Poly[tetra­methyl­ammonium [tri-μ2-formato-κ6O:O′-manganate(II)]]

Han, C.-Y.; Liu, M.-M.; Dang, Q.-Q.

doi:10.1107/S1600536813024045

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 10| October 2013| Page m541

doi:10.1107/S1600536813024045

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Poly[tetramethylammonium [tri-μ₂-formato-κ⁶O:O′-manganate(II)]]

Cai-Yun Han,^a Min-Min Liu ^a and Qin-Qin Dang ^a ^*

^aSchool of Chemistry and Material Science, Shanxi Normal University, Linfen 041004, People's Republic of China
^*Correspondence e-mail: dangqq820116@163.com

(Received 24 July 2013; accepted 27 August 2013; online 12 September 2013)

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 tetramethylammonium 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_r = 264.14
Orthorhombic, P n m a
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[F² > 2σ(F²)] = 0.027
wR(F²) = 0.075
S = 0.98
1189 reflections
77 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.43 e Å⁻³

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) $[-x+{\script{1\over 2}}, -y+1, z+{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z+1; (iii) $[x+{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ .

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⋯O2^iv	0.96	2.41	3.367 (3)	171
C5—H5B⋯O1ⁱⁱⁱ	0.96	2.41	3.349 (3)	167
Symmetry codes: (ii) -x+1, -y+1, -z+1; (iii) $[x+{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (iv) $[-x+1, y+{\script{1\over 2}}, -z+1]$ .

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).

Supporting information

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536813024045/zs2272sup1.cif

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

checkCIF report

Comment top

Recently, metal formate frameworks templated by protonated amines attract considerable attention because their special structures and interesting properties (Liu et al., 2012; Zhang et al., 2007). A series of protonated ammonium cations (methylamine, ethylamine, dimethylamine, cyclotrimethyleneamine, N,N-dimethylethylenediammonium) have been employed to synthesize metal formate frameworks (Gao et al., 2010; Wang et al., 2010; Wang et al., 2004). In the present contribution, we report a new manganese formate complex {(Me₄N) [Mn(HCO₂)]₃}_n, templated using tetramethylamine cations. The formate ligand and tetramethylamine cation result from an in situ decomposition reaction of the N,N-dimethylformamide solvent.

In the title complex (Fig. 1), the Mn^II cations lie on crystallographic inversion centres and are coordinated by six O-atom donors from bridging formate ligands, one of which lies across a crystallographic mirror plane and gives an anti-anti mode. A slightly distorted octahedral geometry is found about Mn^II[Mn1—O1, Mn1—O2 and Mn1—O3 are 2.2176 (16), 2.2010 (15) and 2.2089 (16) Å, respectively (Table 1)] while the Mn—Mn separations across the bridging formates are 6.3835 (20)–6.4078 (20) Å. A three-dimensional NaCl-type framework is generated in which the protonated tetramethylamine cations, which also lie on crystallographic mirror planes, occupy the polymer cavities, acting as templates for charge-compensation and space-filling (Fig.2) and are weakly associated with the formate cations through C—H···O hydrogen bonds (Table 2).

Related literature top

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 top

The title compound compound was synthesized hydrothermally under autogenous pressure. Typically, a mixture of manganese(II) acetate (0.049 g, 0.2 mmol), sodium hydroxide(0.008 g, 0.2 mmol), N,N-dimethylformamide (4 ml) and methanol (2.5 ml) was loaded into a 15 ml Teflon-lined stainless container and stirred in air for 20 minutes, then heated to 180 °C for 5 days. After cooling to room temperature and filtering, colorless block crystals were recovered in 90% yield.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2007); 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).

Figures top

	Fig. 1. Atom numbering scheme for the cation and anion species in the title complex, with displacement ellipsoids drawn at the 50% probability level. For symmetry codes: (a) -x +1, -y +1, -z +1; (b) x +1/2, y, -z +1/2; (c) -x +1/2, -y +1, z +1/2; (e) x, -y +3/2, z.
	Fig. 2. A view of the three-dimensional NaCl-like structure of the title compound

Poly[tetramethylammonium [tri-µ₂-formato-κ⁶O:O'-manganate(II)]] top

Crystal data top

(C₄H₁₂N)[Mn(HCO₂)₃]	F(000) = 548
M_r = 264.14	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.041P)² + 0.4246P] where P = (F_o² + 2F_c²)/3
1189 reflections	(Δ/σ)_max < 0.001
77 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.43 e Å⁻³

Crystal data top

(C₄H₁₂N)[Mn(HCO₂)₃]	V = 1048.0 (8) Å³
M_r = 264.14	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 8.926 (4) Å	µ = 1.27 mm⁻¹
b = 12.767 (6) Å	T = 298 K
c = 9.196 (4) Å	0.22 × 0.22 × 0.15 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1189 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	1012 reflections with I > 2σ(I)
T_min = 0.768, T_max = 0.833	R_int = 0.023
5907 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	0 restraints
wR(F²) = 0.075	H-atom parameters constrained
S = 0.98	Δρ_max = 0.27 e Å⁻³
1189 reflections	Δρ_min = −0.43 e Å⁻³
77 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

Mn1—O1	2.2176 (16)	N1—C5^iv	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—H3B^iv	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—H4B^iv	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—O1^iv	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)	O1^iv—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—H3B^iv	109.00
O1ⁱⁱ—Mn1—O3ⁱ	89.73 (5)	H3A—C3—H3B	109.00
O2ⁱⁱ—Mn1—O3ⁱ	88.11 (4)	H3A—C3—H3B^iv	109.00
O3ⁱ—Mn1—O3ⁱⁱⁱ	180.00	H3B—C3—H3B^iv	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—H4B^iv	109.00
Mn1—O1—C1	135.15 (14)	H4A—C4—H4B	109.00
Mn1—O2—C2	132.47 (11)	H4A—C4—H4B^iv	109.00
Mn1^v—O3—C2	139.49 (11)	H4B—C4—H4B^iv	110.00
C3—N1—C5	109.20 (13)	N1—C5—H5A	109.00
C3—N1—C5^iv	109.20 (13)	N1—C5—H5B	109.00
C4—N1—C5	108.99 (13)	N1—C5—H5C	109.00
C4—N1—C5^iv	108.99 (13)	H5A—C5—H5B	110.00
C5—N1—C5^iv	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—O1^iv	176.99 (17)
O3ⁱⁱⁱ—Mn1—O1—C1	−139.5 (2)	Mn1—O2—C2—O3	−176.16 (12)
O1—Mn1—O2—C2	40.66 (14)	Mn1^v—O3—C2—O2	168.34 (12)
O3ⁱ—Mn1—O2—C2	130.92 (14)

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

Hydrogen-bond geometry (Å, º) top

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···O2^vi	0.96	2.41	3.367 (3)	171
C5—H5B···O1ⁱⁱⁱ	0.96	2.41	3.349 (3)	167

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

Selected bond lengths (Å) top

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

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

Hydrogen-bond geometry (Å, º) top

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···O2^iv	0.96	2.41	3.367 (3)	171
C5—H5B···O1ⁱⁱⁱ	0.96	2.41	3.349 (3)	167

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

Acknowledgements

The authors thank the Shanxi Province Science Foundation for Youths (2012021008–2), the National Natural Science Foundation of China (21101102) and the National Science Fund for Distinguished Young Scholars (20925101).

References

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