Hemipiperazinediium bis­(pyridine-2,6-dicarboxyl­ato-κ3O,N,O′)gallate(III) pyridine-2,6-dicarboxylic acid dihydrate

Rafizadeh, M.; Nemati, A.; Derikvand, Z.

doi:10.1107/S1600536808029140

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 10| October 2008| Pages m1298-m1299

doi:10.1107/S1600536808029140

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Hemipiperazinediium bis(pyridine-2,6-dicarboxylato-κ³O,N,O′)gallate(III) pyridine-2,6-dicarboxylic acid dihydrate

Masoud Rafizadeh,^a ^* Andya Nemati ^a and Zohreh Derikvand ^a

^aFaculty of Chemistry, Tarbiat Moallem University, Tehran, Iran
^*Correspondence e-mail: m_rafizadeh6@yahoo.com

(Received 25 August 2008; accepted 11 September 2008; online 20 September 2008)

The asymmetric unit of the title compound, (C₄H₁₂N₂)_0.5[Ga(pydc)₂]·pydcH₂·2H₂O, where pydcH₂ is pyridine-2,6-dicarboxylic acid, C₇H₅NO₄, contains one half of a centrosymmetric piperazinediium dication, one anion, one uncoordinated pydcH₂ molecule and two uncoordinated water molecules, one of which is disordered over two sites in a 1:1 ratio. In the anion, the Ga^III ion is coordinated by four O atoms [Ga—O = 1.9706 (16)–2.0494 (15) Å] and two N atoms [Ga—N = 1.9660 (18) and 1.9709 (17) Å] from two pydc ligands in a distorted octahedral geometry. The crystal structure exhibits intermolecular O—H⋯O, N—H⋯O and O—H⋯N hydrogen bonds and π–π interactions [centroid–centroid distances of 3.5359 (13) and 3.6550 (14) Å].

Related literature

For self-assembling systems involving pydcH₂, see: Aghabozorg et al. (2006a ,b ). For related complexes of the pyridine-2,6-dicarboxylate ligand with transition metals, see: Rafizadeh et al. (2005 , 2006 ); Rafizadeh & Amani (2006 ); Aghabozorg et al. (2007 , 2008 ). For details of the synthesis, see: Sheshmani et al. (2006 ).

Experimental

Crystal data

(C₄H₁₂N₂)_0.5[Ga(C₇H₃NO₄)₂·C₇H₅NO₄·2H₂O
M_r = 647.16
Triclinic, $[P \overline 1]$
a = 8.6434 (4) Å
b = 11.8582 (5) Å
c = 13.7907 (6) Å
α = 65.7151 (10)°
β = 80.0391 (10)°
γ = 86.9150 (11)°
V = 1268.74 (10) Å³
Z = 2
Mo Kα radiation
μ = 1.17 mm⁻¹
T = 120 (2) K
0.25 × 0.20 × 0.18 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1998 ) T_min = 0.749, T_max = 0.807
13018 measured reflections
6067 independent reflections
5263 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.099
S = 1.00
6067 reflections
382 parameters
H-atom parameters constrained
Δρ_max = 0.86 e Å⁻³
Δρ_min = −0.84 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4B⋯O13ⁱ	0.92	1.84	2.754 (3)	169
N4—H4C⋯O14	0.92	1.94	2.818 (4)	160
N4—H4C⋯O14′	0.92	1.85	2.681 (4)	150
O9—H9O⋯O8ⁱⁱ	0.89	1.90	2.710 (2)	150
O11—H11O⋯O8ⁱⁱ	0.87	1.91	2.725 (2)	155
O13—H13A⋯O4	0.97	1.88	2.823 (3)	163
O13—H13B⋯O2ⁱⁱⁱ	0.92	1.84	2.765 (3)	175
O14—H14A⋯O10	0.91	1.95	2.798 (5)	153
O14—H14B⋯O1^iv	0.96	2.15	2.974 (5)	143
N4—H4C⋯O12ⁱⁱ	0.92	2.50	2.863 (3)	104
O9—H9O⋯N3	0.89	2.20	2.678 (3)	113
O11—H11O⋯N3	0.87	2.22	2.690 (2)	114
Symmetry codes: (i) x-1, y, z; (ii) -x+1, -y+1, -z; (iii) -x+1, -y+1, -z+1; (iv) x, y-1, z.

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT-Plus (Bruker, 1998); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); 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/S1600536808029140/cv2438sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808029140/cv2438Isup2.hkl

checkCIF report

Comment top

In continuation of our study of self-assembling systems (pipzH₂)₃²⁺[In(pydc)₃]₂^3-.12H₂O, (pipzH₂)²⁺[Tl₂(pydc)₂Cl₄(H₂O)₂]^2-.4H₂O and some others (Aghabozorg et al., 2006a,b), we present here the crystal structure of the title compound, (I).

In (I) (Fig. 1), all bond lengths and angles are normal and correspond to those observed in the related complexes of pyridine-2,6-dicarboxylate ligand with transition metals (Rafizadeh et al., 2005; Rafizadeh, Mehrabi & Amani, 2006; Rafizadeh & Amani, 2006; Aghabozorg et al., 2007, 2008). In the anion, the angles O1—Ga—O3 [158.69 (6)°], O5—Ga—O7 [158.65 (6)°] and N1—Ga—N2 [171.11 (7)°] indicate that the coordination environment around Ga^III ion is a distorted octahedron.

In the crystal, the π–π interactions (Table 1) and extensive three-dimensional network of intermolecular O—H···O, O—H···N and N—H···O hydrogen bonds (Table 2) contribute to the crystal packing stability.

Related literature top

For self-assembling systems involving pydcH₂, see: Aghabozorg et al. (2006a,b).For related complexes of the pyridine-2,6-dicarboxylate ligand with transition metals, see: Rafizadeh et al. (2005); Rafizadeh & Amani (2006); Rafizadeh, Mehrabi & Amani (2006); Aghabozorg et al., 2007, 2008). For details of the synthesis, see: Sheshmani et al., 2006).

Experimental top

The proton transfer compound (pipzH₂)(pydcH)₂.3H₂O, was prepared by the reaction of pyridine-2,6-dicarboxylic acid, pydcH₂, with piperazine, pipz, (Sheshmani et al., 2006). The reaction between Ga(NO₃)₃.8H₂O (200.0 mg, 0.5 mmol) in water (25 ml) and the proton transfer compound (pipzH₂)(pydcH)₂.3H₂O (253.0 mg, 1.0 mmol) in water (25 ml), in a 1:2 molar ratio was carried by slow evaporation of the solvent at room temperature.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1998); data reduction: SAINT-Plus(Bruker, 1998); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. Molecular structure of the title compound, showing the atomic numbering, 50% probability displacement ellipsoids and disordered water molecule. Hydrogen bonds are shown as dashed lines.

Hemipiperazinediium bis(pyridine-2,6-dicarboxylato-κ³O,N,O')gallate(III) pyridine-2,6-dicarboxylic acid dihydrate top

Crystal data top

(C₄H₁₂N₂)_0.5[Ga(C₇H₃NO₄)₂]·C₇H₅NO₄·2H₂O	Z = 2
M_r = 647.16	F(000) = 660
Triclinic, P1	D_x = 1.694 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.6434 (4) Å	Cell parameters from 6643 reflections
b = 11.8582 (5) Å	θ = 2.4–29.9°
c = 13.7907 (6) Å	µ = 1.17 mm⁻¹
α = 65.7151 (10)°	T = 120 K
β = 80.0391 (10)°	Prism, colourless
γ = 86.9150 (11)°	0.25 × 0.20 × 0.18 mm
V = 1268.74 (10) Å³

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	6067 independent reflections
Radiation source: fine-focus sealed tube	5263 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ϕ and ω scans	θ_max = 28.0°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1998a)	h = −11→11
T_min = 0.749, T_max = 0.807	k = −15→15
13018 measured reflections	l = −18→18

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)] = 0.039	Hydrogen site location: mixed
wR(F²) = 0.099	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.043P)² + 2.120P] where P = (F_o² + 2F_c²)/3
6067 reflections	(Δ/σ)_max = 0.001
382 parameters	Δρ_max = 0.86 e Å⁻³
0 restraints	Δρ_min = −0.84 e Å⁻³

Crystal data top

(C₄H₁₂N₂)_0.5[Ga(C₇H₃NO₄)₂]·C₇H₅NO₄·2H₂O	γ = 86.9150 (11)°
M_r = 647.16	V = 1268.74 (10) Å³
Triclinic, P1	Z = 2
a = 8.6434 (4) Å	Mo Kα radiation
b = 11.8582 (5) Å	µ = 1.17 mm⁻¹
c = 13.7907 (6) Å	T = 120 K
α = 65.7151 (10)°	0.25 × 0.20 × 0.18 mm
β = 80.0391 (10)°

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	6067 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1998a)	5263 reflections with I > 2σ(I)
T_min = 0.749, T_max = 0.807	R_int = 0.024
13018 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.099	H-atom parameters constrained
S = 1.00	Δρ_max = 0.86 e Å⁻³
6067 reflections	Δρ_min = −0.84 e Å⁻³
382 parameters

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.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ga1	0.69834 (3)	0.81449 (2)	0.236980 (18)	0.01489 (8)
O1	0.49972 (19)	0.87108 (15)	0.30323 (13)	0.0197 (3)
O2	0.3151 (2)	0.80985 (17)	0.45133 (15)	0.0282 (4)
O3	0.89040 (18)	0.71384 (14)	0.22836 (12)	0.0172 (3)
O4	1.00566 (19)	0.53668 (15)	0.31985 (13)	0.0221 (3)
O5	0.82240 (19)	0.95577 (14)	0.22476 (13)	0.0196 (3)
O6	0.9372 (2)	1.13613 (15)	0.10526 (14)	0.0247 (4)
O7	0.56973 (18)	0.71043 (14)	0.19088 (12)	0.0175 (3)
O8	0.49004 (19)	0.70052 (14)	0.04916 (13)	0.0197 (3)
N1	0.6764 (2)	0.69072 (16)	0.38696 (14)	0.0149 (3)
N2	0.7106 (2)	0.91756 (16)	0.08145 (14)	0.0136 (3)
C1	0.5515 (3)	0.6960 (2)	0.45659 (17)	0.0167 (4)
C2	0.5309 (3)	0.6093 (2)	0.56250 (18)	0.0210 (4)
H2A	0.4444	0.6131	0.6139	0.025*
C3	0.6416 (3)	0.5158 (2)	0.59122 (18)	0.0219 (5)
H3A	0.6310	0.4555	0.6635	0.026*
C4	0.7666 (3)	0.5101 (2)	0.51542 (17)	0.0192 (4)
H4A	0.8400	0.4452	0.5342	0.023*
C5	0.7816 (3)	0.60203 (19)	0.41114 (17)	0.0156 (4)
C6	0.4444 (3)	0.8002 (2)	0.40167 (18)	0.0191 (4)
C7	0.9052 (3)	0.6166 (2)	0.31338 (17)	0.0166 (4)
C8	0.7917 (2)	1.02317 (19)	0.04205 (17)	0.0153 (4)
C9	0.8099 (3)	1.0982 (2)	−0.06768 (18)	0.0186 (4)
H9A	0.8670	1.1745	−0.0976	0.022*
C10	0.7412 (3)	1.0574 (2)	−0.13246 (18)	0.0203 (4)
H10A	0.7516	1.1069	−0.2077	0.024*
C11	0.6578 (3)	0.9454 (2)	−0.08861 (17)	0.0174 (4)
H11A	0.6120	0.9174	−0.1328	0.021*
C12	0.6438 (2)	0.87575 (19)	0.02216 (17)	0.0147 (4)
C13	0.8575 (3)	1.0439 (2)	0.12937 (18)	0.0172 (4)
C14	0.5601 (2)	0.75183 (19)	0.09115 (17)	0.0151 (4)
O9	0.58636 (19)	0.23498 (15)	0.14907 (13)	0.0210 (3)
H9O	0.5960	0.2683	0.0773	0.025*
O10	0.6888 (2)	0.25644 (16)	0.27682 (13)	0.0254 (4)
O11	0.6148 (2)	0.53088 (15)	−0.19160 (13)	0.0217 (3)
H11O	0.6047	0.4592	−0.1367	0.026*
O12	0.7671 (2)	0.69899 (16)	−0.25682 (14)	0.0280 (4)
N3	0.7038 (2)	0.45536 (16)	0.00267 (14)	0.0157 (3)
C15	0.7399 (2)	0.4193 (2)	0.10158 (17)	0.0167 (4)
C16	0.8334 (3)	0.4892 (2)	0.12957 (18)	0.0195 (4)
H16A	0.8564	0.4600	0.2007	0.023*
C17	0.8921 (3)	0.6026 (2)	0.05116 (19)	0.0207 (4)
H17A	0.9560	0.6529	0.0676	0.025*
C18	0.8560 (3)	0.6413 (2)	−0.05174 (19)	0.0192 (4)
H18A	0.8950	0.7184	−0.1072	0.023*
C19	0.7612 (2)	0.56477 (19)	−0.07202 (17)	0.0158 (4)
C20	0.6712 (3)	0.2969 (2)	0.18329 (18)	0.0182 (4)
C21	0.7167 (3)	0.6045 (2)	−0.18171 (18)	0.0191 (4)
N4	0.1327 (2)	0.08293 (17)	0.44706 (15)	0.0178 (4)
H4B	0.0905	0.1566	0.4452	0.021*
H4C	0.2365	0.0977	0.4152	0.021*
C22	0.1227 (3)	−0.0079 (2)	0.56174 (17)	0.0183 (4)
H22A	0.1770	0.0268	0.6012	0.022*
H22B	0.1760	−0.0849	0.5644	0.022*
C23	0.0474 (3)	0.0373 (2)	0.38454 (17)	0.0193 (4)
H23A	0.0981	−0.0380	0.3808	0.023*
H23B	0.0525	0.1012	0.3100	0.023*
O13	0.9874 (2)	0.28616 (16)	0.46782 (16)	0.0303 (4)
H13A	0.9995	0.3653	0.4063	0.045*
H13B	0.8844	0.2583	0.4939	0.045*
O14	0.4588 (4)	0.0692 (4)	0.3846 (3)	0.0273 (6)	0.50
H14B	0.4838	0.0384	0.3297	0.041*	0.50
O14'	0.4459 (4)	0.0981 (4)	0.4270 (3)	0.0273 (6)	0.50
H14C	0.4715	0.0321	0.4851	0.041*	0.50
H14A	0.5272	0.1322	0.3704	0.041*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ga1	0.01791 (13)	0.01363 (12)	0.01235 (12)	−0.00172 (8)	−0.00268 (8)	−0.00423 (9)
O1	0.0207 (8)	0.0183 (7)	0.0188 (8)	0.0022 (6)	−0.0022 (6)	−0.0070 (6)
O2	0.0233 (9)	0.0275 (9)	0.0299 (9)	0.0030 (7)	0.0045 (7)	−0.0114 (8)
O3	0.0182 (7)	0.0171 (7)	0.0150 (7)	−0.0004 (6)	−0.0020 (6)	−0.0055 (6)
O4	0.0207 (8)	0.0224 (8)	0.0225 (8)	0.0047 (6)	−0.0045 (6)	−0.0085 (7)
O5	0.0254 (8)	0.0175 (7)	0.0172 (7)	−0.0038 (6)	−0.0056 (6)	−0.0070 (6)
O6	0.0277 (9)	0.0187 (8)	0.0281 (9)	−0.0082 (7)	−0.0054 (7)	−0.0086 (7)
O7	0.0219 (8)	0.0161 (7)	0.0135 (7)	−0.0050 (6)	−0.0041 (6)	−0.0039 (6)
O8	0.0232 (8)	0.0178 (7)	0.0201 (8)	−0.0044 (6)	−0.0056 (6)	−0.0082 (6)
N1	0.0157 (8)	0.0153 (8)	0.0133 (8)	−0.0020 (7)	−0.0018 (6)	−0.0055 (7)
N2	0.0136 (8)	0.0127 (8)	0.0129 (8)	0.0003 (6)	−0.0021 (6)	−0.0038 (6)
C1	0.0176 (10)	0.0184 (10)	0.0163 (10)	−0.0015 (8)	0.0001 (8)	−0.0101 (8)
C2	0.0266 (12)	0.0225 (11)	0.0154 (10)	−0.0037 (9)	0.0018 (8)	−0.0107 (9)
C3	0.0341 (13)	0.0176 (10)	0.0129 (10)	−0.0028 (9)	−0.0041 (9)	−0.0045 (8)
C4	0.0255 (11)	0.0163 (10)	0.0162 (10)	−0.0006 (8)	−0.0071 (8)	−0.0054 (8)
C5	0.0182 (10)	0.0137 (9)	0.0159 (10)	−0.0016 (8)	−0.0046 (8)	−0.0062 (8)
C6	0.0204 (11)	0.0180 (10)	0.0211 (10)	−0.0006 (8)	−0.0024 (8)	−0.0105 (8)
C7	0.0178 (10)	0.0176 (10)	0.0162 (10)	−0.0011 (8)	−0.0056 (8)	−0.0076 (8)
C8	0.0147 (9)	0.0128 (9)	0.0178 (10)	−0.0013 (7)	−0.0021 (8)	−0.0057 (8)
C9	0.0180 (10)	0.0146 (10)	0.0201 (10)	−0.0020 (8)	−0.0024 (8)	−0.0038 (8)
C10	0.0207 (11)	0.0210 (11)	0.0144 (10)	−0.0006 (8)	−0.0011 (8)	−0.0030 (8)
C11	0.0183 (10)	0.0191 (10)	0.0150 (10)	0.0008 (8)	−0.0046 (8)	−0.0065 (8)
C12	0.0135 (9)	0.0149 (9)	0.0169 (10)	0.0006 (7)	−0.0030 (7)	−0.0075 (8)
C13	0.0170 (10)	0.0155 (10)	0.0183 (10)	−0.0007 (8)	−0.0035 (8)	−0.0059 (8)
C14	0.0138 (9)	0.0151 (9)	0.0163 (9)	−0.0001 (7)	−0.0024 (7)	−0.0064 (8)
O9	0.0271 (8)	0.0175 (7)	0.0158 (7)	−0.0077 (6)	−0.0034 (6)	−0.0032 (6)
O10	0.0305 (9)	0.0269 (9)	0.0154 (8)	−0.0071 (7)	−0.0040 (7)	−0.0043 (7)
O11	0.0283 (9)	0.0197 (8)	0.0155 (7)	−0.0052 (6)	−0.0070 (6)	−0.0035 (6)
O12	0.0339 (10)	0.0209 (8)	0.0213 (8)	−0.0081 (7)	−0.0045 (7)	0.0002 (7)
N3	0.0173 (9)	0.0148 (8)	0.0161 (8)	−0.0028 (7)	−0.0026 (7)	−0.0071 (7)
C15	0.0166 (10)	0.0190 (10)	0.0145 (9)	0.0000 (8)	−0.0007 (8)	−0.0075 (8)
C16	0.0188 (10)	0.0245 (11)	0.0185 (10)	−0.0008 (8)	−0.0023 (8)	−0.0121 (9)
C17	0.0190 (10)	0.0236 (11)	0.0256 (11)	−0.0048 (8)	−0.0006 (9)	−0.0168 (9)
C18	0.0181 (10)	0.0154 (10)	0.0240 (11)	−0.0032 (8)	0.0007 (8)	−0.0093 (9)
C19	0.0167 (10)	0.0143 (9)	0.0161 (9)	−0.0012 (8)	−0.0006 (8)	−0.0064 (8)
C20	0.0164 (10)	0.0198 (10)	0.0175 (10)	−0.0018 (8)	−0.0020 (8)	−0.0069 (8)
C21	0.0189 (10)	0.0182 (10)	0.0187 (10)	−0.0024 (8)	−0.0015 (8)	−0.0061 (8)
N4	0.0179 (9)	0.0150 (8)	0.0186 (9)	−0.0022 (7)	−0.0011 (7)	−0.0054 (7)
C22	0.0209 (11)	0.0168 (10)	0.0169 (10)	0.0004 (8)	−0.0057 (8)	−0.0057 (8)
C23	0.0239 (11)	0.0184 (10)	0.0148 (10)	−0.0005 (8)	−0.0023 (8)	−0.0061 (8)
O13	0.0278 (9)	0.0159 (8)	0.0394 (10)	−0.0010 (7)	0.0036 (8)	−0.0069 (7)
O14	0.0209 (11)	0.0258 (15)	0.0248 (18)	−0.0049 (10)	−0.0007 (13)	−0.0006 (11)
O14'	0.0209 (11)	0.0258 (15)	0.0248 (18)	−0.0049 (10)	−0.0007 (13)	−0.0006 (11)

Geometric parameters (Å, º) top

Ga1—N1	1.9660 (18)	C12—C14	1.521 (3)
Ga1—O5	1.9706 (16)	O9—C20	1.328 (3)
Ga1—N2	1.9709 (17)	O9—H9O	0.8922
Ga1—O3	2.0073 (16)	O10—C20	1.212 (3)
Ga1—O1	2.0175 (16)	O11—C21	1.334 (3)
Ga1—O7	2.0494 (15)	O11—H11O	0.8710
O1—C6	1.288 (3)	O12—C21	1.208 (3)
O2—C6	1.232 (3)	N3—C19	1.336 (3)
O3—C7	1.282 (3)	N3—C15	1.340 (3)
O4—C7	1.236 (3)	C15—C16	1.390 (3)
O5—C13	1.296 (3)	C15—C20	1.498 (3)
O6—C13	1.218 (3)	C16—C17	1.387 (3)
O7—C14	1.272 (3)	C16—H16A	0.9500
O8—C14	1.234 (3)	C17—C18	1.387 (3)
N1—C5	1.326 (3)	C17—H17A	0.9500
N1—C1	1.332 (3)	C18—C19	1.393 (3)
N2—C8	1.326 (3)	C18—H18A	0.9500
N2—C12	1.333 (3)	C19—C21	1.501 (3)
C1—C2	1.385 (3)	N4—C23	1.492 (3)
C1—C6	1.519 (3)	N4—C22	1.493 (3)
C2—C3	1.399 (3)	N4—H4B	0.9200
C2—H2A	0.9500	N4—H4C	0.9200
C3—C4	1.387 (3)	C22—C23ⁱ	1.516 (3)
C3—H3A	0.9500	C22—H22A	0.9900
C4—C5	1.391 (3)	C22—H22B	0.9900
C4—H4A	0.9500	C23—C22ⁱ	1.516 (3)
C5—C7	1.523 (3)	C23—H23A	0.9900
C8—C9	1.390 (3)	C23—H23B	0.9900
C8—C13	1.526 (3)	O13—H13A	0.9680
C9—C10	1.398 (3)	O13—H13B	0.9241
C9—H9A	0.9500	O14—H14B	0.9561
C10—C11	1.393 (3)	O14—H14A	0.9136
C10—H10A	0.9500	O14'—H14C	0.9120
C11—C12	1.393 (3)	O14'—H14A	0.9201
C11—H11A	0.9500

Cg1···Cg1ⁱⁱ	3.5359 (13)	Cg2···Cg2ⁱⁱⁱ	3.6550 (14)

N1—Ga1—O5	108.00 (7)	C10—C11—H11A	121.1
N1—Ga1—N2	171.11 (7)	N2—C12—C11	119.35 (19)
O5—Ga1—N2	80.53 (7)	N2—C12—C14	111.43 (18)
N1—Ga1—O3	79.40 (7)	C11—C12—C14	129.22 (19)
O5—Ga1—O3	92.73 (7)	O6—C13—O5	126.4 (2)
N2—Ga1—O3	98.00 (7)	O6—C13—C8	119.7 (2)
N1—Ga1—O1	79.32 (7)	O5—C13—C8	113.88 (18)
O5—Ga1—O1	92.66 (7)	O8—C14—O7	125.60 (19)
N2—Ga1—O1	103.22 (7)	O8—C14—C12	119.95 (19)
O3—Ga1—O1	158.69 (6)	O7—C14—C12	114.45 (18)
N1—Ga1—O7	93.34 (7)	C20—O9—H9O	111.7
O5—Ga1—O7	158.65 (6)	C21—O11—H11O	111.4
N2—Ga1—O7	78.18 (7)	C19—N3—C15	117.42 (18)
O3—Ga1—O7	91.71 (6)	N3—C15—C16	123.5 (2)
O1—Ga1—O7	90.73 (7)	N3—C15—C20	115.68 (19)
C6—O1—Ga1	115.97 (14)	C16—C15—C20	120.8 (2)
C7—O3—Ga1	116.61 (14)	C17—C16—C15	118.4 (2)
C13—O5—Ga1	116.85 (14)	C17—C16—H16A	120.8
C14—O7—Ga1	116.91 (13)	C15—C16—H16A	120.8
C5—N1—C1	123.75 (19)	C16—C17—C18	118.9 (2)
C5—N1—Ga1	117.85 (14)	C16—C17—H17A	120.6
C1—N1—Ga1	118.25 (15)	C18—C17—H17A	120.6
C8—N2—C12	124.25 (18)	C17—C18—C19	118.6 (2)
C8—N2—Ga1	116.74 (14)	C17—C18—H18A	120.7
C12—N2—Ga1	118.95 (14)	C19—C18—H18A	120.7
N1—C1—C2	119.9 (2)	N3—C19—C18	123.2 (2)
N1—C1—C6	111.16 (18)	N3—C19—C21	116.56 (19)
C2—C1—C6	128.9 (2)	C18—C19—C21	120.18 (19)
C1—C2—C3	117.7 (2)	O10—C20—O9	120.9 (2)
C1—C2—H2A	121.1	O10—C20—C15	122.2 (2)
C3—C2—H2A	121.1	O9—C20—C15	116.82 (19)
C4—C3—C2	120.8 (2)	O12—C21—O11	121.3 (2)
C4—C3—H3A	119.6	O12—C21—C19	122.4 (2)
C2—C3—H3A	119.6	O11—C21—C19	116.24 (19)
C3—C4—C5	118.2 (2)	C23—N4—C22	111.88 (16)
C3—C4—H4A	120.9	C23—N4—H4B	109.2
C5—C4—H4A	120.9	C22—N4—H4B	109.2
N1—C5—C4	119.5 (2)	C23—N4—H4C	109.2
N1—C5—C7	111.65 (18)	C22—N4—H4C	109.2
C4—C5—C7	128.8 (2)	H4B—N4—H4C	107.9
O2—C6—O1	125.6 (2)	N4—C22—C23ⁱ	110.48 (17)
O2—C6—C1	119.7 (2)	N4—C22—H22A	109.6
O1—C6—C1	114.70 (19)	C23ⁱ—C22—H22A	109.6
O4—C7—O3	125.8 (2)	N4—C22—H22B	109.6
O4—C7—C5	120.05 (19)	C23ⁱ—C22—H22B	109.6
O3—C7—C5	114.15 (18)	H22A—C22—H22B	108.1
N2—C8—C9	119.8 (2)	N4—C23—C22ⁱ	109.99 (18)
N2—C8—C13	111.98 (18)	N4—C23—H23A	109.7
C9—C8—C13	128.25 (19)	C22ⁱ—C23—H23A	109.7
C8—C9—C10	117.6 (2)	N4—C23—H23B	109.7
C8—C9—H9A	121.2	C22ⁱ—C23—H23B	109.7
C10—C9—H9A	121.2	H23A—C23—H23B	108.2
C11—C10—C9	121.2 (2)	H13A—O13—H13B	114.1
C11—C10—H10A	119.4	H14B—O14—H14C	137.1
C9—C10—H10A	119.4	H14B—O14—H14A	109.3
C12—C11—C10	117.8 (2)	H14C—O14—H14A	87.3
C12—C11—H11A	121.1	H14C—O14'—H14A	115.4

N1—Ga1—O1—C6	−6.27 (15)	N1—C1—C6—O1	−6.8 (3)
O5—Ga1—O1—C6	−114.09 (16)	C2—C1—C6—O1	176.0 (2)
N2—Ga1—O1—C6	165.03 (15)	Ga1—O3—C7—O4	171.78 (17)
O3—Ga1—O1—C6	−9.6 (3)	Ga1—O3—C7—C5	−6.4 (2)
O7—Ga1—O1—C6	87.00 (16)	N1—C5—C7—O4	−174.74 (19)
N1—Ga1—O3—C7	5.46 (15)	C4—C5—C7—O4	3.7 (3)
O5—Ga1—O3—C7	113.27 (15)	N1—C5—C7—O3	3.5 (3)
N2—Ga1—O3—C7	−165.92 (15)	C4—C5—C7—O3	−178.0 (2)
O1—Ga1—O3—C7	8.8 (3)	C12—N2—C8—C9	0.5 (3)
O7—Ga1—O3—C7	−87.62 (15)	Ga1—N2—C8—C9	177.69 (16)
N1—Ga1—O5—C13	175.84 (15)	C12—N2—C8—C13	−178.39 (18)
N2—Ga1—O5—C13	−1.56 (16)	Ga1—N2—C8—C13	−1.2 (2)
O3—Ga1—O5—C13	96.10 (16)	N2—C8—C9—C10	−0.4 (3)
O1—Ga1—O5—C13	−104.53 (16)	C13—C8—C9—C10	178.3 (2)
O7—Ga1—O5—C13	−5.7 (3)	C8—C9—C10—C11	−0.1 (3)
N1—Ga1—O7—C14	−174.98 (16)	C9—C10—C11—C12	0.6 (3)
O5—Ga1—O7—C14	6.5 (3)	C8—N2—C12—C11	0.0 (3)
N2—Ga1—O7—C14	2.31 (15)	Ga1—N2—C12—C11	−177.16 (15)
O3—Ga1—O7—C14	−95.50 (15)	C8—N2—C12—C14	179.72 (18)
O1—Ga1—O7—C14	105.67 (15)	Ga1—N2—C12—C14	2.6 (2)
O5—Ga1—N1—C5	−92.75 (16)	C10—C11—C12—N2	−0.5 (3)
O3—Ga1—N1—C5	−3.32 (15)	C10—C11—C12—C14	179.8 (2)
O1—Ga1—N1—C5	177.91 (16)	Ga1—O5—C13—O6	−177.41 (19)
O7—Ga1—N1—C5	87.80 (16)	Ga1—O5—C13—C8	1.3 (2)
O5—Ga1—N1—C1	91.47 (16)	N2—C8—C13—O6	178.7 (2)
O3—Ga1—N1—C1	−179.09 (17)	C9—C8—C13—O6	0.0 (4)
O1—Ga1—N1—C1	2.14 (15)	N2—C8—C13—O5	−0.1 (3)
O7—Ga1—N1—C1	−87.97 (16)	C9—C8—C13—O5	−178.9 (2)
O5—Ga1—N2—C8	1.50 (15)	Ga1—O7—C14—O8	178.77 (17)
O3—Ga1—N2—C8	−89.95 (16)	Ga1—O7—C14—C12	−1.6 (2)
O1—Ga1—N2—C8	92.02 (16)	N2—C12—C14—O8	179.09 (19)
O7—Ga1—N2—C8	179.97 (16)	C11—C12—C14—O8	−1.2 (3)
O5—Ga1—N2—C12	178.85 (16)	N2—C12—C14—O7	−0.6 (3)
O3—Ga1—N2—C12	87.40 (16)	C11—C12—C14—O7	179.2 (2)
O1—Ga1—N2—C12	−90.63 (16)	C19—N3—C15—C16	−0.2 (3)
O7—Ga1—N2—C12	−2.69 (15)	C19—N3—C15—C20	179.14 (19)
C5—N1—C1—C2	3.5 (3)	N3—C15—C16—C17	0.2 (3)
Ga1—N1—C1—C2	179.03 (16)	C20—C15—C16—C17	−179.1 (2)
C5—N1—C1—C6	−173.91 (19)	C15—C16—C17—C18	−0.3 (3)
Ga1—N1—C1—C6	1.6 (2)	C16—C17—C18—C19	0.3 (3)
N1—C1—C2—C3	−2.1 (3)	C15—N3—C19—C18	0.2 (3)
C6—C1—C2—C3	174.9 (2)	C15—N3—C19—C21	−178.88 (19)
C1—C2—C3—C4	−0.7 (3)	C17—C18—C19—N3	−0.3 (3)
C2—C3—C4—C5	2.1 (3)	C17—C18—C19—C21	178.8 (2)
C1—N1—C5—C4	−2.1 (3)	N3—C15—C20—O10	−176.5 (2)
Ga1—N1—C5—C4	−177.58 (15)	C16—C15—C20—O10	2.9 (3)
C1—N1—C5—C7	176.57 (19)	N3—C15—C20—O9	2.1 (3)
Ga1—N1—C5—C7	1.0 (2)	C16—C15—C20—O9	−178.5 (2)
C3—C4—C5—N1	−0.8 (3)	N3—C19—C21—O12	−176.7 (2)
C3—C4—C5—C7	−179.1 (2)	C18—C19—C21—O12	4.1 (3)
Ga1—O1—C6—O2	−170.02 (19)	N3—C19—C21—O11	4.8 (3)
Ga1—O1—C6—C1	8.8 (2)	C18—C19—C21—O11	−174.3 (2)
N1—C1—C6—O2	172.1 (2)	C23—N4—C22—C23ⁱ	−57.1 (3)
C2—C1—C6—O2	−5.1 (4)	C22—N4—C23—C22ⁱ	56.8 (2)

Symmetry codes: (i) −x, −y, −z+1; (ii) −x+2, −y+1, −z; (iii) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4B···O13^iv	0.92	1.84	2.754 (3)	169
N4—H4C···O14	0.92	1.94	2.818 (4)	160
N4—H4C···O14′	0.92	1.85	2.681 (4)	150
O9—H9O···O8^v	0.89	1.90	2.710 (2)	150
O11—H11O···O8^v	0.87	1.91	2.725 (2)	155
O13—H13A···O4	0.97	1.88	2.823 (3)	163
O13—H13B···O2ⁱⁱⁱ	0.92	1.84	2.765 (3)	175
O14—H14A···O10	0.91	1.95	2.798 (5)	153
O14—H14B···O1^vi	0.96	2.15	2.974 (5)	143
O14′—H14C···O14^vii	0.91	1.89	2.774 (6)	164
N4—H4C···O12^v	0.92	2.50	2.863 (3)	104
O9—H9O···N3	0.89	2.20	2.678 (3)	113
O11—H11O···N3	0.87	2.22	2.690 (2)	114
C3—H3A···O11^viii	0.95	2.48	3.042 (3)	117
C9—H9A···O3^ix	0.95	2.54	3.341 (3)	143
C17—H17A···O3	0.95	2.57	3.217 (3)	126
C18—H18A···O6^ix	0.95	2.32	3.026 (3)	130
C22—H22A···O5ⁱⁱⁱ	0.99	2.49	3.360 (3)	146
C22—H22B···O2^vi	0.99	2.50	3.346 (3)	144
C23—H23A···O2^vi	0.99	2.56	3.391 (3)	142

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

Experimental details

Crystal data
Chemical formula	(C₄H₁₂N₂)_0.5[Ga(C₇H₃NO₄)₂]·C₇H₅NO₄·2H₂O
M_r	647.16
Crystal system, space group	Triclinic, P1
Temperature (K)	120
a, b, c (Å)	8.6434 (4), 11.8582 (5), 13.7907 (6)
α, β, γ (°)	65.7151 (10), 80.0391 (10), 86.9150 (11)
V (Å³)	1268.74 (10)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.17
Crystal size (mm)	0.25 × 0.20 × 0.18

Data collection
Diffractometer	Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1998a)
T_min, T_max	0.749, 0.807
No. of measured, independent and observed [I > 2σ(I)] reflections	13018, 6067, 5263
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.099, 1.00
No. of reflections	6067
No. of parameters	382
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.86, −0.84

Computer programs: SMART (Bruker, 1998), SAINT-Plus (Bruker, 1998), SAINT-Plus(Bruker, 1998), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4B···O13ⁱ	0.92	1.84	2.754 (3)	169
N4—H4C···O14	0.92	1.94	2.818 (4)	160
N4—H4C···O14'	0.92	1.85	2.681 (4)	150
O9—H9O···O8ⁱⁱ	0.89	1.90	2.710 (2)	150
O11—H11O···O8ⁱⁱ	0.87	1.91	2.725 (2)	155
O13—H13A···O4	0.97	1.88	2.823 (3)	163
O13—H13B···O2ⁱⁱⁱ	0.92	1.84	2.765 (3)	175
O14—H14A···O10	0.91	1.95	2.798 (5)	153
O14—H14B···O1^iv	0.96	2.15	2.974 (5)	143
N4—H4C···O12ⁱⁱ	0.92	2.50	2.863 (3)	104
O9—H9O···N3	0.89	2.20	2.678 (3)	113
O11—H11O···N3	0.87	2.22	2.690 (2)	114

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

References

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