A new two-dimensional manganese(II) coordination polymer based on thio­phene-3,4-di­carb­oxy­lic acid

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.

Computing details

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)]

Crystal data

[Mn(C6H2O4S)]	F(000) = 444
Mr = 225.08	Dx = 2.124 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 4.608 (4) Å	Cell parameters from 1490 reflections
b = 26.40 (2) Å	θ = 3.1–28.3°
c = 6.123 (5) Å	µ = 2.13 mm^−1
β = 109.044 (8)°	T = 296 K
V = 704.0 (10) Å^3	Block, yellow
Z = 4	0.39 × 0.20 × 0.11 mm

Data collection

Bruker SMART CCD area-detector diffractometer	665 independent reflections
Radiation source: fine-focus sealed tube	637 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
φ and ω scans	θmax = 25.5°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −5→5
Tmin = 0.490, Tmax = 0.799	k = −31→28
1773 measured reflections	l = −5→7

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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.067	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0398P)^2 + 1.3961P] where P = (Fo^2 + 2Fc^2)/3
665 reflections	(Δ/σ)max = 0.001
56 parameters	Δρmax = 0.58 e Å^−3
0 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	0.0000	0.277059 (16)	0.7500	0.01560 (18)
S1	0.0000	0.03781 (3)	0.7500	0.0408 (3)
O1	−0.0271 (3)	0.21506 (6)	0.5120 (3)	0.0181 (3)
O2	0.3444 (3)	0.16949 (6)	0.4462 (3)	0.0221 (4)
C1	0.1363 (5)	0.17486 (8)	0.5338 (3)	0.0164 (4)
C2	0.0688 (5)	0.13060 (8)	0.6597 (4)	0.0185 (5)
C3	0.1172 (6)	0.08310 (9)	0.5969 (4)	0.0282 (5)
H3	0.2045	0.0758	0.4833	0.034*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0161 (3)	0.0195 (3)	0.0117 (3)	0.000	0.00519 (19)	0.000
S1	0.0706 (7)	0.0181 (5)	0.0496 (6)	0.000	0.0412 (6)	0.000
O1	0.0189 (8)	0.0203 (8)	0.0148 (7)	0.0021 (6)	0.0052 (6)	−0.0012 (6)
O2	0.0211 (8)	0.0276 (8)	0.0217 (8)	0.0036 (6)	0.0127 (7)	0.0047 (7)
C1	0.0167 (10)	0.0211 (11)	0.0105 (10)	−0.0006 (8)	0.0032 (8)	−0.0011 (8)
C2	0.0180 (10)	0.0216 (11)	0.0172 (11)	0.0010 (8)	0.0076 (9)	0.0000 (9)
C3	0.0399 (14)	0.0235 (12)	0.0285 (13)	0.0008 (10)	0.0214 (11)	−0.0011 (10)

Geometric parameters (Å, º)

Mn1—O2^i	2.1238 (19)	O1—C1	1.283 (3)
Mn1—O2^ii	2.1238 (19)	O1—Mn1^v	2.255 (2)
Mn1—O1^iii	2.168 (2)	O2—C1	1.250 (3)
Mn1—O1	2.168 (2)	O2—Mn1^ii	2.1238 (19)
Mn1—O1^iv	2.255 (2)	C1—C2	1.488 (3)
Mn1—O1^v	2.255 (2)	C2—C3	1.351 (3)
S1—C3	1.712 (3)	C2—C2^iii	1.443 (4)
S1—C3^iii	1.712 (2)	C3—H3	0.9300
O2^i—Mn1—O2^ii	96.74 (10)	C3—S1—C3^iii	91.39 (17)
O2^i—Mn1—O1^iii	94.43 (8)	C1—O1—Mn1	130.66 (14)
O2^ii—Mn1—O1^iii	157.79 (6)	C1—O1—Mn1^v	123.27 (13)
O2^i—Mn1—O1	157.79 (6)	Mn1—O1—Mn1^v	103.83 (7)
O2^ii—Mn1—O1	94.43 (8)	C1—O2—Mn1^ii	127.96 (15)
O1^iii—Mn1—O1	81.95 (10)	O2—C1—O1	123.77 (19)
O2^i—Mn1—O1^iv	87.85 (7)	O2—C1—C2	116.92 (19)
O2^ii—Mn1—O1^iv	85.12 (7)	O1—C1—C2	119.24 (18)
O1^iii—Mn1—O1^iv	76.17 (7)	C3—C2—C2^iii	111.88 (13)
O1—Mn1—O1^iv	112.23 (6)	C3—C2—C1	119.96 (19)
O2^i—Mn1—O1^v	85.12 (7)	C2^iii—C2—C1	128.01 (11)
O2^ii—Mn1—O1^v	87.85 (7)	C2—C3—S1	112.43 (17)
O1^iii—Mn1—O1^v	112.23 (6)	C2—C3—H3	123.8
O1—Mn1—O1^v	76.17 (7)	S1—C3—H3	123.8
O1^iv—Mn1—O1^v	169.41 (8)
O2^i—Mn1—O1—C1	−129.6 (2)	Mn1—O1—C1—O2	−101.7 (2)
O2^ii—Mn1—O1—C1	110.33 (18)	Mn1^v—O1—C1—O2	98.2 (2)
O1^iii—Mn1—O1—C1	−47.62 (16)	Mn1—O1—C1—C2	81.5 (2)
O1^iv—Mn1—O1—C1	23.79 (19)	Mn1^v—O1—C1—C2	−78.6 (2)
O1^v—Mn1—O1—C1	−163.0 (2)	O2—C1—C2—C3	−29.2 (3)
O2^i—Mn1—O1—Mn1^v	33.41 (18)	O1—C1—C2—C3	147.9 (2)
O2^ii—Mn1—O1—Mn1^v	−86.68 (8)	O2—C1—C2—C2^iii	155.7 (3)
O1^iii—Mn1—O1—Mn1^v	115.36 (8)	O1—C1—C2—C2^iii	−27.3 (4)
O1^iv—Mn1—O1—Mn1^v	−173.22 (5)	C2^iii—C2—C3—S1	0.2 (3)
O1^v—Mn1—O1—Mn1^v	0.0	C1—C2—C3—S1	−175.72 (16)
Mn1^ii—O2—C1—O1	1.9 (3)	C3^iii—S1—C3—C2	−0.06 (12)
Mn1^ii—O2—C1—C2	178.75 (13)

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