Poly[[diaqua­(N,N-dimethyl­formamide-[kappa]O)manganese(II)]-[mu]₃-sulfato]

In the title complex, [Mn(SO₄)(C₃H₇NO)(H₂O)₂]_n, each Mn^II ion has a distorted octa­hedral geometry formed by three O atoms of three different sulfate groups, one O atom of a dimethyl­formamide ligand and two water mol­ecules. The sulfate groups act as tridentate bridging ligands connecting the Mn^II ions into a two-dimensional layer structure which can be regraded as a 4.8² network.

S1. Comment

Inorganic open-framework structures involving aluminosilicates (Breck, 1974), silicates (Breck, 1974), phosphates (Cheetham et al., 1999) and carboxylates (Guillou et al., 2002), which include not only three-dimensional structures with channels but also structures with two-dimensional layers and one-dimensional chains (Rao et al., 2001), have been widely investigated in the past few years. Recently, there has been growing interest in the study of open-framework architectures containing oxoanions of sulfur and selenium (Choudhury et al., 2002, and references therein). To date, several layered sulfates of iron (Paul, Choudhury, Sampathkumaran et al., 2002), nickel (Behera et al., 2004) and cadmium (Paul, Choudhury & Rao, 2002), have been reported, but among the transition metal sulfates, layered manganese sulfates have not been synthesized. In this article, we report the synthesis and structure of the title compound, [Mn(SO₄)(DMF)(H₂O)₂]_n (DMF is dimethylformamide), (I), which was obtained by accident in the reaction of 2-(2-hydroxy-3-methoxybenzylidene)-N-phenylhydrazinecarbothioamide and MnSO₄·6H₂O in MeOH–DMF solution.

The molecular structure of complex (I) is shown in Fig. 1, and selected bond distances and angles are given in Table 1. The asymmetric unit of (I) consists of one Mn^II ion, one DMF ligand, one sulfate ion and two coordinated water molecules. The coordinated water molecule O1W forms intramolecular hydrogen bonds with O atoms of the sulfate group. Each Mn^II ion displays a slightly distorted octahedral geometry involving three O atoms of three different SO₄^2- groups, one O atom of the DMF ligand and two water molecules. The equatorial plane is defined by atoms O1W, O1, O2ⁱ and O3ⁱ [the deviation from the mean plane is 0.06 (3) Å and the displacement of the Mn^II atom from this plane is 0.119 (3) Å; symmetry code: (i) x + 1/2, -y + 3/2, z + 1/2], while the axial positions are occupied by atoms O2W and O5. The average Mn—O(water) distance is somewhat longer than that of Mn—O(SO₄^2-), while the Mn—O(DMF) distance is the shortest.

In the previously reported layered transition metal sulfates, the sulfate groups have two kinds of coordination modes, namely tridentate bridging for Fe, tetradentate bridging for Cd and both for Ni. For (I), the sulfate groups only act as tridentate bridging ligands to connect the Mn^II ions into a two-dimensional inorganic layer structure. By treating the Mn centre and S atoms of the µ₃-sulfate groups as nodes and connecting the nodes according to the connectivity, the two-dimensional structure is comprised of an octagonal and rhombic mesh with a three-connected (4.8²) topology (Fig. 2a). The diagonals of the distorted rhombic windows are about 4.385 (2) and 5.247 (2) Å, while the dimensions of the distorted octagonal windows, estimated from the maximum distances between opposite vertices, are about 9.743 (2) and 11.01 (2) Å. Therefore, the inorganic layer is built up of eight-membered rings formed by two MnO₆ octahedra and two SO₄ tetrahedra and 16-membered rings formed by four MnO₆ octahedra and four SO₄ tetrahedra linked through shared vertices (Fig. 2 b). Such layers are further held together by van der waals interactions to form eight- and 16-membered channels along the a axis, in which the 16-membered channels are filled by the DMF molecules and coordinated water molecules which interact with the framework O atoms through strong O—H···O hydrogen bonds (Table 2).

Related literature

For related literature, see: Behera et al. (2004); Breck (1974); Cheetham et al. (1999); Choudhury et al. (2002); Guillou et al. (2002); Paul, Choudhury & Rao (2002); Paul, Choudhury, Sampathkumaran & Rao (2002); Rao et al. (2001).

S2. Experimental

A methanol solution (10 ml) containing manganese sulfate hexahydrate (0.130 g, 0.5 mmol) was added to a dimethlformamide solution (5 ml) of 2-(2-hydroxy-3-methoxybenzylidene)-N-phenylhydrazinecarbothioamide (0.15 g, 0.5 mmol). The final solution was allowed to evaporate at room temperature, and colourless prismatic crystals of (I) were separated from the filtered solution after several weeks. Analysis, calculated for C₃H₁₁NO₇SMn: C 13.85, H 4.26, N 5.38%; found: C 13.76, H 4.33, N 5.44%.

S3. Refinement

Carbon-bound H atoms were placed in calculated positions, with C—H = 0.93 Å, and were refined in the riding-model approximation, with U_iso(H) = 1.2U_eq(C). The H atoms of the water molecules were located in a difference Fourier map and refined with O—H and H···H distance restraints of 0.85 (1) and 1.39 (1) Å, respectively, and with U_iso(H) = 1.5U_eq(O).

Computing details

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. ORTEPII plot (Johnson, 1976) of the title complex, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. The hydrogen bond is denoted by a dashed line.
	Fig. 2. (a) The layer structure of (4.8^2) topology. (b) Polyhedral representation of the inorganic layer in (I) in the bc plane.

Poly[[diaqua(N,N-dimethylformamide-κO)manganese(II)]-µ₃-sulfato]

Crystal data

[Mn(SO4)(C3H7NO)(H2O)2]	F(000) = 532
Mr = 260.13	Dx = 1.794 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 8836 reflections
a = 10.890 (2) Å	θ = 3.2–27.5°
b = 7.7642 (16) Å	µ = 1.60 mm^−1
c = 12.272 (3) Å	T = 295 K
β = 111.87 (3)°	Prism, colourless
V = 963.0 (4) Å^3	0.36 × 0.28 × 0.19 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID diffractometer	2201 independent reflections
Radiation source: fine-focus sealed tube	2117 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
Detector resolution: 10.000 pixels mm^-1	θmax = 27.5°, θmin = 3.2°
ω scans	h = −14→14
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −10→10
Tmin = 0.593, Tmax = 0.731	l = −15→15
9196 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.020	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.055	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0314P)^2 + 0.3428P] where P = (Fo^2 + 2Fc^2)/3
2201 reflections	(Δ/σ)max = 0.001
132 parameters	Δρmax = 0.29 e Å^−3
6 restraints	Δρmin = −0.41 e Å^−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 (Ų)

	x	y	z	Uiso*/Ueq
Mn1	0.413302 (17)	0.68135 (2)	0.305694 (15)	0.01787 (7)
S1	0.11627 (3)	0.77530 (4)	0.08880 (2)	0.01757 (8)
O1W	0.43319 (10)	0.93755 (12)	0.23250 (9)	0.0264 (2)
H1W1	0.4643 (15)	1.0187 (19)	0.2815 (13)	0.040*
H1W2	0.3541 (10)	0.962 (2)	0.1896 (13)	0.040*
O2W	0.29697 (10)	0.80786 (12)	0.39954 (9)	0.0253 (2)
H2W1	0.3467 (16)	0.797 (2)	0.4715 (9)	0.038*
H2W2	0.2851 (17)	0.9129 (13)	0.3830 (14)	0.038*
O1	0.23191 (9)	0.66033 (11)	0.14478 (8)	0.0236 (2)
O2	0.08493 (9)	0.77621 (14)	−0.03830 (8)	0.0265 (2)
O3	0.15469 (10)	0.94977 (12)	0.13683 (9)	0.0290 (2)
O4	0.00263 (9)	0.71352 (13)	0.11487 (9)	0.0269 (2)
O5	0.53170 (11)	0.56400 (15)	0.22225 (10)	0.0353 (2)
N1	0.60913 (14)	0.36990 (19)	0.12679 (12)	0.0367 (3)
C1	0.52497 (15)	0.4227 (2)	0.17348 (13)	0.0320 (3)
H1	0.4560	0.3493	0.1697	0.038*
C2	0.7187 (2)	0.4779 (3)	0.1300 (2)	0.0701 (7)
H2A	0.7016	0.5947	0.1458	0.105*
H2B	0.7288	0.4723	0.0557	0.105*
H2C	0.7984	0.4383	0.1908	0.105*
C3	0.5949 (3)	0.2051 (3)	0.0667 (2)	0.0609 (6)
H3A	0.5232	0.1419	0.0751	0.091*
H3B	0.6753	0.1404	0.1005	0.091*
H3C	0.5767	0.2245	−0.0151	0.091*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.01755 (11)	0.01788 (11)	0.01642 (11)	−0.00011 (6)	0.00428 (8)	−0.00094 (6)
S1	0.01795 (15)	0.01505 (14)	0.01580 (14)	0.00122 (10)	0.00176 (11)	−0.00016 (10)
O1W	0.0272 (5)	0.0222 (5)	0.0282 (5)	−0.0018 (4)	0.0085 (4)	−0.0023 (4)
O2W	0.0266 (5)	0.0231 (5)	0.0248 (5)	0.0059 (4)	0.0078 (4)	0.0023 (4)
O1	0.0231 (5)	0.0163 (4)	0.0227 (4)	0.0035 (3)	−0.0015 (4)	−0.0006 (3)
O2	0.0212 (5)	0.0388 (6)	0.0161 (4)	0.0034 (4)	0.0031 (4)	0.0022 (4)
O3	0.0271 (5)	0.0168 (5)	0.0371 (5)	0.0012 (4)	0.0050 (4)	−0.0061 (4)
O4	0.0242 (5)	0.0308 (5)	0.0245 (5)	−0.0022 (4)	0.0079 (4)	0.0030 (4)
O5	0.0363 (6)	0.0379 (6)	0.0382 (6)	0.0051 (5)	0.0214 (5)	−0.0052 (5)
N1	0.0410 (7)	0.0387 (7)	0.0377 (7)	0.0047 (6)	0.0230 (6)	−0.0047 (6)
C1	0.0329 (7)	0.0369 (8)	0.0301 (7)	0.0015 (6)	0.0162 (6)	0.0014 (6)
C2	0.0524 (12)	0.0868 (17)	0.0933 (18)	−0.0164 (11)	0.0529 (13)	−0.0316 (14)
C3	0.0936 (17)	0.0425 (11)	0.0615 (13)	0.0047 (11)	0.0463 (13)	−0.0116 (9)

Geometric parameters (Å, º)

Mn1—O1W	2.2261 (11)	O2—Mn1^iii	2.1450 (13)
Mn1—O2W	2.2322 (11)	O3—Mn1^iv	2.1605 (10)
Mn1—O1	2.2185 (13)	O5—C1	1.2389 (19)
Mn1—O2^i	2.1450 (13)	N1—C1	1.3143 (19)
Mn1—O3^ii	2.1605 (10)	N1—C2	1.447 (3)
Mn1—O5	2.1271 (11)	N1—C3	1.455 (2)
S1—O2	1.4671 (10)	C1—H1	0.9300
S1—O4	1.4693 (10)	C2—H2A	0.9600
S1—O3	1.4744 (10)	C2—H2B	0.9600
S1—O1	1.4866 (10)	C2—H2C	0.9600
O1W—H1W1	0.849 (9)	C3—H3A	0.9600
O1W—H1W2	0.848 (9)	C3—H3B	0.9600
O2W—H2W1	0.851 (9)	C3—H3C	0.9600
O2W—H2W2	0.838 (9)
O5—Mn1—O2^i	90.72 (4)	Mn1—O2W—H2W2	111.6 (13)
O5—Mn1—O3^ii	98.26 (4)	H2W1—O2W—H2W2	109.3 (13)
O2^i—Mn1—O3^ii	97.30 (4)	S1—O1—Mn1	133.41 (6)
O5—Mn1—O1	92.20 (4)	S1—O2—Mn1^iii	136.88 (6)
O2^i—Mn1—O1	175.27 (4)	S1—O3—Mn1^iv	144.53 (6)
O3^ii—Mn1—O1	85.96 (4)	C1—O5—Mn1	132.42 (10)
O5—Mn1—O1W	91.20 (4)	C1—N1—C2	120.62 (15)
O2^i—Mn1—O1W	92.26 (4)	C1—N1—C3	122.31 (16)
O3^ii—Mn1—O1W	166.43 (4)	C2—N1—C3	117.04 (16)
O1—Mn1—O1W	83.96 (4)	O5—C1—N1	124.15 (15)
O5—Mn1—O2W	177.55 (4)	O5—C1—H1	117.9
O2^i—Mn1—O2W	86.86 (4)	N1—C1—H1	117.9
O3^ii—Mn1—O2W	82.44 (4)	N1—C2—H2A	109.5
O1—Mn1—O2W	90.19 (4)	N1—C2—H2B	109.5
O1W—Mn1—O2W	88.52 (4)	H2A—C2—H2B	109.5
O2—S1—O4	110.60 (6)	N1—C2—H2C	109.5
O2—S1—O3	109.85 (6)	H2A—C2—H2C	109.5
O4—S1—O3	110.45 (6)	H2B—C2—H2C	109.5
O2—S1—O1	108.41 (6)	N1—C3—H3A	109.5
O4—S1—O1	109.91 (6)	N1—C3—H3B	109.5
O3—S1—O1	107.55 (6)	H3A—C3—H3B	109.5
Mn1—O1W—H1W1	116.8 (13)	N1—C3—H3C	109.5
Mn1—O1W—H1W2	103.0 (13)	H3A—C3—H3C	109.5
H1W1—O1W—H1W2	108.4 (13)	H3B—C3—H3C	109.5
Mn1—O2W—H2W1	103.1 (13)
O2—S1—O1—Mn1	137.27 (8)	O2—S1—O3—Mn1^iv	99.93 (12)
O4—S1—O1—Mn1	−101.75 (9)	O4—S1—O3—Mn1^iv	−22.33 (13)
O3—S1—O1—Mn1	18.54 (10)	O1—S1—O3—Mn1^iv	−142.27 (11)
O5—Mn1—O1—S1	−141.66 (9)	O2^i—Mn1—O5—C1	125.98 (14)
O3^ii—Mn1—O1—S1	120.22 (9)	O3^ii—Mn1—O5—C1	28.50 (14)
O1W—Mn1—O1—S1	−50.68 (8)	O1—Mn1—O5—C1	−57.74 (14)
O2W—Mn1—O1—S1	37.81 (9)	O1W—Mn1—O5—C1	−141.74 (14)
O4—S1—O2—Mn1^iii	32.98 (11)	Mn1—O5—C1—N1	−179.29 (11)
O3—S1—O2—Mn1^iii	−89.20 (10)	C2—N1—C1—O5	0.1 (3)
O1—S1—O2—Mn1^iii	153.54 (9)	C3—N1—C1—O5	−177.83 (17)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···O4^iv	0.85 (1)	1.92 (2)	2.7591 (16)	168 (2)
O1W—H1W2···O3	0.85 (1)	2.02 (1)	2.8164 (16)	155 (2)
O2W—H2W1···O4^i	0.85 (1)	1.94 (1)	2.7599 (18)	162 (2)
O2W—H2W2···O1^iv	0.84 (1)	1.95 (1)	2.7851 (14)	176 (2)

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