	0.1958	0.7804	0.095*
H24B	0.0883	0.2409	0.8333	0.095*
H24C	0.1894	0.1840	0.8382	0.095*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.02428 (18)	0.0346 (2)	0.02019 (18)	−0.00324 (14)	0.00571 (13)	0.00115 (14)
Fe2	0.02236 (18)	0.0318 (2)	0.01830 (17)	0.000	0.00385 (12)	0.000
S1	0.0230 (2)	0.0449 (3)	0.0184 (2)	−0.00246 (17)	0.00465 (16)	0.00322 (17)
O1	0.0312 (7)	0.0534 (8)	0.0241 (6)	−0.0044 (6)	0.0112 (5)	0.0018 (6)
O2	0.0411 (8)	0.0563 (9)	0.0203 (6)	−0.0082 (6)	0.0000 (5)	0.0051 (6)
O3	0.0550 (10)	0.0692 (11)	0.0627 (10)	0.0278 (8)	0.0291 (8)	0.0227 (9)
O4	0.0518 (9)	0.0755 (11)	0.0356 (8)	−0.0345 (8)	0.0090 (7)	−0.0054 (7)
N1	0.0399 (9)	0.0386 (9)	0.0325 (8)	−0.0024 (7)	0.0074 (7)	0.0014 (7)
N2	0.0285 (8)	0.0402 (9)	0.0262 (8)	−0.0036 (7)	0.0039 (6)	0.0017 (6)
N3	0.0283 (8)	0.0359 (8)	0.0291 (8)	−0.0020 (6)	0.0060 (6)	−0.0011 (6)
N4	0.0309 (8)	0.0348 (8)	0.0314 (8)	0.0005 (6)	0.0093 (6)	0.0015 (6)
C1	0.0578 (14)	0.0454 (13)	0.0527 (13)	−0.0091 (10)	0.0240 (11)	−0.0024 (10)
C2	0.100 (2)	0.0436 (14)	0.088 (2)	−0.0173 (14)	0.0481 (18)	0.0003 (13)
C3	0.118 (3)	0.0377 (13)	0.082 (2)	0.0009 (15)	0.0445 (19)	0.0022 (13)
C4	0.0807 (18)	0.0494 (14)	0.0609 (15)	0.0148 (13)	0.0320 (13)	0.0041 (12)
C5	0.0498 (12)	0.0427 (12)	0.0450 (12)	0.0048 (10)	0.0167 (10)	0.0062 (9)
C6	0.212 (5)	0.0458 (19)	0.192 (5)	−0.003 (2)	0.110 (4)	−0.009 (2)
C7	0.0389 (11)	0.0592 (13)	0.0282 (10)	−0.0125 (10)	0.0040 (8)	0.0066 (9)
C8	0.0306 (10)	0.0749 (16)	0.0388 (11)	−0.0155 (10)	0.0067 (8)	0.0047 (10)
C9	0.0291 (10)	0.0568 (13)	0.0350 (10)	−0.0006 (9)	0.0035 (8)	−0.0030 (9)
C10	0.0343 (10)	0.0602 (14)	0.0314 (10)	0.0031 (9)	0.0042 (8)	0.0112 (9)
C11	0.0280 (9)	0.0521 (12)	0.0343 (10)	−0.0022 (8)	0.0055 (8)	0.0113 (9)
C12	0.0339 (12)	0.125 (3)	0.0539 (15)	0.0001 (14)	−0.0042 (11)	0.0076 (16)
C13	0.0411 (11)	0.0383 (11)	0.0360 (10)	−0.0047 (9)	−0.0002 (8)	0.0016 (8)
C14	0.0655 (15)	0.0410 (12)	0.0401 (11)	−0.0060 (10)	0.0105 (10)	0.0084 (9)
C15	0.0484 (12)	0.0482 (13)	0.0561 (13)	−0.0122 (10)	0.0237 (11)	−0.0008 (10)
C16	0.0318 (11)	0.0664 (16)	0.0595 (14)	−0.0100 (10)	0.0087 (10)	0.0042 (12)
C17	0.0312 (10)	0.0545 (13)	0.0396 (11)	−0.0036 (9)	0.0049 (8)	0.0061 (9)
C18	0.081 (2)	0.078 (2)	0.099 (2)	−0.0275 (17)	0.0440 (18)	0.0116 (17)
C19	0.0362 (10)	0.0396 (11)	0.0376 (10)	0.0031 (8)	0.0080 (8)	0.0047 (8)
C20	0.0533 (12)	0.0388 (11)	0.0431 (11)	0.0012 (10)	0.0139 (10)	0.0108 (9)
C21	0.0513 (12)	0.0384 (11)	0.0438 (11)	−0.0078 (9)	0.0196 (10)	−0.0032 (9)
C22	0.0439 (11)	0.0547 (13)	0.0400 (11)	−0.0143 (10)	0.0074 (9)	−0.0012 (10)
C23	0.0390 (11)	0.0455 (12)	0.0320 (10)	−0.0068 (9)	0.0061 (8)	0.0042 (8)
C24	0.0746 (17)	0.0559 (15)	0.0639 (16)	−0.0226 (13)	0.0269 (13)	0.0025 (12)

Geometric parameters (Å, º) top

Fe1—O1ⁱ	2.0558 (12)	C7—H7	0.9300
Fe1—O1	2.0558 (12)	C7—C8	1.373 (3)
Fe1—N1	2.2289 (17)	C8—H8	0.9300
Fe1—N1ⁱ	2.2289 (17)	C8—C9	1.377 (3)
Fe1—N2ⁱ	2.2400 (15)	C9—C10	1.372 (3)
Fe1—N2	2.2400 (15)	C9—C12	1.498 (3)
Fe2—O2ⁱⁱ	2.0254 (13)	C10—H10	0.9300
Fe2—O2	2.0254 (12)	C10—C11	1.375 (3)
Fe2—N3	2.2415 (15)	C11—H11	0.9300
Fe2—N3ⁱⁱ	2.2415 (15)	C12—H12A	0.9600
Fe2—N4	2.2570 (16)	C12—H12B	0.9600
Fe2—N4ⁱⁱ	2.2570 (15)	C12—H12C	0.9600
S1—O1	1.4856 (12)	C13—H13	0.9300
S1—O2	1.4819 (13)	C13—C14	1.376 (3)
S1—O3	1.4437 (17)	C14—H14	0.9300
S1—O4	1.4418 (16)	C14—C15	1.373 (3)
N1—C1	1.337 (3)	C15—C16	1.379 (3)
N1—C5	1.334 (3)	C15—C18	1.508 (3)
N2—C7	1.337 (2)	C16—H16	0.9300
N2—C11	1.334 (2)	C16—C17	1.377 (3)
N3—C13	1.335 (2)	C17—H17	0.9300
N3—C17	1.336 (2)	C18—H18A	0.9600
N4—C19	1.338 (2)	C18—H18B	0.9600
N4—C23	1.340 (2)	C18—H18C	0.9600
C1—H1	0.9300	C19—H19	0.9300
C1—C2	1.370 (4)	C19—C20	1.381 (3)
C2—H2	0.9300	C20—H20	0.9300
C2—C3	1.384 (4)	C20—C21	1.379 (3)
C3—C4	1.369 (4)	C21—C22	1.382 (3)
C3—C6	1.515 (4)	C21—C24	1.505 (3)
C4—H4	0.9300	C22—H22	0.9300
C4—C5	1.375 (3)	C22—C23	1.375 (3)
C5—H5	0.9300	C23—H23	0.9300
C6—H6A	0.9600	C24—H24A	0.9600
C6—H6B	0.9600	C24—H24B	0.9600
C6—H6C	0.9600	C24—H24C	0.9600

O1ⁱ—Fe1—O1	180.0	C3—C6—H6C	109.5
O1—Fe1—N1	88.47 (6)	H6A—C6—H6B	109.5
O1ⁱ—Fe1—N1	91.53 (6)	H6A—C6—H6C	109.5
O1—Fe1—N1ⁱ	91.53 (6)	H6B—C6—H6C	109.5
O1ⁱ—Fe1—N1ⁱ	88.47 (6)	N2—C7—H7	118.4
O1ⁱ—Fe1—N2	89.36 (5)	N2—C7—C8	123.21 (18)
O1ⁱ—Fe1—N2ⁱ	90.64 (5)	C8—C7—H7	118.4
O1—Fe1—N2	90.64 (5)	C7—C8—H8	119.8
O1—Fe1—N2ⁱ	89.36 (5)	C7—C8—C9	120.44 (19)
N1ⁱ—Fe1—N1	180.00 (8)	C9—C8—H8	119.8
N1—Fe1—N2ⁱ	87.87 (6)	C8—C9—C12	122.1 (2)
N1ⁱ—Fe1—N2	87.87 (6)	C10—C9—C8	116.38 (18)
N1ⁱ—Fe1—N2ⁱ	92.13 (6)	C10—C9—C12	121.6 (2)
N1—Fe1—N2	92.13 (6)	C9—C10—H10	119.8
N2—Fe1—N2ⁱ	180.00 (11)	C9—C10—C11	120.33 (18)
O2ⁱⁱ—Fe2—O2	178.03 (9)	C11—C10—H10	119.8
O2ⁱⁱ—Fe2—N3ⁱⁱ	87.92 (5)	N2—C11—C10	123.43 (18)
O2—Fe2—N3ⁱⁱ	93.47 (6)	N2—C11—H11	118.3
O2ⁱⁱ—Fe2—N3	93.47 (6)	C10—C11—H11	118.3
O2—Fe2—N3	87.92 (6)	C9—C12—H12A	109.5
O2—Fe2—N4	88.25 (6)	C9—C12—H12B	109.5
O2ⁱⁱ—Fe2—N4ⁱⁱ	88.25 (6)	C9—C12—H12C	109.5
O2—Fe2—N4ⁱⁱ	90.29 (6)	H12A—C12—H12B	109.5
O2ⁱⁱ—Fe2—N4	90.29 (6)	H12A—C12—H12C	109.5
N3ⁱⁱ—Fe2—N3	90.47 (8)	H12B—C12—H12C	109.5
N3—Fe2—N4ⁱⁱ	92.81 (5)	N3—C13—H13	118.3
N3ⁱⁱ—Fe2—N4	92.81 (6)	N3—C13—C14	123.39 (19)
N3—Fe2—N4	175.09 (5)	C14—C13—H13	118.3
N3ⁱⁱ—Fe2—N4ⁱⁱ	175.09 (5)	C13—C14—H14	119.8
N4—Fe2—N4ⁱⁱ	84.16 (8)	C15—C14—C13	120.3 (2)
O2—S1—O1	106.66 (8)	C15—C14—H14	119.8
O3—S1—O1	109.27 (9)	C14—C15—C16	116.39 (19)
O3—S1—O2	109.12 (10)	C14—C15—C18	122.2 (2)
O4—S1—O1	110.14 (9)	C16—C15—C18	121.4 (2)
O4—S1—O2	108.67 (9)	C15—C16—H16	119.8
O4—S1—O3	112.79 (11)	C17—C16—C15	120.4 (2)
S1—O1—Fe1	162.52 (9)	C17—C16—H16	119.8
S1—O2—Fe2	170.32 (11)	N3—C17—C16	123.2 (2)
C1—N1—Fe1	123.25 (14)	N3—C17—H17	118.4
C5—N1—Fe1	120.15 (14)	C16—C17—H17	118.4
C5—N1—C1	116.59 (19)	C15—C18—H18A	109.5
C7—N2—Fe1	126.50 (13)	C15—C18—H18B	109.5
C11—N2—Fe1	117.23 (12)	C15—C18—H18C	109.5
C11—N2—C7	116.20 (16)	H18A—C18—H18B	109.5
C13—N3—Fe2	121.74 (13)	H18A—C18—H18C	109.5
C13—N3—C17	116.32 (17)	H18B—C18—H18C	109.5
C17—N3—Fe2	121.75 (13)	N4—C19—H19	118.4
C19—N4—Fe2	120.99 (13)	N4—C19—C20	123.25 (19)
C19—N4—C23	116.25 (17)	C20—C19—H19	118.4
C23—N4—Fe2	122.75 (13)	C19—C20—H20	119.8
N1—C1—H1	118.5	C21—C20—C19	120.33 (19)
N1—C1—C2	123.0 (2)	C21—C20—H20	119.8
C2—C1—H1	118.5	C20—C21—C22	116.37 (19)
C1—C2—H2	119.8	C20—C21—C24	122.4 (2)
C1—C2—C3	120.4 (2)	C22—C21—C24	121.3 (2)
C3—C2—H2	119.8	C21—C22—H22	119.9
C2—C3—C6	122.2 (3)	C23—C22—C21	120.3 (2)
C4—C3—C2	116.4 (2)	C23—C22—H22	119.9
C4—C3—C6	121.4 (3)	N4—C23—C22	123.49 (19)
C3—C4—H4	119.8	N4—C23—H23	118.3
C3—C4—C5	120.4 (2)	C22—C23—H23	118.3
C5—C4—H4	119.8	C21—C24—H24A	109.5
N1—C5—C4	123.2 (2)	C21—C24—H24B	109.5
N1—C5—H5	118.4	C21—C24—H24C	109.5
C4—C5—H5	118.4	H24A—C24—H24B	109.5
C3—C6—H6A	109.5	H24A—C24—H24C	109.5
C3—C6—H6B	109.5	H24B—C24—H24C	109.5

Fe1—N1—C1—C2	178.3 (2)	C7—N2—C11—C10	0.1 (3)
Fe1—N1—C5—C4	−179.33 (19)	C7—C8—C9—C10	−0.1 (4)
Fe1—N2—C7—C8	177.35 (18)	C7—C8—C9—C12	−180.0 (2)
Fe1—N2—C11—C10	−177.06 (17)	C8—C9—C10—C11	0.7 (3)
Fe2—N3—C13—C14	−173.88 (16)	C9—C10—C11—N2	−0.7 (4)
Fe2—N3—C17—C16	173.95 (18)	C11—N2—C7—C8	0.5 (3)
Fe2—N4—C19—C20	177.08 (15)	C12—C9—C10—C11	−179.5 (2)
Fe2—N4—C23—C22	−176.84 (16)	C13—N3—C17—C16	−1.1 (3)
O2—S1—O1—Fe1	178.2 (3)	C13—C14—C15—C16	−1.6 (3)
O3—S1—O1—Fe1	−64.0 (3)	C13—C14—C15—C18	178.6 (2)
O4—S1—O1—Fe1	60.4 (3)	C14—C15—C16—C17	1.7 (4)
N1—C1—C2—C3	0.9 (5)	C15—C16—C17—N3	−0.3 (4)
N2—C7—C8—C9	−0.5 (4)	C17—N3—C13—C14	1.2 (3)
N3—C13—C14—C15	0.2 (3)	C18—C15—C16—C17	−178.6 (2)
N4—C19—C20—C21	0.1 (3)	C19—N4—C23—C22	2.2 (3)
C1—N1—C5—C4	0.1 (3)	C19—C20—C21—C22	1.7 (3)
C1—C2—C3—C4	0.3 (5)	C19—C20—C21—C24	−177.8 (2)
C1—C2—C3—C6	179.7 (4)	C20—C21—C22—C23	−1.5 (3)
C2—C3—C4—C5	−1.3 (5)	C21—C22—C23—N4	−0.5 (3)
C3—C4—C5—N1	1.1 (4)	C23—N4—C19—C20	−2.0 (3)
C5—N1—C1—C2	−1.1 (4)	C24—C21—C22—C23	178.0 (2)
C6—C3—C4—C5	179.3 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O4	0.93	2.46	3.355 (3)	163
C5—H5···O3ⁱ	0.93	2.43	3.299 (3)	156
C7—H7···S1	0.93	2.88	3.620 (2)	138
C7—H7···O4	0.93	2.47	3.381 (3)	168
C11—H11···O1ⁱ	0.93	2.42	3.019 (2)	122
C13—H13···O2	0.93	2.55	3.059 (2)	115
C17—H17···O3ⁱⁱ	0.93	2.59	3.320 (3)	136
C19—H19···O2ⁱⁱ	0.93	2.56	3.114 (3)	119
C23—H23···O2	0.93	2.54	3.094 (2)	118
C23—H23···O4	0.93	2.59	3.439 (2)	152

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

catena-Poly[[tetrakis(4-methylpyridine-κN)cobalt(II)]-sulfato-κ²O:O'] (umd1358_a) top

Crystal data top

[Co(SO₄)(C₆H₇N)₄]	F(000) = 2200
M_r = 527.49	D_x = 1.380 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.3904 (10) Å	Cell parameters from 9954 reflections
b = 18.7098 (16) Å	θ = 3.1–25.7°
c = 24.145 (2) Å	µ = 0.80 mm⁻¹
β = 99.324 (3)°	T = 297 K
V = 5077.6 (8) Å³	BLOCK, pink
Z = 8	0.36 × 0.3 × 0.24 mm

Data collection top

Bruker D8 Venture CMOS diffractometer	3999 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.039
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θ_max = 25.8°, θ_min = 3.1°
T_min = 0.518, T_max = 0.562	h = −13→13
58263 measured reflections	k = −22→22
4853 independent reflections	l = −29→29

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.031	w = 1/[σ²(F_o²) + (0.0387P)² + 6.6062P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.084	(Δ/σ)_max = 0.002
S = 1.06	Δρ_max = 0.55 e Å⁻³
4853 reflections	Δρ_min = −0.29 e Å⁻³
314 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
6 restraints	Extinction coefficient: 0.00134 (11)
Primary atom site location: structure-invariant direct methods

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Co1	0.5000	0.5000	0.5000	0.02482 (11)
Co2	0.5000	0.46925 (2)	0.2500	0.02267 (11)
S1	0.65907 (4)	0.47838 (3)	0.38723 (2)	0.02747 (13)
O1	0.57321 (12)	0.48643 (8)	0.42671 (6)	0.0340 (3)
O2	0.58914 (14)	0.46684 (9)	0.33098 (6)	0.0402 (4)
O3	0.72749 (16)	0.54361 (11)	0.38679 (8)	0.0605 (5)
O4	0.73364 (15)	0.41659 (11)	0.40208 (7)	0.0539 (5)
N1	0.51127 (16)	0.61564 (10)	0.49367 (7)	0.0345 (4)
N2	0.32237 (14)	0.49777 (9)	0.44950 (7)	0.0296 (4)
N3	0.61651 (14)	0.55148 (9)	0.22427 (7)	0.0288 (4)
N4	0.38306 (14)	0.38189 (9)	0.26959 (7)	0.0294 (4)
C1	0.5965 (2)	0.64537 (13)	0.46927 (10)	0.0417 (6)
H1	0.6502	0.6156	0.4553	0.050*
C2	0.6082 (3)	0.71812 (14)	0.46383 (12)	0.0570 (7)
H2	0.6698	0.7363	0.4470	0.068*
C3	0.5299 (3)	0.76398 (15)	0.48299 (14)	0.0728 (9)
C4	0.4420 (3)	0.73299 (15)	0.50832 (14)	0.0711 (9)
H4	0.3867	0.7617	0.5220	0.085*
C5	0.4360 (2)	0.66030 (14)	0.51334 (11)	0.0487 (6)
H5	0.3769	0.6410	0.5312	0.058*
C6	0.5409 (5)	0.8442 (2)	0.4769 (2)	0.1310 (19)
H6A	0.5904	0.8545	0.4493	0.197*
H6B	0.5758	0.8644	0.5123	0.197*
H6C	0.4634	0.8645	0.4653	0.197*
C7	0.2222 (2)	0.52253 (13)	0.46490 (9)	0.0407 (6)
H7	0.2270	0.5445	0.4997	0.049*
C8	0.1127 (2)	0.51696 (15)	0.43170 (10)	0.0462 (6)
H8	0.0458	0.5353	0.4443	0.055*
C9	0.10114 (19)	0.48443 (13)	0.38004 (9)	0.0386 (5)
C10	0.20364 (19)	0.45862 (13)	0.36442 (9)	0.0398 (5)
H10	0.2005	0.4357	0.3300	0.048*
C11	0.31084 (19)	0.46640 (12)	0.39919 (9)	0.0357 (5)
H11	0.3789	0.4490	0.3871	0.043*
C12	−0.0170 (2)	0.4774 (2)	0.34265 (13)	0.0703 (9)
H12A	−0.0691	0.5147	0.3512	0.105*
H12B	−0.0512	0.4318	0.3487	0.105*
H12C	−0.0062	0.4813	0.3041	0.105*
C13	0.72826 (18)	0.56053 (13)	0.25047 (10)	0.0398 (5)
H13	0.7542	0.5340	0.2827	0.048*
C14	0.8065 (2)	0.60716 (15)	0.23192 (11)	0.0498 (6)
H14	0.8834	0.6115	0.2517	0.060*
C15	0.7721 (2)	0.64756 (14)	0.18426 (11)	0.0473 (6)
C16	0.6566 (2)	0.63943 (13)	0.15825 (10)	0.0465 (6)
H16	0.6283	0.6663	0.1265	0.056*
C17	0.5824 (2)	0.59176 (12)	0.17893 (9)	0.0367 (5)
H17	0.5046	0.5874	0.1603	0.044*
C18	0.8571 (3)	0.69786 (18)	0.16216 (16)	0.0785 (10)
H18A	0.9036	0.7227	0.1929	0.118*
H18B	0.8129	0.7318	0.1372	0.118*
H18C	0.9089	0.6711	0.1423	0.118*
C19	0.27944 (19)	0.36630 (12)	0.23693 (9)	0.0364 (5)
H19	0.2580	0.3921	0.2039	0.044*
C20	0.2033 (2)	0.31420 (13)	0.24978 (10)	0.0440 (6)
H20	0.1322	0.3058	0.2258	0.053*
C21	0.2319 (2)	0.27413 (12)	0.29823 (10)	0.0410 (5)
C22	0.3401 (2)	0.28864 (13)	0.33079 (10)	0.0427 (6)
H22	0.3647	0.2624	0.3633	0.051*
C23	0.41222 (19)	0.34187 (12)	0.31547 (9)	0.0358 (5)
H23	0.4849	0.3503	0.3383	0.043*
C24	0.1476 (3)	0.21859 (15)	0.31421 (12)	0.0604 (8)
H24A	0.1086	0.1948	0.2810	0.091*
H24B	0.0891	0.2413	0.3328	0.091*
H24C	0.1912	0.1843	0.3390	0.091*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0230 (2)	0.0323 (2)	0.01965 (19)	0.00332 (15)	0.00493 (14)	−0.00122 (15)
Co2	0.02097 (19)	0.0293 (2)	0.01818 (19)	0.000	0.00437 (14)	0.000
S1	0.0219 (2)	0.0430 (3)	0.0179 (2)	0.0022 (2)	0.00470 (18)	−0.0034 (2)
O1	0.0300 (8)	0.0511 (9)	0.0232 (7)	0.0045 (7)	0.0114 (6)	−0.0013 (6)
O2	0.0418 (9)	0.0573 (10)	0.0197 (7)	0.0091 (7)	−0.0004 (6)	−0.0053 (7)
O3	0.0550 (11)	0.0675 (13)	0.0665 (12)	−0.0288 (9)	0.0323 (10)	−0.0246 (10)
O4	0.0510 (10)	0.0762 (13)	0.0357 (9)	0.0358 (9)	0.0102 (8)	0.0066 (9)
N1	0.0375 (10)	0.0366 (10)	0.0304 (10)	0.0040 (8)	0.0082 (8)	−0.0012 (8)
N2	0.0278 (9)	0.0376 (10)	0.0236 (9)	0.0035 (7)	0.0043 (7)	−0.0017 (7)
N3	0.0265 (9)	0.0327 (9)	0.0274 (9)	−0.0010 (7)	0.0054 (7)	−0.0014 (7)
N4	0.0299 (9)	0.0325 (9)	0.0274 (9)	−0.0006 (7)	0.0097 (7)	0.0011 (7)
C1	0.0470 (14)	0.0417 (14)	0.0390 (13)	−0.0039 (11)	0.0151 (11)	−0.0060 (10)
C2	0.0749 (19)	0.0454 (16)	0.0568 (17)	−0.0128 (14)	0.0294 (14)	−0.0019 (13)
C3	0.108 (3)	0.0367 (15)	0.083 (2)	−0.0006 (16)	0.043 (2)	−0.0013 (15)
C4	0.095 (2)	0.0425 (16)	0.087 (2)	0.0183 (16)	0.0480 (19)	0.0014 (15)
C5	0.0561 (15)	0.0430 (14)	0.0526 (15)	0.0107 (12)	0.0254 (13)	0.0039 (12)
C6	0.189 (5)	0.047 (2)	0.178 (5)	0.003 (3)	0.094 (4)	0.010 (2)
C7	0.0359 (12)	0.0581 (15)	0.0277 (11)	0.0127 (11)	0.0037 (9)	−0.0084 (10)
C8	0.0308 (12)	0.0720 (18)	0.0363 (13)	0.0163 (11)	0.0072 (10)	−0.0037 (12)
C9	0.0286 (11)	0.0539 (15)	0.0327 (12)	0.0011 (10)	0.0031 (9)	0.0033 (10)
C10	0.0333 (12)	0.0569 (15)	0.0290 (11)	−0.0043 (10)	0.0042 (9)	−0.0114 (10)
C11	0.0264 (11)	0.0491 (14)	0.0319 (12)	0.0022 (9)	0.0058 (9)	−0.0104 (10)
C12	0.0318 (14)	0.126 (3)	0.0502 (17)	−0.0003 (15)	−0.0022 (12)	−0.0057 (17)
C13	0.0277 (11)	0.0537 (15)	0.0377 (12)	−0.0029 (10)	0.0044 (9)	0.0065 (11)
C14	0.0298 (12)	0.0625 (17)	0.0574 (16)	−0.0097 (11)	0.0082 (11)	0.0049 (13)
C15	0.0483 (15)	0.0452 (14)	0.0537 (15)	−0.0120 (11)	0.0245 (12)	−0.0028 (12)
C16	0.0638 (16)	0.0392 (14)	0.0372 (13)	−0.0069 (12)	0.0101 (12)	0.0081 (11)
C17	0.0389 (12)	0.0351 (12)	0.0346 (12)	−0.0032 (10)	0.0013 (10)	0.0010 (10)
C18	0.077 (2)	0.073 (2)	0.095 (3)	−0.0234 (18)	0.0439 (19)	0.0115 (19)
C19	0.0365 (12)	0.0437 (13)	0.0290 (11)	−0.0068 (10)	0.0049 (9)	0.0040 (9)
C20	0.0419 (13)	0.0519 (15)	0.0383 (13)	−0.0137 (11)	0.0069 (10)	−0.0015 (11)
C21	0.0500 (14)	0.0356 (13)	0.0413 (13)	−0.0071 (10)	0.0186 (11)	−0.0031 (10)
C22	0.0527 (15)	0.0371 (13)	0.0407 (13)	0.0027 (11)	0.0151 (11)	0.0107 (10)
C23	0.0361 (12)	0.0379 (12)	0.0340 (12)	0.0034 (10)	0.0073 (9)	0.0043 (10)
C24	0.0732 (19)	0.0528 (17)	0.0601 (17)	−0.0211 (14)	0.0253 (15)	0.0035 (14)

Geometric parameters (Å, º) top

Co1—O1ⁱ	2.0903 (13)	C7—H7	0.9300
Co1—O1	2.0903 (13)	C7—C8	1.373 (3)
Co1—N1	2.1743 (19)	C8—H8	0.9300
Co1—N1ⁱ	2.1743 (19)	C8—C9	1.375 (3)
Co1—N2	2.1869 (17)	C9—C10	1.372 (3)
Co1—N2ⁱ	2.1869 (17)	C9—C12	1.500 (3)
Co2—O2ⁱⁱ	2.0525 (14)	C10—H10	0.9300
Co2—O2	2.0525 (14)	C10—C11	1.373 (3)
Co2—N3	2.1866 (17)	C11—H11	0.9300
Co2—N3ⁱⁱ	2.1866 (17)	C12—H12A	0.9600
Co2—N4	2.2077 (17)	C12—H12B	0.9600
Co2—N4ⁱⁱ	2.2078 (17)	C12—H12C	0.9600
S1—O1	1.4799 (14)	C13—H13	0.9300
S1—O2	1.4748 (15)	C13—C14	1.373 (3)
S1—O3	1.4490 (18)	C14—H14	0.9300
S1—O4	1.4449 (17)	C14—C15	1.380 (4)
N1—C1	1.335 (3)	C15—C16	1.371 (4)
N1—C5	1.338 (3)	C15—C18	1.508 (3)
N2—C7	1.339 (3)	C16—H16	0.9300
N2—C11	1.336 (3)	C16—C17	1.377 (3)
N3—C13	1.337 (3)	C17—H17	0.9300
N3—C17	1.334 (3)	C18—H18A	0.9600
N4—C19	1.341 (3)	C18—H18B	0.9600
N4—C23	1.334 (3)	C18—H18C	0.9600
C1—H1	0.9300	C19—H19	0.9300
C1—C2	1.376 (4)	C19—C20	1.373 (3)
C2—H2	0.9300	C20—H20	0.9300
C2—C3	1.371 (4)	C20—C21	1.383 (3)
C3—C4	1.382 (4)	C21—C22	1.377 (3)
C3—C6	1.515 (5)	C21—C24	1.507 (3)
C4—H4	0.9300	C22—H22	0.9300
C4—C5	1.368 (4)	C22—C23	1.379 (3)
C5—H5	0.9300	C23—H23	0.9300
C6—H6A	0.9600	C24—H24A	0.9600
C6—H6B	0.9600	C24—H24B	0.9600
C6—H6C	0.9600	C24—H24C	0.9600

O1ⁱ—Co1—O1	180.00 (3)	C3—C6—H6C	109.5
O1ⁱ—Co1—N1	88.56 (6)	H6A—C6—H6B	109.5
O1ⁱ—Co1—N1ⁱ	91.44 (6)	H6A—C6—H6C	109.5
O1—Co1—N1	91.44 (6)	H6B—C6—H6C	109.5
O1—Co1—N1ⁱ	88.56 (6)	N2—C7—H7	118.4
O1ⁱ—Co1—N2ⁱ	89.18 (6)	N2—C7—C8	123.1 (2)
O1—Co1—N2	89.18 (6)	C8—C7—H7	118.4
O1ⁱ—Co1—N2	90.82 (6)	C7—C8—H8	119.8
O1—Co1—N2ⁱ	90.82 (6)	C7—C8—C9	120.5 (2)
N1ⁱ—Co1—N1	180.0	C9—C8—H8	119.8
N1ⁱ—Co1—N2	87.73 (7)	C8—C9—C12	122.0 (2)
N1—Co1—N2ⁱ	87.73 (7)	C10—C9—C8	116.4 (2)
N1—Co1—N2	92.27 (7)	C10—C9—C12	121.6 (2)
N1ⁱ—Co1—N2ⁱ	92.27 (7)	C9—C10—H10	119.8
N2ⁱ—Co1—N2	180.0	C9—C10—C11	120.5 (2)
O2ⁱⁱ—Co2—O2	177.48 (10)	C11—C10—H10	119.8
O2ⁱⁱ—Co2—N3ⁱⁱ	93.26 (6)	N2—C11—C10	123.3 (2)
O2ⁱⁱ—Co2—N3	88.52 (6)	N2—C11—H11	118.3
O2—Co2—N3ⁱⁱ	88.52 (6)	C10—C11—H11	118.3
O2—Co2—N3	93.26 (6)	C9—C12—H12A	109.5
O2—Co2—N4	90.12 (7)	C9—C12—H12B	109.5
O2—Co2—N4ⁱⁱ	88.01 (6)	C9—C12—H12C	109.5
O2ⁱⁱ—Co2—N4ⁱⁱ	90.12 (7)	H12A—C12—H12B	109.5
O2ⁱⁱ—Co2—N4	88.01 (6)	H12A—C12—H12C	109.5
N3ⁱⁱ—Co2—N3	90.57 (9)	H12B—C12—H12C	109.5
N3ⁱⁱ—Co2—N4	92.58 (6)	N3—C13—H13	118.5
N3ⁱⁱ—Co2—N4ⁱⁱ	175.44 (6)	N3—C13—C14	123.0 (2)
N3—Co2—N4ⁱⁱ	92.58 (6)	C14—C13—H13	118.5
N3—Co2—N4	175.43 (6)	C13—C14—H14	119.7
N4—Co2—N4ⁱⁱ	84.47 (9)	C13—C14—C15	120.5 (2)
O2—S1—O1	107.06 (9)	C15—C14—H14	119.7
O3—S1—O1	109.36 (10)	C14—C15—C18	121.7 (3)
O3—S1—O2	109.11 (11)	C16—C15—C14	116.3 (2)
O4—S1—O1	110.17 (9)	C16—C15—C18	122.0 (3)
O4—S1—O2	108.63 (10)	C15—C16—H16	119.8
O4—S1—O3	112.36 (12)	C15—C16—C17	120.4 (2)
S1—O1—Co1	162.48 (10)	C17—C16—H16	119.8
S1—O2—Co2	169.75 (12)	N3—C17—C16	123.3 (2)
C1—N1—Co1	120.06 (15)	N3—C17—H17	118.3
C1—N1—C5	116.7 (2)	C16—C17—H17	118.3
C5—N1—Co1	123.22 (16)	C15—C18—H18A	109.5
C7—N2—Co1	126.28 (14)	C15—C18—H18B	109.5
C11—N2—Co1	117.45 (13)	C15—C18—H18C	109.5
C11—N2—C7	116.22 (18)	H18A—C18—H18B	109.5
C13—N3—Co2	121.99 (15)	H18A—C18—H18C	109.5
C17—N3—Co2	121.42 (14)	H18B—C18—H18C	109.5
C17—N3—C13	116.42 (19)	N4—C19—H19	118.3
C19—N4—Co2	122.63 (14)	N4—C19—C20	123.3 (2)
C23—N4—Co2	121.05 (14)	C20—C19—H19	118.3
C23—N4—C19	116.32 (18)	C19—C20—H20	119.8
N1—C1—H1	118.6	C19—C20—C21	120.3 (2)
N1—C1—C2	122.9 (2)	C21—C20—H20	119.8
C2—C1—H1	118.6	C20—C21—C24	121.2 (2)
C1—C2—H2	119.7	C22—C21—C20	116.3 (2)
C3—C2—C1	120.5 (3)	C22—C21—C24	122.6 (2)
C3—C2—H2	119.7	C21—C22—H22	119.8
C2—C3—C4	116.4 (3)	C21—C22—C23	120.4 (2)
C2—C3—C6	121.2 (3)	C23—C22—H22	119.8
C4—C3—C6	122.4 (3)	N4—C23—C22	123.3 (2)
C3—C4—H4	119.8	N4—C23—H23	118.3
C5—C4—C3	120.4 (3)	C22—C23—H23	118.3
C5—C4—H4	119.8	C21—C24—H24A	109.5
N1—C5—C4	123.0 (2)	C21—C24—H24B	109.5
N1—C5—H5	118.5	C21—C24—H24C	109.5
C4—C5—H5	118.5	H24A—C24—H24B	109.5
C3—C6—H6A	109.5	H24A—C24—H24C	109.5
C3—C6—H6B	109.5	H24B—C24—H24C	109.5

Co1—N1—C1—C2	179.9 (2)	C5—N1—C1—C2	−0.2 (4)
Co1—N1—C5—C4	−178.7 (2)	C6—C3—C4—C5	−179.4 (4)
Co1—N2—C7—C8	−177.52 (19)	C7—N2—C11—C10	−0.5 (3)
Co1—N2—C11—C10	177.07 (19)	C7—C8—C9—C10	0.0 (4)
Co2—N3—C13—C14	173.74 (19)	C7—C8—C9—C12	−180.0 (3)
Co2—N3—C17—C16	−173.79 (18)	C8—C9—C10—C11	−0.7 (4)
Co2—N4—C19—C20	−177.09 (18)	C9—C10—C11—N2	1.0 (4)
Co2—N4—C23—C22	177.27 (17)	C11—N2—C7—C8	−0.2 (4)
O1—S1—O2—Co2	105.8 (6)	C12—C9—C10—C11	179.3 (3)
O2—S1—O1—Co1	177.7 (3)	C13—N3—C17—C16	1.5 (3)
O3—S1—O1—Co1	−64.3 (4)	C13—C14—C15—C16	1.5 (4)
O3—S1—O2—Co2	−12.5 (6)	C13—C14—C15—C18	−178.5 (3)
O4—S1—O1—Co1	59.7 (4)	C14—C15—C16—C17	−1.5 (4)
O4—S1—O2—Co2	−135.3 (6)	C15—C16—C17—N3	0.0 (4)
N1—C1—C2—C3	−1.0 (4)	C17—N3—C13—C14	−1.5 (3)
N2—C7—C8—C9	0.4 (4)	C18—C15—C16—C17	178.5 (3)
N3—C13—C14—C15	0.0 (4)	C19—N4—C23—C22	−2.2 (3)
N4—C19—C20—C21	−0.5 (4)	C19—C20—C21—C22	−1.5 (3)
C1—N1—C5—C4	1.4 (4)	C19—C20—C21—C24	177.7 (2)
C1—C2—C3—C4	1.1 (5)	C20—C21—C22—C23	1.7 (3)
C1—C2—C3—C6	−179.5 (4)	C21—C22—C23—N4	0.2 (4)
C2—C3—C4—C5	0.0 (5)	C23—N4—C19—C20	2.4 (3)
C3—C4—C5—N1	−1.3 (5)	C24—C21—C22—C23	−177.5 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O3	0.93	2.41	3.284 (3)	157
C5—H5···O4ⁱ	0.93	2.45	3.355 (3)	165
C7—H7···S1ⁱ	0.93	2.86	3.607 (2)	138
C7—H7···O4ⁱ	0.93	2.45	3.368 (3)	169
C11—H11···O1	0.93	2.37	2.978 (3)	123
C13—H13···O3	0.93	2.59	3.308 (3)	135
C17—H17···S1ⁱⁱ	0.93	2.87	3.632 (2)	140
C17—H17···O2ⁱⁱ	0.93	2.52	3.031 (3)	115
C19—H19···O2ⁱⁱ	0.93	2.48	3.044 (3)	119
C23—H23···O2	0.93	2.50	3.070 (3)	120

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

catena-Poly[[tetrakis(4-methylpyridine-κN)nickel(II)]-sulfato-κ²O:O'] (umd1307) top

Crystal data top

[Ni(SO₄)(C₆H₇N)₄]	F(000) = 2208
M_r = 527.27	D_x = 1.394 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.3610 (17) Å	Cell parameters from 9925 reflections
b = 18.546 (3) Å	θ = 3.1–25.7°
c = 24.178 (4) Å	µ = 0.89 mm⁻¹
β = 99.459 (5)°	T = 297 K
V = 5025.1 (13) Å³	PRISM, green
Z = 8	0.25 × 0.19 × 0.12 mm

Data collection top

Bruker D8 Venture CMOS diffractometer	4037 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.044
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θ_max = 25.7°, θ_min = 2.9°
T_min = 0.289, T_max = 0.332	h = −13→13
62062 measured reflections	k = −22→22
4798 independent reflections	l = −29→29

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.029	w = 1/[σ²(F_o²) + (0.0338P)² + 6.8591P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.077	(Δ/σ)_max = 0.001
S = 1.05	Δρ_max = 0.53 e Å⁻³
4798 reflections	Δρ_min = −0.29 e Å⁻³
314 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00116 (10)
Primary atom site location: structure-invariant direct methods

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Ni1	0.5000	0.5000	0.5000	0.02536 (11)
Ni2	0.5000	0.46852 (2)	0.7500	0.02357 (10)
S1	0.34019 (4)	0.47765 (3)	0.61271 (2)	0.02773 (13)
O1	0.42614 (12)	0.48641 (8)	0.57336 (6)	0.0335 (3)
O2	0.40988 (14)	0.46594 (9)	0.66890 (6)	0.0414 (4)
O3	0.27061 (16)	0.54326 (10)	0.61312 (8)	0.0602 (5)
O4	0.26541 (15)	0.41507 (10)	0.59764 (6)	0.0519 (5)
N1	0.48860 (15)	0.61365 (9)	0.50649 (7)	0.0334 (4)
N2	0.67325 (14)	0.49832 (9)	0.54977 (7)	0.0299 (4)
N3	0.38519 (14)	0.38311 (9)	0.76961 (7)	0.0300 (4)
N4	0.61420 (14)	0.54921 (9)	0.72508 (7)	0.0288 (4)
C1	0.5636 (2)	0.65898 (13)	0.48683 (10)	0.0480 (6)
H1	0.6231	0.6398	0.4690	0.058*
C2	0.5565 (3)	0.73261 (15)	0.49175 (13)	0.0664 (8)
H2	0.6113	0.7619	0.4778	0.080*
C3	0.4685 (3)	0.76356 (14)	0.51732 (13)	0.0640 (8)
C4	0.3904 (2)	0.71672 (14)	0.53641 (11)	0.0528 (6)
H4	0.3285	0.7348	0.5531	0.063*
C5	0.4031 (2)	0.64333 (12)	0.53101 (9)	0.0401 (5)
H5	0.3497	0.6131	0.5450	0.048*
C6	0.4574 (4)	0.84444 (18)	0.5235 (2)	0.1170 (17)
H6A	0.4079	0.8547	0.5511	0.176*
H6B	0.4222	0.8649	0.4882	0.176*
H6C	0.5351	0.8649	0.5351	0.176*
C7	0.7735 (2)	0.52382 (14)	0.53425 (9)	0.0426 (6)
H7	0.7683	0.5460	0.4994	0.051*
C8	0.8838 (2)	0.51860 (15)	0.56761 (10)	0.0482 (6)
H8	0.9503	0.5379	0.5552	0.058*
C9	0.89660 (19)	0.48533 (13)	0.61890 (9)	0.0406 (5)
C10	0.79391 (19)	0.45863 (13)	0.63449 (9)	0.0403 (5)
H10	0.7975	0.4353	0.6688	0.048*
C11	0.68613 (18)	0.46613 (12)	0.59981 (9)	0.0351 (5)
H11	0.6184	0.4478	0.6118	0.042*
C12	1.0162 (2)	0.4780 (2)	0.65665 (13)	0.0706 (9)
H12A	1.0691	0.5150	0.6478	0.106*
H12B	1.0497	0.4316	0.6511	0.106*
H12C	1.0057	0.4827	0.6951	0.106*
C13	0.41554 (19)	0.34230 (12)	0.81550 (9)	0.0369 (5)
H13	0.4887	0.3506	0.8382	0.044*
C14	0.3429 (2)	0.28850 (12)	0.83055 (10)	0.0436 (5)
H14	0.3679	0.2617	0.8628	0.052*
C15	0.2339 (2)	0.27407 (12)	0.79831 (10)	0.0425 (5)
C16	0.2046 (2)	0.31492 (13)	0.75013 (10)	0.0445 (6)
H16	0.1329	0.3067	0.7263	0.053*
C17	0.28103 (19)	0.36763 (12)	0.73722 (9)	0.0372 (5)
H17	0.2592	0.3938	0.7043	0.045*
C18	0.1496 (3)	0.21803 (15)	0.81438 (12)	0.0628 (8)
H18A	0.1937	0.1832	0.8389	0.094*
H18B	0.1098	0.1943	0.7812	0.094*
H18C	0.0915	0.2409	0.8332	0.094*
C19	0.57846 (19)	0.59043 (12)	0.68007 (9)	0.0365 (5)
H19	0.5000	0.5864	0.6619	0.044*
C20	0.6525 (2)	0.63862 (13)	0.65933 (10)	0.0450 (6)
H20	0.6233	0.6661	0.6279	0.054*
C21	0.7689 (2)	0.64654 (13)	0.68459 (10)	0.0460 (6)
C22	0.8049 (2)	0.60531 (14)	0.73190 (11)	0.0496 (6)
H22	0.8825	0.6095	0.7512	0.060*
C23	0.72652 (18)	0.55802 (13)	0.75068 (9)	0.0393 (5)
H23	0.7532	0.5310	0.7827	0.047*
C24	0.8539 (3)	0.69725 (18)	0.66225 (15)	0.0769 (9)
H24A	0.8092	0.7329	0.6388	0.115*
H24B	0.9029	0.6705	0.6408	0.115*
H24C	0.9035	0.7207	0.6930	0.115*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.02605 (19)	0.0310 (2)	0.01982 (17)	−0.00419 (14)	0.00613 (13)	0.00076 (14)
Ni2	0.02264 (18)	0.0295 (2)	0.01939 (17)	0.000	0.00592 (13)	0.000
S1	0.0242 (2)	0.0410 (3)	0.0189 (2)	−0.0030 (2)	0.00638 (18)	0.00281 (19)
O1	0.0305 (7)	0.0491 (9)	0.0233 (7)	−0.0041 (6)	0.0120 (6)	0.0016 (6)
O2	0.0447 (9)	0.0575 (10)	0.0203 (7)	−0.0109 (7)	0.0003 (6)	0.0057 (6)
O3	0.0561 (11)	0.0625 (12)	0.0703 (12)	0.0262 (9)	0.0347 (9)	0.0239 (10)
O4	0.0513 (10)	0.0692 (12)	0.0363 (9)	−0.0343 (9)	0.0103 (7)	−0.0053 (8)
N1	0.0380 (10)	0.0358 (10)	0.0274 (9)	−0.0045 (8)	0.0080 (7)	0.0007 (7)
N2	0.0303 (9)	0.0363 (9)	0.0237 (8)	−0.0044 (7)	0.0063 (7)	0.0000 (7)
N3	0.0312 (9)	0.0333 (9)	0.0275 (8)	0.0010 (7)	0.0109 (7)	0.0012 (7)
N4	0.0274 (8)	0.0322 (9)	0.0274 (8)	−0.0005 (7)	0.0066 (7)	−0.0019 (7)
C1	0.0565 (15)	0.0409 (13)	0.0527 (14)	−0.0096 (11)	0.0272 (12)	−0.0030 (11)
C2	0.088 (2)	0.0405 (14)	0.081 (2)	−0.0174 (14)	0.0443 (17)	−0.0010 (14)
C3	0.095 (2)	0.0347 (14)	0.0683 (18)	−0.0012 (14)	0.0320 (17)	−0.0005 (13)
C4	0.0682 (17)	0.0431 (14)	0.0522 (15)	0.0121 (12)	0.0248 (13)	0.0024 (11)
C5	0.0431 (12)	0.0412 (13)	0.0378 (12)	0.0015 (10)	0.0126 (10)	0.0053 (10)
C6	0.168 (4)	0.0375 (17)	0.166 (4)	−0.002 (2)	0.087 (4)	−0.008 (2)
C7	0.0413 (13)	0.0602 (15)	0.0267 (11)	−0.0148 (11)	0.0064 (9)	0.0049 (10)
C8	0.0338 (12)	0.0726 (17)	0.0394 (13)	−0.0201 (12)	0.0098 (10)	0.0004 (12)
C9	0.0299 (11)	0.0570 (15)	0.0347 (12)	−0.0019 (10)	0.0048 (9)	−0.0059 (10)
C10	0.0333 (11)	0.0581 (15)	0.0299 (11)	0.0037 (10)	0.0060 (9)	0.0090 (10)
C11	0.0275 (10)	0.0476 (13)	0.0308 (11)	−0.0019 (9)	0.0068 (8)	0.0084 (9)
C12	0.0308 (13)	0.121 (3)	0.0581 (18)	−0.0025 (15)	0.0028 (12)	−0.0044 (17)
C13	0.0388 (12)	0.0383 (12)	0.0350 (11)	0.0057 (9)	0.0100 (9)	0.0056 (9)
C14	0.0571 (15)	0.0367 (12)	0.0403 (13)	0.0051 (11)	0.0180 (11)	0.0110 (10)
C15	0.0560 (14)	0.0352 (12)	0.0413 (13)	−0.0092 (10)	0.0225 (11)	−0.0050 (10)
C16	0.0444 (13)	0.0507 (14)	0.0393 (12)	−0.0146 (11)	0.0096 (10)	−0.0013 (11)
C17	0.0389 (12)	0.0432 (13)	0.0301 (11)	−0.0060 (10)	0.0073 (9)	0.0038 (9)
C18	0.081 (2)	0.0537 (16)	0.0601 (17)	−0.0204 (15)	0.0295 (15)	0.0030 (13)
C19	0.0380 (12)	0.0347 (12)	0.0353 (11)	−0.0024 (9)	0.0017 (9)	0.0008 (9)
C20	0.0606 (15)	0.0385 (13)	0.0368 (12)	−0.0052 (11)	0.0106 (11)	0.0053 (10)
C21	0.0497 (14)	0.0419 (13)	0.0522 (14)	−0.0115 (11)	0.0254 (12)	−0.0024 (11)
C22	0.0311 (12)	0.0606 (16)	0.0582 (15)	−0.0091 (11)	0.0102 (11)	0.0040 (13)
C23	0.0296 (11)	0.0516 (14)	0.0368 (11)	−0.0036 (10)	0.0058 (9)	0.0065 (10)
C24	0.078 (2)	0.072 (2)	0.090 (2)	−0.0243 (17)	0.0430 (19)	0.0097 (17)

Geometric parameters (Å, º) top

Ni1—O1ⁱ	2.0984 (13)	C7—H7	0.9300
Ni1—O1	2.0984 (13)	C7—C8	1.377 (3)
Ni1—N1	2.1191 (18)	C8—H8	0.9300
Ni1—N1ⁱ	2.1190 (18)	C8—C9	1.371 (3)
Ni1—N2	2.1318 (16)	C9—C10	1.376 (3)
Ni1—N2ⁱ	2.1318 (16)	C9—C12	1.513 (3)
Ni2—O2ⁱⁱ	2.0581 (14)	C10—H10	0.9300
Ni2—O2	2.0581 (14)	C10—C11	1.373 (3)
Ni2—N3	2.1537 (17)	C11—H11	0.9300
Ni2—N3ⁱⁱ	2.1537 (17)	C12—H12A	0.9600
Ni2—N4ⁱⁱ	2.1313 (16)	C12—H12B	0.9600
Ni2—N4	2.1313 (17)	C12—H12C	0.9600
S1—O1	1.4800 (13)	C13—H13	0.9300
S1—O2	1.4719 (15)	C13—C14	1.381 (3)
S1—O3	1.4520 (18)	C14—H14	0.9300
S1—O4	1.4491 (16)	C14—C15	1.377 (3)
N1—C1	1.338 (3)	C15—C16	1.384 (3)
N1—C5	1.337 (3)	C15—C18	1.507 (3)
N2—C7	1.342 (3)	C16—H16	0.9300
N2—C11	1.335 (3)	C16—C17	1.377 (3)
N3—C13	1.341 (3)	C17—H17	0.9300
N3—C17	1.338 (3)	C18—H18A	0.9600
N4—C19	1.337 (3)	C18—H18B	0.9600
N4—C23	1.334 (3)	C18—H18C	0.9600
C1—H1	0.9300	C19—H19	0.9300
C1—C2	1.374 (4)	C19—C20	1.377 (3)
C2—H2	0.9300	C20—H20	0.9300
C2—C3	1.384 (4)	C20—C21	1.370 (3)
C3—C4	1.374 (4)	C21—C22	1.381 (4)
C3—C6	1.515 (4)	C21—C24	1.510 (3)
C4—H4	0.9300	C22—H22	0.9300
C4—C5	1.377 (3)	C22—C23	1.379 (3)
C5—H5	0.9300	C23—H23	0.9300
C6—H6A	0.9600	C24—H24A	0.9600
C6—H6B	0.9600	C24—H24B	0.9600
C6—H6C	0.9600	C24—H24C	0.9600

O1ⁱ—Ni1—O1	180.0	C3—C6—H6C	109.5
O1—Ni1—N1	91.10 (6)	H6A—C6—H6B	109.5
O1ⁱ—Ni1—N1	88.90 (6)	H6A—C6—H6C	109.5
O1—Ni1—N1ⁱ	88.90 (6)	H6B—C6—H6C	109.5
O1ⁱ—Ni1—N1ⁱ	91.10 (6)	N2—C7—H7	118.5
O1ⁱ—Ni1—N2ⁱ	88.94 (6)	N2—C7—C8	122.9 (2)
O1ⁱ—Ni1—N2	91.06 (6)	C8—C7—H7	118.5
O1—Ni1—N2ⁱ	91.06 (6)	C7—C8—H8	119.6
O1—Ni1—N2	88.94 (6)	C9—C8—C7	120.8 (2)
N1ⁱ—Ni1—N1	180.00 (9)	C9—C8—H8	119.6
N1—Ni1—N2	91.99 (7)	C8—C9—C10	116.2 (2)
N1ⁱ—Ni1—N2ⁱ	91.99 (7)	C8—C9—C12	122.5 (2)
N1ⁱ—Ni1—N2	88.01 (7)	C10—C9—C12	121.3 (2)
N1—Ni1—N2ⁱ	88.01 (7)	C9—C10—H10	119.7
N2ⁱ—Ni1—N2	180.0	C11—C10—C9	120.5 (2)
O2ⁱⁱ—Ni2—O2	177.34 (9)	C11—C10—H10	119.7
O2ⁱⁱ—Ni2—N3ⁱⁱ	88.18 (6)	N2—C11—C10	123.55 (19)
O2ⁱⁱ—Ni2—N3	89.86 (7)	N2—C11—H11	118.2
O2—Ni2—N3	88.18 (6)	C10—C11—H11	118.2
O2—Ni2—N3ⁱⁱ	89.86 (7)	C9—C12—H12A	109.5
O2ⁱⁱ—Ni2—N4ⁱⁱ	88.72 (6)	C9—C12—H12B	109.5
O2—Ni2—N4	88.72 (6)	C9—C12—H12C	109.5
O2ⁱⁱ—Ni2—N4	93.16 (6)	H12A—C12—H12B	109.5
O2—Ni2—N4ⁱⁱ	93.15 (6)	H12A—C12—H12C	109.5
N3ⁱⁱ—Ni2—N3	85.30 (9)	H12B—C12—H12C	109.5
N4—Ni2—N3ⁱⁱ	92.02 (6)	N3—C13—H13	118.6
N4ⁱⁱ—Ni2—N3ⁱⁱ	175.91 (6)	N3—C13—C14	122.8 (2)
N4—Ni2—N3	175.91 (6)	C14—C13—H13	118.6
N4ⁱⁱ—Ni2—N3	92.02 (6)	C13—C14—H14	119.6
N4ⁱⁱ—Ni2—N4	90.81 (9)	C15—C14—C13	120.8 (2)
O2—S1—O1	107.33 (9)	C15—C14—H14	119.6
O3—S1—O1	109.26 (9)	C14—C15—C16	116.1 (2)
O3—S1—O2	109.15 (11)	C14—C15—C18	122.6 (2)
O4—S1—O1	110.35 (9)	C16—C15—C18	121.3 (2)
O4—S1—O2	108.55 (10)	C15—C16—H16	119.8
O4—S1—O3	112.06 (12)	C17—C16—C15	120.4 (2)
S1—O1—Ni1	162.62 (9)	C17—C16—H16	119.8
S1—O2—Ni2	169.73 (12)	N3—C17—C16	123.3 (2)
C1—N1—Ni1	123.25 (15)	N3—C17—H17	118.3
C5—N1—Ni1	119.99 (14)	C16—C17—H17	118.3
C5—N1—C1	116.8 (2)	C15—C18—H18A	109.5
C7—N2—Ni1	125.74 (14)	C15—C18—H18B	109.5
C11—N2—Ni1	118.13 (13)	C15—C18—H18C	109.5
C11—N2—C7	116.04 (18)	H18A—C18—H18B	109.5
C13—N3—Ni2	120.98 (14)	H18A—C18—H18C	109.5
C17—N3—Ni2	122.56 (14)	H18B—C18—H18C	109.5
C17—N3—C13	116.46 (18)	N4—C19—H19	118.5
C19—N4—Ni2	120.92 (14)	N4—C19—C20	123.0 (2)
C23—N4—Ni2	122.36 (14)	C20—C19—H19	118.5
C23—N4—C19	116.56 (18)	C19—C20—H20	119.7
N1—C1—H1	118.5	C21—C20—C19	120.7 (2)
N1—C1—C2	123.0 (2)	C21—C20—H20	119.7
C2—C1—H1	118.5	C20—C21—C22	116.2 (2)
C1—C2—H2	119.8	C20—C21—C24	122.3 (2)
C1—C2—C3	120.5 (2)	C22—C21—C24	121.5 (2)
C3—C2—H2	119.8	C21—C22—H22	119.8
C2—C3—C6	122.2 (3)	C23—C22—C21	120.4 (2)
C4—C3—C2	116.2 (2)	C23—C22—H22	119.8
C4—C3—C6	121.6 (3)	N4—C23—C22	123.1 (2)
C3—C4—H4	119.7	N4—C23—H23	118.5
C3—C4—C5	120.7 (2)	C22—C23—H23	118.5
C5—C4—H4	119.7	C21—C24—H24A	109.5
N1—C5—C4	122.9 (2)	C21—C24—H24B	109.5
N1—C5—H5	118.5	C21—C24—H24C	109.5
C4—C5—H5	118.5	H24A—C24—H24B	109.5
C3—C6—H6A	109.5	H24A—C24—H24C	109.5
C3—C6—H6B	109.5	H24B—C24—H24C	109.5

Ni1—N1—C1—C2	−179.2 (2)	C5—N1—C1—C2	1.0 (4)
Ni1—N1—C5—C4	−179.76 (19)	C6—C3—C4—C5	−179.2 (3)
Ni1—N2—C7—C8	−177.41 (19)	C7—N2—C11—C10	0.1 (3)
Ni1—N2—C11—C10	176.88 (18)	C7—C8—C9—C10	−0.4 (4)
Ni2—N3—C13—C14	177.94 (16)	C7—C8—C9—C12	179.6 (3)
Ni2—N3—C17—C16	−177.65 (17)	C8—C9—C10—C11	−0.3 (4)
Ni2—N4—C19—C20	−173.89 (17)	C9—C10—C11—N2	0.5 (4)
Ni2—N4—C23—C22	173.78 (19)	C11—N2—C7—C8	−0.9 (3)
O1—S1—O2—Ni2	103.4 (6)	C12—C9—C10—C11	179.7 (2)
O2—S1—O1—Ni1	176.0 (3)	C13—N3—C17—C16	2.5 (3)
O3—S1—O1—Ni1	−65.7 (4)	C13—C14—C15—C16	1.7 (3)
O3—S1—O2—Ni2	−15.0 (6)	C13—C14—C15—C18	−177.4 (2)
O4—S1—O1—Ni1	57.9 (4)	C14—C15—C16—C17	−1.5 (3)
O4—S1—O2—Ni2	−137.4 (5)	C15—C16—C17—N3	−0.7 (4)
N1—C1—C2—C3	−0.8 (5)	C17—N3—C13—C14	−2.2 (3)
N2—C7—C8—C9	1.1 (4)	C18—C15—C16—C17	177.7 (2)
N3—C13—C14—C15	0.1 (3)	C19—N4—C23—C22	−1.7 (3)
N4—C19—C20—C21	0.0 (4)	C19—C20—C21—C22	−1.6 (4)
C1—N1—C5—C4	0.0 (3)	C19—C20—C21—C24	178.3 (2)
C1—C2—C3—C4	−0.5 (5)	C20—C21—C22—C23	1.6 (4)
C1—C2—C3—C6	−179.9 (3)	C21—C22—C23—N4	0.1 (4)
C2—C3—C4—C5	1.5 (4)	C23—N4—C19—C20	1.7 (3)
C3—C4—C5—N1	−1.3 (4)	C24—C21—C22—C23	−178.4 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O1ⁱ	0.93	2.58	3.075 (3)	114
C1—H1···O4ⁱ	0.93	2.43	3.337 (3)	165
C5—H5···O1	0.93	2.56	3.082 (3)	116
C5—H5···O3	0.93	2.38	3.261 (3)	157
C7—H7···S1ⁱ	0.93	2.82	3.576 (2)	139
C7—H7···O4ⁱ	0.93	2.43	3.345 (3)	170
C11—H11···O1	0.93	2.34	2.942 (2)	122
C13—H13···O2ⁱⁱ	0.93	2.45	3.015 (3)	119
C17—H17···O2	0.93	2.44	2.999 (3)	119
C19—H19···S1	0.93	2.84	3.593 (2)	139
C19—H19···O2	0.93	2.47	2.984 (3)	115
C23—H23···O3ⁱⁱ	0.93	2.59	3.299 (3)	134

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

Di-µ-sulfato-κ⁴O:O-bis[tris(4-methylpyridine-κN)copper(II)] (umd1301_a) top

Crystal data top

[Cu₂(SO₄)₂(C₆H₇N)₆]	F(000) = 908
M_r = 877.95	D_x = 1.546 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.1304 (8) Å	Cell parameters from 9831 reflections
b = 21.2148 (19) Å	θ = 2.9–25.7°
c = 9.9359 (8) Å	µ = 1.30 mm⁻¹
β = 101.544 (3)°	T = 200 K
V = 1885.6 (3) Å³	BLOCK, blue
Z = 2	0.28 × 0.14 × 0.11 mm

Data collection top

Bruker D8 Venture CMOS diffractometer	3110 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.053
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θ_max = 25.7°, θ_min = 3.4°
T_min = 0.380, T_max = 0.429	h = −11→11
59469 measured reflections	k = −25→25
3580 independent reflections	l = −12→12

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.027	w = 1/[σ²(F_o²) + (0.0237P)² + 2.015P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.065	(Δ/σ)_max = 0.003
S = 1.06	Δρ_max = 0.27 e Å⁻³
3580 reflections	Δρ_min = −0.31 e Å⁻³
248 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0044 (5)
Primary atom site location: structure-invariant direct methods

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cu1	0.34858 (3)	0.54221 (2)	0.48079 (2)	0.01881 (10)
S1	0.30849 (6)	0.42609 (2)	0.63867 (5)	0.02033 (13)
O1	0.42042 (15)	0.46049 (7)	0.56673 (14)	0.0193 (3)
O2	0.2810 (2)	0.36429 (8)	0.57543 (19)	0.0404 (4)
O3	0.37729 (18)	0.42162 (8)	0.78368 (15)	0.0336 (4)
O4	0.17490 (17)	0.46582 (8)	0.61602 (16)	0.0309 (4)
N1	0.41898 (19)	0.59060 (8)	0.65957 (17)	0.0213 (4)
N2	0.25128 (19)	0.62219 (8)	0.39875 (17)	0.0220 (4)
N3	0.25106 (19)	0.49886 (8)	0.30406 (17)	0.0199 (4)
C1	0.5258 (2)	0.63458 (10)	0.6657 (2)	0.0245 (5)
H1	0.5709	0.6403	0.5883	0.029*
C2	0.5725 (3)	0.67179 (10)	0.7800 (2)	0.0261 (5)
H2	0.6478	0.7027	0.7795	0.031*
C3	0.5105 (3)	0.66455 (10)	0.8957 (2)	0.0268 (5)
C4	0.4017 (3)	0.61830 (11)	0.8888 (2)	0.0304 (5)
H4	0.3564	0.6111	0.9656	0.037*
C5	0.3590 (2)	0.58275 (10)	0.7717 (2)	0.0257 (5)
H5	0.2843	0.5514	0.7699	0.031*
C6	0.5586 (3)	0.70482 (12)	1.0209 (2)	0.0409 (6)
H6A	0.4706	0.7244	1.0460	0.061*
H6B	0.6267	0.7377	1.0013	0.061*
H6C	0.6099	0.6786	1.0971	0.061*
C7	0.3149 (3)	0.66404 (11)	0.3272 (2)	0.0292 (5)
H7	0.4151	0.6572	0.3175	0.035*
C8	0.2403 (3)	0.71650 (11)	0.2672 (2)	0.0319 (5)
H8	0.2893	0.7450	0.2172	0.038*
C9	0.0942 (3)	0.72788 (10)	0.2794 (2)	0.0276 (5)
C10	0.0286 (2)	0.68434 (11)	0.3534 (2)	0.0269 (5)
H10	−0.0713	0.6902	0.3649	0.032*
C11	0.1090 (2)	0.63269 (10)	0.4097 (2)	0.0256 (5)
H11	0.0618	0.6030	0.4587	0.031*
C12	0.0077 (3)	0.78367 (13)	0.2126 (3)	0.0501 (7)
H12A	0.0771	0.8149	0.1884	0.075*
H12B	−0.0488	0.8025	0.2765	0.075*
H12C	−0.0616	0.7700	0.1293	0.075*
C13	0.1195 (2)	0.46930 (10)	0.2929 (2)	0.0245 (5)
H13	0.0717	0.4692	0.3695	0.029*
C14	0.0515 (2)	0.43909 (11)	0.1740 (2)	0.0270 (5)
H14	−0.0426	0.4192	0.1694	0.032*
C15	0.1192 (2)	0.43750 (10)	0.0612 (2)	0.0236 (5)
C16	0.2530 (2)	0.46990 (10)	0.0720 (2)	0.0245 (5)
H16	0.3020	0.4713	−0.0038	0.029*
C17	0.3146 (2)	0.50015 (10)	0.1932 (2)	0.0225 (4)
H17	0.4054	0.5228	0.1984	0.027*
C18	0.0528 (3)	0.40159 (12)	−0.0668 (2)	0.0364 (6)
H18A	0.0920	0.4184	−0.1445	0.055*
H18B	−0.0562	0.4061	−0.0855	0.055*
H18C	0.0793	0.3569	−0.0541	0.055*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01960 (14)	0.02127 (15)	0.01567 (14)	−0.00091 (10)	0.00378 (9)	−0.00101 (10)
S1	0.0188 (3)	0.0233 (3)	0.0215 (3)	−0.0043 (2)	0.0102 (2)	0.0006 (2)
O1	0.0173 (7)	0.0230 (7)	0.0193 (7)	−0.0034 (6)	0.0077 (6)	0.0030 (6)
O2	0.0462 (10)	0.0296 (9)	0.0547 (11)	−0.0177 (8)	0.0322 (9)	−0.0132 (8)
O3	0.0314 (9)	0.0492 (11)	0.0219 (8)	−0.0029 (8)	0.0091 (7)	0.0118 (7)
O4	0.0186 (8)	0.0425 (10)	0.0329 (9)	0.0013 (7)	0.0086 (7)	0.0002 (7)
N1	0.0229 (9)	0.0223 (9)	0.0192 (9)	0.0017 (7)	0.0051 (7)	−0.0010 (7)
N2	0.0213 (9)	0.0234 (9)	0.0210 (9)	−0.0024 (7)	0.0034 (7)	−0.0016 (7)
N3	0.0200 (9)	0.0217 (9)	0.0178 (8)	−0.0001 (7)	0.0032 (7)	0.0005 (7)
C1	0.0272 (11)	0.0261 (11)	0.0217 (11)	−0.0009 (9)	0.0089 (9)	0.0000 (9)
C2	0.0285 (12)	0.0236 (11)	0.0263 (11)	−0.0032 (9)	0.0058 (9)	−0.0005 (9)
C3	0.0381 (13)	0.0207 (11)	0.0206 (11)	0.0049 (10)	0.0037 (9)	−0.0013 (9)
C4	0.0429 (14)	0.0293 (12)	0.0235 (11)	−0.0005 (11)	0.0175 (10)	−0.0016 (9)
C5	0.0280 (12)	0.0258 (12)	0.0262 (11)	−0.0026 (9)	0.0121 (9)	−0.0023 (9)
C6	0.0651 (18)	0.0314 (14)	0.0252 (12)	−0.0027 (13)	0.0069 (12)	−0.0064 (11)
C7	0.0233 (11)	0.0326 (13)	0.0334 (12)	−0.0029 (10)	0.0096 (10)	0.0005 (10)
C8	0.0328 (13)	0.0282 (12)	0.0365 (13)	−0.0069 (10)	0.0109 (10)	0.0056 (10)
C9	0.0324 (12)	0.0218 (11)	0.0282 (12)	−0.0013 (10)	0.0048 (10)	−0.0036 (9)
C10	0.0220 (11)	0.0298 (12)	0.0297 (12)	−0.0013 (9)	0.0071 (9)	−0.0044 (10)
C11	0.0263 (11)	0.0254 (11)	0.0261 (11)	−0.0053 (9)	0.0077 (9)	−0.0008 (9)
C12	0.0527 (17)	0.0364 (15)	0.0621 (19)	0.0109 (13)	0.0135 (15)	0.0147 (14)
C13	0.0227 (11)	0.0292 (12)	0.0228 (11)	−0.0013 (9)	0.0069 (9)	−0.0004 (9)
C14	0.0218 (11)	0.0277 (12)	0.0312 (12)	−0.0065 (9)	0.0043 (9)	−0.0021 (10)
C15	0.0259 (11)	0.0210 (11)	0.0217 (11)	0.0029 (9)	−0.0003 (9)	−0.0012 (9)
C16	0.0257 (11)	0.0308 (12)	0.0171 (10)	0.0020 (9)	0.0049 (9)	0.0001 (9)
C17	0.0209 (10)	0.0260 (11)	0.0205 (10)	−0.0009 (9)	0.0041 (8)	0.0035 (9)
C18	0.0399 (14)	0.0375 (14)	0.0287 (13)	−0.0038 (11)	−0.0004 (11)	−0.0097 (11)

Geometric parameters (Å, º) top

Cu1—O1	1.9853 (14)	C6—H6B	0.9800
Cu1—O1ⁱ	2.2525 (14)	C6—H6C	0.9800
Cu1—N1	2.0408 (17)	C7—H7	0.9500
Cu1—N2	2.0106 (18)	C7—C8	1.377 (3)
Cu1—N3	2.0240 (17)	C8—H8	0.9500
S1—O1	1.5428 (14)	C8—C9	1.385 (3)
S1—O2	1.4538 (17)	C9—C10	1.388 (3)
S1—O3	1.4551 (16)	C9—C12	1.502 (3)
S1—O4	1.4625 (16)	C10—H10	0.9500
O1—Cu1ⁱ	2.2525 (14)	C10—C11	1.374 (3)
N1—C1	1.342 (3)	C11—H11	0.9500
N1—C5	1.346 (3)	C12—H12A	0.9800
N2—C7	1.340 (3)	C12—H12B	0.9800
N2—C11	1.344 (3)	C12—H12C	0.9800
N3—C13	1.340 (3)	C13—H13	0.9500
N3—C17	1.344 (3)	C13—C14	1.378 (3)
C1—H1	0.9500	C14—H14	0.9500
C1—C2	1.378 (3)	C14—C15	1.385 (3)
C2—H2	0.9500	C15—C16	1.387 (3)
C2—C3	1.388 (3)	C15—C18	1.503 (3)
C3—C4	1.388 (3)	C16—H16	0.9500
C3—C6	1.500 (3)	C16—C17	1.381 (3)
C4—H4	0.9500	C17—H17	0.9500
C4—C5	1.376 (3)	C18—H18A	0.9800
C5—H5	0.9500	C18—H18B	0.9800
C6—H6A	0.9800	C18—H18C	0.9800

O1—Cu1—O1ⁱ	79.94 (6)	H6A—C6—H6B	109.5
O1—Cu1—N1	92.61 (6)	H6A—C6—H6C	109.5
O1—Cu1—N2	172.98 (6)	H6B—C6—H6C	109.5
O1—Cu1—N3	91.51 (6)	N2—C7—H7	118.8
N1—Cu1—O1ⁱ	92.88 (6)	N2—C7—C8	122.4 (2)
N2—Cu1—O1ⁱ	107.02 (6)	C8—C7—H7	118.8
N2—Cu1—N1	88.00 (7)	C7—C8—H8	119.8
N2—Cu1—N3	87.12 (7)	C7—C8—C9	120.3 (2)
N3—Cu1—O1ⁱ	94.26 (6)	C9—C8—H8	119.8
N3—Cu1—N1	172.28 (7)	C8—C9—C10	117.1 (2)
O2—S1—O1	107.41 (9)	C8—C9—C12	121.9 (2)
O2—S1—O3	111.85 (11)	C10—C9—C12	120.9 (2)
O2—S1—O4	112.76 (10)	C9—C10—H10	120.2
O3—S1—O1	107.15 (9)	C11—C10—C9	119.7 (2)
O3—S1—O4	111.80 (10)	C11—C10—H10	120.2
O4—S1—O1	105.39 (9)	N2—C11—C10	123.0 (2)
Cu1—O1—Cu1ⁱ	100.06 (5)	N2—C11—H11	118.5
S1—O1—Cu1	114.83 (8)	C10—C11—H11	118.5
S1—O1—Cu1ⁱ	145.08 (9)	C9—C12—H12A	109.5
C1—N1—Cu1	119.26 (14)	C9—C12—H12B	109.5
C1—N1—C5	117.40 (18)	C9—C12—H12C	109.5
C5—N1—Cu1	123.27 (15)	H12A—C12—H12B	109.5
C7—N2—Cu1	124.81 (15)	H12A—C12—H12C	109.5
C7—N2—C11	117.51 (19)	H12B—C12—H12C	109.5
C11—N2—Cu1	117.56 (14)	N3—C13—H13	119.0
C13—N3—Cu1	121.04 (14)	N3—C13—C14	122.1 (2)
C13—N3—C17	117.95 (18)	C14—C13—H13	119.0
C17—N3—Cu1	120.98 (14)	C13—C14—H14	119.8
N1—C1—H1	118.7	C13—C14—C15	120.5 (2)
N1—C1—C2	122.6 (2)	C15—C14—H14	119.8
C2—C1—H1	118.7	C14—C15—C16	117.06 (19)
C1—C2—H2	119.7	C14—C15—C18	121.8 (2)
C1—C2—C3	120.6 (2)	C16—C15—C18	121.1 (2)
C3—C2—H2	119.7	C15—C16—H16	120.1
C2—C3—C4	116.4 (2)	C17—C16—C15	119.7 (2)
C2—C3—C6	121.6 (2)	C17—C16—H16	120.1
C4—C3—C6	122.1 (2)	N3—C17—C16	122.55 (19)
C3—C4—H4	119.7	N3—C17—H17	118.7
C5—C4—C3	120.5 (2)	C16—C17—H17	118.7
C5—C4—H4	119.7	C15—C18—H18A	109.5
N1—C5—C4	122.6 (2)	C15—C18—H18B	109.5
N1—C5—H5	118.7	C15—C18—H18C	109.5
C4—C5—H5	118.7	H18A—C18—H18B	109.5
C3—C6—H6A	109.5	H18A—C18—H18C	109.5
C3—C6—H6B	109.5	H18B—C18—H18C	109.5
C3—C6—H6C	109.5

Cu1—N1—C1—C2	175.95 (17)	C2—C3—C4—C5	−0.6 (3)
Cu1—N1—C5—C4	−176.14 (17)	C3—C4—C5—N1	0.0 (4)
Cu1—N2—C7—C8	176.59 (17)	C5—N1—C1—C2	−1.2 (3)
Cu1—N2—C11—C10	−177.43 (17)	C6—C3—C4—C5	179.2 (2)
Cu1—N3—C13—C14	−179.55 (16)	C7—N2—C11—C10	−1.1 (3)
Cu1—N3—C17—C16	178.49 (16)	C7—C8—C9—C10	−0.2 (3)
O2—S1—O1—Cu1ⁱ	−60.22 (17)	C7—C8—C9—C12	−178.5 (2)
O2—S1—O1—Cu1	122.28 (11)	C8—C9—C10—C11	−0.3 (3)
O3—S1—O1—Cu1	−117.39 (10)	C9—C10—C11—N2	1.0 (3)
O3—S1—O1—Cu1ⁱ	60.10 (17)	C11—N2—C7—C8	0.6 (3)
O4—S1—O1—Cu1ⁱ	179.32 (14)	C12—C9—C10—C11	178.0 (2)
O4—S1—O1—Cu1	1.82 (11)	C13—N3—C17—C16	−3.1 (3)
N1—C1—C2—C3	0.6 (3)	C13—C14—C15—C16	−3.0 (3)
N2—C7—C8—C9	0.1 (4)	C13—C14—C15—C18	176.1 (2)
N3—C13—C14—C15	1.0 (3)	C14—C15—C16—C17	2.0 (3)
C1—N1—C5—C4	0.9 (3)	C15—C16—C17—N3	1.1 (3)
C1—C2—C3—C4	0.3 (3)	C17—N3—C13—C14	2.0 (3)
C1—C2—C3—C6	−179.5 (2)	C18—C15—C16—C17	−177.2 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O2ⁱ	0.95	2.32	3.247 (3)	166
C5—H5···O4	0.95	2.45	3.214 (3)	137
C10—H10···O2ⁱⁱ	0.95	2.41	3.218 (3)	143
C11—H11···O4ⁱⁱ	0.95	2.59	3.299 (3)	132
C13—H13···O4	0.95	2.44	3.149 (3)	131
C16—H16···O3ⁱⁱⁱ	0.95	2.57	3.441 (3)	152
C17—H17···O1ⁱ	0.95	2.57	3.152 (2)	120
C17—H17···O3ⁱ	0.95	2.28	3.235 (3)	178

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

catena-Poly[[bis(4-methylpyridine-κN)zinc(II)]-sulfato-κ²O:O'] (UMD1448_a) top

Crystal data top

[Zn(SO₄)(C₆H₇N)₂]	F(000) = 712
M_r = 347.68	D_x = 1.635 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.9703 (10) Å	Cell parameters from 9901 reflections
b = 9.7229 (7) Å	θ = 3.0–25.4°
c = 9.8290 (6) Å	µ = 1.90 mm⁻¹
β = 99.161 (2)°	T = 295 K
V = 1412.41 (16) Å³	BLOCK, colourless
Z = 4	0.33 × 0.18 × 0.17 mm

Data collection top

Bruker D8 Venture CMOS diffractometer	2245 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.047
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θ_max = 25.4°, θ_min = 3.0°
T_min = 0.368, T_max = 0.429	h = −18→18
36405 measured reflections	k = −11→11
2587 independent reflections	l = −11→11

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.029	w = 1/[σ²(F_o²) + (0.0106P)² + 2.2444P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.063	(Δ/σ)_max = 0.001
S = 1.05	Δρ_max = 0.28 e Å⁻³
2587 reflections	Δρ_min = −0.26 e Å⁻³
184 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0064 (4)
Primary atom site location: structure-invariant direct methods

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Zn1	0.73426 (2)	0.67083 (3)	0.34428 (3)	0.03279 (12)
S1	0.77109 (4)	0.91047 (7)	0.56007 (6)	0.03436 (17)
O1	0.75464 (16)	0.8521 (2)	0.41889 (19)	0.0534 (6)
O2	0.86570 (14)	0.9318 (3)	0.6042 (3)	0.0683 (7)
O3	0.71701 (16)	1.0322 (2)	0.5637 (2)	0.0584 (6)
O4	0.73861 (14)	0.8018 (2)	0.64984 (18)	0.0452 (5)
N1	0.60062 (15)	0.6304 (2)	0.3468 (2)	0.0400 (5)
N2	0.81748 (15)	0.5253 (2)	0.4368 (2)	0.0353 (5)
C1	0.5570 (2)	0.6899 (3)	0.4395 (3)	0.0506 (8)
H1A	0.5906	0.7376	0.5123	0.061*
C2	0.4647 (2)	0.6836 (3)	0.4320 (3)	0.0510 (8)
H2A	0.4372	0.7274	0.4986	0.061*
C3	0.41246 (18)	0.6127 (3)	0.3264 (3)	0.0406 (7)
C4	0.45827 (19)	0.5495 (3)	0.2325 (3)	0.0490 (8)
H4A	0.4262	0.4995	0.1601	0.059*
C5	0.5506 (2)	0.5595 (3)	0.2445 (3)	0.0466 (7)
H5A	0.5796	0.5157	0.1796	0.056*
C6	0.3116 (2)	0.6041 (4)	0.3144 (4)	0.0618 (9)
H6A	0.2909	0.6711	0.3741	0.093*
H6B	0.2948	0.5138	0.3406	0.093*
H6C	0.2844	0.6220	0.2209	0.093*
C7	0.8198 (2)	0.3996 (3)	0.3815 (3)	0.0465 (7)
H7A	0.7821	0.3813	0.2987	0.056*
C8	0.8752 (2)	0.2967 (3)	0.4412 (3)	0.0477 (7)
H8A	0.8738	0.2107	0.3993	0.057*
C9	0.93307 (17)	0.3198 (3)	0.5629 (3)	0.0381 (6)
C10	0.92991 (19)	0.4486 (3)	0.6201 (3)	0.0449 (7)
H10A	0.9670	0.4688	0.7028	0.054*
C11	0.87254 (19)	0.5478 (3)	0.5561 (3)	0.0418 (7)
H11A	0.8719	0.6338	0.5973	0.050*
C12	0.9960 (2)	0.2102 (3)	0.6282 (4)	0.0561 (9)
H12A	1.0340	0.1801	0.5641	0.084*
H12B	0.9615	0.1338	0.6534	0.084*
H12C	1.0329	0.2465	0.7091	0.084*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.03253 (18)	0.03542 (19)	0.02896 (17)	−0.00093 (13)	0.00042 (12)	0.00190 (13)
S1	0.0396 (4)	0.0349 (4)	0.0276 (3)	−0.0059 (3)	0.0023 (3)	−0.0029 (3)
O1	0.0915 (17)	0.0413 (12)	0.0273 (10)	−0.0098 (11)	0.0094 (10)	−0.0040 (9)
O2	0.0416 (12)	0.0901 (19)	0.0710 (16)	−0.0201 (13)	0.0020 (11)	−0.0040 (14)
O3	0.0808 (16)	0.0455 (13)	0.0483 (13)	0.0172 (12)	0.0084 (11)	−0.0002 (10)
O4	0.0614 (13)	0.0453 (12)	0.0276 (10)	−0.0145 (10)	0.0038 (9)	0.0006 (8)
N1	0.0355 (12)	0.0463 (14)	0.0371 (13)	−0.0036 (10)	0.0024 (10)	0.0001 (11)
N2	0.0371 (12)	0.0349 (12)	0.0319 (12)	−0.0033 (10)	−0.0008 (9)	0.0030 (10)
C1	0.0433 (16)	0.064 (2)	0.0440 (17)	−0.0114 (15)	0.0053 (13)	−0.0160 (15)
C2	0.0433 (17)	0.060 (2)	0.0517 (18)	−0.0053 (15)	0.0147 (14)	−0.0157 (16)
C3	0.0346 (14)	0.0445 (16)	0.0415 (16)	−0.0054 (13)	0.0028 (12)	0.0045 (13)
C4	0.0399 (16)	0.062 (2)	0.0435 (17)	−0.0141 (15)	0.0021 (13)	−0.0104 (15)
C5	0.0449 (17)	0.0548 (19)	0.0411 (16)	−0.0053 (14)	0.0099 (13)	−0.0113 (14)
C6	0.0374 (17)	0.077 (2)	0.071 (2)	−0.0071 (17)	0.0090 (16)	−0.0064 (19)
C7	0.0587 (19)	0.0421 (17)	0.0330 (15)	−0.0027 (14)	−0.0102 (13)	−0.0016 (13)
C8	0.064 (2)	0.0331 (16)	0.0420 (17)	0.0021 (14)	−0.0041 (14)	−0.0022 (13)
C9	0.0328 (14)	0.0377 (15)	0.0429 (16)	−0.0051 (12)	0.0031 (11)	0.0096 (13)
C10	0.0447 (16)	0.0421 (17)	0.0412 (16)	−0.0048 (13)	−0.0135 (13)	0.0006 (13)
C11	0.0429 (16)	0.0363 (15)	0.0426 (16)	−0.0049 (13)	−0.0039 (13)	−0.0015 (13)
C12	0.0490 (18)	0.0463 (19)	0.068 (2)	0.0035 (15)	−0.0045 (16)	0.0178 (16)

Geometric parameters (Å, º) top

Zn1—O1	1.915 (2)	C4—H4A	0.9300
Zn1—O4ⁱ	1.9410 (18)	C4—C5	1.372 (4)
Zn1—N1	2.043 (2)	C5—H5A	0.9300
Zn1—N2	2.005 (2)	C6—H6A	0.9600
S1—O1	1.483 (2)	C6—H6B	0.9600
S1—O2	1.429 (2)	C6—H6C	0.9600
S1—O3	1.438 (2)	C7—H7A	0.9300
S1—O4	1.506 (2)	C7—C8	1.370 (4)
O4—Zn1ⁱⁱ	1.9409 (18)	C8—H8A	0.9300
N1—C1	1.334 (4)	C8—C9	1.379 (4)
N1—C5	1.344 (4)	C9—C10	1.377 (4)
N2—C7	1.341 (4)	C9—C12	1.498 (4)
N2—C11	1.340 (3)	C10—H10A	0.9300
C1—H1A	0.9300	C10—C11	1.375 (4)
C1—C2	1.374 (4)	C11—H11A	0.9300
C2—H2A	0.9300	C12—H12A	0.9600
C2—C3	1.381 (4)	C12—H12B	0.9600
C3—C4	1.379 (4)	C12—H12C	0.9600
C3—C6	1.498 (4)

O1—Zn1—O4ⁱ	102.86 (8)	C5—C4—H4A	119.6
O1—Zn1—N1	105.61 (10)	N1—C5—C4	122.3 (3)
O1—Zn1—N2	115.24 (9)	N1—C5—H5A	118.8
O4ⁱ—Zn1—N1	102.98 (9)	C4—C5—H5A	118.8
O4ⁱ—Zn1—N2	115.32 (9)	C3—C6—H6A	109.5
N2—Zn1—N1	113.43 (9)	C3—C6—H6B	109.5
O1—S1—O4	105.01 (11)	C3—C6—H6C	109.5
O2—S1—O1	110.40 (15)	H6A—C6—H6B	109.5
O2—S1—O3	114.06 (16)	H6A—C6—H6C	109.5
O2—S1—O4	108.72 (14)	H6B—C6—H6C	109.5
O3—S1—O1	109.13 (13)	N2—C7—H7A	118.5
O3—S1—O4	109.11 (13)	N2—C7—C8	123.0 (3)
S1—O1—Zn1	134.66 (13)	C8—C7—H7A	118.5
S1—O4—Zn1ⁱⁱ	123.04 (12)	C7—C8—H8A	119.8
C1—N1—Zn1	120.74 (19)	C7—C8—C9	120.4 (3)
C1—N1—C5	117.3 (2)	C9—C8—H8A	119.8
C5—N1—Zn1	121.3 (2)	C8—C9—C12	121.4 (3)
C7—N2—Zn1	120.91 (18)	C10—C9—C8	116.4 (3)
C11—N2—Zn1	122.21 (19)	C10—C9—C12	122.2 (3)
C11—N2—C7	116.9 (2)	C9—C10—H10A	119.6
N1—C1—H1A	118.6	C11—C10—C9	120.7 (3)
N1—C1—C2	122.8 (3)	C11—C10—H10A	119.6
C2—C1—H1A	118.6	N2—C11—C10	122.5 (3)
C1—C2—H2A	119.8	N2—C11—H11A	118.7
C1—C2—C3	120.5 (3)	C10—C11—H11A	118.7
C3—C2—H2A	119.8	C9—C12—H12A	109.5
C2—C3—C6	122.0 (3)	C9—C12—H12B	109.5
C4—C3—C2	116.3 (3)	C9—C12—H12C	109.5
C4—C3—C6	121.7 (3)	H12A—C12—H12B	109.5
C3—C4—H4A	119.6	H12A—C12—H12C	109.5
C5—C4—C3	120.8 (3)	H12B—C12—H12C	109.5

Zn1—N1—C1—C2	169.3 (3)	C1—C2—C3—C4	0.6 (5)
Zn1—N1—C5—C4	−169.5 (2)	C1—C2—C3—C6	−179.7 (3)
Zn1—N2—C7—C8	−179.7 (2)	C2—C3—C4—C5	−0.8 (5)
Zn1—N2—C11—C10	−179.9 (2)	C3—C4—C5—N1	−0.1 (5)
O1—S1—O4—Zn1ⁱⁱ	−174.58 (14)	C5—N1—C1—C2	−1.5 (5)
O2—S1—O1—Zn1	98.2 (2)	C6—C3—C4—C5	179.4 (3)
O2—S1—O4—Zn1ⁱⁱ	67.26 (19)	C7—N2—C11—C10	0.6 (4)
O3—S1—O1—Zn1	−135.7 (2)	C7—C8—C9—C10	1.4 (5)
O3—S1—O4—Zn1ⁱⁱ	−57.70 (18)	C7—C8—C9—C12	−178.4 (3)
O4—S1—O1—Zn1	−18.8 (2)	C8—C9—C10—C11	−1.0 (4)
N1—C1—C2—C3	0.6 (5)	C9—C10—C11—N2	0.0 (5)
N2—C7—C8—C9	−0.9 (5)	C11—N2—C7—C8	−0.1 (4)
C1—N1—C5—C4	1.2 (5)	C12—C9—C10—C11	178.8 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O4	0.93	2.48	3.325 (3)	150
C5—H5A···O3ⁱ	0.93	2.55	3.401 (4)	153
C7—H7A···O3ⁱ	0.93	2.51	3.321 (4)	147

Symmetry code: (i) x, −y+3/2, z−1/2.

catena-Poly[[tris(4-methylpyridine-κN)zinc(II)]-sulfato-κ²O:O'] (umd1540c_a) top

Crystal data top

[Zn(SO₄)(C₆H₇N)₂]	D_x = 1.499 Mg m⁻³
M_r = 440.81	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 8899 reflections
a = 9.4926 (5) Å	θ = 2.9–25.2°
b = 11.4128 (7) Å	µ = 1.39 mm⁻¹
c = 18.0235 (11) Å	T = 296 K
V = 1952.6 (2) Å³	ROD, colourless
Z = 4	0.2 × 0.03 × 0.03 mm
F(000) = 912

Data collection top

Bruker D8 Venture CMOS diffractometer	3118 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.060
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θ_max = 25.4°, θ_min = 2.9°
T_min = 0.450, T_max = 0.490	h = −11→8
24507 measured reflections	k = −13→13
3561 independent reflections	l = −21→21

Refinement top

Refinement on F²	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.0216P)² + 0.4739P] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.027	(Δ/σ)_max = 0.001
wR(F²) = 0.056	Δρ_max = 0.21 e Å⁻³
S = 1.03	Δρ_min = −0.33 e Å⁻³
3561 reflections	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
248 parameters	Extinction coefficient: 0.0025 (6)
0 restraints	Absolute structure: Flack x determined using 1244 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.002 (7)
Hydrogen site location: inferred from neighbouring sites

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Zn1	0.63333 (4)	0.71323 (4)	0.53749 (2)	0.02618 (13)
S1	0.32426 (9)	0.70122 (9)	0.59603 (5)	0.0257 (2)
O1	0.4259 (2)	0.7098 (3)	0.53201 (14)	0.0312 (6)
O2	0.3635 (3)	0.7833 (3)	0.65349 (13)	0.0458 (7)
O3	0.3196 (3)	0.5814 (3)	0.62307 (16)	0.0414 (7)
O4	0.1848 (3)	0.7333 (2)	0.56397 (13)	0.0297 (6)
N1	0.7391 (3)	0.6428 (3)	0.62840 (18)	0.0294 (8)
N2	0.6501 (3)	0.8884 (3)	0.58363 (17)	0.0299 (7)
N3	0.6465 (4)	0.5285 (3)	0.49194 (17)	0.0378 (8)
C1	0.8793 (4)	0.6460 (3)	0.6338 (2)	0.0358 (9)
H1	0.9290	0.6929	0.6007	0.043*
C2	0.9538 (4)	0.5834 (4)	0.6859 (2)	0.0390 (11)
H2	1.0516	0.5886	0.6875	0.047*
C3	0.8829 (4)	0.5126 (3)	0.7359 (2)	0.0300 (9)
C4	0.7381 (4)	0.5124 (4)	0.7321 (2)	0.0326 (10)
H4	0.6859	0.4692	0.7661	0.039*
C5	0.6702 (4)	0.5761 (3)	0.6778 (2)	0.0325 (10)
H5	0.5725	0.5727	0.6754	0.039*
C6	0.9593 (5)	0.4383 (4)	0.7926 (3)	0.0505 (13)
H6A	1.0235	0.4865	0.8201	0.076*
H6B	1.0108	0.3775	0.7676	0.076*
H6C	0.8922	0.4038	0.8258	0.076*
C7	0.6571 (4)	0.9810 (3)	0.5392 (2)	0.0391 (10)
H7	0.6566	0.9690	0.4882	0.047*
C8	0.6649 (6)	1.0932 (4)	0.5655 (3)	0.0560 (15)
H8	0.6700	1.1553	0.5322	0.067*
C9	0.6653 (5)	1.1157 (4)	0.6403 (3)	0.0495 (13)
C10	0.6562 (5)	1.0207 (4)	0.6866 (2)	0.0420 (11)
H10	0.6555	1.0311	0.7378	0.050*
C11	0.6481 (5)	0.9097 (4)	0.6566 (2)	0.0381 (10)
H11	0.6409	0.8463	0.6888	0.046*
C12	0.6763 (9)	1.2407 (5)	0.6692 (3)	0.102 (3)
H12A	0.7370	1.2424	0.7118	0.153*
H12B	0.5844	1.2683	0.6829	0.153*
H12C	0.7145	1.2903	0.6311	0.153*
C13	0.7642 (5)	0.4938 (4)	0.4579 (3)	0.0504 (12)
H13	0.8426	0.5425	0.4602	0.061*
C14	0.7758 (6)	0.3903 (4)	0.4196 (3)	0.0558 (14)
H14	0.8603	0.3706	0.3966	0.067*
C15	0.6629 (6)	0.3163 (4)	0.4152 (3)	0.0531 (13)
C16	0.5436 (6)	0.3499 (4)	0.4520 (3)	0.0592 (14)
H16	0.4652	0.3010	0.4520	0.071*
C17	0.5381 (5)	0.4556 (4)	0.4891 (3)	0.0467 (12)
H17	0.4550	0.4764	0.5130	0.056*
C18	0.6692 (8)	0.2030 (5)	0.3704 (3)	0.092 (2)
H18A	0.7471	0.1564	0.3871	0.138*
H18B	0.6812	0.2213	0.3188	0.138*
H18C	0.5832	0.1601	0.3771	0.138*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0254 (2)	0.0290 (2)	0.0242 (2)	0.0005 (2)	−0.00078 (19)	0.0021 (2)
S1	0.0231 (5)	0.0323 (5)	0.0216 (4)	0.0001 (4)	−0.0011 (3)	−0.0004 (4)
O1	0.0250 (12)	0.0431 (15)	0.0254 (13)	−0.0037 (12)	0.0028 (10)	−0.0028 (16)
O2	0.0448 (16)	0.0613 (18)	0.0312 (14)	−0.0061 (19)	−0.0037 (13)	−0.0188 (15)
O3	0.0409 (18)	0.0413 (18)	0.0421 (18)	0.0013 (13)	−0.0021 (14)	0.0162 (14)
O4	0.0230 (13)	0.0404 (17)	0.0257 (13)	0.0063 (12)	−0.0027 (10)	0.0015 (12)
N1	0.0284 (19)	0.0284 (19)	0.0315 (19)	−0.0021 (14)	−0.0045 (14)	0.0022 (16)
N2	0.0310 (19)	0.0318 (17)	0.0269 (17)	−0.0018 (15)	0.0010 (15)	−0.0010 (14)
N3	0.046 (2)	0.0337 (18)	0.0343 (19)	0.0044 (18)	−0.0013 (18)	−0.0034 (15)
C1	0.032 (2)	0.040 (2)	0.035 (2)	−0.004 (2)	0.004 (2)	0.0093 (19)
C2	0.026 (2)	0.052 (3)	0.038 (3)	0.003 (2)	−0.0035 (19)	0.009 (2)
C3	0.033 (2)	0.032 (2)	0.024 (2)	0.0062 (19)	−0.0027 (18)	−0.0011 (16)
C4	0.037 (2)	0.030 (2)	0.030 (2)	−0.0056 (18)	0.0040 (19)	0.0067 (19)
C5	0.027 (2)	0.037 (2)	0.034 (2)	−0.0069 (18)	−0.0008 (18)	0.0049 (19)
C6	0.051 (3)	0.060 (3)	0.041 (3)	0.016 (2)	−0.005 (2)	0.012 (2)
C7	0.057 (3)	0.032 (2)	0.028 (2)	0.0040 (19)	0.008 (2)	−0.003 (2)
C8	0.093 (4)	0.036 (3)	0.039 (3)	0.001 (3)	0.014 (3)	0.000 (2)
C9	0.068 (4)	0.034 (2)	0.047 (3)	−0.003 (2)	0.010 (2)	−0.015 (2)
C10	0.047 (3)	0.048 (3)	0.031 (2)	−0.004 (2)	0.001 (2)	−0.014 (2)
C11	0.040 (3)	0.045 (2)	0.029 (2)	−0.002 (2)	−0.003 (2)	−0.0006 (19)
C12	0.192 (8)	0.046 (4)	0.069 (4)	−0.009 (4)	0.022 (5)	−0.029 (3)
C13	0.048 (3)	0.043 (3)	0.060 (3)	0.009 (2)	0.007 (3)	−0.001 (3)
C14	0.068 (4)	0.047 (3)	0.052 (3)	0.023 (3)	0.011 (3)	−0.006 (3)
C15	0.084 (4)	0.037 (3)	0.038 (3)	0.018 (3)	−0.010 (3)	−0.004 (2)
C16	0.066 (3)	0.039 (3)	0.072 (4)	−0.008 (2)	−0.015 (3)	−0.007 (3)
C17	0.048 (3)	0.036 (3)	0.055 (3)	0.002 (2)	0.000 (2)	−0.003 (2)
C18	0.157 (7)	0.048 (3)	0.072 (4)	0.018 (5)	−0.020 (4)	−0.029 (3)

Geometric parameters (Å, º) top

Zn1—O1	1.972 (2)	C6—H6B	0.9600
Zn1—O4ⁱ	1.989 (2)	C6—H6C	0.9600
Zn1—N1	2.083 (3)	C7—H7	0.9300
Zn1—N2	2.172 (3)	C7—C8	1.368 (6)
Zn1—N3	2.265 (3)	C8—H8	0.9300
S1—O1	1.507 (2)	C8—C9	1.372 (6)
S1—O2	1.445 (3)	C9—C10	1.371 (6)
S1—O3	1.452 (3)	C9—C12	1.523 (6)
S1—O4	1.490 (3)	C10—H10	0.9300
O4—Zn1ⁱⁱ	1.989 (2)	C10—C11	1.380 (5)
N1—C1	1.334 (5)	C11—H11	0.9300
N1—C5	1.342 (5)	C12—H12A	0.9600
N2—C7	1.327 (5)	C12—H12B	0.9600
N2—C11	1.338 (5)	C12—H12C	0.9600
N3—C13	1.335 (5)	C13—H13	0.9300
N3—C17	1.325 (6)	C13—C14	1.373 (7)
C1—H1	0.9300	C14—H14	0.9300
C1—C2	1.376 (6)	C14—C15	1.367 (7)
C2—H2	0.9300	C15—C16	1.368 (7)
C2—C3	1.386 (6)	C15—C18	1.525 (6)
C3—C4	1.376 (6)	C16—H16	0.9300
C3—C6	1.512 (5)	C16—C17	1.380 (7)
C4—H4	0.9300	C17—H17	0.9300
C4—C5	1.378 (6)	C18—H18A	0.9600
C5—H5	0.9300	C18—H18B	0.9600
C6—H6A	0.9600	C18—H18C	0.9600

O1—Zn1—O4ⁱ	101.86 (10)	H6A—C6—H6B	109.5
O1—Zn1—N1	120.88 (12)	H6A—C6—H6C	109.5
O1—Zn1—N2	96.34 (12)	H6B—C6—H6C	109.5
O1—Zn1—N3	91.06 (13)	N2—C7—H7	118.7
O4ⁱ—Zn1—N1	136.31 (12)	N2—C7—C8	122.6 (4)
O4ⁱ—Zn1—N2	92.97 (11)	C8—C7—H7	118.7
O4ⁱ—Zn1—N3	86.48 (11)	C7—C8—H8	119.5
N1—Zn1—N2	91.08 (12)	C7—C8—C9	121.0 (4)
N1—Zn1—N3	84.23 (13)	C9—C8—H8	119.5
N2—Zn1—N3	172.53 (14)	C8—C9—C12	120.7 (5)
O2—S1—O1	109.97 (16)	C10—C9—C8	116.8 (4)
O2—S1—O3	112.19 (18)	C10—C9—C12	122.5 (4)
O2—S1—O4	110.32 (17)	C9—C10—H10	120.3
O3—S1—O1	109.74 (17)	C9—C10—C11	119.4 (4)
O3—S1—O4	109.55 (16)	C11—C10—H10	120.3
O4—S1—O1	104.81 (14)	N2—C11—C10	123.4 (4)
S1—O1—Zn1	127.02 (15)	N2—C11—H11	118.3
S1—O4—Zn1ⁱⁱ	130.57 (15)	C10—C11—H11	118.3
C1—N1—Zn1	121.8 (3)	C9—C12—H12A	109.5
C1—N1—C5	117.0 (4)	C9—C12—H12B	109.5
C5—N1—Zn1	120.4 (3)	C9—C12—H12C	109.5
C7—N2—Zn1	120.4 (3)	H12A—C12—H12B	109.5
C7—N2—C11	116.7 (3)	H12A—C12—H12C	109.5
C11—N2—Zn1	122.8 (3)	H12B—C12—H12C	109.5
C13—N3—Zn1	119.3 (3)	N3—C13—H13	118.2
C17—N3—Zn1	123.8 (3)	N3—C13—C14	123.6 (5)
C17—N3—C13	116.4 (4)	C14—C13—H13	118.2
N1—C1—H1	118.4	C13—C14—H14	120.1
N1—C1—C2	123.2 (4)	C15—C14—C13	119.8 (5)
C2—C1—H1	118.4	C15—C14—H14	120.1
C1—C2—H2	120.1	C14—C15—C16	116.7 (4)
C1—C2—C3	119.8 (4)	C14—C15—C18	121.6 (5)
C3—C2—H2	120.1	C16—C15—C18	121.8 (5)
C2—C3—C6	122.2 (4)	C15—C16—H16	119.6
C4—C3—C2	117.0 (4)	C15—C16—C17	120.7 (5)
C4—C3—C6	120.8 (4)	C17—C16—H16	119.6
C3—C4—H4	119.9	N3—C17—C16	122.6 (5)
C3—C4—C5	120.1 (4)	N3—C17—H17	118.7
C5—C4—H4	119.9	C16—C17—H17	118.7
N1—C5—C4	122.8 (4)	C15—C18—H18A	109.5
N1—C5—H5	118.6	C15—C18—H18B	109.5
C4—C5—H5	118.6	C15—C18—H18C	109.5
C3—C6—H6A	109.5	H18A—C18—H18B	109.5
C3—C6—H6B	109.5	H18A—C18—H18C	109.5
C3—C6—H6C	109.5	H18B—C18—H18C	109.5

Zn1—N1—C1—C2	−168.4 (3)	C2—C3—C4—C5	3.2 (6)
Zn1—N1—C5—C4	169.5 (3)	C3—C4—C5—N1	−2.0 (7)
Zn1—N2—C7—C8	178.7 (4)	C5—N1—C1—C2	1.2 (6)
Zn1—N2—C11—C10	−178.8 (3)	C6—C3—C4—C5	−176.8 (4)
Zn1—N3—C13—C14	−170.6 (4)	C7—N2—C11—C10	−1.6 (6)
Zn1—N3—C17—C16	170.8 (4)	C7—C8—C9—C10	−0.6 (8)
O1—S1—O4—Zn1ⁱⁱ	−3.6 (3)	C7—C8—C9—C12	179.1 (5)
O2—S1—O1—Zn1	47.0 (3)	C8—C9—C10—C11	0.4 (7)
O2—S1—O4—Zn1ⁱⁱ	114.7 (2)	C9—C10—C11—N2	0.7 (7)
O3—S1—O1—Zn1	−76.8 (2)	C11—N2—C7—C8	1.3 (6)
O3—S1—O4—Zn1ⁱⁱ	−121.3 (2)	C12—C9—C10—C11	−179.3 (5)
O4—S1—O1—Zn1	165.61 (19)	C13—N3—C17—C16	−1.2 (7)
N1—C1—C2—C3	0.1 (7)	C13—C14—C15—C16	−1.7 (8)
N2—C7—C8—C9	−0.2 (8)	C13—C14—C15—C18	177.2 (5)
N3—C13—C14—C15	−0.3 (8)	C14—C15—C16—C17	2.2 (8)
C1—N1—C5—C4	−0.3 (6)	C15—C16—C17—N3	−0.8 (8)
C1—C2—C3—C4	−2.3 (6)	C17—N3—C13—C14	1.7 (7)
C1—C2—C3—C6	177.7 (4)	C18—C15—C16—C17	−176.7 (5)

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

catena-Poly[[tetrakis(4-methylpyridine-κN)cadmium(II)]-sulfato-κ²O:O'] (umd1375_a) top

Crystal data top

[Cd(SO₄)(C₆H₇N)₄]	F(000) = 2368
M_r = 580.96	D_x = 1.487 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.4545 (12) Å	Cell parameters from 9677 reflections
b = 18.657 (2) Å	θ = 3.0–25.7°
c = 24.714 (3) Å	µ = 0.96 mm⁻¹
β = 100.691 (3)°	T = 297 K
V = 5190.0 (10) Å³	BLOCK, colourless
Z = 8	0.34 × 0.2 × 0.18 mm

Data collection top

Bruker D8 Venture CMOS diffractometer	4336 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.038
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θ_max = 25.8°, θ_min = 3.0°
T_min = 0.224, T_max = 0.259	h = −13→13
89835 measured reflections	k = −22→22
4957 independent reflections	l = −30→30

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.026	w = 1/[σ²(F_o²) + (0.0313P)² + 8.6618P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.071	(Δ/σ)_max = 0.001
S = 1.09	Δρ_max = 0.74 e Å⁻³
4957 reflections	Δρ_min = −0.34 e Å⁻³
314 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
18 restraints	Extinction coefficient: 0.00105 (7)
Primary atom site location: structure-invariant direct methods

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cd1	0.5000	0.5000	0.5000	0.03761 (9)
Cd2	0.5000	0.47768 (2)	0.2500	0.03604 (9)
S1	0.67059 (5)	0.47963 (4)	0.39044 (2)	0.03846 (15)
O1	0.57078 (17)	0.48567 (12)	0.42023 (8)	0.0565 (5)
O2	0.6224 (2)	0.47972 (15)	0.33195 (8)	0.0767 (7)
O3	0.7461 (3)	0.54068 (17)	0.40324 (14)	0.1038 (10)
O4	0.7339 (2)	0.41422 (16)	0.40457 (10)	0.0870 (8)
N1	0.69302 (19)	0.49835 (12)	0.55385 (9)	0.0416 (5)
N2	0.48552 (19)	0.37501 (13)	0.50421 (9)	0.0475 (5)
N3	0.62050 (18)	0.56493 (12)	0.21844 (8)	0.0411 (5)
N4	0.37958 (19)	0.38282 (12)	0.27345 (9)	0.0447 (5)
C1	0.7931 (2)	0.47415 (17)	0.53984 (11)	0.0522 (7)
H1	0.7889	0.4536	0.5053	0.063*
C2	0.9015 (3)	0.47826 (19)	0.57395 (12)	0.0606 (8)
H2	0.9686	0.4606	0.5623	0.073*
C3	0.9119 (2)	0.50853 (17)	0.62568 (12)	0.0508 (7)
C4	0.8090 (2)	0.53346 (17)	0.63967 (11)	0.0521 (7)
H4	0.8109	0.5549	0.6738	0.062*
C5	0.7035 (2)	0.52700 (16)	0.60374 (11)	0.0477 (7)
H5	0.6351	0.5436	0.6148	0.057*
C6	1.0286 (3)	0.5145 (3)	0.66412 (16)	0.0960 (15)
H6A	1.0913	0.5169	0.6433	0.144*
H6B	1.0401	0.4733	0.6878	0.144*
H6C	1.0293	0.5571	0.6860	0.144*
C7	0.5607 (3)	0.33064 (17)	0.48611 (13)	0.0577 (8)
H7	0.6182	0.3498	0.4683	0.069*
C8	0.5566 (4)	0.25743 (19)	0.49280 (15)	0.0755 (10)
H8	0.6115	0.2284	0.4800	0.091*
C9	0.4720 (4)	0.22718 (19)	0.51828 (16)	0.0754 (10)
C10	0.3928 (3)	0.27309 (18)	0.53557 (14)	0.0640 (8)
H10	0.3323	0.2550	0.5520	0.077*
C11	0.4028 (3)	0.34583 (16)	0.52866 (12)	0.0524 (7)
H11	0.3494	0.3759	0.5416	0.063*
C12	0.4641 (6)	0.1468 (2)	0.5266 (3)	0.132 (2)
H12A	0.4193	0.1374	0.5550	0.198*
H12B	0.5427	0.1274	0.5372	0.198*
H12C	0.4255	0.1248	0.4929	0.198*
C13	0.5875 (3)	0.59980 (15)	0.17102 (11)	0.0484 (6)
H13	0.5120	0.5914	0.1507	0.058*
C14	0.6599 (3)	0.64749 (17)	0.15084 (13)	0.0608 (8)
H14	0.6327	0.6708	0.1176	0.073*
C15	0.7720 (3)	0.66099 (18)	0.17936 (15)	0.0626 (8)
C16	0.8052 (3)	0.6257 (2)	0.22835 (16)	0.0692 (9)
H16	0.8803	0.6335	0.2494	0.083*
C17	0.7286 (2)	0.57882 (18)	0.24682 (13)	0.0563 (7)
H17	0.7533	0.5560	0.2804	0.068*
C18	0.8554 (4)	0.7123 (2)	0.1581 (2)	0.1022 (15)
H18A	0.8101	0.7462	0.1336	0.153*
H18B	0.9068	0.6859	0.1388	0.153*
H18C	0.9024	0.7373	0.1885	0.153*
C19	0.4080 (3)	0.34684 (16)	0.32063 (12)	0.0514 (7)
H19	0.4793	0.3575	0.3439	0.062*
C20	0.3363 (3)	0.29446 (17)	0.33643 (14)	0.0597 (8)
H20	0.3598	0.2707	0.3697	0.072*
C21	0.2299 (3)	0.27737 (17)	0.30290 (14)	0.0609 (8)
C22	0.2021 (3)	0.31364 (19)	0.25367 (14)	0.0638 (8)
H22	0.1319	0.3034	0.2294	0.077*
C23	0.2781 (3)	0.36497 (17)	0.24042 (12)	0.0542 (7)
H23	0.2578	0.3884	0.2068	0.065*
C24	0.1456 (4)	0.2226 (2)	0.31918 (17)	0.0899 (13)
H24A	0.1899	0.1877	0.3432	0.135*
H24B	0.1034	0.1992	0.2868	0.135*
H24C	0.0901	0.2462	0.3379	0.135*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.03155 (14)	0.04792 (17)	0.03387 (14)	0.00385 (10)	0.00739 (10)	0.00098 (10)
Cd2	0.03247 (14)	0.04608 (17)	0.03132 (14)	0.000	0.01050 (10)	0.000
S1	0.0296 (3)	0.0605 (4)	0.0262 (3)	0.0049 (3)	0.0075 (2)	−0.0016 (2)
O1	0.0434 (11)	0.0866 (15)	0.0451 (11)	0.0059 (10)	0.0227 (9)	0.0010 (10)
O2	0.0671 (14)	0.130 (2)	0.0306 (10)	0.0288 (13)	0.0030 (10)	−0.0046 (11)
O3	0.0834 (18)	0.113 (2)	0.131 (2)	−0.0468 (17)	0.0617 (18)	−0.0550 (19)
O4	0.0931 (18)	0.104 (2)	0.0715 (15)	0.0555 (16)	0.0351 (13)	0.0270 (14)
N1	0.0368 (11)	0.0494 (13)	0.0384 (12)	0.0039 (9)	0.0062 (9)	−0.0011 (9)
N2	0.0480 (13)	0.0514 (14)	0.0446 (13)	0.0025 (10)	0.0122 (10)	−0.0014 (10)
N3	0.0355 (11)	0.0474 (13)	0.0411 (12)	−0.0035 (9)	0.0092 (9)	−0.0011 (9)
N4	0.0413 (12)	0.0460 (13)	0.0501 (13)	0.0009 (10)	0.0171 (10)	−0.0014 (10)
C1	0.0470 (16)	0.074 (2)	0.0370 (14)	0.0145 (14)	0.0102 (12)	−0.0046 (13)
C2	0.0435 (16)	0.096 (2)	0.0444 (16)	0.0218 (15)	0.0140 (13)	0.0004 (15)
C3	0.0346 (14)	0.076 (2)	0.0414 (15)	0.0014 (13)	0.0056 (11)	0.0057 (13)
C4	0.0451 (15)	0.072 (2)	0.0393 (14)	−0.0031 (14)	0.0083 (12)	−0.0132 (13)
C5	0.0340 (13)	0.0639 (18)	0.0467 (15)	0.0031 (12)	0.0113 (11)	−0.0137 (13)
C6	0.0418 (19)	0.183 (5)	0.059 (2)	0.005 (2)	−0.0025 (16)	−0.007 (2)
C7	0.0604 (18)	0.0611 (19)	0.0569 (18)	0.0072 (15)	0.0251 (15)	−0.0006 (14)
C8	0.099 (3)	0.055 (2)	0.081 (2)	0.0172 (19)	0.040 (2)	−0.0067 (17)
C9	0.105 (3)	0.0510 (19)	0.076 (2)	−0.0013 (19)	0.033 (2)	−0.0039 (17)
C10	0.075 (2)	0.058 (2)	0.064 (2)	−0.0127 (16)	0.0251 (17)	−0.0039 (15)
C11	0.0526 (17)	0.0557 (18)	0.0509 (17)	−0.0011 (13)	0.0153 (13)	−0.0062 (13)
C12	0.190 (6)	0.053 (2)	0.175 (5)	0.005 (3)	0.091 (5)	0.005 (3)
C13	0.0498 (15)	0.0516 (16)	0.0426 (15)	−0.0060 (12)	0.0053 (12)	0.0001 (12)
C14	0.077 (2)	0.0550 (18)	0.0525 (18)	−0.0102 (16)	0.0177 (16)	0.0036 (14)
C15	0.0604 (19)	0.0580 (19)	0.077 (2)	−0.0128 (15)	0.0322 (17)	−0.0038 (16)
C16	0.0366 (16)	0.081 (2)	0.088 (3)	−0.0143 (15)	0.0079 (15)	−0.001 (2)
C17	0.0380 (15)	0.070 (2)	0.0585 (18)	−0.0054 (13)	0.0019 (13)	0.0089 (15)
C18	0.101 (3)	0.089 (3)	0.132 (4)	−0.036 (3)	0.062 (3)	0.000 (3)
C19	0.0501 (16)	0.0513 (17)	0.0556 (17)	0.0051 (13)	0.0173 (13)	0.0028 (13)
C20	0.071 (2)	0.0539 (18)	0.0591 (18)	0.0036 (15)	0.0254 (16)	0.0075 (14)
C21	0.072 (2)	0.0558 (18)	0.0632 (19)	−0.0140 (15)	0.0328 (17)	−0.0090 (15)
C22	0.0589 (19)	0.074 (2)	0.061 (2)	−0.0203 (16)	0.0163 (15)	−0.0097 (16)
C23	0.0531 (17)	0.0617 (19)	0.0496 (16)	−0.0073 (14)	0.0142 (13)	−0.0017 (14)
C24	0.106 (3)	0.085 (3)	0.089 (3)	−0.037 (2)	0.044 (2)	−0.005 (2)

Geometric parameters (Å, º) top

Cd1—O1ⁱ	2.2822 (19)	C7—H7	0.9300
Cd1—O1	2.2822 (19)	C7—C8	1.378 (5)
Cd1—N1ⁱ	2.360 (2)	C8—H8	0.9300
Cd1—N1	2.360 (2)	C8—C9	1.371 (5)
Cd1—N2	2.342 (2)	C9—C10	1.372 (5)
Cd1—N2ⁱ	2.342 (2)	C9—C12	1.518 (6)
Cd2—O2ⁱⁱ	2.240 (2)	C10—H10	0.9300
Cd2—O2	2.240 (2)	C10—C11	1.375 (4)
Cd2—N3ⁱⁱ	2.358 (2)	C11—H11	0.9300
Cd2—N3	2.358 (2)	C12—H12A	0.9600
Cd2—N4	2.381 (2)	C12—H12B	0.9600
Cd2—N4ⁱⁱ	2.381 (2)	C12—H12C	0.9600
S1—O1	1.4745 (19)	C13—H13	0.9300
S1—O2	1.448 (2)	C13—C14	1.372 (4)
S1—O3	1.430 (3)	C14—H14	0.9300
S1—O4	1.429 (2)	C14—C15	1.368 (5)
N1—C1	1.336 (3)	C15—C16	1.369 (5)
N1—C5	1.329 (3)	C15—C18	1.514 (4)
N2—C7	1.330 (4)	C16—H16	0.9300
N2—C11	1.332 (4)	C16—C17	1.375 (4)
N3—C13	1.332 (3)	C17—H17	0.9300
N3—C17	1.330 (3)	C18—H18A	0.9600
N4—C19	1.332 (4)	C18—H18B	0.9600
N4—C23	1.332 (4)	C18—H18C	0.9600
C1—H1	0.9300	C19—H19	0.9300
C1—C2	1.367 (4)	C19—C20	1.378 (4)
C2—H2	0.9300	C20—H20	0.9300
C2—C3	1.382 (4)	C20—C21	1.378 (5)
C3—C4	1.370 (4)	C21—C22	1.377 (5)
C3—C6	1.493 (4)	C21—C24	1.510 (4)
C4—H4	0.9300	C22—H22	0.9300
C4—C5	1.365 (4)	C22—C23	1.374 (4)
C5—H5	0.9300	C23—H23	0.9300
C6—H6A	0.9600	C24—H24A	0.9600
C6—H6B	0.9600	C24—H24B	0.9600
C6—H6C	0.9600	C24—H24C	0.9600

O1ⁱ—Cd1—O1	180.0	C3—C6—H6C	109.5
O1—Cd1—N1	92.28 (7)	H6A—C6—H6B	109.5
O1ⁱ—Cd1—N1	87.72 (7)	H6A—C6—H6C	109.5
O1—Cd1—N1ⁱ	87.72 (7)	H6B—C6—H6C	109.5
O1ⁱ—Cd1—N1ⁱ	92.28 (7)	N2—C7—H7	118.7
O1ⁱ—Cd1—N2	92.23 (8)	N2—C7—C8	122.6 (3)
O1ⁱ—Cd1—N2ⁱ	87.77 (8)	C8—C7—H7	118.7
O1—Cd1—N2	87.77 (8)	C7—C8—H8	119.8
O1—Cd1—N2ⁱ	92.23 (8)	C9—C8—C7	120.4 (3)
N1—Cd1—N1ⁱ	180.0	C9—C8—H8	119.8
N2—Cd1—N1ⁱ	88.36 (8)	C8—C9—C10	116.8 (3)
N2ⁱ—Cd1—N1ⁱ	91.64 (8)	C8—C9—C12	122.2 (4)
N2—Cd1—N1	91.64 (8)	C10—C9—C12	121.0 (4)
N2ⁱ—Cd1—N1	88.36 (8)	C9—C10—H10	119.9
N2—Cd1—N2ⁱ	180.0	C9—C10—C11	120.2 (3)
O2ⁱⁱ—Cd2—O2	178.05 (15)	C11—C10—H10	119.9
O2ⁱⁱ—Cd2—N3ⁱⁱ	88.89 (9)	N2—C11—C10	122.8 (3)
O2ⁱⁱ—Cd2—N3	89.77 (8)	N2—C11—H11	118.6
O2—Cd2—N3ⁱⁱ	89.77 (8)	C10—C11—H11	118.6
O2—Cd2—N3	88.89 (9)	C9—C12—H12A	109.5
O2—Cd2—N4	94.95 (9)	C9—C12—H12B	109.5
O2—Cd2—N4ⁱⁱ	86.50 (8)	C9—C12—H12C	109.5
O2ⁱⁱ—Cd2—N4ⁱⁱ	94.95 (9)	H12A—C12—H12B	109.5
O2ⁱⁱ—Cd2—N4	86.50 (8)	H12A—C12—H12C	109.5
N3ⁱⁱ—Cd2—N3	92.71 (10)	H12B—C12—H12C	109.5
N3ⁱⁱ—Cd2—N4	91.81 (7)	N3—C13—H13	118.5
N3ⁱⁱ—Cd2—N4ⁱⁱ	174.08 (7)	N3—C13—C14	123.0 (3)
N3—Cd2—N4ⁱⁱ	91.81 (7)	C14—C13—H13	118.5
N3—Cd2—N4	174.08 (7)	C13—C14—H14	119.8
N4—Cd2—N4ⁱⁱ	83.95 (10)	C15—C14—C13	120.3 (3)
O2—S1—O1	108.14 (13)	C15—C14—H14	119.8
O3—S1—O1	108.78 (14)	C14—C15—C16	116.6 (3)
O3—S1—O2	108.82 (19)	C14—C15—C18	122.0 (4)
O4—S1—O1	110.40 (14)	C16—C15—C18	121.4 (3)
O4—S1—O2	109.08 (15)	C15—C16—H16	119.7
O4—S1—O3	111.6 (2)	C15—C16—C17	120.7 (3)
S1—O1—Cd1	150.80 (13)	C17—C16—H16	119.7
S1—O2—Cd2	163.96 (16)	N3—C17—C16	122.5 (3)
C1—N1—Cd1	128.14 (18)	N3—C17—H17	118.7
C5—N1—Cd1	115.61 (17)	C16—C17—H17	118.7
C5—N1—C1	116.2 (2)	C15—C18—H18A	109.5
C7—N2—Cd1	123.3 (2)	C15—C18—H18B	109.5
C7—N2—C11	117.2 (3)	C15—C18—H18C	109.5
C11—N2—Cd1	119.31 (18)	H18A—C18—H18B	109.5
C13—N3—Cd2	122.70 (17)	H18A—C18—H18C	109.5
C17—N3—Cd2	120.31 (18)	H18B—C18—H18C	109.5
C17—N3—C13	116.9 (2)	N4—C19—H19	118.5
C19—N4—Cd2	121.96 (19)	N4—C19—C20	122.9 (3)
C23—N4—Cd2	121.02 (19)	C20—C19—H19	118.5
C23—N4—C19	117.0 (2)	C19—C20—H20	120.0
N1—C1—H1	118.5	C21—C20—C19	120.0 (3)
N1—C1—C2	123.1 (3)	C21—C20—H20	120.0
C2—C1—H1	118.5	C20—C21—C24	122.3 (3)
C1—C2—H2	119.8	C22—C21—C20	116.8 (3)
C1—C2—C3	120.4 (3)	C22—C21—C24	120.9 (3)
C3—C2—H2	119.8	C21—C22—H22	120.0
C2—C3—C6	122.1 (3)	C23—C22—C21	120.0 (3)
C4—C3—C2	116.2 (3)	C23—C22—H22	120.0
C4—C3—C6	121.7 (3)	N4—C23—C22	123.2 (3)
C3—C4—H4	119.8	N4—C23—H23	118.4
C5—C4—C3	120.3 (3)	C22—C23—H23	118.4
C5—C4—H4	119.8	C21—C24—H24A	109.5
N1—C5—C4	123.8 (2)	C21—C24—H24B	109.5
N1—C5—H5	118.1	C21—C24—H24C	109.5
C4—C5—H5	118.1	H24A—C24—H24B	109.5
C3—C6—H6A	109.5	H24A—C24—H24C	109.5
C3—C6—H6B	109.5	H24B—C24—H24C	109.5

Cd1—N1—C1—C2	177.6 (2)	C5—N1—C1—C2	−0.3 (5)
Cd1—N1—C5—C4	−177.2 (2)	C6—C3—C4—C5	−179.7 (3)
Cd1—N2—C7—C8	174.8 (3)	C7—N2—C11—C10	0.0 (4)
Cd1—N2—C11—C10	−176.2 (2)	C7—C8—C9—C10	0.8 (6)
Cd2—N3—C13—C14	−176.0 (2)	C7—C8—C9—C12	−180.0 (4)
Cd2—N3—C17—C16	175.6 (3)	C8—C9—C10—C11	−2.1 (6)
Cd2—N4—C19—C20	176.3 (2)	C9—C10—C11—N2	1.7 (5)
Cd2—N4—C23—C22	−175.9 (2)	C11—N2—C7—C8	−1.2 (5)
O1—S1—O2—Cd2	−8.4 (7)	C12—C9—C10—C11	178.7 (4)
O2—S1—O1—Cd1	−172.5 (3)	C13—N3—C17—C16	−1.3 (5)
O3—S1—O1—Cd1	−54.5 (3)	C13—C14—C15—C16	−1.1 (5)
O3—S1—O2—Cd2	−126.4 (7)	C13—C14—C15—C18	179.0 (3)
O4—S1—O1—Cd1	68.2 (3)	C14—C15—C16—C17	0.6 (5)
O4—S1—O2—Cd2	111.7 (7)	C15—C16—C17—N3	0.6 (5)
N1—C1—C2—C3	−0.1 (5)	C17—N3—C13—C14	0.8 (4)
N2—C7—C8—C9	0.9 (6)	C18—C15—C16—C17	−179.5 (4)
N3—C13—C14—C15	0.4 (5)	C19—N4—C23—C22	1.9 (4)
N4—C19—C20—C21	−0.1 (5)	C19—C20—C21—C22	1.4 (5)
C1—N1—C5—C4	1.0 (4)	C19—C20—C21—C24	−177.4 (3)
C1—C2—C3—C4	−0.2 (5)	C20—C21—C22—C23	−1.1 (5)
C1—C2—C3—C6	−179.6 (4)	C21—C22—C23—N4	−0.6 (5)
C2—C3—C4—C5	0.8 (5)	C23—N4—C19—C20	−1.6 (4)
C3—C4—C5—N1	−1.3 (5)	C24—C21—C22—C23	177.8 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O4	0.93	2.56	3.471 (4)	167
C5—H5···O1ⁱ	0.93	2.42	3.097 (3)	130
C7—H7···O4	0.93	2.54	3.452 (4)	167
C11—H11···O3ⁱ	0.93	2.45	3.360 (4)	164
C17—H17···O2	0.93	2.57	3.205 (4)	126
C23—H23···O2ⁱⁱ	0.93	2.49	3.136 (4)	127

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

Synthetic conditions for the isolation of crystals of compounds (1)–(7) top

Compound	Salt	mg of Salt	H₂O (ml)	4-Picoline (ml)	T (°C)
(1)	Fe(SO₄)·7H₂O	8.8	0.0	2.0	90
(2)	Co(SO₄)·7H₂O	4.8	0.2	2.0	85
(3)	Ni(SO₄)·6H₂O	3.7	0.2	2.0	90
(4)	Cu(SO₄) anhydrous	11.6	0.2	3.0	90
(5)	Zn(SO₄)·7H₂O	9.8	0.1	2.0	50
(6)	Zn(SO₄)·7H₂O	23.0	0.0	2.0	60
(7)	Cd(SO₄)·8/3H₂O	9.8	0.0	1.5	80

Geometric parameters (Å, °) for the reported complexes top

	M = Fe, (1)		M = Co, (2)		M = Ni, (3)	M = Cd, (7)
M—O	Fe1—O1	2.056 (1)		Co1—O1	2.090 (1)	Ni1—O1	2.098 (1)	Cd1—O1	2.282 (2)
	Fe2—O2	2.025 (1)		Co2—O2	2.053 (1)	Ni2—O2	2.058 (1)	Cd2—O2	2.240 (2)
M—N	Fe1—N1	2.229 (2)		Co1—N1	2.174 (2)	Ni1—N1	2.119 (2)	Cd1—N1	2.360 (2)
	Fe1—N2	2.240 (2)		Co1—N2	2.187 (2)	Ni1—N2	2.132 (2)	Cd1—N2	2.343 (2)
	Fe2—N3	2.242 (2)		Co2—N3	2.187 (2)	Ni2—N3	2.154 (2)	Cd2—N3	2.358 (2)
	Fe2—N4	2.257 (2)		Co2—N4	2.208 (2)	Ni2—N4	2.131 (2)	Cd2—N4	2.381 (2)
O—M—O	O1—Fe1—O1ⁱ	180.0		O1—Co1—O1ⁱ	180.0	O1—Ni1—O1ⁱ	180.0	O1—Cd1—O1ⁱ	180.0
	O2—Fe2—O2ⁱⁱ	178.03 (9)		O2—Co2—O2ⁱⁱⁱ	177.5 (1)	O2—Ni2—O2ⁱⁱ	180.0	O2—Cd2—O2ⁱⁱⁱ	178.1 (2)
N—M—N	N1—Fe1—N2	92.13 (6)		N1—Co1—N2	92.27 (7)	N1—Ni1—N2	91.99 (7)	N1—Cd1—N2	91.64 (8)
	N1—Fe1—N2ⁱ	87.87 (6)		N1—Co1—N2ⁱ	87.73 (7)	N1—Ni1—N2ⁱ	88.01 (7)	N1—Cd1—N2ⁱ	88.36 (8)
	N1—Fe1—N1ⁱ	180.0		N1—Co1—N1ⁱ	180.0	N1—Ni1—N1ⁱ	180.00 (9)	N1—Cd1—N1ⁱ	180.0
	N2—Fe1—N2ⁱ	180.0		N2—Co1—N2ⁱ	180.0	N2—Ni1—N2ⁱ	180.0	N2—Cd1—N2ⁱ	180.0
	N3—Fe2—N3ⁱⁱ	92.81 (5)		N3—Co2—N3ⁱⁱⁱ	90.57 (9)	N3—Ni2—N3ⁱⁱ	85.30 (9)	N3—Cd2—N3ⁱⁱⁱ	92.7 (1)
	N3—Fe2—N4ⁱⁱ	90.47 (8)		N3—Co2—N4ⁱⁱⁱ	92.58 (6)	N3—Ni2—N4ⁱⁱ	92.02 (6)	N3—Cd2—N4ⁱⁱⁱ	91.81 (7)
	N4—Fe2—N4ⁱⁱ	84.16 (8)		N4—Co2—N4ⁱⁱⁱ	84.47 (9)	N4—Ni2—N4ⁱⁱ	90.81 (9)	N4—Cd2—N4ⁱⁱⁱ	84.0 (1)
	N3—Fe2—N4	175.09 (5)		N3—Co2—N4	175.43 (6)	N3—Ni2—N4	175.91 (6)	N3—Cd2—N4	174.08 (7)
	M = Cu, (4)		M = Zn, (5)		M = Zn, (6)
M—O	Cu1—O1	1.985 (1)		Zn1—O1	1.915 (2)	Zn1—O1	1.972 (2)
	Cu1—O1ⁱ	2.253 (1)		Zn1—O4^iv	1.941 (2)	Zn1—O4^v	1.989 (2)
M—N	Cu1—N1	2.041 (2)		Zn1—N1	2.043 (2)	Zn1—N1	2.083 (3)
	Cu1—N2	2.011 (2)		Zn1—N2	2.005 (2)	Zn1—N2	2.172 (3)
	Cu1—N3	2.024 (2)				Zn1—N3	2.265 (3)
O—M—O	O1—Cu1—O1ⁱ	79.94 (6)		O1—Zn1—O4^iv	102.86 (8)	O1—Zn1—O4^v	101.9 (1)
N—M—N	N1—Cu1—N2	88.00 (7)		N1—Zn1—N2	113.43 (9)	N1—Zn1—N2	91.1 (1)
	N1—Cu1—N3	172.28 (7)				N1—Zn1—N3	84.2 (1)
	N2—Cu1—N3	87.12 (7)				N2—Zn1—N3	172.5 (1)

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

Crystal field stabilization energy [units are Dq (O_h)] top

Observed geometries are highlighted in bold.

	Tetrahedral	Trigonal bipyramidal	Square pyramidal	Octahedral
Iron (d⁶)	2.67	2.73	4.57	4
Cobalt (d⁷)	5.34	5.45	9.14	8
Nickel (d⁸)	3.56	6.27	10	12
Copper (d⁹)	1.78	7.09	9.14	6
Zinc (d¹⁰)	0	0	0	0
Cadmium (d¹⁰)	0	0	0	0

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