Hexaaqua­cobalt(II) bis­(4-amino-3-methyl­benzene­sulfonate)

Zhang, W.; Chen, Y.-T.

doi:10.1107/S1600536809046583

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page m1548

doi:10.1107/S1600536809046583

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Hexaaquacobalt(II) bis(4-amino-3-methylbenzenesulfonate)

Wei Zhang ^a and Yuan-Tao Chen ^a ^*

^aDepartment of Chemistry, Qinghai Normal University, Xining 810008, People's Republic of China
^*Correspondence e-mail: chenyt@qhnu.edu.cn

(Received 26 October 2009; accepted 4 November 2009; online 11 November 2009)

In the title molecular salt, [Co(H₂O)₆](C₇H₈NO₃S)₂, the Co²⁺ cation lies on an inversion centre. In the crystal, the components are linked by N—H⋯O and O—H⋯O hydrogen bonds, thereby generating sheets parallel to (001).

Related literature

For background to hydrogen-bonded networks, see: Tai et al. (2007 ).

Experimental

Crystal data

[Co(H₂O)₆](C₇H₈NO₃S)₂
M_r = 539.43
Monoclinic, P 2₁ /n
a = 6.309 (1) Å
b = 7.0513 (11) Å
c = 24.262 (4) Å
β = 94.080 (2)°
V = 1076.6 (3) Å³
Z = 2
Mo Kα radiation
μ = 1.06 mm⁻¹
T = 293 K
0.21 × 0.16 × 0.12 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.809, T_max = 0.884
5530 measured reflections
1921 independent reflections
1690 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.073
S = 1.10
1921 reflections
143 parameters
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Selected bond lengths (Å)

Co1—O6	2.0515 (14)
Co1—O4	2.0866 (13)
Co1—O5	2.0868 (13)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2ⁱ	0.86	2.47	3.214 (2)	145
N1—H1B⋯O4	0.86	2.56	3.129 (2)	125
O4—H7⋯O2ⁱ	0.85	2.00	2.8300 (19)	167
O4—H8⋯O3ⁱⁱ	0.85	1.92	2.7675 (19)	176
O5—H9⋯O1ⁱⁱⁱ	0.85	1.94	2.7828 (19)	170
O5—H10⋯O3^iv	0.85	1.95	2.7963 (19)	174
O6—H11⋯O1^iv	0.85	1.93	2.7711 (19)	169
O6—H12⋯O2ⁱⁱ	0.85	1.90	2.7419 (19)	173
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809046583/hb5188sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809046583/hb5188Isup2.hkl

checkCIF report

Related literature top

For background to hydrogen-bonded networks, see: Tai et al. (2007).

Experimental top

A solution of 1.0 mmol 4-amino-3-methyl-benzenesulfonic acid and 1.0 mmol NaOH in 10 ml ethanol was added to a solution of 0.5 mmol Co(CH₃COO)₂4H₂O in 5 ml e thanol at room temperature. The mixture was refluxed for 4 h with stirring, then the resulting precipitate was filtered, washed, and dried in vacuo over P₄O₁₀ for 48 h. Pink blocks of (I) were obtained by slowly evaporating from methanol at room temperature.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I) showing 30% displacement ellipsoids. Atosm with suffix A are generated by the symmetry operation (1–x, 1–y, –z).

Hexaaquacobalt(II) bis(4-amino-3-methylbenzenesulfonate) top

Crystal data top

[Co(H₂O)₆](C₇H₈NO₃S)₂	F(000) = 562
M_r = 539.43	D_x = 1.664 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3103 reflections
a = 6.309 (1) Å	θ = 3.3–28.3°
b = 7.0513 (11) Å	µ = 1.06 mm⁻¹
c = 24.262 (4) Å	T = 293 K
β = 94.080 (2)°	Block, pink
V = 1076.6 (3) Å³	0.21 × 0.16 × 0.12 mm
Z = 2

Data collection top

Bruker SMART CCD diffractometer	1921 independent reflections
Radiation source: fine-focus sealed tube	1690 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
ϕ and ω scans	θ_max = 25.1°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −7→7
T_min = 0.809, T_max = 0.884	k = −8→6
5530 measured reflections	l = −25→28

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.025	H-atom parameters constrained
wR(F²) = 0.073	w = 1/[σ²(F_o²) + (0.035P)² + 0.4723P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max < 0.001
1921 reflections	Δρ_max = 0.42 e Å⁻³
143 parameters	Δρ_min = −0.33 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0268 (16)

Crystal data top

[Co(H₂O)₆](C₇H₈NO₃S)₂	V = 1076.6 (3) Å³
M_r = 539.43	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.309 (1) Å	µ = 1.06 mm⁻¹
b = 7.0513 (11) Å	T = 293 K
c = 24.262 (4) Å	0.21 × 0.16 × 0.12 mm
β = 94.080 (2)°

Data collection top

Bruker SMART CCD diffractometer	1921 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1690 reflections with I > 2σ(I)
T_min = 0.809, T_max = 0.884	R_int = 0.019
5530 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	0 restraints
wR(F²) = 0.073	H-atom parameters constrained
S = 1.10	Δρ_max = 0.42 e Å⁻³
1921 reflections	Δρ_min = −0.33 e Å⁻³
143 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

	x	y	z	U_iso*/U_eq
Co1	0.5000	0.5000	0.0000	0.02153 (14)
S1	0.59383 (7)	0.51047 (6)	0.403529 (19)	0.02233 (15)
O1	0.5037 (2)	0.66812 (19)	0.43304 (5)	0.0324 (3)
O2	0.5014 (2)	0.32921 (19)	0.41856 (5)	0.0315 (3)
O3	0.8256 (2)	0.50668 (17)	0.41067 (6)	0.0311 (3)
O4	0.3989 (2)	0.73519 (19)	0.04326 (6)	0.0363 (3)
H7	0.2775	0.7762	0.0506	0.054*
H8	0.4888	0.8156	0.0567	0.054*
O5	0.4048 (2)	0.3100 (2)	0.05939 (6)	0.0365 (4)
H9	0.2842	0.2560	0.0589	0.055*
H10	0.4924	0.2201	0.0664	0.055*
O6	0.7970 (2)	0.50949 (18)	0.04025 (7)	0.0418 (4)
H12	0.8684	0.6054	0.0519	0.063*
H11	0.8706	0.4134	0.0507	0.063*
N1	0.3463 (3)	0.6380 (3)	0.16739 (7)	0.0474 (5)
H1A	0.2229	0.6845	0.1580	0.057*
H1B	0.4320	0.6115	0.1425	0.057*
C1	0.5244 (3)	0.5467 (2)	0.33285 (7)	0.0232 (4)
C2	0.6647 (3)	0.5036 (2)	0.29306 (8)	0.0247 (4)
H2	0.7980	0.4545	0.3039	0.030*
C3	0.6088 (3)	0.5326 (2)	0.23743 (8)	0.0260 (4)
C4	0.4060 (3)	0.6062 (3)	0.22179 (8)	0.0289 (4)
C5	0.2676 (3)	0.6489 (3)	0.26221 (8)	0.0307 (4)
H5	0.1341	0.6985	0.2518	0.037*
C6	0.3248 (3)	0.6188 (3)	0.31715 (8)	0.0289 (4)
H6	0.2301	0.6467	0.3437	0.035*
C7	0.7578 (4)	0.4865 (3)	0.19380 (9)	0.0360 (5)
H7A	0.8888	0.4387	0.2110	0.054*
H7B	0.7854	0.5991	0.1733	0.054*
H7C	0.6945	0.3923	0.1693	0.054*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0198 (2)	0.0217 (2)	0.0232 (2)	−0.00091 (13)	0.00196 (14)	−0.00005 (12)
S1	0.0203 (3)	0.0220 (3)	0.0245 (3)	−0.00008 (16)	−0.00023 (18)	0.00040 (16)
O1	0.0316 (7)	0.0326 (7)	0.0328 (7)	0.0041 (6)	0.0005 (6)	−0.0082 (6)
O2	0.0299 (7)	0.0284 (7)	0.0359 (8)	−0.0036 (6)	0.0002 (6)	0.0071 (6)
O3	0.0220 (7)	0.0343 (8)	0.0362 (8)	0.0004 (5)	−0.0024 (6)	0.0012 (5)
O4	0.0278 (7)	0.0340 (8)	0.0476 (9)	−0.0019 (6)	0.0072 (6)	−0.0164 (6)
O5	0.0270 (7)	0.0361 (8)	0.0474 (9)	0.0027 (6)	0.0088 (6)	0.0160 (7)
O6	0.0311 (8)	0.0281 (8)	0.0633 (11)	−0.0004 (6)	−0.0171 (7)	−0.0025 (6)
N1	0.0528 (12)	0.0596 (13)	0.0288 (9)	0.0205 (10)	−0.0043 (8)	0.0047 (9)
C1	0.0247 (9)	0.0198 (8)	0.0248 (9)	−0.0011 (7)	−0.0006 (7)	0.0021 (7)
C2	0.0236 (9)	0.0197 (9)	0.0307 (10)	0.0007 (7)	0.0009 (8)	0.0008 (7)
C3	0.0304 (10)	0.0196 (9)	0.0283 (10)	−0.0003 (7)	0.0041 (8)	−0.0009 (7)
C4	0.0375 (11)	0.0222 (9)	0.0263 (10)	0.0008 (8)	−0.0019 (8)	0.0025 (7)
C5	0.0268 (10)	0.0306 (10)	0.0338 (11)	0.0077 (8)	−0.0042 (8)	0.0003 (8)
C6	0.0261 (10)	0.0307 (10)	0.0299 (10)	0.0031 (8)	0.0031 (8)	−0.0011 (8)
C7	0.0418 (12)	0.0335 (11)	0.0334 (11)	0.0050 (9)	0.0085 (10)	0.0004 (8)

Geometric parameters (Å, º) top

Co1—O6ⁱ	2.0515 (14)	N1—C4	1.365 (2)
Co1—O6	2.0515 (14)	N1—H1A	0.8600
Co1—O4ⁱ	2.0866 (13)	N1—H1B	0.8600
Co1—O4	2.0866 (13)	C1—C6	1.386 (2)
Co1—O5	2.0868 (13)	C1—C2	1.389 (3)
Co1—O5ⁱ	2.0868 (13)	C2—C3	1.386 (3)
S1—O1	1.4593 (13)	C2—H2	0.9300
S1—O3	1.4603 (14)	C3—C4	1.407 (3)
S1—O2	1.4617 (13)	C3—C7	1.500 (3)
S1—C1	1.7580 (18)	C4—C5	1.392 (3)
O4—H7	0.8498	C5—C6	1.372 (3)
O4—H8	0.8498	C5—H5	0.9300
O5—H9	0.8500	C6—H6	0.9300
O5—H10	0.8499	C7—H7A	0.9600
O6—H12	0.8499	C7—H7B	0.9600
O6—H11	0.8499	C7—H7C	0.9600

O6ⁱ—Co1—O6	180.0	H12—O6—H11	105.7
O6ⁱ—Co1—O4ⁱ	92.07 (6)	C4—N1—H1A	120.0
O6—Co1—O4ⁱ	87.93 (6)	C4—N1—H1B	120.0
O6ⁱ—Co1—O4	87.93 (6)	H1A—N1—H1B	120.0
O6—Co1—O4	92.07 (6)	C6—C1—C2	120.05 (17)
O4ⁱ—Co1—O4	180.0	C6—C1—S1	118.67 (14)
O6ⁱ—Co1—O5	90.56 (6)	C2—C1—S1	121.28 (14)
O6—Co1—O5	89.44 (6)	C3—C2—C1	120.94 (17)
O4ⁱ—Co1—O5	87.15 (6)	C3—C2—H2	119.5
O4—Co1—O5	92.85 (6)	C1—C2—H2	119.5
O6ⁱ—Co1—O5ⁱ	89.44 (6)	C2—C3—C4	118.72 (17)
O6—Co1—O5ⁱ	90.56 (6)	C2—C3—C7	121.77 (18)
O4ⁱ—Co1—O5ⁱ	92.85 (6)	C4—C3—C7	119.51 (17)
O4—Co1—O5ⁱ	87.15 (6)	N1—C4—C5	120.13 (17)
O5—Co1—O5ⁱ	180.0	N1—C4—C3	120.29 (18)
O1—S1—O3	112.18 (8)	C5—C4—C3	119.58 (17)
O1—S1—O2	111.56 (9)	C6—C5—C4	121.08 (17)
O3—S1—O2	111.60 (7)	C6—C5—H5	119.5
O1—S1—C1	106.81 (8)	C4—C5—H5	119.5
O3—S1—C1	107.24 (8)	C5—C6—C1	119.63 (17)
O2—S1—C1	107.10 (8)	C5—C6—H6	120.2
Co1—O4—H7	133.5	C1—C6—H6	120.2
Co1—O4—H8	120.2	C3—C7—H7A	109.5
H7—O4—H8	106.2	C3—C7—H7B	109.5
Co1—O5—H9	125.3	H7A—C7—H7B	109.5
Co1—O5—H10	113.7	C3—C7—H7C	109.5
H9—O5—H10	103.7	H7A—C7—H7C	109.5
Co1—O6—H12	129.0	H7B—C7—H7C	109.5
Co1—O6—H11	125.2

O1—S1—C1—C6	−38.02 (17)	C2—C3—C4—N1	179.47 (17)
O3—S1—C1—C6	−158.47 (14)	C7—C3—C4—N1	−0.9 (3)
O2—S1—C1—C6	81.62 (16)	C2—C3—C4—C5	0.3 (3)
O1—S1—C1—C2	142.30 (14)	C7—C3—C4—C5	179.96 (17)
O3—S1—C1—C2	21.85 (16)	N1—C4—C5—C6	−179.70 (19)
O2—S1—C1—C2	−98.06 (15)	C3—C4—C5—C6	−0.6 (3)
C6—C1—C2—C3	0.4 (3)	C4—C5—C6—C1	0.7 (3)
S1—C1—C2—C3	−179.97 (13)	C2—C1—C6—C5	−0.6 (3)
C1—C2—C3—C4	−0.2 (3)	S1—C1—C6—C5	179.75 (15)
C1—C2—C3—C7	−179.85 (17)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱⁱ	0.86	2.47	3.214 (2)	145
N1—H1B···O4	0.86	2.56	3.129 (2)	125
O4—H7···O2ⁱⁱ	0.85	2.00	2.8300 (19)	167
O4—H8···O3ⁱⁱⁱ	0.85	1.92	2.7675 (19)	176
O5—H9···O1^iv	0.85	1.94	2.7828 (19)	170
O5—H10···O3^v	0.85	1.95	2.7963 (19)	174
O6—H11···O1^v	0.85	1.93	2.7711 (19)	169
O6—H12···O2ⁱⁱⁱ	0.85	1.90	2.7419 (19)	173

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

Experimental details

Crystal data
Chemical formula	[Co(H₂O)₆](C₇H₈NO₃S)₂
M_r	539.43
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	6.309 (1), 7.0513 (11), 24.262 (4)
β (°)	94.080 (2)
V (Å³)	1076.6 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.06
Crystal size (mm)	0.21 × 0.16 × 0.12

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.809, 0.884
No. of measured, independent and observed [I > 2σ(I)] reflections	5530, 1921, 1690
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.073, 1.10
No. of reflections	1921
No. of parameters	143
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.33

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Co1—O6	2.0515 (14)	Co1—O5	2.0868 (13)
Co1—O4	2.0866 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱ	0.86	2.47	3.214 (2)	145
N1—H1B···O4	0.86	2.56	3.129 (2)	125
O4—H7···O2ⁱ	0.85	2.00	2.8300 (19)	167
O4—H8···O3ⁱⁱ	0.85	1.92	2.7675 (19)	176
O5—H9···O1ⁱⁱⁱ	0.85	1.94	2.7828 (19)	170
O5—H10···O3^iv	0.85	1.95	2.7963 (19)	174
O6—H11···O1^iv	0.85	1.93	2.7711 (19)	169
O6—H12···O2ⁱⁱ	0.85	1.90	2.7419 (19)	173

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

Acknowledgements

The authors would like to thank the Program for New Century Excellent Talents in Universities for a research grant.

References

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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tai, X. S., Yin, J., Feng, Y. M. & Kong, F. Y. (2007). Chin. J. Inorg. Chem. 24, 1812–1814. Google Scholar