Tetra-aqua-bis[2-(thio-semi-carbazono-methyl)benzene-sulfonato]manganese(II).

In the title compound, [Mn(C(8)H(8)N(3)O(3)S(2))(2)(H(2)O)(4)], the Mn(II) atom (site symmetry ) adopts a slightly distorted octa-hedral MnO(6) geometry. The mol-ecular conformation is supported by N-H⋯N and O-H⋯O hydrogen bonds. In the crystal, mol-ecules inter-act 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 = 643.59

Triclinic,

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[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 ▶); 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.

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

[Mn(C8H8N3O3S2)2(H2O)4]	Z = 1
Mr = 643.59	F(000) = 331
Triclinic, P1	Dx = 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

Bruker SMART CCD diffractometer	2207 independent reflections
Radiation source: fine-focus sealed tube	2005 reflections with I > 2σ(I)
graphite	Rint = 0.015
ω scans	θmax = 25.1°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −8→8
Tmin = 0.845, Tmax = 0.898	k = −11→11
3329 measured reflections	l = −9→12

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(Fo2) + (0.0384P)2 + 0.3206P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max = 0.001
2207 reflections	Δρmax = 0.36 e Å−3
170 parameters	Δρmin = −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)

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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···S2iv	0.85	2.36	3.182 (2)	162
O5—H11···S2v	0.85	2.46	3.2603 (19)	156
O5—H12···O2vi	0.85	1.87	2.712 (3)	172

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⋯S2iv	0.85	2.46	3.2603 (19)	156
O5—H12⋯O2v	0.85	1.87	2.712 (3)	172

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .