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

Tai, X.-S.; Zhao, Z.-B.

doi:10.1107/S160053680904495X

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page m1491

https://doi.org/10.1107/S160053680904495X

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

Xi-Shi Tai ^a ^* and Zeng-Bing Zhao ^b

^aCollege of Chemistry and Chemical Engineering, Weifang University, Weifang 261061, People's Republic of China, and ^bDepartment of Chemistry, Qinghai Normal University, Xining 810008, People's Republic of China
^*Correspondence e-mail: taixishi@lzu.edu.cn

(Received 27 October 2009; accepted 27 October 2009; online 31 October 2009)

In the title compound, [Mn(C₈H₈N₃O₃S₂)₂(H₂O)₄], the Mn^II atom (site symmetry $[\overline{1}]$ ) 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 ).

Experimental

Crystal data

[Mn(C₈H₈N₃O₃S₂)₂(H₂O)₄]
M_r = 643.59
Triclinic, $[P \overline 1]$
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 ) 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[F² > 2σ(F²)] = 0.028
wR(F²) = 0.077
S = 1.07
2207 reflections
170 parameters
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Selected bond lengths (Å)

Mn1—O4	2.1369 (17)
Mn1—O5	2.1495 (16)
Mn1—O1	2.2166 (14)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯N3	0.86	2.29	2.638 (3)	104
O4—H10⋯O3	0.85	2.02	2.761 (3)	146
N1—H1B⋯O3ⁱ	0.86	2.33	2.986 (3)	134
N2—H2⋯S2ⁱⁱ	0.86	2.57	3.4231 (19)	170
O4—H9⋯S2ⁱⁱⁱ	0.85	2.36	3.182 (2)	162
O5—H11⋯S2^iv	0.85	2.46	3.2603 (19)	156
O5—H12⋯O2^v	0.85	1.87	2.712 (3)	172
Symmetry codes: (i) x, y-1, z+1; (ii) -x+2, -y, -z+1; (iii) x-1, y+1, z-1; (iv) x, y+1, z-1; (v) -x+2, -y+1, -z.

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: https://doi.org/10.1107/S160053680904495X/hb5192sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053680904495X/hb5192Isup2.hkl

checkCIF report

Related literature top

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

Experimental top

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.

Structure description top

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

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. Atoms with the suffix A are generated by the symmetry operation (1-x, 1-y, -z).

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

Crystal data top

[Mn(C₈H₈N₃O₃S₂)₂(H₂O)₄]	Z = 1
M_r = 643.59	F(000) = 331
Triclinic, P1	D_x = 1.700 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.8096 (6) Å	Cell parameters from 2123 reflections
b = 9.5498 (8) Å	θ = 2.4–28.2°
c = 10.7898 (9) Å	µ = 0.92 mm⁻¹
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 top

Bruker SMART CCD diffractometer	2207 independent reflections
Radiation source: fine-focus sealed tube	2005 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.015
ω scans	θ_max = 25.1°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −8→8
T_min = 0.845, T_max = 0.898	k = −11→11
3329 measured reflections	l = −9→12

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)] = 0.028	H-atom parameters constrained
wR(F²) = 0.077	w = 1/[σ²(F_o²) + (0.0384P)² + 0.3206P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
2207 reflections	Δρ_max = 0.36 e Å⁻³
170 parameters	Δρ_min = −0.34 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: 0.049 (3)

Crystal data top

[Mn(C₈H₈N₃O₃S₂)₂(H₂O)₄]	γ = 83.791 (1)°
M_r = 643.59	V = 628.83 (9) Å³
Triclinic, P1	Z = 1
a = 6.8096 (6) Å	Mo Kα radiation
b = 9.5498 (8) Å	µ = 0.92 mm⁻¹
c = 10.7898 (9) Å	T = 273 K
α = 64.386 (1)°	0.19 × 0.14 × 0.12 mm
β = 88.495 (1)°

Data collection top

Bruker SMART CCD diffractometer	2207 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	2005 reflections with I > 2σ(I)
T_min = 0.845, T_max = 0.898	R_int = 0.015
3329 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.077	H-atom parameters constrained
S = 1.07	Δρ_max = 0.36 e Å⁻³
2207 reflections	Δρ_min = −0.34 e Å⁻³
170 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
Mn1	0.5000	0.5000	0.0000	0.02389 (16)
S1	0.73935 (8)	0.67535 (6)	0.15413 (5)	0.02518 (16)
S2	1.00275 (9)	−0.13908 (6)	0.71686 (6)	0.03340 (18)
O1	0.6334 (2)	0.54631 (17)	0.16197 (15)	0.0333 (4)
O2	0.9517 (2)	0.6407 (2)	0.15616 (17)	0.0417 (4)
O3	0.6673 (3)	0.82183 (18)	0.04065 (15)	0.0386 (4)
O4	0.3965 (3)	0.7431 (2)	−0.0981 (2)	0.0652 (6)
H9	0.2884	0.7905	−0.1404	0.098*
H10	0.4415	0.7985	−0.0637	0.098*
O5	0.7698 (2)	0.5559 (2)	−0.11007 (18)	0.0433 (4)
H12	0.8605	0.4911	−0.1165	0.065*
H11	0.8157	0.6433	−0.1363	0.065*
N1	0.8828 (3)	0.0620 (2)	0.81969 (19)	0.0400 (5)
H1A	0.8452	0.1545	0.8118	0.048*
H1B	0.8919	−0.0160	0.8996	0.048*
N2	0.9104 (3)	0.16402 (19)	0.58726 (18)	0.0271 (4)
H2	0.9474	0.1543	0.5143	0.033*
N3	0.8342 (2)	0.30737 (19)	0.57900 (17)	0.0257 (4)
C1	0.9263 (3)	0.0400 (2)	0.7097 (2)	0.0269 (5)
C2	0.8091 (3)	0.4167 (2)	0.4577 (2)	0.0242 (4)
H2A	0.8437	0.3975	0.3821	0.029*
C3	0.7252 (3)	0.5734 (2)	0.4382 (2)	0.0216 (4)
C4	0.6849 (3)	0.6967 (2)	0.3074 (2)	0.0212 (4)
C5	0.6053 (3)	0.8429 (2)	0.2938 (2)	0.0284 (5)
H5A	0.5780	0.9236	0.2066	0.034*
C6	0.5664 (3)	0.8694 (3)	0.4078 (2)	0.0345 (5)
H6	0.5140	0.9679	0.3979	0.041*
C7	0.6056 (3)	0.7491 (3)	0.5373 (2)	0.0329 (5)
H7	0.5791	0.7667	0.6147	0.040*
C8	0.6835 (3)	0.6034 (3)	0.5523 (2)	0.0283 (5)
H8	0.7090	0.5235	0.6401	0.034*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0270 (3)	0.0197 (2)	0.0237 (3)	−0.00156 (17)	−0.00312 (17)	−0.00820 (19)
S1	0.0331 (3)	0.0220 (3)	0.0199 (3)	−0.0055 (2)	0.0001 (2)	−0.0080 (2)
S2	0.0437 (3)	0.0198 (3)	0.0306 (3)	0.0006 (2)	−0.0044 (2)	−0.0057 (2)
O1	0.0521 (10)	0.0266 (8)	0.0230 (8)	−0.0120 (7)	−0.0042 (7)	−0.0104 (6)
O2	0.0352 (9)	0.0540 (11)	0.0448 (10)	−0.0042 (8)	0.0067 (7)	−0.0301 (9)
O3	0.0603 (11)	0.0259 (8)	0.0221 (8)	−0.0100 (7)	−0.0032 (7)	−0.0020 (7)
O4	0.0675 (13)	0.0263 (9)	0.0932 (16)	0.0101 (9)	−0.0507 (12)	−0.0182 (10)
O5	0.0405 (10)	0.0403 (10)	0.0559 (11)	−0.0125 (8)	0.0177 (8)	−0.0262 (9)
N1	0.0639 (14)	0.0245 (10)	0.0246 (10)	−0.0001 (9)	0.0020 (9)	−0.0051 (8)
N2	0.0313 (9)	0.0206 (9)	0.0239 (9)	0.0028 (7)	−0.0010 (7)	−0.0056 (7)
N3	0.0269 (9)	0.0203 (9)	0.0267 (10)	−0.0011 (7)	−0.0023 (7)	−0.0074 (8)
C1	0.0250 (11)	0.0235 (11)	0.0261 (11)	−0.0033 (8)	−0.0033 (8)	−0.0047 (9)
C2	0.0263 (10)	0.0228 (10)	0.0225 (10)	−0.0017 (8)	−0.0020 (8)	−0.0091 (9)
C3	0.0206 (10)	0.0211 (10)	0.0238 (10)	−0.0031 (8)	−0.0027 (8)	−0.0100 (8)
C4	0.0217 (10)	0.0212 (10)	0.0216 (10)	−0.0043 (8)	−0.0016 (8)	−0.0095 (8)
C5	0.0320 (11)	0.0194 (10)	0.0308 (12)	−0.0016 (9)	−0.0024 (9)	−0.0080 (9)
C6	0.0375 (13)	0.0260 (12)	0.0450 (14)	0.0009 (10)	−0.0004 (10)	−0.0210 (11)
C7	0.0362 (12)	0.0367 (13)	0.0361 (12)	−0.0053 (10)	0.0022 (10)	−0.0250 (11)
C8	0.0306 (11)	0.0297 (11)	0.0240 (11)	−0.0039 (9)	−0.0013 (9)	−0.0108 (9)

Geometric parameters (Å, º) top

Mn1—O4ⁱ	2.1369 (17)	N1—H1B	0.8600
Mn1—O4	2.1369 (17)	N2—C1	1.337 (3)
Mn1—O5ⁱ	2.1495 (16)	N2—N3	1.376 (2)
Mn1—O5	2.1495 (16)	N2—H2	0.8600
Mn1—O1	2.2166 (14)	N3—C2	1.274 (3)
Mn1—O1ⁱ	2.2166 (14)	C2—C3	1.469 (3)
S1—O2	1.4468 (17)	C2—H2A	0.9300
S1—O3	1.4489 (16)	C3—C8	1.396 (3)
S1—O1	1.4647 (15)	C3—C4	1.403 (3)
S1—C4	1.7767 (19)	C4—C5	1.388 (3)
S2—C1	1.702 (2)	C5—C6	1.374 (3)
O4—H9	0.8500	C5—H5A	0.9300
O4—H10	0.8499	C6—C7	1.381 (3)
O5—H12	0.8499	C6—H6	0.9300
O5—H11	0.8499	C7—C8	1.376 (3)
N1—C1	1.313 (3)	C7—H7	0.9300
N1—H1A	0.8600	C8—H8	0.9300

O4ⁱ—Mn1—O4	180.0	H1A—N1—H1B	120.0
O4ⁱ—Mn1—O5ⁱ	88.04 (8)	C1—N2—N3	119.42 (18)
O4—Mn1—O5ⁱ	91.96 (8)	C1—N2—H2	120.3
O4ⁱ—Mn1—O5	91.96 (8)	N3—N2—H2	120.3
O4—Mn1—O5	88.04 (8)	C2—N3—N2	115.48 (18)
O5ⁱ—Mn1—O5	180.0	N1—C1—N2	118.31 (19)
O4ⁱ—Mn1—O1	92.72 (7)	N1—C1—S2	122.79 (16)
O4—Mn1—O1	87.28 (7)	N2—C1—S2	118.89 (16)
O5ⁱ—Mn1—O1	92.43 (6)	N3—C2—C3	119.54 (19)
O5—Mn1—O1	87.57 (6)	N3—C2—H2A	120.2
O4ⁱ—Mn1—O1ⁱ	87.28 (7)	C3—C2—H2A	120.2
O4—Mn1—O1ⁱ	92.72 (7)	C8—C3—C4	117.81 (18)
O5ⁱ—Mn1—O1ⁱ	87.57 (6)	C8—C3—C2	119.86 (18)
O5—Mn1—O1ⁱ	92.43 (6)	C4—C3—C2	122.33 (18)
O1—Mn1—O1ⁱ	180.0	C5—C4—C3	120.37 (18)
O2—S1—O3	113.09 (10)	C5—C4—S1	117.47 (15)
O2—S1—O1	112.81 (10)	C3—C4—S1	122.14 (15)
O3—S1—O1	111.89 (9)	C6—C5—C4	120.6 (2)
O2—S1—C4	105.67 (9)	C6—C5—H5A	119.7
O3—S1—C4	106.74 (9)	C4—C5—H5A	119.7
O1—S1—C4	105.98 (9)	C5—C6—C7	119.6 (2)
S1—O1—Mn1	131.56 (9)	C5—C6—H6	120.2
Mn1—O4—H9	131.3	C7—C6—H6	120.2
Mn1—O4—H10	115.1	C8—C7—C6	120.3 (2)
H9—O4—H10	108.1	C8—C7—H7	119.8
Mn1—O5—H12	126.2	C6—C7—H7	119.8
Mn1—O5—H11	124.0	C7—C8—C3	121.2 (2)
H12—O5—H11	108.1	C7—C8—H8	119.4
C1—N1—H1A	120.0	C3—C8—H8	119.4
C1—N1—H1B	120.0

O2—S1—O1—Mn1	−96.18 (14)	C8—C3—C4—S1	177.75 (15)
O3—S1—O1—Mn1	32.68 (16)	C2—C3—C4—S1	−2.0 (3)
C4—S1—O1—Mn1	148.66 (12)	O2—S1—C4—C5	115.31 (17)
O4ⁱ—Mn1—O1—S1	138.91 (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—S1	47.06 (13)	O3—S1—C4—C3	176.53 (15)
O1ⁱ—Mn1—O1—S1	−25 (100)	O1—S1—C4—C3	57.11 (18)
C1—N2—N3—C2	−174.55 (18)	C3—C4—C5—C6	0.6 (3)
N3—N2—C1—N1	−5.3 (3)	S1—C4—C5—C6	−177.58 (17)
N3—N2—C1—S2	174.98 (14)	C4—C5—C6—C7	−0.5 (3)
N2—N3—C2—C3	178.94 (17)	C5—C6—C7—C8	0.2 (3)
N3—C2—C3—C8	3.4 (3)	C6—C7—C8—C3	0.1 (3)
N3—C2—C3—C4	−176.81 (18)	C4—C3—C8—C7	0.0 (3)
C8—C3—C4—C5	−0.3 (3)	C2—C3—C8—C7	179.78 (19)
C2—C3—C4—C5	179.89 (19)

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···N3	0.86	2.29	2.638 (3)	104
O4—H10···O3	0.85	2.02	2.761 (3)	146
N1—H1B···O3ⁱⁱ	0.86	2.33	2.986 (3)	134
N2—H2···S2ⁱⁱⁱ	0.86	2.57	3.4231 (19)	170
O4—H9···S2^iv	0.85	2.36	3.182 (2)	162
O5—H11···S2^v	0.85	2.46	3.2603 (19)	156
O5—H12···O2^vi	0.85	1.87	2.712 (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.

Experimental details

Crystal data
Chemical formula	[Mn(C₈H₈N₃O₃S₂)₂(H₂O)₄]
M_r	643.59
Crystal system, space group	Triclinic, P1
Temperature (K)	273
a, b, c (Å)	6.8096 (6), 9.5498 (8), 10.7898 (9)
α, β, γ (°)	64.386 (1), 88.495 (1), 83.791 (1)
V (Å³)	628.83 (9)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.92
Crystal size (mm)	0.19 × 0.14 × 0.12

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.845, 0.898
No. of measured, independent and observed [I > 2σ(I)] reflections	3329, 2207, 2005
R_int	0.015
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.077, 1.07
No. of reflections	2207
No. of parameters	170
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.34

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

Selected bond lengths (Å) top

Mn1—O4	2.1369 (17)	Mn1—O1	2.2166 (14)
Mn1—O5	2.1495 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N3	0.86	2.29	2.638 (3)	104
O4—H10···O3	0.85	2.02	2.761 (3)	146
N1—H1B···O3ⁱ	0.86	2.33	2.986 (3)	134
N2—H2···S2ⁱⁱ	0.86	2.57	3.4231 (19)	170
O4—H9···S2ⁱⁱⁱ	0.85	2.36	3.182 (2)	162
O5—H11···S2^iv	0.85	2.46	3.2603 (19)	156
O5—H12···O2^v	0.85	1.87	2.712 (3)	172

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

Acknowledgements

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.

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