Triammonium hexa­hydroxidoocta­deca­oxidohexa­molybdogallate(III) hepta­hydrate

Mensinger, Z.L.; Zakharov, L.N.; Johnson, D.W.

doi:10.1107/S1600536807068067

inorganic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Pages i8-i9

doi:10.1107/S1600536807068067

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Triammonium hexahydroxidooctadecaoxidohexamolybdogallate(III) heptahydrate

Zachary L. Mensinger,^a Lev N. Zakharov ^a and Darren W. Johnson ^a ^*

^aOregon Nanoscience and Microtechnologies Institute (ONAMI), and Department of Chemistry, 1253 University of Oregon, Eugene, OR 97403-1253, USA
^*Correspondence e-mail: dwj@uoregon.edu

(Received 1 November 2007; accepted 21 December 2007; online 9 January 2008)

The title compound, (NH₄)₃[GaMo₆(OH)₆O₁₈]·7H₂O, contains two centrosymmetric GaMo₆ B-type Anderson cluster units consisting of central GaO₆ octahedra surrounded by a hexagonal assembly of MoO₆ edge-sharing octahedra. Like other B-type Anderson clusters, where the central Mo atom is substituted with a di- or trivalent metal ion, the central six μ₃-oxido bridges are protonated. The average Ga—O bond length is 1.97 (1) Å, whereas the average Mo—O distances are 2.29 (2), 1.94 (1) and 1.709 (5) Å, respectively, for Mo—(μ₃-OH), Mo—(μ₂-O) and Mo=O bonds. In the crystal structure, the Ga(μ₃-OH)₆Mo₆O₁₈³⁻ polyanionic clusters are surrounded by NH₄⁺ cations and solvent water molecules, forming an extended network of hydrogen bonds.

Related literature

The gallium-substituted B-type Anderson cluster has been observed previously in solution and the solid state (Rollins & Earley, 1959 ; Kitazumi et al., 2003 ), but crystal structures have not been reported. Anderson–Evans clusters are well known and many papers dealing with their preparation have been published (Anderson, 1937 ; Lorenzo-Luis & Gili, 2000 ; Lee et al., 2001 , and references therein). A similar planar core of seven metals is observed in the recently reported structure of [Ga₁₃(μ₃-OH)₆(μ₂-OH)₁₈(H₂O)₂₄](NO₃)₁₅ (Rather et al., 2005 ). Research into this structure led to isolation of the title compound.

Experimental

Crystal data

(NH₄)₃[GaMo₆(OH)₆O₁₈]·7H₂O
M_r = 1215.65
Monoclinic, P 2₁ /c
a = 22.7642 (15) Å
b = 10.9651 (7) Å
c = 11.7599 (8) Å
β = 100.2120 (10)°
V = 2888.9 (3) Å³
Z = 4
Mo Kα radiation
μ = 3.56 mm⁻¹
T = 173 (2) K
0.38 × 0.20 × 0.03 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1995 ) T_min = 0.345, T_max = 0.901
15163 measured reflections
6225 independent reflections
4471 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.110
S = 1.17
6225 reflections
397 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.02 e Å⁻³
Δρ_min = −1.10 e Å⁻³

Table 1
Selected bond lengths (Å)

Ga1—O3	1.953 (3)
Ga1—O1	1.954 (4)
Ga1—O2	1.972 (3)
Ga2—O15	1.968 (3)
Ga2—O13	1.969 (3)
Ga2—O14	1.978 (3)
Mo1—O7	1.703 (4)
Mo1—O8	1.711 (4)
Mo1—O5	1.918 (4)
Mo1—O4	1.939 (4)
Mo1—O1	2.293 (4)
Mo1—O2	2.307 (4)
Mo2—O9	1.704 (4)
Mo2—O10	1.714 (4)
Mo2—O6	1.943 (4)
Mo2—O5	1.948 (4)
Mo2—O3	2.287 (4)
Mo2—O2	2.300 (3)
Mo3—O12	1.711 (4)
Mo3—O11	1.715 (4)
Mo3—O4ⁱ	1.918 (4)
Mo3—O6	1.949 (4)
Mo3—O3	2.252 (4)
Mo3—O1ⁱ	2.286 (4)
Mo4—O19	1.705 (4)
Mo4—O20	1.713 (4)
Mo4—O17	1.939 (3)
Mo4—O16	1.948 (3)
Mo4—O13	2.286 (3)
Mo4—O14	2.324 (3)
Mo5—O21	1.702 (4)
Mo5—O22	1.708 (3)
Mo5—O17	1.932 (4)
Mo5—O18	1.956 (3)
Mo5—O15	2.285 (3)
Mo5—O14	2.284 (3)
Mo6—O23	1.712 (3)
Mo6—O24	1.719 (4)
Mo6—O16ⁱⁱ	1.917 (4)
Mo6—O18	1.944 (4)
Mo6—O15	2.273 (3)
Mo6—O13ⁱⁱ	2.290 (3)
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x, -y+1, -z+1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O10ⁱⁱⁱ	0.84 (2)	2.00 (3)	2.822 (5)	166 (6)
O13—H13⋯O23^iv	0.84 (2)	1.86 (2)	2.691 (5)	173 (7)
O14—H14⋯O22^v	0.84 (2)	1.98 (2)	2.808 (5)	168 (6)
O3—H3⋯O4S^vi	0.85 (2)	1.76 (3)	2.602 (5)	169 (8)
O1—H1⋯O11^vii	0.85 (2)	1.87 (4)	2.682 (5)	159 (9)
O15—H15⋯O1S	0.83 (2)	1.87 (3)	2.645 (5)	155 (7)
Symmetry codes: (iii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iv) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (vi) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (vii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Table 3
Short contact geometry (Å)

N1S⋯O24ⁱⁱ	2.911 (7)
N1S⋯O6S^vi	2.784 (8)
N2S⋯O16	2.779 (6)
N2S⋯O21ⁱⁱⁱ	2.979 (6)
N2S⋯O24^vii	2.901 (6)
N2S⋯O3S^viii	2.899 (7)
N2S⋯O7S	2.898 (7)
N3S⋯O5ⁱ	2.775 (6)
N3S⋯O12^xii	2.907 (7)
N3S⋯O5S	2.801 (8)
N3S⋯O7Sⁱ	3.030 (8)
O1S⋯O18^x	2.794 (5)
O1S⋯O18ⁱⁱ	2.905 (6)
O2S⋯O4^xi	2.718 (5)
O2S⋯O12	2.797 (6)
O2S⋯O3S^xii	2.830 (7)
O2S⋯O6S^ix	2.704 (7)
O3S⋯O9	3.016 (6)
O3S⋯O19	3.034 (7)
O3S⋯O5S^iv	2.917 (8)
O4S⋯O3^xiii	2.602 (5)
O4S⋯O6	2.773 (6)
O4S⋯O6^xii	2.934 (6)
O5S⋯O8	2.782 (6)
O5S⋯O16ⁱ	3.083 (6)
O6S⋯O20	2.776 (6)
O6S⋯O7S	2.769 (7)
O7S⋯O7^xiv	2.973 (6)
Symmetry codes (i): $[x, -y+{1\over 2}, z-{1\over 2}]$ ; (ii): $[-x, y-{1\over 2}, -z+{1\over 2}]$ ; (iii): $[x, -y+{3\over 2}, z+{1\over 2}]$ ; (iv): $[ x, -y+{1\over 2}, z+{1\over 2}]$ ; (v): $[-x+1, y+{1\over 2}, -z+{3\over 2}]$ ; (vi): $[x, -y+{3\over 2}, z-{1\over 2}]$ ; (vii): $[-x, y-{1\over 2}, -z+{3\over 2}]$ ; (viii): $[x, -y+{1\over 2}, z+{1\over 2}]$ ; (ix): 1-x, 1-y, 1-z; (x): $[x, -y+{3\over 2}, z-{1\over 2}]$ ; (xi): $[-x+1, y-{1\over 2}, -z+{1\over 2}]$ ; (xii): -x+1, -y, -z+1; (xiii): $[x, -y+{1\over 2}, z-{1\over 2}]$ ; (xiv): $[x, -y+{3\over 2}, z+{1\over 2}]$

Data collection: SMART (Bruker, 2000 ); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807068067/wm2161sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536807068067/wm2161Isup2.hkl

checkCIF report

Comment top

Compounds containing Anderson-type clusters have been explored for applications as structural aesthetics, biologically active compounds, and catalysts (Rollins & Earley, 1959; Lorenzo-Luis & Gili, 2000). They have also been shown to act as building blocks for larger molecular assemblies, where they can be linked to form extended networks with pores and cavities (Lorenzo-Luis & Gili, 2000). The majority of Anderson clusters are based on Mo₇O₂₄^6- or W₇O₂₄^6- frameworks, and many structures have been synthesized with substitution of the central octahedron or variable bridging ligands (Lorenzo-Luis & Gili, 2000). Due to the similarity of the structure of the Mo₇O₂₄^6- complex to the inner planar core of our recently reported flat-Ga₁₃ metal-hydroxo cluster [Ga₁₃(µ₃-OH)₆(µ₂-OH)₁₈(H₂O)₂₄](NO₃)₁₅ (Rather et al., 2005), it was hypothesized that a mixed-metal Mo₇Ga₆ compound could be obtained by reaction of (NH₄)₆Mo₇O₂₄ with six or more equivalents of Ga(NO₃)₃. Setting up the reaction in a similar manner to the synthesis of flat-Ga₁₃ (dissolving starting materials in a MeOH:H₂O mixture and adding N-nitroso-di-n-butylamine), single crystals of the gallium-substituted B-type Anderson cluster, (NH₄)₃[Ga(µ₃-OH)₆Mo₆O₁₈]^.7H₂O, (I), were isolated and structurally characterized by X-ray crystallography.

Anderson-type polyanions were first described by Anderson (1937). The planar structure consisting of seven metals observed in that compound is also observed in the structure of (I), with average Ga—O bond lengths of 1.97 (1) Å. The average Mo—O distances are 2.29 (2), 1.94 (1) and 1.710 (5) Å, respectively, for Mo-(µ₃-OH), Mo-(µ₂-O) and Mo=O. There are six µ₃-OH bridges, six µ₂-oxo bridges, and twelve terminal oxo ligands for each of the two independent cluster anions (Figure 1).

Extensive literature reports have covered the different structural variants and chemistry of hexamolybdoaluminate(III) polyanions (Lorenzo-Luis & Gili, 2000). The synthesis reported herein also represents an alternative preparation of the Al-substituted structure, with no acid addition required (as is usually the case). Synthesis by this method also represents a far more benign method than that previously reported. The Ga-substituted B-type Anderson compound had been synthesized previously by adding a solution of Ga metal in concentrated HNO₃ to a solution of MoO₃ in aqueous NaOH. The mixture was heated overnight and rinsed several times with acetone, and vacuum dried overnight, affording product as the sodium salt. However, a crystal structure determination of the title compound has not been reported previously (Rollins & Earley, 1959; Kitazumi et al., 2003).

Related literature top

The gallium substituted B-type Anderson cluster has been observed previously in solution and the solid state (Rollins & Earley, 1959; Kitazumi et al., 2003), but the crystal structure has not been reported. Anderson–Evans clusters are well known and many papers dealing with their preparation have been published (Anderson, 1937; Lorenzo-Luis & Gili, 2000; Lee et al., 2001, and references therein). A similar planar core of seven metals is observed in the recently reported structure of [Ga₁₃(µ₃-OH)₆(µ₂-OH)₁₈(H₂O)₂₄](NO₃)₁₅ (Rather et al., 2005) Inquiries into this structure led to isolation of the title compound.

Experimental top

Commercial products (NH₄)₆Mo₇O₂₄ (Baker and Adamson) and Ga(NO₃)₃ (Strem) were used to obtain the title compound, (I). (NH₄)₆Mo₇O₂₄ (0.25 g, 0.2 mmol) and Ga(NO₃)₃ (0.7 g, 1.92 mmol) were dissolved in a 1:1 H₂O/MeOH mixture (10 ml) in a 20 ml scintillation vial. The mixture was heated slightly, with some cloudiness remaining in the mixture. N-nitroso-di-n-butylamine (0.45 g, 0.5 ml, 2.8 mmol) was added, and was not initially miscible. Additional MeOH (~2 ml) brought most into solution, and the mixture was then filtered. The remaining solution was evaporated, and after 9 d clear, colorless crystals with block-like habit had formed around the outside edge of the vial. The crystals were isolated in 90% crude yield. Fewer equivalents of Ga(NO₃)₃ (relative to (NH₄)₆Mo₇O₂₄) and no organic additive (H₂O as solvent only) have also been used successfully to produce crystals of (I).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL (Bruker, 2000; molecular graphics: SHELXTL (Bruker, 2000; software used to prepare material for publication: SHELXTL (Bruker, 2000.

Figures top

	Fig. 1. One of the two symmetrically independent Ga(µ₃-OH)₆Mo₆O₁₈^-3 anions in the crystal structure of (I). Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code (i): 1 - x, 1 - y, 1 - z].
	Fig. 2. The second polyanionic cluster, displayed at the same probability level than in Fig. 1. [Symmetry code: (ii) -x, 1 - y, 1 - z.]

Triammonium hexahydroxidooctadecaoxidohexamolybdogallate(III) heptahydrate top

Crystal data top

(NH₄)₃[GaMo₆(OH)₆O₁₈]·7H₂O	F(000) = 2336
M_r = 1215.65	D_x = 2.795 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4958 reflections
a = 22.7642 (15) Å	θ = 2.6–27.0°
b = 10.9651 (7) Å	µ = 3.56 mm⁻¹
c = 11.7599 (8) Å	T = 173 K
β = 100.212 (1)°	Plate, colorless
V = 2888.9 (3) Å³	0.38 × 0.20 × 0.03 mm
Z = 4

Data collection top

Bruker SMART APEX CCD diffractometer	6225 independent reflections
Radiation source: fine-focus sealed tube	4471 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
ϕ and ω scans	θ_max = 27.0°, θ_min = 0.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1995)	h = −29→28
T_min = 0.345, T_max = 0.901	k = −13→12
15163 measured reflections	l = −15→8

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.110	H atoms treated by a mixture of independent and constrained refinement
S = 1.17	w = 1/[σ²(F_o²) + (0.0387P)² + 12.6663P] where P = (F_o² + 2F_c²)/3
6225 reflections	(Δ/σ)_max = 0.001
397 parameters	Δρ_max = 1.02 e Å⁻³
6 restraints	Δρ_min = −1.10 e Å⁻³

Crystal data top

(NH₄)₃[GaMo₆(OH)₆O₁₈]·7H₂O	V = 2888.9 (3) Å³
M_r = 1215.65	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 22.7642 (15) Å	µ = 3.56 mm⁻¹
b = 10.9651 (7) Å	T = 173 K
c = 11.7599 (8) Å	0.38 × 0.20 × 0.03 mm
β = 100.212 (1)°

Data collection top

Bruker SMART APEX CCD diffractometer	6225 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1995)	4471 reflections with I > 2σ(I)
T_min = 0.345, T_max = 0.901	R_int = 0.020
15163 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	6 restraints
wR(F²) = 0.110	H atoms treated by a mixture of independent and constrained refinement
S = 1.17	w = 1/[σ²(F_o²) + (0.0387P)² + 12.6663P] where P = (F_o² + 2F_c²)/3
6225 reflections	Δρ_max = 1.02 e Å⁻³
397 parameters	Δρ_min = −1.10 e Å⁻³

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Ga1	0.5000	0.5000	0.5000	0.01123 (17)
Ga2	0.0000	0.5000	0.5000	0.00902 (16)
Mo1	0.35141 (2)	0.51841 (4)	0.45196 (4)	0.01479 (12)
Mo2	0.41872 (2)	0.26668 (4)	0.56993 (4)	0.01458 (12)
Mo3	0.56707 (2)	0.25263 (4)	0.62097 (4)	0.01402 (12)
Mo4	0.149068 (19)	0.48479 (4)	0.54667 (4)	0.01355 (12)
Mo5	0.079304 (19)	0.73509 (4)	0.42939 (4)	0.01232 (11)
Mo6	−0.069381 (19)	0.74690 (4)	0.37855 (4)	0.01178 (11)
O1	0.43873 (16)	0.6143 (3)	0.5303 (3)	0.0141 (7)
O2	0.43179 (15)	0.4003 (3)	0.4257 (3)	0.0129 (7)
O3	0.49702 (16)	0.3947 (3)	0.6328 (3)	0.0134 (7)
O4	0.37835 (15)	0.6157 (3)	0.3335 (3)	0.0158 (8)
O5	0.37155 (16)	0.4126 (3)	0.5830 (3)	0.0170 (8)
O6	0.49123 (16)	0.1923 (3)	0.5366 (3)	0.0156 (7)
O7	0.31028 (18)	0.6221 (4)	0.5119 (3)	0.0246 (9)
O8	0.30144 (17)	0.4316 (4)	0.3604 (3)	0.0237 (9)
O9	0.36921 (17)	0.1825 (4)	0.4758 (3)	0.0231 (9)
O10	0.41851 (18)	0.2072 (4)	0.7046 (3)	0.0236 (9)
O11	0.56491 (18)	0.1958 (4)	0.7561 (3)	0.0226 (9)
O12	0.61044 (18)	0.1536 (4)	0.5596 (3)	0.0238 (9)
O13	0.06252 (15)	0.3866 (3)	0.4699 (3)	0.0102 (7)
O14	0.06773 (16)	0.6024 (3)	0.5736 (3)	0.0116 (7)
O15	0.00201 (15)	0.6053 (3)	0.3652 (3)	0.0110 (7)
O16	0.12375 (16)	0.3851 (3)	0.6664 (3)	0.0162 (8)
O17	0.12752 (16)	0.5927 (3)	0.4152 (3)	0.0151 (7)
O18	0.00595 (15)	0.8078 (3)	0.4637 (3)	0.0136 (7)
O19	0.19123 (17)	0.3843 (4)	0.4850 (3)	0.0226 (9)
O20	0.19832 (17)	0.5724 (4)	0.6393 (3)	0.0234 (9)
O21	0.12650 (17)	0.8245 (4)	0.5225 (3)	0.0211 (8)
O22	0.07868 (17)	0.7965 (3)	0.2957 (3)	0.0189 (8)
O23	−0.06660 (17)	0.8033 (3)	0.2438 (3)	0.0193 (8)
O24	−0.11382 (17)	0.8471 (3)	0.4373 (3)	0.0202 (8)
N1S	0.1801 (2)	0.5087 (5)	0.2359 (5)	0.0322 (12)
N2S	0.1667 (2)	0.4712 (5)	0.8877 (4)	0.0248 (11)
N3S	0.3235 (3)	0.0134 (5)	0.2727 (5)	0.0359 (14)
O1S	−0.0158 (3)	0.5433 (4)	0.1444 (4)	0.0396 (13)
O2S	0.6662 (2)	0.0517 (4)	0.3883 (4)	0.0323 (10)
O3S	0.2536 (2)	0.1465 (5)	0.5634 (4)	0.0427 (12)
O4S	0.4997 (3)	0.0459 (5)	0.3479 (4)	0.063 (2)
O5S	0.2479 (2)	0.2149 (5)	0.2729 (5)	0.0456 (13)
O6S	0.2500 (2)	0.8016 (5)	0.6761 (4)	0.0430 (12)
O7S	0.2491 (2)	0.6706 (5)	0.8771 (4)	0.0446 (13)
H1	0.428 (4)	0.643 (8)	0.591 (5)	0.07 (3)*
H2	0.434 (3)	0.373 (6)	0.360 (3)	0.032 (19)*
H3	0.493 (4)	0.416 (8)	0.701 (3)	0.06 (3)*
H13	0.062 (3)	0.365 (6)	0.401 (2)	0.027 (18)*
H14	0.065 (3)	0.634 (6)	0.638 (3)	0.027 (18)*
H15	0.003 (3)	0.568 (5)	0.304 (3)	0.031 (19)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ga1	0.0137 (4)	0.0111 (4)	0.0095 (4)	0.0004 (3)	0.0037 (3)	0.0004 (3)
Ga2	0.0122 (4)	0.0076 (4)	0.0078 (4)	0.0004 (3)	0.0033 (3)	0.0009 (3)
Mo1	0.0136 (2)	0.0175 (3)	0.0137 (2)	0.00039 (17)	0.00386 (17)	0.00109 (18)
Mo2	0.0179 (2)	0.0135 (2)	0.0132 (2)	−0.00216 (17)	0.00494 (17)	0.00214 (17)
Mo3	0.0182 (2)	0.0129 (2)	0.0114 (2)	0.00243 (17)	0.00382 (17)	0.00248 (17)
Mo4	0.0130 (2)	0.0149 (2)	0.0130 (2)	0.00026 (16)	0.00294 (17)	0.00230 (17)
Mo5	0.0163 (2)	0.0106 (2)	0.0105 (2)	−0.00180 (16)	0.00373 (17)	0.00182 (16)
Mo6	0.0164 (2)	0.0102 (2)	0.0094 (2)	0.00274 (16)	0.00408 (16)	0.00240 (16)
O1	0.0144 (19)	0.018 (2)	0.0103 (18)	0.0022 (14)	0.0039 (14)	0.0003 (15)
O2	0.0146 (18)	0.0135 (18)	0.0107 (18)	−0.0024 (14)	0.0026 (14)	0.0000 (15)
O3	0.0168 (19)	0.0130 (18)	0.0111 (18)	0.0005 (14)	0.0045 (14)	0.0018 (15)
O4	0.0149 (18)	0.020 (2)	0.0115 (17)	0.0002 (15)	−0.0002 (14)	0.0015 (15)
O5	0.0157 (19)	0.019 (2)	0.0188 (19)	−0.0008 (15)	0.0090 (15)	0.0015 (15)
O6	0.020 (2)	0.0124 (18)	0.0147 (18)	0.0008 (14)	0.0045 (14)	−0.0014 (15)
O7	0.024 (2)	0.028 (2)	0.023 (2)	0.0061 (17)	0.0100 (17)	0.0019 (18)
O8	0.018 (2)	0.026 (2)	0.027 (2)	−0.0047 (16)	0.0038 (16)	0.0017 (18)
O9	0.024 (2)	0.022 (2)	0.023 (2)	−0.0078 (16)	0.0037 (16)	−0.0005 (17)
O10	0.026 (2)	0.023 (2)	0.024 (2)	−0.0022 (17)	0.0092 (17)	0.0061 (17)
O11	0.028 (2)	0.022 (2)	0.0181 (19)	0.0011 (17)	0.0039 (16)	0.0082 (17)
O12	0.029 (2)	0.023 (2)	0.020 (2)	0.0043 (17)	0.0072 (17)	−0.0003 (17)
O13	0.0146 (18)	0.0108 (17)	0.0059 (16)	0.0017 (13)	0.0037 (13)	−0.0002 (14)
O14	0.0200 (19)	0.0109 (18)	0.0046 (16)	−0.0005 (14)	0.0037 (14)	−0.0001 (14)
O15	0.0197 (19)	0.0091 (17)	0.0050 (16)	0.0009 (14)	0.0042 (13)	−0.0008 (14)
O16	0.0175 (19)	0.0160 (19)	0.0148 (18)	0.0015 (15)	0.0025 (14)	0.0037 (15)
O17	0.0184 (19)	0.0167 (19)	0.0113 (17)	0.0001 (14)	0.0058 (14)	0.0023 (14)
O18	0.0173 (19)	0.0097 (17)	0.0140 (17)	−0.0011 (14)	0.0037 (14)	−0.0001 (14)
O19	0.021 (2)	0.025 (2)	0.025 (2)	0.0058 (16)	0.0134 (16)	0.0031 (17)
O20	0.022 (2)	0.027 (2)	0.019 (2)	−0.0062 (17)	−0.0009 (16)	0.0002 (17)
O21	0.022 (2)	0.020 (2)	0.021 (2)	−0.0041 (16)	0.0043 (16)	0.0008 (16)
O22	0.029 (2)	0.018 (2)	0.0110 (18)	0.0026 (16)	0.0067 (15)	0.0024 (15)
O23	0.028 (2)	0.019 (2)	0.0114 (18)	0.0017 (16)	0.0044 (15)	0.0040 (15)
O24	0.023 (2)	0.018 (2)	0.022 (2)	0.0041 (16)	0.0089 (16)	−0.0009 (16)
N1S	0.031 (3)	0.041 (3)	0.025 (3)	0.000 (2)	0.005 (2)	−0.007 (2)
N2S	0.027 (3)	0.029 (3)	0.021 (2)	0.001 (2)	0.011 (2)	−0.005 (2)
N3S	0.036 (3)	0.042 (3)	0.032 (3)	0.006 (3)	0.014 (3)	0.016 (3)
O1S	0.086 (4)	0.019 (2)	0.018 (2)	0.004 (2)	0.022 (2)	−0.0010 (18)
O2S	0.034 (3)	0.041 (3)	0.021 (2)	0.005 (2)	0.0056 (18)	−0.001 (2)
O3S	0.032 (3)	0.051 (3)	0.042 (3)	−0.005 (2)	−0.001 (2)	−0.002 (2)
O4S	0.159 (7)	0.021 (3)	0.013 (2)	0.008 (3)	0.021 (3)	0.0012 (19)
O5S	0.038 (3)	0.041 (3)	0.057 (3)	−0.010 (2)	0.008 (2)	−0.014 (3)
O6S	0.044 (3)	0.040 (3)	0.044 (3)	−0.012 (2)	0.007 (2)	−0.005 (2)
O7S	0.053 (3)	0.038 (3)	0.038 (3)	−0.011 (2)	−0.004 (2)	−0.003 (2)

Geometric parameters (Å, º) top

Ga1—O3ⁱ	1.953 (3)	Mo3—O6	1.949 (4)
Ga1—O3	1.953 (3)	Mo3—O3	2.252 (4)
Ga1—O1ⁱ	1.954 (4)	Mo3—O1ⁱ	2.286 (4)
Ga1—O1	1.954 (4)	Mo4—O19	1.705 (4)
Ga1—O2ⁱ	1.972 (3)	Mo4—O20	1.713 (4)
Ga1—O2	1.972 (3)	Mo4—O17	1.939 (3)
Ga2—O15ⁱⁱ	1.968 (3)	Mo4—O16	1.948 (3)
Ga2—O15	1.968 (3)	Mo4—O13	2.286 (3)
Ga2—O13ⁱⁱ	1.969 (3)	Mo4—O14	2.324 (3)
Ga2—O13	1.969 (3)	Mo5—O21	1.702 (4)
Ga2—O14	1.978 (3)	Mo5—O22	1.708 (3)
Ga2—O14ⁱⁱ	1.978 (3)	Mo5—O17	1.932 (4)
Mo1—O7	1.703 (4)	Mo5—O18	1.956 (3)
Mo1—O8	1.711 (4)	Mo5—O15	2.285 (3)
Mo1—O5	1.918 (4)	Mo5—O14	2.284 (3)
Mo1—O4	1.939 (4)	Mo6—O23	1.712 (3)
Mo1—O1	2.293 (4)	Mo6—O24	1.719 (4)
Mo1—O2	2.307 (4)	Mo6—O16ⁱⁱ	1.917 (4)
Mo2—O9	1.704 (4)	Mo6—O18	1.944 (4)
Mo2—O10	1.714 (4)	Mo6—O15	2.273 (3)
Mo2—O6	1.943 (4)	Mo6—O13ⁱⁱ	2.290 (3)
Mo2—O5	1.948 (4)	O1—H1	0.85 (2)
Mo2—O3	2.287 (4)	O2—H2	0.84 (2)
Mo2—O2	2.300 (3)	O3—H3	0.85 (2)
Mo3—O12	1.711 (4)	O13—H13	0.84 (2)
Mo3—O11	1.715 (4)	O14—H14	0.84 (2)
Mo3—O4ⁱ	1.918 (4)	O15—H15	0.83 (2)

O3ⁱ—Ga1—O3	180.0	O19—Mo4—O13	92.19 (16)
O3ⁱ—Ga1—O1ⁱ	96.11 (15)	O20—Mo4—O13	159.49 (16)
O3—Ga1—O1ⁱ	83.89 (15)	O17—Mo4—O13	83.94 (14)
O3ⁱ—Ga1—O1	83.89 (15)	O16—Mo4—O13	71.12 (13)
O3—Ga1—O1	96.11 (15)	O19—Mo4—O14	159.82 (16)
O1ⁱ—Ga1—O1	180.00 (14)	O20—Mo4—O14	92.85 (16)
O3ⁱ—Ga1—O2ⁱ	83.70 (15)	O17—Mo4—O14	71.01 (13)
O3—Ga1—O2ⁱ	96.30 (15)	O16—Mo4—O14	82.43 (13)
O1ⁱ—Ga1—O2ⁱ	84.55 (15)	O13—Mo4—O14	70.34 (12)
O1—Ga1—O2ⁱ	95.45 (15)	O21—Mo5—O22	105.42 (18)
O3ⁱ—Ga1—O2	96.30 (15)	O21—Mo5—O17	102.56 (17)
O3—Ga1—O2	83.70 (15)	O22—Mo5—O17	98.72 (16)
O1ⁱ—Ga1—O2	95.45 (15)	O21—Mo5—O18	95.58 (17)
O1—Ga1—O2	84.55 (15)	O22—Mo5—O18	99.26 (16)
O2ⁱ—Ga1—O2	179.999 (1)	O17—Mo5—O18	149.97 (15)
O15ⁱⁱ—Ga2—O15	180.0	O21—Mo5—O15	158.85 (15)
O15ⁱⁱ—Ga2—O13ⁱⁱ	96.04 (14)	O22—Mo5—O15	93.52 (16)
O15—Ga2—O13ⁱⁱ	83.96 (14)	O17—Mo5—O15	83.36 (14)
O15ⁱⁱ—Ga2—O13	83.96 (14)	O18—Mo5—O15	71.71 (13)
O15—Ga2—O13	96.04 (14)	O21—Mo5—O14	91.86 (15)
O13ⁱⁱ—Ga2—O13	180.0	O22—Mo5—O14	161.99 (16)
O15ⁱⁱ—Ga2—O14	96.23 (14)	O17—Mo5—O14	72.03 (13)
O15—Ga2—O14	83.77 (14)	O18—Mo5—O14	83.77 (13)
O13ⁱⁱ—Ga2—O14	95.44 (14)	O15—Mo5—O14	70.43 (12)
O13—Ga2—O14	84.56 (14)	O23—Mo6—O24	105.18 (18)
O15ⁱⁱ—Ga2—O14ⁱⁱ	83.77 (14)	O23—Mo6—O16ⁱⁱ	98.37 (17)
O15—Ga2—O14ⁱⁱ	96.23 (14)	O24—Mo6—O16ⁱⁱ	101.31 (17)
O13ⁱⁱ—Ga2—O14ⁱⁱ	84.56 (14)	O23—Mo6—O18	100.29 (17)
O13—Ga2—O14ⁱⁱ	95.45 (14)	O24—Mo6—O18	95.85 (17)
O14—Ga2—O14ⁱⁱ	180.0	O16ⁱⁱ—Mo6—O18	150.31 (15)
O7—Mo1—O8	106.2 (2)	O23—Mo6—O15	92.21 (15)
O7—Mo1—O5	98.15 (17)	O24—Mo6—O15	160.59 (15)
O8—Mo1—O5	101.91 (18)	O16ⁱⁱ—Mo6—O15	84.25 (14)
O7—Mo1—O4	101.41 (17)	O18—Mo6—O15	72.17 (13)
O8—Mo1—O4	96.51 (17)	O23—Mo6—O13ⁱⁱ	160.43 (15)
O5—Mo1—O4	148.11 (15)	O24—Mo6—O13ⁱⁱ	93.42 (15)
O7—Mo1—O1	91.64 (17)	O16ⁱⁱ—Mo6—O13ⁱⁱ	71.55 (13)
O8—Mo1—O1	160.15 (16)	O18—Mo6—O13ⁱⁱ	83.48 (13)
O5—Mo1—O1	83.59 (14)	O15—Mo6—O13ⁱⁱ	70.50 (12)
O4—Mo1—O1	70.98 (13)	Ga1—O1—Mo3ⁱ	102.26 (14)
O7—Mo1—O2	159.64 (17)	Ga1—O1—Mo1	103.21 (16)
O8—Mo1—O2	93.31 (16)	Mo3ⁱ—O1—Mo1	93.09 (13)
O5—Mo1—O2	71.66 (13)	Ga1—O1—H1	135 (6)
O4—Mo1—O2	81.56 (14)	Mo3ⁱ—O1—H1	115 (6)
O1—Mo1—O2	70.09 (13)	Mo1—O1—H1	99 (6)
O9—Mo2—O10	106.50 (19)	Ga1—O2—Mo2	102.79 (14)
O9—Mo2—O6	97.41 (17)	Ga1—O2—Mo1	102.15 (15)
O10—Mo2—O6	99.69 (17)	Mo2—O2—Mo1	92.85 (12)
O9—Mo2—O5	100.70 (18)	Ga1—O2—H2	116 (5)
O10—Mo2—O5	98.51 (17)	Mo2—O2—H2	119 (5)
O6—Mo2—O5	149.42 (15)	Mo1—O2—H2	120 (5)
O9—Mo2—O3	158.51 (16)	Ga1—O3—Mo3	103.53 (15)
O10—Mo2—O3	93.70 (16)	Ga1—O3—Mo2	103.88 (15)
O6—Mo2—O3	71.45 (14)	Mo3—O3—Mo2	94.30 (13)
O5—Mo2—O3	83.06 (14)	Ga1—O3—H3	128 (6)
O9—Mo2—O2	91.34 (16)	Mo3—O3—H3	116 (6)
O10—Mo2—O2	161.06 (17)	Mo2—O3—H3	106 (6)
O6—Mo2—O2	83.87 (14)	Mo3ⁱ—O4—Mo1	119.01 (17)
O5—Mo2—O2	71.34 (14)	Mo1—O5—Mo2	119.36 (18)
O3—Mo2—O2	69.63 (12)	Mo2—O6—Mo3	117.54 (18)
O12—Mo3—O11	105.88 (19)	Ga2—O13—Mo4	103.36 (14)
O12—Mo3—O4ⁱ	101.65 (17)	Ga2—O13—Mo6ⁱⁱ	102.45 (13)
O11—Mo3—O4ⁱ	97.94 (17)	Mo4—O13—Mo6ⁱⁱ	93.37 (12)
O12—Mo3—O6	95.45 (17)	Ga2—O13—H13	117 (4)
O11—Mo3—O6	100.37 (17)	Mo4—O13—H13	113 (4)
O4ⁱ—Mo3—O6	150.41 (15)	Mo6ⁱⁱ—O13—H13	124 (5)
O12—Mo3—O3	158.97 (16)	Ga2—O14—Mo5	102.74 (14)
O11—Mo3—O3	93.27 (16)	Ga2—O14—Mo4	101.74 (14)
O4ⁱ—Mo3—O3	83.83 (14)	Mo5—O14—Mo4	93.04 (12)
O6—Mo3—O3	72.14 (14)	Ga2—O14—H14	117 (4)
O12—Mo3—O1ⁱ	92.00 (16)	Mo5—O14—H14	116 (5)
O11—Mo3—O1ⁱ	160.95 (16)	Mo4—O14—H14	122 (4)
O4ⁱ—Mo3—O1ⁱ	71.47 (14)	Ga2—O15—Mo6	103.08 (14)
O6—Mo3—O1ⁱ	84.08 (14)	Ga2—O15—Mo5	103.06 (14)
O3—Mo3—O1ⁱ	70.29 (13)	Mo6—O15—Mo5	94.02 (13)
O19—Mo4—O20	106.2 (2)	Ga2—O15—H15	115 (5)
O19—Mo4—O17	97.87 (17)	Mo6—O15—H15	121 (5)
O20—Mo4—O17	102.08 (17)	Mo5—O15—H15	117 (5)
O19—Mo4—O16	101.89 (17)	Mo6ⁱⁱ—O16—Mo4	118.93 (18)
O20—Mo4—O16	95.69 (17)	Mo5—O17—Mo4	119.45 (17)
O17—Mo4—O16	148.51 (15)	Mo6—O18—Mo5	117.47 (17)

O3ⁱ—Ga1—O1—Mo3ⁱ	1.23 (15)	O15—Ga2—O13—Mo4	82.62 (15)
O3—Ga1—O1—Mo3ⁱ	−178.77 (15)	O13ⁱⁱ—Ga2—O13—Mo4	64 (8)
O2ⁱ—Ga1—O1—Mo3ⁱ	84.27 (15)	O14—Ga2—O13—Mo4	−0.50 (13)
O2—Ga1—O1—Mo3ⁱ	−95.73 (15)	O14ⁱⁱ—Ga2—O13—Mo4	179.50 (13)
O3ⁱ—Ga1—O1—Mo1	97.41 (16)	O15ⁱⁱ—Ga2—O13—Mo6ⁱⁱ	−0.82 (14)
O3—Ga1—O1—Mo1	−82.59 (16)	O15—Ga2—O13—Mo6ⁱⁱ	179.18 (14)
O2ⁱ—Ga1—O1—Mo1	−179.54 (14)	O14—Ga2—O13—Mo6ⁱⁱ	96.06 (15)
O2—Ga1—O1—Mo1	0.46 (14)	O14ⁱⁱ—Ga2—O13—Mo6ⁱⁱ	−83.94 (15)
O7—Mo1—O1—Ga1	170.39 (18)	O19—Mo4—O13—Ga2	−169.21 (17)
O8—Mo1—O1—Ga1	−35.1 (5)	O20—Mo4—O13—Ga2	36.9 (5)
O5—Mo1—O1—Ga1	72.37 (16)	O17—Mo4—O13—Ga2	−71.52 (15)
O4—Mo1—O1—Ga1	−88.10 (17)	O16—Mo4—O13—Ga2	88.98 (16)
O2—Mo1—O1—Ga1	−0.41 (13)	O14—Mo4—O13—Ga2	0.45 (12)
O7—Mo1—O1—Mo3ⁱ	−86.25 (16)	O19—Mo4—O13—Mo6ⁱⁱ	87.14 (16)
O8—Mo1—O1—Mo3ⁱ	68.3 (5)	O20—Mo4—O13—Mo6ⁱⁱ	−66.7 (5)
O5—Mo1—O1—Mo3ⁱ	175.73 (15)	O17—Mo4—O13—Mo6ⁱⁱ	−175.17 (14)
O4—Mo1—O1—Mo3ⁱ	15.26 (13)	O16—Mo4—O13—Mo6ⁱⁱ	−14.67 (13)
O2—Mo1—O1—Mo3ⁱ	102.96 (14)	O14—Mo4—O13—Mo6ⁱⁱ	−103.20 (13)
O3ⁱ—Ga1—O2—Mo2	−179.47 (14)	O15ⁱⁱ—Ga2—O14—Mo5	179.66 (14)
O3—Ga1—O2—Mo2	0.53 (14)	O15—Ga2—O14—Mo5	−0.34 (14)
O1ⁱ—Ga1—O2—Mo2	83.75 (15)	O13ⁱⁱ—Ga2—O14—Mo5	−83.63 (15)
O1—Ga1—O2—Mo2	−96.25 (15)	O13—Ga2—O14—Mo5	96.37 (15)
O3ⁱ—Ga1—O2—Mo1	−83.67 (15)	O15ⁱⁱ—Ga2—O14—Mo4	83.78 (14)
O3—Ga1—O2—Mo1	96.33 (15)	O15—Ga2—O14—Mo4	−96.22 (14)
O1ⁱ—Ga1—O2—Mo1	179.55 (14)	O13ⁱⁱ—Ga2—O14—Mo4	−179.51 (13)
O1—Ga1—O2—Mo1	−0.45 (14)	O13—Ga2—O14—Mo4	0.49 (13)
O9—Mo2—O2—Ga1	−170.25 (18)	O14ⁱⁱ—Ga2—O14—Mo4	130 (9)
O10—Mo2—O2—Ga1	29.1 (6)	O21—Mo5—O14—Ga2	168.49 (18)
O6—Mo2—O2—Ga1	−72.94 (16)	O22—Mo5—O14—Ga2	−27.7 (6)
O5—Mo2—O2—Ga1	88.91 (17)	O17—Mo5—O14—Ga2	−88.91 (17)
O3—Mo2—O2—Ga1	−0.48 (13)	O18—Mo5—O14—Ga2	73.08 (16)
O9—Mo2—O2—Mo1	86.60 (17)	O15—Mo5—O14—Ga2	0.31 (12)
O10—Mo2—O2—Mo1	−74.1 (5)	O21—Mo5—O14—Mo4	−88.75 (16)
O6—Mo2—O2—Mo1	−176.08 (14)	O22—Mo5—O14—Mo4	75.0 (5)
O5—Mo2—O2—Mo1	−14.24 (13)	O17—Mo5—O14—Mo4	13.85 (13)
O3—Mo2—O2—Mo1	−103.63 (14)	O18—Mo5—O14—Mo4	175.84 (14)
O7—Mo1—O2—Ga1	−26.9 (5)	O15—Mo5—O14—Mo4	103.06 (14)
O8—Mo1—O2—Ga1	169.24 (17)	O19—Mo4—O14—Ga2	30.9 (5)
O5—Mo1—O2—Ga1	−89.30 (17)	O20—Mo4—O14—Ga2	−168.40 (17)
O4—Mo1—O2—Ga1	73.15 (16)	O17—Mo4—O14—Ga2	89.81 (16)
O1—Mo1—O2—Ga1	0.41 (12)	O16—Mo4—O14—Ga2	−73.04 (15)
O7—Mo1—O2—Mo2	76.8 (5)	O13—Mo4—O14—Ga2	−0.44 (12)
O8—Mo1—O2—Mo2	−87.02 (16)	O19—Mo4—O14—Mo5	−72.8 (5)
O5—Mo1—O2—Mo2	14.43 (13)	O20—Mo4—O14—Mo5	87.92 (16)
O4—Mo1—O2—Mo2	176.88 (14)	O17—Mo4—O14—Mo5	−13.88 (13)
O1—Mo1—O2—Mo2	104.14 (14)	O16—Mo4—O14—Mo5	−176.72 (14)
O1ⁱ—Ga1—O3—Mo3	1.25 (15)	O13—Mo4—O14—Mo5	−104.13 (13)
O1—Ga1—O3—Mo3	−178.75 (15)	O13ⁱⁱ—Ga2—O15—Mo6	−0.83 (14)
O2ⁱ—Ga1—O3—Mo3	−82.55 (16)	O13—Ga2—O15—Mo6	179.18 (14)
O2—Ga1—O3—Mo3	97.45 (16)	O14—Ga2—O15—Mo6	−97.00 (15)
O1ⁱ—Ga1—O3—Mo2	−96.74 (16)	O14ⁱⁱ—Ga2—O15—Mo6	83.00 (15)
O1—Ga1—O3—Mo2	83.26 (16)	O13ⁱⁱ—Ga2—O15—Mo5	96.51 (15)
O2ⁱ—Ga1—O3—Mo2	179.46 (14)	O13—Ga2—O15—Mo5	−83.49 (15)
O2—Ga1—O3—Mo2	−0.54 (14)	O14—Ga2—O15—Mo5	0.34 (14)
O12—Mo3—O3—Ga1	−35.2 (5)	O14ⁱⁱ—Ga2—O15—Mo5	−179.66 (14)
O11—Mo3—O3—Ga1	169.01 (18)	O23—Mo6—O15—Ga2	−169.88 (18)
O4ⁱ—Mo3—O3—Ga1	71.36 (16)	O24—Mo6—O15—Ga2	36.2 (5)
O6—Mo3—O3—Ga1	−91.15 (17)	O16ⁱⁱ—Mo6—O15—Ga2	−71.69 (16)
O1ⁱ—Mo3—O3—Ga1	−1.13 (13)	O18—Mo6—O15—Ga2	90.02 (16)
O12—Mo3—O3—Mo2	70.2 (5)	O13ⁱⁱ—Mo6—O15—Ga2	0.75 (13)
O11—Mo3—O3—Mo2	−85.60 (17)	O23—Mo6—O15—Mo5	85.71 (16)
O4ⁱ—Mo3—O3—Mo2	176.76 (14)	O24—Mo6—O15—Mo5	−68.2 (5)
O6—Mo3—O3—Mo2	14.25 (13)	O16ⁱⁱ—Mo6—O15—Mo5	−176.10 (14)
O1ⁱ—Mo3—O3—Mo2	104.27 (15)	O18—Mo6—O15—Mo5	−14.39 (12)
O9—Mo2—O3—Ga1	29.5 (5)	O13ⁱⁱ—Mo6—O15—Mo5	−103.66 (14)
O10—Mo2—O3—Ga1	−170.27 (18)	O21—Mo5—O15—Ga2	−34.9 (5)
O6—Mo2—O3—Ga1	90.74 (17)	O22—Mo5—O15—Ga2	171.32 (17)
O5—Mo2—O3—Ga1	−72.14 (16)	O17—Mo5—O15—Ga2	72.94 (16)
O2—Mo2—O3—Ga1	0.49 (13)	O18—Mo5—O15—Ga2	−90.09 (16)
O9—Mo2—O3—Mo3	−75.6 (5)	O14—Mo5—O15—Ga2	−0.31 (12)
O10—Mo2—O3—Mo3	84.64 (17)	O21—Mo5—O15—Mo6	69.6 (5)
O6—Mo2—O3—Mo3	−14.35 (13)	O22—Mo5—O15—Mo6	−84.26 (15)
O5—Mo2—O3—Mo3	−177.23 (14)	O17—Mo5—O15—Mo6	177.37 (13)
O2—Mo2—O3—Mo3	−104.60 (14)	O18—Mo5—O15—Mo6	14.34 (12)
O7—Mo1—O4—Mo3ⁱ	66.8 (2)	O14—Mo5—O15—Mo6	104.12 (14)
O8—Mo1—O4—Mo3ⁱ	174.9 (2)	O19—Mo4—O16—Mo6ⁱⁱ	−68.1 (2)
O5—Mo1—O4—Mo3ⁱ	−59.9 (4)	O20—Mo4—O16—Mo6ⁱⁱ	−175.9 (2)
O1—Mo1—O4—Mo3ⁱ	−20.98 (17)	O17—Mo4—O16—Mo6ⁱⁱ	59.7 (4)
O2—Mo1—O4—Mo3ⁱ	−92.7 (2)	O13—Mo4—O16—Mo6ⁱⁱ	20.19 (17)
O7—Mo1—O5—Mo2	178.4 (2)	O14—Mo4—O16—Mo6ⁱⁱ	91.9 (2)
O8—Mo1—O5—Mo2	69.8 (2)	O21—Mo5—O17—Mo4	68.7 (2)
O4—Mo1—O5—Mo2	−54.1 (4)	O22—Mo5—O17—Mo4	176.7 (2)
O1—Mo1—O5—Mo2	−90.8 (2)	O18—Mo5—O17—Mo4	−57.1 (4)
O2—Mo1—O5—Mo2	−19.71 (18)	O15—Mo5—O17—Mo4	−90.7 (2)
O9—Mo2—O5—Mo1	−68.0 (2)	O14—Mo5—O17—Mo4	−19.20 (18)
O10—Mo2—O5—Mo1	−176.7 (2)	O19—Mo4—O17—Mo5	−178.4 (2)
O6—Mo2—O5—Mo1	57.3 (4)	O20—Mo4—O17—Mo5	−69.9 (2)
O3—Mo2—O5—Mo1	90.6 (2)	O16—Mo4—O17—Mo5	53.0 (4)
O2—Mo2—O5—Mo1	19.81 (18)	O13—Mo4—O17—Mo5	90.2 (2)
O9—Mo2—O6—Mo3	179.9 (2)	O14—Mo4—O17—Mo5	18.98 (17)
O10—Mo2—O6—Mo3	−71.9 (2)	O23—Mo6—O18—Mo5	−70.0 (2)
O5—Mo2—O6—Mo3	53.9 (4)	O24—Mo6—O18—Mo5	−176.6 (2)
O3—Mo2—O6—Mo3	18.79 (17)	O16ⁱⁱ—Mo6—O18—Mo5	58.1 (4)
O2—Mo2—O6—Mo3	89.33 (19)	O15—Mo6—O18—Mo5	19.05 (16)
O12—Mo3—O6—Mo2	178.4 (2)	O13ⁱⁱ—Mo6—O18—Mo5	90.61 (18)
O11—Mo3—O6—Mo2	71.1 (2)	O21—Mo5—O18—Mo6	178.3 (2)
O4ⁱ—Mo3—O6—Mo2	−56.3 (4)	O22—Mo5—O18—Mo6	71.7 (2)
O3—Mo3—O6—Mo2	−19.01 (17)	O17—Mo5—O18—Mo6	−54.4 (4)
O1ⁱ—Mo3—O6—Mo2	−90.18 (19)	O15—Mo5—O18—Mo6	−19.00 (16)
O15ⁱⁱ—Ga2—O13—Mo4	−97.38 (15)	O14—Mo5—O18—Mo6	−90.41 (19)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O10ⁱⁱⁱ	0.84 (2)	2.00 (3)	2.822 (5)	166 (6)
O13—H13···O23^iv	0.84 (2)	1.86 (2)	2.691 (5)	173 (7)
O14—H14···O22^v	0.84 (2)	1.98 (2)	2.808 (5)	168 (6)
O3—H3···O4S^vi	0.85 (2)	1.76 (3)	2.602 (5)	169 (8)
O1—H1···O11^vii	0.85 (2)	1.87 (4)	2.682 (5)	159 (9)
O15—H15···O1S	0.83 (2)	1.87 (3)	2.645 (5)	155 (7)

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

Experimental details

Crystal data
Chemical formula	(NH₄)₃[GaMo₆(OH)₆O₁₈]·7H₂O
M_r	1215.65
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	22.7642 (15), 10.9651 (7), 11.7599 (8)
β (°)	100.212 (1)
V (Å³)	2888.9 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.56
Crystal size (mm)	0.38 × 0.20 × 0.03

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1995)
T_min, T_max	0.345, 0.901
No. of measured, independent and observed [I > 2σ(I)] reflections	15163, 6225, 4471
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.110, 1.17
No. of reflections	6225
No. of parameters	397
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
	w = 1/[σ²(F_o²) + (0.0387P)² + 12.6663P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	1.02, −1.10

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT (Bruker, 2000, SHELXTL (Bruker, 2000), SHELXTL (Bruker, 2000.

Selected bond lengths (Å) top

Ga1—O3	1.953 (3)	Mo3—O6	1.949 (4)
Ga1—O1	1.954 (4)	Mo3—O3	2.252 (4)
Ga1—O2	1.972 (3)	Mo3—O1ⁱ	2.286 (4)
Ga2—O15	1.968 (3)	Mo4—O19	1.705 (4)
Ga2—O13	1.969 (3)	Mo4—O20	1.713 (4)
Ga2—O14	1.978 (3)	Mo4—O17	1.939 (3)
Mo1—O7	1.703 (4)	Mo4—O16	1.948 (3)
Mo1—O8	1.711 (4)	Mo4—O13	2.286 (3)
Mo1—O5	1.918 (4)	Mo4—O14	2.324 (3)
Mo1—O4	1.939 (4)	Mo5—O21	1.702 (4)
Mo1—O1	2.293 (4)	Mo5—O22	1.708 (3)
Mo1—O2	2.307 (4)	Mo5—O17	1.932 (4)
Mo2—O9	1.704 (4)	Mo5—O18	1.956 (3)
Mo2—O10	1.714 (4)	Mo5—O15	2.285 (3)
Mo2—O6	1.943 (4)	Mo5—O14	2.284 (3)
Mo2—O5	1.948 (4)	Mo6—O23	1.712 (3)
Mo2—O3	2.287 (4)	Mo6—O24	1.719 (4)
Mo2—O2	2.300 (3)	Mo6—O16ⁱⁱ	1.917 (4)
Mo3—O12	1.711 (4)	Mo6—O18	1.944 (4)
Mo3—O11	1.715 (4)	Mo6—O15	2.273 (3)
Mo3—O4ⁱ	1.918 (4)	Mo6—O13ⁱⁱ	2.290 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O10ⁱⁱⁱ	0.84 (2)	2.00 (3)	2.822 (5)	166 (6)
O13—H13···O23^iv	0.84 (2)	1.86 (2)	2.691 (5)	173 (7)
O14—H14···O22^v	0.84 (2)	1.98 (2)	2.808 (5)	168 (6)
O3—H3···O4S^vi	0.85 (2)	1.76 (3)	2.602 (5)	169 (8)
O1—H1···O11^vii	0.85 (2)	1.87 (4)	2.682 (5)	159 (9)
O15—H15···O1S	0.83 (2)	1.87 (3)	2.645 (5)	155 (7)

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

Short contact geometry (Å). top

N1S···O24ⁱⁱ	2.911 (7)
N1S···O6S^vi	2.784 (8)
N2S···O16	2.779 (6)
N2S···O21ⁱⁱⁱ	2.979 (6)
N2S···O24^vii	2.901 (6)
N2S···O3S^viii	2.899 (7)
N2S···O7S	2.898 (7)
N3S···O5ⁱ	2.775 (6)
N3S···O12^xii	2.907 (7)
N3S···O5S	2.801 (8)
N3S···O7Sⁱ	3.030 (8)
O1S···O18^x	2.794 (5)
O1S···O18ⁱⁱ	2.905 (6)
O2S···O4^xi	2.718 (5)
O2S···O12	2.797 (6)
O2S···O3S^xii	2.830 (7)
O2S···O6S^ix	2.704 (7)
O3S···O9	3.016 (6)
O3S···O19	3.034 (7)
O3S···O5S^iv	2.917 (8)
O4S···O3^xiii	2.602 (5)
O4S···O6	2.773 (6)
O4S···O6^xii	2.934 (6)
O5S···O8	2.782 (6)
O5S···O16ⁱ	3.083 (6)
O6S···O20	2.776 (6)
O6S···O7S	2.769 (7)
O7S···O7^xiv	2.973 (6)

Symmetry codes (i): x, -y+1/2, z-1/2; (ii): -x, y-1/2, -z+1/2; (iii): x, -y+3/2, z+1/2; (iv): x, -y+1/2, z+1/2; (v): -x+1, y+1/2, -z+3/2; (vi): x, -y+3/2, z-1/2; (vii): -x, y-1/2, -z+3/2; (viii): x, -y+1/2, z+1/2; (ix): 1-x, 1-y, 1-z; (x): x, -y+3/2, z-1/2; (xi): -x+1, y-1/2, -z+1/2; (xii): -x+1, -y, -z+1; (xiii): x, -y+1/2, z-1/2; (xiv): x, -y+3/2, z+1/2

Acknowledgements

The authors gratefully acknowledge the ARL-ONAMI Nanoarchitectures for Enhanced Performance Center and the University of Oregon for generous financial support. DWJ is a Cottrell Scholar of Research Corporation and thanks the University of Oregon for generous financial support. DWJ gratefully acknowledges the NSF for a CAREER award. The purchase of the X-ray diffractometer was made possible by a grant from the NSF (grant No. CHE-0234965) to the University of Oregon.

References

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Lorenzo-Luis, P. A. & Gili, P. (2000). Recent Res. Dev. Inorg. Chem. 2, 185–196. CAS Google Scholar
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Volume 64| Part 2| February 2008| Pages i8-i9

doi:10.1107/S1600536807068067

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

Tri­ammonium hexa­hydroxido­octa­deca­oxidohexa­molybdogallate(III) hepta­hydrate

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

inorganic compounds

Triammonium hexahydroxidooctadecaoxidohexamolybdogallate(III) heptahydrate