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Acta Crystallogr Sect E Struct Rep Online. 2009 November 1; 65(Pt 11): m1491.
Published online 2009 October 31. doi:  10.1107/S160053680904495X
PMCID: PMC2971282

Tetra­aqua­bis[2-(thio­semi­carbazono­methyl)benzene­sulfonato]manganese(II)

Abstract

In the title compound, [Mn(C8H8N3O3S2)2(H2O)4], the MnII atom (site symmetry An external file that holds a picture, illustration, etc.
Object name is e-65-m1491-efi1.jpg) adopts a slightly distorted octa­hedral MnO6 geometry. The mol­ecular conformation is supported by N—H(...)N and O—H(...)O hydrogen bonds. In the crystal, mol­ecules inter­act by O—H(...)O, O—H(...)S, N—H(...)O and N—H(...)S hydrogen bonds, thereby forming (011) sheets.

Related literature

For background to coordination networks, see: Ranford et al. (1998 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-m1491-scheme1.jpg

Experimental

Crystal data

  • [Mn(C8H8N3O3S2)2(H2O)4]
  • M r = 643.59
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-m1491-efi2.jpg
  • a = 6.8096 (6) Å
  • b = 9.5498 (8) Å
  • c = 10.7898 (9) Å
  • α = 64.386 (1)°
  • β = 88.495 (1)°
  • γ = 83.791 (1)°
  • V = 628.83 (9) Å3
  • Z = 1
  • Mo Kα radiation
  • μ = 0.92 mm−1
  • T = 273 K
  • 0.19 × 0.14 × 0.12 mm

Data collection

  • Bruker SMART CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2000 [triangle]) T min = 0.845, T max = 0.898
  • 3329 measured reflections
  • 2207 independent reflections
  • 2005 reflections with I > 2σ(I)
  • R int = 0.015

Refinement

  • R[F 2 > 2σ(F 2)] = 0.028
  • wR(F 2) = 0.077
  • S = 1.07
  • 2207 reflections
  • 170 parameters
  • H-atom parameters constrained
  • Δρmax = 0.36 e Å−3
  • Δρmin = −0.34 e Å−3

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

Table 1
Selected bond lengths (Å)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680904495X/hb5192sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680904495X/hb5192Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This project was supported by the National Natural Science Foundation of China (20671073), the Natural Science Foundation of Shandong (Y2007B60) and the Science Foundation of Weifang University.

supplementary crystallographic information

Experimental

A solution of 1.0 mmol 2-formyl-benzenesulfonate-thiosemicarbazide was added to a solution of 0.5 mmol MnCl2.4H2O in 5 ml ethanol 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.

Refinement

The H atoms were positioned geometrically (C—H = 0.93, N—H = 0.86, O—H = 0.85Å) and refined as riding with Uiso(H)= 1.2 Ueq(C, N) or 1.5Ueq(O).

Figures

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

Crystal data

[Mn(C8H8N3O3S2)2(H2O)4]Z = 1
Mr = 643.59F(000) = 331
Triclinic, P1Dx = 1.700 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.8096 (6) ÅCell parameters from 2123 reflections
b = 9.5498 (8) Åθ = 2.4–28.2°
c = 10.7898 (9) ŵ = 0.92 mm1
α = 64.386 (1)°T = 273 K
β = 88.495 (1)°Block, pink
γ = 83.791 (1)°0.19 × 0.14 × 0.12 mm
V = 628.83 (9) Å3

Data collection

Bruker SMART CCD diffractometer2207 independent reflections
Radiation source: fine-focus sealed tube2005 reflections with I > 2σ(I)
graphiteRint = 0.015
ω scansθmax = 25.1°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2000)h = −8→8
Tmin = 0.845, Tmax = 0.898k = −11→11
3329 measured reflectionsl = −9→12

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.028H-atom parameters constrained
wR(F2) = 0.077w = 1/[σ2(Fo2) + (0.0384P)2 + 0.3206P] where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.001
2207 reflectionsΔρmax = 0.36 e Å3
170 parametersΔρmin = −0.34 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.049 (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 (Å2)

xyzUiso*/Ueq
Mn10.50000.50000.00000.02389 (16)
S10.73935 (8)0.67535 (6)0.15413 (5)0.02518 (16)
S21.00275 (9)−0.13908 (6)0.71686 (6)0.03340 (18)
O10.6334 (2)0.54631 (17)0.16197 (15)0.0333 (4)
O20.9517 (2)0.6407 (2)0.15616 (17)0.0417 (4)
O30.6673 (3)0.82183 (18)0.04065 (15)0.0386 (4)
O40.3965 (3)0.7431 (2)−0.0981 (2)0.0652 (6)
H90.28840.7905−0.14040.098*
H100.44150.7985−0.06370.098*
O50.7698 (2)0.5559 (2)−0.11007 (18)0.0433 (4)
H120.86050.4911−0.11650.065*
H110.81570.6433−0.13630.065*
N10.8828 (3)0.0620 (2)0.81969 (19)0.0400 (5)
H1A0.84520.15450.81180.048*
H1B0.8919−0.01600.89960.048*
N20.9104 (3)0.16402 (19)0.58726 (18)0.0271 (4)
H20.94740.15430.51430.033*
N30.8342 (2)0.30737 (19)0.57900 (17)0.0257 (4)
C10.9263 (3)0.0400 (2)0.7097 (2)0.0269 (5)
C20.8091 (3)0.4167 (2)0.4577 (2)0.0242 (4)
H2A0.84370.39750.38210.029*
C30.7252 (3)0.5734 (2)0.4382 (2)0.0216 (4)
C40.6849 (3)0.6967 (2)0.3074 (2)0.0212 (4)
C50.6053 (3)0.8429 (2)0.2938 (2)0.0284 (5)
H5A0.57800.92360.20660.034*
C60.5664 (3)0.8694 (3)0.4078 (2)0.0345 (5)
H60.51400.96790.39790.041*
C70.6056 (3)0.7491 (3)0.5373 (2)0.0329 (5)
H70.57910.76670.61470.040*
C80.6835 (3)0.6034 (3)0.5523 (2)0.0283 (5)
H80.70900.52350.64010.034*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Mn10.0270 (3)0.0197 (2)0.0237 (3)−0.00156 (17)−0.00312 (17)−0.00820 (19)
S10.0331 (3)0.0220 (3)0.0199 (3)−0.0055 (2)0.0001 (2)−0.0080 (2)
S20.0437 (3)0.0198 (3)0.0306 (3)0.0006 (2)−0.0044 (2)−0.0057 (2)
O10.0521 (10)0.0266 (8)0.0230 (8)−0.0120 (7)−0.0042 (7)−0.0104 (6)
O20.0352 (9)0.0540 (11)0.0448 (10)−0.0042 (8)0.0067 (7)−0.0301 (9)
O30.0603 (11)0.0259 (8)0.0221 (8)−0.0100 (7)−0.0032 (7)−0.0020 (7)
O40.0675 (13)0.0263 (9)0.0932 (16)0.0101 (9)−0.0507 (12)−0.0182 (10)
O50.0405 (10)0.0403 (10)0.0559 (11)−0.0125 (8)0.0177 (8)−0.0262 (9)
N10.0639 (14)0.0245 (10)0.0246 (10)−0.0001 (9)0.0020 (9)−0.0051 (8)
N20.0313 (9)0.0206 (9)0.0239 (9)0.0028 (7)−0.0010 (7)−0.0056 (7)
N30.0269 (9)0.0203 (9)0.0267 (10)−0.0011 (7)−0.0023 (7)−0.0074 (8)
C10.0250 (11)0.0235 (11)0.0261 (11)−0.0033 (8)−0.0033 (8)−0.0047 (9)
C20.0263 (10)0.0228 (10)0.0225 (10)−0.0017 (8)−0.0020 (8)−0.0091 (9)
C30.0206 (10)0.0211 (10)0.0238 (10)−0.0031 (8)−0.0027 (8)−0.0100 (8)
C40.0217 (10)0.0212 (10)0.0216 (10)−0.0043 (8)−0.0016 (8)−0.0095 (8)
C50.0320 (11)0.0194 (10)0.0308 (12)−0.0016 (9)−0.0024 (9)−0.0080 (9)
C60.0375 (13)0.0260 (12)0.0450 (14)0.0009 (10)−0.0004 (10)−0.0210 (11)
C70.0362 (12)0.0367 (13)0.0361 (12)−0.0053 (10)0.0022 (10)−0.0250 (11)
C80.0306 (11)0.0297 (11)0.0240 (11)−0.0039 (9)−0.0013 (9)−0.0108 (9)

Geometric parameters (Å, °)

Mn1—O4i2.1369 (17)N1—H1B0.8600
Mn1—O42.1369 (17)N2—C11.337 (3)
Mn1—O5i2.1495 (16)N2—N31.376 (2)
Mn1—O52.1495 (16)N2—H20.8600
Mn1—O12.2166 (14)N3—C21.274 (3)
Mn1—O1i2.2166 (14)C2—C31.469 (3)
S1—O21.4468 (17)C2—H2A0.9300
S1—O31.4489 (16)C3—C81.396 (3)
S1—O11.4647 (15)C3—C41.403 (3)
S1—C41.7767 (19)C4—C51.388 (3)
S2—C11.702 (2)C5—C61.374 (3)
O4—H90.8500C5—H5A0.9300
O4—H100.8499C6—C71.381 (3)
O5—H120.8499C6—H60.9300
O5—H110.8499C7—C81.376 (3)
N1—C11.313 (3)C7—H70.9300
N1—H1A0.8600C8—H80.9300
O4i—Mn1—O4180.0H1A—N1—H1B120.0
O4i—Mn1—O5i88.04 (8)C1—N2—N3119.42 (18)
O4—Mn1—O5i91.96 (8)C1—N2—H2120.3
O4i—Mn1—O591.96 (8)N3—N2—H2120.3
O4—Mn1—O588.04 (8)C2—N3—N2115.48 (18)
O5i—Mn1—O5180.0N1—C1—N2118.31 (19)
O4i—Mn1—O192.72 (7)N1—C1—S2122.79 (16)
O4—Mn1—O187.28 (7)N2—C1—S2118.89 (16)
O5i—Mn1—O192.43 (6)N3—C2—C3119.54 (19)
O5—Mn1—O187.57 (6)N3—C2—H2A120.2
O4i—Mn1—O1i87.28 (7)C3—C2—H2A120.2
O4—Mn1—O1i92.72 (7)C8—C3—C4117.81 (18)
O5i—Mn1—O1i87.57 (6)C8—C3—C2119.86 (18)
O5—Mn1—O1i92.43 (6)C4—C3—C2122.33 (18)
O1—Mn1—O1i180.0C5—C4—C3120.37 (18)
O2—S1—O3113.09 (10)C5—C4—S1117.47 (15)
O2—S1—O1112.81 (10)C3—C4—S1122.14 (15)
O3—S1—O1111.89 (9)C6—C5—C4120.6 (2)
O2—S1—C4105.67 (9)C6—C5—H5A119.7
O3—S1—C4106.74 (9)C4—C5—H5A119.7
O1—S1—C4105.98 (9)C5—C6—C7119.6 (2)
S1—O1—Mn1131.56 (9)C5—C6—H6120.2
Mn1—O4—H9131.3C7—C6—H6120.2
Mn1—O4—H10115.1C8—C7—C6120.3 (2)
H9—O4—H10108.1C8—C7—H7119.8
Mn1—O5—H12126.2C6—C7—H7119.8
Mn1—O5—H11124.0C7—C8—C3121.2 (2)
H12—O5—H11108.1C7—C8—H8119.4
C1—N1—H1A120.0C3—C8—H8119.4
C1—N1—H1B120.0
O2—S1—O1—Mn1−96.18 (14)C8—C3—C4—S1177.75 (15)
O3—S1—O1—Mn132.68 (16)C2—C3—C4—S1−2.0 (3)
C4—S1—O1—Mn1148.66 (12)O2—S1—C4—C5115.31 (17)
O4i—Mn1—O1—S1138.91 (14)O3—S1—C4—C5−5.33 (19)
O4—Mn1—O1—S1−41.09 (14)O1—S1—C4—C5−124.75 (17)
O5i—Mn1—O1—S1−132.94 (13)O2—S1—C4—C3−62.83 (18)
O5—Mn1—O1—S147.06 (13)O3—S1—C4—C3176.53 (15)
O1i—Mn1—O1—S1−25 (100)O1—S1—C4—C357.11 (18)
C1—N2—N3—C2−174.55 (18)C3—C4—C5—C60.6 (3)
N3—N2—C1—N1−5.3 (3)S1—C4—C5—C6−177.58 (17)
N3—N2—C1—S2174.98 (14)C4—C5—C6—C7−0.5 (3)
N2—N3—C2—C3178.94 (17)C5—C6—C7—C80.2 (3)
N3—C2—C3—C83.4 (3)C6—C7—C8—C30.1 (3)
N3—C2—C3—C4−176.81 (18)C4—C3—C8—C70.0 (3)
C8—C3—C4—C5−0.3 (3)C2—C3—C8—C7179.78 (19)
C2—C3—C4—C5179.89 (19)

Symmetry codes: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···N30.862.292.638 (3)104
O4—H10···O30.852.022.761 (3)146
N1—H1B···O3ii0.862.332.986 (3)134
N2—H2···S2iii0.862.573.4231 (19)170
O4—H9···S2iv0.852.363.182 (2)162
O5—H11···S2v0.852.463.2603 (19)156
O5—H12···O2vi0.851.872.712 (3)172

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5192).

References

  • Bruker (2000). SMART, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Ranford, J. D., Vittal, J. J. & Wang, Y. M. (1998). Inorg. Chem.37, 1226–1231. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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