Hexaaqua­gallium(III) trinitrate trihydrate

Arthur D Hendsbee; Cory C Pye; Jason D Masuda

doi:10.1107/S1600536809028086

. 2009 Jul 22;65(Pt 8):i65. doi: 10.1107/S1600536809028086

Hexaaquagallium(III) trinitrate trihydrate

Arthur D Hendsbee ^a, Cory C Pye ^a, Jason D Masuda ^a,^*

PMCID: PMC2977161 PMID: 21583299

Abstract

The title compound, [Ga(H₂O)₆](NO₃)₃·3H₂O, is isostructural to other known M ^III nitrate hydrates (M = Al, Cr, Fe). The structure contains two distinct octahedral Ga(OH₂)₆ units (each of Inline graphic symmetry) which are involved in intermolecular hydrogen bonding with the three nitrate anions and three water molecules within the asymmetric unit.

Related literature

For the the aluminium analogue, see: Lazar, Ribár, Divjaković & Mészáros (1991 ▶). For the chromium analogue, see: Lazar, Ribár & Prelesnik (1991 ▶). For the iron analogue, see: Hair & Beattie (1977 ▶). For ionic radii, see: Shannon & Prewitt (1969 ▶). Gallium nitrate, used in the preparation, easily forms supersaturated solutions, see: Rudolph et al. (2002 ▶), and hence the sample was cooled to 248 K and a seed crystal was introduced to initiate crystallization.

Experimental

Crystal data

[Ga(H₂O)₆](NO₃)₃·3H₂O
M _r = 417.89
Monoclinic,
a = 13.9609 (6) Å
b = 9.6498 (5) Å
c = 10.9743 (5) Å
β = 95.448 (1)°
V = 1471.78 (12) Å³
Z = 4
Mo Kα radiation
μ = 1.97 mm⁻¹
T = 296 K
0.40 × 0.34 × 0.29 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.479, T _max = 0.564
10587 measured reflections
3037 independent reflections
2509 reflections with I > 2σ(I)
R _int = 0.015

Refinement

R[F ² > 2σ(F ²)] = 0.021
wR(F ²) = 0.058
S = 1.05
3037 reflections
274 parameters
18 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809028086/mg2076sup1.cif

e-65-00i65-sup1.cif^{(17.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809028086/mg2076Isup2.hkl

e-65-00i65-Isup2.hkl^{(149.1KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O18—H18⋯O8	0.801 (16)	2.26 (2)	2.9348 (18)	142 (2)
O16—H14⋯O18	0.825 (15)	2.072 (15)	2.8732 (19)	163.8 (19)
O5—H10⋯O7	0.823 (16)	1.908 (17)	2.7052 (17)	163 (2)
O1—H1⋯O16	0.814 (15)	1.846 (16)	2.6474 (16)	168 (2)
O4—H7⋯O14	0.809 (15)	1.833 (15)	2.6399 (15)	175 (2)
O5—H9⋯O17	0.810 (16)	1.869 (16)	2.676 (2)	174 (2)
O18—H17⋯O14	0.816 (16)	2.082 (17)	2.8729 (18)	163 (2)
O3—H6⋯O15ⁱ	0.814 (15)	1.903 (16)	2.7150 (16)	175 (2)
O1—H2⋯O10ⁱ	0.808 (15)	1.848 (16)	2.6545 (16)	175 (2)
O2—H4⋯O16ⁱ	0.790 (16)	1.901 (16)	2.6895 (18)	175 (2)
O4—H8⋯O17ⁱⁱ	0.821 (15)	1.816 (15)	2.6312 (16)	171 (2)
O17—H15⋯O9ⁱⁱ	0.808 (15)	1.977 (16)	2.7791 (19)	171 (2)
O3—H5⋯O13ⁱⁱⁱ	0.792 (15)	1.961 (16)	2.7454 (16)	171 (2)
O6—H12⋯O12^iv	0.796 (15)	1.926 (16)	2.7179 (16)	174 (2)
O16—H13⋯O18^v	0.820 (16)	1.934 (16)	2.7525 (19)	177 (3)
O6—H11⋯O11^vi	0.800 (15)	1.895 (16)	2.6938 (17)	176 (2)
O2—H3⋯O8^vii	0.794 (15)	1.943 (16)	2.7269 (17)	169 (2)
O17—H16⋯O7^viii	0.802 (16)	2.026 (18)	2.7675 (18)	154 (2)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) .

Acknowledgments

The authors thank Saint Mary’s University, the Saint Mary’s University Student Employment Experience Program (ADH) and the Natural Sciences and Engineering Research Council (CCP) for financial support.

supplementary crystallographic information

Comment

The title compound is isostructural with [Al(H₂O)₆](NO₃)₃.3H₂O (Lazar, Ribár, Divjaković & Mészáros, 1991), [Cr(H₂O)₆](NO₃)₃.3H₂O (Lazar, Ribár & Prelesnik, 1991) and [Fe(H₂O)₆](NO₃)₃.3H₂O (Hair & Beattie, 1977). Its unit cell volume is almost identical to that of the chromium derivative (1473.87 (17) Å³) and intermediate between those of the aluminum (1448.9 (4) Å³) and iron derivatives 1489.8 (2) Å³), consistent with the values of ionic radii (Ga³⁺, 0.760 Å; Cr³⁺, 0.755 Å; Al³⁺, 0.670 Å; Fe³⁺, 0.785 Å) (Shannon & Prewitt, 1969). On each of the octahedral units there are two symmetry-related water molecules which hydrogen bond to two NO₃^- anions. The remaining metal-bound water molecules participate in intermolecular hydrogen bonding with one NO₃^- anion and one of the interstitial H₂O molecules.

Experimental

The title compound was prepared by dissolving 5 grams of gallium(III) nitrate hydrate (Aldrich Chemical Company) in a minimum of H₂O (approximately 7 ml) and adding three drops of concentrated nitric acid to suppress hydrolysis. Because gallium nitrate easily forms supersaturated solutions (Rudolph et al., 2002), the sample was cooled to 248 K and a seed crystal was introduced to initiate crystallization. A suitable crystal was sealed in a glass capillary to prevent water loss from this hygroscopic material.