Bis(4-amino­benzene­sulfonato-κN)tetra­aqua­nickel(II)

In the title complex, [Ni(C₆H₂O₃S)₂(H₂O)₄], the Ni^II atom is octa­hedrally coordinated by two 4-amino­benzene­sulfonate N atoms and four water mol­ecules. The mol­ecular complex is centrosymmetic, with the Ni^II ion located on an inversion centre.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.030
• wR factor = 0.091
• Data-to-parameter ratio = 14.3

checkCIF/PLATON results

No syntax errors found



Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
            Tmin and Tmax reported:      0.735     1.000
            Tmin(prime) and Tmax expected:      0.772     0.893
            RR(prime) =      0.850
            Please check that your absorption correction is appropriate.
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large .............       0.85
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.89
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT480_ALERT_4_C Long H...A H-Bond Reported H4A    ..  S1      ..       2.96 Ang.
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          5
            N1  -NI1 -N1  -C4      1.00  0.00   5.657   1.555   1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.91(3), Rep   0.905(10) ......       3.00 su-Ra
              N1   -H1B     1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.90(3), Rep   0.898(10) ......       3.00 su-Ra
              O4   -H4B     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.91(3), Rep   0.905(10) ......       3.00 su-Ra
              N1   -H1B     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.90(3), Rep   0.898(10) ......       3.00 su-Ra
              O4   -H4B     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.90(3), Rep   0.898(10) ......       3.00 su-Ra
              O4   -H4B     1.555   1.555
PLAT736_ALERT_1_C H...A   Calc     2.21(3), Rep   2.209(13) ......       2.31 su-Ra
              H1B  -O3      1.555   7.647
PLAT736_ALERT_1_C H...A   Calc     1.90(4), Rep   1.896(14) ......       2.86 su-Ra
              H4B  -O1      1.555   8.445

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.893
            Tmax scaled      0.893 Tmin scaled      0.656
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          9

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
  13 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   8 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

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).

Related literature

For related literature, see: Gunderman et al. (1996); Shakeri & Haussuhl (1992a, 1992b); Zhou et al. (2004).

S2. Experimental

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.

S3. Refinement

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 U_iso(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 U_iso(H) = 1.5Ueq(O). The amine protons were refined isotropically.

Computing details

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.

Figures

	Fig. 1. ORTEP diagram of the title compound with atoms drawn as 30% probability ellipsoids (H atoms are not labled).
	Fig. 2. The three-dimensional net work structure formed by the hydrogen bonds(all H atoms were omitted for clarity).

Bis(4-aminobenzenesulfonato-κN)tetraaquanickel(II)

Crystal data

[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) Å^3	Prism, green
Z = 4	0.18 × 0.12 × 0.08 mm

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.091	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0314P)^2 + 10.4033P] where P = (Fo^2 + 2Fc^2)/3
1997 reflections	(Δ/σ)max = 0.030
140 parameters	Δρmax = 0.44 e Å^−3
9 restraints	Δρmin = −0.49 e Å^−3

Special details

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 (Ų)

	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)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

Ni1—O5	2.060 (2)	C1—C6	1.389 (4)
Ni1—O5^i	2.060 (2)	C2—C3	1.385 (4)
Ni1—O4	2.064 (2)	C2—H2A	0.9500
Ni1—O4^i	2.064 (2)	C3—C4	1.384 (4)
Ni1—N1^i	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—O5^i	180.000 (1)	H1A—N1—H1B	111.5 (16)
O5—Ni1—O4	89.45 (9)	C2—C1—C6	120.0 (3)
O5^i—Ni1—O4	90.55 (9)	C2—C1—S1	120.2 (2)
O5—Ni1—O4^i	90.55 (9)	C6—C1—S1	119.5 (2)
O5^i—Ni1—O4^i	89.45 (9)	C1—C2—C3	119.7 (3)
O4—Ni1—O4^i	180.0	C1—C2—H2A	120.1
O5—Ni1—N1^i	95.55 (9)	C3—C2—H2A	120.1
O5^i—Ni1—N1^i	84.45 (9)	C4—C3—C2	120.5 (3)
O4—Ni1—N1^i	89.34 (10)	C4—C3—H3A	119.8
O4^i—Ni1—N1^i	90.66 (10)	C2—C3—H3A	119.8
O5—Ni1—N1	84.45 (9)	C3—C4—C5	119.5 (3)
O5^i—Ni1—N1	95.55 (9)	C3—C4—N1	119.4 (3)
O4—Ni1—N1	90.66 (10)	C5—C4—N1	121.0 (3)
O4^i—Ni1—N1	89.34 (10)	C6—C5—C4	120.1 (3)
N1^i—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)
O5^i—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)
O4^i—Ni1—N1—C4	92.9 (2)	C2—C3—C4—N1	172.5 (3)
N1^i—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.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2^ii	0.90 (1)	2.22 (2)	3.084 (4)	162 (3)
N1—H1B···O3^iii	0.91 (1)	2.21 (1)	3.106 (4)	171 (4)
O4—H4A···S1^iii	0.84	2.96	3.768 (3)	161
O4—H4B···O1^iv	0.90 (1)	1.90 (1)	2.777 (3)	166 (2)
O4—H4B···S1^iv	0.90 (1)	2.82 (3)	3.595 (3)	145 (3)
O5—H5A···O3^iv	0.84	1.94	2.773 (3)	169
O5—H5B···O1^v	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.