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Acta Cryst. (2009). E65, i65    [ doi:10.1107/S1600536809028086 ]

Hexaaquagallium(III) trinitrate trihydrate

A. D. Hendsbee, C. C. Pye and J. D. Masuda

Abstract top

The title compound, [Ga(H2O)6](NO3)3·3H2O, is isostructural to other known MIII nitrate hydrates (M = Al, Cr, Fe). The structure contains two distinct octahedral Ga(OH2)6 units (each of \overline{1} symmetry) which are involved in intermolecular hydrogen bonding with the three nitrate anions and three water molecules within the asymmetric unit.

Comment top

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.

Related literature top

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 top

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.

Refinement top

The H atoms were found in the electron difference map and O-H distances fixed to 0.82 Å.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); 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).

Figures top
[Figure 1] Fig. 1. [Ga(H2O)6](NO3).3H2O with thermal ellipsoids shown at 50% probability level.
[Figure 2] Fig. 2. Packing diagram viewed down the c-axis with hydrogen bonds indicated by dashed lines.
Hexaaquagallium(III) trinitrate trihydrate top
Crystal data top
[Ga(H2O)6](NO3)3·3H2OF000 = 856
Mr = 417.89Dx = 1.886 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5403 reflections
a = 13.9609 (6) Åθ = 2.3–28.3º
b = 9.6498 (5) ŵ = 1.97 mm−1
c = 10.9743 (5) ÅT = 296 K
β = 95.4480 (10)ºIrregular, colourless
V = 1471.78 (12) Å30.40 × 0.34 × 0.29 mm
Z = 4
Data collection top
Bruker APEXII CCD
diffractometer		3037 independent reflections
Radiation source: fine-focus sealed tube2509 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.015
T = 296 Kθmax = 26.5º
φ and ω scansθmin = 2.6º
Absorption correction: multi-scan
(SADABS; Bruker, 2008)		h = −17→17
Tmin = 0.479, Tmax = 0.564k = −12→10
10587 measured reflectionsl = −13→13
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.021H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.058  w = 1/[σ2(Fo2) + (0.0301P)2 + 0.4119P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
3037 reflectionsΔρmax = 0.48 e Å−3
274 parametersΔρmin = −0.33 e Å−3
18 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Ga(H2O)6](NO3)3·3H2OV = 1471.78 (12) Å3
Mr = 417.89Z = 4
Monoclinic, P21/cMo Kα
a = 13.9609 (6) ŵ = 1.97 mm−1
b = 9.6498 (5) ÅT = 296 K
c = 10.9743 (5) Å0.40 × 0.34 × 0.29 mm
β = 95.4480 (10)º
Data collection top
Bruker APEXII CCD
diffractometer		3037 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2008)		2509 reflections with I > 2σ(I)
Tmin = 0.479, Tmax = 0.564Rint = 0.015
10587 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.02118 restraints
wR(F2) = 0.058H atoms treated by a mixture of
independent and constrained refinement
S = 1.05Δρmax = 0.48 e Å−3
3037 reflectionsΔρmin = −0.33 e Å−3
274 parameters
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
xyzUiso*/Ueq
Ga10.50000.00000.00000.01867 (8)
Ga20.00000.00000.50000.02131 (8)
N10.19260 (10)0.00919 (13)0.12573 (13)0.0285 (3)
N20.29851 (9)0.18907 (14)0.70878 (11)0.0268 (3)
N30.78610 (9)0.28563 (14)0.71869 (11)0.0293 (3)
O10.57018 (8)0.08802 (13)0.13967 (10)0.0306 (3)
H20.6187 (12)0.132 (2)0.1335 (19)0.051 (6)*
H10.5546 (14)0.088 (2)0.2093 (15)0.051 (6)*
O20.57327 (8)0.10539 (13)−0.11126 (10)0.0294 (2)
H40.5629 (16)0.1854 (17)−0.121 (2)0.053 (7)*
H30.6243 (12)0.082 (2)−0.1307 (18)0.054 (6)*
O30.40601 (8)0.14903 (12)−0.00574 (10)0.0269 (2)
H60.3964 (15)0.190 (2)0.0569 (16)0.051 (6)*
H50.3607 (13)0.150 (2)−0.0550 (17)0.051 (6)*
O40.07132 (8)0.09427 (14)0.63446 (10)0.0327 (3)
H80.0636 (14)0.093 (2)0.7077 (14)0.043 (5)*
H70.1244 (12)0.121 (2)0.6219 (19)0.051 (6)*
O50.07408 (9)0.10908 (14)0.39031 (10)0.0339 (3)
H100.0971 (15)0.084 (2)0.3275 (17)0.065 (7)*
H90.0633 (16)0.1911 (17)0.381 (2)0.054 (7)*
O6−0.09607 (8)0.14720 (14)0.49563 (11)0.0358 (3)
H12−0.1406 (13)0.147 (2)0.4446 (18)0.054 (7)*
H11−0.1078 (16)0.183 (2)0.5582 (17)0.055 (7)*
O70.11323 (8)0.04401 (15)0.16045 (11)0.0439 (3)
O80.26475 (9)−0.00369 (13)0.19969 (12)0.0430 (3)
O90.19968 (11)−0.01084 (15)0.01616 (12)0.0529 (4)
O100.72635 (8)0.25702 (13)0.62972 (10)0.0369 (3)
O110.87278 (8)0.26164 (15)0.71226 (11)0.0473 (3)
O120.75836 (8)0.33667 (15)0.81328 (10)0.0424 (3)
O130.26276 (8)0.16544 (14)0.80530 (10)0.0395 (3)
O140.24653 (7)0.18488 (13)0.60783 (9)0.0339 (3)
O150.38523 (7)0.21721 (14)0.70780 (10)0.0400 (3)
O160.53516 (9)0.12179 (13)0.37069 (11)0.0333 (3)
H140.4793 (11)0.108 (2)0.3864 (17)0.043 (6)*
H130.5662 (15)0.076 (2)0.4232 (18)0.063 (7)*
O170.05170 (9)0.38374 (14)0.36978 (11)0.0362 (3)
H150.0906 (14)0.427 (2)0.4140 (19)0.057 (7)*
H160.0021 (13)0.420 (2)0.383 (2)0.056 (7)*
O180.35675 (10)0.02473 (15)0.45021 (13)0.0410 (3)
H170.3188 (14)0.075 (2)0.482 (2)0.064 (8)*
H180.3232 (17)−0.016 (2)0.399 (2)0.062 (8)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ga10.01679 (12)0.02124 (13)0.01796 (12)0.00073 (8)0.00156 (8)−0.00138 (8)
Ga20.01777 (12)0.02999 (15)0.01606 (12)−0.00007 (8)0.00097 (8)−0.00210 (8)
N10.0297 (7)0.0278 (8)0.0280 (7)−0.0019 (5)0.0029 (6)0.0003 (5)
N20.0238 (6)0.0302 (7)0.0261 (6)−0.0027 (5)0.0002 (5)0.0037 (5)
N30.0290 (7)0.0308 (7)0.0275 (7)0.0044 (6)−0.0005 (5)−0.0004 (5)
O10.0271 (6)0.0417 (7)0.0227 (6)−0.0094 (5)0.0012 (4)−0.0071 (5)
O20.0258 (6)0.0284 (7)0.0356 (6)0.0032 (5)0.0116 (5)0.0065 (5)
O30.0245 (5)0.0316 (6)0.0240 (6)0.0097 (5)−0.0002 (4)−0.0029 (5)
O40.0246 (6)0.0536 (8)0.0196 (6)−0.0108 (5)0.0018 (4)−0.0078 (5)
O50.0395 (6)0.0376 (8)0.0265 (6)−0.0047 (6)0.0119 (5)0.0013 (5)
O60.0314 (6)0.0480 (8)0.0269 (6)0.0158 (5)−0.0024 (5)−0.0064 (5)
O70.0317 (6)0.0576 (8)0.0446 (7)0.0009 (6)0.0141 (5)−0.0047 (6)
O80.0379 (7)0.0536 (9)0.0361 (7)0.0013 (5)−0.0045 (5)0.0039 (5)
O90.0524 (9)0.0741 (11)0.0329 (7)0.0144 (7)0.0072 (6)−0.0110 (6)
O100.0353 (6)0.0431 (7)0.0301 (6)0.0072 (5)−0.0080 (5)−0.0057 (5)
O110.0271 (6)0.0721 (10)0.0422 (7)0.0116 (6)0.0006 (5)−0.0133 (6)
O120.0339 (6)0.0605 (9)0.0324 (6)0.0064 (6)0.0018 (5)−0.0149 (6)
O130.0301 (6)0.0633 (9)0.0255 (6)−0.0049 (6)0.0053 (5)0.0088 (6)
O140.0262 (5)0.0503 (7)0.0242 (5)−0.0054 (5)−0.0023 (4)0.0028 (5)
O150.0214 (5)0.0629 (9)0.0350 (6)−0.0103 (5)−0.0009 (4)0.0128 (6)
O160.0336 (6)0.0346 (7)0.0323 (6)0.0031 (5)0.0066 (5)0.0016 (5)
O170.0311 (6)0.0496 (8)0.0279 (6)−0.0003 (6)0.0024 (5)−0.0019 (5)
O180.0383 (7)0.0469 (8)0.0365 (7)−0.0027 (6)−0.0027 (6)−0.0091 (6)
Geometric parameters (Å, °) top
Ga1—O11.9354 (10)Ga2—O51.9654 (11)
Ga1—O1i1.9354 (10)N1—O91.2311 (19)
Ga1—O31.9438 (10)N1—O81.2385 (18)
Ga1—O3i1.9438 (10)N1—O71.2513 (18)
Ga1—O21.9515 (11)N2—O131.2343 (16)
Ga1—O2i1.9515 (11)N2—O151.2418 (16)
Ga2—O4ii1.9280 (10)N2—O141.2660 (16)
Ga2—O41.9280 (10)N3—O111.2407 (17)
Ga2—O6ii1.9510 (12)N3—O121.2435 (17)
Ga2—O61.9510 (12)N3—O101.2533 (16)
Ga2—O5ii1.9654 (11)
O1—Ga1—O1i180.0O6ii—Ga2—O6180.00 (8)
O1—Ga1—O389.45 (5)O4ii—Ga2—O5ii87.28 (5)
O1i—Ga1—O390.55 (5)O4—Ga2—O5ii92.72 (5)
O1—Ga1—O3i90.55 (5)O6ii—Ga2—O5ii89.74 (6)
O1i—Ga1—O3i89.45 (5)O6—Ga2—O5ii90.26 (6)
O3—Ga1—O3i180.0O4ii—Ga2—O592.72 (5)
O1—Ga1—O290.62 (5)O4—Ga2—O587.28 (5)
O1i—Ga1—O289.38 (5)O6ii—Ga2—O590.26 (6)
O3—Ga1—O289.23 (5)O6—Ga2—O589.74 (6)
O3i—Ga1—O290.77 (5)O5ii—Ga2—O5180.0
O1—Ga1—O2i89.38 (5)O9—N1—O8119.25 (15)
O1i—Ga1—O2i90.62 (5)O9—N1—O7119.68 (14)
O3—Ga1—O2i90.77 (5)O8—N1—O7121.06 (14)
O3i—Ga1—O2i89.23 (5)O13—N2—O15121.45 (12)
O2—Ga1—O2i179.999 (2)O13—N2—O14120.01 (12)
O4ii—Ga2—O4180.0O15—N2—O14118.54 (12)
O4ii—Ga2—O6ii88.81 (5)O11—N3—O12120.28 (13)
O4—Ga2—O6ii91.19 (5)O11—N3—O10119.68 (13)
O4ii—Ga2—O691.19 (5)O12—N3—O10120.04 (12)
O4—Ga2—O688.81 (5)
Symmetry codes: (i) −x+1, −y, −z; (ii) −x, −y, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O18—H18···O80.801 (16)2.26 (2)2.9348 (18)142 (2)
O16—H14···O180.825 (15)2.072 (15)2.8732 (19)163.8 (19)
O5—H10···O70.823 (16)1.908 (17)2.7052 (17)163 (2)
O1—H1···O160.814 (15)1.846 (16)2.6474 (16)168 (2)
O4—H7···O140.809 (15)1.833 (15)2.6399 (15)175 (2)
O5—H9···O170.810 (16)1.869 (16)2.676 (2)174 (2)
O18—H17···O140.816 (16)2.082 (17)2.8729 (18)163 (2)
O3—H6···O15iii0.814 (15)1.903 (16)2.7150 (16)175 (2)
O1—H2···O10iii0.808 (15)1.848 (16)2.6545 (16)175 (2)
O2—H4···O16iii0.790 (16)1.901 (16)2.6895 (18)175 (2)
O4—H8···O17iv0.821 (15)1.816 (15)2.6312 (16)171 (2)
O17—H15···O9iv0.808 (15)1.977 (16)2.7791 (19)171 (2)
O3—H5···O13v0.792 (15)1.961 (16)2.7454 (16)171 (2)
O6—H12···O12vi0.796 (15)1.926 (16)2.7179 (16)174 (2)
O16—H13···O18vii0.820 (16)1.934 (16)2.7525 (19)177 (3)
O6—H11···O11viii0.800 (15)1.895 (16)2.6938 (17)176 (2)
O2—H3···O8i0.794 (15)1.943 (16)2.7269 (17)169 (2)
O17—H16···O7ix0.802 (16)2.026 (18)2.7675 (18)154 (2)
Symmetry codes: (iii) x, −y+1/2, z−1/2; (iv) x, −y+1/2, z+1/2; (v) x, y, z−1; (vi) x−1, −y+1/2, z−1/2; (vii) −x+1, −y, −z+1; (viii) x−1, y, z; (i) −x+1, −y, −z; (ix) −x, y+1/2, −z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O18—H18···O80.801 (16)2.26 (2)2.9348 (18)142 (2)
O16—H14···O180.825 (15)2.072 (15)2.8732 (19)163.8 (19)
O5—H10···O70.823 (16)1.908 (17)2.7052 (17)163 (2)
O1—H1···O160.814 (15)1.846 (16)2.6474 (16)168 (2)
O4—H7···O140.809 (15)1.833 (15)2.6399 (15)175 (2)
O5—H9···O170.810 (16)1.869 (16)2.676 (2)174 (2)
O18—H17···O140.816 (16)2.082 (17)2.8729 (18)163 (2)
O3—H6···O15i0.814 (15)1.903 (16)2.7150 (16)175 (2)
O1—H2···O10i0.808 (15)1.848 (16)2.6545 (16)175 (2)
O2—H4···O16i0.790 (16)1.901 (16)2.6895 (18)175 (2)
O4—H8···O17ii0.821 (15)1.816 (15)2.6312 (16)171 (2)
O17—H15···O9ii0.808 (15)1.977 (16)2.7791 (19)171 (2)
O3—H5···O13iii0.792 (15)1.961 (16)2.7454 (16)171 (2)
O6—H12···O12iv0.796 (15)1.926 (16)2.7179 (16)174 (2)
O16—H13···O18v0.820 (16)1.934 (16)2.7525 (19)177 (3)
O6—H11···O11vi0.800 (15)1.895 (16)2.6938 (17)176 (2)
O2—H3···O8vii0.794 (15)1.943 (16)2.7269 (17)169 (2)
O17—H16···O7viii0.802 (16)2.026 (18)2.7675 (18)154 (2)
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x, −y+1/2, z+1/2; (iii) x, y, z−1; (iv) x−1, −y+1/2, z−1/2; (v) −x+1, −y, −z+1; (vi) x−1, y, z; (vii) −x+1, −y, −z; (viii) −x, y+1/2, −z+1/2.
Acknowledgements top

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.

references
References top

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