Poly[[diaqua­(μ2-5,5-dioxodibenzo[b,d]thio­phene-3,7-dicarboxyl­ato)(μ2-ethyl­ene glycol)manganese(II)] dimethyl­acetamide solvate]

Yi, X.-C.; Yan, L.; Gao, E.-Q.

doi:10.1107/S1600536810045411

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page m1554

https://doi.org/10.1107/S1600536810045411

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Poly[[diaqua(μ₂-5,5-dioxodibenzo[b,d]thiophene-3,7-dicarboxylato)(μ₂-ethylene glycol)manganese(II)] dimethylacetamide solvate]

Xiu-Chun Yi,^a Li Yan ^a and En-Qing Gao ^a ^*

^aShanghai Key Laboratory of Green Chemistry and Chemical Processes, Department of Chemistry, East China Normal University, Shanghai 200062, People's Republic of China
^*Correspondence e-mail: eqgao@chem.ecnu.edu.cn

(Received 22 October 2010; accepted 5 November 2010; online 13 November 2010)

In the title complex, {[Mn(C₁₄H₆O₆S)(C₂H₆O₂)(H₂O)₂]·C₄H₉NO}_n, the Mn^II ion is six-coordinated in a trans-octahedral geometry by two carboxylate O atoms from two 5,5-dioxodibenzo[b,d]thiophene-3,7-dicarboxylate (L) ligands in a monodentate mode, two O atoms from two ethylene glycol (EG) molecules and two aqua O atoms. The metal ions are linked by the EG and L ligands, forming two-dimensional coordination networks, which are associated into the three-dimensional structure through O—H⋯O hydrogen bonds.

Related literature

For the use of H₂L ligands in the construction of coordination polymers, including metal-organic frameworks with functionalized pores, see: Neofotistou et al. (2010 ). Kanaizuka et al. (2010 ). Yan et al. (2009 ). For the ligand synthesis, see: Neofotistou et al. (2009 ).

Experimental

Crystal data

[Mn(C₁₄H₆O₆S)(C₂H₆O₂)(H₂O)₂]·C₄H₉NO
M_r = 542.41
Monoclinic, P 2₁ /c
a = 7.0564 (3) Å
b = 11.8142 (4) Å
c = 28.0008 (10) Å
β = 100.544 (1)°
V = 2294.89 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.73 mm⁻¹
T = 296 K
0.30 × 0.20 × 0.10 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.811, T_max = 0.931
30673 measured reflections
5716 independent reflections
5221 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.083
S = 1.07
5716 reflections
335 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Table 1
Selected bond lengths (Å)

Mn1—O9	2.1191 (12)
Mn1—O3ⁱ	2.1437 (10)
Mn1—O1	2.1710 (10)
Mn1—O10	2.1897 (12)
Mn1—O8ⁱⁱ	2.2138 (12)
Mn1—O7	2.2253 (11)
Symmetry codes: (i) $[x-1, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) x+1, y, z.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H7⋯O4ⁱⁱⁱ	0.84 (2)	1.83 (2)	2.6623 (16)	175 (2)
O8—H8⋯O2^iv	0.82 (2)	1.88 (2)	2.6865 (16)	169 (2)
O9—H9C⋯O11	0.83 (2)	1.89 (2)	2.7086 (17)	171 (2)
O9—H9B⋯O2	0.83 (2)	1.84 (2)	2.6135 (16)	156 (2)
O10—H10C⋯O11^iv	0.83 (3)	1.96 (3)	2.7877 (19)	172 (2)
O10—H10B⋯O4ⁱ	0.82 (3)	1.98 (3)	2.7663 (16)	161 (3)
Symmetry codes: (i) $[x-1, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iii) -x+1, -y+2, -z+1; (iv) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); 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 I, global. DOI: https://doi.org/10.1107/S1600536810045411/fk2028sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810045411/fk2028Isup2.hkl

checkCIF report

Comment top

In this paper, we report the coordination and hydrogen-bond structure of the title complex (I) derived from S,S-dioxodibenzothiophen-3,7-dicarboxylic acid (H₂L). These sulfone-functionalized dicarboxylic ligands have recently been used to construct coordination polymers, including metal-organic frameworks with functionalized pores (Kanaizuka et al. (2010); Neofotistou et al. (2010); Neofotistou et al. (2009); Yan et al. (2009)). The asymmetric unit of I contains a Mn(II) ion, an L ligand, two aqua ligands, an ethylene glycol (EG) ligand, and an N,N-dimethylacetamide (DMA) solvent molecule (Fig. 1). Each Mn atom resides in a trans-octahedral coordination geometry completed by two carboxylate O atoms (O1 and O3) from two L ligands, two O atoms (O7 and O8) from two EG molecules, and two O atoms (O9 and O10) from two water molecules. The Mn—O distances lie in the range of 2.1191 (12)–2.2253 (11) Å (Table 1). The L ligand binds two Mn atoms through two monodentate carboxylate groups, and the EG ligand also binds two Mn atoms through its two hydroxyl groups. Consequently, the metal ions are linked into a two-dimensional layer (Fig. 2). The carboxylate, hydroxyl, and aqua groups from the coordination sphere and the carbonyl group from the DMA molecule provide plenty of sites for hydrogen bonding (Table 2). Each uncoordinated carboxylate oxygen atom (O2 or O4) serves as a bifurcate acceptor to form an intralayer hydrogen bond with a coordinated aqua molecule and an interlayer one with a EG hydroxyl group from the neighboring layer. The oxygen atom (O11) of the DMA solvent is also bifurcately hydrogen-bonded, to two independent aqua ligands from different coordination layers. The above hydrogen bonds collaborate to assemble the two-dimensional coordination layers into a three-dimensional structure.

Related literature top

For the use of H₂L ligands in the construction of coordination polymers, including metal-organic frameworks with functionalized pores, see: Neofotistou et al. (2010). Kanaizuka et al. (2010). Yan et al. (2009). For the ligand synthesis, see: Neofotistou et al. (2009).

Experimental top

The ligand was synthesized from dimethyl ester of 4,4'-biphenyldicarboxylic acid and H₂SO_4,20%SO₃ (oleum) according to the procedure for similar compounds (Neofotistou et al., 2009). The ligand (0.006 g, 0.03 mmol) and MnCl₂.6H₂O (0.006 g, 0.03 mmol) were dissolved under stirring in a mixture of ethylene glycol (1.0 ml) and DMA (2.0 ml). The resulting solution was left to stand at room temperature for 20 days to afford colorless block crystals of the title compound.

Structure description top

For the use of H₂L ligands in the construction of coordination polymers, including metal-organic frameworks with functionalized pores, see: Neofotistou et al. (2010). Kanaizuka et al. (2010). Yan et al. (2009). For the ligand synthesis, see: Neofotistou et al. (2009).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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. Coordination enviroment in the title compound showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and the H atoms attached to C are omitted for clarity. [Symmetry code: (i)-1/2 + x, 1/2 - y, 1/2 + z (ii) 1 + x, y, z (iii) -1 + x, y, z (iv)1/2 + x, 1/2 - y, -1/2 + z]
	Fig. 2. Two-dimensional layer connected through L and EG. The intralayer hydrogen bonds are shown as dot lines. The H atoms attached to C are omitted for clarity.

Poly[[diaqua(µ₂-5,5-dioxodibenzo[b,d]thiophene- 3,7-dicarboxylato)(µ₂-ethylene glycol)manganese(II)] dimethylacetamide solvate] top

Crystal data top

[Mn(C₁₄H₆O₆S)(C₂H₆O₂)(H₂O)₂]·C₄H₉NO	F(000) = 1124
M_r = 542.41	D_x = 1.570 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9208 reflections
a = 7.0564 (3) Å	θ = 2.3–26°
b = 11.8142 (4) Å	µ = 0.73 mm⁻¹
c = 28.0008 (10) Å	T = 296 K
β = 100.544 (1)°	Columnar, colourless
V = 2294.89 (15) Å³	0.30 × 0.20 × 0.10 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	5716 independent reflections
Radiation source: fine-focus sealed tube	5221 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
φ and ω scans	θ_max = 28.4°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −9→7
T_min = 0.811, T_max = 0.931	k = −15→14
30673 measured reflections	l = −37→36

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: geom and difmap
R[F² > 2σ(F²)] = 0.030	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.083	w = 1/[σ²(F_o²) + (0.0425P)² + 1.0021P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
5716 reflections	Δρ_max = 0.32 e Å⁻³
335 parameters	Δρ_min = −0.36 e Å⁻³
4 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: 0.0011 (3)

Crystal data top

[Mn(C₁₄H₆O₆S)(C₂H₆O₂)(H₂O)₂]·C₄H₉NO	V = 2294.89 (15) Å³
M_r = 542.41	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.0564 (3) Å	µ = 0.73 mm⁻¹
b = 11.8142 (4) Å	T = 296 K
c = 28.0008 (10) Å	0.30 × 0.20 × 0.10 mm
β = 100.544 (1)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	5716 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	5221 reflections with I > 2σ(I)
T_min = 0.811, T_max = 0.931	R_int = 0.025
30673 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	4 restraints
wR(F²) = 0.083	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.32 e Å⁻³
5716 reflections	Δρ_min = −0.36 e Å⁻³
335 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	0.22688 (3)	0.673463 (17)	0.267191 (7)	0.02227 (7)
C1	0.43784 (19)	0.86846 (12)	0.33374 (5)	0.0236 (3)
C2	0.53981 (19)	0.90349 (12)	0.38359 (5)	0.0225 (3)
C3	0.5765 (2)	1.01741 (12)	0.39461 (5)	0.0249 (3)
H3A	0.5433	1.0713	0.3703	0.030*
C4	0.5922 (2)	0.82195 (11)	0.41959 (5)	0.0247 (3)
H4A	0.5704	0.7454	0.4130	0.030*
C5	0.6613 (2)	1.05261 (12)	0.44092 (5)	0.0247 (3)
H5A	0.6842	1.1290	0.4476	0.030*
C6	0.67736 (19)	0.85829 (12)	0.46533 (5)	0.0229 (3)
C7	0.71153 (19)	0.97220 (11)	0.47712 (5)	0.0216 (2)
C8	0.79778 (19)	0.98999 (11)	0.52870 (5)	0.0213 (2)
C9	0.8502 (2)	1.09104 (11)	0.55269 (5)	0.0244 (3)
H9A	0.8314	1.1596	0.5362	0.029*
C10	0.8262 (2)	0.88924 (11)	0.55495 (5)	0.0229 (3)
C11	0.9316 (2)	1.08823 (12)	0.60187 (5)	0.0242 (3)
H11A	0.9687	1.1557	0.6180	0.029*
C12	0.90422 (19)	0.88466 (12)	0.60378 (5)	0.0235 (3)
H12A	0.9199	0.8161	0.6203	0.028*
C13	0.95877 (18)	0.98663 (11)	0.62747 (5)	0.0215 (3)
C14	1.05227 (19)	0.98394 (12)	0.68052 (5)	0.0224 (3)
O1	0.39522 (15)	0.76549 (9)	0.32753 (4)	0.0290 (2)
O2	0.39864 (18)	0.94438 (10)	0.30224 (4)	0.0366 (3)
O3	1.05942 (16)	0.88879 (9)	0.70073 (4)	0.0316 (2)
O4	1.11941 (17)	1.07339 (9)	0.70058 (4)	0.0339 (2)
O5	0.5980 (2)	0.71159 (11)	0.53019 (4)	0.0437 (3)
O6	0.92266 (19)	0.70701 (10)	0.51083 (4)	0.0411 (3)
S1	0.75616 (5)	0.77206 (3)	0.516692 (12)	0.02602 (9)
C15	−0.2116 (2)	0.65002 (14)	0.28938 (6)	0.0334 (3)
H15A	−0.2780	0.6571	0.3167	0.040*
H15B	−0.1888	0.5702	0.2847	0.040*
C16	−0.3383 (2)	0.69648 (15)	0.24442 (6)	0.0334 (3)
H16A	−0.3629	0.7761	0.2490	0.040*
H16B	−0.2730	0.6894	0.2169	0.040*
O7	−0.03049 (15)	0.70750 (10)	0.30054 (4)	0.0312 (2)
H7	−0.052 (3)	0.777 (2)	0.3005 (8)	0.048 (6)*
O8	−0.51664 (16)	0.63629 (11)	0.23467 (5)	0.0381 (3)
H8	−0.495 (3)	0.5748 (15)	0.2233 (8)	0.052 (6)*
O9	0.1821 (2)	0.83273 (10)	0.23213 (5)	0.0471 (3)
H9C	0.135 (3)	0.854 (2)	0.2043 (6)	0.056 (7)*
H9B	0.246 (3)	0.8828 (18)	0.2484 (7)	0.057 (7)*
O10	0.24423 (19)	0.49977 (10)	0.29494 (5)	0.0352 (3)
H10C	0.182 (3)	0.474 (2)	0.3150 (9)	0.057 (7)*
H10B	0.210 (4)	0.463 (2)	0.2701 (10)	0.072 (9)*
C17	−0.0751 (4)	1.0498 (2)	0.08416 (8)	0.0639 (6)
H17A	−0.1888	1.0591	0.0981	0.096*
H17B	−0.1115	1.0281	0.0507	0.096*
H17C	−0.0053	1.1199	0.0863	0.096*
C18	0.0504 (3)	0.95932 (15)	0.11144 (6)	0.0391 (4)
C19	0.3395 (3)	0.8464 (2)	0.12584 (8)	0.0578 (5)
H19A	0.2600	0.7865	0.1344	0.087*
H19B	0.4142	0.8782	0.1548	0.087*
H19C	0.4244	0.8168	0.1057	0.087*
C20	0.2899 (5)	0.9857 (2)	0.05873 (11)	0.0830 (9)
H20A	0.2025	1.0437	0.0443	0.125*
H20B	0.3005	0.9288	0.0349	0.125*
H20C	0.4144	1.0184	0.0703	0.125*
O11	−0.0072 (2)	0.90934 (12)	0.14522 (4)	0.0461 (3)
N1	0.2175 (2)	0.93427 (13)	0.09933 (6)	0.0440 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.02329 (11)	0.02213 (11)	0.01900 (11)	−0.00047 (7)	−0.00245 (8)	−0.00162 (7)
C1	0.0221 (6)	0.0278 (7)	0.0191 (6)	−0.0016 (5)	−0.0007 (5)	−0.0006 (5)
C2	0.0211 (6)	0.0267 (6)	0.0184 (6)	−0.0021 (5)	0.0002 (5)	−0.0018 (5)
C3	0.0283 (7)	0.0253 (7)	0.0193 (6)	−0.0009 (5)	−0.0004 (5)	0.0015 (5)
C4	0.0268 (7)	0.0227 (6)	0.0228 (6)	−0.0024 (5)	−0.0006 (5)	−0.0026 (5)
C5	0.0302 (7)	0.0217 (6)	0.0207 (6)	−0.0010 (5)	0.0009 (5)	−0.0008 (5)
C6	0.0244 (6)	0.0235 (6)	0.0190 (6)	0.0005 (5)	−0.0006 (5)	0.0014 (5)
C7	0.0212 (6)	0.0247 (6)	0.0177 (6)	−0.0004 (5)	0.0005 (5)	−0.0012 (5)
C8	0.0216 (6)	0.0236 (6)	0.0178 (6)	0.0000 (5)	0.0013 (5)	−0.0002 (5)
C9	0.0301 (7)	0.0212 (6)	0.0204 (6)	0.0001 (5)	0.0010 (5)	0.0014 (5)
C10	0.0255 (6)	0.0211 (6)	0.0206 (6)	−0.0014 (5)	0.0006 (5)	−0.0020 (5)
C11	0.0276 (6)	0.0225 (6)	0.0209 (6)	−0.0011 (5)	0.0004 (5)	−0.0026 (5)
C12	0.0257 (6)	0.0231 (6)	0.0203 (6)	0.0011 (5)	0.0003 (5)	0.0020 (5)
C13	0.0203 (6)	0.0255 (6)	0.0176 (6)	0.0015 (5)	0.0002 (5)	−0.0005 (5)
C14	0.0213 (6)	0.0256 (6)	0.0187 (6)	0.0031 (5)	−0.0004 (5)	−0.0007 (5)
O1	0.0348 (5)	0.0260 (5)	0.0221 (5)	−0.0033 (4)	−0.0054 (4)	−0.0028 (4)
O2	0.0494 (7)	0.0311 (6)	0.0234 (5)	−0.0091 (5)	−0.0092 (5)	0.0045 (4)
O3	0.0397 (6)	0.0270 (5)	0.0222 (5)	−0.0004 (4)	−0.0094 (4)	0.0035 (4)
O4	0.0472 (6)	0.0264 (5)	0.0234 (5)	−0.0010 (5)	−0.0062 (4)	−0.0033 (4)
O5	0.0572 (8)	0.0372 (6)	0.0347 (6)	−0.0207 (6)	0.0036 (5)	0.0026 (5)
O6	0.0543 (7)	0.0313 (6)	0.0340 (6)	0.0154 (5)	−0.0022 (5)	−0.0037 (5)
S1	0.03603 (19)	0.01997 (16)	0.01953 (16)	−0.00206 (13)	−0.00157 (13)	−0.00020 (11)
C15	0.0273 (7)	0.0319 (7)	0.0406 (8)	−0.0013 (6)	0.0048 (6)	0.0038 (6)
C16	0.0256 (7)	0.0369 (8)	0.0372 (8)	−0.0023 (6)	0.0044 (6)	−0.0012 (6)
O7	0.0269 (5)	0.0278 (5)	0.0375 (6)	0.0006 (4)	0.0022 (4)	−0.0058 (4)
O8	0.0257 (5)	0.0373 (6)	0.0516 (7)	−0.0023 (5)	0.0076 (5)	−0.0186 (5)
O9	0.0779 (10)	0.0270 (6)	0.0266 (6)	−0.0056 (6)	−0.0164 (6)	0.0035 (5)
O10	0.0474 (7)	0.0284 (6)	0.0280 (6)	−0.0012 (5)	0.0018 (5)	0.0029 (5)
C17	0.0792 (16)	0.0631 (14)	0.0481 (12)	0.0237 (12)	0.0083 (11)	0.0178 (10)
C18	0.0535 (10)	0.0349 (8)	0.0253 (7)	0.0019 (7)	−0.0021 (7)	−0.0032 (6)
C19	0.0607 (13)	0.0621 (13)	0.0526 (12)	0.0184 (11)	0.0155 (10)	0.0050 (10)
C20	0.103 (2)	0.0651 (16)	0.095 (2)	0.0174 (15)	0.0574 (18)	0.0312 (15)
O11	0.0525 (8)	0.0550 (8)	0.0298 (6)	0.0113 (6)	0.0049 (5)	0.0074 (5)
N1	0.0569 (10)	0.0382 (8)	0.0377 (8)	0.0020 (7)	0.0109 (7)	−0.0011 (6)

Geometric parameters (Å, º) top

Mn1—O9	2.1191 (12)	C14—O3	1.2553 (17)
Mn1—O3ⁱ	2.1437 (10)	O3—Mn1ⁱⁱⁱ	2.1437 (10)
Mn1—O1	2.1710 (10)	O5—S1	1.4329 (13)
Mn1—O10	2.1897 (12)	O6—S1	1.4382 (13)
Mn1—O8ⁱⁱ	2.2138 (12)	C15—O7	1.4303 (18)
Mn1—O7	2.2253 (11)	C15—C16	1.508 (2)
C1—O2	1.2529 (17)	C15—H15A	0.9700
C1—O1	1.2576 (18)	C15—H15B	0.9700
C1—C2	1.5066 (18)	C16—O8	1.4275 (19)
C2—C3	1.3943 (19)	C16—H16A	0.9700
C2—C4	1.3945 (19)	C16—H16B	0.9700
C3—C5	1.3889 (19)	O7—H7	0.84 (2)
C3—H3A	0.9300	O8—Mn1^iv	2.2138 (11)
C4—C6	1.3799 (18)	O8—H8	0.818 (16)
C4—H4A	0.9300	O9—H9C	0.827 (15)
C5—C7	1.3871 (18)	O9—H9B	0.827 (15)
C5—H5A	0.9300	O10—H10C	0.83 (3)
C6—C7	1.3961 (19)	O10—H10B	0.82 (3)
C6—S1	1.7671 (14)	C17—C18	1.504 (3)
C7—C8	1.4762 (17)	C17—H17A	0.9600
C8—C9	1.3864 (18)	C17—H17B	0.9600
C8—C10	1.3941 (18)	C17—H17C	0.9600
C9—C11	1.3919 (18)	C18—O11	1.245 (2)
C9—H9A	0.9300	C18—N1	1.318 (2)
C10—C12	1.3784 (18)	C19—N1	1.461 (3)
C10—S1	1.7648 (13)	C19—H19A	0.9600
C11—C13	1.3932 (19)	C19—H19B	0.9600
C11—H11A	0.9300	C19—H19C	0.9600
C12—C13	1.3950 (19)	C20—N1	1.462 (3)
C12—H12A	0.9300	C20—H20A	0.9600
C13—C14	1.5114 (17)	C20—H20B	0.9600
C14—O4	1.2488 (17)	C20—H20C	0.9600

O9—Mn1—O3ⁱ	83.73 (4)	C1—O1—Mn1	132.45 (9)
O9—Mn1—O1	85.98 (4)	C14—O3—Mn1ⁱⁱⁱ	131.98 (9)
O3ⁱ—Mn1—O1	169.61 (4)	O5—S1—O6	117.10 (8)
O9—Mn1—O10	172.07 (5)	O5—S1—C10	112.10 (7)
O3ⁱ—Mn1—O10	88.43 (4)	O6—S1—C10	110.15 (7)
O1—Mn1—O10	101.89 (4)	O5—S1—C6	110.96 (7)
O9—Mn1—O8ⁱⁱ	92.82 (6)	O6—S1—C6	110.93 (7)
O3ⁱ—Mn1—O8ⁱⁱ	86.40 (4)	C10—S1—C6	93.06 (6)
O1—Mn1—O8ⁱⁱ	92.72 (4)	O7—C15—C16	112.28 (13)
O10—Mn1—O8ⁱⁱ	87.89 (5)	O7—C15—H15A	109.1
O9—Mn1—O7	88.29 (6)	C16—C15—H15A	109.1
O3ⁱ—Mn1—O7	93.65 (4)	O7—C15—H15B	109.1
O1—Mn1—O7	87.44 (4)	C16—C15—H15B	109.1
O10—Mn1—O7	91.00 (5)	H15A—C15—H15B	107.9
O8ⁱⁱ—Mn1—O7	178.89 (5)	O8—C16—C15	110.22 (14)
O2—C1—O1	125.37 (12)	O8—C16—H16A	109.6
O2—C1—C2	117.52 (12)	C15—C16—H16A	109.6
O1—C1—C2	117.09 (12)	O8—C16—H16B	109.6
C3—C2—C4	119.54 (12)	C15—C16—H16B	109.6
C3—C2—C1	120.53 (12)	H16A—C16—H16B	108.1
C4—C2—C1	119.90 (12)	C15—O7—Mn1	125.99 (10)
C5—C3—C2	121.77 (13)	C15—O7—H7	108.4 (15)
C5—C3—H3A	119.1	Mn1—O7—H7	109.7 (16)
C2—C3—H3A	119.1	C16—O8—Mn1^iv	125.51 (10)
C6—C4—C2	117.96 (12)	C16—O8—H8	107.4 (16)
C6—C4—H4A	121.0	Mn1^iv—O8—H8	123.9 (16)
C2—C4—H4A	121.0	Mn1—O9—H9C	134.6 (16)
C7—C5—C3	119.08 (13)	Mn1—O9—H9B	111.1 (16)
C7—C5—H5A	120.5	H9C—O9—H9B	113 (2)
C3—C5—H5A	120.5	Mn1—O10—H10C	125.2 (17)
C4—C6—C7	123.13 (12)	Mn1—O10—H10B	102 (2)
C4—C6—S1	126.50 (11)	H10C—O10—H10B	106 (2)
C7—C6—S1	110.38 (10)	C18—C17—H17A	109.5
C5—C7—C6	118.52 (12)	C18—C17—H17B	109.5
C5—C7—C8	128.45 (12)	H17A—C17—H17B	109.5
C6—C7—C8	113.03 (12)	C18—C17—H17C	109.5
C9—C8—C10	118.68 (12)	H17A—C17—H17C	109.5
C9—C8—C7	128.49 (12)	H17B—C17—H17C	109.5
C10—C8—C7	112.83 (12)	O11—C18—N1	121.38 (16)
C8—C9—C11	118.95 (12)	O11—C18—C17	118.61 (18)
C8—C9—H9A	120.5	N1—C18—C17	120.01 (18)
C11—C9—H9A	120.5	N1—C19—H19A	109.5
C12—C10—C8	123.32 (12)	N1—C19—H19B	109.5
C12—C10—S1	126.02 (11)	H19A—C19—H19B	109.5
C8—C10—S1	110.64 (10)	N1—C19—H19C	109.5
C9—C11—C13	121.50 (12)	H19A—C19—H19C	109.5
C9—C11—H11A	119.2	H19B—C19—H19C	109.5
C13—C11—H11A	119.2	N1—C20—H20A	109.5
C10—C12—C13	117.59 (12)	N1—C20—H20B	109.5
C10—C12—H12A	121.2	H20A—C20—H20B	109.5
C13—C12—H12A	121.2	N1—C20—H20C	109.5
C11—C13—C12	119.96 (12)	H20A—C20—H20C	109.5
C11—C13—C14	121.20 (12)	H20B—C20—H20C	109.5
C12—C13—C14	118.82 (12)	C18—N1—C19	120.01 (16)
O4—C14—O3	125.06 (12)	C18—N1—C20	124.28 (18)
O4—C14—C13	119.06 (12)	C19—N1—C20	115.66 (19)
O3—C14—C13	115.87 (12)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7···O4^v	0.84 (2)	1.83 (2)	2.6623 (16)	175 (2)
O8—H8···O2^vi	0.82 (2)	1.88 (2)	2.6865 (16)	169 (2)
O9—H9C···O11	0.83 (2)	1.89 (2)	2.7086 (17)	171 (2)
O9—H9B···O2	0.83 (2)	1.84 (2)	2.6135 (16)	156 (2)
O10—H10C···O11^vi	0.83 (3)	1.96 (3)	2.7877 (19)	172 (2)
O10—H10B···O4ⁱ	0.82 (3)	1.98 (3)	2.7663 (16)	161 (3)

Symmetry codes: (i) x−1, −y+3/2, z−1/2; (v) −x+1, −y+2, −z+1; (vi) −x, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Mn(C₁₄H₆O₆S)(C₂H₆O₂)(H₂O)₂]·C₄H₉NO
M_r	542.41
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	7.0564 (3), 11.8142 (4), 28.0008 (10)
β (°)	100.544 (1)
V (Å³)	2294.89 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.73
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.811, 0.931
No. of measured, independent and observed [I > 2σ(I)] reflections	30673, 5716, 5221
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.083, 1.07
No. of reflections	5716
No. of parameters	335
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.36

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Mn1—O9	2.1191 (12)	Mn1—O10	2.1897 (12)
Mn1—O3ⁱ	2.1437 (10)	Mn1—O8ⁱⁱ	2.2138 (12)
Mn1—O1	2.1710 (10)	Mn1—O7	2.2253 (11)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7···O4ⁱⁱⁱ	0.84 (2)	1.83 (2)	2.6623 (16)	175 (2)
O8—H8···O2^iv	0.818 (16)	1.879 (16)	2.6865 (16)	169 (2)
O9—H9C···O11	0.827 (15)	1.889 (16)	2.7086 (17)	171 (2)
O9—H9B···O2	0.827 (15)	1.837 (16)	2.6135 (16)	156 (2)
O10—H10C···O11^iv	0.83 (3)	1.96 (3)	2.7877 (19)	172 (2)
O10—H10B···O4ⁱ	0.82 (3)	1.98 (3)	2.7663 (16)	161 (3)

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

Acknowledgements

We are thankful for financial support from the NSFC (20771038) and the Shanghai Leading Academic Discipline Project (B409).

References

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