Poly[hexa-aqua-(μ9-cyclo-hexane-1,2,3,4,5,6-hexa-carboxyl-ato)trimanganese(II)].

The asymmetric unit of the title compound, [Mn3(C12H6O12)(H2O)6] n , comprises one Mn(II) ion, one third of a cyclo-hexane-1,2,3,4,5,6-hexa-carboxyl-ate anion and two aqua ligands. The anion is completed by application of a -3 axis. The Mn(II) ion is six-coordinated by six O atoms from two aqua ligands and three different cyclo-hexa-carboxyl-ate anions in an octa-hedral geometry. The six carboxyl-ate groups adopt a bridging bidentate mode to ligate the Mn(II) ions. Thus, each cyclo-hexane-1,2,3,4,5,6-hexa-carboxyl-ate anion adopts a μ9-connected mode, ligating nine different Mn(II) ions and forming a three-dimensional framework. In the framework, there are strong O-H⋯O hydrogen-bonding inter-actions, which further stabilize the crystal structure.

Related literature

For background to compounds with metal-organic framework structures, see: Wang et al. (2010 ▶); Bourne et al. (2001 ▶). For their properties, uses and topologies, see: O’Keeffe et al. (2000 ▶); Song et al. (2012 ▶).

Experimental

Crystal data

[Mn3(C12H6O12)(H2O)6]

M = 615.09

Trigonal,

a = 14.5432 (4) Å

c = 14.9445 (10) Å

V = 2737.4 (2) Å3

Z = 6

Mo Kα radiation

μ = 2.15 mm−1

T = 185 K

0.25 × 0.18 × 0.16 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.616, T max = 0.725

5063 measured reflections

1200 independent reflections

1098 reflections with I > 2σ(I)

R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.025

wR(F 2) = 0.064

S = 1.08

1200 reflections

112 parameters

4 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.75 e Å−3

Δρmin = −0.28 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: XP in SHELXTL and DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813015626/bx2441sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813015626/bx2441Isup2.hkl

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

[Mn3(C12H6O12)(H2O)6]	Dx = 2.239 Mg m−3
Mr = 615.09	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3	Cell parameters from 11080 reflections
Hall symbol: -R 3	θ = 1.0–25.0°
a = 14.5432 (4) Å	µ = 2.15 mm−1
c = 14.9445 (10) Å	T = 185 K
V = 2737.4 (2) Å3	Needle, colorless
Z = 6	0.25 × 0.18 × 0.16 mm
F(000) = 1854

Bruker APEXII CCD diffractometer	1200 independent reflections
Radiation source: fine-focus sealed tube	1098 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
φ and ω scans	θmax = 26.1°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −17→17
Tmin = 0.616, Tmax = 0.725	k = −11→17
5063 measured reflections	l = −18→18

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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.064	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ2(Fo2) + (0.0259P)2 + 11.1009P] where P = (Fo2 + 2Fc2)/3
1200 reflections	(Δ/σ)max = 0.001
112 parameters	Δρmax = 0.75 e Å−3
4 restraints	Δρmin = −0.28 e Å−3

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.

	x	y	z	Uiso*/Ueq
C1	0.72468 (17)	0.55633 (17)	0.56658 (15)	0.0119 (5)
C2	0.69763 (17)	0.44523 (17)	0.59739 (16)	0.0124 (5)
H2	0.6975	0.4445	0.6643	0.015*
C3	0.58420 (17)	0.36429 (17)	0.56474 (16)	0.0126 (5)
H3	0.5819	0.3650	0.4979	0.015*
C4	0.50129 (18)	0.38891 (17)	0.60281 (16)	0.0139 (5)
O1	0.68842 (14)	0.60269 (13)	0.61426 (11)	0.0181 (4)
O2	0.77520 (13)	0.59359 (13)	0.49548 (12)	0.0180 (4)
O1W	0.53786 (15)	0.68488 (15)	0.66743 (13)	0.0228 (4)
O3	0.50339 (13)	0.40393 (14)	0.68557 (11)	0.0190 (4)
O2W	0.78828 (15)	0.80851 (14)	0.46574 (12)	0.0211 (4)
O4	0.43295 (13)	0.38944 (13)	0.55035 (11)	0.0187 (4)
Mn1	0.65353 (3)	0.71812 (3)	0.55736 (2)	0.01313 (13)
H2A	0.8391 (18)	0.804 (2)	0.4826 (19)	0.020*
H1B	0.5862 (19)	0.704 (2)	0.7082 (16)	0.020*
H2B	0.775 (2)	0.786 (2)	0.4129 (13)	0.020*
H1A	0.4847 (18)	0.6230 (16)	0.6686 (19)	0.020*

	U11	U22	U33	U12	U13	U23
C1	0.0076 (10)	0.0110 (11)	0.0147 (12)	0.0029 (9)	−0.0035 (8)	−0.0014 (9)
C2	0.0108 (11)	0.0094 (11)	0.0169 (12)	0.0050 (9)	0.0007 (9)	−0.0006 (9)
C3	0.0100 (11)	0.0102 (11)	0.0165 (12)	0.0043 (9)	−0.0001 (9)	0.0003 (9)
C4	0.0119 (11)	0.0081 (10)	0.0186 (12)	0.0027 (9)	0.0013 (9)	0.0002 (9)
O1	0.0263 (9)	0.0155 (8)	0.0179 (9)	0.0145 (8)	0.0027 (7)	0.0008 (7)
O2	0.0161 (8)	0.0203 (9)	0.0201 (9)	0.0108 (7)	0.0054 (7)	0.0064 (7)
O1W	0.0189 (9)	0.0241 (10)	0.0229 (10)	0.0089 (8)	0.0011 (8)	0.0057 (8)
O3	0.0166 (8)	0.0255 (9)	0.0154 (9)	0.0109 (8)	0.0008 (7)	−0.0015 (7)
O2W	0.0208 (9)	0.0246 (10)	0.0196 (10)	0.0126 (8)	0.0038 (8)	0.0016 (8)
O4	0.0179 (9)	0.0217 (9)	0.0198 (9)	0.0125 (7)	−0.0066 (7)	−0.0052 (7)
Mn1	0.0142 (2)	0.0124 (2)	0.0134 (2)	0.00709 (15)	−0.00102 (13)	0.00031 (13)

C1—O2	1.251 (3)	O2—Mn1iii	2.1866 (17)
C1—O1	1.263 (3)	O1W—Mn1	2.2263 (19)
C1—C2	1.530 (3)	O1W—H1B	0.866 (17)
C2—C3i	1.540 (3)	O1W—H1A	0.843 (17)
C2—C3	1.550 (3)	O3—Mn1iv	2.1581 (17)
C2—H2	1.0000	O2W—Mn1	2.2062 (18)
C3—C4	1.529 (3)	O2W—H2A	0.811 (17)
C3—C2ii	1.540 (3)	O2W—H2B	0.838 (17)
C3—H3	1.0000	O4—Mn1v	2.1569 (17)
C4—O3	1.254 (3)	Mn1—O4v	2.1569 (17)
C4—O4	1.269 (3)	Mn1—O3vi	2.1581 (17)
O1—Mn1	2.1565 (16)	Mn1—O2vii	2.1866 (17)
O2—C1—O1	124.0 (2)	H1B—O1W—H1A	119 (3)
O2—C1—C2	119.9 (2)	C4—O3—Mn1iv	131.39 (15)
O1—C1—C2	116.0 (2)	Mn1—O2W—H2A	110 (2)
C1—C2—C3i	111.91 (18)	Mn1—O2W—H2B	113 (2)
C1—C2—C3	108.74 (18)	H2A—O2W—H2B	108 (3)
C3i—C2—C3	111.7 (2)	C4—O4—Mn1v	129.13 (15)
C1—C2—H2	108.1	O1—Mn1—O4v	90.49 (6)
C3i—C2—H2	108.1	O1—Mn1—O3vi	89.74 (7)
C3—C2—H2	108.1	O4v—Mn1—O3vi	168.84 (7)
C4—C3—C2ii	107.13 (18)	O1—Mn1—O2vii	171.49 (7)
C4—C3—C2	111.68 (18)	O4v—Mn1—O2vii	86.09 (6)
C2ii—C3—C2	109.3 (2)	O3vi—Mn1—O2vii	95.12 (6)
C4—C3—H3	109.6	O1—Mn1—O2W	102.94 (7)
C2ii—C3—H3	109.6	O4v—Mn1—O2W	89.49 (7)
C2—C3—H3	109.6	O3vi—Mn1—O2W	79.59 (7)
O3—C4—O4	124.0 (2)	O2vii—Mn1—O2W	84.84 (7)
O3—C4—C3	117.0 (2)	O1—Mn1—O1W	89.19 (7)
O4—C4—C3	118.9 (2)	O4v—Mn1—O1W	106.90 (7)
C1—O1—Mn1	121.10 (15)	O3vi—Mn1—O1W	84.26 (7)
C1—O2—Mn1iii	139.24 (15)	O2vii—Mn1—O1W	84.36 (7)
Mn1—O1W—H1B	92.6 (19)	O2W—Mn1—O1W	159.65 (7)
Mn1—O1W—H1A	116 (2)
O2—C1—C2—C3i	28.8 (3)	C2—C1—O1—Mn1	−151.73 (15)
O1—C1—C2—C3i	−154.7 (2)	O1—C1—O2—Mn1iii	113.2 (2)
O2—C1—C2—C3	−95.1 (2)	C2—C1—O2—Mn1iii	−70.6 (3)
O1—C1—C2—C3	81.4 (2)	O4—C4—O3—Mn1iv	16.8 (3)
C1—C2—C3—C4	−60.2 (2)	C3—C4—O3—Mn1iv	−160.75 (15)
C3i—C2—C3—C4	175.81 (16)	O3—C4—O4—Mn1v	−136.2 (2)
C1—C2—C3—C2ii	−178.55 (15)	C3—C4—O4—Mn1v	41.3 (3)
C3i—C2—C3—C2ii	57.4 (3)	C1—O1—Mn1—O4v	48.74 (18)
C2ii—C3—C4—O3	69.9 (3)	C1—O1—Mn1—O3vi	−120.11 (18)
C2—C3—C4—O3	−49.8 (3)	C1—O1—Mn1—O2vii	115.0 (4)
C2ii—C3—C4—O4	−107.7 (2)	C1—O1—Mn1—O2W	−40.85 (18)
C2—C3—C4—O4	132.6 (2)	C1—O1—Mn1—O1W	155.63 (18)
O2—C1—O1—Mn1	24.6 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O2W—H2A···O2Wiii	0.81 (2)	2.31 (2)	3.116 (2)	178 (3)
O2W—H2A···O3viii	0.81 (2)	2.56 (3)	2.955 (2)	111 (2)
O1W—H1B···O4vi	0.87 (2)	1.92 (2)	2.774 (3)	169 (3)
O1W—H1B···O3vi	0.87 (2)	2.52 (3)	2.942 (3)	111 (2)
O2W—H2B···O1viii	0.84 (2)	2.06 (2)	2.883 (3)	169 (3)
O1W—H1A···O1Wiv	0.84 (2)	2.01 (2)	2.8513 (18)	175 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2W—H2A⋯O2W i	0.81 (2)	2.31 (2)	3.116 (2)	178 (3)
O2W—H2A⋯O3ii	0.81 (2)	2.56 (3)	2.955 (2)	111 (2)
O1W—H1B⋯O4iii	0.87 (2)	1.92 (2)	2.774 (3)	169 (3)
O1W—H1B⋯O3iii	0.87 (2)	2.52 (3)	2.942 (3)	111 (2)
O2W—H2B⋯O1ii	0.84 (2)	2.06 (2)	2.883 (3)	169 (3)
O1W—H1A⋯O1W iv	0.84 (2)	2.01 (2)	2.8513 (18)	175 (3)

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