Nickel(II) cluster-based mixed-cation coordination polymer synthesized from 2-mercapto­benzoic acid and its application

High-nuclearity metal clusters have received considerable attention not only because of their diverse architectures and topologies, but also because of their potential applications as functional materials in many fields. To explore new types of clusters and their potential applications, a new nickel(II) cluster-based mixed-cation coordination polymer, namely poly[hexa­kis­[μ₄-(2-carboxyl­atophen­yl)sulfanido]di-μ₃-chlorido-tri-μ₂-hydroxido-octa­nickel(II)sodium(I)], [Ni₈NaCl₂(OH)₃(C₇H₄O₂S)₆]_n, 1, was synthesized using nickel chloride hexa­hydrate and mercapto­benzoic acid (H₂mba) as starting reactants under hydro­thermal conditions. The material was characterized by single-crystal X-ray diffraction (SCXRD), Fourier transform IR spectroscopy, thermogravimetric analysis, powder X-ray diffraction and X-ray photoelectron spectroscopy analysis. SCXRD shows that 1 consists of a hexa­nuclear nickel(II) [Ni₆] cluster, dinuclear Ni^II nodes and a mononuclear Na^I node, resulting in the formation of a complex covalent three-dimensional network. In addition, a tightly packed NiO/C&S nanocomposite is fabricated by sinter­ing the coordination precursor at 400 °C. The uniform nanocomposite consists of NiO nanoparticles, incompletely carbonized carbon and incompletely vulcanized sulfur. When used as a supercapacitor electrode, the synthesized composite shows an extra-long cycling stability (>5000 cycles) during the charge/discharge process.

Computing details

Data collection: APEX3 (Bruker, 2014); cell refinement: APEX3 (Bruker, 2014); data reduction: APEX3 (Bruker, 2014); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b) and OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: SHELXL2018 (Sheldrick, 2015b).

Poly[hexakis[µ₄-(2-carboxylatophenyl)sulfanido]di-µ₃-chlorido-tri-µ₂-hydroxido-octanickel(II)sodium(I)]

Crystal data

[Ni8NaCl2(OH)3(C7H4O2S)6]	Dx = 1.835 Mg m^−3
Mr = 1527.56	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P63/m	Cell parameters from 7580 reflections
a = 13.2027 (7) Å	θ = 2.9–28.2°
c = 18.3116 (12) Å	µ = 3.05 mm^−1
V = 2764.3 (3) Å^3	T = 100 K
Z = 2	Prism, black
F(000) = 1528	0.2 × 0.2 × 0.15 mm

Data collection

Bruker APEXIII area-detector diffractometer	1442 reflections with I > 2σ(I)
ω scans	Rint = 0.055
Absorption correction: multi-scan (SADABS; Krause, L., Herbst-Irmer, R., Sheldrick G.M. & Stalke D., J. Appl. Cryst. 48 (2015) 3-10)	θmax = 25.0°, θmin = 2.1°
Tmin = 0.187, Tmax = 0.263	h = −15→15
19761 measured reflections	k = −14→15
1679 independent reflections	l = −18→21

Refinement

Refinement on F^2	1 restraint
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.068	H-atom parameters constrained
wR(F^2) = 0.213	w = 1/[σ^2(Fo^2) + (0.1205P)^2 + 36.4479P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max < 0.001
1679 reflections	Δρmax = 2.97 e Å^−3
118 parameters	Δρmin = −2.10 e Å^−3

Special details

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

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

	x	y	z	Uiso*/Ueq
Ni1	0.000000	0.000000	0.66416 (11)	0.0402 (6)
Na1	0.000000	0.000000	0.500000	0.0176 (14)
O1	0.0313 (5)	0.1424 (5)	0.5905 (3)	0.0274 (12)
C1	0.1634 (7)	0.5226 (7)	0.4667 (5)	0.0321 (19)
H1	0.189294	0.584615	0.432392	0.039*
S1	0.04395 (18)	0.47486 (16)	0.67157 (10)	0.0244 (5)
Ni2	0.02284 (14)	0.34698 (12)	0.750000	0.0270 (5)
O2	0.0062 (6)	0.2348 (5)	0.6813 (3)	0.0363 (15)
C2	0.1567 (8)	0.4172 (9)	0.4466 (5)	0.040 (2)
H2	0.180219	0.407978	0.399222	0.048*
O3	−0.1104 (7)	0.0167 (7)	0.750000	0.042 (2)
H3A	−0.080237	0.090589	0.750000	0.063*
Ni3	0.18990 (13)	0.57426 (12)	0.750000	0.0269 (5)
Cl3	0.333333	0.666667	0.82575 (19)	0.0317 (8)
C3	0.1158 (7)	0.3279 (8)	0.4958 (4)	0.0320 (19)
H3	0.109301	0.255836	0.481263	0.038*
C4	0.0830 (6)	0.3384 (7)	0.5672 (4)	0.0242 (16)
C7	0.0394 (7)	0.2348 (6)	0.6151 (4)	0.0250 (17)
C6	0.1325 (7)	0.5365 (7)	0.5366 (4)	0.0276 (17)
H6	0.139475	0.609197	0.550159	0.033*
C5	0.0916 (6)	0.4465 (7)	0.5871 (4)	0.0225 (16)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0446 (8)	0.0446 (8)	0.0312 (12)	0.0223 (4)	0.000	0.000
Na1	0.021 (2)	0.021 (2)	0.011 (3)	0.0105 (10)	0.000	0.000
O1	0.029 (3)	0.027 (3)	0.029 (3)	0.016 (2)	−0.009 (2)	−0.013 (2)
C1	0.029 (4)	0.030 (4)	0.026 (4)	0.006 (3)	−0.002 (3)	0.004 (3)
S1	0.0367 (11)	0.0255 (10)	0.0168 (10)	0.0198 (9)	−0.0023 (8)	−0.0010 (7)
Ni2	0.0475 (10)	0.0231 (8)	0.0158 (7)	0.0217 (7)	0.000	0.000
O2	0.073 (4)	0.025 (3)	0.016 (3)	0.028 (3)	−0.001 (3)	−0.002 (2)
C2	0.040 (5)	0.053 (6)	0.022 (4)	0.018 (4)	0.003 (4)	−0.007 (4)
O3	0.025 (4)	0.023 (4)	0.080 (7)	0.013 (4)	0.000	0.000
Ni3	0.0299 (8)	0.0274 (8)	0.0227 (8)	0.0139 (6)	0.000	0.000
Cl3	0.0356 (12)	0.0356 (12)	0.0241 (17)	0.0178 (6)	0.000	0.000
C3	0.030 (4)	0.031 (4)	0.029 (4)	0.011 (4)	0.004 (3)	−0.007 (3)
C4	0.023 (4)	0.030 (4)	0.018 (4)	0.012 (3)	−0.008 (3)	−0.007 (3)
C7	0.028 (4)	0.021 (4)	0.027 (4)	0.013 (3)	−0.011 (3)	−0.005 (3)
C6	0.029 (4)	0.030 (4)	0.025 (4)	0.016 (3)	−0.007 (3)	−0.002 (3)
C5	0.026 (4)	0.028 (4)	0.016 (4)	0.015 (3)	−0.006 (3)	−0.002 (3)

Geometric parameters (Å, º)

Ni1—O1^i	2.179 (6)	S1—Ni3	2.229 (2)
Ni1—O1^ii	2.179 (6)	Ni2—O2	1.870 (5)
Ni1—O1	2.179 (6)	Ni2—O2^vi	1.870 (5)
Ni1—O3^ii	2.229 (6)	Ni2—Ni3	2.693 (2)
Ni1—O3^i	2.229 (6)	O2—C7	1.288 (10)
Ni1—O3	2.229 (6)	C2—C3	1.362 (13)
Ni1—Na1	3.006 (2)	C2—H2	0.9500
Na1—O1^iii	2.382 (5)	O3—H3A	0.8498
Na1—O1^iv	2.382 (5)	Ni3—Cl3	2.165 (2)
Na1—O1^ii	2.382 (5)	Ni3—Cl3^vi	2.165 (2)
Na1—O1^v	2.382 (5)	Ni3—Ni3^vii	2.880 (3)
Na1—O1^i	2.382 (5)	Ni3—Ni3^viii	2.880 (3)
Na1—O1	2.382 (5)	C3—C4	1.406 (11)
O1—C7	1.254 (9)	C3—H3	0.9500
C1—C6	1.383 (12)	C4—C5	1.422 (11)
C1—C2	1.398 (13)	C4—C7	1.478 (11)
C1—H1	0.9500	C6—C5	1.386 (11)
S1—C5	1.778 (8)	C6—H6	0.9500
S1—Ni2	2.126 (2)
O1^i—Ni1—O1^ii	85.7 (2)	Ni2—S1—Ni3	76.34 (8)
O1^i—Ni1—O1	85.7 (2)	O2—Ni2—O2^vi	84.5 (3)
O1^ii—Ni1—O1	85.7 (2)	O2—Ni2—S1^vi	179.2 (2)
O1^i—Ni1—O3^ii	172.3 (2)	O2^vi—Ni2—S1^vi	95.24 (17)
O1^ii—Ni1—O3^ii	101.7 (2)	O2—Ni2—S1	95.24 (17)
O1—Ni1—O3^ii	96.7 (2)	O2^vi—Ni2—S1	179.2 (2)
O1^i—Ni1—O3^i	101.7 (2)	S1^vi—Ni2—S1	84.98 (11)
O1^ii—Ni1—O3^i	96.7 (2)	O2—Ni2—Ni3	126.1 (2)
O1—Ni1—O3^i	172.3 (2)	O2^vi—Ni2—Ni3	126.1 (2)
O3^ii—Ni1—O3^i	75.7 (2)	S1^vi—Ni2—Ni3	53.55 (6)
O1^i—Ni1—O3	96.7 (2)	S1—Ni2—Ni3	53.55 (6)
O1^ii—Ni1—O3	172.3 (2)	C7—O2—Ni2	136.7 (5)
O1—Ni1—O3	101.7 (2)	C3—C2—C1	119.2 (8)
O3^ii—Ni1—O3	75.7 (2)	C3—C2—H2	120.4
O3^i—Ni1—O3	75.7 (2)	C1—C2—H2	120.4
O1^i—Ni1—Na1	51.76 (14)	Ni1—O3—Ni1^vi	89.7 (3)
O1^ii—Ni1—Na1	51.76 (14)	Ni1—O3—H3A	99.1
O1—Ni1—Na1	51.76 (14)	Ni1^vi—O3—H3A	99.1
O3^ii—Ni1—Na1	134.86 (15)	Cl3—Ni3—Cl3^vi	79.68 (15)
O3^i—Ni1—Na1	134.86 (15)	Cl3—Ni3—S1^vi	100.02 (9)
O3—Ni1—Na1	134.86 (15)	Cl3^vi—Ni3—S1^vi	178.18 (9)
O1^iii—Na1—O1^iv	76.9 (2)	Cl3—Ni3—S1	178.18 (9)
O1^iii—Na1—O1^ii	103.1 (2)	Cl3^vi—Ni3—S1	100.02 (9)
O1^iv—Na1—O1^ii	180.0 (2)	S1^vi—Ni3—S1	80.22 (11)
O1^iii—Na1—O1^v	76.9 (2)	Cl3—Ni3—Ni2	128.77 (7)
O1^iv—Na1—O1^v	76.9 (2)	Cl3^vi—Ni3—Ni2	128.77 (7)
O1^ii—Na1—O1^v	103.1 (2)	S1^vi—Ni3—Ni2	50.11 (6)
O1^iii—Na1—O1^i	103.1 (2)	S1—Ni3—Ni2	50.11 (6)
O1^iv—Na1—O1^i	103.1 (2)	Cl3—Ni3—Ni3^vii	48.32 (5)
O1^ii—Na1—O1^i	76.9 (2)	Cl3^vi—Ni3—Ni3^vii	48.32 (5)
O1^v—Na1—O1^i	180.0	S1^vi—Ni3—Ni3^vii	132.64 (7)
O1^iii—Na1—O1	180.0	S1—Ni3—Ni3^vii	132.64 (7)
O1^iv—Na1—O1	103.1 (2)	Ni2—Ni3—Ni3^vii	174.64 (8)
O1^ii—Na1—O1	76.9 (2)	Cl3—Ni3—Ni3^viii	48.32 (5)
O1^v—Na1—O1	103.1 (2)	Cl3^vi—Ni3—Ni3^viii	48.32 (5)
O1^i—Na1—O1	76.9 (2)	S1^vi—Ni3—Ni3^viii	130.25 (7)
O1^iii—Na1—Ni1^iii	45.91 (14)	S1—Ni3—Ni3^viii	130.25 (7)
O1^iv—Na1—Ni1^iii	45.91 (14)	Ni2—Ni3—Ni3^viii	114.64 (8)
O1^ii—Na1—Ni1^iii	134.09 (14)	Ni3^vii—Ni3—Ni3^viii	59.999 (1)
O1^v—Na1—Ni1^iii	45.91 (14)	Ni3^vii—Cl3—Ni3^viii	83.36 (11)
O1^i—Na1—Ni1^iii	134.09 (14)	Ni3^vii—Cl3—Ni3	83.36 (11)
O1—Na1—Ni1^iii	134.09 (14)	Ni3^viii—Cl3—Ni3	83.36 (11)
O1^iii—Na1—Ni1	134.09 (14)	C2—C3—C4	122.6 (8)
O1^iv—Na1—Ni1	134.09 (14)	C2—C3—H3	118.7
O1^ii—Na1—Ni1	45.91 (14)	C4—C3—H3	118.7
O1^v—Na1—Ni1	134.09 (14)	C3—C4—C5	117.6 (7)
O1^i—Na1—Ni1	45.91 (14)	C3—C4—C7	117.3 (7)
O1—Na1—Ni1	45.91 (14)	C5—C4—C7	125.1 (7)
Ni1^iii—Na1—Ni1	180.0	O1—C7—O2	118.4 (7)
C7—O1—Ni1	120.3 (5)	O1—C7—C4	119.4 (7)
C7—O1—Na1	156.2 (5)	O2—C7—C4	122.2 (7)
Ni1—O1—Na1	82.32 (18)	C1—C6—C5	121.2 (8)
C6—C1—C2	120.0 (8)	C1—C6—H6	119.4
C6—C1—H1	120.0	C5—C6—H6	119.4
C2—C1—H1	120.0	C6—C5—C4	119.4 (7)
C5—S1—Ni2	109.9 (3)	C6—C5—S1	115.3 (6)
C5—S1—Ni3	113.1 (3)	C4—C5—S1	125.2 (6)
O2^vi—Ni2—O2—C7	−152.7 (7)	C5—C4—C7—O1	177.1 (7)
S1—Ni2—O2—C7	26.6 (8)	C3—C4—C7—O2	−179.5 (8)
Ni3—Ni2—O2—C7	−21.3 (9)	C5—C4—C7—O2	−1.1 (12)
C6—C1—C2—C3	2.1 (13)	C2—C1—C6—C5	−1.7 (12)
C1—C2—C3—C4	−1.8 (14)	C1—C6—C5—C4	1.0 (11)
C2—C3—C4—C5	1.1 (12)	C1—C6—C5—S1	−174.8 (6)
C2—C3—C4—C7	179.6 (8)	C3—C4—C5—C6	−0.7 (11)
Ni1—O1—C7—O2	−13.5 (9)	C7—C4—C5—C6	−179.1 (7)
Na1—O1—C7—O2	146.1 (10)	C3—C4—C5—S1	174.7 (6)
Ni1—O1—C7—C4	168.2 (5)	C7—C4—C5—S1	−3.7 (11)
Na1—O1—C7—C4	−32.1 (17)	Ni2—S1—C5—C6	−166.7 (5)
Ni2—O2—C7—O1	165.9 (6)	Ni3—S1—C5—C6	−83.5 (6)
Ni2—O2—C7—C4	−15.8 (13)	Ni2—S1—C5—C4	17.8 (7)
C3—C4—C7—O1	−1.3 (11)	Ni3—S1—C5—C4	100.9 (6)

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