Bis­(μ-pyridine-2,3-dicarboxyl­ato)bis­[aqua­(3-carb­oxy­pyridine-2-carboxyl­ato)indium(III)] tetra­hydrate

Eshtiagh-Hosseini, H.; Mirzaei, M.; Mousavinezhad, A.; Necas, M.; Mague, J.T.

doi:10.1107/S1600536811053566

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 1| January 2012| Pages m71-m72

doi:10.1107/S1600536811053566

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Bis(μ-pyridine-2,3-dicarboxylato)bis[aqua(3-carboxypyridine-2-carboxylato)indium(III)] tetrahydrate

H. Eshtiagh-Hosseini,^a M. Mirzaei,^a A. Mousavinezhad,^a M. Necas ^b and J. T. Mague ^c ^*

^aDepartment of Chemistry, Ferdowsi University of Mashhad, 917791436 Mashhad, Iran, ^bDepartment of Chemistry, Faculty of Science, Masaryk University, Kamenice 5, Brno 625 00, Czech Republic, and ^cDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA
^*Correspondence e-mail: joelt@tulane.edu

(Received 9 December 2011; accepted 12 December 2011; online 21 December 2011)

In the binuclear centrosymmetric title compound, [In₂(C₇H₃NO₄)₂(C₇H₄NO₄)₂(H₂O)₂]·4H₂O, which contains both pyridine-2,3-dicarboxylate and 3-carboxypyridine-2-carboxylate ligands, the In^III atom is six-coordinated in a distorted octahedral geometry. One pyridine ligand is N,O-chelated while the other is N,O-chelated and at the same time bridging to the other via the second carboxyl group. In the crystal, an extensive O—H⋯O hydrogen-bonding network, involving the coordinated and lattice water molecules and the carboxyl groups of the ligands, together with C—H⋯O and π–π interactions [centroid–centroid distance = 3.793 (1) Å], leads to the formation of a three-dimensional structure.

Related literature

For metal complexes with polycarboxylate ligands, see: Aghabozorg, Daneshvar et al. (2007 ); Aghabozorg, Khadivi et al. (2008 ); Aghabozorg, Ramezanipour et al. (2006 ); Eshtiagh-Hosseini et al. (2010 ); Mirzaei et al. (2011 ). For examples of self-assembly, see: Kondo et al. (1999 ); Beobide et al. (2006 ). For a discussion of hard–soft acid base concepts, see: Schlemper et al. (1967 ). For examples of π–π stacking, see: Janiak (2000 ). For three-dimensional network structures, see: Krygowski et al. (1998 ).

Experimental

Crystal data

[In₂(C₇H₃NO₄)₂(C₇H₄NO₄)₂(H₂O)₂]·4H₂O
M_r = 1000.17
Triclinic, $[P \overline 1]$
a = 8.0166 (3) Å
b = 10.0890 (4) Å
c = 11.9838 (5) Å
α = 110.069 (4)°
β = 96.236 (3)°
γ = 109.076 (3)°
V = 833.36 (6) Å³
Z = 1
Mo Kα radiation
μ = 1.49 mm⁻¹
T = 120 K
0.40 × 0.30 × 0.30 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Sapphire2 detector
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.588, T_max = 0.664
10774 measured reflections
3373 independent reflections
3168 reflections with I > 2σ(I)
R_int = 0.013

Refinement

R[F² > 2σ(F²)] = 0.016
wR(F²) = 0.039
S = 1.10
3373 reflections
254 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O9—H91⋯O11ⁱ	0.84	1.75	2.5938 (19)	178
O9—H92⋯O3ⁱ	0.84	1.80	2.6402 (17)	175
O11—H112⋯O7ⁱⁱ	0.84	1.95	2.7595 (18)	162
O10—H101⋯O5ⁱⁱⁱ	0.84	1.97	2.8065 (18)	175
O10—H102⋯O7^iv	0.84	1.88	2.7237 (19)	178
O4—H4O⋯O10	0.84	1.67	2.5124 (17)	178
C4—H4⋯O1^v	0.95	2.35	3.231 (2)	154
C5—H5⋯O6^vi	0.95	2.36	3.293 (2)	168
C11—H11⋯O3^vii	0.95	2.61	3.495 (2)	156
C12—H12⋯O2^vii	0.95	2.33	2.993 (2)	126
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x, y-1, z-1; (iii) x, y, z-1; (iv) -x+1, -y+2, -z+1; (v) x-1, y, z; (vi) -x+1, -y+2, -z+2; (vii) -x+2, -y+2, -z+1.

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811053566/su2349sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811053566/su2349Isup2.hkl

checkCIF report

Comment top

For several years our research group, among others, has been interested in the synthesis of new coordination compounds from polycarboxylic acids and amines using a proton transfer methodology (Aghabozorg, Daneshvar, et al., 2007; Aghabozorg, Khadivi, et al., 2008; Aghabozorg, Ramezanipour, et al., 2006; Eshtiagh-Hosseini et al., 2010; Mirzaei et al., 2011). Polycarboxylate ligands are versatile because of their diversity of coordination modes and also because of their ability to initiate self assembly processes by supramolecular interactions (Kondo et al., 1999; Beobide et al., 2006). In the majority of the complexes obtained by proton-transfer methods the metal complex is anionic with the cation derived from the amine used in the synthesis. Among these multicarboxylate ligands, pyridine-2,3-dicarboxylic acid (py-2,3dcH₂) has rarely been used under the conditions generally employed in our studies. In the course of this work we prepared the title binuclear indium(II) compound, whose crystal structure we report on herein.

In addition to being a neutral complex, the title compound (Fig. 1) appears to be the first indium^III complex N,O chelated by one py-2,3-dcH^- ion and one py-2,3-dc^2-ion, with the latter using the carboxyl group in the 3-position to bridge to a second metal. In the resulting centrosymmetric dimer, the coordination sphere of each metal is completed by a water molecule. The O₄N₂ coordination sphere adopts a distorted octahedral geometry with the largest departure being the 75.30 (5)° angles subtended by the chelating ligands (Fig. 1). The average In—O distance of 2.1253 (14) Å is slightly shorter than the average In—N of 2.2478 (17) Å. This can be explained by Pearson's hard and soft acid-base concept (Schlemper et al., 1967).

The solid state structure can be described as chains of dimers associated via hydrogen bonding interactions between the coordinated water molecule, the monoprotonated carboxyl group and oxygen atoms in the pyridine dicarboxylate ligand as well as C—H···O interactons between ring hydrogen atoms and carboxylate oxygen atoms (Table 1). Additionally there is a slipped π-π stacking interaction (Fig. 2) between the (N1,C1-C5) ring and its counterpart in the dimer at -x+1, -y+2, -z+1 [perpendicular separation = 3.107 (1) Å, centroid-to-centroid distance = 3.793 (1) Å, slippage = 1.37 Å, angle between planes = 11.28 (8)° (Janiak, 2000)]. The chains are associated via hydrogen bonding interactions between the lattice water molecules, the coordinated water molecule and oxygen atoms of the carboxylate ligands (Table 1, Fig. 3) to complete the three-dimensional network structure (Krygowski et al., 1998).

A final interaction of significance is a complementary π-π stacking interaction (Fig. 2) between the C13═O6 moiety in one half of the dimer and the (N2,C8-C12) ring in the other half (centroid-to-centroid distance = 3.347 (2) Å, angle of the line joining the centroids to the plane of the ring = 74.7 (1)°).

Related literature top

For metal complexes with polycarboxylate ligands, see: Aghabozorg, Daneshvar et al. (2007); Aghabozorg, Khadivi et al. (2008); Aghabozorg, Ramezanipour et al. (2006); Eshtiagh-Hosseini et al. (2010); Mirzaei et al. (2011). For examples of self-assembly, see: Kondo et al. (1999); Beobide et al. (2006). For a discussion of hard–soft acid base concepts, see: Schlemper et al. (1967). For examples of π–π stacking, see: Janiak (2000). For three-dimensional network structures, see: Krygowski et al. (1998).

Experimental top

A solution of In₂(SO₄)₃.xH₂O (34 mg, 0.06 mmol) in water (5 ml) was added dropwise to an aqueous solution of pyridine-2,3-dicarboxylic acid (10 mg, 0.06 mmol) and 2-amino-6-methyl pyridine (13 mg, 0.12 mmol) in a 1:1:2 molar ratio at reflux. The solution was cooled to room temperature and upon slow evaporation, X-ray quality crystals were formed which were collected and washed with distilled water.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis CCD (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. View of the local coordination environments of In^III atoms in the title molecule, with 50% probability thermal ellipsoids. Primed atoms are related to the non-primed atoms by the center of symmetry.
	Fig. 2. Perspective view of the π···π and C—O···π stacking interactions (dashed lines) in the title compound (In = large green circles, H = small green circles, O = red circles, N = blue circles).
	Fig. 3. Perspective view of the crystal packing of the title compound, showing the intermolecular hydrogen bonds as dashed lines (In = large green circles, H = small green circles, O = red circles, N = blue circles; see Table 1 for details).

bis(µ-pyridine-2,3-dicarboxylato)bis[aqua(3-carboxypyridine-2- carboxylato)indium(III)] tetrahydrate top

Crystal data top

[In₂(C₇H₃NO₄)₂(C₇H₄NO₄)₂(H₂O)₂]·4H₂O	Z = 1
M_r = 1000.17	F(000) = 496
Triclinic, P1	D_x = 1.993 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.0166 (3) Å	Cell parameters from 8569 reflections
b = 10.0890 (4) Å	θ = 2.8–27.2°
c = 11.9838 (5) Å	µ = 1.49 mm⁻¹
α = 110.069 (4)°	T = 120 K
β = 96.236 (3)°	Block, colourless
γ = 109.076 (3)°	0.40 × 0.30 × 0.30 mm
V = 833.36 (6) Å³

Data collection top

Oxford Diffraction Xcalibur diffractometer with a Sapphire2 detector	3373 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3168 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.013
Detector resolution: 8.4353 pixels mm^-1	θ_max = 27.2°, θ_min = 3.3°
ω scan	h = −8→10
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	k = −12→12
T_min = 0.588, T_max = 0.664	l = −15→15
10774 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.016	H-atom parameters constrained
wR(F²) = 0.039	w = 1/[σ²(F_o²) + (0.0197P)² + 0.3217P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max = 0.002
3373 reflections	Δρ_max = 0.38 e Å⁻³
254 parameters	Δρ_min = −0.31 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0083 (5)

Crystal data top

[In₂(C₇H₃NO₄)₂(C₇H₄NO₄)₂(H₂O)₂]·4H₂O	γ = 109.076 (3)°
M_r = 1000.17	V = 833.36 (6) Å³
Triclinic, P1	Z = 1
a = 8.0166 (3) Å	Mo Kα radiation
b = 10.0890 (4) Å	µ = 1.49 mm⁻¹
c = 11.9838 (5) Å	T = 120 K
α = 110.069 (4)°	0.40 × 0.30 × 0.30 mm
β = 96.236 (3)°

Data collection top

Oxford Diffraction Xcalibur diffractometer with a Sapphire2 detector	3373 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	3168 reflections with I > 2σ(I)
T_min = 0.588, T_max = 0.664	R_int = 0.013
10774 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.016	0 restraints
wR(F²) = 0.039	H-atom parameters constrained
S = 1.10	Δρ_max = 0.38 e Å⁻³
3373 reflections	Δρ_min = −0.31 e Å⁻³
254 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
In1	0.716069 (17)	0.792788 (13)	0.730349 (10)	0.00941 (5)
O1	0.81082 (17)	0.78122 (15)	0.57022 (11)	0.0132 (3)
O2	0.77166 (18)	0.81433 (15)	0.39645 (11)	0.0165 (3)
O3	0.43118 (19)	0.60530 (14)	0.22385 (11)	0.0154 (3)
O4	0.38691 (19)	0.80920 (15)	0.21595 (11)	0.0179 (3)
H4O	0.3870	0.7721	0.1416	0.021*
O5	0.64775 (17)	0.86624 (14)	0.90207 (10)	0.0127 (3)
O6	0.73152 (19)	1.05169 (15)	1.08983 (11)	0.0171 (3)
O7	0.92356 (19)	1.40964 (15)	1.17662 (11)	0.0165 (3)
O8	1.10615 (18)	1.31541 (14)	1.24362 (11)	0.0144 (3)
O9	0.50749 (18)	0.56958 (14)	0.66940 (11)	0.0168 (3)
H91	0.3972	0.5539	0.6473	0.020*
H92	0.5325	0.5180	0.7057	0.020*
N1	0.5111 (2)	0.83155 (16)	0.61329 (13)	0.0105 (3)
N2	0.9159 (2)	1.03454 (17)	0.83361 (13)	0.0104 (3)
C1	0.5347 (2)	0.80161 (19)	0.49914 (15)	0.0101 (4)
C2	0.4018 (3)	0.78340 (19)	0.40403 (16)	0.0120 (4)
C3	0.2455 (3)	0.8044 (2)	0.43128 (17)	0.0159 (4)
H3	0.1527	0.7938	0.3685	0.019*
C4	0.2254 (3)	0.8406 (2)	0.54992 (17)	0.0165 (4)
H4	0.1209	0.8583	0.5699	0.020*
C5	0.3595 (3)	0.8508 (2)	0.63908 (16)	0.0135 (4)
H5	0.3442	0.8717	0.7200	0.016*
C6	0.7195 (2)	0.79807 (19)	0.48430 (15)	0.0107 (4)
C7	0.4120 (3)	0.7255 (2)	0.27281 (16)	0.0124 (4)
C8	0.9017 (3)	1.0999 (2)	0.94915 (15)	0.0100 (3)
C9	1.0201 (3)	1.2475 (2)	1.02728 (15)	0.0113 (4)
C10	1.1540 (3)	1.3289 (2)	0.98329 (16)	0.0153 (4)
H10	1.2361	1.4305	1.0348	0.018*
C11	1.1667 (3)	1.2612 (2)	0.86462 (16)	0.0158 (4)
H11	1.2570	1.3154	0.8335	0.019*
C12	1.0452 (3)	1.1130 (2)	0.79220 (16)	0.0131 (4)
H12	1.0537	1.0655	0.7107	0.016*
C13	0.7493 (3)	1.0014 (2)	0.98602 (15)	0.0113 (4)
C14	1.0119 (3)	1.3270 (2)	1.15813 (15)	0.0121 (4)
O10	0.39345 (18)	0.69562 (15)	−0.00496 (11)	0.0167 (3)
H101	0.4704	0.7512	−0.0293	0.020*
H102	0.2944	0.6616	−0.0572	0.020*
O11	0.83456 (19)	0.48403 (16)	0.39983 (12)	0.0217 (3)
H111	0.8943	0.5668	0.4609	0.026*
H112	0.8849	0.4755	0.3413	0.026*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
In1	0.00961 (8)	0.01133 (8)	0.00717 (7)	0.00362 (6)	0.00213 (5)	0.00400 (5)
O1	0.0104 (7)	0.0217 (7)	0.0097 (6)	0.0077 (6)	0.0033 (5)	0.0072 (5)
O2	0.0164 (8)	0.0241 (7)	0.0127 (6)	0.0077 (6)	0.0072 (6)	0.0105 (6)
O3	0.0209 (8)	0.0118 (6)	0.0123 (6)	0.0055 (6)	0.0014 (6)	0.0050 (5)
O4	0.0275 (9)	0.0184 (7)	0.0112 (6)	0.0112 (6)	0.0027 (6)	0.0084 (5)
O5	0.0112 (7)	0.0143 (6)	0.0108 (6)	0.0026 (6)	0.0040 (5)	0.0049 (5)
O6	0.0181 (8)	0.0196 (7)	0.0113 (6)	0.0046 (6)	0.0074 (6)	0.0049 (5)
O7	0.0191 (8)	0.0186 (7)	0.0129 (6)	0.0119 (6)	0.0014 (6)	0.0039 (5)
O8	0.0164 (8)	0.0191 (7)	0.0098 (6)	0.0102 (6)	0.0018 (5)	0.0055 (5)
O9	0.0132 (7)	0.0150 (7)	0.0218 (7)	0.0033 (6)	−0.0003 (6)	0.0106 (6)
N1	0.0104 (8)	0.0097 (7)	0.0111 (7)	0.0032 (6)	0.0033 (6)	0.0046 (6)
N2	0.0103 (8)	0.0124 (7)	0.0098 (7)	0.0047 (7)	0.0026 (6)	0.0054 (6)
C1	0.0104 (10)	0.0068 (8)	0.0122 (8)	0.0017 (7)	0.0028 (7)	0.0044 (7)
C2	0.0130 (10)	0.0083 (8)	0.0135 (8)	0.0021 (8)	0.0013 (7)	0.0056 (7)
C3	0.0128 (10)	0.0173 (9)	0.0183 (9)	0.0062 (8)	0.0001 (8)	0.0087 (8)
C4	0.0124 (10)	0.0161 (9)	0.0238 (10)	0.0074 (8)	0.0067 (8)	0.0089 (8)
C5	0.0145 (10)	0.0109 (9)	0.0158 (9)	0.0048 (8)	0.0068 (8)	0.0057 (7)
C6	0.0100 (10)	0.0088 (8)	0.0100 (8)	0.0015 (7)	0.0013 (7)	0.0023 (7)
C7	0.0072 (9)	0.0135 (9)	0.0136 (8)	0.0008 (8)	−0.0013 (7)	0.0063 (7)
C8	0.0104 (10)	0.0131 (9)	0.0094 (8)	0.0063 (8)	0.0027 (7)	0.0062 (7)
C9	0.0115 (10)	0.0142 (9)	0.0100 (8)	0.0068 (8)	0.0012 (7)	0.0058 (7)
C10	0.0149 (11)	0.0139 (9)	0.0139 (8)	0.0027 (8)	0.0007 (8)	0.0054 (7)
C11	0.0147 (11)	0.0171 (9)	0.0153 (9)	0.0027 (8)	0.0056 (8)	0.0090 (8)
C12	0.0142 (10)	0.0158 (9)	0.0107 (8)	0.0057 (8)	0.0050 (7)	0.0065 (7)
C13	0.0104 (10)	0.0148 (9)	0.0113 (8)	0.0070 (8)	0.0017 (7)	0.0067 (7)
C14	0.0103 (10)	0.0110 (9)	0.0115 (8)	0.0009 (8)	0.0015 (7)	0.0038 (7)
O10	0.0133 (7)	0.0224 (7)	0.0134 (6)	0.0027 (6)	0.0014 (5)	0.0106 (6)
O11	0.0204 (8)	0.0215 (7)	0.0203 (7)	0.0069 (6)	0.0059 (6)	0.0061 (6)

Geometric parameters (Å, º) top

In1—O8ⁱ	2.1153 (12)	C1—C2	1.390 (2)
In1—O1	2.1199 (12)	C1—C6	1.522 (2)
In1—O9	2.1319 (13)	C2—C3	1.392 (3)
In1—O5	2.1324 (11)	C2—C7	1.500 (2)
In1—N2	2.2339 (15)	C3—C4	1.383 (3)
In1—N1	2.2618 (14)	C3—H3	0.9500
O1—C6	1.289 (2)	C4—C5	1.383 (3)
O2—C6	1.216 (2)	C4—H4	0.9500
O3—C7	1.221 (2)	C5—H5	0.9500
O4—C7	1.302 (2)	C8—C9	1.386 (3)
O4—H4O	0.8401	C8—C13	1.517 (3)
O5—C13	1.300 (2)	C9—C10	1.396 (3)
O6—C13	1.216 (2)	C9—C14	1.517 (2)
O7—C14	1.240 (2)	C10—C11	1.382 (2)
O8—C14	1.268 (2)	C10—H10	0.9500
O8—In1ⁱ	2.1152 (12)	C11—C12	1.383 (3)
O9—H91	0.8400	C11—H11	0.9500
O9—H92	0.8400	C12—H12	0.9500
N1—C5	1.343 (2)	O10—H101	0.8400
N1—C1	1.345 (2)	O10—H102	0.8400
N2—C12	1.339 (2)	O11—H111	0.8400
N2—C8	1.350 (2)	O11—H112	0.8400

O8ⁱ—In1—O1	83.58 (5)	C2—C3—H3	120.0
O8ⁱ—In1—O9	84.44 (5)	C5—C4—C3	119.06 (17)
O1—In1—O9	101.63 (5)	C5—C4—H4	120.5
O8ⁱ—In1—O5	104.07 (5)	C3—C4—H4	120.5
O1—In1—O5	165.16 (5)	N1—C5—C4	121.17 (16)
O9—In1—O5	91.87 (5)	N1—C5—H5	119.4
O8ⁱ—In1—N2	97.32 (5)	C4—C5—H5	119.4
O1—In1—N2	91.20 (5)	O2—C6—O1	125.21 (17)
O9—In1—N2	167.17 (5)	O2—C6—C1	119.13 (15)
O5—In1—N2	75.36 (5)	O1—C6—C1	115.64 (14)
O8ⁱ—In1—N1	153.16 (5)	O3—C7—O4	124.16 (16)
O1—In1—N1	75.34 (5)	O3—C7—C2	121.80 (15)
O9—In1—N1	83.75 (5)	O4—C7—C2	113.89 (15)
O5—In1—N1	100.33 (5)	N2—C8—C9	121.27 (16)
N2—In1—N1	99.52 (5)	N2—C8—C13	115.55 (15)
C6—O1—In1	119.19 (11)	C9—C8—C13	123.18 (15)
C7—O4—H4O	112.4	C8—C9—C10	118.45 (16)
C13—O5—In1	118.93 (11)	C8—C9—C14	123.82 (16)
C14—O8—In1ⁱ	140.24 (11)	C10—C9—C14	117.73 (16)
In1—O9—H91	121.2	C11—C10—C9	119.83 (18)
In1—O9—H92	112.4	C11—C10—H10	120.1
H91—O9—H92	117.5	C9—C10—H10	120.1
C5—N1—C1	120.12 (15)	C10—C11—C12	118.58 (18)
C5—N1—In1	126.80 (11)	C10—C11—H11	120.7
C1—N1—In1	111.76 (11)	C12—C11—H11	120.7
C12—N2—C8	119.97 (16)	N2—C12—C11	121.89 (16)
C12—N2—In1	126.11 (11)	N2—C12—H12	119.1
C8—N2—In1	113.89 (12)	C11—C12—H12	119.1
N1—C1—C2	121.65 (16)	O6—C13—O5	124.90 (17)
N1—C1—C6	115.19 (15)	O6—C13—C8	119.05 (16)
C2—C1—C6	123.09 (15)	O5—C13—C8	116.05 (14)
C1—C2—C3	118.00 (16)	O7—C14—O8	123.27 (15)
C1—C2—C7	122.31 (16)	O7—C14—C9	117.88 (15)
C3—C2—C7	119.33 (16)	O8—C14—C9	118.63 (15)
C4—C3—C2	119.91 (17)	H101—O10—H102	105.0
C4—C3—H3	120.0	H111—O11—H112	111.8

O8ⁱ—In1—O1—C6	162.67 (13)	C2—C3—C4—C5	−2.0 (3)
O9—In1—O1—C6	79.72 (13)	C1—N1—C5—C4	−0.1 (3)
O5—In1—O1—C6	−75.3 (2)	In1—N1—C5—C4	−165.89 (13)
N2—In1—O1—C6	−100.10 (13)	C3—C4—C5—N1	2.5 (3)
N1—In1—O1—C6	−0.57 (12)	In1—O1—C6—O2	169.57 (14)
O8ⁱ—In1—O5—C13	89.72 (12)	In1—O1—C6—C1	−8.69 (19)
O1—In1—O5—C13	−30.0 (2)	N1—C1—C6—O2	−159.83 (16)
O9—In1—O5—C13	174.45 (12)	C2—C1—C6—O2	16.9 (3)
N2—In1—O5—C13	−4.31 (11)	N1—C1—C6—O1	18.5 (2)
N1—In1—O5—C13	−101.56 (12)	C2—C1—C6—O1	−164.68 (16)
O8ⁱ—In1—N1—C5	138.04 (14)	C1—C2—C7—O3	53.6 (3)
O1—In1—N1—C5	177.42 (15)	C3—C2—C7—O3	−119.3 (2)
O9—In1—N1—C5	73.64 (15)	C1—C2—C7—O4	−130.59 (18)
O5—In1—N1—C5	−17.12 (15)	C3—C2—C7—O4	56.5 (2)
N2—In1—N1—C5	−93.83 (15)	C12—N2—C8—C9	−0.6 (2)
O8ⁱ—In1—N1—C1	−28.73 (19)	In1—N2—C8—C9	177.46 (12)
O1—In1—N1—C1	10.65 (11)	C12—N2—C8—C13	179.38 (15)
O9—In1—N1—C1	−93.12 (12)	In1—N2—C8—C13	−2.56 (18)
O5—In1—N1—C1	176.11 (12)	N2—C8—C9—C10	0.9 (2)
N2—In1—N1—C1	99.40 (12)	C13—C8—C9—C10	−179.06 (16)
O8ⁱ—In1—N2—C12	78.74 (14)	N2—C8—C9—C14	−179.73 (16)
O1—In1—N2—C12	−4.94 (14)	C13—C8—C9—C14	0.3 (3)
O9—In1—N2—C12	175.85 (19)	C8—C9—C10—C11	−0.5 (3)
O5—In1—N2—C12	−178.56 (15)	C14—C9—C10—C11	−179.94 (16)
N1—In1—N2—C12	−80.27 (14)	C9—C10—C11—C12	−0.1 (3)
O8ⁱ—In1—N2—C8	−99.18 (12)	C8—N2—C12—C11	−0.1 (3)
O1—In1—N2—C8	177.14 (12)	In1—N2—C12—C11	−177.90 (13)
O9—In1—N2—C8	−2.1 (3)	C10—C11—C12—N2	0.4 (3)
O5—In1—N2—C8	3.52 (11)	In1—O5—C13—O6	−174.77 (13)
N1—In1—N2—C8	101.80 (12)	In1—O5—C13—C8	4.34 (18)
C5—N1—C1—C2	−2.7 (3)	N2—C8—C13—O6	178.18 (15)
In1—N1—C1—C2	165.07 (13)	C9—C8—C13—O6	−1.8 (3)
C5—N1—C1—C6	174.13 (15)	N2—C8—C13—O5	−1.0 (2)
In1—N1—C1—C6	−18.10 (17)	C9—C8—C13—O5	179.00 (15)
N1—C1—C2—C3	3.0 (3)	In1ⁱ—O8—C14—O7	−176.98 (13)
C6—C1—C2—C3	−173.52 (16)	In1ⁱ—O8—C14—C9	−2.6 (3)
N1—C1—C2—C7	−169.95 (16)	C8—C9—C14—O7	−93.8 (2)
C6—C1—C2—C7	13.5 (3)	C10—C9—C14—O7	85.6 (2)
C1—C2—C3—C4	−0.7 (3)	C8—C9—C14—O8	91.5 (2)
C7—C2—C3—C4	172.56 (17)	C10—C9—C14—O8	−89.1 (2)

Symmetry code: (i) −x+2, −y+2, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O9—H91···O11ⁱⁱ	0.84	1.75	2.5938 (19)	178
O9—H92···O3ⁱⁱ	0.84	1.80	2.6402 (17)	175
O11—H112···O7ⁱⁱⁱ	0.84	1.95	2.7595 (18)	162
O10—H101···O5^iv	0.84	1.97	2.8065 (18)	175
O10—H102···O7^v	0.84	1.88	2.7237 (19)	178
O4—H4O···O10	0.84	1.67	2.5124 (17)	178
C4—H4···O1^vi	0.95	2.35	3.231 (2)	154
C5—H5···O6^vii	0.95	2.36	3.293 (2)	168
C11—H11···O3^viii	0.95	2.61	3.495 (2)	156
C12—H12···O2^viii	0.95	2.33	2.993 (2)	126

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

Experimental details

Crystal data
Chemical formula	[In₂(C₇H₃NO₄)₂(C₇H₄NO₄)₂(H₂O)₂]·4H₂O
M_r	1000.17
Crystal system, space group	Triclinic, P1
Temperature (K)	120
a, b, c (Å)	8.0166 (3), 10.0890 (4), 11.9838 (5)
α, β, γ (°)	110.069 (4), 96.236 (3), 109.076 (3)
V (Å³)	833.36 (6)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.49
Crystal size (mm)	0.40 × 0.30 × 0.30

Data collection
Diffractometer	Oxford Diffraction Xcalibur diffractometer with a Sapphire2 detector
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2009)
T_min, T_max	0.588, 0.664
No. of measured, independent and observed [I > 2σ(I)] reflections	10774, 3373, 3168
R_int	0.013
(sin θ/λ)_max (Å⁻¹)	0.644

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.016, 0.039, 1.10
No. of reflections	3373
No. of parameters	254
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.31

Computer programs: CrysAlis CCD (Oxford Diffraction, 2009), CrysAlis RED (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O9—H91···O11ⁱ	0.84	1.75	2.5938 (19)	178
O9—H92···O3ⁱ	0.84	1.80	2.6402 (17)	175
O11—H112···O7ⁱⁱ	0.84	1.95	2.7595 (18)	162
O10—H101···O5ⁱⁱⁱ	0.84	1.97	2.8065 (18)	175
O10—H102···O7^iv	0.84	1.88	2.7237 (19)	178
O4—H4O···O10	0.84	1.67	2.5124 (17)	178
C4—H4···O1^v	0.95	2.35	3.231 (2)	154
C5—H5···O6^vi	0.95	2.36	3.293 (2)	168
C11—H11···O3^vii	0.95	2.61	3.495 (2)	156
C12—H12···O2^vii	0.95	2.33	2.993 (2)	126

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

Acknowledgements

The authors wish to thank to the Ferdowsi University of Mashhad for financial support (grant No. P/2098).

References

Aghabozorg, H., Daneshvar, S., Motyeian, E., Ghadermazi, M. & Attar Gharamaleki, J. (2007). Acta Cryst. E63, m2468–m2469. Web of Science CSD CrossRef IUCr Journals Google Scholar
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Volume 68| Part 1| January 2012| Pages m71-m72

doi:10.1107/S1600536811053566

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

Bis­(μ-pyridine-2,3-di­carboxyl­ato)bis­­[aqua­(3-carb­­oxy­pyridine-2-carboxyl­ato)indium(III)] tetra­hydrate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

Bis(μ-pyridine-2,3-dicarboxylato)bis[aqua(3-carboxypyridine-2-carboxylato)indium(III)] tetrahydrate