catena-Poly[[diaqua­manganese(II)]-di-μ-pyridine-3-sulfonato-κ²N:O;κ²O:N]

In the title polymeric complex, [Mn(C₅H₄NO₃S)₂(H₂O)₂]_n, the Mn atom is located on a centre of inversion and is coordinated by two O atoms and two N atoms derived from four different pyridine-3-sulfonate (pySO₃) ligands, and two O atoms derived from two water mol­ecules in a distorted trans-N₂O₄ octa­hedral geometry. The metal atoms are bridged by the pySO₃ ligands to form a one-dimensional chain. The chains are further connected into a three-dimensional architecture via hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C)= 0.003 Å
• R factor = 0.027
• wR factor = 0.070
• Data-to-parameter ratio = 14.0

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S1. Comment

Structures of complexes or salts based on pyridinium-3-sulfonate are not numerous in the Cambridge Structural Database (CSD; Version 5.25; Allen, 2002). Some six-coordinate metal complexes with pyridine-3-sulfonate (pySO₃) ligands that are closely related to the title complex have been reported (Walsh & Hathaway, 1980; Cotton et al., 1992a). Other pySO₃ complexes are also available (Brodersen et al., 1980; Cotton et al., 1992b; Mäkinen et al., 2001; van der Lee & Barboiu, 2004), as well as that of the pySO₃H acid (Chandrasekhar, 1977). There are two structures of the [M(pySO₃)₂(H₂O)₂] type in the CSD. One of them is isostructural with the title compound (Walsh & Hathaway, 1980; Cotton et al., 1992a) and the other structure is a two-dimensional coordination polymer (Brodersen et al.,1980).

The Mn atom is located on a centre of inversion and is six-coordinated by two N atoms and two O atoms derived from four different pySO₃, and two O atoms derived from two water molecules (Fig. 1). The resulting trans-N₂O₄ donor set defines a distorted octahedral environment for Mn. The bond angles deviate considerably from 90°; those derived from the bulkier groups deviate by nearly 6°. The Mn—O(water) distance of 2.1681 (15) Å and Mn—O(pySO₃) distance of 2.1772 (15) Å are in the usual range.The Mn—N distance is also in the usual range for pyridine-like ligands.

The metal ions are bridgeding pySO₃ anions to form a chain. In the crystal structure, chains are linked into a 3-D architecture via hydrogen bonding interactions (Table 1 & Fig. 2).

Related literature

For related structures, see: Brodersen et al. (1980); Chandrasekhar (1977); Cotton et al. (1992a,b); Mäkinen et al.(2001); van der Lee & Barboiu (2004); Walsh & Hathaway (1980). For a description of the Cambridge Structural Database, see: Allen (2002).

S2. Experimental

Pyridinium-3-sulfonate, (1 mmol,159 mg) was dissolved in methanol (A.R.,99.9%) (10 ml). To the resulting clear solution was added MnCl₂.4H₂O (0.5 mmol, 98 mg) in methanol (10 ml). After keeping the resulting mixture in air to evaporate about half of the solvent, colourless blocks of the title compound were deposited. The crystals were isolated and washed with alcohol three times (yield 82%). Analysis found (%): C 29.38, H 2.90, N 6.89, S 15.80; C₁₀H₁₂MnN₂O₈S₂ requires (%): C 29.47, H 2.94, N 6.87, S 15.71.

S3. Refinement

The H atoms of the water molecules were located in a difference map. The H atoms bonded to C atoms were placed at calculated positions and refined in a riding-model approximation [C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C)]. The O-H distances were standardized to 0.89 Å and the H atoms of the water molecules were refined in a riding-model approximation with U_iso(H) = 1.2U_eq(O).

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SMART (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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

	Fig. 1. The atom-numbering scheme and 50% probability displacement ellipsoids for the title compound. The Mn atom is located at a center of inversion. H atoms are shown as small spheres of arbitrary radii [symmetry code: (a) -1 + x,y,z].
	Fig. 2. Crystal packing of the title compound viewed approximately down the a-direction showing the hydrogen bonding interactions as dashed lines.

catena-Poly[[diaquamanganese(II)]-di-µ-pyridine-3-sulfonato- κ²N:O;κ²O:N]

Crystal data

[Mn(C5H4NO3S)2(H2O)2]	F(000) = 414
Mr = 407.28	Dx = 1.859 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2334 reflections
a = 7.6299 (13) Å	θ = 2.7–26.4°
b = 13.201 (2) Å	µ = 1.24 mm^−1
c = 7.2714 (12) Å	T = 294 K
β = 96.516 (3)°	Block, colourless
V = 727.7 (2) Å^3	0.24 × 0.22 × 0.18 mm
Z = 2

Data collection

Bruker SMART CCD area-detector diffractometer	1485 independent reflections
Radiation source: fine-focus sealed tube	1301 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
Detector resolution: 0 pixels mm^-1	θmax = 26.4°, θmin = 2.7°
ϕ and ω scans	h = −8→9
Absorption correction: multi-scan (SADABS; Bruker, 1998)	k = −16→15
Tmin = 0.755, Tmax = 0.808	l = −9→7
4034 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.026	H-atom parameters constrained
wR(F^2) = 0.069	w = 1/[σ^2(Fo^2) + (0.0952P)^2 + 1.5031P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.001
1485 reflections	Δρmax = 0.24 e Å^−3
106 parameters	Δρmin = −0.37 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.087 (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	0.0000	1.0000	0.0000	0.01892 (13)
S1	0.72645 (6)	0.87969 (4)	0.28519 (7)	0.01996 (14)
O1	0.7153 (2)	0.95339 (12)	0.4310 (2)	0.0344 (4)
O2	0.8234 (2)	0.78954 (11)	0.3466 (2)	0.0345 (4)
O3	0.7864 (2)	0.92419 (13)	0.1200 (2)	0.0364 (4)
O4	0.0783 (2)	1.09357 (11)	0.2404 (2)	0.0316 (4)
H4A	0.1331	1.0735	0.3492	0.038*
H4B	0.1133	1.1574	0.2295	0.038*
N1	0.2084 (2)	0.88314 (12)	0.1103 (2)	0.0232 (4)
C1	0.1706 (3)	0.78382 (15)	0.1017 (3)	0.0249 (4)
H1	0.0547	0.7645	0.0646	0.030*
C2	0.2946 (3)	0.70884 (16)	0.1449 (3)	0.0296 (5)
H2	0.2627	0.6409	0.1363	0.035*
C3	0.4668 (3)	0.73661 (15)	0.2010 (3)	0.0263 (4)
H3	0.5534	0.6878	0.2303	0.032*
C4	0.5079 (2)	0.83896 (15)	0.2129 (3)	0.0188 (4)
C5	0.3761 (3)	0.90965 (14)	0.1666 (3)	0.0224 (4)
H5	0.4047	0.9781	0.1747	0.027*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0134 (2)	0.0187 (2)	0.0237 (2)	−0.00056 (15)	−0.00157 (16)	0.00122 (16)
S1	0.0146 (2)	0.0193 (2)	0.0250 (3)	0.00040 (17)	−0.00246 (18)	0.00251 (18)
O1	0.0305 (8)	0.0318 (9)	0.0386 (9)	0.0022 (7)	−0.0057 (7)	−0.0107 (7)
O2	0.0252 (8)	0.0247 (8)	0.0499 (10)	0.0067 (6)	−0.0114 (7)	0.0029 (7)
O3	0.0228 (8)	0.0506 (10)	0.0356 (9)	−0.0106 (7)	0.0022 (6)	0.0125 (8)
O4	0.0398 (9)	0.0249 (8)	0.0281 (8)	−0.0042 (7)	−0.0054 (7)	−0.0024 (6)
N1	0.0170 (8)	0.0215 (8)	0.0302 (9)	−0.0009 (7)	−0.0012 (7)	0.0025 (7)
C1	0.0186 (10)	0.0253 (10)	0.0298 (11)	−0.0038 (8)	−0.0014 (8)	0.0006 (9)
C2	0.0281 (12)	0.0184 (10)	0.0416 (13)	−0.0043 (8)	0.0011 (10)	−0.0005 (9)
C3	0.0213 (10)	0.0182 (10)	0.0393 (12)	0.0042 (8)	0.0025 (9)	0.0039 (8)
C4	0.0152 (9)	0.0206 (10)	0.0205 (9)	−0.0006 (7)	0.0009 (7)	0.0013 (7)
C5	0.0186 (10)	0.0156 (9)	0.0322 (11)	−0.0011 (7)	−0.0009 (8)	0.0012 (8)

Geometric parameters (Å, º)

Mn1—O4	2.1681 (15)	N1—C5	1.345 (3)
Mn1—O3^i	2.1773 (15)	C1—C2	1.381 (3)
Mn1—N1	2.2937 (16)	C1—H1	0.9300
S1—O2	1.4449 (15)	C2—C3	1.380 (3)
S1—O1	1.4489 (16)	C2—H2	0.9300
S1—O3	1.4570 (16)	C3—C4	1.388 (3)
S1—C4	1.7737 (19)	C3—H3	0.9300
O4—H4A	0.8922	C4—C5	1.385 (3)
O4—H4B	0.8897	C5—H5	0.9300
N1—C1	1.342 (3)
O4—Mn1—O4^ii	180.0	C1—N1—C5	117.40 (17)
O4—Mn1—O3^i	95.12 (6)	C1—N1—Mn1	120.26 (13)
O4^ii—Mn1—O3^i	84.88 (6)	C5—N1—Mn1	121.96 (13)
O3^iii—Mn1—O3^i	180.0	N1—C1—C2	123.47 (18)
O4—Mn1—N1	89.13 (6)	N1—C1—H1	118.3
O4^ii—Mn1—N1	90.87 (6)	C2—C1—H1	118.3
O3^iii—Mn1—N1	85.90 (6)	C1—C2—C3	118.80 (19)
O3^i—Mn1—N1	94.09 (6)	C1—C2—H2	120.6
N1^ii—Mn1—N1	180.00 (6)	C3—C2—H2	120.6
O2—S1—O1	113.41 (10)	C2—C3—C4	118.54 (18)
O2—S1—O3	112.91 (10)	C2—C3—H3	120.7
O1—S1—O3	112.51 (10)	C4—C3—H3	120.7
O2—S1—C4	105.84 (9)	C5—C4—C3	119.22 (18)
O1—S1—C4	106.81 (9)	C5—C4—S1	119.99 (15)
O3—S1—C4	104.50 (9)	C3—C4—S1	120.79 (15)
S1—O3—Mn1^iv	146.62 (10)	N1—C5—C4	122.57 (18)
Mn1—O4—H4A	127.1	N1—C5—H5	118.7
Mn1—O4—H4B	121.7	C4—C5—H5	118.7
H4A—O4—H4B	104.2
O2—S1—O3—Mn1^iv	−66.4 (2)	C1—C2—C3—C4	0.4 (3)
O1—S1—O3—Mn1^iv	63.6 (2)	C2—C3—C4—C5	−0.6 (3)
C4—S1—O3—Mn1^iv	179.06 (19)	C2—C3—C4—S1	179.69 (16)
O4—Mn1—N1—C1	137.80 (16)	O2—S1—C4—C5	172.26 (16)
O4^ii—Mn1—N1—C1	−42.20 (16)	O1—S1—C4—C5	51.12 (18)
O3^iii—Mn1—N1—C1	−137.26 (16)	O3—S1—C4—C5	−68.31 (18)
O3^i—Mn1—N1—C1	42.73 (16)	O2—S1—C4—C3	−8.1 (2)
O4—Mn1—N1—C5	−49.49 (16)	O1—S1—C4—C3	−129.20 (18)
O4^ii—Mn1—N1—C5	130.51 (16)	O3—S1—C4—C3	111.38 (18)
O3^iii—Mn1—N1—C5	35.44 (16)	C1—N1—C5—C4	0.7 (3)
O3^i—Mn1—N1—C5	−144.56 (16)	Mn1—N1—C5—C4	−172.23 (14)
C5—N1—C1—C2	−0.9 (3)	C3—C4—C5—N1	0.1 (3)
Mn1—N1—C1—C2	172.13 (16)	S1—C4—C5—N1	179.77 (16)
N1—C1—C2—C3	0.4 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4B···O2^v	0.89	1.91	2.786 (2)	168
O4—H4A···O1^vi	0.89	1.90	2.778 (2)	169

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