A novel gallium arsenate organically templated by propane-1,3-diyldi­ammonium with a ULM-3-type open framework: [Ga₃(AsO₄)₃(OH)F](C₃H₁₂N₂)·H₂O

Crystals of the title oxy­fluorinated gallium arsenate, viz. tris­(arsenato)­fluoro­hydro­xotrigallium ­propane-1,3-diyldiammonium monohydrate, were synthesized hydro­thermally at 453 K under autogenous pressure, using 1,3-di­amino­propane as the structure-directing agent. The solid crystallizes in the ortho­rhombic system and its structure was determined from single-crystal X-ray diffraction analysis. The structure is similar to that of gallium or aluminium phosphates with the ULM-3 structural type and is built up from a three-dimensional anionic framework composed of corner-linked hexameric Ga₃(AsO₄)₃(OH)F units. The Ga atoms have an octahedral [GaO₄(OH)F] or trigonal-bipyramidal [GaO₄(OH) and GaO₄F] coordination. These units are connected to one another and to the tetrahedral AsO₄ groups via OH or F bridges. The three-dimensional framework contains ten-ring channels along [010], crosslinked by eight-ring channels along [110] and [10]. The diprotonated organic species and water mol­ecules reside within the ten-ring channels. The cation is linked to the framework via an N—H...F hydrogen bond. A strong N—H...O hydrogen bond links the cation and the water mol­ecule.

S1. Comment

Nanoporous metal phosphates have attracted significant attention because of their potential applications in diverse areas, such as catalysis, gas separation and ionic exchangers. During the past two decades, the open-framework phosphate series has been studied extensively (Cheetham et al., 1999), and structural analyses of several aluminium phosphates showed that they possess three-dimensional networks identical to those encountered in the aluminosilicate zeolite family. The replacement of aluminium by gallium in these structures and the use of HF as a mineralizing agent have led to the discovery of novel large-pore open-framework compounds. For example, the gallium phosphates MIL-50 (Beitone et al., 2003), Cloverite (Estermann et al., 1991) and Ga₂(DETA)(PO₄)₂·2H₂O (Lin et al., 2001) are characterized by unique topologies with pores delimited by 18-, 20- and 24-ring channels, respectively.

One of the structural features of the fluorinated gallium phosphate series (Sassoye et al., 2002) is the occurrence of the hexameric building species (Ga₃P₃), comprising three phosphate groups and three gallium polyhedra (one central GaO₄X₂ octahedra connected to two GaO₄X trigonal biyramids via bridging X atoms; X = OH or F). This type of building unit is specifically reported in the aluminium (Renaudin et al., 1996; Natarajan et al. 1996) and gallium phosphates ULM-3 (Loiseau et al., 1994; Yin & Nazar, 1994; Loiseau et al., 1996; Brouca-Carrabecq & Mosset, 2000), and the gallium phosphates ULM-4 (Cavellec et al., 1994; Loiseau et al., 1997) and TREN-GaPO (Weigel et al., 1997; Beitone et al., 2002). These observations originated in structure-prediction calculations based on the building-unit concept by means of the AASBU method (Mellot-Draznieks et al., 2002).

A variety of possible three-dimensional frameworks have been investigated using the hexameric M₃P₃ unit (M = Al or Ga), and several new topologies have been generated. In this series, the network of ULM-4 is found to be closely related to that of the gallium arsenate GaAsO₄-2 (Chen et al., 1989). As discussed by Loiseau et al. (1997), only the orientation of the adjacent hexameric units differs in the two structures, leading to two distinct structure descriptions, although the crystal system remains monoclinic. It seems that the replacement of phosphate by arsenate groups plays a critical role for the formation of such three-dimensionnal open frameworks. This observation promted us to study gallium arsenate, in order to compare the crystal chemistry of the gallium arsenates and phosphates.

The synthesis of organically templated aluminium or gallium arsenates has rarely been reported in the literature. Besides the preparation of GaAsO₄-2, the structural characterization of two aluminium and gallium arsenates has been described in a few contributions (Yang et al., 1989; Li et al., 1991; Liao et al., 2000; Luo et al., 2001; Feng et al., 2001). This paper deals with the synthesis and structural characterization of the novel gallium arsenate Ga₃(AsO₄)₃(OH)F·N₂C₃H₁₂·H₂O templated by 1,3-diaminopropane. The structure of this solid is similar to the gallium phosphate ULM-3 (Loiseau et al., 1994) obtained with the same diamine.

The structure is built up via the connection by vertices of AsO₄ tetrahedra to GaO₄ octahedra(OH)F, and GaO₄(OH) and GaO₄F trigonal bipyramids. The three crystallographically inequivalent As atoms are tetrahedrally coordinated to O atoms, with typical As—O distances ranging from 1.677 (3) to 1.698 (3) Å. One of the three Ga atoms, Ga2, is octahedrally connected to four O atoms, atom F1 and one hydroxy group (O13; the OH group and F atom are in cis positions). The location of the OH group was confirmed by bond-valence calculations (O'Keeffe & Brese, 1992); the bond-valence sum is 0.983 valence units for atom O13. The position of the F atom was deduced from single-crystal X-ray diffraction and chemical analyses. The Ga2—O distances range from 1.962 (3) to 1.970 (3) Å, the Ga2—O13 distance is 1.970 (3) Å and the Ga2—F distance is 1.985 (3) Å. This gallium octahedron is linked to the two other Ga atoms, Ga1 and Ga3, via the OH⁻ and F⁻ anions. These two Ga atoms are fivefold coordinated to four O atoms [Ga—O = 1.832 (3)–1.977 (3) Å] and one OH group [Ga3—O13 = 2.017 (3) Å] or one F atom [Ga1—F1 = 2.010 (3) Å]. The resulting gallium trimer is linked to the three arsenate groups. The As2O₄ group shares corners with the three gallium polyhedra, whereas the As1O₄ and As3O₄ sgroups hare corners with one octahedron and one trigonal bipyramid. This connection mode generates the specific moiety Ga₃(AsO₄)₃(OH)F (Fig. 1), which was previously encountered in the gallium arsenate GaAsO₄-2 (Chen et al., 1989) and gallium phosphates ULM-n and MIL-n (Sassoye et al., 2002).

The arrangement of these hexameric blocks connected to one another via all their remaining free O atoms describes a three-dimensional framework, delimiting marquize-shaped ten-ring channels (4.5 x 3 Å, based on the ionic radius of 1.35 Å for oxygen) running along [010] (Fig. 2) and eight-ring cheannels along [110] and [1–10]. A strict gallium and arsenic alternation is observed in this structure, except for the occurrence of the Ga1—Ga2—Ga3 linkage present in the hexameric block. The 1,3-diaminopropane species is trapped in the ten-ring tunnels, together with a water molecule (OW).

The organic [N₂C₃H₁₂]²⁺ ion is diprotonated and its two positive charges balance the negative charges of the [Ga₃(AsO₄)₃(OH)F]²⁻ anionic framework. One of the ammonium head-groups is connected to the anions of the framework via hydrogen-bond interactions with the anion. Preferential N1—H1A···O5 [2.042 (3) Å], N1—H1B···O9 [2.020 (3) Å] and N1—H1···F1 [2.362 (3) Å] interactions occur. The other ammonium group interacts with the free water molecule via a very strong N2—HB···OW hydrogen bond [1.850 (6) Å], thus defining a monohydrated propanediammonium moiety that seems to play the role of structure-directing agent for the formation of the title gallium arsenate. This compound exhibits a framework topology identical to that of the phosphate-based solids ULM-3, and no structural difference is observed between the gallium arsenate and phosphate series. This situation differs for ULM-4 (Loiseau et al., 1997), for which two three-dimensional networks based on the hexameric Ga₃T₃ unit (T = P or As) have been synthesized.

S2. Experimental

The title compound was prepared hydrothermally from a mixture of gallium oxohydroxide (GaOOH), arsenic acid (H₃AsO₄, 75%), hydrofluoric acid (HF, 40%), 1,3-diaminopropane (N₂C₃H₁₀, 98%) and deionized water with the molar ratio 1:1:0.5:1.1:50. This mixture was sealed in a teflon-lined Parr autoclave and then heated for 48 h at 453 K under autogeneous pressure. The pH was 4–5 during the synthesis. After cooling to room temperature, the solid was separated from the liquid phase by filtration, washed with water then dried in air. A single-crystal was selected optically for the diffraction study and glued to a glass fiber. The presence of fluorine was established by chemical analysis; found: F 2.3%; calculated for one F per Ga₃(As₃O₄) unit: 2.5%. The location of this atom, in one of the bridging sites between the Ga atoms, was deduced from consideration of the thermal parameters and confirmed by bond-valence calculations (O'Keeffe & Brese, 1992).

S3. Refinement

H atoms bonded to N and C atoms were included as riding atoms, with C—H distances of 0.97 Å and N—H distances of 0.89 Å; H atoms bonded to O atoms could not be located.

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SHELXTL (Sheldrick, 1997b); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: Diamond (Brandenburg, 1996); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. : A displcaement ellipsoid plot (50% probability level) of the hexameric Ga3(AsO4)3(OH)F building unit, with the 1,3-diaminopropane and free water molecules (OW). Dotted lines indicate the preferential hydrogen-bond interactions between atoms N1, H1C and F1, and N2, H2B and the water molecule OW.
	Fig. 2. : Polyhedral projection of the structure of Ga3(AsO4)3(OH)F·N2C3H12·H2O (ULM-3 type) along [010], showing the ten-ring channels encapsulating 1,3-diaminopropane (grey circles: N atoms; black circles: C atoms; small open circles: H atoms) and the water molecule (open circles). Light grey polyhedra represent Ga polyhedra; dark grey tetrahedra represent As polyhedra.

tris(arsenato)fluorohydroxotrigallium 1,3-diaminopropane monohydrate

Crystal data

Ga3(AsO4)3(OH)F·C3H12N2·H2O	F(000) = 2880
Mr = 756.09	Dx = 3.133 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 15102 reflections
a = 16.1522 (1) Å	θ = 2.2–28.5°
b = 10.4928 (1) Å	µ = 11.24 mm^−1
c = 18.9161 (3) Å	T = 293 K
V = 3205.93 (6) Å^3	Parallelepiped, colourless
Z = 8	0.70 × 0.22 × 0.12 mm

Data collection

Bruket SMART CCD area-detector diffractometer	4029 independent reflections
Radiation source: fine-focus sealed tube	3267 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.070
ϕ and ω scans	θmax = 28.5°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→21
Tmin = 0.035, Tmax = 0.260	k = −14→14
20592 measured reflections	l = −25→22

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)] = 0.035	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.087	w = 1/[σ^2(Fo^2) + (0.0482P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.001
4029 reflections	Δρmax = 1.63 e Å^−3
239 parameters	Δρmin = −2.32 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00183 (10)

Special details

Experimental. 'Blessing, Acta Cryst. (1995) A51, 33–38'

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
As1	0.18723 (3)	0.85176 (4)	0.16795 (2)	0.00761 (12)
As2	−0.06130 (3)	0.61635 (4)	0.18501 (2)	0.00794 (12)
As3	0.01863 (3)	0.63599 (4)	0.42473 (2)	0.00739 (12)
Ga1	−0.14935 (3)	0.66191 (5)	0.32886 (2)	0.00832 (12)
Ga2	0.04309 (3)	0.81296 (5)	0.28219 (2)	0.00819 (12)
Ga3	0.00337 (3)	0.84748 (4)	0.09632 (2)	0.00825 (12)
F1	0.92709 (17)	0.8115 (3)	0.31679 (14)	0.0156 (6)
O13	0.0040 (2)	0.9055 (3)	0.19795 (15)	0.0122 (7)
O1	0.0234 (2)	0.6506 (3)	0.23262 (17)	0.0113 (7)
O2	0.0557 (2)	0.9639 (3)	0.34252 (16)	0.0124 (7)
O3	0.0202 (2)	0.7815 (3)	−0.00019 (15)	0.0136 (7)
O4	−0.0803 (2)	0.6077 (3)	0.40012 (17)	0.0165 (7)
O5	0.1159 (2)	0.8068 (3)	0.10730 (16)	0.0130 (7)
O6	−0.0694 (2)	0.7093 (3)	0.11244 (16)	0.0131 (7)
O7	0.0589 (2)	0.4875 (3)	0.43418 (16)	0.0113 (7)
O8	−0.1498 (2)	0.6392 (3)	0.23149 (17)	0.0141 (7)
O9	0.2160 (2)	1.0053 (3)	0.15949 (17)	0.0133 (7)
O10	0.1594 (2)	0.8145 (3)	0.25098 (16)	0.0127 (7)
O11	0.0780 (2)	0.7126 (3)	0.36451 (16)	0.0109 (7)
O12	0.2697 (2)	0.7693 (3)	0.13879 (17)	0.0139 (7)
OW	0.1919 (4)	0.9759 (5)	−0.1885 (3)	0.0664 (18)
N1	0.3743 (3)	1.0299 (4)	0.0906 (2)	0.0264 (11)
H1A	0.3777	1.1145	0.0918	0.040*
H1B	0.4180	0.9963	0.1123	0.040*
H1C	0.3282	1.0049	0.1123	0.040*
N2	0.2461 (4)	0.6664 (5)	−0.1049 (3)	0.0438 (15)
H2A	0.1947	0.6832	−0.1189	0.066*
H2B	0.2663	0.6020	−0.1302	0.066*
H2C	0.2776	0.7351	−0.1111	0.066*
C1	0.2544 (5)	1.1316 (7)	−0.0300 (3)	0.0452 (19)
H1D	0.1985	1.1386	−0.0116	0.054*
H1E	0.2888	1.1917	−0.0044	0.054*
C2	0.2862 (5)	0.9974 (6)	−0.0164 (4)	0.0436 (18)
H2D	0.2858	0.9515	−0.0609	0.052*
H2E	0.2474	0.9549	0.0149	0.052*
C3	0.3725 (5)	0.9862 (6)	0.0156 (3)	0.0408 (17)
H3A	0.3905	0.8981	0.0134	0.049*
H3B	0.4110	1.0370	−0.0119	0.049*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
As1	0.0061 (2)	0.0118 (2)	0.0050 (2)	0.00032 (16)	0.00033 (17)	0.00001 (16)
As2	0.0097 (2)	0.0106 (2)	0.0035 (2)	−0.00063 (16)	0.00048 (17)	0.00034 (16)
As3	0.0087 (2)	0.0108 (2)	0.0027 (2)	−0.00068 (16)	−0.00071 (17)	0.00094 (16)
Ga1	0.0069 (3)	0.0126 (3)	0.0055 (2)	0.00074 (18)	0.00024 (19)	−0.00040 (18)
Ga2	0.0088 (3)	0.0119 (2)	0.0039 (2)	−0.00069 (18)	0.00047 (19)	0.00084 (18)
Ga3	0.0088 (3)	0.0115 (2)	0.0044 (2)	0.00046 (18)	−0.00045 (19)	0.00122 (17)
F1	0.0108 (14)	0.0179 (14)	0.0179 (14)	−0.0028 (11)	0.0036 (12)	−0.0001 (11)
O13	0.0163 (19)	0.0171 (17)	0.0032 (14)	0.0023 (13)	−0.0023 (13)	−0.0001 (12)
O1	0.0091 (17)	0.0148 (16)	0.0100 (15)	−0.0009 (12)	−0.0037 (13)	−0.0024 (12)
O2	0.0186 (19)	0.0093 (15)	0.0094 (15)	−0.0030 (13)	−0.0031 (14)	0.0002 (12)
O3	0.022 (2)	0.0143 (17)	0.0042 (14)	0.0016 (13)	0.0026 (14)	−0.0012 (12)
O4	0.0097 (18)	0.0227 (18)	0.0173 (17)	−0.0049 (13)	−0.0056 (15)	0.0086 (14)
O5	0.0069 (17)	0.0234 (18)	0.0088 (15)	0.0007 (13)	−0.0020 (13)	−0.0055 (13)
O6	0.0195 (18)	0.0155 (17)	0.0045 (14)	−0.0055 (13)	−0.0021 (14)	0.0052 (12)
O7	0.0121 (18)	0.0120 (16)	0.0099 (15)	−0.0007 (12)	−0.0030 (13)	0.0014 (12)
O8	0.0075 (18)	0.0251 (19)	0.0097 (15)	−0.0012 (13)	0.0031 (13)	−0.0035 (13)
O9	0.0105 (17)	0.0128 (16)	0.0165 (16)	0.0010 (13)	0.0007 (14)	0.0004 (13)
O10	0.0086 (17)	0.0219 (18)	0.0078 (14)	−0.0016 (13)	−0.0009 (13)	0.0021 (13)
O11	0.0097 (17)	0.0162 (17)	0.0070 (14)	−0.0025 (12)	0.0015 (13)	0.0033 (12)
O12	0.0131 (19)	0.0175 (17)	0.0110 (15)	0.0052 (13)	−0.0010 (14)	0.0007 (13)
OW	0.064 (4)	0.063 (4)	0.072 (4)	−0.035 (3)	0.048 (3)	−0.038 (3)
N1	0.024 (3)	0.024 (2)	0.031 (3)	−0.0043 (19)	−0.005 (2)	−0.003 (2)
N2	0.062 (4)	0.037 (3)	0.033 (3)	−0.004 (3)	0.000 (3)	0.000 (2)
C1	0.057 (5)	0.051 (4)	0.027 (3)	0.002 (4)	−0.003 (3)	−0.010 (3)
C2	0.065 (5)	0.041 (4)	0.025 (3)	−0.009 (3)	−0.012 (3)	0.001 (3)
C3	0.058 (5)	0.037 (4)	0.027 (3)	0.006 (3)	0.010 (3)	−0.010 (3)

Geometric parameters (Å, º)

As1—O10	1.680 (3)	Ga3—O3	1.971 (3)
As1—O12	1.681 (3)	Ga3—O13	2.017 (3)
As1—O9	1.684 (3)	F1—Ga2^vi	1.985 (3)
As1—O5	1.694 (3)	F1—Ga1^vi	2.010 (3)
As2—O1	1.677 (3)	O2—As2^v	1.684 (3)
As2—O2^i	1.684 (3)	O3—As3^vii	1.663 (3)
As2—O6	1.689 (3)	O7—Ga3^i	1.872 (3)
As2—O8	1.695 (3)	O9—Ga1^v	1.977 (3)
As3—O3^ii	1.663 (3)	O12—Ga1^viii	1.832 (3)
As3—O4	1.691 (3)	N1—C3	1.490 (8)
As3—O11	1.692 (3)	N1—H1A	0.8900
As3—O7	1.698 (3)	N1—H1B	0.8900
Ga1—O12^iii	1.832 (3)	N1—H1C	0.8900
Ga1—O4	1.840 (3)	N2—C1^ix	1.462 (8)
Ga1—O8	1.857 (3)	N2—H2A	0.8900
Ga1—O9^i	1.977 (3)	N2—H2B	0.8900
Ga1—F1^iv	2.010 (3)	N2—H2C	0.8900
Ga2—O11	1.962 (3)	C1—N2^x	1.462 (8)
Ga2—O2	1.963 (3)	C1—C2	1.521 (9)
Ga2—O13	1.970 (3)	C1—H1D	0.9700
Ga2—O10	1.970 (3)	C1—H1E	0.9700
Ga2—O1	1.970 (3)	C2—C3	1.525 (10)
Ga2—F1^iv	1.985 (3)	C2—H2D	0.9700
Ga3—O7^v	1.872 (3)	C2—H2E	0.9700
Ga3—O5	1.878 (3)	C3—H3A	0.9700
Ga3—O6	1.892 (3)	C3—H3B	0.9700
O10—As1—O12	113.51 (16)	O7^v—Ga3—O13	93.42 (13)
O10—As1—O9	112.65 (16)	O5—Ga3—O13	87.60 (14)
O12—As1—O9	104.03 (16)	O6—Ga3—O13	94.66 (14)
O10—As1—O5	112.74 (16)	O3—Ga3—O13	171.18 (14)
O12—As1—O5	100.00 (15)	Ga2^vi—F1—Ga1^vi	128.55 (15)
O9—As1—O5	112.96 (16)	Ga2—O13—Ga3	128.60 (17)
O1—As2—O2^i	108.99 (16)	As2—O1—Ga2	124.91 (18)
O1—As2—O6	112.11 (16)	As2^v—O2—Ga2	126.31 (18)
O2^i—As2—O6	107.52 (15)	As3^vii—O3—Ga3	127.31 (18)
O1—As2—O8	112.26 (16)	As3—O4—Ga1	136.1 (2)
O2^i—As2—O8	109.90 (16)	As1—O5—Ga3	132.07 (18)
O6—As2—O8	105.92 (17)	As2—O6—Ga3	121.67 (18)
O3^ii—As3—O4	109.92 (17)	As3—O7—Ga3^i	118.78 (18)
O3^ii—As3—O11	108.60 (15)	As2—O8—Ga1	121.99 (19)
O4—As3—O11	115.69 (15)	As1—O9—Ga1^v	129.38 (19)
O3^ii—As3—O7	112.44 (15)	As1—O10—Ga2	122.49 (18)
O4—As3—O7	103.33 (16)	As3—O11—Ga2	128.79 (18)
O11—As3—O7	106.83 (15)	As1—O12—Ga1^viii	140.6 (2)
O12^iii—Ga1—O4	112.23 (15)	C3—N1—H1A	109.5
O12^iii—Ga1—O8	114.06 (15)	C3—N1—H1B	109.5
O4—Ga1—O8	133.57 (16)	H1A—N1—H1B	109.5
O12^iii—Ga1—O9^i	94.91 (15)	C3—N1—H1C	109.5
O4—Ga1—O9^i	89.51 (14)	H1A—N1—H1C	109.5
O8—Ga1—O9^i	90.12 (14)	H1B—N1—H1C	109.5
O12^iii—Ga1—F1^iv	89.76 (13)	C1^ix—N2—H2A	109.5
O4—Ga1—F1^iv	87.27 (13)	C1^ix—N2—H2B	109.5
O8—Ga1—F1^iv	89.40 (13)	H2A—N2—H2B	109.5
O9^i—Ga1—F1^iv	175.07 (13)	C1^ix—N2—H2C	109.5
O11—Ga2—O2	86.66 (13)	H2A—N2—H2C	109.5
O11—Ga2—O13	176.76 (14)	H2B—N2—H2C	109.5
O2—Ga2—O13	96.05 (13)	N2^x—C1—C2	113.4 (5)
O11—Ga2—O10	88.18 (13)	N2^x—C1—H1D	108.9
O2—Ga2—O10	93.94 (14)	C2—C1—H1D	108.9
O13—Ga2—O10	93.38 (14)	N2^x—C1—H1E	108.9
O11—Ga2—O1	87.71 (13)	C2—C1—H1E	108.9
O2—Ga2—O1	172.35 (14)	H1D—C1—H1E	107.7
O13—Ga2—O1	89.42 (13)	C1—C2—C3	116.6 (6)
O10—Ga2—O1	91.06 (14)	C1—C2—H2D	108.1
O11—Ga2—F1^iv	90.31 (12)	C3—C2—H2D	108.1
O2—Ga2—F1^iv	84.96 (13)	C1—C2—H2E	108.1
O13—Ga2—F1^iv	88.19 (13)	C3—C2—H2E	108.1
O10—Ga2—F1^iv	178.18 (12)	H2D—C2—H2E	107.3
O1—Ga2—F1^iv	89.89 (13)	N1—C3—C2	111.8 (5)
O7^v—Ga3—O5	137.12 (14)	N1—C3—H3A	109.2
O7^v—Ga3—O6	108.48 (15)	C2—C3—H3A	109.2
O5—Ga3—O6	114.16 (14)	N1—C3—H3B	109.2
O7^v—Ga3—O3	93.68 (13)	C2—C3—H3B	109.2
O5—Ga3—O3	83.64 (14)	H3A—C3—H3B	107.9
O6—Ga3—O3	88.04 (14)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O5^x	0.89	2.04	2.927 (5)	173
N1—H1B···F1^iii	0.89	2.36	3.008 (5)	130
N1—H1B···O2^viii	0.89	2.41	3.265 (6)	162
N1—H1C···O9	0.89	2.02	2.882 (6)	163
N2—H2A···O11^vii	0.89	2.20	3.053 (7)	160
N2—H2A···O10^vii	0.89	2.53	3.071 (6)	120
N2—H2B···OW^ix	0.89	1.85	2.738 (8)	176
N2—H2C···O6^xi	0.89	2.54	3.256 (7)	138

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