(μ-Ethane-1,1,2,2-tetra­carboxyl­ato)bis­[tetra­aqua­manganese(II)]

Xue, M.-W.; Chen, C.-Y.

doi:10.1107/S1600536811008063

metal-organic compounds

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Volume 67| Part 4| April 2011| Page m449

doi:10.1107/S1600536811008063

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(μ-Ethane-1,1,2,2-tetracarboxylato)bis[tetraaquamanganese(II)]

Meng-Wei Xue ^a and Chang-Yun Chen ^a ^*

^aSchool of Biochemical and Environmental Engineering, Nanjing Xiaozhuang College, Nanjing 210017, People's Republic of China
^*Correspondence e-mail: cychen@njxzc.edu.cn

(Received 26 February 2011; accepted 3 March 2011; online 15 March 2011)

In the centrosymmetric title molecule, [Mn₂(C₆H₂O₈)(H₂O)₈], the Mn^II atom is in an octahedral environment coordinated by six O-atom donors from water molecules and ethane-1,1,2,2-tetracarboxylate ligands. The crystal structure features a three-dimensional hydrogen-bonding network based on a strong and distinctive pattern of O—H⋯O hydrogen-bonding interactions.

Related literature

For related literature on metal–organic frameworks, see: Chen et al. (2007 ); Fan & Zhu (2006 ); Li & Yang (2006 ). For related literature on hydrogen bonding, see: Forster & Cheetham (2002 ); Kim & Jung (2000 ).

Experimental

Crystal data

[Mn₂(C₆H₂O₈)(H₂O)₈]
M_r = 456.08
Triclinic, $[P \overline 1]$
a = 6.2901 (12) Å
b = 8.0212 (15) Å
c = 8.0769 (15) Å
α = 108.522 (3)°
β = 95.068 (3)°
γ = 97.086 (3)°
V = 379.92 (12) Å³
Z = 1
Mo Kα radiation
μ = 1.75 mm⁻¹
T = 293 K
0.30 × 0.26 × 0.24 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.785, T_max = 0.823
1956 measured reflections
1379 independent reflections
1309 reflections with I > 2σ(I)
R_int = 0.044

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.069
S = 1.05
1379 reflections
144 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811008063/pb2059sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811008063/pb2059Isup2.hkl

checkCIF report

Comment top

The design and synthesis of metal-organic frameworks(MOFs) has become a very interesting research field. This not only stems from their potential application as functional materials but also from their intriguing structural topologies(Chen et al., 2007; Fan & Zhu, 2006; Li & Yang, 2006). However, frankly speaking, the designed synthesis of coordination networks and supramolecular architectures is still a difficult challenge. The formation of coordination polymers is not only influenced by the geometrical and electronic properties of metal ions but also relying on other factors such as the rigidity or flexibility of the ligands and diversity of metal ions and organic ligands in coordination and noncovalent interactions such as hydrogen bonding (Kim & Jung, 2000; Forster et al., 2002). Therefore, the rational design and construction of coordination polymers based upon assembly of metal ions and multifunctional organic ligands is an interesting research field. Herein we report the crystal structure of the title compound (I).

The molecular structure of (I) is illustrated in Fig. 1., where selected bond distances and bond angles are given in Table 1.

Single-crystal X-ray analysis reveals that 1 crystallizes in the triclinic space group P-1, The structure of 1 is a single molecule in which the asymmetric unit contains one Mn atom, half tce anion, four coordinated water molecules. In complex 1, there is one kind of crystallographically independent Mn^II center.1 features a 3-D hydrogen bonding network based on a strong and distinctive pattern of hydrogen bonding interactions. As show in Fig. 2., a one-dimensional chain is formed by bond generated by coordinated water molecule and uncoordinated oxygen atom of ligand tce, Further, one-dimensional chains are linked by bonds to form two-dimensional layers, and two-dimensional layers are also jointed by hydrogen bonds to give rise to three-dimensional structure.

Related literature top

For related literature on metal–organic frameworks, see: Chen et al. (2007); Fan & Zhu (2006); Li & Yang (2006). For related literature on hydrogen bonding, see: Forster & Cheetham (2002); Kim & Jung (2000).

Experimental top

A H₂O solution (10 ml) of sodium 1,1,2,2-tetracarboxyl-ethylene (29.4 mg, 1 mmol) was added to a CH₃OH solution (10 ml) of Mn(OAc)₂2.5H₂O (17.3 mg,1 mmol). The pH of the mixture was adjusted to about 7. The mixture was stirred for 2 h and then filtered.Single crystals appeared after the filtered solution was allowed to stand at room temperature for 2 days.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SMART (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL (Bruker, 2000); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).

Figures top

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme and displacement ellipsoids at the 30% probability level.
	Fig. 2. Crystal packing diagram of l.

(µ-Ethane-1,1,2,2-tetracarboxylato)bis[tetraaquamanganese(II)] top

Crystal data top

[Mn₂(C₆H₂O₈)(H₂O)₈]	Z = 1
M_r = 456.08	F(000) = 232.0
Triclinic, P1	D_x = 1.993 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.2901 (12) Å	Cell parameters from 924 reflections
b = 8.0212 (15) Å	θ = 2.2–20.2°
c = 8.0769 (15) Å	µ = 1.75 mm⁻¹
α = 108.522 (3)°	T = 293 K
β = 95.068 (3)°	Block, brown
γ = 97.086 (3)°	0.30 × 0.26 × 0.24 mm
V = 379.92 (12) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	1379 independent reflections
Radiation source: fine-focus sealed tube	1309 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
ϕ and ω scans	θ_max = 25.5°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −6→7
T_min = 0.785, T_max = 0.823	k = −9→9
1956 measured reflections	l = −9→9

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.069	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0451P)²] where P = (F_o² + 2F_c²)/3
1379 reflections	(Δ/σ)_max = 0.001
144 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

[Mn₂(C₆H₂O₈)(H₂O)₈]	γ = 97.086 (3)°
M_r = 456.08	V = 379.92 (12) Å³
Triclinic, P1	Z = 1
a = 6.2901 (12) Å	Mo Kα radiation
b = 8.0212 (15) Å	µ = 1.75 mm⁻¹
c = 8.0769 (15) Å	T = 293 K
α = 108.522 (3)°	0.30 × 0.26 × 0.24 mm
β = 95.068 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1379 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1309 reflections with I > 2σ(I)
T_min = 0.785, T_max = 0.823	R_int = 0.044
1956 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	0 restraints
wR(F²) = 0.069	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.30 e Å⁻³
1379 reflections	Δρ_min = −0.30 e Å⁻³
144 parameters

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

	x	y	z	U_iso*/U_eq
Mn1	0.30762 (4)	0.25813 (4)	0.70315 (3)	0.02040 (14)
O1	−0.0280 (3)	0.2382 (3)	0.6000 (2)	0.0407 (4)
O2	0.6555 (2)	0.3118 (2)	0.8276 (2)	0.0249 (3)
O3	0.3825 (3)	0.5167 (2)	0.6758 (2)	0.0388 (4)
O4	0.3632 (3)	0.1354 (2)	0.43505 (19)	0.0293 (3)
O5	0.2172 (2)	0.34158 (18)	0.96515 (17)	0.0238 (3)
O6	0.2933 (2)	−0.00729 (18)	0.72542 (18)	0.0246 (3)
O7	0.1900 (2)	0.28929 (19)	1.21579 (17)	0.0282 (3)
O8	0.3028 (2)	−0.1656 (2)	0.90616 (19)	0.0297 (3)
C1	0.1621 (3)	0.2406 (2)	1.0530 (2)	0.0186 (4)
C2	0.0577 (3)	0.0477 (2)	0.9454 (2)	0.0184 (4)
H9	−0.050 (3)	0.053 (3)	0.853 (3)	0.022*
C3	0.2319 (3)	−0.0512 (2)	0.8542 (2)	0.0192 (4)
H3	0.685 (4)	0.421 (5)	0.890 (4)	0.046 (8)*
H4	0.669 (4)	0.260 (4)	0.883 (4)	0.036 (8)*
H7	0.292 (4)	0.177 (4)	0.373 (3)	0.034 (7)*
H8	0.475 (6)	0.111 (5)	0.400 (5)	0.077 (12)*
H5	0.519 (9)	0.581 (8)	0.691 (7)	0.15 (2)*
H1	−0.108 (7)	0.278 (6)	0.663 (6)	0.100 (15)*
H2	−0.092 (6)	0.175 (5)	0.510 (5)	0.067 (11)*
H6	0.332 (6)	0.591 (6)	0.719 (5)	0.077 (13)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0220 (2)	0.02101 (19)	0.01841 (19)	0.00202 (12)	0.00384 (12)	0.00706 (13)
O1	0.0267 (9)	0.0621 (12)	0.0257 (9)	0.0078 (8)	0.0007 (7)	0.0045 (8)
O2	0.0274 (8)	0.0220 (8)	0.0251 (8)	0.0022 (6)	0.0024 (6)	0.0086 (7)
O3	0.0508 (11)	0.0237 (8)	0.0427 (10)	0.0047 (8)	0.0128 (8)	0.0110 (7)
O4	0.0338 (9)	0.0375 (9)	0.0210 (7)	0.0145 (7)	0.0088 (7)	0.0114 (7)
O5	0.0331 (8)	0.0176 (7)	0.0200 (7)	0.0006 (6)	0.0069 (6)	0.0059 (5)
O6	0.0310 (8)	0.0234 (7)	0.0234 (7)	0.0073 (6)	0.0126 (6)	0.0098 (6)
O7	0.0389 (8)	0.0245 (7)	0.0180 (7)	−0.0011 (6)	0.0012 (6)	0.0057 (6)
O8	0.0345 (8)	0.0312 (8)	0.0317 (8)	0.0145 (6)	0.0116 (6)	0.0168 (6)
C1	0.0167 (9)	0.0192 (9)	0.0200 (9)	0.0048 (7)	0.0041 (7)	0.0056 (7)
C2	0.0196 (9)	0.0184 (9)	0.0177 (9)	0.0023 (7)	0.0031 (7)	0.0067 (7)
C3	0.0216 (9)	0.0163 (9)	0.0173 (9)	0.0006 (7)	0.0024 (7)	0.0032 (7)

Geometric parameters (Å, º) top

Mn1—O3	2.1541 (18)	O3—H6	0.71 (4)
Mn1—O4	2.1552 (15)	O4—H7	0.82 (3)
Mn1—O5	2.1578 (13)	O4—H8	0.80 (4)
Mn1—O1	2.1674 (18)	O5—C1	1.273 (2)
Mn1—O6	2.1845 (14)	O6—C3	1.275 (2)
Mn1—O2	2.2557 (16)	O7—C1	1.236 (2)
O1—H1	0.77 (4)	O8—C3	1.237 (2)
O1—H2	0.78 (4)	C1—C2	1.541 (3)
O2—H3	0.85 (3)	C2—C2ⁱ	1.515 (3)
O2—H4	0.71 (3)	C2—C3	1.536 (2)
O3—H5	0.92 (6)	C2—H9	0.98 (2)

O3—Mn1—O4	89.71 (7)	Mn1—O3—H5	126 (3)
O3—Mn1—O5	98.50 (6)	Mn1—O3—H6	123 (3)
O4—Mn1—O5	170.75 (6)	H5—O3—H6	96 (4)
O3—Mn1—O1	90.76 (8)	Mn1—O4—H7	107.7 (18)
O4—Mn1—O1	87.24 (7)	Mn1—O4—H8	128 (3)
O5—Mn1—O1	88.40 (6)	H7—O4—H8	113 (3)
O3—Mn1—O6	169.57 (7)	C1—O5—Mn1	126.22 (12)
O4—Mn1—O6	86.03 (6)	C3—O6—Mn1	125.18 (11)
O5—Mn1—O6	86.55 (5)	O7—C1—O5	123.56 (17)
O1—Mn1—O6	98.54 (7)	O7—C1—C2	120.04 (16)
O3—Mn1—O2	84.27 (8)	O5—C1—C2	116.39 (16)
O4—Mn1—O2	96.98 (6)	C2ⁱ—C2—C3	112.65 (19)
O5—Mn1—O2	88.12 (6)	C2ⁱ—C2—C1	112.95 (19)
O1—Mn1—O2	173.45 (7)	C3—C2—C1	108.56 (14)
O6—Mn1—O2	86.79 (6)	C2ⁱ—C2—H9	107.6 (13)
Mn1—O1—H1	120 (3)	C3—C2—H9	107.4 (13)
Mn1—O1—H2	129 (3)	C1—C2—H9	107.4 (15)
H1—O1—H2	109 (4)	O8—C3—O6	124.24 (16)
Mn1—O2—H3	107.8 (18)	O8—C3—C2	120.15 (16)
Mn1—O2—H4	110 (2)	O6—C3—C2	115.61 (16)
H3—O2—H4	109 (3)

Symmetry code: (i) −x, −y, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H3···O5ⁱⁱ	0.85 (3)	1.88 (3)	2.726 (2)	174 (3)
O2—H4···O8ⁱⁱⁱ	0.71 (3)	2.07 (3)	2.765 (2)	166 (3)
O4—H7···O7^iv	0.82 (3)	1.89 (3)	2.689 (2)	167 (2)
O4—H8···O6^v	0.80 (4)	1.97 (4)	2.757 (2)	167 (4)
O3—H5···O7ⁱⁱ	0.92 (6)	1.95 (6)	2.847 (2)	165 (5)
O1—H1···O2^vi	0.77 (4)	2.07 (4)	2.818 (2)	164 (5)
O1—H2···O6^vii	0.78 (4)	2.14 (4)	2.914 (2)	175 (4)
O3—H6···O8^viii	0.71 (4)	2.10 (4)	2.771 (2)	158 (4)

Symmetry codes: (ii) −x+1, −y+1, −z+2; (iii) −x+1, −y, −z+2; (iv) x, y, z−1; (v) −x+1, −y, −z+1; (vi) x−1, y, z; (vii) −x, −y, −z+1; (viii) x, y+1, z.

Experimental details

Crystal data
Chemical formula	[Mn₂(C₆H₂O₈)(H₂O)₈]
M_r	456.08
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	6.2901 (12), 8.0212 (15), 8.0769 (15)
α, β, γ (°)	108.522 (3), 95.068 (3), 97.086 (3)
V (Å³)	379.92 (12)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.75
Crystal size (mm)	0.30 × 0.26 × 0.24

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.785, 0.823
No. of measured, independent and observed [I > 2σ(I)] reflections	1956, 1379, 1309
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.069, 1.05
No. of reflections	1379
No. of parameters	144
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.30

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Bruker, 2000).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H3···O5ⁱ	0.85 (3)	1.88 (3)	2.726 (2)	174 (3)
O2—H4···O8ⁱⁱ	0.71 (3)	2.07 (3)	2.765 (2)	166 (3)
O4—H7···O7ⁱⁱⁱ	0.82 (3)	1.89 (3)	2.689 (2)	167 (2)
O4—H8···O6^iv	0.80 (4)	1.97 (4)	2.757 (2)	167 (4)
O3—H5···O7ⁱ	0.92 (6)	1.95 (6)	2.847 (2)	165 (5)
O1—H1···O2^v	0.77 (4)	2.07 (4)	2.818 (2)	164 (5)
O1—H2···O6^vi	0.78 (4)	2.14 (4)	2.914 (2)	175 (4)
O3—H6···O8^vii	0.71 (4)	2.10 (4)	2.771 (2)	158 (4)

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

References

Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chen, X. N., Zhang, W. X. & Chen, X. M. (2007). J. Am. Chem. Soc. 129, 15738–15739. Web of Science PubMed Google Scholar
Fan, S. R. & Zhu, L. G. (2006). Inorg. Chem. 45, 7935–7942. Web of Science CSD CrossRef PubMed CAS Google Scholar
Forster, P. M. & Cheetham, A. K. (2002). Angew. Chem. Int. Ed. 41, 457–459. Web of Science CSD CrossRef CAS Google Scholar
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Li, Y. N. & Yang, R. T. (2006). J. Am. Chem. Soc. 128, 726–727. Web of Science CrossRef PubMed CAS Google Scholar
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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 4| April 2011| Page m449

doi:10.1107/S1600536811008063

Open

access