Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807025512/bv2057sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807025512/bv2057Isup2.hkl |
CCDC reference: 650580
A mixture of nickel(II) chloride hexahydrate (0.24 g, 1 mmol), sodium hydroxide (0.08 g, 2 mmol), sulfanilic acid (0.17 g, 1 mmol) and water (17 mmol) was placed in a Teflon-lined stainless-steel bomb. The bomb was heated at 343 K for 72 h. Red crystals suitable for single-crystal X-ray analysis were isolated from the cool solution in about 50% yield.
H atoms attached to C atoms were placed in calculated positions and treated using a riding-model approximation (C—H = 0.95 for benzene ring H atoms with Uiso(H) = 1.2Ueq(C)). The H atoms bonded to O atoms were visible in the difference Fourier map and were included in the refinement with O—H distance restraint of 0.90, and with Uiso(H) = 1.5Ueq(O). The amine protons were refined isotropically.
The 4-aminobenzenesulfonic acid can bind to transition metals through the amino as well as the carboxylate ends. Crystal structures of metal and 4-aminobenzenesulfonic acid that have been reported include, for example, (C12H16CdN2O8S2)n (Zhou, et al.,2004), [Cu(H2NC6H4SO3)2(H2O)2].2H2O and [Mn(H2NC6H4SO3)2(H2O)2] (Gunderman et al., 1996). In two other derivatives, the isostructural compounds [M(H2NC6H4SO3)2(H2O)2].2H2O (M=Co, Zn; Shakeri & Haussuhl, 1992a; Shakeri & Haussuhl, 1992b), both ends engage in coordination.
The reaction of the sulfanilic anion with nickel(II) gives the title compound, in which the anion coordinates through the amine group. There are extensive hydrogen bonds (N—H···O, O—H···O) in the title compound. The sulfonic O atoms are linked to the coordinated water molecules and 4-aminobenzenesulfonic acid N atoms by H bonds. The complex attains a three-dimensional supramolecular by hydrogen bonds (Fig.2).
For related literature, see: Gunderman et al. (1996); Shakeri & Haussuhl (1992a, 1992b); Zhou et al. (2004).
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL.
[Ni(C6H2O3S)2(H2O)4] | F(000) = 984 |
Mr = 475.13 | Dx = 1.809 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 20.800 (11) Å | Cell parameters from 2071 reflections |
b = 6.450 (3) Å | θ = 2.0–27.5° |
c = 13.566 (7) Å | µ = 1.41 mm−1 |
β = 106.593 (9)° | T = 293 K |
V = 1744.1 (15) Å3 | Prism, green |
Z = 4 | 0.18 × 0.12 × 0.08 mm |
Bruker SMART diffractometer | 1997 independent reflections |
Radiation source: fine-focus sealed tube | 1722 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
Detector resolution: 14.6306 pixels mm-1 | θmax = 27.5°, θmin = 2.0° |
CCD_Profile_fitting scans | h = −26→26 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −7→8 |
Tmin = 0.735, Tmax = 1.000 | l = −17→17 |
6482 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.091 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0314P)2 + 10.4033P] where P = (Fo2 + 2Fc2)/3 |
1997 reflections | (Δ/σ)max = 0.030 |
140 parameters | Δρmax = 0.44 e Å−3 |
9 restraints | Δρmin = −0.49 e Å−3 |
[Ni(C6H2O3S)2(H2O)4] | V = 1744.1 (15) Å3 |
Mr = 475.13 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 20.800 (11) Å | µ = 1.41 mm−1 |
b = 6.450 (3) Å | T = 293 K |
c = 13.566 (7) Å | 0.18 × 0.12 × 0.08 mm |
β = 106.593 (9)° |
Bruker SMART diffractometer | 1997 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1722 reflections with I > 2σ(I) |
Tmin = 0.735, Tmax = 1.000 | Rint = 0.027 |
6482 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 9 restraints |
wR(F2) = 0.091 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0314P)2 + 10.4033P] where P = (Fo2 + 2Fc2)/3 |
1997 reflections | Δρmax = 0.44 e Å−3 |
140 parameters | Δρmin = −0.49 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | ||
Ni1 | 0.5000 | 0.0000 | 1.0000 | 0.01645 (14) | |
S1 | 0.87523 (3) | −0.09331 (11) | 1.20823 (6) | 0.01997 (17) | |
N1 | 0.59233 (12) | 0.0734 (4) | 0.96894 (19) | 0.0206 (5) | |
H1A | 0.5919 (18) | 0.2081 (18) | 0.951 (2) | 0.029 (9)* | |
H1B | 0.596 (2) | −0.010 (4) | 0.917 (2) | 0.057 (14)* | |
C1 | 0.78851 (14) | −0.0450 (5) | 1.1547 (2) | 0.0192 (6) | |
C2 | 0.74470 (15) | −0.2073 (5) | 1.1195 (3) | 0.0278 (7) | |
H2A | 0.7593 | −0.3463 | 1.1345 | 0.033* | |
C3 | 0.67935 (15) | −0.1665 (5) | 1.0622 (2) | 0.0257 (7) | |
H3A | 0.6490 | −0.2780 | 1.0386 | 0.031* | |
C4 | 0.65795 (13) | 0.0354 (4) | 1.0390 (2) | 0.0186 (6) | |
C5 | 0.70049 (15) | 0.1979 (5) | 1.0810 (2) | 0.0258 (6) | |
H5C | 0.6848 | 0.3367 | 1.0703 | 0.031* | |
C6 | 0.76580 (15) | 0.1582 (5) | 1.1385 (2) | 0.0256 (7) | |
H6A | 0.7951 | 0.2697 | 1.1669 | 0.031* | |
O1 | 0.89542 (11) | 0.0018 (4) | 1.31048 (17) | 0.0283 (5) | |
O2 | 0.90761 (11) | 0.0044 (4) | 1.13772 (19) | 0.0306 (5) | |
O3 | 0.88359 (11) | −0.3179 (3) | 1.21135 (17) | 0.0277 (5) | |
O4 | 0.50276 (11) | −0.2964 (3) | 0.94394 (17) | 0.0264 (5) | |
H4A | 0.5372 | −0.3104 | 0.9241 | 0.040* | |
H4B | 0.4639 (7) | −0.353 (7) | 0.907 (3) | 0.064 (15)* | |
O5 | 0.45678 (11) | 0.1030 (3) | 0.85214 (16) | 0.0251 (5) | |
H5A | 0.4360 | 0.0050 | 0.8160 | 0.038* | |
H5B | 0.4369 (15) | 0.2296 (19) | 0.841 (3) | 0.058 (14)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0141 (2) | 0.0153 (2) | 0.0175 (3) | 0.0006 (2) | 0.00051 (18) | −0.0002 (2) |
S1 | 0.0164 (3) | 0.0181 (3) | 0.0224 (4) | 0.0030 (3) | 0.0008 (3) | 0.0010 (3) |
N1 | 0.0171 (11) | 0.0202 (12) | 0.0223 (12) | 0.0002 (10) | 0.0021 (10) | 0.0019 (10) |
C1 | 0.0148 (12) | 0.0233 (15) | 0.0171 (13) | 0.0014 (11) | 0.0008 (10) | −0.0003 (11) |
C2 | 0.0247 (15) | 0.0174 (14) | 0.0364 (18) | 0.0034 (12) | 0.0011 (13) | 0.0044 (13) |
C3 | 0.0202 (14) | 0.0199 (14) | 0.0330 (17) | −0.0040 (12) | 0.0011 (12) | −0.0011 (13) |
C4 | 0.0145 (12) | 0.0223 (15) | 0.0191 (13) | 0.0021 (11) | 0.0049 (10) | 0.0010 (11) |
C5 | 0.0222 (14) | 0.0191 (14) | 0.0332 (17) | 0.0048 (12) | 0.0033 (12) | −0.0016 (13) |
C6 | 0.0203 (14) | 0.0199 (14) | 0.0324 (17) | −0.0018 (12) | 0.0009 (12) | −0.0050 (13) |
O1 | 0.0256 (11) | 0.0279 (12) | 0.0257 (11) | 0.0014 (10) | −0.0018 (9) | −0.0051 (10) |
O2 | 0.0240 (11) | 0.0306 (12) | 0.0392 (13) | 0.0041 (10) | 0.0125 (10) | 0.0084 (11) |
O3 | 0.0289 (11) | 0.0194 (11) | 0.0292 (12) | 0.0073 (9) | −0.0005 (9) | 0.0005 (9) |
O4 | 0.0239 (10) | 0.0200 (11) | 0.0341 (12) | −0.0023 (9) | 0.0065 (9) | −0.0085 (9) |
O5 | 0.0285 (11) | 0.0200 (11) | 0.0209 (11) | 0.0016 (9) | −0.0025 (9) | 0.0004 (9) |
Ni1—O5 | 2.060 (2) | C1—C6 | 1.389 (4) |
Ni1—O5i | 2.060 (2) | C2—C3 | 1.385 (4) |
Ni1—O4 | 2.064 (2) | C2—H2A | 0.9500 |
Ni1—O4i | 2.064 (2) | C3—C4 | 1.384 (4) |
Ni1—N1i | 2.133 (3) | C3—H3A | 0.9500 |
Ni1—N1 | 2.133 (3) | C4—C5 | 1.385 (4) |
S1—O3 | 1.458 (2) | C5—C6 | 1.384 (4) |
S1—O2 | 1.461 (2) | C5—H5C | 0.9500 |
S1—O1 | 1.464 (2) | C6—H6A | 0.9500 |
S1—C1 | 1.769 (3) | O4—H4A | 0.8400 |
N1—C4 | 1.444 (4) | O4—H4B | 0.898 (10) |
N1—H1A | 0.900 (10) | O5—H5A | 0.8400 |
N1—H1B | 0.905 (10) | O5—H5B | 0.908 (10) |
C1—C2 | 1.381 (4) | ||
O5—Ni1—O5i | 180.000 (1) | H1A—N1—H1B | 111.5 (16) |
O5—Ni1—O4 | 89.45 (9) | C2—C1—C6 | 120.0 (3) |
O5i—Ni1—O4 | 90.55 (9) | C2—C1—S1 | 120.2 (2) |
O5—Ni1—O4i | 90.55 (9) | C6—C1—S1 | 119.5 (2) |
O5i—Ni1—O4i | 89.45 (9) | C1—C2—C3 | 119.7 (3) |
O4—Ni1—O4i | 180.0 | C1—C2—H2A | 120.1 |
O5—Ni1—N1i | 95.55 (9) | C3—C2—H2A | 120.1 |
O5i—Ni1—N1i | 84.45 (9) | C4—C3—C2 | 120.5 (3) |
O4—Ni1—N1i | 89.34 (10) | C4—C3—H3A | 119.8 |
O4i—Ni1—N1i | 90.66 (10) | C2—C3—H3A | 119.8 |
O5—Ni1—N1 | 84.45 (9) | C3—C4—C5 | 119.5 (3) |
O5i—Ni1—N1 | 95.55 (9) | C3—C4—N1 | 119.4 (3) |
O4—Ni1—N1 | 90.66 (10) | C5—C4—N1 | 121.0 (3) |
O4i—Ni1—N1 | 89.34 (10) | C6—C5—C4 | 120.1 (3) |
N1i—Ni1—N1 | 180.000 (1) | C6—C5—H5C | 120.0 |
O3—S1—O2 | 111.96 (14) | C4—C5—H5C | 120.0 |
O3—S1—O1 | 112.91 (14) | C5—C6—C1 | 119.9 (3) |
O2—S1—O1 | 112.23 (15) | C5—C6—H6A | 120.0 |
O3—S1—C1 | 106.63 (14) | C1—C6—H6A | 120.0 |
O2—S1—C1 | 105.20 (14) | Ni1—O4—H4A | 109.5 |
O1—S1—C1 | 107.33 (13) | Ni1—O4—H4B | 118 (2) |
C4—N1—Ni1 | 124.58 (19) | H4A—O4—H4B | 119.4 |
C4—N1—H1A | 106 (2) | Ni1—O5—H5A | 109.5 |
Ni1—N1—H1A | 109 (2) | Ni1—O5—H5B | 120 (2) |
C4—N1—H1B | 98 (3) | H5A—O5—H5B | 116.5 |
Ni1—N1—H1B | 107 (3) | ||
O5—Ni1—N1—C4 | −176.5 (2) | S1—C1—C2—C3 | −169.0 (3) |
O5i—Ni1—N1—C4 | 3.5 (2) | C1—C2—C3—C4 | 0.8 (5) |
O4—Ni1—N1—C4 | −87.1 (2) | C2—C3—C4—C5 | −5.7 (5) |
O4i—Ni1—N1—C4 | 92.9 (2) | C2—C3—C4—N1 | 172.5 (3) |
N1i—Ni1—N1—C4 | 11 (100) | Ni1—N1—C4—C3 | 66.7 (4) |
O3—S1—C1—C2 | −4.2 (3) | Ni1—N1—C4—C5 | −115.1 (3) |
O2—S1—C1—C2 | 114.9 (3) | C3—C4—C5—C6 | 5.5 (5) |
O1—S1—C1—C2 | −125.4 (3) | N1—C4—C5—C6 | −172.7 (3) |
O3—S1—C1—C6 | −177.5 (2) | C4—C5—C6—C1 | −0.4 (5) |
O2—S1—C1—C6 | −58.4 (3) | C2—C1—C6—C5 | −4.5 (5) |
O1—S1—C1—C6 | 61.3 (3) | S1—C1—C6—C5 | 168.8 (2) |
C6—C1—C2—C3 | 4.3 (5) |
Symmetry code: (i) −x+1, −y, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2ii | 0.90 (1) | 2.22 (2) | 3.084 (4) | 162 (3) |
N1—H1B···O3iii | 0.91 (1) | 2.21 (1) | 3.106 (4) | 171 (4) |
O4—H4A···S1iii | 0.84 | 2.96 | 3.768 (3) | 161 |
O4—H4B···O1iv | 0.90 (1) | 1.90 (1) | 2.777 (3) | 166 (2) |
O4—H4B···S1iv | 0.90 (1) | 2.82 (3) | 3.595 (3) | 145 (3) |
O5—H5A···O3iv | 0.84 | 1.94 | 2.773 (3) | 169 |
O5—H5B···O1v | 0.91 (1) | 1.93 (1) | 2.834 (3) | 177 (4) |
Symmetry codes: (ii) −x+3/2, −y+1/2, −z+2; (iii) −x+3/2, −y−1/2, −z+2; (iv) x−1/2, −y−1/2, z−1/2; (v) x−1/2, −y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [Ni(C6H2O3S)2(H2O)4] |
Mr | 475.13 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 20.800 (11), 6.450 (3), 13.566 (7) |
β (°) | 106.593 (9) |
V (Å3) | 1744.1 (15) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.41 |
Crystal size (mm) | 0.18 × 0.12 × 0.08 |
Data collection | |
Diffractometer | Bruker SMART |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.735, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6482, 1997, 1722 |
Rint | 0.027 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.091, 1.00 |
No. of reflections | 1997 |
No. of parameters | 140 |
No. of restraints | 9 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
w = 1/[σ2(Fo2) + (0.0314P)2 + 10.4033P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.44, −0.49 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1999), SHELXTL.
Ni1—O5 | 2.060 (2) | Ni1—O4i | 2.064 (2) |
Ni1—O5i | 2.060 (2) | Ni1—N1i | 2.133 (3) |
Ni1—O4 | 2.064 (2) | Ni1—N1 | 2.133 (3) |
O5—Ni1—O5i | 180.000 (1) | O5i—Ni1—N1 | 95.55 (9) |
O5—Ni1—O4 | 89.45 (9) | O4—Ni1—N1 | 90.66 (10) |
O5i—Ni1—O4 | 90.55 (9) | O4i—Ni1—N1 | 89.34 (10) |
O5—Ni1—O4i | 90.55 (9) | N1i—Ni1—N1 | 180.000 (1) |
O5i—Ni1—O4i | 89.45 (9) | C4—N1—Ni1 | 124.58 (19) |
O4—Ni1—O4i | 180.0 | Ni1—O4—H4A | 109.5 |
O5—Ni1—N1i | 95.55 (9) | Ni1—O4—H4B | 118 (2) |
O5i—Ni1—N1i | 84.45 (9) | H4A—O4—H4B | 119.4 |
O4—Ni1—N1i | 89.34 (10) | Ni1—O5—H5A | 109.5 |
O4i—Ni1—N1i | 90.66 (10) | Ni1—O5—H5B | 120 (2) |
O5—Ni1—N1 | 84.45 (9) | H5A—O5—H5B | 116.5 |
Symmetry code: (i) −x+1, −y, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2ii | 0.900 (10) | 2.215 (15) | 3.084 (4) | 162 (3) |
N1—H1B···O3iii | 0.905 (10) | 2.209 (13) | 3.106 (4) | 171 (4) |
O4—H4A···S1iii | 0.84 | 2.96 | 3.768 (3) | 160.9 |
O4—H4B···O1iv | 0.898 (10) | 1.896 (14) | 2.777 (3) | 166 (2) |
O4—H4B···S1iv | 0.898 (10) | 2.82 (3) | 3.595 (3) | 145 (3) |
O5—H5A···O3iv | 0.84 | 1.94 | 2.773 (3) | 168.9 |
O5—H5B···O1v | 0.908 (10) | 1.927 (11) | 2.834 (3) | 177 (4) |
Symmetry codes: (ii) −x+3/2, −y+1/2, −z+2; (iii) −x+3/2, −y−1/2, −z+2; (iv) x−1/2, −y−1/2, z−1/2; (v) x−1/2, −y+1/2, z−1/2. |
The 4-aminobenzenesulfonic acid can bind to transition metals through the amino as well as the carboxylate ends. Crystal structures of metal and 4-aminobenzenesulfonic acid that have been reported include, for example, (C12H16CdN2O8S2)n (Zhou, et al.,2004), [Cu(H2NC6H4SO3)2(H2O)2].2H2O and [Mn(H2NC6H4SO3)2(H2O)2] (Gunderman et al., 1996). In two other derivatives, the isostructural compounds [M(H2NC6H4SO3)2(H2O)2].2H2O (M=Co, Zn; Shakeri & Haussuhl, 1992a; Shakeri & Haussuhl, 1992b), both ends engage in coordination.
The reaction of the sulfanilic anion with nickel(II) gives the title compound, in which the anion coordinates through the amine group. There are extensive hydrogen bonds (N—H···O, O—H···O) in the title compound. The sulfonic O atoms are linked to the coordinated water molecules and 4-aminobenzenesulfonic acid N atoms by H bonds. The complex attains a three-dimensional supramolecular by hydrogen bonds (Fig.2).