Topological study of diverse hydrogen-bonded patterns found in a system of a nickel(II) complex and the sulfate anion

Harvey, M.A.; Suarez, S.; Zolotarev, P.N.; Proserpio, D.M.; Baggio, R.

doi:10.1107/S2053229618002413

Buy article online - an online subscription or single-article purchase is required to access this article.

Topological study of diverse hydrogen-bonded patterns found in a system of a nickel(II) complex and the sulfate anion

M. A. Harvey, S. Suarez, P. N. Zolotarev, D. M. Proserpio and R. Baggio

A nickel(II) coordination complex, bis[2,6-bis(1H-benzimidazol-2-yl-κN³)pyridine-κN]nickel(II) sulfate, [Ni(C₁₉H₁₃N₅)₂]SO₄ or [Ni(H₂L)₂]SO₄, having four peripheral tetrahedrally oriented N—H donor units, combines with sulfate bridges to create hydrogen-bonded structures of varied dimensionality. The three crystal structures reported herein in the space groups P2₁2₁2₁, I $\overline{4}$ and Pccn are defined solely by strong charge-assisted N—H

O hydrogen bonds and contain disordered guests (water and dimethylformamide) that vary in size, shape and degree of hydrophilicity. Two of the compounds are channelled solids with three-dimensional structures, while the third is one-dimensional in nature. In spite of their differences, all three present a striking resemblance to the previously reported anhydrous relative [Guo et al. (2011). Chin. J. Inorg. Chem. 27, 1517–1520], which is considered as the reference framework from which all three title compounds are derived. The hydrogen-bonded frameworks are described and compared using crystallographic and topological approaches.

Keywords: hydrogen-bonded porous structures; crystal structure; sulfate bridge; topological analysis.

Read article Similar articles

Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229618002413/sk3681sup1.cif Contains datablocks I, II, III, global
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229618002413/sk3681Isup2.hkl Contains datablock I
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229618002413/sk3681IIsup3.hkl Contains datablock II
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229618002413/sk3681IIIsup4.hkl Contains datablock III
	Portable Document Format (PDF) file https://doi.org/10.1107/S2053229618002413/sk3681sup5.pdf Document SD1 and Figure S1
	Microsoft Excel (XLSX) file https://doi.org/10.1107/S2053229618002413/sk3681sup6.xlsx Tables S1-S5

CCDC references: 1823175; 1823174; 1823173

Computing details top

For all structures, data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).

Bis[2,6-bis(1H-benzimidazol-2-yl-κN³)pyridine-κN]nickel(II) sulfate (I) top

Crystal data top

[Ni(C₁₉H₁₃N₅)₂]SO₄	D_x = 1.158 Mg m⁻³
M_r = 777.46	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 4887 reflections
a = 9.8015 (6) Å	θ = 3.8–28.1°
b = 20.9572 (15) Å	µ = 0.53 mm⁻¹
c = 21.7012 (17) Å	T = 294 K
V = 4457.7 (5) Å³	Needle, light_red
Z = 4	0.50 × 0.24 × 0.18 mm
F(000) = 1600

Data collection top

Oxford Diffraction Gemini CCD S Ultra diffractometer	9840 independent reflections
Radiation source: fine-focus sealed tube	5651 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.085
ω scans, thick slices	θ_max = 28.9°, θ_min = 3.6°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	h = −12→11
T_min = 0.82, T_max = 0.92	k = −26→28
19326 measured reflections	l = −26→28

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.074	w = 1/[σ²(F_o²) + (0.0908P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.210	(Δ/σ)_max < 0.001
S = 0.98	Δρ_max = 0.47 e Å⁻³
9840 reflections	Δρ_min = −0.31 e Å⁻³
487 parameters	Absolute structure: Flack x determined using 1523 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
586 restraints	Absolute structure parameter: 0.006 (19)

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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

	x	y	z	U_iso*/U_eq
Ni1	0.88293 (9)	0.08567 (5)	0.84243 (4)	0.0392 (3)
N1A	0.6872 (5)	0.0444 (3)	0.8476 (3)	0.0448 (15)
N2A	0.8989 (5)	0.0117 (3)	0.7826 (3)	0.0424 (14)
N3A	1.0826 (5)	0.0964 (3)	0.8072 (3)	0.0439 (14)
N4A	0.5513 (6)	−0.0333 (3)	0.8142 (3)	0.0555 (18)
H4NA	0.523803	−0.066115	0.793923	0.067*
N5A	1.2442 (6)	0.0573 (3)	0.7459 (3)	0.0508 (17)
H5NA	1.285383	0.031955	0.720939	0.061*
C1A	0.5640 (7)	0.0489 (4)	0.8785 (4)	0.0469 (18)
C2A	0.5188 (8)	0.0932 (4)	0.9213 (4)	0.061 (2)
H2AA	0.572642	0.126997	0.934752	0.074*
C3A	0.3880 (8)	0.0832 (5)	0.9424 (5)	0.080 (3)
H3AA	0.353593	0.111188	0.971828	0.096*
C4A	0.3063 (9)	0.0350 (5)	0.9228 (5)	0.075 (3)
H4AA	0.219539	0.030882	0.939718	0.090*
C5A	0.3475 (7)	−0.0071 (5)	0.8795 (4)	0.066 (2)
H5AA	0.290457	−0.039530	0.865700	0.079*
C6A	0.4781 (7)	0.0003 (4)	0.8567 (4)	0.0482 (18)
C7A	0.6749 (7)	−0.0053 (3)	0.8099 (3)	0.0461 (19)
C8A	0.7926 (7)	−0.0270 (4)	0.7752 (4)	0.052 (2)
C9A	0.8036 (8)	−0.0816 (5)	0.7394 (5)	0.076 (3)
H9AA	0.728977	−0.108296	0.733392	0.091*
C10A	0.9262 (9)	−0.0949 (5)	0.7132 (5)	0.090 (4)
H10A	0.935425	−0.131541	0.689406	0.108*
C11A	1.0384 (9)	−0.0550 (4)	0.7212 (5)	0.072 (3)
H11A	1.122472	−0.064533	0.703554	0.086*
C12A	1.0199 (6)	−0.0005 (3)	0.7564 (4)	0.0457 (18)
C13A	1.1186 (7)	0.0496 (3)	0.7702 (3)	0.0435 (16)
C14A	1.2933 (7)	0.1143 (3)	0.7692 (4)	0.0482 (18)
C15A	1.4155 (8)	0.1466 (4)	0.7584 (5)	0.067 (3)
H15A	1.483524	0.129796	0.733345	0.081*
C16A	1.4288 (9)	0.2035 (5)	0.7866 (5)	0.076 (3)
H16A	1.508808	0.226567	0.780600	0.092*
C17A	1.3282 (8)	0.2293 (4)	0.8244 (5)	0.071 (3)
H17A	1.342304	0.269074	0.842373	0.086*
C18A	1.2091 (8)	0.1975 (4)	0.8356 (5)	0.061 (2)
H18A	1.141536	0.214640	0.860656	0.073*
C19A	1.1936 (7)	0.1381 (3)	0.8076 (4)	0.0469 (18)
N1B	0.8202 (6)	0.1655 (3)	0.7902 (3)	0.0430 (15)
N2B	0.8719 (6)	0.1553 (2)	0.9068 (2)	0.0371 (13)
N3B	0.9392 (6)	0.0370 (2)	0.9242 (3)	0.0411 (14)
N4B	0.7729 (6)	0.2694 (3)	0.7912 (3)	0.0458 (15)
H4NB	0.760629	0.307484	0.804941	0.055*
N5B	0.9636 (7)	0.0440 (3)	1.0261 (3)	0.0473 (15)
H5NB	0.965944	0.060504	1.062391	0.057*
C1B	0.7895 (7)	0.1843 (3)	0.7306 (3)	0.0454 (17)
C2B	0.7839 (10)	0.1499 (4)	0.6764 (3)	0.065 (2)
H2BA	0.804359	0.106636	0.674822	0.078*
C3B	0.7462 (11)	0.1837 (5)	0.6247 (4)	0.075 (3)
H3BA	0.740590	0.162069	0.587424	0.090*
C4B	0.7168 (11)	0.2469 (5)	0.6253 (4)	0.075 (3)
H4BA	0.690994	0.266911	0.588882	0.090*
C5B	0.7242 (10)	0.2814 (4)	0.6777 (4)	0.067 (3)
H5BA	0.704945	0.324872	0.677771	0.080*
C6B	0.7615 (8)	0.2499 (3)	0.7314 (3)	0.0460 (17)
C7B	0.8070 (8)	0.2178 (3)	0.8246 (3)	0.0411 (16)
C8B	0.8339 (9)	0.2138 (3)	0.8902 (3)	0.0477 (19)
C9B	0.8197 (15)	0.2618 (4)	0.9337 (4)	0.099 (4)
H9BA	0.792888	0.302607	0.922180	0.118*
C10B	0.8460 (17)	0.2477 (5)	0.9936 (4)	0.123 (6)
H10B	0.831651	0.278571	1.023653	0.148*
C11B	0.8940 (15)	0.1877 (4)	1.0108 (4)	0.099 (4)
H11B	0.920952	0.179170	1.051076	0.119*
C12B	0.8998 (9)	0.1412 (3)	0.9654 (3)	0.050 (2)
C13B	0.9343 (7)	0.0740 (3)	0.9728 (3)	0.0408 (15)
C14B	0.9891 (8)	−0.0188 (3)	1.0106 (3)	0.0447 (17)
C15B	1.0240 (9)	−0.0708 (3)	1.0469 (4)	0.064 (2)
H15B	1.034589	−0.067328	1.089340	0.077*
C16B	1.0417 (11)	−0.1266 (4)	1.0173 (5)	0.079 (3)
H16B	1.063909	−0.162706	1.040103	0.095*
C17B	1.0280 (11)	−0.1322 (4)	0.9537 (5)	0.077 (3)
H17B	1.043347	−0.171601	0.935233	0.093*
C18B	0.9925 (9)	−0.0814 (4)	0.9179 (4)	0.062 (2)
H18B	0.980261	−0.085581	0.875547	0.074*
C19B	0.9754 (8)	−0.0230 (3)	0.9475 (3)	0.0464 (18)
S1	1.0813 (2)	0.09127 (10)	1.17397 (10)	0.0506 (5)
O1	1.1035 (7)	0.0222 (3)	1.1762 (3)	0.0732 (19)
O2	1.0534 (7)	0.1175 (3)	1.2361 (3)	0.0677 (18)
O3	0.9641 (6)	0.1041 (3)	1.1343 (3)	0.0707 (19)
O4	1.2034 (6)	0.1228 (3)	1.1497 (3)	0.0699 (18)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0392 (5)	0.0372 (5)	0.0412 (5)	−0.0011 (5)	0.0003 (4)	−0.0053 (5)
N1A	0.043 (3)	0.043 (3)	0.048 (4)	−0.001 (3)	0.002 (3)	−0.009 (3)
N2A	0.041 (3)	0.038 (3)	0.048 (4)	−0.002 (2)	0.005 (2)	−0.010 (3)
N3A	0.042 (3)	0.044 (3)	0.046 (3)	−0.004 (2)	0.004 (2)	−0.006 (3)
N4A	0.053 (3)	0.050 (4)	0.064 (4)	−0.016 (3)	0.005 (3)	−0.012 (4)
N5A	0.046 (3)	0.054 (3)	0.053 (4)	−0.003 (3)	0.014 (3)	−0.006 (3)
C1A	0.039 (3)	0.047 (4)	0.055 (4)	0.003 (3)	0.000 (3)	0.000 (3)
C2A	0.053 (4)	0.053 (4)	0.078 (6)	−0.004 (4)	0.017 (4)	−0.012 (4)
C3A	0.057 (4)	0.073 (5)	0.109 (8)	−0.003 (4)	0.029 (4)	−0.007 (6)
C4A	0.056 (5)	0.076 (5)	0.093 (7)	−0.007 (4)	0.021 (5)	0.005 (5)
C5A	0.045 (4)	0.076 (6)	0.077 (6)	−0.009 (4)	0.002 (4)	0.005 (5)
C6A	0.044 (3)	0.048 (4)	0.053 (5)	−0.001 (3)	−0.002 (3)	0.005 (3)
C7A	0.046 (3)	0.045 (4)	0.048 (4)	−0.009 (3)	0.004 (3)	−0.008 (3)
C8A	0.049 (3)	0.051 (4)	0.056 (5)	−0.013 (3)	0.008 (3)	−0.016 (4)
C9A	0.072 (5)	0.069 (5)	0.088 (7)	−0.021 (5)	0.015 (5)	−0.041 (5)
C10A	0.086 (5)	0.066 (6)	0.118 (9)	−0.016 (4)	0.032 (5)	−0.053 (7)
C11A	0.072 (5)	0.060 (4)	0.083 (7)	−0.006 (4)	0.025 (5)	−0.029 (5)
C12A	0.044 (3)	0.046 (3)	0.047 (5)	−0.001 (3)	0.008 (3)	−0.008 (3)
C13A	0.042 (3)	0.044 (3)	0.044 (4)	−0.001 (3)	0.008 (3)	−0.003 (3)
C14A	0.046 (3)	0.050 (3)	0.049 (5)	−0.003 (3)	−0.001 (3)	0.006 (3)
C15A	0.055 (4)	0.074 (5)	0.073 (6)	−0.017 (4)	0.008 (4)	0.004 (5)
C16A	0.058 (5)	0.083 (5)	0.088 (7)	−0.027 (4)	0.005 (4)	−0.006 (5)
C17A	0.066 (4)	0.069 (6)	0.079 (7)	−0.024 (4)	0.001 (4)	−0.008 (5)
C18A	0.058 (4)	0.056 (4)	0.068 (6)	−0.013 (3)	0.004 (4)	−0.011 (4)
C19A	0.045 (3)	0.048 (3)	0.048 (4)	−0.007 (3)	−0.002 (3)	0.002 (3)
N1B	0.049 (4)	0.039 (3)	0.041 (3)	−0.001 (3)	−0.003 (3)	−0.004 (2)
N2B	0.038 (3)	0.035 (2)	0.038 (3)	0.001 (3)	−0.002 (3)	0.000 (2)
N3B	0.040 (3)	0.035 (2)	0.048 (3)	0.001 (3)	0.000 (3)	−0.004 (2)
N4B	0.048 (4)	0.046 (3)	0.044 (3)	0.006 (3)	−0.003 (3)	0.007 (3)
N5B	0.053 (4)	0.040 (3)	0.049 (3)	−0.001 (3)	−0.006 (3)	0.000 (3)
C1B	0.040 (4)	0.055 (3)	0.041 (3)	−0.001 (3)	−0.001 (3)	0.002 (3)
C2B	0.081 (6)	0.068 (5)	0.045 (3)	0.011 (5)	−0.005 (4)	−0.006 (3)
C3B	0.094 (7)	0.092 (5)	0.039 (4)	0.011 (5)	−0.011 (5)	−0.004 (4)
C4B	0.087 (7)	0.093 (5)	0.045 (4)	0.013 (5)	0.002 (5)	0.010 (4)
C5B	0.080 (6)	0.076 (6)	0.044 (3)	0.018 (5)	0.003 (4)	0.017 (4)
C6B	0.042 (4)	0.056 (3)	0.040 (3)	0.003 (3)	0.005 (3)	0.009 (3)
C7B	0.048 (4)	0.036 (3)	0.039 (3)	0.002 (3)	−0.003 (3)	0.000 (2)
C8B	0.069 (5)	0.034 (3)	0.040 (3)	0.006 (3)	−0.007 (3)	0.000 (3)
C9B	0.198 (13)	0.047 (5)	0.051 (4)	0.037 (7)	−0.033 (6)	−0.012 (4)
C10B	0.261 (17)	0.057 (5)	0.051 (4)	0.051 (8)	−0.040 (7)	−0.017 (5)
C11B	0.198 (12)	0.053 (4)	0.045 (5)	0.032 (6)	−0.033 (7)	−0.012 (4)
C12B	0.072 (5)	0.041 (3)	0.039 (3)	0.008 (4)	−0.008 (3)	−0.002 (3)
C13B	0.040 (4)	0.037 (3)	0.046 (3)	0.000 (3)	−0.004 (3)	−0.004 (2)
C14B	0.042 (4)	0.038 (3)	0.055 (3)	−0.003 (3)	−0.003 (3)	0.004 (3)
C15B	0.076 (6)	0.047 (4)	0.068 (5)	0.007 (4)	−0.001 (5)	0.015 (3)
C16B	0.096 (7)	0.047 (4)	0.096 (5)	0.015 (5)	0.002 (6)	0.010 (5)
C17B	0.095 (7)	0.039 (4)	0.098 (5)	0.009 (5)	0.001 (6)	0.000 (4)
C18B	0.070 (5)	0.040 (3)	0.075 (5)	0.001 (4)	−0.004 (4)	−0.010 (3)
C19B	0.047 (4)	0.036 (3)	0.056 (4)	−0.001 (3)	−0.005 (3)	−0.002 (3)
S1	0.0652 (13)	0.0423 (10)	0.0444 (11)	−0.0060 (11)	−0.0112 (9)	0.0104 (11)
O1	0.086 (4)	0.039 (3)	0.094 (5)	−0.008 (3)	−0.038 (4)	0.012 (3)
O2	0.096 (4)	0.070 (4)	0.037 (3)	−0.033 (4)	0.001 (3)	0.004 (3)
O3	0.072 (4)	0.083 (5)	0.057 (4)	0.014 (4)	−0.025 (3)	0.002 (4)
O4	0.076 (4)	0.055 (3)	0.079 (5)	−0.019 (3)	0.015 (4)	0.003 (4)

Geometric parameters (Å, º) top

Ni1—N2B	2.022 (5)	C18A—H18A	0.9300
Ni1—N2A	2.029 (5)	N1B—C7B	1.333 (7)
Ni1—N1A	2.108 (5)	N1B—C1B	1.384 (8)
Ni1—N1B	2.112 (6)	N2B—C8B	1.330 (7)
Ni1—N3A	2.113 (5)	N2B—C12B	1.335 (7)
Ni1—N3B	2.120 (6)	N3B—C13B	1.311 (7)
N1A—C7A	1.328 (7)	N3B—C19B	1.400 (7)
N1A—C1A	1.385 (8)	N4B—C7B	1.345 (7)
N2A—C8A	1.330 (7)	N4B—C6B	1.366 (8)
N2A—C12A	1.339 (7)	N4B—H4NB	0.8600
N3A—C13A	1.315 (7)	N5B—C13B	1.350 (7)
N3A—C19A	1.396 (7)	N5B—C14B	1.381 (7)
N4A—C7A	1.349 (7)	N5B—H5NB	0.8600
N4A—C6A	1.364 (8)	C1B—C2B	1.381 (9)
N4A—H4NA	0.8600	C1B—C6B	1.403 (9)
N5A—C13A	1.349 (7)	C2B—C3B	1.377 (9)
N5A—C14A	1.382 (7)	C2B—H2BA	0.9300
N5A—H5NA	0.8600	C3B—C4B	1.355 (11)
C1A—C2A	1.385 (9)	C3B—H3BA	0.9300
C1A—C6A	1.403 (9)	C4B—C5B	1.348 (11)
C2A—C3A	1.378 (9)	C4B—H4BA	0.9300
C2A—H2AA	0.9300	C5B—C6B	1.389 (9)
C3A—C4A	1.357 (11)	C5B—H5BA	0.9300
C3A—H3AA	0.9300	C7B—C8B	1.450 (9)
C4A—C5A	1.351 (10)	C8B—C9B	1.387 (9)
C4A—H4AA	0.9300	C9B—C10B	1.357 (11)
C5A—C6A	1.382 (9)	C9B—H9BA	0.9300
C5A—H5AA	0.9300	C10B—C11B	1.393 (10)
C7A—C8A	1.451 (9)	C10B—H10B	0.9300
C8A—C9A	1.388 (9)	C11B—C12B	1.387 (9)
C9A—C10A	1.358 (10)	C11B—H11B	0.9300
C9A—H9AA	0.9300	C12B—C13B	1.456 (8)
C10A—C11A	1.393 (10)	C14B—C19B	1.380 (9)
C10A—H10A	0.9300	C14B—C15B	1.387 (8)
C11A—C12A	1.387 (9)	C15B—C16B	1.345 (10)
C11A—H11A	0.9300	C15B—H15B	0.9300
C12A—C13A	1.458 (8)	C16B—C17B	1.390 (11)
C14A—C19A	1.378 (9)	C16B—H16B	0.9300
C14A—C15A	1.394 (8)	C17B—C18B	1.364 (9)
C15A—C16A	1.348 (10)	C17B—H17B	0.9300
C15A—H15A	0.9300	C18B—C19B	1.393 (9)
C16A—C17A	1.392 (10)	C18B—H18B	0.9300
C16A—H16A	0.9300	S1—O3	1.461 (6)
C17A—C18A	1.367 (9)	S1—O1	1.464 (6)
C17A—H17A	0.9300	S1—O4	1.465 (6)
C18A—C19A	1.393 (8)	S1—O2	1.481 (6)

N2B—Ni1—N2A	176.0 (2)	C19A—C18A—H18A	121.5
N2B—Ni1—N1A	102.2 (2)	C14A—C19A—C18A	120.6 (6)
N2A—Ni1—N1A	77.9 (2)	C14A—C19A—N3A	108.8 (6)
N2B—Ni1—N1B	77.5 (2)	C18A—C19A—N3A	130.3 (6)
N2A—Ni1—N1B	106.5 (2)	C7B—N1B—C1B	105.6 (5)
N1A—Ni1—N1B	95.1 (3)	C7B—N1B—Ni1	112.2 (4)
N2B—Ni1—N3A	102.9 (2)	C1B—N1B—Ni1	142.2 (5)
N2A—Ni1—N3A	77.2 (2)	C8B—N2B—C12B	121.3 (6)
N1A—Ni1—N3A	154.9 (2)	C8B—N2B—Ni1	119.5 (4)
N1B—Ni1—N3A	89.5 (3)	C12B—N2B—Ni1	119.2 (4)
N2B—Ni1—N3B	77.5 (2)	C13B—N3B—C19B	104.5 (5)
N2A—Ni1—N3B	98.5 (2)	C13B—N3B—Ni1	112.2 (4)
N1A—Ni1—N3B	89.7 (3)	C19B—N3B—Ni1	143.2 (5)
N1B—Ni1—N3B	155.0 (2)	C7B—N4B—C6B	107.0 (5)
N3A—Ni1—N3B	96.5 (2)	C7B—N4B—H4NB	126.5
C7A—N1A—C1A	105.8 (5)	C6B—N4B—H4NB	126.5
C7A—N1A—Ni1	111.8 (4)	C13B—N5B—C14B	105.9 (6)
C1A—N1A—Ni1	142.3 (5)	C13B—N5B—H5NB	127.0
C8A—N2A—C12A	121.8 (5)	C14B—N5B—H5NB	127.0
C8A—N2A—Ni1	118.8 (4)	C2B—C1B—N1B	131.0 (7)
C12A—N2A—Ni1	119.0 (4)	C2B—C1B—C6B	120.9 (6)
C13A—N3A—C19A	105.1 (5)	N1B—C1B—C6B	108.1 (6)
C13A—N3A—Ni1	113.0 (4)	C3B—C2B—C1B	115.9 (7)
C19A—N3A—Ni1	141.8 (4)	C3B—C2B—H2BA	122.0
C7A—N4A—C6A	107.1 (5)	C1B—C2B—H2BA	122.0
C7A—N4A—H4NA	126.5	C4B—C3B—C2B	123.5 (8)
C6A—N4A—H4NA	126.5	C4B—C3B—H3BA	118.2
C13A—N5A—C14A	106.2 (6)	C2B—C3B—H3BA	118.2
C13A—N5A—H5NA	126.9	C5B—C4B—C3B	121.4 (8)
C14A—N5A—H5NA	126.9	C5B—C4B—H4BA	119.3
C2A—C1A—N1A	130.5 (6)	C3B—C4B—H4BA	119.3
C2A—C1A—C6A	121.4 (6)	C4B—C5B—C6B	117.8 (8)
N1A—C1A—C6A	108.0 (6)	C4B—C5B—H5BA	121.1
C3A—C2A—C1A	114.7 (7)	C6B—C5B—H5BA	121.1
C3A—C2A—H2AA	122.6	N4B—C6B—C5B	132.6 (7)
C1A—C2A—H2AA	122.6	N4B—C6B—C1B	106.8 (6)
C4A—C3A—C2A	123.9 (8)	C5B—C6B—C1B	120.5 (7)
C4A—C3A—H3AA	118.0	N1B—C7B—N4B	112.6 (5)
C2A—C3A—H3AA	118.0	N1B—C7B—C8B	119.0 (6)
C5A—C4A—C3A	121.8 (8)	N4B—C7B—C8B	128.4 (6)
C5A—C4A—H4AA	119.1	N2B—C8B—C9B	120.8 (6)
C3A—C4A—H4AA	119.1	N2B—C8B—C7B	111.7 (6)
C4A—C5A—C6A	116.9 (8)	C9B—C8B—C7B	127.5 (6)
C4A—C5A—H5AA	121.5	C10B—C9B—C8B	118.4 (7)
C6A—C5A—H5AA	121.5	C10B—C9B—H9BA	120.8
N4A—C6A—C5A	132.2 (7)	C8B—C9B—H9BA	120.8
N4A—C6A—C1A	106.7 (6)	C9B—C10B—C11B	121.2 (8)
C5A—C6A—C1A	121.1 (7)	C9B—C10B—H10B	119.4
N1A—C7A—N4A	112.3 (5)	C11B—C10B—H10B	119.4
N1A—C7A—C8A	119.5 (6)	C12B—C11B—C10B	117.2 (7)
N4A—C7A—C8A	127.8 (6)	C12B—C11B—H11B	121.4
N2A—C8A—C9A	120.6 (6)	C10B—C11B—H11B	121.4
N2A—C8A—C7A	111.7 (6)	N2B—C12B—C11B	120.9 (6)
C9A—C8A—C7A	127.7 (6)	N2B—C12B—C13B	111.5 (5)
C10A—C9A—C8A	118.2 (7)	C11B—C12B—C13B	127.6 (6)
C10A—C9A—H9AA	120.9	N3B—C13B—N5B	114.0 (5)
C8A—C9A—H9AA	120.9	N3B—C13B—C12B	119.5 (6)
C9A—C10A—C11A	121.6 (7)	N5B—C13B—C12B	126.5 (6)
C9A—C10A—H10A	119.2	C19B—C14B—N5B	106.5 (6)
C11A—C10A—H10A	119.2	C19B—C14B—C15B	122.5 (7)
C12A—C11A—C10A	117.4 (7)	N5B—C14B—C15B	130.9 (7)
C12A—C11A—H11A	121.3	C16B—C15B—C14B	116.3 (8)
C10A—C11A—H11A	121.3	C16B—C15B—H15B	121.8
N2A—C12A—C11A	120.4 (6)	C14B—C15B—H15B	121.8
N2A—C12A—C13A	111.3 (5)	C15B—C16B—C17B	122.3 (8)
C11A—C12A—C13A	128.3 (6)	C15B—C16B—H16B	118.8
N3A—C13A—N5A	113.2 (5)	C17B—C16B—H16B	118.8
N3A—C13A—C12A	118.9 (5)	C18B—C17B—C16B	121.6 (8)
N5A—C13A—C12A	127.7 (6)	C18B—C17B—H17B	119.2
C19A—C14A—N5A	106.6 (6)	C16B—C17B—H17B	119.2
C19A—C14A—C15A	122.3 (7)	C17B—C18B—C19B	117.0 (7)
N5A—C14A—C15A	131.1 (7)	C17B—C18B—H18B	121.5
C16A—C15A—C14A	115.9 (8)	C19B—C18B—H18B	121.5
C16A—C15A—H15A	122.0	C14B—C19B—C18B	120.1 (7)
C14A—C15A—H15A	122.0	C14B—C19B—N3B	109.1 (6)
C15A—C16A—C17A	122.9 (8)	C18B—C19B—N3B	130.7 (7)
C15A—C16A—H16A	118.6	O3—S1—O1	108.6 (4)
C17A—C16A—H16A	118.6	O3—S1—O4	110.3 (4)
C18A—C17A—C16A	121.3 (8)	O1—S1—O4	109.7 (4)
C18A—C17A—H17A	119.3	O3—S1—O2	108.8 (4)
C16A—C17A—H17A	119.3	O1—S1—O2	111.4 (4)
C17A—C18A—C19A	116.9 (7)	O4—S1—O2	108.1 (4)
C17A—C18A—H18A	121.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4A—H4NA···O2ⁱ	0.86	1.82	2.654 (8)	163
N5A—H5NA···O1ⁱⁱ	0.86	1.85	2.701 (8)	171
N4B—H4NB···O4ⁱⁱⁱ	0.86	1.85	2.685 (9)	164
N5B—H5NB···O3	0.86	1.81	2.663 (9)	173

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

Bis[2,6-bis(1H-benzimidazol-2-yl-κN³)pyridine-κN]nickel(II) sulfate (II) top

Crystal data top

[Ni(C₁₉H₁₃N₅)₂]SO₄	D_x = 0.933 Mg m⁻³
M_r = 777.46	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4	Cell parameters from 3126 reflections
a = 28.596 (2) Å	θ = 4.0–24.9°
c = 13.5438 (9) Å	µ = 0.43 mm⁻¹
V = 11075.0 (17) Å³	T = 294 K
Z = 8	Needles, light_red
F(000) = 3200	0.38 × 0.14 × 0.12 mm

Data collection top

Oxford Diffraction Gemini CCD S Ultra diffractometer	11374 independent reflections
Radiation source: fine-focus sealed tube	4172 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.095
ω scans, thick slices	θ_max = 28.9°, θ_min = 3.6°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	h = −31→33
T_min = 0.96, T_max = 0.98	k = −38→37
16294 measured reflections	l = −18→9

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.078	w = 1/[σ²(F_o²) + (0.0593P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.220	(Δ/σ)_max < 0.001
S = 0.89	Δρ_max = 0.55 e Å⁻³
11374 reflections	Δρ_min = −0.23 e Å⁻³
488 parameters	Absolute structure: Refined as an inversion twin
586 restraints	Absolute structure parameter: 0.45 (3)

Special details top

Refinement. Refined as a 2-component inversion twin

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

	x	y	z	U_iso*/U_eq
Ni1	0.64892 (5)	0.18669 (5)	0.10607 (8)	0.0538 (4)
N1A	0.5815 (2)	0.2131 (3)	0.1423 (5)	0.062 (2)
N2A	0.6099 (2)	0.1636 (3)	−0.0099 (5)	0.0531 (19)
N3A	0.6974 (2)	0.1497 (3)	0.0178 (5)	0.061 (2)
N4A	0.5075 (3)	0.2189 (3)	0.0920 (5)	0.075 (2)
H4NA	0.483254	0.217136	0.054487	0.089*
N5A	0.7103 (3)	0.1091 (3)	−0.1203 (5)	0.068 (2)
H5NA	0.704557	0.094781	−0.174876	0.082*
C1A	0.5558 (3)	0.2366 (4)	0.2124 (6)	0.078 (3)
C2A	0.5689 (4)	0.2539 (5)	0.3048 (7)	0.116 (5)
H2AA	0.599239	0.250325	0.328178	0.139*
C3A	0.5360 (4)	0.2759 (6)	0.3593 (8)	0.126 (5)
H3AA	0.544595	0.290804	0.417519	0.151*
C4A	0.4893 (5)	0.2765 (8)	0.3294 (10)	0.190 (9)
H4AA	0.467164	0.287917	0.373500	0.228*
C5A	0.4733 (4)	0.2606 (6)	0.2344 (9)	0.138 (6)
H5AA	0.442980	0.264417	0.211100	0.165*
C6A	0.5091 (3)	0.2388 (5)	0.1817 (7)	0.084 (3)
C7A	0.5506 (3)	0.2021 (4)	0.0710 (6)	0.056 (2)
C8A	0.5646 (3)	0.1756 (3)	−0.0156 (6)	0.056 (2)
C9A	0.5358 (3)	0.1621 (4)	−0.0931 (6)	0.079 (3)
H9AA	0.504281	0.170180	−0.095187	0.094*
C10A	0.5563 (4)	0.1363 (5)	−0.1659 (7)	0.091 (4)
H10A	0.538173	0.125808	−0.218326	0.109*
C11A	0.6050 (3)	0.1251 (4)	−0.1639 (7)	0.079 (3)
H11A	0.619238	0.109115	−0.215507	0.095*
C12A	0.6297 (3)	0.1391 (3)	−0.0818 (6)	0.055 (2)
C13A	0.6780 (3)	0.1318 (3)	−0.0631 (6)	0.057 (2)
C14A	0.7533 (3)	0.1129 (4)	−0.0763 (6)	0.070 (3)
C15A	0.7965 (3)	0.1010 (5)	−0.1081 (8)	0.094 (4)
H15A	0.801520	0.086460	−0.168601	0.112*
C16A	0.8319 (4)	0.1116 (5)	−0.0462 (9)	0.114 (5)
H16A	0.862131	0.102871	−0.063832	0.137*
C17A	0.8253 (4)	0.1354 (6)	0.0443 (8)	0.116 (5)
H17A	0.850964	0.142010	0.084021	0.139*
C18A	0.7822 (3)	0.1485 (4)	0.0737 (7)	0.080 (3)
H18A	0.777337	0.164500	0.132678	0.096*
C19A	0.7450 (3)	0.1369 (4)	0.0108 (6)	0.065 (3)
N1B	0.6459 (3)	0.1332 (2)	0.2173 (5)	0.0525 (18)
N2B	0.6829 (3)	0.2170 (2)	0.2206 (5)	0.0533 (19)
N3B	0.6708 (3)	0.2514 (3)	0.0476 (5)	0.063 (2)
N4B	0.6554 (3)	0.1188 (3)	0.3777 (5)	0.068 (2)
H4NB	0.663031	0.122576	0.438651	0.081*
N5B	0.7053 (3)	0.3203 (3)	0.0782 (5)	0.067 (2)
H5NB	0.719367	0.341965	0.110748	0.080*
C1B	0.6283 (3)	0.0894 (3)	0.2377 (6)	0.058 (2)
C2B	0.6095 (4)	0.0554 (3)	0.1762 (7)	0.082 (3)
H2BA	0.607350	0.060309	0.108477	0.098*
C3B	0.5944 (5)	0.0151 (4)	0.2172 (9)	0.104 (4)
H3BA	0.581404	−0.007986	0.177407	0.125*
C4B	0.5983 (5)	0.0078 (4)	0.3186 (9)	0.120 (5)
H4BA	0.587447	−0.020378	0.344123	0.144*
C5B	0.6179 (4)	0.0410 (3)	0.3860 (8)	0.086 (3)
H5BA	0.619811	0.036275	0.453831	0.103*
C6B	0.6339 (4)	0.0811 (3)	0.3389 (6)	0.070 (3)
C7B	0.6630 (4)	0.1495 (3)	0.3036 (6)	0.064 (3)
C8B	0.6850 (4)	0.1950 (3)	0.3084 (6)	0.063 (3)
C9B	0.7042 (4)	0.2157 (3)	0.3924 (7)	0.076 (3)
H9BA	0.703975	0.200865	0.453502	0.091*
C10B	0.7233 (4)	0.2590 (4)	0.3793 (7)	0.094 (4)
H10B	0.737897	0.273297	0.432737	0.113*
C11B	0.7220 (4)	0.2832 (3)	0.2871 (7)	0.077 (3)
H11B	0.734631	0.312904	0.279180	0.093*
C12B	0.7006 (4)	0.2597 (3)	0.2109 (6)	0.061 (3)
C13B	0.6930 (4)	0.2774 (3)	0.1145 (6)	0.064 (3)
C14B	0.6915 (4)	0.3231 (3)	−0.0184 (7)	0.074 (3)
C15B	0.6943 (4)	0.3587 (4)	−0.0847 (7)	0.090 (3)
H15B	0.708964	0.386891	−0.070613	0.108*
C16B	0.6739 (5)	0.3497 (4)	−0.1730 (8)	0.100 (4)
H16B	0.673751	0.373328	−0.220207	0.120*
C17B	0.6529 (5)	0.3064 (4)	−0.1973 (7)	0.094 (4)
H17B	0.641722	0.301502	−0.260922	0.113*
C18B	0.6489 (4)	0.2721 (3)	−0.1290 (6)	0.076 (3)
H18B	0.634138	0.243910	−0.143115	0.092*
C19B	0.6683 (3)	0.2813 (3)	−0.0361 (6)	0.060 (2)
S1	0.79506 (12)	0.40472 (10)	0.1171 (2)	0.0672 (8)
O1	0.7526 (3)	0.3852 (3)	0.1690 (5)	0.099 (3)
O2	0.8230 (3)	0.4275 (3)	0.1943 (5)	0.086 (2)
O3	0.7816 (3)	0.4362 (3)	0.0395 (5)	0.095 (3)
O4	0.8206 (4)	0.3659 (3)	0.0714 (5)	0.110 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0611 (9)	0.0644 (9)	0.0361 (6)	−0.0025 (7)	−0.0033 (7)	−0.0036 (7)
N1A	0.068 (3)	0.079 (5)	0.040 (3)	−0.001 (2)	−0.0065 (16)	−0.008 (3)
N2A	0.062 (2)	0.062 (4)	0.036 (2)	−0.004 (2)	−0.001 (2)	−0.001 (3)
N3A	0.069 (3)	0.073 (4)	0.042 (3)	0.000 (3)	−0.0023 (18)	−0.007 (3)
N4A	0.067 (3)	0.105 (6)	0.052 (4)	0.009 (3)	−0.003 (2)	−0.017 (4)
N5A	0.076 (3)	0.086 (6)	0.042 (3)	0.011 (3)	0.002 (2)	−0.004 (3)
C1A	0.085 (4)	0.103 (7)	0.046 (3)	0.015 (4)	−0.005 (2)	−0.014 (4)
C2A	0.106 (6)	0.176 (11)	0.066 (4)	0.048 (7)	−0.024 (4)	−0.052 (5)
C3A	0.117 (5)	0.182 (13)	0.078 (7)	0.053 (7)	−0.014 (4)	−0.051 (7)
C4A	0.120 (5)	0.34 (2)	0.107 (7)	0.074 (8)	−0.023 (5)	−0.112 (10)
C5A	0.106 (5)	0.221 (14)	0.085 (6)	0.055 (7)	−0.011 (4)	−0.063 (7)
C6A	0.086 (4)	0.113 (8)	0.054 (4)	0.018 (4)	−0.008 (3)	−0.021 (4)
C7A	0.063 (3)	0.071 (5)	0.035 (3)	−0.001 (3)	−0.002 (2)	−0.005 (3)
C8A	0.062 (2)	0.069 (5)	0.035 (3)	−0.002 (3)	−0.002 (2)	−0.004 (3)
C9A	0.078 (4)	0.110 (8)	0.048 (3)	−0.005 (4)	−0.013 (3)	−0.017 (4)
C10A	0.086 (4)	0.131 (9)	0.055 (5)	0.003 (5)	−0.014 (3)	−0.028 (5)
C11A	0.084 (4)	0.103 (9)	0.050 (3)	−0.003 (4)	−0.011 (3)	−0.015 (4)
C12A	0.066 (2)	0.062 (5)	0.037 (3)	−0.003 (3)	0.0007 (19)	−0.001 (3)
C13A	0.066 (2)	0.067 (6)	0.039 (3)	−0.002 (3)	0.000 (2)	−0.004 (3)
C14A	0.077 (3)	0.092 (7)	0.041 (3)	0.006 (3)	0.001 (2)	0.004 (4)
C15A	0.079 (3)	0.140 (11)	0.062 (5)	0.012 (4)	0.002 (3)	−0.018 (6)
C16A	0.083 (4)	0.178 (12)	0.081 (5)	0.020 (6)	−0.006 (4)	−0.041 (6)
C17A	0.081 (3)	0.187 (12)	0.080 (5)	0.039 (6)	−0.017 (4)	−0.043 (6)
C18A	0.076 (3)	0.097 (9)	0.067 (5)	0.020 (4)	−0.013 (3)	−0.016 (5)
C19A	0.070 (3)	0.086 (6)	0.040 (3)	0.005 (2)	0.0014 (18)	0.007 (4)
N1B	0.056 (5)	0.060 (3)	0.042 (2)	0.001 (2)	0.002 (2)	−0.004 (2)
N2B	0.063 (4)	0.056 (3)	0.041 (2)	0.002 (3)	−0.005 (3)	−0.0037 (16)
N3B	0.072 (5)	0.072 (3)	0.045 (2)	−0.006 (3)	−0.006 (3)	0.001 (2)
N4B	0.076 (6)	0.073 (3)	0.054 (3)	−0.007 (3)	−0.011 (4)	0.009 (2)
N5B	0.078 (6)	0.069 (3)	0.053 (3)	−0.004 (3)	−0.005 (3)	0.004 (2)
C1B	0.053 (5)	0.061 (3)	0.059 (3)	0.000 (3)	−0.005 (3)	0.002 (2)
C2B	0.103 (8)	0.068 (4)	0.073 (4)	−0.010 (4)	−0.025 (5)	0.001 (3)
C3B	0.131 (11)	0.074 (5)	0.107 (4)	−0.013 (6)	−0.009 (6)	0.011 (4)
C4B	0.154 (13)	0.098 (7)	0.108 (4)	−0.029 (7)	−0.013 (6)	0.016 (4)
C5B	0.084 (7)	0.081 (4)	0.094 (5)	−0.004 (4)	0.004 (6)	0.019 (3)
C6B	0.075 (7)	0.075 (4)	0.060 (3)	−0.008 (4)	−0.009 (3)	0.005 (2)
C7B	0.086 (6)	0.060 (3)	0.045 (3)	−0.006 (4)	−0.008 (3)	−0.002 (2)
C8B	0.087 (7)	0.061 (3)	0.043 (2)	−0.006 (3)	−0.010 (3)	−0.001 (2)
C9B	0.099 (7)	0.080 (4)	0.048 (3)	−0.011 (5)	−0.013 (4)	−0.008 (3)
C10B	0.128 (10)	0.089 (5)	0.065 (4)	−0.028 (5)	−0.037 (5)	0.005 (4)
C11B	0.105 (8)	0.069 (5)	0.058 (3)	−0.006 (5)	−0.025 (4)	−0.007 (3)
C12B	0.079 (6)	0.059 (3)	0.045 (2)	−0.006 (3)	−0.010 (3)	−0.001 (2)
C13B	0.078 (6)	0.069 (3)	0.046 (2)	−0.006 (3)	−0.010 (3)	0.0026 (19)
C14B	0.077 (7)	0.091 (4)	0.054 (3)	−0.015 (4)	−0.005 (4)	0.010 (2)
C15B	0.114 (9)	0.095 (4)	0.062 (4)	−0.004 (5)	0.011 (4)	0.015 (3)
C16B	0.141 (10)	0.093 (5)	0.066 (4)	−0.014 (6)	0.000 (6)	0.020 (4)
C17B	0.126 (10)	0.088 (5)	0.069 (4)	−0.004 (5)	−0.010 (6)	0.024 (4)
C18B	0.095 (8)	0.078 (5)	0.057 (3)	−0.009 (5)	−0.019 (4)	0.013 (3)
C19B	0.048 (5)	0.083 (4)	0.050 (2)	0.000 (3)	0.000 (3)	0.008 (2)
S1	0.102 (2)	0.0547 (18)	0.0452 (15)	−0.0061 (17)	−0.0069 (17)	0.0074 (15)
O1	0.124 (4)	0.104 (7)	0.070 (4)	−0.041 (5)	0.020 (4)	−0.007 (4)
O2	0.121 (5)	0.067 (5)	0.070 (4)	0.002 (4)	−0.032 (5)	−0.011 (4)
O3	0.137 (7)	0.082 (4)	0.065 (4)	0.002 (5)	−0.015 (4)	0.033 (5)
O4	0.181 (7)	0.071 (4)	0.077 (5)	0.032 (5)	0.028 (5)	0.007 (4)

Geometric parameters (Å, º) top

Ni1—N2B	2.026 (6)	C18A—H18A	0.9300
Ni1—N2A	2.037 (6)	N1B—C7B	1.350 (8)
Ni1—N3B	2.109 (7)	N1B—C1B	1.378 (9)
Ni1—N3A	2.115 (7)	N2B—C12B	1.327 (9)
Ni1—N1A	2.128 (7)	N2B—C8B	1.346 (8)
Ni1—N1B	2.149 (7)	N3B—C13B	1.332 (8)
N1A—C7A	1.346 (8)	N3B—C19B	1.421 (9)
N1A—C1A	1.375 (9)	N4B—C7B	1.351 (9)
N2A—C12A	1.326 (8)	N4B—C6B	1.349 (9)
N2A—C8A	1.343 (9)	N4B—H4NB	0.8600
N3A—C13A	1.330 (8)	N5B—C13B	1.369 (9)
N3A—C19A	1.413 (9)	N5B—C14B	1.369 (9)
N4A—C6A	1.342 (9)	N5B—H5NB	0.8600
N4A—C7A	1.354 (9)	C1B—C2B	1.387 (10)
N4A—H4NA	0.8600	C1B—C6B	1.399 (10)
N5A—C13A	1.370 (9)	C2B—C3B	1.350 (11)
N5A—C14A	1.372 (9)	C2B—H2BA	0.9300
N5A—H5NA	0.8600	C3B—C4B	1.394 (12)
C1A—C6A	1.400 (10)	C3B—H3BA	0.9300
C1A—C2A	1.397 (11)	C4B—C5B	1.432 (13)
C2A—C3A	1.350 (11)	C4B—H4BA	0.9300
C2A—H2AA	0.9300	C5B—C6B	1.389 (11)
C3A—C4A	1.395 (12)	C5B—H5BA	0.9300
C3A—H3AA	0.9300	C7B—C8B	1.449 (10)
C4A—C5A	1.438 (13)	C8B—C9B	1.394 (10)
C4A—H4AA	0.9300	C9B—C10B	1.365 (11)
C5A—C6A	1.395 (11)	C9B—H9BA	0.9300
C5A—H5AA	0.9300	C10B—C11B	1.429 (11)
C7A—C8A	1.453 (10)	C10B—H10B	0.9300
C8A—C9A	1.390 (10)	C11B—C12B	1.375 (10)
C9A—C10A	1.365 (11)	C11B—H11B	0.9300
C9A—H9AA	0.9300	C12B—C13B	1.417 (9)
C10A—C11A	1.427 (11)	C14B—C15B	1.359 (10)
C10A—H10A	0.9300	C14B—C19B	1.388 (10)
C11A—C12A	1.377 (9)	C15B—C16B	1.354 (11)
C11A—H11A	0.9300	C15B—H15B	0.9300
C12A—C13A	1.419 (9)	C16B—C17B	1.415 (12)
C14A—C15A	1.352 (10)	C16B—H16B	0.9300
C14A—C19A	1.385 (10)	C17B—C18B	1.353 (11)
C15A—C16A	1.349 (11)	C17B—H17B	0.9300
C15A—H15A	0.9300	C18B—C19B	1.401 (10)
C16A—C17A	1.414 (12)	C18B—H18B	0.9300
C16A—H16A	0.9300	S1—O3	1.436 (7)
C17A—C18A	1.350 (11)	S1—O4	1.464 (9)
C17A—H17A	0.9300	S1—O2	1.469 (8)
C18A—C19A	1.403 (10)	S1—O1	1.509 (8)

N2B—Ni1—N2A	172.9 (3)	C19A—C18A—H18A	121.7
N2B—Ni1—N3B	76.7 (3)	C14A—C19A—C18A	120.3 (8)
N2A—Ni1—N3B	99.1 (3)	C14A—C19A—N3A	110.6 (7)
N2B—Ni1—N3A	109.4 (3)	C18A—C19A—N3A	128.9 (8)
N2A—Ni1—N3A	76.1 (3)	C7B—N1B—C1B	105.8 (7)
N3B—Ni1—N3A	91.8 (3)	C7B—N1B—Ni1	110.2 (5)
N2B—Ni1—N1A	96.1 (3)	C1B—N1B—Ni1	143.4 (5)
N2A—Ni1—N1A	78.3 (3)	C12B—N2B—C8B	120.0 (7)
N3B—Ni1—N1A	92.5 (3)	C12B—N2B—Ni1	120.0 (5)
N3A—Ni1—N1A	154.4 (3)	C8B—N2B—Ni1	119.9 (5)
N2B—Ni1—N1B	77.7 (2)	C13B—N3B—C19B	103.4 (6)
N2A—Ni1—N1B	106.7 (3)	C13B—N3B—Ni1	112.0 (5)
N3B—Ni1—N1B	154.2 (3)	C19B—N3B—Ni1	144.3 (5)
N3A—Ni1—N1B	93.8 (3)	C7B—N4B—C6B	107.6 (7)
N1A—Ni1—N1B	93.2 (3)	C7B—N4B—H4NB	126.2
C7A—N1A—C1A	105.0 (7)	C6B—N4B—H4NB	126.2
C7A—N1A—Ni1	110.3 (5)	C13B—N5B—C14B	108.7 (7)
C1A—N1A—Ni1	144.7 (6)	C13B—N5B—H5NB	125.6
C12A—N2A—C8A	120.4 (7)	C14B—N5B—H5NB	125.6
C12A—N2A—Ni1	120.2 (5)	N1B—C1B—C2B	131.1 (8)
C8A—N2A—Ni1	119.2 (5)	N1B—C1B—C6B	108.0 (7)
C13A—N3A—C19A	104.3 (6)	C2B—C1B—C6B	120.9 (8)
C13A—N3A—Ni1	112.6 (5)	C3B—C2B—C1B	118.3 (9)
C19A—N3A—Ni1	143.1 (5)	C3B—C2B—H2BA	120.8
C6A—N4A—C7A	107.9 (7)	C1B—C2B—H2BA	120.8
C6A—N4A—H4NA	126.0	C2B—C3B—C4B	120.5 (10)
C7A—N4A—H4NA	126.0	C2B—C3B—H3BA	119.7
C13A—N5A—C14A	108.7 (7)	C4B—C3B—H3BA	119.7
C13A—N5A—H5NA	125.6	C3B—C4B—C5B	124.1 (10)
C14A—N5A—H5NA	125.6	C3B—C4B—H4BA	118.0
N1A—C1A—C6A	109.1 (7)	C5B—C4B—H4BA	118.0
N1A—C1A—C2A	130.5 (8)	C6B—C5B—C4B	112.5 (9)
C6A—C1A—C2A	120.3 (8)	C6B—C5B—H5BA	123.7
C3A—C2A—C1A	118.0 (9)	C4B—C5B—H5BA	123.7
C3A—C2A—H2AA	121.0	N4B—C6B—C5B	129.0 (8)
C1A—C2A—H2AA	121.0	N4B—C6B—C1B	107.4 (8)
C2A—C3A—C4A	120.9 (10)	C5B—C6B—C1B	123.5 (9)
C2A—C3A—H3AA	119.6	N4B—C7B—N1B	111.2 (7)
C4A—C3A—H3AA	119.6	N4B—C7B—C8B	128.4 (7)
C3A—C4A—C5A	124.0 (10)	N1B—C7B—C8B	120.5 (7)
C3A—C4A—H4AA	118.0	N2B—C8B—C9B	122.8 (8)
C5A—C4A—H4AA	118.0	N2B—C8B—C7B	111.1 (7)
C6A—C5A—C4A	111.5 (9)	C9B—C8B—C7B	126.0 (8)
C6A—C5A—H5AA	124.3	C10B—C9B—C8B	115.8 (9)
C4A—C5A—H5AA	124.3	C10B—C9B—H9BA	122.1
N4A—C6A—C1A	106.5 (8)	C8B—C9B—H9BA	122.1
N4A—C6A—C5A	128.8 (9)	C9B—C10B—C11B	122.8 (9)
C1A—C6A—C5A	124.6 (9)	C9B—C10B—H10B	118.6
N1A—C7A—N4A	111.4 (7)	C11B—C10B—H10B	118.6
N1A—C7A—C8A	121.3 (7)	C12B—C11B—C10B	115.5 (8)
N4A—C7A—C8A	127.3 (7)	C12B—C11B—H11B	122.2
N2A—C8A—C9A	123.0 (8)	C10B—C11B—H11B	122.2
N2A—C8A—C7A	110.7 (7)	N2B—C12B—C11B	123.0 (8)
C9A—C8A—C7A	126.2 (8)	N2B—C12B—C13B	111.2 (7)
C10A—C9A—C8A	116.1 (8)	C11B—C12B—C13B	125.8 (8)
C10A—C9A—H9AA	121.9	N3B—C13B—N5B	112.2 (7)
C8A—C9A—H9AA	121.9	N3B—C13B—C12B	120.1 (7)
C9A—C10A—C11A	121.8 (9)	N5B—C13B—C12B	127.7 (7)
C9A—C10A—H10A	119.1	C15B—C14B—N5B	131.2 (9)
C11A—C10A—H10A	119.1	C15B—C14B—C19B	123.9 (8)
C12A—C11A—C10A	116.8 (8)	N5B—C14B—C19B	104.6 (7)
C12A—C11A—H11A	121.6	C16B—C15B—C14B	114.7 (9)
C10A—C11A—H11A	121.6	C16B—C15B—H15B	122.7
N2A—C12A—C11A	121.7 (8)	C14B—C15B—H15B	122.7
N2A—C12A—C13A	111.2 (7)	C15B—C16B—C17B	123.6 (10)
C11A—C12A—C13A	127.0 (8)	C15B—C16B—H16B	118.2
N3A—C13A—N5A	111.5 (7)	C17B—C16B—H16B	118.2
N3A—C13A—C12A	119.8 (7)	C18B—C17B—C16B	120.8 (9)
N5A—C13A—C12A	128.6 (7)	C18B—C17B—H17B	119.6
C15A—C14A—N5A	131.4 (8)	C16B—C17B—H17B	119.6
C15A—C14A—C19A	123.6 (9)	C17B—C18B—C19B	116.4 (9)
N5A—C14A—C19A	104.8 (7)	C17B—C18B—H18B	121.8
C14A—C15A—C16A	115.5 (9)	C19B—C18B—H18B	121.8
C14A—C15A—H15A	122.2	C14B—C19B—C18B	120.4 (8)
C16A—C15A—H15A	122.2	C14B—C19B—N3B	110.8 (7)
C15A—C16A—C17A	123.1 (10)	C18B—C19B—N3B	128.6 (8)
C15A—C16A—H16A	118.5	O3—S1—O4	107.4 (5)
C17A—C16A—H16A	118.5	O3—S1—O2	112.8 (5)
C18A—C17A—C16A	120.9 (9)	O4—S1—O2	111.5 (5)
C18A—C17A—H17A	119.6	O3—S1—O1	111.0 (6)
C16A—C17A—H17A	119.6	O4—S1—O1	108.4 (5)
C17A—C18A—C19A	116.5 (9)	O2—S1—O1	105.7 (5)
C17A—C18A—H18A	121.7

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4A—H4NA···O3ⁱ	0.86	1.85	2.706 (10)	172
N5A—H5NA···O2ⁱⁱ	0.86	2.04	2.883 (11)	165
N4B—H4NB···O4ⁱⁱⁱ	0.86	1.89	2.746 (10)	177
N5B—H5NB···O1	0.86	1.75	2.605 (10)	174

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

Bis[2,6-bis(1H-benzimidazol-2-yl-κN³)pyridine-κN]nickel(II) sulfate–dimethylformamide–water (1/1/4.25) (III) top

Crystal data top

[Ni(C₁₉H₁₃N₅)₂]SO₄·C₃H₇NO·4.25H₂O	D_x = 1.338 Mg m⁻³
M_r = 925.10	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pccn	Cell parameters from 5212 reflections
a = 13.406 (5) Å	θ = 3.6–28.0°
b = 24.365 (5) Å	µ = 0.53 mm⁻¹
c = 28.114 (5) Å	T = 294 K
V = 9183 (4) Å³	Fragment, light_red
Z = 8	0.28 × 0.18 × 0.14 mm
F(000) = 3844

Data collection top

Oxford Diffraction Gemini CCD S Ultra diffractometer	10959 independent reflections
Radiation source: fine-focus sealed tube	4106 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.166
ω scans, thick slices	θ_max = 29.4°, θ_min = 3.7°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	h = −16→18
T_min = 0.90, T_max = 0.94	k = −33→30
32970 measured reflections	l = −37→35

Refinement top

Refinement on F²	552 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.086	H-atom parameters constrained
wR(F²) = 0.334	w = 1/[σ²(F_o²) + (0.1868P)²] where P = (F_o² + 2F_c²)/3
S = 0.85	(Δ/σ)_max < 0.001
10959 reflections	Δρ_max = 0.67 e Å⁻³
581 parameters	Δρ_min = −0.52 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ni1	0.76257 (5)	0.45859 (3)	0.36949 (3)	0.0429 (3)
N1A	0.8559 (3)	0.5276 (2)	0.35855 (18)	0.0468 (11)
N2A	0.8718 (3)	0.4458 (2)	0.41757 (17)	0.0435 (10)
N3A	0.7174 (3)	0.3858 (2)	0.40197 (18)	0.0497 (12)
N4A	0.9952 (4)	0.5700 (2)	0.38078 (18)	0.0505 (12)
H4AA	1.049741	0.576304	0.395923	0.061*
N5A	0.7388 (3)	0.3281 (2)	0.46274 (19)	0.0553 (13)
H5AA	0.765735	0.313306	0.487346	0.066*
C1A	0.8650 (4)	0.5757 (3)	0.3333 (2)	0.0511 (14)
C2A	0.8038 (5)	0.5982 (3)	0.2980 (3)	0.0691 (19)
H2A	0.746253	0.580038	0.288211	0.083*
C3A	0.8301 (6)	0.6472 (4)	0.2781 (3)	0.093 (3)
H3A	0.789639	0.663026	0.255010	0.111*
C4A	0.9189 (6)	0.6741 (3)	0.2926 (3)	0.088 (2)
H4A	0.936407	0.707106	0.278141	0.106*
C5A	0.9805 (5)	0.6528 (3)	0.3277 (3)	0.080 (2)
H5A	1.037865	0.670817	0.337802	0.096*
C6A	0.9515 (4)	0.6033 (3)	0.3466 (2)	0.0551 (14)
C7A	0.9359 (4)	0.5258 (3)	0.3857 (2)	0.0434 (12)
C8A	0.9517 (4)	0.4791 (2)	0.41858 (19)	0.0392 (11)
C9A	1.0338 (4)	0.4684 (3)	0.4457 (2)	0.0495 (14)
H9A	1.089451	0.491149	0.444945	0.059*
C10A	1.0310 (5)	0.4218 (3)	0.4746 (2)	0.0566 (15)
H10A	1.085433	0.413438	0.493752	0.068*
C11A	0.9491 (4)	0.3883 (3)	0.4751 (2)	0.0534 (15)
H11A	0.947521	0.357633	0.494835	0.064*
C12A	0.8689 (4)	0.4002 (2)	0.4461 (2)	0.0461 (12)
C13A	0.7750 (4)	0.3711 (3)	0.4375 (2)	0.0468 (12)
C14A	0.6507 (4)	0.3128 (3)	0.4415 (2)	0.0568 (15)
C15A	0.5796 (5)	0.2716 (3)	0.4507 (3)	0.079 (2)
H15A	0.586130	0.248240	0.476645	0.095*
C16A	0.5005 (6)	0.2671 (4)	0.4201 (3)	0.086 (2)
H16A	0.453090	0.239953	0.425587	0.103*
C17A	0.4883 (6)	0.3022 (3)	0.3808 (3)	0.081 (2)
H17A	0.434175	0.297596	0.360529	0.097*
C18A	0.5560 (5)	0.3431 (3)	0.3724 (3)	0.0628 (17)
H18A	0.547589	0.366991	0.346841	0.075*
C19A	0.6383 (4)	0.3485 (3)	0.4028 (2)	0.0521 (14)
N1B	0.8208 (3)	0.4178 (2)	0.30917 (18)	0.0481 (11)
N2B	0.6529 (3)	0.4703 (2)	0.32124 (17)	0.0445 (11)
N3B	0.6567 (3)	0.5035 (2)	0.40849 (17)	0.0464 (11)
N4B	0.7954 (4)	0.3962 (2)	0.23290 (18)	0.0540 (12)
H4BA	0.765711	0.393393	0.205878	0.065*
N5B	0.5092 (4)	0.5443 (2)	0.40806 (19)	0.0553 (13)
H5BA	0.452919	0.556436	0.397816	0.066*
C1B	0.9025 (4)	0.3893 (3)	0.2918 (2)	0.0520 (14)
C2B	0.9899 (5)	0.3719 (3)	0.3153 (3)	0.071 (2)
H2B	0.999623	0.378303	0.347550	0.085*
C3B	1.0604 (5)	0.3450 (4)	0.2882 (3)	0.089 (3)
H3B	1.119765	0.334159	0.302469	0.107*
C4B	1.0455 (5)	0.3334 (3)	0.2398 (3)	0.075 (2)
H4B	1.095094	0.315615	0.222607	0.090*
C5B	0.9590 (5)	0.3481 (3)	0.2179 (3)	0.0712 (19)
H5B	0.948269	0.339847	0.185998	0.085*
C6B	0.8871 (4)	0.3757 (3)	0.2442 (2)	0.0535 (14)
C7B	0.7601 (4)	0.4215 (3)	0.2716 (2)	0.0469 (13)
C8B	0.6649 (4)	0.4508 (3)	0.2758 (2)	0.0472 (13)
C9B	0.5934 (5)	0.4584 (3)	0.2424 (2)	0.0616 (17)
H9B	0.602302	0.445324	0.211601	0.074*
C10B	0.5063 (5)	0.4861 (3)	0.2549 (3)	0.075 (2)
H10B	0.455736	0.490905	0.232645	0.090*
C11B	0.4953 (5)	0.5068 (3)	0.3016 (2)	0.0596 (16)
H11B	0.438064	0.525831	0.310438	0.072*
C12B	0.5709 (4)	0.4982 (2)	0.3337 (2)	0.0464 (13)
C13B	0.5761 (4)	0.5152 (3)	0.3831 (2)	0.0463 (13)
C14B	0.5470 (4)	0.5508 (3)	0.4526 (2)	0.0507 (13)
C15B	0.5101 (5)	0.5775 (3)	0.4933 (3)	0.0720 (19)
H15B	0.449117	0.595702	0.493034	0.086*
C16B	0.5678 (5)	0.5756 (3)	0.5333 (3)	0.0718 (19)
H16B	0.544805	0.592263	0.561015	0.086*
C17B	0.6605 (5)	0.5494 (3)	0.5338 (3)	0.073 (2)
H17B	0.698427	0.550032	0.561528	0.087*
C18B	0.6966 (5)	0.5229 (3)	0.4948 (2)	0.0582 (16)
H18B	0.756945	0.504184	0.495799	0.070*
C19B	0.6401 (4)	0.5250 (3)	0.4536 (2)	0.0463 (13)
O1C	0.7965 (6)	0.6719 (3)	0.5069 (3)	0.141 (3)
N1C	0.6856 (6)	0.6834 (3)	0.4458 (3)	0.108 (2)
C1C	0.7529 (10)	0.6622 (6)	0.4125 (5)	0.187 (6)
H1C1	0.804412	0.642226	0.428683	0.280*
H1C2	0.782140	0.691813	0.394775	0.280*
H1C3	0.718286	0.638075	0.391136	0.280*
C2C	0.5885 (9)	0.7037 (6)	0.4343 (6)	0.186 (6)
H2C1	0.559437	0.720396	0.461972	0.279*
H2C2	0.547135	0.673844	0.423929	0.279*
H2C3	0.593710	0.730421	0.409372	0.279*
C3C	0.7163 (9)	0.6863 (5)	0.4926 (4)	0.117 (3)
H3C	0.671491	0.700508	0.514672	0.140*
S1	0.74643 (10)	0.41339 (7)	0.61042 (6)	0.0524 (5)
O1	0.6698 (4)	0.3806 (3)	0.5878 (2)	0.103 (2)
O2	0.7929 (3)	0.3821 (2)	0.64958 (16)	0.0685 (13)
O3	0.6975 (6)	0.4610 (2)	0.6293 (2)	0.100 (2)
O4	0.8231 (3)	0.4251 (3)	0.57542 (17)	0.0831 (16)
O1W	0.8030 (7)	0.6612 (3)	0.6051 (3)	0.154 (3)
O2WA	0.7889 (11)	0.5565 (6)	0.6535 (5)	0.107 (5)	0.5
O2WB	0.714 (2)	0.5724 (12)	0.6580 (11)	0.107 (5)	0.25
O3W	0.8399 (4)	0.3018 (2)	0.54695 (17)	0.0882 (17)
O4W	0.6274 (5)	0.2747 (3)	0.6159 (2)	0.1013 (19)
O5W	0.750000	0.750000	0.6651 (5)	0.146 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0302 (4)	0.0524 (5)	0.0462 (5)	0.0020 (3)	−0.0044 (3)	0.0016 (4)
N1A	0.0295 (19)	0.055 (2)	0.056 (3)	0.0014 (19)	−0.0023 (18)	0.005 (2)
N2A	0.0279 (18)	0.055 (2)	0.048 (2)	0.0039 (17)	−0.003 (2)	0.0034 (19)
N3A	0.039 (2)	0.055 (3)	0.054 (3)	−0.0014 (19)	−0.003 (2)	0.001 (2)
N4A	0.034 (2)	0.056 (3)	0.061 (3)	−0.0064 (19)	−0.001 (2)	−0.002 (2)
N5A	0.045 (2)	0.057 (3)	0.064 (3)	−0.001 (2)	0.002 (2)	0.008 (2)
C1A	0.038 (2)	0.056 (3)	0.059 (3)	0.003 (2)	0.000 (2)	0.008 (2)
C2A	0.052 (3)	0.072 (4)	0.083 (4)	0.003 (3)	−0.013 (3)	0.023 (3)
C3A	0.058 (4)	0.090 (4)	0.130 (7)	0.005 (3)	−0.008 (4)	0.053 (5)
C4A	0.060 (4)	0.082 (5)	0.123 (6)	0.003 (3)	0.004 (4)	0.044 (5)
C5A	0.054 (4)	0.073 (4)	0.113 (5)	−0.005 (3)	0.001 (4)	0.029 (4)
C6A	0.041 (3)	0.057 (3)	0.067 (4)	0.000 (2)	0.001 (2)	0.003 (2)
C7A	0.029 (2)	0.050 (2)	0.051 (3)	0.0007 (19)	−0.0006 (19)	0.000 (2)
C8A	0.0256 (18)	0.050 (3)	0.042 (3)	0.0070 (17)	0.0031 (18)	−0.005 (2)
C9A	0.034 (2)	0.057 (3)	0.057 (3)	0.001 (2)	−0.011 (2)	−0.003 (2)
C10A	0.046 (3)	0.057 (3)	0.067 (4)	0.004 (2)	−0.018 (3)	0.000 (3)
C11A	0.051 (2)	0.052 (3)	0.057 (3)	0.003 (2)	−0.013 (3)	0.004 (3)
C12A	0.042 (2)	0.051 (3)	0.045 (3)	0.003 (2)	−0.003 (2)	0.000 (2)
C13A	0.041 (2)	0.049 (3)	0.051 (3)	0.003 (2)	0.001 (2)	−0.001 (2)
C14A	0.044 (3)	0.055 (3)	0.071 (3)	0.003 (2)	0.001 (2)	0.003 (3)
C15A	0.056 (3)	0.061 (4)	0.120 (6)	−0.004 (3)	0.011 (3)	0.005 (4)
C16A	0.059 (4)	0.074 (5)	0.124 (6)	−0.013 (4)	0.009 (4)	0.002 (4)
C17A	0.052 (4)	0.076 (4)	0.115 (5)	−0.009 (3)	0.004 (4)	−0.004 (4)
C18A	0.045 (3)	0.070 (4)	0.074 (4)	−0.003 (3)	−0.004 (3)	−0.003 (3)
C19A	0.039 (2)	0.052 (3)	0.066 (3)	0.001 (2)	0.002 (2)	−0.002 (2)
N1B	0.037 (2)	0.053 (3)	0.055 (2)	0.004 (2)	−0.0016 (17)	0.001 (2)
N2B	0.0304 (19)	0.051 (3)	0.052 (2)	0.0024 (18)	−0.0052 (19)	0.000 (2)
N3B	0.0297 (19)	0.057 (3)	0.053 (2)	0.003 (2)	−0.0032 (18)	−0.005 (2)
N4B	0.043 (2)	0.065 (3)	0.054 (2)	0.000 (2)	0.001 (2)	−0.008 (2)
N5B	0.035 (2)	0.067 (3)	0.063 (2)	0.010 (2)	−0.0027 (19)	0.004 (2)
C1B	0.037 (2)	0.059 (3)	0.061 (3)	0.001 (2)	0.002 (2)	−0.003 (3)
C2B	0.045 (3)	0.094 (5)	0.074 (4)	0.018 (3)	−0.002 (3)	−0.004 (4)
C3B	0.050 (4)	0.119 (6)	0.099 (4)	0.024 (4)	0.000 (3)	−0.023 (5)
C4B	0.048 (3)	0.084 (5)	0.093 (4)	0.008 (3)	0.013 (3)	−0.013 (4)
C5B	0.051 (3)	0.083 (5)	0.079 (4)	0.000 (3)	0.008 (3)	−0.019 (4)
C6B	0.040 (2)	0.062 (4)	0.059 (3)	−0.005 (2)	0.001 (2)	−0.003 (3)
C7B	0.039 (2)	0.052 (3)	0.050 (2)	−0.001 (2)	0.0001 (18)	−0.001 (2)
C8B	0.038 (2)	0.054 (3)	0.050 (2)	−0.001 (2)	−0.0026 (19)	0.002 (2)
C9B	0.060 (3)	0.066 (4)	0.059 (3)	0.008 (3)	−0.020 (3)	−0.009 (3)
C10B	0.064 (4)	0.091 (5)	0.071 (3)	0.020 (3)	−0.024 (3)	−0.014 (4)
C11B	0.043 (3)	0.068 (4)	0.067 (3)	0.013 (3)	−0.016 (3)	−0.003 (3)
C12B	0.028 (2)	0.055 (3)	0.056 (2)	0.003 (2)	−0.0050 (18)	0.005 (2)
C13B	0.030 (2)	0.054 (3)	0.054 (2)	−0.002 (2)	−0.0022 (17)	0.007 (2)
C14B	0.034 (2)	0.059 (4)	0.059 (2)	−0.006 (2)	0.005 (2)	0.006 (2)
C15B	0.053 (4)	0.091 (5)	0.072 (3)	−0.003 (4)	0.014 (3)	−0.010 (3)
C16B	0.071 (3)	0.078 (5)	0.066 (3)	−0.002 (3)	0.011 (3)	−0.011 (4)
C17B	0.068 (3)	0.091 (5)	0.059 (3)	−0.003 (3)	−0.004 (3)	−0.017 (3)
C18B	0.049 (3)	0.070 (4)	0.056 (3)	−0.006 (3)	−0.006 (2)	−0.005 (3)
C19B	0.034 (2)	0.053 (3)	0.052 (2)	−0.006 (2)	0.0035 (19)	−0.003 (2)
O1C	0.110 (5)	0.125 (6)	0.187 (7)	0.006 (5)	−0.010 (5)	0.031 (6)
N1C	0.110 (5)	0.080 (5)	0.133 (5)	0.012 (4)	0.010 (4)	0.013 (5)
C1C	0.209 (13)	0.138 (11)	0.212 (12)	0.006 (9)	0.087 (10)	−0.030 (10)
C2C	0.119 (6)	0.173 (12)	0.266 (16)	0.019 (8)	−0.025 (8)	0.058 (12)
C3C	0.103 (5)	0.114 (8)	0.133 (6)	0.008 (6)	0.011 (5)	0.020 (6)
S1	0.0344 (8)	0.0605 (11)	0.0623 (10)	0.0042 (8)	0.0034 (7)	0.0013 (8)
O1	0.068 (3)	0.110 (4)	0.131 (5)	−0.035 (3)	−0.039 (3)	0.013 (4)
O2	0.051 (2)	0.094 (4)	0.061 (3)	0.022 (3)	0.008 (2)	0.008 (3)
O3	0.130 (5)	0.083 (4)	0.089 (4)	0.051 (4)	0.016 (4)	−0.009 (3)
O4	0.041 (2)	0.146 (5)	0.063 (3)	−0.012 (3)	0.002 (2)	0.012 (3)
O1W	0.184 (7)	0.103 (5)	0.177 (7)	−0.026 (6)	−0.060 (7)	−0.012 (5)
O2WA	0.138 (12)	0.085 (8)	0.099 (7)	−0.043 (10)	−0.044 (11)	0.010 (7)
O2WB	0.138 (12)	0.085 (8)	0.099 (7)	−0.043 (10)	−0.044 (11)	0.010 (7)
O3W	0.131 (5)	0.075 (3)	0.059 (3)	0.017 (3)	0.017 (3)	0.002 (3)
O4W	0.104 (4)	0.087 (4)	0.113 (4)	−0.012 (4)	0.033 (4)	−0.021 (4)
O5W	0.107 (7)	0.161 (10)	0.170 (11)	0.013 (7)	0.000	0.000

Geometric parameters (Å, º) top

Ni1—N2A	2.017 (4)	N3B—C19B	1.389 (7)
Ni1—N2B	2.021 (4)	N4B—C7B	1.337 (7)
Ni1—N3A	2.086 (5)	N4B—C6B	1.365 (7)
Ni1—N3B	2.101 (5)	N4B—H4BA	0.8600
Ni1—N1B	2.116 (5)	N5B—C13B	1.341 (7)
Ni1—N1A	2.118 (5)	N5B—C14B	1.360 (8)
N1A—C7A	1.316 (7)	N5B—H5BA	0.8600
N1A—C1A	1.376 (8)	C1B—C6B	1.395 (9)
N2A—C8A	1.344 (7)	C1B—C2B	1.410 (8)
N2A—C12A	1.372 (7)	C2B—C3B	1.379 (9)
N3A—C13A	1.311 (7)	C2B—H2B	0.9300
N3A—C19A	1.396 (7)	C3B—C4B	1.403 (11)
N4A—C7A	1.345 (7)	C3B—H3B	0.9300
N4A—C6A	1.388 (8)	C4B—C5B	1.361 (10)
N4A—H4AA	0.8600	C4B—H4B	0.9300
N5A—C13A	1.356 (8)	C5B—C6B	1.388 (9)
N5A—C14A	1.375 (7)	C5B—H5B	0.9300
N5A—H5AA	0.8600	C7B—C8B	1.468 (8)
C1A—C6A	1.392 (8)	C8B—C9B	1.355 (8)
C1A—C2A	1.400 (9)	C9B—C10B	1.393 (10)
C2A—C3A	1.365 (10)	C9B—H9B	0.9300
C2A—H2A	0.9300	C10B—C11B	1.416 (9)
C3A—C4A	1.420 (11)	C10B—H10B	0.9300
C3A—H3A	0.9300	C11B—C12B	1.372 (8)
C4A—C5A	1.388 (10)	C11B—H11B	0.9300
C4A—H4A	0.9300	C12B—C13B	1.453 (8)
C5A—C6A	1.373 (9)	C14B—C19B	1.399 (8)
C5A—H5A	0.9300	C14B—C15B	1.407 (9)
C7A—C8A	1.482 (8)	C15B—C16B	1.366 (9)
C8A—C9A	1.364 (7)	C15B—H15B	0.9300
C9A—C10A	1.396 (9)	C16B—C17B	1.397 (10)
C9A—H9A	0.9300	C16B—H16B	0.9300
C10A—C11A	1.368 (8)	C17B—C18B	1.362 (9)
C10A—H10A	0.9300	C17B—H17B	0.9300
C11A—C12A	1.379 (8)	C18B—C19B	1.385 (8)
C11A—H11A	0.9300	C18B—H18B	0.9300
C12A—C13A	1.466 (8)	O1C—C3C	1.201 (12)
C14A—C19A	1.404 (9)	N1C—C3C	1.379 (13)
C14A—C15A	1.407 (9)	N1C—C1C	1.399 (13)
C15A—C16A	1.369 (10)	N1C—C2C	1.429 (13)
C15A—H15A	0.9300	C1C—H1C1	0.9600
C16A—C17A	1.407 (11)	C1C—H1C2	0.9600
C16A—H16A	0.9300	C1C—H1C3	0.9600
C17A—C18A	1.370 (10)	C2C—H2C1	0.9600
C17A—H17A	0.9300	C2C—H2C2	0.9600
C18A—C19A	1.402 (8)	C2C—H2C3	0.9600
C18A—H18A	0.9300	C3C—H3C	0.9300
N1B—C7B	1.336 (7)	S1—O3	1.434 (5)
N1B—C1B	1.385 (7)	S1—O1	1.448 (5)
N2B—C12B	1.339 (7)	S1—O4	1.451 (5)
N2B—C8B	1.372 (7)	S1—O2	1.476 (5)
N3B—C13B	1.324 (7)

N2A—Ni1—N2B	179.2 (2)	C8B—N2B—Ni1	119.4 (4)
N2A—Ni1—N3A	77.65 (19)	C13B—N3B—C19B	106.3 (5)
N2B—Ni1—N3A	101.70 (19)	C13B—N3B—Ni1	112.5 (4)
N2A—Ni1—N3B	102.78 (19)	C19B—N3B—Ni1	141.3 (4)
N2B—Ni1—N3B	77.59 (19)	C7B—N4B—C6B	107.3 (5)
N3A—Ni1—N3B	91.07 (19)	C7B—N4B—H4BA	126.3
N2A—Ni1—N1B	101.35 (19)	C6B—N4B—H4BA	126.3
N2B—Ni1—N1B	78.27 (19)	C13B—N5B—C14B	107.1 (5)
N3A—Ni1—N1B	93.32 (19)	C13B—N5B—H5BA	126.5
N3B—Ni1—N1B	155.86 (18)	C14B—N5B—H5BA	126.5
N2A—Ni1—N1A	77.93 (19)	N1B—C1B—C6B	109.9 (5)
N2B—Ni1—N1A	102.73 (19)	N1B—C1B—C2B	130.0 (6)
N3A—Ni1—N1A	155.57 (19)	C6B—C1B—C2B	120.0 (6)
N3B—Ni1—N1A	93.53 (19)	C3B—C2B—C1B	117.0 (7)
N1B—Ni1—N1A	92.23 (19)	C3B—C2B—H2B	121.5
C7A—N1A—C1A	104.8 (5)	C1B—C2B—H2B	121.5
C7A—N1A—Ni1	111.8 (4)	C2B—C3B—C4B	122.2 (7)
C1A—N1A—Ni1	143.4 (4)	C2B—C3B—H3B	118.9
C8A—N2A—C12A	119.9 (5)	C4B—C3B—H3B	118.9
C8A—N2A—Ni1	120.0 (4)	C5B—C4B—C3B	120.5 (7)
C12A—N2A—Ni1	119.8 (4)	C5B—C4B—H4B	119.8
C13A—N3A—C19A	105.0 (5)	C3B—C4B—H4B	119.8
C13A—N3A—Ni1	113.2 (4)	C4B—C5B—C6B	118.5 (7)
C19A—N3A—Ni1	141.4 (4)	C4B—C5B—H5B	120.7
C7A—N4A—C6A	106.9 (5)	C6B—C5B—H5B	120.7
C7A—N4A—H4AA	126.6	N4B—C6B—C5B	132.8 (6)
C6A—N4A—H4AA	126.6	N4B—C6B—C1B	105.6 (5)
C13A—N5A—C14A	106.9 (5)	C5B—C6B—C1B	121.6 (6)
C13A—N5A—H5AA	126.6	N1B—C7B—N4B	113.4 (5)
C14A—N5A—H5AA	126.6	N1B—C7B—C8B	120.0 (5)
N1A—C1A—C6A	110.3 (5)	N4B—C7B—C8B	126.7 (6)
N1A—C1A—C2A	130.4 (6)	C9B—C8B—N2B	121.1 (5)
C6A—C1A—C2A	119.4 (6)	C9B—C8B—C7B	128.7 (6)
C3A—C2A—C1A	118.7 (7)	N2B—C8B—C7B	110.2 (5)
C3A—C2A—H2A	120.6	C8B—C9B—C10B	118.9 (6)
C1A—C2A—H2A	120.6	C8B—C9B—H9B	120.5
C2A—C3A—C4A	120.3 (7)	C10B—C9B—H9B	120.5
C2A—C3A—H3A	119.9	C9B—C10B—C11B	119.6 (6)
C4A—C3A—H3A	119.9	C9B—C10B—H10B	120.2
C5A—C4A—C3A	122.0 (7)	C11B—C10B—H10B	120.2
C5A—C4A—H4A	119.0	C12B—C11B—C10B	118.6 (6)
C3A—C4A—H4A	119.0	C12B—C11B—H11B	120.7
C6A—C5A—C4A	115.9 (7)	C10B—C11B—H11B	120.7
C6A—C5A—H5A	122.1	N2B—C12B—C11B	120.8 (6)
C4A—C5A—H5A	122.1	N2B—C12B—C13B	110.8 (5)
C5A—C6A—N4A	131.5 (6)	C11B—C12B—C13B	128.4 (6)
C5A—C6A—C1A	123.8 (7)	N3B—C13B—N5B	112.2 (5)
N4A—C6A—C1A	104.7 (5)	N3B—C13B—C12B	119.6 (5)
N1A—C7A—N4A	113.3 (5)	N5B—C13B—C12B	128.2 (5)
N1A—C7A—C8A	120.2 (5)	N5B—C14B—C19B	107.3 (5)
N4A—C7A—C8A	126.4 (5)	N5B—C14B—C15B	132.3 (6)
N2A—C8A—C9A	122.7 (5)	C19B—C14B—C15B	120.4 (6)
N2A—C8A—C7A	109.7 (5)	C16B—C15B—C14B	117.1 (7)
C9A—C8A—C7A	127.7 (5)	C16B—C15B—H15B	121.4
C8A—C9A—C10A	117.3 (6)	C14B—C15B—H15B	121.4
C8A—C9A—H9A	121.4	C15B—C16B—C17B	121.8 (7)
C10A—C9A—H9A	121.4	C15B—C16B—H16B	119.1
C11A—C10A—C9A	120.9 (6)	C17B—C16B—H16B	119.1
C11A—C10A—H10A	119.6	C18B—C17B—C16B	121.6 (7)
C9A—C10A—H10A	119.6	C18B—C17B—H17B	119.2
C10A—C11A—C12A	119.5 (6)	C16B—C17B—H17B	119.2
C10A—C11A—H11A	120.2	C17B—C18B—C19B	117.6 (6)
C12A—C11A—H11A	120.2	C17B—C18B—H18B	121.2
N2A—C12A—C11A	119.7 (5)	C19B—C18B—H18B	121.2
N2A—C12A—C13A	108.5 (5)	C18B—C19B—N3B	131.5 (6)
C11A—C12A—C13A	131.8 (6)	C18B—C19B—C14B	121.3 (6)
N3A—C13A—N5A	113.5 (5)	N3B—C19B—C14B	107.1 (5)
N3A—C13A—C12A	120.1 (6)	C3C—N1C—C1C	117.7 (11)
N5A—C13A—C12A	126.4 (5)	C3C—N1C—C2C	118.0 (11)
N5A—C14A—C19A	105.6 (5)	C1C—N1C—C2C	124.3 (12)
N5A—C14A—C15A	134.1 (7)	N1C—C1C—H1C1	109.5
C19A—C14A—C15A	120.2 (6)	N1C—C1C—H1C2	109.5
C16A—C15A—C14A	117.8 (8)	H1C1—C1C—H1C2	109.5
C16A—C15A—H15A	121.1	N1C—C1C—H1C3	109.5
C14A—C15A—H15A	121.1	H1C1—C1C—H1C3	109.5
C15A—C16A—C17A	122.3 (8)	H1C2—C1C—H1C3	109.5
C15A—C16A—H16A	118.9	N1C—C2C—H2C1	109.5
C17A—C16A—H16A	118.9	N1C—C2C—H2C2	109.5
C18A—C17A—C16A	120.2 (8)	H2C1—C2C—H2C2	109.5
C18A—C17A—H17A	119.9	N1C—C2C—H2C3	109.5
C16A—C17A—H17A	119.9	H2C1—C2C—H2C3	109.5
C17A—C18A—C19A	118.9 (7)	H2C2—C2C—H2C3	109.5
C17A—C18A—H18A	120.5	O1C—C3C—N1C	124.8 (12)
C19A—C18A—H18A	120.5	O1C—C3C—H3C	117.6
N3A—C19A—C18A	130.4 (6)	N1C—C3C—H3C	117.6
N3A—C19A—C14A	109.0 (5)	O3—S1—O1	106.5 (4)
C18A—C19A—C14A	120.6 (6)	O3—S1—O4	114.6 (4)
C7B—N1B—C1B	103.7 (5)	O1—S1—O4	108.3 (4)
C7B—N1B—Ni1	112.1 (4)	O3—S1—O2	109.6 (3)
C1B—N1B—Ni1	144.1 (4)	O1—S1—O2	110.0 (3)
C12B—N2B—C8B	121.0 (5)	O4—S1—O2	107.9 (3)
C12B—N2B—Ni1	119.6 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4A—H4AA···O4ⁱ	0.86	1.89	2.732 (7)	168
N4B—H4BA···S1ⁱⁱ	0.86	2.73	3.514 (5)	152
N4B—H4BA···O2ⁱⁱ	0.86	1.79	2.646 (7)	176

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

Table 1. Crystal and refinement data for (I), (II) and (III) (herein reported), and (IV) (Guo et al., 2011) (included for comparison). top

	(I)	(II)	(III)	(IV)(CSD refcode OYAKEF)
Crystal data
Chemical formula	C₃₈H₂₆N₁₀Ni·O₄S + Solv.	C₃₈H₂₆N₁₀Ni·O₄S + Solv.	C₃₈H₂₆N₁₀Ni·O₄S .C₄ H₇O. 4.25(H₂O) + Solv.	C₃₈H₂₆N₁₀Ni·O₄S
M_r	777.46	777.46	925.10	777.44
Crystal system, space group	Orthorhombic, P2₁2₁2₁	Tetragonal, I4	Orthorhombic, Pccn	Monoclinic, P2₁/c
Temperature (K)	294	294	294	296
a, b, c (Å)	9.8015 (6), 20.9572 (15), 21.7012 (17)	28.596 (2), 28.596 (2), 13.5438 (9)	13.406 (5), 24.365 (5), 28.114 (5)	13.735 (8), 13.838 (8), 20.270 (11)
α, β, γ (°)	90,90,90	90,90,90	90,90,90	90,106.133 (10),90
V (Å³)	4457.7 (5)	11075.0 (19)	9183 (4)	3701 (4)
Z	4	8	8	4
Radiation type	Mo Kα	Mo Kα	Mo Kα	Mo Ka
µ (mm^-1)	0.53	0.43	0.53	0.64
Crystal size (mm)	0.50 × 0.24 × 0.18	0.38 × 0.14 × 0.12	0.28 × 0.18 × 0.14	0.27 × 0.24 × 0.21
Data collection
Diffractometer	Oxford Diffraction Gemini CCD S Ultra diffractometer	Oxford Diffraction Gemini CCD S Ultra diffractometer	Oxford Diffraction Gemini CCD S Ultra diffractometer	Bruker APEX-II CCD diffractometer
Absorption correction	Multi-scan CrysAlis PRO, Oxford Diffraction (2009)	Multi-scan CrysAlis PRO, Oxford Diffraction (2009)	Multi-scan CrysAlis PRO, Oxford Diffraction (2009	Multi-scan SADABS
T_min, T_max	0.82, 0.92	0.96, 0.98	0.90, 0.94	0.847, 0.878
No. of measured, independent and observed [I > 2σ(I)] reflections	19326, 9840, 5651	16294, 11374, 4172	32970, 10959, 4106	17697, 6347, 4602
R_int	0.085	0.095	0.166	0.052
(sin θ/λ)_max (Å^-1)	0.680	0.679	0.691	0.595
Refinement
R[F² > 2σ(F²)], wR(F²), S	0.074, 0.210, 0.98	0.078 0.220, 0.89	0.086, 0.334, 0.85	0.085, 0.193, 1.08
No. of reflections	9840	11374	10959	6347
No. of parameters	487	488	581	487
No. of restraints	586	586	552	0
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å^-3)	0.47, -0.31	0.55, -0.23	0.67, -0.52	1.83, -1.22

Table 2 Selected coordination distances (Å) for (I), (II), (III) and (IV) top

Bond	(I)	(II)	(III)	(IV)
Ni1—N1A	2.108 (5)	2.128 (7)	2.118 (5)	2.117 (6)
Ni1—N2A	2.029 (5)	2.037 (6)	2.017 (4)	2.023 (6)
Ni1—N3A	2.113 (5)	2.115 (7)	2.086 (5)	2.128 (6)
Ni1—N1B	2.112 (6)	2.1149 (7)	2.116 (5)	2.101 (6)
Ni1—N2B	2.022 (5)	2.026 (6)	2.021 (4)	1.998 (6)
Ni1—N3B	2.120 (6)	2.109 (7)	2.101 (5)	2.101 (6)

Table 3 Hydrogen-bond geometry (Å, °) for (I), (II), (III) and (IV) top

Structure	D—H···A	D—H	H···A	D···A	D—H···A
(I)	N4A—H4NA···O2ⁱ	0.86	1.82	2.654 (8)	163
	N5A—H5NA···O1ⁱⁱ	0.86	1.85	2.700 (8)	171
	N4B—H4NB···O4ⁱⁱⁱ	0.86	1.85	2.686 (9)	164
	N5B—H5NB···O3	0.86	1.81	2.664 (9)	173
(II)	N4A—H4NA···O3ⁱ	0.86	1.85	2.705 (10)	172
	N5A—H5NA···O1ⁱⁱ	0.86	2.51	3.048 (10)	121
	N5A—H5NA···O2ⁱⁱ	0.86	2.04	2.884 (11)	165
	N4B—H4NB···O4ⁱⁱⁱ	0.86	1.89	2.745 (10)	177
	N5B—H5NB···O1	0.86	1.75	2.606 (10)	174
(III)	N4A—H4AA···O4ⁱ	0.86	1.89	2.733 (7)	168
	N5A—H5AA···O3W	0.86	1.97	2.805 (7)	163
	N4B—H4BA···O2ⁱⁱ	0.86	1.79	2.647 (7)	175
	N5B—H5BA···O1ⁱⁱⁱ	0.86	2.29	3.024 (8)	143
	N5B—H5BA···O3ⁱⁱⁱ	0.86	2.19	2.959 (9)	149
(IV)	N4A—H4NA···O2ⁱ	0.86	2.04	2.7418 (16)	138
	N5A—H5NA···O3	0.86	1.94	2.7966 (16)	176
	N4B—H4NB···O1ⁱⁱ	0.86	1.82	2.6806 (16)	179
	N5B—H5NB···O4ⁱⁱⁱ	0.86	2.11	2.8356 (17)	142

Symmetry codes for (I): (i) -x+3/2, -y, z-1/2; (ii) -x+5/2, -y, z-1/2; (iii) x-1/2, -y+1/2, -z+2. Symmetry codes for (II): (i) y, -x+1, -z; (ii) -x+3/2, -y+1/2, z-1/2; (iii) -x+3/2, -y+1/2, z+1/2. Symmetry codes for (III): (i) -x+2, -y+1, -z+1; (ii) -x+3/2, y, z-1/2; (iii) -x+1, -y+1, -z+1. Symmetry codes for (IV): (i) y, -x+1, -z; (ii) -x+3/2, -y+1/2, z-1/2; (iii) -x+3/2, -y+1/2, z+1/2.

Subscribe to Acta Crystallographica Section C: Structural Chemistry

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.

E-mail address*
Repeat e-mail address* (for error checking)

Format*	PDF (US $40)
	HTML (US $40)
	PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number (non-UK EC countries only)
Country*

Terms and conditions of use
Contact us

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page