Poly[tetra-methyl-ammonium [tri-μ2-formato-κ(6) O:O'-manganate(II)]].

In the title compound, {(C4H12N)[Mn(HCO2)3]} n , the Mn(II) atom lies on an inversion centre and is coordinated by O-atom donors from the three double-bridging formate ligands, one of which lies across a crystallographic mirror plane, giving a slightly distorted octahedral coordination sphere. A three-dimensional NaCl-type framework is generated in which the tetra-methyl-ammonium cations, which lie across mirror planes and occupy the cavities in the polymer structure, form weak C-H⋯O hydrogen bonds with the formate ligands.

Related literature

For related structures, see: Gao & Ng (2010 ▶); Wang et al. (2004 ▶, 2010 ▶). For background to the properties of structures with metal–formate frameworks templated by protonated amines, see: Liu et al. (2012 ▶); Zhang et al. (2007 ▶).

Experimental

Crystal data

(C4H12N)[Mn(HCO2)3]

M = 264.14

Orthorhombic,

a = 8.926 (4) Å

b = 12.767 (6) Å

c = 9.196 (4) Å

V = 1048.0 (8) Å3

Z = 4

Mo Kα radiation

μ = 1.27 mm−1

T = 298 K

0.22 × 0.22 × 0.15 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T min = 0.768, T max = 0.833

5907 measured reflections

1189 independent reflections

1012 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.027

wR(F 2) = 0.075

S = 0.98

1189 reflections

77 parameters

H-atom parameters constrained

Δρmax = 0.27 e Å−3

Δρmin = −0.43 e Å−3

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT-Plus (Bruker, 2007 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2006 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536813024045/zs2272sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813024045/zs2272Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

(C4H12N)[Mn(HCO2)3]	F(000) = 548
Mr = 264.14	Dx = 1.674 Mg m−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 2391 reflections
a = 8.926 (4) Å	θ = 3.2–28.6°
b = 12.767 (6) Å	µ = 1.27 mm−1
c = 9.196 (4) Å	T = 298 K
V = 1048.0 (8) Å3	Block, colorless
Z = 4	0.22 × 0.22 × 0.15 mm

Bruker SMART CCD area-detector diffractometer	1189 independent reflections
Radiation source: fine-focus sealed tube	1012 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
Φ and ω scans	θmax = 27.0°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −11→8
Tmin = 0.768, Tmax = 0.833	k = −16→16
5907 measured reflections	l = −11→11

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.075	H-atom parameters constrained
S = 0.98	w = 1/[σ2(Fo2) + (0.041P)2 + 0.4246P] where P = (Fo2 + 2Fc2)/3
1189 reflections	(Δ/σ)max < 0.001
77 parameters	Δρmax = 0.27 e Å−3
0 restraints	Δρmin = −0.43 e Å−3

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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.

	x	y	z	Uiso*/Ueq
Mn1	0.50000	0.50000	0.50000	0.0196 (1)
O1	0.48275 (14)	0.66330 (9)	0.41954 (13)	0.0353 (4)
O2	0.29850 (13)	0.45825 (9)	0.37482 (12)	0.0328 (3)
O3	0.13485 (14)	0.45849 (10)	0.19299 (12)	0.0370 (4)
C1	0.4883 (3)	0.75000	0.4754 (3)	0.0294 (7)
C2	0.25485 (17)	0.48251 (13)	0.25112 (16)	0.0264 (5)
N1	1.0114 (2)	0.75000	0.4921 (2)	0.0310 (7)
C3	1.0293 (4)	0.75000	0.6524 (3)	0.0565 (12)
C4	0.8494 (3)	0.75000	0.4525 (4)	0.0515 (10)
C5	1.0830 (2)	0.65471 (15)	0.4312 (2)	0.0461 (6)
H1	0.49830	0.75000	0.57610	0.0350*
H2	0.31980	0.52340	0.19600	0.0320*
H3A	1.13400	0.75000	0.67640	0.0680*
H3B	0.98280	0.68860	0.69230	0.0680*
H4A	0.83940	0.75000	0.34860	0.0620*
H4B	0.80230	0.81140	0.49170	0.0620*
H5A	1.18770	0.65480	0.45470	0.0690*
H5B	1.07080	0.65410	0.32740	0.0690*
H5C	1.03660	0.59360	0.47200	0.0690*

	U11	U22	U33	U12	U13	U23
Mn1	0.0205 (2)	0.0185 (2)	0.0197 (2)	−0.0002 (1)	−0.0002 (1)	0.0001 (1)
O1	0.0513 (8)	0.0212 (6)	0.0335 (7)	0.0006 (5)	−0.0021 (5)	0.0020 (5)
O2	0.0316 (6)	0.0361 (6)	0.0306 (6)	−0.0047 (5)	−0.0094 (5)	0.0038 (5)
O3	0.0361 (7)	0.0417 (7)	0.0332 (6)	−0.0044 (6)	−0.0128 (5)	0.0073 (5)
C1	0.0396 (15)	0.0277 (13)	0.0210 (10)	0.0000	−0.0014 (9)	0.0000
C2	0.0277 (9)	0.0245 (7)	0.0271 (9)	−0.0021 (6)	0.0012 (7)	0.0010 (6)
N1	0.0359 (13)	0.0271 (12)	0.0301 (12)	0.0000	0.0039 (8)	0.0000
C3	0.103 (3)	0.0385 (16)	0.0279 (14)	0.0000	0.0075 (15)	0.0000
C4	0.0307 (14)	0.0389 (15)	0.085 (2)	0.0000	0.0086 (15)	0.0000
C5	0.0478 (11)	0.0430 (11)	0.0474 (11)	0.0158 (9)	−0.0043 (9)	−0.0143 (9)

Mn1—O1	2.2176 (16)	N1—C5iv	1.484 (2)
Mn1—O2	2.2010 (15)	C1—H1	0.9300
Mn1—O3i	2.2089 (16)	C2—H2	0.9300
Mn1—O1ii	2.2176 (16)	C3—H3A	0.9600
Mn1—O2ii	2.2010 (15)	C3—H3B	0.9600
Mn1—O3iii	2.2089 (16)	C3—H3Biv	0.9600
O1—C1	1.2213 (17)	C4—H4A	0.9600
O2—C2	1.2417 (19)	C4—H4B	0.9600
O3—C2	1.236 (2)	C4—H4Biv	0.9600
N1—C4	1.491 (3)	C5—H5A	0.9600
N1—C5	1.484 (2)	C5—H5B	0.9600
N1—C3	1.483 (3)	C5—H5C	0.9600
O1—Mn1—O2	89.80 (4)	O1—C1—O1iv	130.0 (2)
O1—Mn1—O3i	90.27 (5)	O2—C2—O3	127.33 (15)
O1—Mn1—O1ii	180.00	O1—C1—H1	115.00
O1—Mn1—O2ii	90.20 (4)	O1iv—C1—H1	115.00
O1—Mn1—O3iii	89.73 (5)	O3—C2—H2	116.00
O2—Mn1—O3i	91.89 (4)	O2—C2—H2	116.00
O1ii—Mn1—O2	90.20 (4)	N1—C3—H3A	109.00
O2—Mn1—O2ii	180.00	N1—C3—H3B	109.00
O2—Mn1—O3iii	88.11 (4)	N1—C3—H3Biv	109.00
O1ii—Mn1—O3i	89.73 (5)	H3A—C3—H3B	109.00
O2ii—Mn1—O3i	88.11 (4)	H3A—C3—H3Biv	109.00
O3i—Mn1—O3iii	180.00	H3B—C3—H3Biv	110.00
O1ii—Mn1—O2ii	89.80 (4)	N1—C4—H4A	109.00
O1ii—Mn1—O3iii	90.27 (5)	N1—C4—H4B	109.00
O2ii—Mn1—O3iii	91.89 (4)	N1—C4—H4Biv	109.00
Mn1—O1—C1	135.15 (14)	H4A—C4—H4B	109.00
Mn1—O2—C2	132.47 (11)	H4A—C4—H4Biv	109.00
Mn1v—O3—C2	139.49 (11)	H4B—C4—H4Biv	110.00
C3—N1—C5	109.20 (13)	N1—C5—H5A	109.00
C3—N1—C5iv	109.20 (13)	N1—C5—H5B	109.00
C4—N1—C5	108.99 (13)	N1—C5—H5C	109.00
C4—N1—C5iv	108.99 (13)	H5A—C5—H5B	110.00
C5—N1—C5iv	110.13 (15)	H5A—C5—H5C	109.00
C3—N1—C4	110.3 (2)	H5B—C5—H5C	109.00
O2—Mn1—O1—C1	132.4 (2)	O1ii—Mn1—O2—C2	−139.34 (14)
O3i—Mn1—O1—C1	40.5 (2)	O3iii—Mn1—O2—C2	−49.08 (14)
O2ii—Mn1—O1—C1	−47.7 (2)	Mn1—O1—C1—O1iv	176.99 (17)
O3iii—Mn1—O1—C1	−139.5 (2)	Mn1—O2—C2—O3	−176.16 (12)
O1—Mn1—O2—C2	40.66 (14)	Mn1v—O3—C2—O2	168.34 (12)
O3i—Mn1—O2—C2	130.92 (14)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3B···O3ii	0.96	2.40	3.355 (3)	176
C4—H4B···O2vi	0.96	2.41	3.367 (3)	171
C5—H5B···O1iii	0.96	2.41	3.349 (3)	167

Table 1

Selected bond lengths (Å)

Mn1—O1	2.2176 (16)
Mn1—O2	2.2010 (15)
Mn1—O3i	2.2089 (16)
Mn1—O1ii	2.2176 (16)
Mn1—O2ii	2.2010 (15)
Mn1—O3iii	2.2089 (16)

Symmetry codes: (i) ; (ii) ; (iii) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3B⋯O3ii	0.96	2.40	3.355 (3)	176
C4—H4B⋯O2iv	0.96	2.41	3.367 (3)	171
C5—H5B⋯O1iii	0.96	2.41	3.349 (3)	167

Symmetry codes: (ii) ; (iii) ; (iv) .