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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 NiII nodes and a mononuclear NaI 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.
Supporting information
CCDC reference: 1917362
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[µ
4-(2-carboxylatophenyl)sulfanido]di-µ
3-chlorido-tri-µ
2-hydroxido-octanickel(II)sodium(I)]
top
Crystal data top
[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) Å3 | T = 100 K |
Z = 2 | Prism, black |
F(000) = 1528 | 0.2 × 0.2 × 0.15 mm |
Data collection top
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 top
Refinement on F2 | 1 restraint |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.068 | H-atom parameters constrained |
wR(F2) = 0.213 | w = 1/[σ2(Fo2) + (0.1205P)2 + 36.4479P] where P = (Fo2 + 2Fc2)/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 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 | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
Ni1—O1i | 2.179 (6) | S1—Ni3 | 2.229 (2) |
Ni1—O1ii | 2.179 (6) | Ni2—O2 | 1.870 (5) |
Ni1—O1 | 2.179 (6) | Ni2—O2vi | 1.870 (5) |
Ni1—O3ii | 2.229 (6) | Ni2—Ni3 | 2.693 (2) |
Ni1—O3i | 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—O1iii | 2.382 (5) | O3—H3A | 0.8498 |
Na1—O1iv | 2.382 (5) | Ni3—Cl3 | 2.165 (2) |
Na1—O1ii | 2.382 (5) | Ni3—Cl3vi | 2.165 (2) |
Na1—O1v | 2.382 (5) | Ni3—Ni3vii | 2.880 (3) |
Na1—O1i | 2.382 (5) | Ni3—Ni3viii | 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) | | |
| | | |
O1i—Ni1—O1ii | 85.7 (2) | Ni2—S1—Ni3 | 76.34 (8) |
O1i—Ni1—O1 | 85.7 (2) | O2—Ni2—O2vi | 84.5 (3) |
O1ii—Ni1—O1 | 85.7 (2) | O2—Ni2—S1vi | 179.2 (2) |
O1i—Ni1—O3ii | 172.3 (2) | O2vi—Ni2—S1vi | 95.24 (17) |
O1ii—Ni1—O3ii | 101.7 (2) | O2—Ni2—S1 | 95.24 (17) |
O1—Ni1—O3ii | 96.7 (2) | O2vi—Ni2—S1 | 179.2 (2) |
O1i—Ni1—O3i | 101.7 (2) | S1vi—Ni2—S1 | 84.98 (11) |
O1ii—Ni1—O3i | 96.7 (2) | O2—Ni2—Ni3 | 126.1 (2) |
O1—Ni1—O3i | 172.3 (2) | O2vi—Ni2—Ni3 | 126.1 (2) |
O3ii—Ni1—O3i | 75.7 (2) | S1vi—Ni2—Ni3 | 53.55 (6) |
O1i—Ni1—O3 | 96.7 (2) | S1—Ni2—Ni3 | 53.55 (6) |
O1ii—Ni1—O3 | 172.3 (2) | C7—O2—Ni2 | 136.7 (5) |
O1—Ni1—O3 | 101.7 (2) | C3—C2—C1 | 119.2 (8) |
O3ii—Ni1—O3 | 75.7 (2) | C3—C2—H2 | 120.4 |
O3i—Ni1—O3 | 75.7 (2) | C1—C2—H2 | 120.4 |
O1i—Ni1—Na1 | 51.76 (14) | Ni1—O3—Ni1vi | 89.7 (3) |
O1ii—Ni1—Na1 | 51.76 (14) | Ni1—O3—H3A | 99.1 |
O1—Ni1—Na1 | 51.76 (14) | Ni1vi—O3—H3A | 99.1 |
O3ii—Ni1—Na1 | 134.86 (15) | Cl3—Ni3—Cl3vi | 79.68 (15) |
O3i—Ni1—Na1 | 134.86 (15) | Cl3—Ni3—S1vi | 100.02 (9) |
O3—Ni1—Na1 | 134.86 (15) | Cl3vi—Ni3—S1vi | 178.18 (9) |
O1iii—Na1—O1iv | 76.9 (2) | Cl3—Ni3—S1 | 178.18 (9) |
O1iii—Na1—O1ii | 103.1 (2) | Cl3vi—Ni3—S1 | 100.02 (9) |
O1iv—Na1—O1ii | 180.0 (2) | S1vi—Ni3—S1 | 80.22 (11) |
O1iii—Na1—O1v | 76.9 (2) | Cl3—Ni3—Ni2 | 128.77 (7) |
O1iv—Na1—O1v | 76.9 (2) | Cl3vi—Ni3—Ni2 | 128.77 (7) |
O1ii—Na1—O1v | 103.1 (2) | S1vi—Ni3—Ni2 | 50.11 (6) |
O1iii—Na1—O1i | 103.1 (2) | S1—Ni3—Ni2 | 50.11 (6) |
O1iv—Na1—O1i | 103.1 (2) | Cl3—Ni3—Ni3vii | 48.32 (5) |
O1ii—Na1—O1i | 76.9 (2) | Cl3vi—Ni3—Ni3vii | 48.32 (5) |
O1v—Na1—O1i | 180.0 | S1vi—Ni3—Ni3vii | 132.64 (7) |
O1iii—Na1—O1 | 180.0 | S1—Ni3—Ni3vii | 132.64 (7) |
O1iv—Na1—O1 | 103.1 (2) | Ni2—Ni3—Ni3vii | 174.64 (8) |
O1ii—Na1—O1 | 76.9 (2) | Cl3—Ni3—Ni3viii | 48.32 (5) |
O1v—Na1—O1 | 103.1 (2) | Cl3vi—Ni3—Ni3viii | 48.32 (5) |
O1i—Na1—O1 | 76.9 (2) | S1vi—Ni3—Ni3viii | 130.25 (7) |
O1iii—Na1—Ni1iii | 45.91 (14) | S1—Ni3—Ni3viii | 130.25 (7) |
O1iv—Na1—Ni1iii | 45.91 (14) | Ni2—Ni3—Ni3viii | 114.64 (8) |
O1ii—Na1—Ni1iii | 134.09 (14) | Ni3vii—Ni3—Ni3viii | 59.999 (1) |
O1v—Na1—Ni1iii | 45.91 (14) | Ni3vii—Cl3—Ni3viii | 83.36 (11) |
O1i—Na1—Ni1iii | 134.09 (14) | Ni3vii—Cl3—Ni3 | 83.36 (11) |
O1—Na1—Ni1iii | 134.09 (14) | Ni3viii—Cl3—Ni3 | 83.36 (11) |
O1iii—Na1—Ni1 | 134.09 (14) | C2—C3—C4 | 122.6 (8) |
O1iv—Na1—Ni1 | 134.09 (14) | C2—C3—H3 | 118.7 |
O1ii—Na1—Ni1 | 45.91 (14) | C4—C3—H3 | 118.7 |
O1v—Na1—Ni1 | 134.09 (14) | C3—C4—C5 | 117.6 (7) |
O1i—Na1—Ni1 | 45.91 (14) | C3—C4—C7 | 117.3 (7) |
O1—Na1—Ni1 | 45.91 (14) | C5—C4—C7 | 125.1 (7) |
Ni1iii—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) |
| | | |
O2vi—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. |
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