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In the title compound, [Ni(H2O)6]L2·4H2O, where HL = 3-carboxy-4-hydroxy­benzene­sulfonic acid (C7H6O6S), each NiII cation lies on an inversion center and is octahedrally coordinated by six water mol­ecules. The L- anions do not coordinate to nickel, but act as counter-anions. The crystal structure is composed of alternating layers of [Ni(H2O)6]2+ cations and sulfonate anions. The [Ni(H2O)6]2+ cations, water mol­ecules and L- anions are connected through a complex pattern of hydrogen-bonding interactions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803013072/cf6254sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803013072/cf6254Isup2.hkl
Contains datablock I

CCDC reference: 217377

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.038
  • wR factor = 0.101
  • Data-to-parameter ratio = 12.5

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry








Comment top

The crystal structures of five transition metal (Mn, Co, Ni, Cu and Zn) 3-carboxy-4-hydroxybenzenesulfonates have been determined. The structures of the manganese (Ma et al., 2003a) and cobalt compound (Ma et al., 2003b) have been reported in the preceding papers. The crystal structure of the nickel compound, (I), is presented here. The crystal structures of the other two related compounds are reported in the following papers.

The NiII atom is located on an inversion center, and all other atoms are in general positions. Selected bond lengths and angles are given in Table 1. Fig. 1 shows the asymmetric unit, together with the complete coordination environment of the NiII cation. Compound (I) is isostructural with the cobalt compound (Ma et al., 2003b). The N—O distances range from 2.030 (2) to 2.057 (2) Å. The average Ni—O distance of 2.047 Å is similar to the values in other nickel compounds (Gunderman et al., 1997; Kosnic et al., 1992).

The alternating layers of [Ni(H2O)6]2+ cations and sulfonate anions in (I) are shown in Fig.2. Selected hydrogen-bond parameters are listed in Table 2.

Experimental top

A mixture of 3-carboxy-4-hydroxybenzenesulfonic acid (0.44 g, 2 mmol) and NiCO3 (0.12 g, 1 mmol) in water (10 ml) was stirred at room temperature for 30 min. Green crystals of compound (I) were obtained after leaving the solution to stand at room temperature for several days. Analysis calculated for C14H30NiO22S2: C 24.98, H 4.49%; found: C 24.82, H 4.47%.

Refinement top

All H atoms on C atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C). The H atoms of the carboxyl group and hydroxyl group were also positioned geometrically and refined as riding atoms, with O—H = 0.82 Å and Uiso(H) = 1.5Ueq(O). The water H atoms were located in a difference Fourier map and refined with Uiso(H) = 1.5Ueq(O).

Computing details top

Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1990); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. View of the asymmetric unit, expanded to show the complete coordination of NiII, with the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. View of the alternating layers of cations and anions, along the a axis.
(I) top
Crystal data top
[Ni(H2O)6](C7H5O6S)2·4H2OZ = 1
Mr = 673.21F(000) = 350
Triclinic, P1Dx = 1.686 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.5380 (9) ÅCell parameters from 20 reflections
b = 7.2199 (10) Åθ = 5.9–9.7°
c = 14.534 (4) ŵ = 0.99 mm1
α = 92.931 (16)°T = 293 K
β = 96.494 (16)°Block, green
γ = 102.727 (12)°0.36 × 0.24 × 0.15 mm
V = 662.9 (2) Å3
Data collection top
Siemens P4
diffractometer
2145 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.026
Graphite monochromatorθmax = 26.0°, θmin = 2.8°
ω scansh = 18
Absorption correction: ψ scan
(North et al., 1968)
k = 88
Tmin = 0.687, Tmax = 0.863l = 1717
3424 measured reflections3 standard reflections every 97 reflections
2599 independent reflections intensity decay: none
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.101H atoms treated by a mixture of independent and constrained refinement
S = 1.09 w = 1/[σ2(Fo2) + (0.0506P)2 + 0.1374P]
where P = (Fo2 + 2Fc2)/3
2599 reflections(Δ/σ)max < 0.001
208 parametersΔρmax = 0.58 e Å3
10 restraintsΔρmin = 0.47 e Å3
Crystal data top
[Ni(H2O)6](C7H5O6S)2·4H2Oγ = 102.727 (12)°
Mr = 673.21V = 662.9 (2) Å3
Triclinic, P1Z = 1
a = 6.5380 (9) ÅMo Kα radiation
b = 7.2199 (10) ŵ = 0.99 mm1
c = 14.534 (4) ÅT = 293 K
α = 92.931 (16)°0.36 × 0.24 × 0.15 mm
β = 96.494 (16)°
Data collection top
Siemens P4
diffractometer
2145 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.026
Tmin = 0.687, Tmax = 0.8633 standard reflections every 97 reflections
3424 measured reflections intensity decay: none
2599 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.03810 restraints
wR(F2) = 0.101H atoms treated by a mixture of independent and constrained refinement
S = 1.09Δρmax = 0.58 e Å3
2599 reflectionsΔρmin = 0.47 e Å3
208 parameters
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.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.3984 (4)0.1628 (3)0.35573 (17)0.0278 (5)
C20.3124 (4)0.1629 (3)0.43782 (17)0.0279 (5)
H20.16870.11250.43800.033*
C30.4391 (4)0.2378 (3)0.52047 (17)0.0273 (5)
C40.6558 (4)0.3165 (4)0.51950 (18)0.0295 (6)
C50.7410 (4)0.3130 (4)0.43618 (19)0.0355 (6)
H50.88480.36170.43550.043*
C60.6144 (4)0.2382 (4)0.35461 (19)0.0343 (6)
H60.67220.23780.29900.041*
C70.3473 (4)0.2389 (4)0.60864 (18)0.0316 (6)
O10.0942 (4)0.2087 (3)0.23422 (16)0.0517 (6)
O20.3624 (3)0.0621 (3)0.17979 (14)0.0482 (6)
O30.1033 (3)0.1100 (3)0.26806 (13)0.0381 (5)
O40.1434 (3)0.1633 (3)0.59849 (14)0.0474 (6)
H40.09960.16690.64910.071*
O50.4502 (3)0.3030 (3)0.68376 (13)0.0438 (5)
O60.7848 (3)0.3981 (3)0.59650 (14)0.0432 (5)
H6A0.71750.39160.64100.065*
OW10.7004 (4)0.3312 (3)0.97347 (16)0.0486 (6)
OW20.7265 (3)0.7363 (3)0.97940 (14)0.0395 (5)
OW30.6189 (3)0.5222 (3)1.13815 (13)0.0406 (5)
OW40.7348 (3)0.0508 (3)0.09873 (15)0.0427 (5)
OW50.0476 (4)0.5520 (3)0.16465 (15)0.0440 (5)
S10.23022 (10)0.07503 (9)0.25133 (4)0.02897 (18)
Ni10.50000.50001.00000.02897 (16)
H1A0.750 (5)0.253 (4)1.0117 (19)0.043*
H1B0.803 (4)0.374 (4)0.940 (2)0.043*
H2A0.721 (5)0.787 (4)0.9240 (15)0.043*
H2B0.743 (5)0.835 (3)1.0213 (18)0.043*
H3A0.589 (5)0.595 (4)1.1831 (18)0.043*
H3B0.756 (3)0.523 (4)1.153 (2)0.043*
H4A0.834 (4)0.097 (4)0.1467 (17)0.043*
H4B0.610 (4)0.028 (4)0.122 (2)0.043*
H5A0.086 (5)0.463 (4)0.196 (2)0.043*
H5B0.093 (5)0.658 (3)0.2035 (19)0.043*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0303 (13)0.0270 (12)0.0263 (12)0.0074 (10)0.0026 (10)0.0035 (10)
C20.0257 (12)0.0296 (13)0.0290 (13)0.0062 (10)0.0054 (10)0.0034 (10)
C30.0282 (13)0.0272 (13)0.0287 (13)0.0087 (10)0.0072 (10)0.0035 (10)
C40.0284 (13)0.0279 (13)0.0313 (13)0.0058 (10)0.0012 (11)0.0012 (10)
C50.0248 (13)0.0400 (15)0.0393 (15)0.0005 (11)0.0073 (11)0.0038 (12)
C60.0333 (14)0.0377 (15)0.0330 (14)0.0044 (12)0.0138 (12)0.0063 (11)
C70.0334 (14)0.0327 (14)0.0302 (14)0.0099 (11)0.0064 (11)0.0020 (11)
O10.0559 (14)0.0447 (12)0.0537 (13)0.0218 (11)0.0148 (11)0.0005 (10)
O20.0407 (12)0.0726 (15)0.0281 (10)0.0032 (11)0.0123 (9)0.0001 (10)
O30.0450 (11)0.0347 (10)0.0304 (10)0.0024 (9)0.0118 (9)0.0015 (8)
O40.0347 (11)0.0699 (15)0.0324 (11)0.0017 (10)0.0144 (9)0.0077 (10)
O50.0399 (11)0.0624 (14)0.0275 (10)0.0110 (10)0.0031 (9)0.0053 (9)
O60.0315 (10)0.0584 (13)0.0343 (11)0.0037 (9)0.0023 (8)0.0029 (9)
OW10.0572 (14)0.0538 (14)0.0489 (13)0.0319 (12)0.0238 (11)0.0145 (11)
OW20.0507 (12)0.0374 (11)0.0297 (10)0.0062 (10)0.0090 (9)0.0049 (8)
OW30.0433 (12)0.0544 (13)0.0261 (10)0.0160 (10)0.0047 (9)0.0010 (9)
OW40.0349 (11)0.0509 (13)0.0411 (11)0.0097 (10)0.0022 (9)0.0018 (10)
OW50.0520 (13)0.0351 (11)0.0455 (12)0.0135 (10)0.0037 (10)0.0023 (9)
S10.0312 (3)0.0316 (3)0.0238 (3)0.0055 (3)0.0045 (3)0.0042 (2)
Ni10.0345 (3)0.0309 (3)0.0238 (2)0.0106 (2)0.00686 (19)0.00235 (18)
Geometric parameters (Å, º) top
C1—C21.375 (4)O6—H6A0.820
C1—C61.399 (4)OW1—Ni12.030 (2)
C1—S11.769 (3)OW1—H1A0.898 (18)
C2—C31.390 (4)OW1—H1B0.883 (18)
C2—H20.930OW2—Ni12.057 (2)
C3—C41.407 (4)OW2—H2A0.902 (18)
C3—C71.476 (3)OW2—H2B0.893 (18)
C4—O61.346 (3)OW3—Ni12.054 (2)
C4—C51.390 (4)OW3—H3A0.882 (18)
C5—C61.378 (4)OW3—H3B0.894 (18)
C5—H50.930OW4—H4A0.894 (18)
C6—H60.930OW4—H4B0.902 (18)
C7—O51.226 (3)OW5—H5A0.872 (18)
C7—O41.313 (3)OW5—H5B0.902 (18)
O1—S11.462 (2)Ni1—OW1i2.030 (2)
O2—S11.437 (2)Ni1—OW3i2.054 (2)
O3—S11.4569 (19)Ni1—OW2i2.057 (2)
O4—H40.820
C2—C1—C6120.3 (2)H2A—OW2—H2B105 (3)
C2—C1—S1119.0 (2)Ni1—OW3—H3A127 (2)
C6—C1—S1120.7 (2)Ni1—OW3—H3B118 (2)
C1—C2—C3120.4 (2)H3A—OW3—H3B105 (3)
C1—C2—H2119.8H4A—OW4—H4B106 (3)
C3—C2—H2119.8H5A—OW5—H5B104 (3)
C2—C3—C4119.6 (2)O2—S1—O3112.45 (13)
C2—C3—C7120.5 (2)O2—S1—O1113.34 (15)
C4—C3—C7119.9 (2)O3—S1—O1109.89 (14)
O6—C4—C5118.2 (2)O2—S1—C1107.45 (12)
O6—C4—C3122.4 (2)O3—S1—C1106.75 (12)
C5—C4—C3119.4 (2)O1—S1—C1106.54 (12)
C6—C5—C4120.6 (2)OW1—Ni1—OW1i180.0
C6—C5—H5119.7OW1—Ni1—OW3i91.04 (9)
C4—C5—H5119.7OW1i—Ni1—OW3i88.96 (9)
C5—C6—C1119.7 (3)OW1—Ni1—OW388.96 (9)
C5—C6—H6120.1OW1i—Ni1—OW391.04 (9)
C1—C6—H6120.1OW3i—Ni1—OW3180.0
O5—C7—O4123.3 (3)OW1—Ni1—OW2i90.08 (10)
O5—C7—C3123.7 (3)OW1i—Ni1—OW2i89.92 (10)
O4—C7—C3113.0 (2)OW3i—Ni1—OW2i90.05 (9)
C7—O4—H4109.5OW3—Ni1—OW2i89.95 (9)
C4—O6—H6A109.5OW1—Ni1—OW289.92 (10)
Ni1—OW1—H1A127 (2)OW1i—Ni1—OW290.08 (10)
Ni1—OW1—H1B118 (2)OW3i—Ni1—OW289.95 (9)
H1A—OW1—H1B106 (3)OW3—Ni1—OW290.05 (9)
Ni1—OW2—H2A120 (2)OW2i—Ni1—OW2180.0
Ni1—OW2—H2B115 (2)
C6—C1—C2—C30.0 (4)S1—C1—C6—C5177.3 (2)
S1—C1—C2—C3177.46 (19)C2—C3—C7—O5179.9 (3)
C1—C2—C3—C41.0 (4)C4—C3—C7—O51.2 (4)
C1—C2—C3—C7179.7 (2)C2—C3—C7—O40.3 (4)
C2—C3—C4—O6177.3 (2)C4—C3—C7—O4179.1 (2)
C7—C3—C4—O61.5 (4)C2—C1—S1—O2170.8 (2)
C2—C3—C4—C51.9 (4)C6—C1—S1—O211.8 (3)
C7—C3—C4—C5179.4 (2)C2—C1—S1—O349.9 (2)
O6—C4—C5—C6177.4 (2)C6—C1—S1—O3132.6 (2)
C3—C4—C5—C61.8 (4)C2—C1—S1—O167.4 (2)
C4—C5—C6—C10.8 (4)C6—C1—S1—O1110.0 (2)
C2—C1—C6—C50.1 (4)
Symmetry code: (i) x+1, y+1, z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
OW1—H1A···OW4ii0.90 (2)1.97 (2)2.820 (3)156 (3)
OW1—H1B···OW5iii0.88 (2)1.93 (2)2.786 (3)162 (3)
OW2—H2A···O2iii0.90 (2)2.00 (2)2.867 (3)161 (3)
OW2—H2B···OW4iv0.89 (2)1.89 (2)2.773 (3)170 (3)
OW3—H3B···OW5v0.89 (2)1.86 (2)2.745 (3)169 (3)
OW3—H3A···O5i0.88 (2)2.10 (2)2.946 (3)161 (3)
OW4—H4B···O20.90 (2)1.96 (2)2.837 (3)163 (3)
OW4—H4A···O1vi0.89 (2)1.99 (2)2.871 (3)169 (3)
OW5—H5B···O3vii0.90 (2)1.86 (2)2.731 (3)162 (3)
OW5—H5A···O10.87 (2)1.96 (2)2.789 (3)160 (3)
O4—H4···O3viii0.821.882.650 (3)155
O6—H6A···O50.821.912.631 (3)146
Symmetry codes: (i) x+1, y+1, z+2; (ii) x, y, z+1; (iii) x+1, y+1, z+1; (iv) x, y+1, z+1; (v) x+1, y, z+1; (vi) x+1, y, z; (vii) x, y+1, z; (viii) x, y, z+1.

Experimental details

Crystal data
Chemical formula[Ni(H2O)6](C7H5O6S)2·4H2O
Mr673.21
Crystal system, space groupTriclinic, P1
Temperature (K)293
a, b, c (Å)6.5380 (9), 7.2199 (10), 14.534 (4)
α, β, γ (°)92.931 (16), 96.494 (16), 102.727 (12)
V3)662.9 (2)
Z1
Radiation typeMo Kα
µ (mm1)0.99
Crystal size (mm)0.36 × 0.24 × 0.15
Data collection
DiffractometerSiemens P4
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.687, 0.863
No. of measured, independent and
observed [I > 2σ(I)] reflections
3424, 2599, 2145
Rint0.026
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.101, 1.09
No. of reflections2599
No. of parameters208
No. of restraints10
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.58, 0.47

Computer programs: XSCANS (Siemens, 1994), XSCANS, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL-Plus (Sheldrick, 1990), SHELXL97.

Selected geometric parameters (Å, º) top
C4—O61.346 (3)O3—S11.4569 (19)
C7—O51.226 (3)OW1—Ni12.030 (2)
C7—O41.313 (3)OW2—Ni12.057 (2)
O1—S11.462 (2)OW3—Ni12.054 (2)
O2—S11.437 (2)
O5—C7—O4123.3 (3)OW1—Ni1—OW388.96 (9)
O2—S1—O3112.45 (13)OW1—Ni1—OW289.92 (10)
O2—S1—O1113.34 (15)OW3—Ni1—OW290.05 (9)
O3—S1—O1109.89 (14)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
OW1—H1A···OW4i0.898 (18)1.973 (19)2.820 (3)156 (3)
OW1—H1B···OW5ii0.883 (18)1.934 (19)2.786 (3)162 (3)
OW2—H2A···O2ii0.902 (18)2.001 (19)2.867 (3)161 (3)
OW2—H2B···OW4iii0.893 (18)1.888 (19)2.773 (3)170 (3)
OW3—H3B···OW5iv0.894 (18)1.861 (19)2.745 (3)169 (3)
OW3—H3A···O5v0.882 (18)2.099 (19)2.946 (3)161 (3)
OW4—H4B···O20.902 (18)1.964 (19)2.837 (3)163 (3)
OW4—H4A···O1vi0.894 (18)1.989 (19)2.871 (3)169 (3)
OW5—H5B···O3vii0.902 (18)1.860 (19)2.731 (3)162 (3)
OW5—H5A···O10.872 (18)1.955 (19)2.789 (3)160 (3)
O4—H4···O3viii0.821.882.650 (3)155
O6—H6A···O50.821.912.631 (3)146
Symmetry codes: (i) x, y, z+1; (ii) x+1, y+1, z+1; (iii) x, y+1, z+1; (iv) x+1, y, z+1; (v) x+1, y+1, z+2; (vi) x+1, y, z; (vii) x, y+1, z; (viii) x, y, z+1.
 

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