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Acta Cryst. (2008). E64, m1162-m1163    [ doi:10.1107/S1600536808025579 ]

Poly[[bis([mu]2-4-aminobenzenesulfonato-[kappa]2N:O)diaquamanganese(II)] dihydrate]

Z. L. Li, Y. W. Xuan, W. Wu and D. P. Xie

Abstract top

The title compound, {[Mn(NH2C6H4SO3)2(H2O)2]·2H2O}n, was prepared under mild hydrothermal conditions. The unique MnII ion is located on a crystallographic inversion center and is coordinated by two -NH2 and two -SO3 groups from four 4-aminobenzenesulfonate ligands and by two water molecules in the axial positions, forming a slightly distorted octahedral coordination environment. The 4-aminobenzenesulfonate anions behave as [mu]2-bridging ligands to produce a two-dimensional structure. In the crystal structure, intermolecular N-H...O, O-H...O and C-H...O hydrogen bonds link the layers into a three-dimensional network.

Comment top

The asymmetric unit of the title compound (I) is illustrated in Fig.1. This consists of one half of MnII ion, one 4-aminobenzenesulfonate ligand, one coordinated water molecule and one solvent water molecule. The title compound is isostructural with the Cobalt and Zinc analogs (Shakeri & Haussuhl, 1992). It is interesting to note that the title compound has very similar layered structure as that observed in [Cd(1,5 nds)-(H2O)2]n (Cai et al., 2003) (1,5-nds = 1,5-naphthalenedisulfonate) in which the CdII ion is also coordinated octahedrally by two water molecules occupying the axial positions and the layers are connected by hydrogen bonds formed between the coordinated water molecules and the sulfonate O atoms. In the crystal structure of (I) inter-layered hydrogen bonds formed between the coordinated water molecules and the –NH2 groups with the free –SO3- oxygen atoms generate an extended 3-D structure (Fig.2)

Related literature top

For the isostructural Zn and Co compounds, see: Shakeri & Haussuhl (1992). For a similar layered structure, see: Cai et al. (2003).

Experimental top

All the reagents were of AR grade and used without further purification. p-anilinesulfonic acid (0.8690 g, 5 mmol) were dissolved in 50 ml H2O solution, the mixed solution was basified with 1 mol.L-1 KOH to pH =7.5. Then the resultant solution was added in 10 ml double-distilled water containing MnCl2.4H2O (0.3950 g, 2 mmol), the resulting solution was heated at 423 K for 96 h. After cooling to room temperature, block crystals were obtained in a yield up to 37.6%.

Refinement top

H atoms bonded to O atoms were included in 'as found' positions and refined with Uiso(H)=1.5Ueq(O). Other H atoms were positioned geometrically and refined using a riding model, with C-H = 0.97 Å ; N-H = 0.90 Å and with Uiso(H)=1.2 times Ueq(C,N).

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); 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
[Figure 1] Fig. 1. The asymmetric unit of the title compound showing 30% probability ellipsoids.
[Figure 2] Fig. 2. Part of the crystal structure of the title compound showing hydrogen bonds as dashed lines.
Poly[[bis(µ2-4-aminobenzenesulfonato-κ2N:O)diaquamanganese(II)] dihydrate] top
Crystal data top
[Mn(C6H6NO3S)2(H2O)2]·2H2OF000 = 486
Mr = 471.36Dx = 1.766 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2041 reflections
a = 7.4485 (8) Åθ = 2.5–26.2º
b = 17.4102 (19) ŵ = 1.04 mm−1
c = 7.6509 (9) ÅT = 295 (2) K
β = 116.688 (1)ºBlock, yellow
V = 886.47 (17) Å30.49 × 0.45 × 0.45 mm
Z = 2
Data collection top
Bruker SMART CCD
diffractometer		1637 independent reflections
Radiation source: fine-focus sealed tube1585 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.015
Detector resolution: 0 pixels mm-1θmax = 25.5º
T = 295(2) Kθmin = 2.3º
φ and ω scansh = −9→9
Absorption correction: multi-scan
(SADABS; Bruker, 2002)		k = −19→20
Tmin = 0.547, Tmax = 0.625l = −9→9
6604 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.048H-atom parameters constrained
wR(F2) = 0.149  w = 1/[σ2(Fo2) + (0.0902P)2 + 2.4519P]
where P = (Fo2 + 2Fc2)/3
S = 1.11(Δ/σ)max < 0.001
1637 reflectionsΔρmax = 1.19 e Å−3
124 parametersΔρmin = −1.03 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Mn(C6H6NO3S)2(H2O)2]·2H2OV = 886.47 (17) Å3
Mr = 471.36Z = 2
Monoclinic, P21/nMo Kα
a = 7.4485 (8) ŵ = 1.04 mm−1
b = 17.4102 (19) ÅT = 295 (2) K
c = 7.6509 (9) Å0.49 × 0.45 × 0.45 mm
β = 116.688 (1)º
Data collection top
Bruker SMART CCD
diffractometer		1637 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2002)		1585 reflections with I > 2σ(I)
Tmin = 0.547, Tmax = 0.625Rint = 0.015
6604 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.048124 parameters
wR(F2) = 0.149H-atom parameters constrained
S = 1.11Δρmax = 1.19 e Å−3
1637 reflectionsΔρmin = −1.03 e Å−3
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
Mn10.50001.00000.50000.0103 (3)
S10.65941 (14)0.89771 (5)0.94564 (13)0.0222 (3)
O10.4931 (4)0.92302 (17)0.7611 (4)0.0299 (7)
O20.8422 (4)0.94184 (16)0.9916 (4)0.0315 (7)
O30.6018 (5)0.89731 (17)1.1046 (4)0.0333 (7)
O40.7291 (5)0.9436 (2)0.4921 (4)0.0376 (8)
H1W0.71140.94060.37850.056*
H2W0.84950.94110.57060.056*
N10.8133 (5)0.57368 (19)0.7847 (5)0.0265 (7)
H1A0.86010.57710.69500.032*
H1B0.69180.55120.72530.032*
C10.7134 (6)0.8009 (2)0.9110 (5)0.0238 (8)
C20.8724 (6)0.7854 (2)0.8697 (6)0.0307 (9)
H20.95470.82500.86690.037*
C30.9088 (6)0.7106 (2)0.8325 (6)0.0309 (9)
H31.01670.69970.80650.037*
C40.7828 (6)0.6515 (2)0.8344 (5)0.0236 (8)
C50.6261 (6)0.6673 (2)0.8804 (6)0.0289 (9)
H50.54520.62760.88570.035*
C60.5900 (6)0.7421 (2)0.9184 (6)0.0288 (9)
H60.48470.75290.94850.035*
O50.1093 (5)0.9329 (2)0.7587 (5)0.0484 (9)
H3W0.20660.92850.73620.073*
H4W0.11880.96790.83420.073*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.0192 (4)0.0266 (4)0.0139 (4)−0.0005 (2)0.0062 (3)−0.0015 (2)
S10.0264 (5)0.0180 (5)0.0240 (5)0.0012 (3)0.0129 (4)−0.0003 (3)
O10.0309 (15)0.0283 (15)0.0302 (15)0.0046 (12)0.0134 (12)0.0053 (12)
O20.0311 (15)0.0227 (15)0.0398 (16)−0.0025 (12)0.0153 (13)−0.0021 (12)
O30.0452 (18)0.0300 (16)0.0328 (15)0.0003 (13)0.0246 (14)−0.0025 (12)
O40.0328 (16)0.050 (2)0.0276 (15)0.0088 (14)0.0110 (13)−0.0041 (14)
N10.0320 (18)0.0209 (17)0.0281 (17)−0.0011 (13)0.0147 (15)−0.0042 (13)
C10.0269 (19)0.0205 (18)0.0237 (18)0.0017 (15)0.0110 (15)−0.0006 (14)
C20.036 (2)0.021 (2)0.042 (2)−0.0019 (16)0.023 (2)−0.0006 (17)
C30.031 (2)0.027 (2)0.042 (2)0.0011 (17)0.0226 (19)−0.0010 (17)
C40.028 (2)0.0185 (18)0.0210 (18)0.0038 (14)0.0081 (15)0.0015 (14)
C50.031 (2)0.025 (2)0.032 (2)−0.0039 (16)0.0153 (17)0.0010 (16)
C60.032 (2)0.025 (2)0.035 (2)0.0006 (16)0.0199 (18)−0.0024 (16)
O50.0323 (17)0.064 (2)0.051 (2)−0.0065 (16)0.0208 (16)−0.0216 (18)
Geometric parameters (Å, °) top
Mn1—O41.993 (3)N1—H1A0.9000
Mn1—O4i1.993 (3)N1—H1B0.9000
Mn1—N1ii2.058 (3)C1—C21.383 (6)
Mn1—N1iii2.058 (3)C1—C61.393 (6)
Mn1—O1i2.425 (3)C2—C31.385 (6)
Mn1—O12.425 (3)C2—H20.9300
S1—O31.460 (3)C3—C41.396 (6)
S1—O21.462 (3)C3—H30.9300
S1—O11.467 (3)C4—C51.390 (6)
S1—C11.780 (4)C5—C61.387 (6)
O4—H1W0.8200C5—H50.9300
O4—H2W0.8267C6—H60.9300
N1—C41.453 (5)O5—H3W0.8197
N1—Mn1iv2.058 (3)O5—H4W0.8216
O4—Mn1—O4i180C4—N1—Mn1iv120.1 (2)
O4—Mn1—N1ii92.95 (13)C4—N1—H1A107.3
O4i—Mn1—N1ii87.05 (13)Mn1iv—N1—H1A107.3
O4—Mn1—N1iii87.05 (13)C4—N1—H1B107.3
O4i—Mn1—N1iii92.95 (13)Mn1iv—N1—H1B107.3
N1ii—Mn1—N1iii180H1A—N1—H1B106.9
O4—Mn1—O1i84.94 (12)C2—C1—C6121.0 (4)
O4i—Mn1—O1i95.06 (12)C2—C1—S1119.5 (3)
N1ii—Mn1—O1i93.34 (11)C6—C1—S1119.5 (3)
N1iii—Mn1—O1i86.66 (11)C1—C2—C3119.8 (4)
O4—Mn1—O195.06 (12)C1—C2—H2120.1
O4i—Mn1—O184.94 (12)C3—C2—H2120.1
N1ii—Mn1—O186.66 (11)C2—C3—C4119.7 (4)
N1iii—Mn1—O193.34 (11)C2—C3—H3120.1
O1i—Mn1—O1180C4—C3—H3120.1
O3—S1—O2113.12 (18)C5—C4—C3120.1 (4)
O3—S1—O1111.46 (18)C5—C4—N1119.9 (4)
O2—S1—O1111.50 (18)C3—C4—N1119.9 (4)
O3—S1—C1106.85 (18)C6—C5—C4120.2 (4)
O2—S1—C1106.57 (18)C6—C5—H5119.9
O1—S1—C1106.90 (18)C4—C5—H5119.9
S1—O1—Mn1129.61 (17)C5—C6—C1119.2 (4)
Mn1—O4—H1W109.4C5—C6—H6120.4
Mn1—O4—H2W132.0C1—C6—H6120.4
H1W—O4—H2W111.8H3W—O5—H4W114.3
O3—S1—O1—Mn1143.8 (2)C6—C1—C2—C30.8 (6)
O2—S1—O1—Mn116.3 (3)S1—C1—C2—C3−176.6 (3)
C1—S1—O1—Mn1−99.8 (2)C1—C2—C3—C40.9 (6)
O4—Mn1—O1—S145.3 (2)C2—C3—C4—C5−2.4 (6)
O4i—Mn1—O1—S1−134.7 (2)C2—C3—C4—N1176.5 (4)
N1ii—Mn1—O1—S1−47.3 (2)Mn1iv—N1—C4—C5−91.0 (4)
N1iii—Mn1—O1—S1132.7 (2)Mn1iv—N1—C4—C390.1 (4)
O3—S1—C1—C2−141.2 (3)C3—C4—C5—C62.1 (6)
O2—S1—C1—C2−20.0 (4)N1—C4—C5—C6−176.8 (4)
O1—S1—C1—C299.4 (3)C4—C5—C6—C1−0.4 (6)
O3—S1—C1—C641.3 (4)C2—C1—C6—C5−1.1 (6)
O2—S1—C1—C6162.5 (3)S1—C1—C6—C5176.4 (3)
O1—S1—C1—C6−78.2 (4)
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+3/2, y+1/2, −z+3/2; (iii) x−1/2, −y+3/2, z−1/2; (iv) −x+3/2, y−1/2, −z+3/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1B···O2iv0.902.462.980 (4)117
O5—H3W···O10.822.062.855 (5)164
C2—H2···O20.932.542.920 (5)105
N1—H1B···O2iii0.902.413.217 (4)149
O4—H2W···O5v0.831.832.651 (5)175
C2—H2···O5v0.932.533.431 (6)164
O4—H1W···O3vi0.822.022.795 (4)157
N1—H1A···O3vii0.902.243.070 (5)153
C3—H3···O3vii0.932.553.300 (5)138
O5—H4W···O2viii0.822.002.815 (5)175
Symmetry codes: (iv) −x+3/2, y−1/2, −z+3/2; (iii) x−1/2, −y+3/2, z−1/2; (v) x+1, y, z; (vi) x, y, z−1; (vii) x+1/2, −y+3/2, z−1/2; (viii) −x+1, −y+2, −z+2.
Table 1
Selected geometric parameters (Å, °) top
Mn1—O41.993 (3)Mn1—O12.425 (3)
Mn1—N1i2.058 (3)
O4—Mn1—O4ii180O4—Mn1—O195.06 (12)
O4—Mn1—N1i92.95 (13)O4ii—Mn1—O184.94 (12)
O4—Mn1—N1iii87.05 (13)N1i—Mn1—O186.66 (11)
N1i—Mn1—N1iii180N1iii—Mn1—O193.34 (11)
O4—Mn1—O1ii84.94 (12)O1ii—Mn1—O1180
Symmetry codes: (i) −x+3/2, y+1/2, −z+3/2; (ii) −x+1, −y+2, −z+1; (iii) x−1/2, −y+3/2, z−1/2.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1B···O2iv0.902.462.980 (4)117
O5—H3W···O10.822.062.855 (5)164
C2—H2···O20.932.542.920 (5)105
N1—H1B···O2iii0.902.413.217 (4)149
O4—H2W···O5v0.831.832.651 (5)175
C2—H2···O5v0.932.533.431 (6)164
O4—H1W···O3vi0.822.022.795 (4)157
N1—H1A···O3vii0.902.243.070 (5)153
C3—H3···O3vii0.932.553.300 (5)138
O5—H4W···O2viii0.822.002.815 (5)175
Symmetry codes: (iv) −x+3/2, y−1/2, −z+3/2; (iii) x−1/2, −y+3/2, z−1/2; (v) x+1, y, z; (vi) x, y, z−1; (vii) x+1/2, −y+3/2, z−1/2; (viii) −x+1, −y+2, −z+2.
Acknowledgements top

We thank the Natural Science Foundation of Henan Province and the Key Discipline Foundation of Zhoukou Normal University for financial support of this research.

references
References top

Bruker (2002). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

Cai, J., Zhou, J.-S. & Lin, M.-L. (2003). J. Mater. Chem. 13, 1806–1808.

Shakeri, V. & Haussuhl, S. (1992). Z. Kristallogr. 299, 198–199.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.