Tetra­aqua­tetra­manganese(II) catena-[germanodihydroxidodi(hydrogen­phosphate)diphosphate]

Zhang, X.; Wen, L.; Chen, H.-M.; Mi, J.-X.; Huang, Y.-X.

doi:10.1107/S160053681201673X

inorganic compounds

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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Pages i37-i38

doi:10.1107/S160053681201673X

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Tetraaquatetramanganese(II) catena-[germanodihydroxidodi(hydrogenphosphate)diphosphate]

Xin Zhang,^a Lei Wen,^a Hong-Ming Chen,^a Jin-Xiao Mi ^a and Ya-Xi Huang ^a ^*

^aDepartment of Materials Science and Engineering, College of Materials, Xiamen University, Xiamen 361005, Fujian Province, People's Republic of China
^*Correspondence e-mail: yaxihuang@xmu.edu.cn

(Received 11 April 2012; accepted 17 April 2012; online 25 April 2012)

The title compound, Mn₄(H₂O)₄[Ge(OH)₂(HPO₄)₂(PO₄)₂], was synthesized by the solvothermal method. Its crystal structure is isotypic with the iron and cobalt analogues [Huang et al. (2012 ). Inorg. Chem. 51, 3316–3323]. In the crystal structure, the framework is built from undulating manganese phosphate sheets parallel to (010) interconnected by GeO₆ octahedra (at the inversion center), resulting in a three-dimensional network with eight-membered ring channels into which all the protons point. The undulating manganese phosphate sheet consists of zigzag manganese octahedral chains along [10-1], built from MnO₄(OH)(OH₂) octahedra and MnO₅(OH₂) octahedra by sharing their trans or skew edges, which are interconnected by PO₃(OH) and PO₄ tetrahedra via corner-sharing. The crystal structure features extensive O—H⋯O hydrogen-bonding interactions.

Related literature

For background to germanophosphates, see: Brock et al. (1998 ); Corma (1997 ); Li et al. (2000 ); Liu, Yang, Wang et al. (2008 ); Liu, Yang, Zhang et al. (2008 ); Zhao et al. (2009 ); Zubieta (1994 ). For isotypic structures of the Fe^II and Co^II analogues, see: Huang et al. (2012).

Experimental

Crystal data

Mn₄(H₂O)₄[Ge(OH)₂(HPO₄)₂(PO₄)₂]
M_r = 780.33
Monoclinic, P 2₁ /n
a = 6.5336 (3) Å
b = 16.3869 (7) Å
c = 7.7048 (3) Å
β = 98.506 (4)°
V = 815.84 (6) Å³
Z = 2
Mo Kα radiation
μ = 5.35 mm⁻¹
T = 173 K
0.10 × 0.08 × 0.05 mm

Data collection

Oxford Diffraction CCD area-detector diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2005 $[Oxford Diffraction (2005). CrysAlis CCD and CrysAlis RED. Oxford Diffraction, Abingdon, Oxfordshire, England.]$ ) T_min = 0.604, T_max = 0.765
5173 measured reflections
2215 independent reflections
1808 reflections with I > 2σ(I)
R_int = 0.049

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.064
S = 1.11
2215 reflections
158 parameters
5 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.67 e Å⁻³
Δρ_min = −0.71 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O9ⁱ	0.82 (1)	2.49 (5)	3.039 (5)	126 (5)
O1—H1⋯O7ⁱ	0.82 (1)	2.60 (5)	3.166 (4)	127 (5)
O1—H2⋯O8ⁱⁱ	0.82 (1)	2.33 (3)	3.101 (4)	157 (6)
O1—H2⋯O11ⁱⁱⁱ	0.82 (1)	2.39 (5)	2.878 (4)	119 (5)
O2—H3⋯O9^iv	0.82 (1)	2.01 (3)	2.733 (4)	147 (5)
O2—H4⋯O1ⁱⁱⁱ	0.82 (1)	2.03 (3)	2.765 (5)	149 (6)
O2—H3⋯O10^v	0.82 (1)	2.63 (5)	3.161 (4)	123 (5)
O8—H5⋯O10^vi	0.83	2.11	2.692 (4)	126 (1)
O9—H6⋯O5^vii	0.82 (1)	1.80 (2)	2.584 (4)	160 (6)
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iv) -x+1, -y, -z+2; (v) x-1, y, z; (vi) -x+1, -y, -z+1; (vii) x+1, y, z+1.

Data collection: CrysAlis CCD (Oxford Diffraction, 2005 $[Oxford Diffraction (2005). CrysAlis CCD and CrysAlis RED. Oxford Diffraction, Abingdon, Oxfordshire, England.]$ ); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2005 $[Oxford Diffraction (2005). CrysAlis CCD and CrysAlis RED. Oxford Diffraction, Abingdon, Oxfordshire, England.]$ ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2005 ) and ATOMS (Dowty, 2004 ); software used to prepare material for publication: SHELXL97 and WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681201673X/br2199sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681201673X/br2199Isup2.hkl

checkCIF report

Comment top

Open-framework compounds attract much attention due to their rich structural chemistry and potential catalytic, electrical, optical, and magnetic properties (Brock et al., 1998; Corma, 1997; Zubieta, 1994). Germanophosphates, as one kind of open-framework compounds, have not been fully explored, and only a few compounds had been synthesized up to date (Li et al., 2000; Liu, Yang, Wang et al., 2008; Liu, Yang, Zhang et al., 2008; Zhao et al., 2009). During our systematical investigation on the transition metal germanophosphate system, we obtain the first manganese compound, Mn^II₄(H₂O)₄[Ge(OH)₂(HPO₄)₂(PO₄)₂], which is isostructural with its Fe and Co-analogues (Huang et al., 2012) published recently.

The asymmetric unit of the title compound consists of two distinct Mn atoms, one Ge atom, and two crystallographically independent P atoms (Figure 1). Mn1 is surrounding by four O atoms, an OH-group, and a H₂O molecule forming a distorted octahedron Mn1O₄(OH)(OH₂) with bond distances of 2.159-2.207 Å. Mn2 adopt a nearly regular octahedral coordination to five O atoms and a water molecule with bond distances ranging from 2.176 to 2.224 Å. Ge atom coordinates to four O-atoms in the equatorial plane with shorter bond lengths of 1.846-1.871 Å and two hydroxyl groups in trans-position with longer distance of 1.913 Å. Both P atoms are in tetrahedral coordination with bond lengths of 1.526-1.573 Å. All the bond lengths and angles of the title compound are similar to those of the known germanophosphates (Huang et al., 2012; Liu, Yang, Wang et al., 2008; Liu, Yang, Zhang et al., 2008; Zhao et al., 2009). The Mn2O₅(OH₂) octahedra share their trans-edges with two adjacent Mn1O₄(OH)(OH₂) octahedra, in turn, Mn1-octahedra share skew-edges to two neighboring Mn2-octahedra, resulting in a zigzag chain running along [10-1] (Figure 2a). These manganese octahedral chains are further linked by the P1O₃(OH) and P2O₄ tetrahedra through corner sharing to form undulating sheets (Figure 2b). These sheets are further interconnected by GeO₄(OH)₂ octahedra, sitting at the inverse center, along [010] via common O-corners (Figure 2c) to form a neutral 3-D network with 8-membered ring channels parallel to [100] where all the protons protrude to (Figure 2d). Compared with the two isotypic Fe- and Co-compounds, the Mn-O distances are longer than those of Co- and Fe-compound which is consistent to the longer ionic radius of Mn than those of Fe and Co analogues.

Related literature top

For background to germanophosphates, see: Brock et al. (1998); Corma (1997); Li et al. (2000); Liu, Yang, Wang et al. (2008); Liu, Yang, Zhang et al. (2008); Zhao et al. (2009); Zubieta (1994). For the related structures Fe^II₄(H₂O)₄[Ge(OH)₂(HPO₄)₂(PO₄)₂] and Co^II₄(H₂O)₄[Ge(OH)₂(HPO₄)₂(PO₄)₂], see: Huang et al. (2012).

Experimental top

The crystals of the title compound were solvothermally synthesized by a mixture of GeO₂ (0.073 g), Mn(CH₃COO)₂.4H₂O (0.171 g), H₃PO₄(85 wt%, 1 mL), H₂O (2 mL), triethylamine (1 mL), and 1,2-propanediol (2 mL). The mixture was transferred into a Teflon-lined stainless steel autoclave (internal volume of 15 mL) and heated at 423K for 7 days under static conditions. After the autoclaves cooling to room temperature, the products were filtered off and washed by distilled water for several times and dried in air. Finally light-pink block-shaped crystals were obtained. It is needed to note that the products often contain a minor impurity of GeO₂. Many efforts have been made to get pure phase. However, even the pure phase was obtained but the yield is so low that not enough for further characterization. Thus only single crystal X-ray diffraction of the title compound was carried out.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2005); cell refinement: CrysAlis CCD (Oxford Diffraction, 2005); data reduction: CrysAlis CCD (Oxford Diffraction, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2005) and ATOMS (Dowty, 2004); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and WinGX (Farrugia, 1999).

Figures top

Fig. 1. Asymmetric unit of the title compound, showing the coordination environments of Ge, Mn and P atoms. Thermal ellipsoids are drawn at the 50% probability level. Symmetry codes: (i) –x, –y, –z+1; (ii) –x+1, –y, –z+1; (iii) x–1, y, z; (iv) x–1/2, –y+1/2, z+1/2; (v) x, y, z+1; (vi) x+1, y, z; (vii) x–1/2, –y+1/2, z–1/2.

Fig. 2. Polyhedral presentation of the title compound, a) manganese octahedra share their trans or skew edges to form zigzag chains parallel to [10-1], b) these manganese octahedral chains are linked by phosphate tetrahedra via common O-corners to form undulating manganese phosphate sheets parallel to (010), c) the undulating sheets are further connected by GeO₄(OH)₂ octahedra along [010], resulting in a three-dimensional network structure, d) the network structure comprises 8-membered ring channels running along [100] direction where all the protons protrude to. MnO₆ octahedra: purple, GeO₆ octahedra: green, PO₄ tetrahedra: orange, H atoms: light grey spheres.

Tetraaquatetramanganese(II) catena-[germanodihydroxidodi(hydrogenphosphate)diphosphate] top

Crystal data top

Mn₄(H₂O)₄[Ge(OH)₂(HPO₄)₂(PO₄)₂]	Z = 2
M_r = 780.33	F(000) = 760
Monoclinic, P2₁/n	D_x = 3.176 Mg m⁻³
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 6.5336 (3) Å	θ = 3.0–32.5°
b = 16.3869 (7) Å	µ = 5.35 mm⁻¹
c = 7.7048 (3) Å	T = 173 K
β = 98.506 (4)°	Block-shaped, light pink
V = 815.84 (6) Å³	0.10 × 0.08 × 0.05 mm

Data collection top

Oxford Diffraction CCD area-detector diffractometer	2215 independent reflections
Radiation source: fine-focus sealed tube	1808 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.049
326 images,Δω=1°, Exp time: 40 s. scans	θ_max = 30.7°, θ_min = 3.0°
Absorption correction: multi-scan (CrysAlis CCD; Oxford Diffraction, 2005)	h = −8→8
T_min = 0.604, T_max = 0.765	k = −23→21
5173 measured reflections	l = −10→5

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.042	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.064	w = 1/[σ²(F_o²) + (0.007P)²] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max < 0.001
2215 reflections	Δρ_max = 0.67 e Å⁻³
158 parameters	Δρ_min = −0.71 e Å⁻³
5 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0025 (3)

Crystal data top

Mn₄(H₂O)₄[Ge(OH)₂(HPO₄)₂(PO₄)₂]	V = 815.84 (6) Å³
M_r = 780.33	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.5336 (3) Å	µ = 5.35 mm⁻¹
b = 16.3869 (7) Å	T = 173 K
c = 7.7048 (3) Å	0.10 × 0.08 × 0.05 mm
β = 98.506 (4)°

Data collection top

Oxford Diffraction CCD area-detector diffractometer	2215 independent reflections
Absorption correction: multi-scan (CrysAlis CCD; Oxford Diffraction, 2005)	1808 reflections with I > 2σ(I)
T_min = 0.604, T_max = 0.765	R_int = 0.049
5173 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	5 restraints
wR(F²) = 0.064	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	Δρ_max = 0.67 e Å⁻³
2215 reflections	Δρ_min = −0.71 e Å⁻³
158 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Ge1	0.0000	0.0000	0.5000	0.00570 (15)
Mn1	0.33624 (9)	0.13618 (4)	0.73967 (8)	0.00616 (15)
Mn2	0.10405 (9)	0.27193 (4)	0.97488 (8)	0.00687 (15)
P1	0.85555 (15)	0.10913 (6)	0.78765 (14)	0.0048 (2)
P2	0.06543 (15)	0.18774 (6)	0.37557 (14)	0.0048 (2)
O1	0.0486 (5)	0.3570 (2)	0.7515 (5)	0.0212 (8)
O2	0.3396 (5)	0.05675 (19)	0.9714 (4)	0.0169 (7)
O3	0.6508 (4)	0.13783 (16)	0.6846 (4)	0.0068 (6)
O4	0.0282 (4)	0.17242 (16)	0.7897 (4)	0.0075 (6)
O5	0.0928 (4)	0.18148 (16)	0.1813 (4)	0.0071 (6)
O6	0.2743 (4)	0.20020 (16)	0.4915 (4)	0.0063 (6)
O7	0.4116 (4)	0.24382 (15)	0.9032 (4)	0.0071 (6)
O8	0.2712 (4)	0.02156 (17)	0.5966 (4)	0.0099 (6)
O9	0.8236 (4)	0.09402 (17)	0.9835 (4)	0.0094 (6)
O10	0.9176 (4)	0.02614 (16)	0.7215 (4)	0.0078 (6)
O11	−0.0403 (4)	0.10841 (16)	0.4270 (4)	0.0074 (6)
H1	0.101 (8)	0.336 (3)	0.672 (5)	0.050*
H2	0.117 (8)	0.399 (2)	0.768 (8)	0.050*
H3	0.252 (6)	0.020 (2)	0.959 (8)	0.050*
H4	0.364 (9)	0.076 (3)	1.070 (3)	0.050*
H5	0.296	0.014	0.495	0.050*
H6	0.917 (6)	0.111 (3)	1.056 (6)	0.050*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ge1	0.0067 (3)	0.0038 (3)	0.0065 (3)	−0.0004 (2)	0.0006 (2)	−0.0006 (2)
Mn1	0.0059 (3)	0.0056 (3)	0.0069 (3)	0.0000 (2)	0.0010 (2)	−0.0001 (2)
Mn2	0.0075 (3)	0.0062 (3)	0.0069 (3)	−0.0002 (2)	0.0011 (2)	−0.0009 (3)
P1	0.0050 (5)	0.0048 (5)	0.0048 (5)	−0.0003 (4)	0.0008 (4)	0.0003 (4)
P2	0.0048 (5)	0.0038 (5)	0.0056 (5)	0.0009 (4)	0.0006 (4)	0.0006 (4)
O1	0.0201 (19)	0.024 (2)	0.0185 (19)	−0.0062 (15)	−0.0014 (15)	0.0063 (16)
O2	0.0222 (18)	0.0140 (18)	0.0122 (17)	−0.0081 (13)	−0.0054 (15)	0.0033 (14)
O3	0.0040 (13)	0.0076 (15)	0.0088 (15)	−0.0006 (11)	0.0005 (12)	0.0015 (12)
O4	0.0070 (14)	0.0081 (15)	0.0083 (15)	−0.0002 (11)	0.0043 (12)	−0.0025 (11)
O5	0.0092 (14)	0.0059 (15)	0.0061 (15)	−0.0004 (11)	0.0003 (12)	0.0024 (11)
O6	0.0042 (13)	0.0082 (15)	0.0061 (15)	0.0010 (11)	−0.0010 (11)	0.0011 (11)
O7	0.0080 (14)	0.0040 (14)	0.0090 (15)	0.0000 (11)	0.0000 (12)	−0.0013 (12)
O8	0.0097 (14)	0.0117 (16)	0.0087 (15)	−0.0027 (11)	0.0023 (12)	−0.0027 (12)
O9	0.0110 (15)	0.0136 (16)	0.0031 (15)	−0.0034 (12)	−0.0009 (12)	0.0003 (12)
O10	0.0119 (14)	0.0037 (14)	0.0078 (15)	0.0001 (11)	0.0018 (12)	−0.0005 (11)
O11	0.0089 (14)	0.0038 (14)	0.0092 (15)	0.0008 (11)	0.0000 (12)	0.0004 (12)

Geometric parameters (Å, º) top

Ge1—O8ⁱ	1.851 (3)	Mn2—O7	2.210 (3)
Ge1—O8	1.851 (3)	Mn2—O6^iv	2.225 (3)
Ge1—O11ⁱ	1.870 (3)	P1—O3	1.525 (3)
Ge1—O11	1.870 (3)	P1—O10	1.528 (3)
Ge1—O10ⁱⁱ	1.913 (3)	P1—O4^vi	1.531 (3)
Ge1—O10ⁱⁱⁱ	1.913 (3)	P1—O9	1.573 (3)
Ge1—H5	1.9535	P2—O6	1.530 (3)
Mn1—O3	2.159 (3)	P2—O5	1.537 (3)
Mn1—O6	2.166 (3)	P2—O7^vii	1.542 (3)
Mn1—O7	2.181 (3)	P2—O11	1.551 (3)
Mn1—O4	2.186 (3)	O1—H1	0.817 (10)
Mn1—O8	2.188 (3)	O1—H2	0.818 (10)
Mn1—O2	2.207 (3)	O2—H3	0.822 (10)
Mn2—O4	2.175 (3)	O2—H4	0.815 (10)
Mn2—O3^iv	2.178 (3)	O8—H5	0.83
Mn2—O5^v	2.183 (3)	O9—H6	0.816 (10)
Mn2—O1	2.203 (4)

O8ⁱ—Ge1—O8	180.00 (7)	O5^v—Mn2—O7	99.81 (10)
O8ⁱ—Ge1—O11ⁱ	91.35 (12)	O1—Mn2—O7	89.26 (12)
O8—Ge1—O11ⁱ	88.65 (12)	O4—Mn2—O6^iv	93.62 (10)
O8ⁱ—Ge1—O11	88.65 (12)	O3^iv—Mn2—O6^iv	81.31 (10)
O8—Ge1—O11	91.35 (12)	O5^v—Mn2—O6^iv	87.72 (10)
O11ⁱ—Ge1—O11	180.0	O1—Mn2—O6^iv	82.32 (12)
O8ⁱ—Ge1—O10ⁱⁱ	91.28 (12)	O7—Mn2—O6^iv	168.93 (11)
O8—Ge1—O10ⁱⁱ	88.72 (12)	O3—P1—O10	110.87 (15)
O11ⁱ—Ge1—O10ⁱⁱ	89.43 (12)	O3—P1—O4^vi	112.63 (16)
O11—Ge1—O10ⁱⁱ	90.57 (12)	O10—P1—O4^vi	112.02 (16)
O8ⁱ—Ge1—O10ⁱⁱⁱ	88.72 (12)	O3—P1—O9	108.50 (16)
O8—Ge1—O10ⁱⁱⁱ	91.28 (12)	O10—P1—O9	105.01 (16)
O11ⁱ—Ge1—O10ⁱⁱⁱ	90.57 (12)	O4^vi—P1—O9	107.40 (16)
O11—Ge1—O10ⁱⁱⁱ	89.43 (12)	O6—P2—O5	110.80 (16)
O10ⁱⁱ—Ge1—O10ⁱⁱⁱ	180.0	O6—P2—O7^vii	111.45 (15)
O3—Mn1—O6	83.08 (10)	O5—P2—O7^vii	110.81 (16)
O3—Mn1—O7	87.89 (10)	O6—P2—O11	110.82 (15)
O6—Mn1—O7	96.60 (10)	O5—P2—O11	108.25 (16)
O3—Mn1—O4	163.50 (10)	O7^vii—P2—O11	104.49 (16)
O6—Mn1—O4	88.13 (10)	H1—O1—H2	101 (6)
O7—Mn1—O4	79.25 (10)	H3—O2—H4	115 (6)
O3—Mn1—O8	91.79 (10)	P1—O3—Mn1	132.90 (17)
O6—Mn1—O8	88.50 (10)	P1—O3—Mn2^viii	127.70 (16)
O7—Mn1—O8	174.81 (11)	Mn1—O3—Mn2^viii	96.96 (10)
O4—Mn1—O8	101.94 (10)	P1ⁱⁱ—O4—Mn2	127.63 (17)
O3—Mn1—O2	105.70 (12)	P1ⁱⁱ—O4—Mn1	120.69 (15)
O6—Mn1—O2	167.96 (11)	Mn2—O4—Mn1	101.13 (10)
O7—Mn1—O2	92.02 (11)	P2—O5—Mn2^ix	133.27 (16)
O4—Mn1—O2	85.22 (12)	P2—O6—Mn1	119.00 (15)
O8—Mn1—O2	83.08 (11)	P2—O6—Mn2^viii	141.41 (17)
O4—Mn2—O3^iv	171.44 (11)	Mn1—O6—Mn2^viii	95.39 (10)
O4—Mn2—O5^v	86.56 (10)	P2^x—O7—Mn1	127.21 (17)
O3^iv—Mn2—O5^v	86.36 (10)	P2^x—O7—Mn2	121.22 (15)
O4—Mn2—O1	88.11 (12)	Mn1—O7—Mn2	100.20 (10)
O3^iv—Mn2—O1	97.96 (12)	Ge1—O8—Mn1	118.00 (13)
O5^v—Mn2—O1	168.39 (12)	P1—O10—Ge1^vi	128.35 (17)
O4—Mn2—O7	78.87 (10)	P2—O11—Ge1	145.55 (17)
O3^iv—Mn2—O7	107.09 (10)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O9^vii	0.82 (1)	2.49 (5)	3.039 (5)	126 (5)
O1—H1···O7^vii	0.82 (1)	2.60 (5)	3.166 (4)	127 (5)
O1—H2···O8^xi	0.82 (1)	2.33 (3)	3.101 (4)	157 (6)
O1—H2···O11^x	0.82 (1)	2.39 (5)	2.878 (4)	119 (5)
O2—H3···O9^xii	0.82 (1)	2.01 (3)	2.733 (4)	147 (5)
O2—H4···O1^x	0.82 (1)	2.03 (3)	2.765 (5)	149 (6)
O2—H3···O10ⁱⁱ	0.82 (1)	2.63 (5)	3.161 (4)	123 (5)
O8—H5···O10ⁱⁱⁱ	0.83	2.11	2.692 (4)	126 (1)
O9—H6···O5^xiii	0.82 (1)	1.80 (2)	2.584 (4)	160 (6)

Symmetry codes: (ii) x−1, y, z; (iii) −x+1, −y, −z+1; (vii) x−1/2, −y+1/2, z−1/2; (x) x+1/2, −y+1/2, z+1/2; (xi) −x+1/2, y+1/2, −z+3/2; (xii) −x+1, −y, −z+2; (xiii) x+1, y, z+1.

Experimental details

Crystal data
Chemical formula	Mn₄(H₂O)₄[Ge(OH)₂(HPO₄)₂(PO₄)₂]
M_r	780.33
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	173
a, b, c (Å)	6.5336 (3), 16.3869 (7), 7.7048 (3)
β (°)	98.506 (4)
V (Å³)	815.84 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	5.35
Crystal size (mm)	0.10 × 0.08 × 0.05

Data collection
Diffractometer	Oxford Diffraction CCD area-detector diffractometer
Absorption correction	Multi-scan (CrysAlis CCD; Oxford Diffraction, 2005)
T_min, T_max	0.604, 0.765
No. of measured, independent and observed [I > 2σ(I)] reflections	5173, 2215, 1808
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.718

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.064, 1.11
No. of reflections	2215
No. of parameters	158
No. of restraints	5
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.67, −0.71

Computer programs: CrysAlis CCD (Oxford Diffraction, 2005), SHELXS97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2005) and ATOMS (Dowty, 2004), SHELXL97 (Sheldrick, 2008) and WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O9ⁱ	0.817 (10)	2.49 (5)	3.039 (5)	126 (5)
O1—H1···O7ⁱ	0.817 (10)	2.60 (5)	3.166 (4)	127 (5)
O1—H2···O8ⁱⁱ	0.818 (10)	2.33 (3)	3.101 (4)	157 (6)
O1—H2···O11ⁱⁱⁱ	0.818 (10)	2.39 (5)	2.878 (4)	119 (5)
O2—H3···O9^iv	0.822 (10)	2.01 (3)	2.733 (4)	147 (5)
O2—H4···O1ⁱⁱⁱ	0.815 (10)	2.03 (3)	2.765 (5)	149 (6)
O2—H3···O10^v	0.822 (10)	2.63 (5)	3.161 (4)	123 (5)
O8—H5···O10^vi	0.83	2.11	2.692 (4)	126.2 (2)
O9—H6···O5^vii	0.816 (10)	1.80 (2)	2.584 (4)	160 (6)

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

Acknowledgements

This work was supported by the Scientific Research Foundation for Returned Overseas Chinese Scholars of the State Education Ministry, the National Natural Science Foundation of China (grant No. 40972035), the Natural Science Foundation of Fujian Province of China (grant No. 2010J01308) and the Scientific and Technological Innovation Platform of Fujian Province of China (grant No. 2009J1009).

References

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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Pages i37-i38

doi:10.1107/S160053681201673X

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inorganic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Tetra­aqua­tetra­manganese(II) catena-[germanodi­hydroxidodi(hydrogen­phosphate)diphosphate]

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

inorganic compounds

Tetraaquatetramanganese(II) catena-[germanodihydroxidodi(hydrogenphosphate)diphosphate]