Tetra­sodium (dihydrogenhepta­oxido­digermanato)bis­(dihydrogentetra­oxido­germanato)dicopper(II) monohydrate

Li, Y.-F.; Li, D.-P.; Shi, C.-L.; Hu, Y.-S.; Jin, L.

doi:10.1107/S1600536809007715

inorganic compounds

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ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page i27

doi:10.1107/S1600536809007715

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Tetrasodium (dihydrogenheptaoxidodigermanato)bis(dihydrogentetraoxidogermanato)dicopper(II) monohydrate

Ya-Feng Li,^a ^* Dan-Ping Li,^a Cui-Li Shi,^a Yong-Sheng Hu ^a and Li Jin ^a

^aSchool of Chemical Engineering, Changchun University of Technology, Changchun 130012, People's Republic of China
^*Correspondence e-mail: fly012345@sohu.com

(Received 16 February 2009; accepted 3 March 2009; online 11 March 2009)

In the hydro/solvothermally synthesized title compound, Na₄[Cu₂(H₂Ge₂O₇)(H₂GeO₄)₂]·H₂O, the framework building units include CuO₄, GeO₂(OH)₂ and GeO₃(OH) tetrahedra, the latter being condensed into H₂Ge₂O₇⁴⁻ dimers. All the tetrahedra are connected by corner-sharing into four-membered-ring (4MR) secondary building units containing two CuO₄, one GeO₂(OH)₂ and one GeO₃(OH) entity. The 4MRs form chains by corner-sharing the Cu unit and adjacent chains are linked by H₂Ge₂O₇⁴⁻ dimers, generating layers containing ten-membered rings. Three sodium cations (one with site symmetry $[\overline{1}]$ and one with site symmetry 2) and a water molecule (O-atom site symmetry 2) complete the structure. A network of O—H⋯O hydrogen bonds helps to consolidate the packing.

Related literature

For related structures, see: Bu et al. (2000 ); Cascales et al. (1999 ); Hartman & Kevan (1999 ); Julius et al. (2003 ); Li et al. (2000 ); O'Keeffe & Yaghi (1999 ); Whitfield et al. (2003 ).

Experimental

Crystal data

Na₄[Cu₂(H₂Ge₂O₇)(H₂GeO₄)₂]·H₂O
M_r = 773.56
Orthorhombic, P b c n
a = 13.041 (3) Å
b = 8.7440 (17) Å
c = 12.975 (3) Å
V = 1479.6 (6) Å³
Z = 4
Mo Kα radiation
μ = 11.05 mm⁻¹
T = 293 K
0.20 × 0.15 × 0.05 mm

Data collection

Stoe IPDS diffractometer
Absorption correction: numerical (X-RED; Stoe & Cie, 1997 ) T_min = 0.152, T_max = 0.582
9596 measured reflections
1441 independent reflections
1038 reflections with I > 2σ(I)
R_int = 0.099

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.118
S = 1.03
1441 reflections
129 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 2.11 e Å⁻³
Δρ_min = −1.17 e Å⁻³

Table 1
Selected bond lengths (Å)

Ge1—O1	1.721 (4)
Ge1—O4	1.724 (4)
Ge1—O3	1.781 (4)
Ge1—O2	1.795 (4)
Ge2—O7ⁱ	1.724 (4)
Ge2—O8	1.729 (3)
Ge2—O6	1.772 (2)
Ge2—O5	1.794 (4)
Cu1—O4	1.953 (4)
Cu1—O1ⁱⁱ	1.960 (4)
Cu1—O8	1.961 (4)
Cu1—O7	1.964 (4)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O6ⁱⁱⁱ	0.82	2.59	3.298 (5)	146
O3—H3⋯O1^iv	0.82	1.98	2.765 (6)	161
O5—H5⋯O4^v	0.82	1.94	2.755 (6)	171
O1W—H1⋯O7	0.85 (4)	1.96 (5)	2.773 (6)	159 (6)
Symmetry codes: (iii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iv) -x, -y, -z; (v) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: EXPOSURE in IPDS Software (Stoe & Cie, 1997); cell refinement: CELL in IPDS Software; data reduction: INTEGRATE in IPDS Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2000 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809007715/hb2913sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809007715/hb2913Isup2.hkl

checkCIF report

Comment top

Recently, gernamates have been recieving the extensive attentions owing to their potential applications such as ion-exchange, catalyst and sorption. The four-coordinated Ge has a trendency to form the double four ring geometry with oxygen, which can be observed in several Ge-based zeolites such as ASV, BEC, IWR, IWW, UOZ (O'Keeffe, et al., 1999). This derives from flexible Ge—O—Ge bond angles (130° or so). Incorporation of transition metals into Si-based materials is extremely interesting because transition metals can improve zeolite properties (Hartman, et al., 1999). Following the successful introduction of transition metals into zeolite materials, efforts are also made to incorporate transition metal elements, such as V (Whitfield, et al., 2003), Co (Julius, et al., 2003), Cu (Cascales, et al., 1999), Zn (Bu, et al., 2000) and Zr (Li, et al., 2000), into germanate frameworks. In this paper, a new copper(II) germanate with 10MR network, Na₄[Cu₂Ge₄O₉(OH)₆].H₂O (I), is described.

The asymmetric unit of (I) comprises two crystallographically independent GeO₄–GeO₂(OH)₂ and GeO₃(OH), one CuO₄, three Na cations one of which locates on the center of ac plane, and a half of free water molecule (Fig.1). All of Ge and Cu atoms are tetrahedrally coordinated by oxygen atoms. Both GeO₄ and CuO₄ tetrahedra are lightly distorted with 1.721–1.794 Å of Ge—O and 1.952–1.964 Å of Cu—O. There is no linkage between Ge1 and Ge2, but Ge2 can really form the dimer of H₂Ge₂O₇^4- by sharing O6 with 124.89° of Ge—O—Ge.

The 4MR SBU of (I) is consisted of two CuO₄, one GeO₂(OH)₂ and one GeO₃(OH). The GeO₄ tetrahedra and CuO₄ tetrahedra are connected by sharing corner. The bond angles of Ge—O—Cu range from 117.72° to 122.65°. The corner-sharing '4-rings' chain is constructed by the CuO₄ of 4MR SBU as the corner. In such a chain, every CuO₄ has four Cu—O—Ge linkages, while either GeO₂(OH)₂ or GeO₃(OH) just have two Cu—O—Ge linkages. As the result of the existence of H₂Ge₂O₇^4-, the adjacent corner-sharing '4-rings' chains are connected to the layer of 10MR net (Fig.2). Three crystallographically independent Na atoms, one of which loacates on the special position (1/2,0,1/2), act as the balanced cation and interact with the framework by Na—O electrostatic interactions with 2.372–2.569 Å of Na—O. Except for intramolecular hydrogen bond (O2—H2···O6ⁱ, O3—H3···O1ⁱⁱ, O5—H5···O4ⁱⁱⁱ), there exists the intermolecar hydrogen bond between water molecules and terminal hydroxide anions (O1W—H1···O7).

Related literature top

For related structures, see: Bu et al. (2000); Cascales et al. (1999); Hartman & Kevan (1999); Julius et al. (2003); Li et al. (2000); O'Keeffe & Yaghi (1999); Whitfield et al. (2003).

Experimental top

GeO₂(0.25 g), Cu(Ac)₂.3H₂O (0.28 g) and NaOH (0.38 g) were successively added into a pyridine/water (7.5 ml/1 ml) solution with molar ratio of 1 GeO₂:0.5 Cu(Ac)₂.3H₂O:4 NaOH: 23 H₂O: 38 pyridine. The deep blue mixture was vigoursly stirred for 6 hr. The final mixture was sealed into 23 ml autoclave and heated up to 438 K for 6 days. The autoclave was naturally cooled to room temperature, and the product was filtered, washed by distilled water and alcohol and dried at room temperature. Deep blue prismatic large single crystals of (I) were obtained. The atomic ratio of Ge: Cu: Na determined by EDX was 2:1:2, in agreement with the results of structural determination of (I).

Computing details top

Data collection: EXPOSURE in IPDS Software (Stoe & Cie, 1997); cell refinement: CELL in IPDS Software (Stoe & Cie, 1997); data reduction: INTEGRATE in IPDS Software (Stoe & Cie, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2000); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. A fragment of (I), showing displacement ellipsoids for the non-hydrogen atoms at the 50% probability level. [Symmetry codes: (i) 0.5 - x, -1/2 + y, z; (ii) 0.5 - x, 1/2 + y, z.]
	Fig. 2. The packing diagram of (I), viewed along [021] direction. CuO₄ tetrahedra are shown in green, GeO₄ tetrahedra in cyan, Na atoms in light gray and O atoms in red. H atoms are omitted for clarity.

Tetrasodium (dihydrogenheptaoxidodigermanato)bis(dihydrogentetraoxidogermanato)dicopper(II) monohydrate top

Crystal data top

Na₄[Cu₂(H₂Ge₂O₇)(H₂GeO₄)₂]·H₂O	F(000) = 1464
M_r = 773.56	D_x = 3.472 Mg m⁻³
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 2000 reflections
a = 13.041 (3) Å	θ = 2.8–26.0°
b = 8.7440 (17) Å	µ = 11.05 mm⁻¹
c = 12.975 (3) Å	T = 293 K
V = 1479.6 (6) Å³	Block, dark blue
Z = 4	0.20 × 0.15 × 0.05 mm

Data collection top

Stoe IPDS diffractometer	1441 independent reflections
Radiation source: fine-focus sealed tube	1038 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.099
Detector resolution: 6.0 pixels mm^-1	θ_max = 26.0°, θ_min = 2.8°
ϕ–oscillation, ϕ–incr.=1.8°, 100 exposure scans	h = −16→15
Absorption correction: numerical (X-RED; Stoe & Cie, 1997)	k = −10→10
T_min = 0.152, T_max = 0.582	l = −15→15
9596 measured reflections

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.118	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.076P)²] where P = (F_o² + 2F_c²)/3
1441 reflections	(Δ/σ)_max = 0.001
129 parameters	Δρ_max = 2.11 e Å⁻³
1 restraint	Δρ_min = −1.17 e Å⁻³

Crystal data top

Na₄[Cu₂(H₂Ge₂O₇)(H₂GeO₄)₂]·H₂O	V = 1479.6 (6) Å³
M_r = 773.56	Z = 4
Orthorhombic, Pbcn	Mo Kα radiation
a = 13.041 (3) Å	µ = 11.05 mm⁻¹
b = 8.7440 (17) Å	T = 293 K
c = 12.975 (3) Å	0.20 × 0.15 × 0.05 mm

Data collection top

Stoe IPDS diffractometer	1441 independent reflections
Absorption correction: numerical (X-RED; Stoe & Cie, 1997)	1038 reflections with I > 2σ(I)
T_min = 0.152, T_max = 0.582	R_int = 0.099
9596 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	1 restraint
wR(F²) = 0.118	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 2.11 e Å⁻³
1441 reflections	Δρ_min = −1.17 e Å⁻³
129 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
Ge1	0.12245 (4)	0.12598 (6)	0.00099 (3)	0.0080 (2)
Ge2	0.37958 (4)	0.11778 (5)	0.25132 (4)	0.0076 (2)
Cu1	0.25095 (4)	0.37556 (6)	0.12703 (4)	0.0059 (2)
Na1	0.5000	0.0000	0.5000	0.0192 (8)
Na2	0.5000	0.4894 (4)	0.2500	0.0183 (8)
Na3	0.14907 (19)	0.2426 (3)	0.37481 (16)	0.0160 (5)
O1	0.1236 (3)	−0.0089 (4)	0.0976 (3)	0.0112 (9)
O2	0.1320 (3)	0.0301 (5)	−0.1209 (3)	0.0133 (8)
H2	0.0851	0.0580	−0.1585	0.070 (18)*
O3	0.0009 (3)	0.2188 (5)	0.0010 (3)	0.0137 (9)
H3	−0.0382	0.1736	−0.0380	0.070 (18)*
O4	0.2169 (3)	0.2639 (5)	0.0013 (3)	0.0108 (8)
O5	0.3686 (3)	0.0205 (5)	0.3725 (3)	0.0140 (9)
H5	0.3402	0.0765	0.4144	0.070 (18)*
O6	0.5000	0.2115 (6)	0.2500	0.0106 (11)
O7	0.1210 (3)	0.4809 (4)	0.1556 (3)	0.0121 (8)
O8	0.2863 (3)	0.2583 (4)	0.2509 (3)	0.0105 (7)
O1W	0.0000	0.2609 (7)	0.2500	0.0170 (12)
H1	0.023 (5)	0.333 (6)	0.212 (5)	0.020*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ge1	0.0107 (4)	0.0072 (4)	0.0060 (3)	−0.00028 (19)	−0.0002 (2)	0.00003 (17)
Ge2	0.0096 (3)	0.0070 (3)	0.0062 (3)	0.00035 (18)	−0.0004 (2)	−0.0002 (2)
Cu1	0.0074 (4)	0.0073 (4)	0.0031 (4)	0.0001 (2)	−0.0005 (2)	−0.0002 (2)
Na1	0.0245 (19)	0.0161 (18)	0.0170 (18)	0.0027 (13)	−0.0063 (16)	−0.0008 (11)
Na2	0.0247 (18)	0.0139 (17)	0.0163 (17)	0.000	0.0081 (16)	0.000
Na3	0.0181 (11)	0.0138 (12)	0.0160 (11)	−0.0008 (8)	−0.0016 (9)	0.0011 (9)
O1	0.012 (2)	0.0102 (18)	0.0114 (19)	0.0010 (13)	0.0034 (16)	0.0044 (14)
O2	0.015 (2)	0.013 (2)	0.0116 (18)	−0.0015 (15)	0.0031 (18)	0.0007 (15)
O3	0.0143 (19)	0.013 (2)	0.013 (2)	0.0034 (15)	0.001 (2)	−0.0005 (13)
O4	0.0148 (19)	0.013 (2)	0.0050 (15)	−0.0053 (16)	−0.0005 (15)	−0.0022 (14)
O5	0.017 (2)	0.012 (2)	0.0123 (19)	0.0009 (15)	0.000 (2)	0.0003 (16)
O6	0.007 (2)	0.011 (3)	0.014 (2)	0.000	−0.002 (2)	0.000
O7	0.012 (2)	0.0115 (19)	0.0130 (19)	−0.0026 (14)	−0.0013 (16)	−0.0037 (15)
O8	0.0126 (18)	0.0107 (18)	0.0081 (15)	0.0021 (14)	0.0001 (15)	0.0047 (16)
O1W	0.023 (3)	0.012 (3)	0.016 (3)	0.000	0.006 (3)	0.000

Geometric parameters (Å, º) top

Ge1—O1	1.721 (4)	Na2—O1W^vi	2.375 (8)
Ge1—O4	1.724 (4)	Na2—O2^v	2.408 (4)
Ge1—O3	1.781 (4)	Na2—O2^vii	2.408 (4)
Ge1—O2	1.795 (4)	Na2—O6	2.429 (6)
Ge2—O7ⁱ	1.724 (4)	Na2—O1ⁱⁱ	2.551 (4)
Ge2—O8	1.729 (3)	Na2—O1^vi	2.551 (4)
Ge2—O6	1.772 (2)	Na3—O2^viii	2.395 (5)
Ge2—O5	1.794 (4)	Na3—O4^v	2.398 (4)
Cu1—O4	1.953 (4)	Na3—O8	2.410 (4)
Cu1—O1ⁱⁱ	1.960 (4)	Na3—O5ⁱⁱ	2.441 (5)
Cu1—O8	1.961 (4)	Na3—O1W	2.535 (2)
Cu1—O7	1.964 (4)	Na3—O3^ix	2.543 (5)
Na1—O5ⁱⁱⁱ	2.388 (4)	O2—H2	0.8200
Na1—O3^iv	2.459 (4)	O3—H3	0.8200
Na1—O3^v	2.459 (4)	O5—H5	0.8200
Na1—O7^iv	2.568 (4)	O1W—H1	0.85 (4)
Na1—O7^v	2.568 (4)

O1—Ge1—O4	118.13 (19)	O1W^vi—Na2—Na3ⁱⁱ	48.81 (5)
O1—Ge1—O3	108.67 (19)	O2^v—Na2—Na3ⁱⁱ	45.42 (11)
O4—Ge1—O3	108.5 (2)	O2^vii—Na2—Na3ⁱⁱ	142.64 (15)
O1—Ge1—O2	108.73 (19)	O6—Na2—Na3ⁱⁱ	131.19 (5)
O4—Ge1—O2	106.20 (17)	O1ⁱⁱ—Na2—Na3ⁱⁱ	90.23 (11)
O3—Ge1—O2	105.96 (18)	O1^vi—Na2—Na3ⁱⁱ	89.31 (11)
O7ⁱ—Ge2—O8	119.18 (18)	Na3^vi—Na2—Na3ⁱⁱ	97.61 (10)
O7ⁱ—Ge2—O6	108.55 (17)	O2^viii—Na3—O4^v	91.63 (15)
O8—Ge2—O6	107.15 (19)	O2^viii—Na3—O8	98.11 (15)
O7ⁱ—Ge2—O5	107.56 (19)	O4^v—Na3—O8	85.22 (14)
O8—Ge2—O5	106.51 (18)	O2^viii—Na3—O5ⁱⁱ	169.22 (15)
O6—Ge2—O5	107.36 (15)	O4^v—Na3—O5ⁱⁱ	95.79 (16)
O7ⁱ—Ge2—Na3	122.03 (14)	O8—Na3—O5ⁱⁱ	90.31 (14)
O6—Ge2—Na3	127.45 (13)	O2^viii—Na3—O1W	90.37 (19)
O5—Ge2—Na3	71.65 (14)	O4^v—Na3—O1W	175.92 (17)
O4—Cu1—O1ⁱⁱ	106.53 (14)	O8—Na3—O1W	98.03 (12)
O4—Cu1—O8	118.46 (17)	O5ⁱⁱ—Na3—O1W	81.77 (18)
O1ⁱⁱ—Cu1—O8	103.48 (14)	O2^viii—Na3—O3^ix	80.36 (15)
O4—Cu1—O7	101.33 (15)	O4^v—Na3—O3^ix	97.19 (14)
O1ⁱⁱ—Cu1—O7	120.99 (16)	O8—Na3—O3^ix	177.16 (16)
O8—Cu1—O7	107.05 (14)	O5ⁱⁱ—Na3—O3^ix	90.94 (15)
O4—Cu1—O7	101.33 (15)	O1W—Na3—O3^ix	79.63 (12)
O1ⁱⁱ—Cu1—O7	120.99 (16)	O2^viii—Na3—Na2^xi	45.72 (11)
O8—Cu1—O7	107.05 (14)	O4^v—Na3—Na2^xi	137.34 (13)
O7—Cu1—O7	0.0 (2)	O8—Na3—Na2^xi	98.36 (11)
O5ⁱⁱⁱ—Na1—O3^iv	85.71 (13)	O5ⁱⁱ—Na3—Na2^xi	126.51 (13)
O5ⁱⁱⁱ—Na1—O3^v	94.29 (13)	O1W—Na3—Na2^xi	44.81 (16)
O3^iv—Na1—O3^v	180.0	O3^ix—Na3—Na2^xi	78.85 (11)
O5ⁱⁱⁱ—Na1—O7^iv	95.68 (12)	O2^viii—Na3—Na1^xii	126.64 (12)
O3^iv—Na1—O7^iv	85.86 (13)	O4^v—Na3—Na1^xii	96.07 (12)
O3^v—Na1—O7^iv	94.14 (13)	O8—Na3—Na1^xii	135.08 (12)
O5ⁱⁱⁱ—Na1—O7^v	84.32 (12)	O5ⁱⁱ—Na3—Na1^xii	44.80 (10)
O3^iv—Na1—O7^v	94.14 (13)	O1W—Na3—Na1^xii	79.88 (12)
O3^v—Na1—O7^v	85.86 (13)	O3^ix—Na3—Na1^xii	46.31 (10)
O7^iv—Na1—O7^v	180.0	Na2^xi—Na3—Na1^xii	109.67 (7)
O5ⁱⁱⁱ—Na1—Na3ⁱ	133.93 (11)	O2^viii—Na3—Ge2	77.56 (11)
O3^iv—Na1—Na3ⁱ	48.40 (10)	O4^v—Na3—Ge2	71.75 (11)
O3^v—Na1—Na3ⁱ	131.60 (10)	O8—Na3—Ge2	25.09 (8)
O7^iv—Na1—Na3ⁱ	86.13 (9)	O5ⁱⁱ—Na3—Ge2	112.20 (12)
O7^v—Na1—Na3ⁱ	93.87 (9)	O1W—Na3—Ge2	112.18 (8)
O5ⁱⁱⁱ—Na1—Na3^x	46.07 (11)	O3^ix—Na3—Ge2	154.87 (13)
O3^iv—Na1—Na3^x	131.60 (10)	Na2^xi—Na3—Ge2	93.97 (6)
O3^v—Na1—Na3^x	48.40 (10)	Na1^xii—Na3—Ge2	154.09 (7)
O7^iv—Na1—Na3^x	93.87 (9)	Ge1—O1—Cu1ⁱ	120.2 (2)
O7^v—Na1—Na3^x	86.13 (9)	Ge1—O1—Na2^xi	124.3 (2)
Na3ⁱ—Na1—Na3^x	180.0	Cu1ⁱ—O1—Na2^xi	111.90 (16)
O1W^vi—Na2—O2^v	94.04 (13)	Ge1—O2—H2	109.5
O1W^vi—Na2—O2^vii	94.04 (13)	Ge1—O3—H3	109.5
O2^v—Na2—O2^vii	171.9 (3)	Ge1—O4—Cu1	120.93 (19)
O1W^vi—Na2—O6	180.000 (1)	Ge1—O4—Na3^xiii	120.2 (2)
O2^v—Na2—O6	85.96 (12)	Cu1—O4—Na3^xiii	114.70 (16)
O2^vii—Na2—O6	85.96 (12)	Ge2—O5—H5	109.5
O1W^vi—Na2—O1ⁱⁱ	89.65 (11)	Ge2—O6—Ge2^xiv	124.9 (3)
O2^v—Na2—O1ⁱⁱ	95.04 (12)	Ge2—O6—Na2	117.56 (15)
O2^vii—Na2—O1ⁱⁱ	85.01 (12)	Ge2^xiv—O6—Na2	117.56 (15)
O6—Na2—O1ⁱⁱ	90.35 (12)	Ge2ⁱⁱ—O7—Cu1	117.7 (2)
O1W^vi—Na2—O1^vi	89.65 (12)	Ge2ⁱⁱ—O7—Na1^xiii	121.2 (2)
O2^v—Na2—O1^vi	85.01 (12)	Cu1—O7—Na1^xiii	114.33 (16)
O2^vii—Na2—O1^vi	95.04 (12)	Ge2—O8—Cu1	122.7 (2)
O6—Na2—O1^vi	90.35 (12)	Ge2—O8—Na3	118.67 (19)
O1ⁱⁱ—Na2—O1^vi	179.3 (2)	Cu1—O8—Na3	113.70 (15)
O1W^vi—Na2—Na3^vi	48.81 (5)	Na2^xi—O1W—Na3^ix	86.38 (15)
O2^v—Na2—Na3^vi	142.64 (15)	Na2^xi—O1W—Na3	86.38 (15)
O2^vii—Na2—Na3^vi	45.42 (11)	Na3^ix—O1W—Na3	172.8 (3)
O6—Na2—Na3^vi	131.19 (5)	Na2^xi—O1W—H1	138 (4)
O1ⁱⁱ—Na2—Na3^vi	89.31 (11)	Na3^ix—O1W—H1	87 (5)
O1^vi—Na2—Na3^vi	90.23 (11)	Na3—O1W—H1	98 (5)

O7ⁱ—Ge2—Na3—O2^viii	47.40 (19)	O8—Ge2—O6—Na2	0.66 (13)
O8—Ge2—Na3—O2^viii	144.2 (2)	O5—Ge2—O6—Na2	−113.42 (14)
O6—Ge2—Na3—O2^viii	−150.40 (15)	Na3—Ge2—O6—Na2	−33.55 (8)
O5—Ge2—Na3—O2^viii	−52.23 (17)	O2^v—Na2—O6—Ge2	43.59 (9)
O7ⁱ—Ge2—Na3—O4^v	143.33 (18)	O2^vii—Na2—O6—Ge2	−136.41 (9)
O8—Ge2—Na3—O4^v	−119.8 (2)	O1ⁱⁱ—Na2—O6—Ge2	−51.44 (9)
O6—Ge2—Na3—O4^v	−54.47 (16)	O1^vi—Na2—O6—Ge2	128.56 (9)
O5—Ge2—Na3—O4^v	43.70 (17)	Na3^vi—Na2—O6—Ge2	−140.83 (6)
O7ⁱ—Ge2—Na3—O8	−96.8 (3)	Na3ⁱⁱ—Na2—O6—Ge2	39.17 (6)
O6—Ge2—Na3—O8	65.4 (2)	O2^v—Na2—O6—Ge2^xiv	−136.41 (9)
O5—Ge2—Na3—O8	163.5 (3)	O2^vii—Na2—O6—Ge2^xiv	43.59 (9)
O7ⁱ—Ge2—Na3—O5ⁱⁱ	−127.81 (18)	O1ⁱⁱ—Na2—O6—Ge2^xiv	128.56 (9)
O8—Ge2—Na3—O5ⁱⁱ	−31.0 (2)	O1^vi—Na2—O6—Ge2^xiv	−51.44 (9)
O6—Ge2—Na3—O5ⁱⁱ	34.39 (18)	Na3^vi—Na2—O6—Ge2^xiv	39.17 (6)
O5—Ge2—Na3—O5ⁱⁱ	132.6 (2)	Na3ⁱⁱ—Na2—O6—Ge2^xiv	−140.83 (6)
O7ⁱ—Ge2—Na3—O1W	−37.9 (2)	O4—Cu1—O7—O7	0.00 (9)
O8—Ge2—Na3—O1W	59.0 (3)	O1ⁱⁱ—Cu1—O7—O7	0.00 (16)
O6—Ge2—Na3—O1W	124.35 (18)	O8—Cu1—O7—O7	0.00 (11)
O5—Ge2—Na3—O1W	−137.5 (2)	O4—Cu1—O7—Ge2ⁱⁱ	−170.6 (2)
O7ⁱ—Ge2—Na3—O3^ix	76.5 (3)	O1ⁱⁱ—Cu1—O7—Ge2ⁱⁱ	−53.3 (3)
O8—Ge2—Na3—O3^ix	173.3 (4)	O8—Cu1—O7—Ge2ⁱⁱ	64.6 (2)
O6—Ge2—Na3—O3^ix	−121.3 (3)	O7—Cu1—O7—Ge2ⁱⁱ	0 (49)
O5—Ge2—Na3—O3^ix	−23.2 (3)	O4—Cu1—O7—Na1^xiii	−18.9 (2)
O7ⁱ—Ge2—Na3—Na2^xi	4.45 (16)	O1ⁱⁱ—Cu1—O7—Na1^xiii	98.39 (19)
O8—Ge2—Na3—Na2^xi	101.3 (2)	O8—Cu1—O7—Na1^xiii	−143.67 (16)
O6—Ge2—Na3—Na2^xi	166.65 (12)	O7—Cu1—O7—Na1^xiii	0 (22)
O5—Ge2—Na3—Na2^xi	−95.19 (15)	O7ⁱ—Ge2—O8—Cu1	−48.1 (3)
O7ⁱ—Ge2—Na3—Na1^xii	−151.8 (2)	O6—Ge2—O8—Cu1	75.6 (2)
O8—Ge2—Na3—Na1^xii	−54.9 (2)	O5—Ge2—O8—Cu1	−169.8 (2)
O6—Ge2—Na3—Na1^xii	10.4 (2)	Na3—Ge2—O8—Cu1	−153.5 (4)
O5—Ge2—Na3—Na1^xii	108.6 (2)	O7ⁱ—Ge2—O8—Na3	105.4 (2)
O4—Ge1—O1—Cu1ⁱ	−51.6 (3)	O6—Ge2—O8—Na3	−130.96 (16)
O3—Ge1—O1—Cu1ⁱ	−175.7 (2)	O5—Ge2—O8—Na3	−16.3 (3)
O2—Ge1—O1—Cu1ⁱ	69.4 (3)	O4—Cu1—O8—Ge2	52.6 (3)
O4—Ge1—O1—Na2^xi	105.0 (3)	O1ⁱⁱ—Cu1—O8—Ge2	−65.0 (3)
O3—Ge1—O1—Na2^xi	−19.1 (3)	O7—Cu1—O8—Ge2	166.1 (2)
O2—Ge1—O1—Na2^xi	−134.0 (2)	O7—Cu1—O8—Ge2	166.1 (2)
O1—Ge1—O4—Cu1	−47.6 (3)	O4—Cu1—O8—Na3	−102.1 (2)
O3—Ge1—O4—Cu1	76.6 (3)	O1ⁱⁱ—Cu1—O8—Na3	140.33 (17)
O2—Ge1—O4—Cu1	−169.9 (2)	O7—Cu1—O8—Na3	11.5 (2)
O1—Ge1—O4—Na3^xiii	108.2 (2)	O7—Cu1—O8—Na3	11.5 (2)
O3—Ge1—O4—Na3^xiii	−127.6 (2)	O2^viii—Na3—O8—Ge2	−35.2 (2)
O2—Ge1—O4—Na3^xiii	−14.1 (3)	O4^v—Na3—O8—Ge2	55.8 (2)
O1ⁱⁱ—Cu1—O4—Ge1	170.2 (2)	O5ⁱⁱ—Na3—O8—Ge2	151.5 (2)
O8—Cu1—O4—Ge1	54.2 (3)	O1W—Na3—O8—Ge2	−126.7 (2)
O7—Cu1—O4—Ge1	−62.5 (3)	Na2^xi—Na3—O8—Ge2	−81.4 (2)
O7—Cu1—O4—Ge1	−62.5 (3)	Na1^xii—Na3—O8—Ge2	149.58 (14)
O1ⁱⁱ—Cu1—O4—Na3^xiii	13.1 (2)	O2^viii—Na3—O8—Cu1	120.56 (19)
O8—Cu1—O4—Na3^xiii	−102.9 (2)	O4^v—Na3—O8—Cu1	−148.5 (2)
O7—Cu1—O4—Na3^xiii	140.47 (18)	O5ⁱⁱ—Na3—O8—Cu1	−52.70 (19)
O7—Cu1—O4—Na3^xiii	140.47 (18)	O1W—Na3—O8—Cu1	29.0 (2)
O7ⁱ—Ge2—O6—Ge2^xiv	−49.42 (14)	Na2^xi—Na3—O8—Cu1	74.33 (17)
O8—Ge2—O6—Ge2^xiv	−179.34 (13)	Na1^xii—Na3—O8—Cu1	−54.7 (3)
O5—Ge2—O6—Ge2^xiv	66.58 (14)	Ge2—Na3—O8—Cu1	155.8 (3)
Na3—Ge2—O6—Ge2^xiv	146.45 (8)	O2^viii—Na3—O1W—Na2^xi	−4.43 (10)
O7ⁱ—Ge2—O6—Na2	130.58 (14)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O6^xiii	0.82	2.59	3.298 (5)	146
O3—H3···O1^xv	0.82	1.98	2.765 (6)	161
O5—H5···O4^v	0.82	1.94	2.755 (6)	171
O1W—H1···O7	0.85 (4)	1.96 (5)	2.773 (6)	159 (6)

Symmetry codes: (v) −x+1/2, −y+1/2, z+1/2; (xiii) −x+1/2, −y+1/2, z−1/2; (xv) −x, −y, −z.

Experimental details

Crystal data
Chemical formula	Na₄[Cu₂(H₂Ge₂O₇)(H₂GeO₄)₂]·H₂O
M_r	773.56
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	293
a, b, c (Å)	13.041 (3), 8.7440 (17), 12.975 (3)
V (Å³)	1479.6 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	11.05
Crystal size (mm)	0.20 × 0.15 × 0.05

Data collection
Diffractometer	Stoe IPDS diffractometer
Absorption correction	Numerical (X-RED; Stoe & Cie, 1997)
T_min, T_max	0.152, 0.582
No. of measured, independent and observed [I > 2σ(I)] reflections	9596, 1441, 1038
R_int	0.099
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.118, 1.03
No. of reflections	1441
No. of parameters	129
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	2.11, −1.17

Computer programs: EXPOSURE in IPDS Software (Stoe & Cie, 1997), CELL in IPDS Software (Stoe & Cie, 1997), INTEGRATE in IPDS Software (Stoe & Cie, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2000).

Selected bond lengths (Å) top

Ge1—O1	1.721 (4)	Ge2—O6	1.772 (2)
Ge1—O4	1.724 (4)	Ge2—O5	1.794 (4)
Ge1—O3	1.781 (4)	Cu1—O4	1.953 (4)
Ge1—O2	1.795 (4)	Cu1—O1ⁱⁱ	1.960 (4)
Ge2—O7ⁱ	1.724 (4)	Cu1—O8	1.961 (4)
Ge2—O8	1.729 (3)	Cu1—O7	1.964 (4)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O6ⁱⁱⁱ	0.82	2.59	3.298 (5)	146
O3—H3···O1^iv	0.82	1.98	2.765 (6)	161
O5—H5···O4^v	0.82	1.94	2.755 (6)	171
O1W—H1···O7	0.85 (4)	1.96 (5)	2.773 (6)	159 (6)

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

Acknowledgements

The project is sponsored by the Scientific Research Foundation for Returned Overseas Chinese Scholars, State Education Ministry (grant No. 20071108).

References

Brandenburg, K. (2000). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bu, X., Feng, P. & Stucky, G. D. (2000). Chem. Mater. 12, 1811–1913. Web of Science CSD CrossRef CAS Google Scholar
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Volume 65| Part 4| April 2009| Page i27

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Tetra­sodium (di­hydrogenhepta­oxido­digermanato)bis­­(di­hydrogentetra­oxido­germanato)dicopper(II) monohydrate

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Experimental

Crystal data

Data collection

Refinement

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inorganic compounds

Tetrasodium (dihydrogenheptaoxidodigermanato)bis(dihydrogentetraoxidogermanato)dicopper(II) monohydrate