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A novel manganese coordination polymer, poly[(μ5-thiophene-3,4-dicarboxylato)manganese(II)], [Mn(C6H2O4S)]n, was synthesized hydro­thermally using 3,4-thio­phene­di­car­box­yl­ate (3,4-tdc2−) as the organic linker. The asymmetric unit of the complex contains an Mn2+ cation and one half of a deprotonated 3,4-tdc2− anion, both residing on a twofold axis. Each Mn2+ centre is six-coordinated by O atoms of bridging/chelating carboxyl­ate groups from five 3,4-tdc2− anions, forming a slightly distorted octa­hedron. The Mn2+ centres are bridged by 3,4-tdc2− anions to give an infinite two-di­men­sional layer which incorporates one-dimensional Mn–O gridlike chains, and in which the 3,4-tdc2− anion adopts a novel hexa­dentate chelating and μ5-bridging coordination mode. The fully deprotonated 3,4-tdc2− anion exhibits unexpected efficiency as a ligand towards the Mn2+ centres, which it coordinates through all of its carboxyl­ate O atoms to provide the novel coordination mode. The IR spectrum of the complex is also reported.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S205322961401417X/fa3345sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S205322961401417X/fa3345Isup2.hkl
Contains datablock I

CCDC reference: 1008743

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SMART (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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).

Poly[(µ5-thiophene-3,4-dicarboxylato)manganese(II)] top
Crystal data top
[Mn(C6H2O4S)]F(000) = 444
Mr = 225.08Dx = 2.124 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 4.608 (4) ÅCell parameters from 1490 reflections
b = 26.40 (2) Åθ = 3.1–28.3°
c = 6.123 (5) ŵ = 2.13 mm1
β = 109.044 (8)°T = 296 K
V = 704.0 (10) Å3Block, yellow
Z = 40.39 × 0.20 × 0.11 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
665 independent reflections
Radiation source: fine-focus sealed tube637 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.026
φ and ω scansθmax = 25.5°, θmin = 3.1°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
h = 55
Tmin = 0.490, Tmax = 0.799k = 3128
1773 measured reflectionsl = 57
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.025Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.067H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.0398P)2 + 1.3961P]
where P = (Fo2 + 2Fc2)/3
665 reflections(Δ/σ)max = 0.001
56 parametersΔρmax = 0.58 e Å3
0 restraintsΔρmin = 0.41 e Å3
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
xyzUiso*/Ueq
Mn10.00000.277059 (16)0.75000.01560 (18)
S10.00000.03781 (3)0.75000.0408 (3)
O10.0271 (3)0.21506 (6)0.5120 (3)0.0181 (3)
O20.3444 (3)0.16949 (6)0.4462 (3)0.0221 (4)
C10.1363 (5)0.17486 (8)0.5338 (3)0.0164 (4)
C20.0688 (5)0.13060 (8)0.6597 (4)0.0185 (5)
C30.1172 (6)0.08310 (9)0.5969 (4)0.0282 (5)
H30.20450.07580.48330.034*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.0161 (3)0.0195 (3)0.0117 (3)0.0000.00519 (19)0.000
S10.0706 (7)0.0181 (5)0.0496 (6)0.0000.0412 (6)0.000
O10.0189 (8)0.0203 (8)0.0148 (7)0.0021 (6)0.0052 (6)0.0012 (6)
O20.0211 (8)0.0276 (8)0.0217 (8)0.0036 (6)0.0127 (7)0.0047 (7)
C10.0167 (10)0.0211 (11)0.0105 (10)0.0006 (8)0.0032 (8)0.0011 (8)
C20.0180 (10)0.0216 (11)0.0172 (11)0.0010 (8)0.0076 (9)0.0000 (9)
C30.0399 (14)0.0235 (12)0.0285 (13)0.0008 (10)0.0214 (11)0.0011 (10)
Geometric parameters (Å, º) top
Mn1—O2i2.1238 (19)O1—C11.283 (3)
Mn1—O2ii2.1238 (19)O1—Mn1v2.255 (2)
Mn1—O1iii2.168 (2)O2—C11.250 (3)
Mn1—O12.168 (2)O2—Mn1ii2.1238 (19)
Mn1—O1iv2.255 (2)C1—C21.488 (3)
Mn1—O1v2.255 (2)C2—C31.351 (3)
S1—C31.712 (3)C2—C2iii1.443 (4)
S1—C3iii1.712 (2)C3—H30.9300
O2i—Mn1—O2ii96.74 (10)C3—S1—C3iii91.39 (17)
O2i—Mn1—O1iii94.43 (8)C1—O1—Mn1130.66 (14)
O2ii—Mn1—O1iii157.79 (6)C1—O1—Mn1v123.27 (13)
O2i—Mn1—O1157.79 (6)Mn1—O1—Mn1v103.83 (7)
O2ii—Mn1—O194.43 (8)C1—O2—Mn1ii127.96 (15)
O1iii—Mn1—O181.95 (10)O2—C1—O1123.77 (19)
O2i—Mn1—O1iv87.85 (7)O2—C1—C2116.92 (19)
O2ii—Mn1—O1iv85.12 (7)O1—C1—C2119.24 (18)
O1iii—Mn1—O1iv76.17 (7)C3—C2—C2iii111.88 (13)
O1—Mn1—O1iv112.23 (6)C3—C2—C1119.96 (19)
O2i—Mn1—O1v85.12 (7)C2iii—C2—C1128.01 (11)
O2ii—Mn1—O1v87.85 (7)C2—C3—S1112.43 (17)
O1iii—Mn1—O1v112.23 (6)C2—C3—H3123.8
O1—Mn1—O1v76.17 (7)S1—C3—H3123.8
O1iv—Mn1—O1v169.41 (8)
O2i—Mn1—O1—C1129.6 (2)Mn1—O1—C1—O2101.7 (2)
O2ii—Mn1—O1—C1110.33 (18)Mn1v—O1—C1—O298.2 (2)
O1iii—Mn1—O1—C147.62 (16)Mn1—O1—C1—C281.5 (2)
O1iv—Mn1—O1—C123.79 (19)Mn1v—O1—C1—C278.6 (2)
O1v—Mn1—O1—C1163.0 (2)O2—C1—C2—C329.2 (3)
O2i—Mn1—O1—Mn1v33.41 (18)O1—C1—C2—C3147.9 (2)
O2ii—Mn1—O1—Mn1v86.68 (8)O2—C1—C2—C2iii155.7 (3)
O1iii—Mn1—O1—Mn1v115.36 (8)O1—C1—C2—C2iii27.3 (4)
O1iv—Mn1—O1—Mn1v173.22 (5)C2iii—C2—C3—S10.2 (3)
O1v—Mn1—O1—Mn1v0.0C1—C2—C3—S1175.72 (16)
Mn1ii—O2—C1—O11.9 (3)C3iii—S1—C3—C20.06 (12)
Mn1ii—O2—C1—C2178.75 (13)
Symmetry codes: (i) x1/2, y+1/2, z+1/2; (ii) x+1/2, y+1/2, z+1; (iii) x, y, z+3/2; (iv) x+1/2, y+1/2, z+1/2; (v) x1/2, y+1/2, z+1.
 

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