A three-dimensional open-framework germanate containing four-, five- and six-coordinated germanium

A new three-dimensional open-framework germanate, namely ethylenediamine bis(ethylenediammonium) tetra­hydro­xo­octadecaoxononagermanate, (C₂H₈N₂)(C₂H₁₀N₂)₂[Ge₉O₁₈(OH)₄], has been synthesized hydro­thermally and its structure determined by single-crystal X-ray diffraction. The framework is built of [Ge₉O₂₂(OH)₄] units formed by four-, five- and six-oxy­gen-coordinated germanium and templated by ethyl­enedi­amine. Three types of intersecting channels are formed in the framework, one by eight-membered rings running along the b axis and the other two by ten-membered rings running parallel to the a and c axes, respectively.

Computing details

Data collection: EXPOSE (Stoe & Cie, 1997b); cell refinement: CELL (Stoe & Cie, 1997b); data reduction: INTEGRATE (Stoe & Cie, 1997b); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Bergerhoff, 1996).

(I)

Crystal data

(C2H8N2)(C2H10N2)2[H4Ge9O22]	F(000) = 1148
Mr = 1193.68	Dx = 2.961 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 10.1958 (15) Å	Cell parameters from 5000 reflections
b = 9.9753 (10) Å	θ = 2.9–26.0°
c = 13.1655 (19) Å	µ = 10.06 mm^−1
β = 90.695 (17)°	T = 293 K
V = 1338.9 (3) Å^3	Prism, colourless
Z = 2	0.06 × 0.04 × 0.04 mm

Data collection

STOE IPDS diffractometer	2598 independent reflections
Radiation source: fine-focus sealed tube	2077 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.058
Detector resolution: 6.0 pixels mm^-1	θmax = 26.0°, θmin = 2.9°
φ–oscill., φ–incr. = 1.5°; 133 exposures scans	h = −12→12
Absorption correction: numerical (XRED; Stoe & Cie, 1997a)	k = −11→12
Tmin = 0.577, Tmax = 0.721	l = −16→16
10190 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.027	H-atom parameters constrained
wR(F^2) = 0.058	w = 1/[σ^2(Fo^2) + (0.0315P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.96	(Δ/σ)max = 0.041
2598 reflections	Δρmax = 0.80 e Å^−3
204 parameters	Δρmin = −0.63 e Å^−3
3 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00047 (18)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Ge1	0.5000	0.0000	0.0000	0.00530 (14)
Ge2	0.66385 (4)	0.11685 (4)	0.22083 (3)	0.00670 (12)
Ge3	0.38181 (4)	0.16338 (4)	0.22955 (3)	0.00800 (12)
Ge4	0.37016 (4)	0.17895 (4)	−0.16785 (3)	0.00633 (12)
Ge5	0.66835 (4)	0.13366 (4)	−0.16933 (3)	0.00673 (12)
O1	0.3862 (3)	0.1442 (3)	−0.0388 (2)	0.0099 (6)
O2	0.5145 (3)	0.0677 (3)	0.1338 (2)	0.0073 (6)
O3	0.7882 (3)	0.1684 (3)	0.3194 (2)	0.0113 (6)
O4	0.6463 (3)	0.1004 (3)	−0.0407 (2)	0.0102 (6)
O5	0.2897 (3)	0.0122 (3)	0.2377 (2)	0.0143 (7)
O6	0.7432 (3)	0.2095 (3)	0.1243 (2)	0.0139 (7)
H1	0.7163	0.1846	0.0685	0.017*
O7	0.5342 (3)	0.1864 (3)	0.2947 (2)	0.0129 (7)
O8	0.5254 (3)	0.2072 (3)	−0.2226 (2)	0.0128 (6)
O9	0.3406 (3)	0.2767 (3)	0.1307 (2)	0.0173 (7)
H2	0.3454	0.2383	0.0758	0.021*
O10	0.2939 (3)	0.2503 (3)	0.3284 (2)	0.0132 (7)
O11	0.7151 (3)	−0.0528 (3)	0.2336 (2)	0.0127 (7)
C1	0.5575 (5)	0.4524 (5)	0.0077 (4)	0.0273 (12)
H1A	0.5368	0.3653	−0.0209	0.033*
H1B	0.6346	0.4871	−0.0258	0.033*
N1	0.5825 (5)	0.4405 (5)	0.1180 (3)	0.0293 (11)
H1C	0.6178	0.5164	0.1411	0.035*
H1D	0.6376	0.3729	0.1297	0.035*
H1E	0.5073	0.4251	0.1495	0.035*
C2	0.4830 (7)	0.0688 (7)	0.5199 (5)	0.0409 (16)
H2A	0.4136	0.1064	0.4777	0.049*
H2B	0.4494	0.0598	0.5882	0.049*
N2	0.5918 (6)	0.1605 (6)	−0.4781 (4)	0.0471 (15)
H2C	0.6557	0.1274	−0.4388	0.057*
H2D	0.5658	0.2390	−0.4533	0.057*
H2E	0.6214	0.1719	−0.5408	0.057*
C3	0.5232 (13)	0.5073 (10)	−0.4518 (6)	0.092 (4)
H3A	0.4699	0.5747	−0.4188	0.110*
H3B	0.6114	0.5432	−0.4558	0.110*
N3	0.5281 (6)	0.3920 (7)	−0.3866 (5)	0.0487 (15)
H3C	0.449 (3)	0.366 (7)	−0.366 (4)	0.058*
H3D	0.580 (5)	0.402 (8)	−0.331 (3)	0.058*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ge1	0.0061 (3)	0.0048 (3)	0.0050 (3)	−0.0004 (2)	−0.0009 (2)	0.0004 (2)
Ge2	0.0065 (2)	0.0050 (2)	0.0086 (2)	−0.00009 (16)	−0.00103 (16)	−0.00059 (17)
Ge3	0.0073 (2)	0.0067 (2)	0.0100 (2)	0.00070 (16)	−0.00015 (17)	−0.00085 (18)
Ge4	0.0077 (2)	0.0043 (2)	0.0069 (2)	0.00008 (16)	−0.00225 (16)	0.00046 (17)
Ge5	0.0071 (2)	0.0062 (2)	0.0069 (2)	−0.00028 (16)	0.00108 (17)	0.00076 (17)
O1	0.0113 (15)	0.0091 (16)	0.0092 (15)	0.0027 (12)	−0.0003 (12)	0.0030 (12)
O2	0.0066 (14)	0.0101 (16)	0.0052 (14)	0.0014 (11)	0.0007 (11)	0.0004 (12)
O3	0.0124 (15)	0.0070 (16)	0.0144 (15)	−0.0017 (12)	−0.0084 (12)	0.0020 (12)
O4	0.0098 (15)	0.0119 (16)	0.0088 (15)	−0.0044 (12)	−0.0020 (12)	0.0027 (12)
O5	0.0145 (16)	0.0105 (17)	0.0180 (16)	−0.0040 (12)	0.0078 (13)	−0.0047 (13)
O6	0.0185 (16)	0.0157 (17)	0.0075 (15)	−0.0092 (13)	−0.0025 (12)	0.0005 (13)
O7	0.0079 (14)	0.0180 (18)	0.0126 (15)	0.0019 (13)	−0.0019 (12)	−0.0091 (13)
O8	0.0125 (15)	0.0146 (17)	0.0113 (15)	0.0004 (13)	0.0005 (12)	0.0055 (13)
O9	0.0241 (18)	0.0136 (18)	0.0143 (16)	0.0096 (14)	−0.0009 (14)	0.0010 (13)
O10	0.0154 (16)	0.0126 (17)	0.0115 (16)	0.0047 (12)	−0.0006 (13)	−0.0015 (13)
O11	0.0126 (16)	0.0088 (16)	0.0165 (16)	0.0007 (12)	−0.0090 (13)	−0.0010 (13)
C1	0.030 (3)	0.018 (3)	0.033 (3)	0.004 (2)	−0.013 (2)	0.001 (2)
N1	0.036 (3)	0.017 (2)	0.035 (3)	−0.0064 (19)	−0.020 (2)	0.006 (2)
C2	0.046 (4)	0.048 (4)	0.029 (3)	−0.003 (3)	−0.004 (3)	0.006 (3)
N2	0.057 (4)	0.053 (4)	0.031 (3)	−0.008 (3)	0.008 (3)	−0.004 (3)
C3	0.178 (12)	0.058 (6)	0.040 (4)	−0.013 (7)	−0.011 (6)	0.015 (4)
N3	0.036 (3)	0.062 (4)	0.048 (3)	−0.004 (3)	−0.003 (3)	0.015 (3)

Geometric parameters (Å, º)

Ge1—O4	1.880 (3)	O5—Ge5^i	1.766 (3)
Ge1—O4^i	1.880 (3)	O6—H1	0.8200
Ge1—O2^i	1.890 (3)	O9—H2	0.8200
Ge1—O2	1.890 (3)	O10—Ge5^v	1.726 (3)
Ge1—O1^i	1.914 (3)	O11—Ge4^i	1.752 (3)
Ge1—O1	1.914 (3)	C1—N1	1.475 (7)
Ge2—O6	1.774 (3)	C1—C1^vi	1.520 (10)
Ge2—O11	1.778 (3)	C1—H1A	0.9700
Ge2—O7	1.790 (3)	C1—H1B	0.9700
Ge2—O3	1.874 (3)	N1—H1C	0.8900
Ge2—O2	1.957 (3)	N1—H1D	0.8900
Ge2—Ge3	2.9165 (7)	N1—H1E	0.8900
Ge3—O9	1.770 (3)	C2—N2^vii	1.438 (9)
Ge3—O7	1.781 (3)	C2—C2^viii	1.511 (14)
Ge3—O5	1.781 (3)	C2—H2A	0.9700
Ge3—O10	1.810 (3)	C2—H2B	0.9700
Ge3—O2	2.091 (3)	N2—C2^ix	1.438 (9)
Ge4—O1	1.739 (3)	N2—H2C	0.8900
Ge4—O3^ii	1.744 (3)	N2—H2D	0.8900
Ge4—O11^i	1.752 (3)	N2—H2E	0.8900
Ge4—O8	1.770 (3)	C3—C3^x	1.357 (16)
Ge5—O10^iii	1.726 (3)	C3—N3	1.436 (10)
Ge5—O4	1.743 (3)	C3—H3A	0.9700
Ge5—O5^i	1.766 (3)	C3—H3B	0.9700
Ge5—O8	1.769 (3)	N3—H3C	0.90 (2)
O3—Ge4^iv	1.744 (3)	N3—H3D	0.90 (2)
O4—Ge1—O4^i	180.0 (2)	O10^iii—Ge5—O5^i	111.06 (15)
O4—Ge1—O2^i	88.74 (13)	O4—Ge5—O5^i	111.91 (15)
O4^i—Ge1—O2^i	91.26 (13)	O10^iii—Ge5—O8	108.81 (15)
O4—Ge1—O2	91.26 (13)	O4—Ge5—O8	110.41 (14)
O4^i—Ge1—O2	88.74 (13)	O5^i—Ge5—O8	110.05 (15)
O2^i—Ge1—O2	180.00 (6)	Ge4—O1—Ge1	117.40 (16)
O4—Ge1—O1^i	89.76 (13)	Ge1—O2—Ge2	133.36 (15)
O4^i—Ge1—O1^i	90.24 (13)	Ge1—O2—Ge3	132.93 (15)
O2^i—Ge1—O1^i	91.18 (12)	Ge2—O2—Ge3	92.13 (11)
O2—Ge1—O1^i	88.82 (12)	Ge4^iv—O3—Ge2	128.73 (17)
O4—Ge1—O1	90.24 (13)	Ge5—O4—Ge1	119.40 (16)
O4^i—Ge1—O1	89.76 (13)	Ge5^i—O5—Ge3	122.40 (17)
O2^i—Ge1—O1	88.82 (12)	Ge2—O6—H1	109.5
O2—Ge1—O1	91.18 (12)	Ge3—O7—Ge2	109.51 (15)
O1^i—Ge1—O1	180.0 (2)	Ge4—O8—Ge5	120.59 (17)
O6—Ge2—O11	115.28 (15)	Ge3—O9—H2	109.5
O6—Ge2—O7	122.21 (15)	Ge5^v—O10—Ge3	135.03 (18)
O11—Ge2—O7	122.41 (15)	Ge4^i—O11—Ge2	119.56 (16)
O6—Ge2—O3	92.42 (14)	N1—C1—C1^vi	107.8 (6)
O11—Ge2—O3	90.02 (13)	N1—C1—H1A	110.1
O7—Ge2—O3	90.87 (13)	C1^vi—C1—H1A	110.1
O6—Ge2—O2	93.97 (13)	N1—C1—H1B	110.1
O11—Ge2—O2	92.45 (13)	C1^vi—C1—H1B	110.1
O7—Ge2—O2	80.84 (12)	H1A—C1—H1B	108.5
O3—Ge2—O2	171.39 (13)	C1—N1—H1C	109.5
O6—Ge2—Ge3	113.80 (11)	C1—N1—H1D	109.5
O11—Ge2—Ge3	115.89 (10)	H1C—N1—H1D	109.5
O7—Ge2—Ge3	35.14 (9)	C1—N1—H1E	109.5
O3—Ge2—Ge3	126.00 (10)	H1C—N1—H1E	109.5
O2—Ge2—Ge3	45.76 (8)	H1D—N1—H1E	109.5
O9—Ge3—O7	118.00 (16)	N2^vii—C2—C2^viii	113.8 (7)
O9—Ge3—O5	117.69 (16)	N2^vii—C2—H2A	108.8
O7—Ge3—O5	122.55 (15)	C2^viii—C2—H2A	108.8
O9—Ge3—O10	96.15 (14)	N2^vii—C2—H2B	108.8
O7—Ge3—O10	91.65 (14)	C2^viii—C2—H2B	108.8
O5—Ge3—O10	95.52 (14)	H2A—C2—H2B	107.7
O9—Ge3—O2	89.87 (13)	C2^ix—N2—H2C	109.5
O7—Ge3—O2	77.42 (12)	C2^ix—N2—H2D	109.5
O5—Ge3—O2	89.74 (13)	H2C—N2—H2D	109.5
O10—Ge3—O2	169.04 (12)	C2^ix—N2—H2E	109.5
O9—Ge3—Ge2	107.35 (11)	H2C—N2—H2E	109.5
O7—Ge3—Ge2	35.35 (10)	H2D—N2—H2E	109.5
O5—Ge3—Ge2	112.86 (10)	C3^x—C3—N3	118.8 (11)
O10—Ge3—Ge2	126.99 (10)	C3^x—C3—H3A	107.6
O2—Ge3—Ge2	42.12 (8)	N3—C3—H3A	107.6
O1—Ge4—O3^ii	107.91 (14)	C3^x—C3—H3B	107.6
O1—Ge4—O11^i	112.28 (14)	N3—C3—H3B	107.6
O3^ii—Ge4—O11^i	110.18 (14)	H3A—C3—H3B	107.0
O1—Ge4—O8	110.84 (14)	C3—N3—H3C	113 (5)
O3^ii—Ge4—O8	104.57 (14)	C3—N3—H3D	115 (5)
O11^i—Ge4—O8	110.75 (15)	H3C—N3—H3D	107 (3)
O10^iii—Ge5—O4	104.43 (14)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O6—H1···O4	0.82	1.81	2.614 (4)	169
O9—H2···O1	0.82	1.83	2.641 (4)	170
N1—H1C···O3^xi	0.89	1.87	2.750 (5)	172
N1—H1E···O9	0.89	2.27	2.965 (6)	135
N1—H1D···O6	0.89	1.96	2.828 (6)	166
N1—H1D···O11^xi	0.89	2.45	2.826 (5)	106
N2—H2C···O9^iii	0.89	2.29	2.965 (7)	132
N2—H2D···N3	0.89	1.80	2.687 (9)	171
N2—H2E···O7^ix	0.89	2.34	3.053 (6)	138
N2—H2E···O3^ix	0.89	2.52	3.355 (6)	156
N3—H3C···O6^ii	0.90 (2)	2.23 (3)	3.081 (7)	158 (5)
N3—H3D···O5^iii	0.90 (2)	2.47 (4)	3.256 (7)	146 (5)

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