Bis­(ethyl­enedi­ammonium) di-μ₅-hydrogenphosphato-penta-μ₂-oxo-decaoxopentamolybdenum

The title compound, (C₂H₁₀N₂)₂[Mo₅O₁₅(HPO₄)₂], consists of [Mo₅O₁₅(HPO₄)₂]⁴⁻ clusters with one Mo and one O atom located on a twofold rotation axis linked to [H₃N(CH₂)₂NH₃]²⁺ ions. The [Mo₅O₁₅(HPO₄)₂]⁴⁻ anion consists of five edge-sharing or corner-sharing MoO₆ octahedra, which adopt distorted octahedral geometry, and two corner-sharing PO₄ tetrahedra. The anion clusters are connected by hydrogen bonds with [H₃N(CH₂)₂NH₃]²⁺.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.022
• wR factor = 0.045
• Data-to-parameter ratio = 16.1

checkCIF/PLATON results

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Alert level C
PLAT764_ALERT_4_C Overcomplete CIF Bond list Detected (Rep/Expd)       1.12 Ratio

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion

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S1. Comment

Since the mid-1990 s, organic-inorganic hydrid compounds have become a significant area of research for chemists on account of their pronounced structural diversity and controllability of their chemical and physical properties (Hagrman et al., 1999; Khan et al., 1999). In addition, the potential applications of this type of compound in catalysis (Smith, 1988; Occelli & Robson, 1989), new functional materials (Kresge et al., 1992) and biochemistry (Mann, 1993) etc., have attracted much attention from materials scientists and biological chemists. A class of metal oxide clusters based on anionic molybdenum phosphate framework has received much attention as a consequence of their potential applications in catalysis and materials science (Chen Qin & Hill, 1996). In the past few years, we have obtained several crystals of polyoxomolybdenum-phosphates, such as (NH₃CH₂CH₂—NH₃)_2.5[Mo₅O₁₅(PO₄)(HPO₄)]·7.5H₂O (Lin Zhengzhong et al., 2002) and Na₄-(H₃O)[Na(HPO₄)₂(PO₄)₄Mo₁₈O₄₉].16H₂O (Lin Zhengzhong et al., 2001). We have now synthesized a new crystal of (NH₃CH₂CH₂—NH₃)₂[Mo₅O₁₅(HPO₄)₂].

As shown in Fig. 1, the crystal structure comprises two ethylenediammonium and one [Mo₅O₁₅(HPO₄)₂]⁴⁻ anion. The anion clusters are connected by extensive intermolecular hydrogen bonds involving [H₃N(CH₂)₂NH₃]²⁺. The [Mo₅O₁₅(HPO₄)₂]⁴⁻ cluster anion can be described as a puckered ring of five edge-sharing or corner-sharing distorted [MoO₆] octahedra with two capping [HPO₄] tetrahedra on each side. The five Mo atoms are coplanar. Because of interatomic repulsion, each Mo centre displays typically distorted octahedral coordinations to their O-atom neighbours, with two short molybdyl Mo═O bonds in a cis configuration, two long Mo—O bonds trans to the short bonds, and two Mo—O bonds of intermediate length (Table 1). Bond-valence sum (BVS) calculations shows that the Mo atom exhibits a BVS of +6. In the PO₄ tetrahedron, one of the P—O bonds is longer, which is ascribed to the P—O—H contact. The remaining three O atoms of each PO₄ are shared with five MoO₆ as common corners, thus one of the three O atoms is µ₂-O and the other two are µ₃-O. In the building block, each [Mo₅O₁₅(HPO₄)₂]⁴⁻ cluster is linked to two [H₃N(CH₂)₂NH₃]²⁺. The [Mo₅O₁₅(HPO₄)₂]⁴⁻ clusters are connected by [H₃N(CH₂)₂NH₃]²⁺ through hydrogen bonds to form a layer (Table 2). Within the layer lie many irregular tunnels occupied by ethylenediamine. Here, the addition of the organic template ethylenediamine does not only play a structure-directing role, but also supplies charge-compensating cations, which is not a unique phenomena in the synthesis of the organic–inorganic hydrid organodiamine molybdenum oxides.

S2. Experimental

A mixture of Ti(SO₄)₂ (0.4 g, 1.67 mmol), Na₂MoO₄·2H₂O (0.6 g, 2.48 mmol), Mo (0.05 g, 0.52 mmol), H₂N(CH₂)₂NH₂ (0.2 ml, CR) and H₃PO₄ (0.5 ml, AR) in H₂O (4 ml) was sealed in a 20 ml Teflon-lined stainless steel vessel and heated at 423 K for 4 d under autogeneous pressure. After the reaction was complete, the vessel was cooled slowly to room temperature and green crystals were produced.

S3. Refinement

All H atoms were positioned geometrically and fixed.

Computing details

Data collection: TEXRAY (Molecular Structure Corporation, 1999); cell refinement: TEXRAY; data reduction: TEXSAN (Molecular Structure Corporation, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEX (McArdle, 1995); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. A perspective view of the structure of the crystal. Displacement ellipsoids are drawn at the 50% probability level for non-H atoms. Hydrogen bonds are shown.

Bis(ethylenediammonium) di-µ₅-hydrogenphosphato-penta-µ₂-oxo-decaoxopentamolybdenum

Crystal data

(C2H10N2)2[Mo5O15(HPO4)2]	F(000) = 1992
Mr = 1035.90	Dx = 2.828 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 17.6993 (10) Å	θ = 12–18°
b = 10.0639 (8) Å	µ = 2.75 mm^−1
c = 13.7659 (10) Å	T = 298 K
β = 97.1240 (16)°	Block, green
V = 2433.1 (3) Å^3	0.18 × 0.16 × 0.16 mm
Z = 4

Data collection

Rigaku Weissenberg IP diffractometer	2245 reflections with I > 2σ(I)
Radiation source: rotor target	Rint = 0.000
Graphite monochromator	θmax = 27.5°, θmin = 2.3°
Detector resolution: none pixels mm^-1	h = 0→22
scintillation counter scans	k = 0→13
2782 measured reflections	l = −17→17
2782 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.022	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.045	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0136P)^2] where P = (Fo^2 + 2Fc^2)/3
2782 reflections	(Δ/σ)max = 0.001
173 parameters	Δρmax = 1.33 e Å^−3
0 restraints	Δρmin = −0.93 e Å^−3

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.

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 (Ų)

	x	y	z	Uiso*/Ueq
Mo1	0.604678 (15)	0.60309 (3)	0.25831 (2)	0.01638 (7)
Mo2	0.656380 (14)	0.28068 (3)	0.292770 (19)	0.01433 (7)
Mo3	0.5000	0.08409 (4)	0.2500	0.01370 (9)
P	0.49249 (4)	0.37135 (8)	0.38568 (5)	0.01354 (17)
O1	0.63699 (12)	0.7162 (2)	0.18155 (17)	0.0260 (6)
O2	0.5000	0.6450 (3)	0.2500	0.0199 (7)
O3	0.63934 (12)	0.6600 (2)	0.37244 (17)	0.0255 (5)
O4	0.56630 (11)	0.4097 (2)	0.34348 (15)	0.0174 (5)
O5	0.67249 (11)	0.4550 (2)	0.24293 (15)	0.0186 (5)
O6	0.71425 (12)	0.2853 (2)	0.40266 (15)	0.0222 (5)
O7	0.70707 (12)	0.1923 (2)	0.21807 (16)	0.0238 (5)
O8	0.58954 (11)	0.1411 (2)	0.33264 (14)	0.0158 (5)
O9	0.53646 (13)	−0.0192 (2)	0.16950 (16)	0.0252 (5)
O10	0.44836 (11)	0.2627 (2)	0.32533 (14)	0.0147 (5)
O11	0.44434 (11)	0.4951 (2)	0.39108 (14)	0.0172 (5)
O12	0.51380 (12)	0.3082 (2)	0.48880 (15)	0.0233 (5)
H12A	0.5273	0.3667	0.5286	0.035*
C1	0.7180 (2)	−0.0635 (4)	0.4294 (3)	0.0333 (9)
H1A	0.7245	−0.1553	0.4107	0.040*
H1B	0.6943	−0.0162	0.3722	0.040*
C2	0.6654 (2)	−0.0582 (4)	0.5094 (3)	0.0342 (9)
H2A	0.6222	−0.1159	0.4907	0.041*
H2B	0.6926	−0.0929	0.5695	0.041*
N1	0.79285 (18)	−0.0052 (4)	0.4604 (2)	0.0427 (9)
H1C	0.8212	−0.0098	0.4114	0.064*
H1D	0.8156	−0.0499	0.5117	0.064*
H1E	0.7873	0.0794	0.4769	0.064*
N2	0.63682 (15)	0.0770 (3)	0.52881 (19)	0.0243 (7)
H2C	0.6070	0.0727	0.5763	0.036*
H2D	0.6103	0.1087	0.4746	0.036*
H2E	0.6761	0.1305	0.5472	0.036*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mo1	0.01366 (13)	0.01593 (15)	0.01940 (14)	−0.00173 (11)	0.00147 (11)	0.00100 (12)
Mo2	0.01195 (12)	0.01675 (15)	0.01407 (12)	0.00117 (11)	0.00072 (10)	0.00027 (12)
Mo3	0.01389 (18)	0.0137 (2)	0.01372 (17)	0.000	0.00248 (14)	0.000
P	0.0132 (4)	0.0161 (4)	0.0113 (4)	0.0000 (3)	0.0015 (3)	−0.0024 (3)
O1	0.0215 (11)	0.0243 (15)	0.0323 (13)	−0.0034 (11)	0.0042 (10)	0.0075 (12)
O2	0.0177 (15)	0.0176 (18)	0.0246 (16)	0.000	0.0035 (14)	0.000
O3	0.0230 (12)	0.0242 (14)	0.0288 (12)	−0.0042 (11)	0.0006 (10)	−0.0051 (11)
O4	0.0143 (10)	0.0170 (12)	0.0217 (11)	−0.0009 (10)	0.0050 (9)	−0.0015 (10)
O5	0.0144 (10)	0.0222 (14)	0.0201 (11)	−0.0028 (10)	0.0053 (9)	0.0019 (10)
O6	0.0190 (10)	0.0261 (14)	0.0200 (11)	0.0004 (11)	−0.0030 (9)	0.0010 (11)
O7	0.0178 (10)	0.0307 (15)	0.0234 (11)	0.0036 (11)	0.0045 (9)	−0.0052 (11)
O8	0.0132 (10)	0.0197 (13)	0.0137 (10)	0.0018 (9)	−0.0014 (9)	0.0029 (9)
O9	0.0300 (12)	0.0206 (13)	0.0265 (13)	0.0044 (11)	0.0097 (11)	−0.0053 (11)
O10	0.0142 (10)	0.0155 (12)	0.0144 (10)	0.0001 (9)	0.0020 (9)	−0.0031 (9)
O11	0.0154 (10)	0.0192 (13)	0.0170 (10)	0.0026 (9)	0.0022 (8)	−0.0040 (10)
O12	0.0344 (13)	0.0220 (14)	0.0122 (10)	0.0002 (11)	−0.0022 (10)	−0.0022 (10)
C1	0.034 (2)	0.025 (2)	0.043 (2)	0.0092 (18)	0.0126 (18)	0.0041 (18)
C2	0.034 (2)	0.027 (2)	0.044 (2)	0.0034 (18)	0.0149 (18)	0.0140 (19)
N1	0.046 (2)	0.042 (2)	0.043 (2)	0.0003 (18)	0.0203 (17)	−0.0031 (18)
N2	0.0236 (14)	0.0327 (19)	0.0176 (13)	−0.0002 (14)	0.0063 (12)	0.0021 (13)

Geometric parameters (Å, º)

Mo1—O1	1.699 (2)	P—O4	1.543 (2)
Mo1—O3	1.713 (2)	P—O12	1.559 (2)
Mo1—O2	1.8898 (8)	O2—Mo1^i	1.8898 (8)
Mo1—O5	1.942 (2)	O10—Mo2^i	2.3162 (19)
Mo1—O11^i	2.392 (2)	O11—Mo1^i	2.392 (2)
Mo1—O4	2.413 (2)	O12—H12A	0.8200
Mo2—O7	1.698 (2)	C1—N1	1.462 (5)
Mo2—O6	1.719 (2)	C1—C2	1.529 (5)
Mo2—O5	1.918 (2)	C1—H1A	0.9700
Mo2—O8	1.958 (2)	C1—H1B	0.9700
Mo2—O4	2.234 (2)	C2—N2	1.488 (4)
Mo2—O10^i	2.3162 (19)	C2—H2A	0.9700
Mo3—O9^i	1.704 (2)	C2—H2B	0.9700
Mo3—O9	1.704 (2)	N1—H1C	0.8900
Mo3—O8	1.920 (2)	N1—H1D	0.8900
Mo3—O8^i	1.9204 (19)	N1—H1E	0.8900
Mo3—O10	2.319 (2)	N2—H2C	0.8900
Mo3—O10^i	2.319 (2)	N2—H2D	0.8900
P—O11	1.516 (2)	N2—H2E	0.8900
P—O10	1.528 (2)
O1—Mo1—O3	103.68 (12)	O8^i—Mo3—O10^i	81.11 (8)
O1—Mo1—O2	102.47 (10)	O10—Mo3—O10^i	78.34 (10)
O3—Mo1—O2	102.57 (9)	O11—P—O10	111.21 (12)
O1—Mo1—O5	100.72 (10)	O11—P—O4	108.67 (13)
O3—Mo1—O5	101.59 (10)	O10—P—O4	111.95 (11)
O2—Mo1—O5	141.21 (12)	O11—P—O12	111.38 (12)
O1—Mo1—O11^i	83.33 (9)	O10—P—O12	104.65 (12)
O3—Mo1—O11^i	172.36 (10)	O4—P—O12	108.93 (12)
O2—Mo1—O11^i	78.53 (7)	Mo1^i—O2—Mo1	154.20 (19)
O5—Mo1—O11^i	73.78 (8)	P—O4—Mo2	129.97 (13)
O1—Mo1—O4	168.22 (10)	P—O4—Mo1	133.41 (13)
O3—Mo1—O4	85.09 (10)	Mo2—O4—Mo1	93.56 (7)
O2—Mo1—O4	82.90 (10)	Mo2—O5—Mo1	122.81 (10)
O5—Mo1—O4	69.44 (8)	Mo3—O8—Mo2	122.09 (10)
O11^i—Mo1—O4	87.55 (7)	P—O10—Mo2^i	129.54 (13)
O7—Mo2—O6	104.20 (10)	P—O10—Mo3	126.48 (11)
O7—Mo2—O5	98.58 (10)	Mo2^i—O10—Mo3	94.13 (7)
O6—Mo2—O5	101.02 (10)	P—O11—Mo1^i	118.51 (11)
O7—Mo2—O8	100.21 (10)	P—O12—H12A	109.5
O6—Mo2—O8	95.03 (9)	N1—C1—C2	112.7 (3)
O5—Mo2—O8	151.42 (9)	N1—C1—H1A	109.0
O7—Mo2—O4	160.90 (9)	C2—C1—H1A	109.0
O6—Mo2—O4	94.56 (9)	N1—C1—H1B	109.0
O5—Mo2—O4	73.96 (8)	C2—C1—H1B	109.0
O8—Mo2—O4	81.37 (8)	H1A—C1—H1B	107.8
O7—Mo2—O10^i	88.35 (9)	N2—C2—C1	114.4 (3)
O6—Mo2—O10^i	163.22 (9)	N2—C2—H2A	108.7
O5—Mo2—O10^i	87.81 (8)	C1—C2—H2A	108.7
O8—Mo2—O10^i	71.46 (8)	N2—C2—H2B	108.7
O4—Mo2—O10^i	74.01 (7)	C1—C2—H2B	108.7
O9^i—Mo3—O9	104.79 (16)	H2A—C2—H2B	107.6
O9^i—Mo3—O8	98.54 (10)	C1—N1—H1C	109.5
O9—Mo3—O8	102.50 (10)	C1—N1—H1D	109.5
O9^i—Mo3—O8^i	102.50 (10)	H1C—N1—H1D	109.5
O9—Mo3—O8^i	98.54 (10)	C1—N1—H1E	109.5
O8—Mo3—O8^i	145.22 (14)	H1C—N1—H1E	109.5
O9^i—Mo3—O10	88.86 (10)	H1D—N1—H1E	109.5
O9—Mo3—O10	165.02 (10)	C2—N2—H2C	109.5
O8—Mo3—O10	81.11 (8)	C2—N2—H2D	109.5
O8^i—Mo3—O10	72.01 (8)	H2C—N2—H2D	109.5
O9^i—Mo3—O10^i	165.02 (10)	C2—N2—H2E	109.5
O9—Mo3—O10^i	88.86 (10)	H2C—N2—H2E	109.5
O8—Mo3—O10^i	72.01 (8)	H2D—N2—H2E	109.5

Symmetry code: (i) −x+1, y, −z+1/2.