Literature DB >> 21582342

Poly[hemi(ethyl-enediammonium) [di-μ-oxalato-indium(III)] dihydrate].

Qiaozhen Sun¹, Yang Liu, Hongwu Li, Zhi Luo.

Abstract

In title compound, {(C(2)H(10)N(2))(0.5)[In(C(2)O(4))(2)]·2H(2)O}(n), the unique In(III) ion is coordinated by eight O atoms from four n class="Chemical">oxalate ligands in a distorted square-anti-prismatic environment. The doubly bis-chelating oxalate ligands act as bridging ligands connecting symmetry-related In(III) ions and forming a three-dimensional open framework structure. Ethyl-enediammonium cations and water mol-ecules occupy the voids within the structure. The unique ethyl-enediammonium cation and one water mol-ecule both lie on a twofold rotation axis. One of the other two water mol-ecules residing on general crystallographic sites was refined as disordered with half occupancy. In the crystal structure, cations and water mol-ecules are linked to the anionic framework via inter-molecular O-H⋯O and N-H⋯O hydrogen bonds.

Entities: Chemical Disease Species

Year: 2009 PMID： 21582342 PMCID： PMC2969062 DOI： 10.1107/S1600536809008381

Source DB: PubMed Journal: Acta Crystallogr Sect E Struct Rep Online ISSN： 1600-5368

Related literature

For background information on open-framework materials, see: Fang et al. (2004 ▶); Li et al. (2008 ▶); Serre et al. (2006 ▶); Sun et al. (2006 ▶). For related materials containing the oxalate ligand, see: Audebrand et al. (2001 ▶, 2004 ▶); Kokunov et al. (2004 ▶); Stock et al. (2000 ▶); Chakrabarti & n class="Chemical">Natarajan (2002 ▶); Evans & Lin (2001 ▶); Vaidhyanathan et al. (2001 ▶); Gavilan et al. (2007 ▶); Bataille et al. (2000 ▶); Trombe et al. (2001 ▶); Yuan et al. (2004 ▶). For indium oxaltes, see: Audebrand et al. (2003 ▶); Bulc et al. (1983 ▶); Bulc & Golič (1983 ▶); Chen et al. (2003 ▶); Huang & Lii (1998 ▶); Jeanneau et al. (2003 ▶); Yang et al. (2005 ▶); For the bond-valence method, see: Brown (1996 ▶). For bond distances and angles for bridging bidentate oxalate groups, see: Hann (1957 ▶).

Experimental

Crystal data

(C2H10N2)0.5[In(C2O4)2]·2H2O M = 357.95 Orthorhombic, a = 15.8498 (4) Å b = 31.1643 (8) Å c = 8.6618 (2) Å V = 4278.48 (18) Å3 Z = 16 Mo Kα radiation μ = 2.26 mm−1 T = 293 K 0.40 × 0.38 × 0.38 mm

Data collection

Bruker SMART CCD diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.426, T max = 0.467 (expected range = 0.387–0.424) 7189 measured reflections 1679 independent reflections 1673 reflections with I > 2σ(I) R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.018 wR(F 2) = 0.046 S = 1.06 1679 reflections 160 parameters 13 restraints H-atom parameters constrained Δρmax = 0.45 e Å−3 Δρmin = −0.71 e Å−3 Absolute structure: Flack (1983 ▶), 668 Friedel pairs Flack parameter: 0.00 (3) Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; 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. Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809008381/lh2779sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S1600536809008381/lh2779Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report

(C₂H₁₀N₂)_0.5[In(C₂O₄)₂]·2H₂O	F(000) = 2800
M_r = 357.95	D_x = 2.223 Mg m⁻³
Orthorhombic, Fdd2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2d	Cell parameters from 7228 reflections
a = 15.8498 (4) Å	θ = 2.6–27.9°
b = 31.1643 (8) Å	µ = 2.26 mm⁻¹
c = 8.6618 (2) Å	T = 293 K
V = 4278.48 (18) Å³	Block, colourless
Z = 16	0.4 × 0.38 × 0.38 mm

Bruker SMART CCD diffractometer	1679 independent reflections
Radiation source: fine-focus sealed tube	1673 reflections with I > 2σ(I)
graphite	R_int = 0.025
φ and ω scans	θ_max = 25.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −18→18
T_min = 0.426, T_max = 0.467	k = −36→36
7189 measured reflections	l = −10→10

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.018	w = 1/[σ²(F_o²) + (0.0322P)² + 7.4478P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.046	(Δ/σ)_max = 0.001
S = 1.06	Δρ_max = 0.45 e Å⁻³
1679 reflections	Δρ_min = −0.71 e Å⁻³
160 parameters	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
13 restraints	Extinction coefficient: 0.00087 (5)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 668 Friedel pairs
Secondary atom site location: difference Fourier map	Flack parameter: 0.00 (3)

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.

	x	y	z	U_iso*/U_eq	Occ. (<1)
In1	0.013694 (15)	0.314689 (7)	0.33266 (6)	0.01510 (11)
O1	−0.06449 (17)	0.27864 (9)	0.1683 (4)	0.0277 (6)
O2	0.10165 (19)	0.26861 (9)	0.1750 (4)	0.0290 (7)
O3	0.04152 (19)	0.35822 (9)	0.1416 (3)	0.0241 (6)
O4	0.14920 (17)	0.34173 (8)	0.3713 (3)	0.0220 (6)
C1	−0.0334 (2)	0.25113 (11)	0.0817 (7)	0.0194 (7)
C2	0.0620 (2)	0.24552 (11)	0.0823 (7)	0.0204 (7)
C3	0.1128 (2)	0.37559 (10)	0.1357 (4)	0.0165 (7)
C4	0.1740 (2)	0.36645 (11)	0.2696 (5)	0.0180 (8)
O5	−0.07692 (18)	0.22769 (9)	−0.0061 (3)	0.0259 (7)
O6	0.09025 (18)	0.21856 (9)	−0.0112 (4)	0.0302 (7)
O7	0.13838 (16)	0.39927 (8)	0.0302 (3)	0.0223 (6)
O8	0.24530 (18)	0.38498 (9)	0.2625 (4)	0.0231 (6)
C5	0.2294 (3)	0.2715 (2)	−0.2277 (8)	0.0535 (16)
H5C	0.1687	0.2676	−0.2275	0.064*
H5A	0.2444	0.2864	−0.1332	0.064*
N1	0.2527 (3)	0.29883 (17)	−0.3608 (6)	0.0502 (12)
H1A	0.3035	0.2913	−0.3949	0.075*
H1B	0.2534	0.3262	−0.3316	0.075*
H1C	0.2150	0.2954	−0.4360	0.075*
OW1	0.2500	0.2500	0.3570 (7)	0.0504 (16)
HW1A	0.2938	0.2445	0.3040	0.050*
OW2	0.0119 (6)	0.3117 (3)	−0.173 (3)	0.069 (2)	0.50
HW2B	0.0188	0.2848	−0.1847	0.083*	0.50
HW2A	0.0010	0.3173	−0.0793	0.083*	0.50
OW3	0.1418 (3)	0.36723 (19)	−0.2928 (7)	0.1000 (17)
HW3B	0.1123	0.3788	−0.3632	0.120*
HW3A	0.1542	0.3857	−0.2244	0.120*

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
In1	0.01446 (16)	0.01545 (14)	0.01540 (15)	−0.00012 (8)	−0.00093 (14)	0.00069 (11)
O1	0.0185 (13)	0.0268 (13)	0.0378 (17)	−0.0013 (11)	0.0018 (14)	−0.0157 (13)
O2	0.0224 (15)	0.0289 (15)	0.0358 (17)	0.0008 (12)	−0.0078 (14)	−0.0104 (13)
O3	0.0187 (14)	0.0299 (14)	0.0237 (15)	−0.0058 (12)	−0.0031 (12)	0.0086 (11)
O4	0.0264 (15)	0.0220 (12)	0.0176 (15)	−0.0037 (10)	−0.0021 (11)	0.0065 (10)
C1	0.0209 (18)	0.0154 (15)	0.0218 (17)	−0.0017 (14)	0.001 (2)	0.0002 (16)
C2	0.0220 (19)	0.0194 (16)	0.0199 (17)	0.0002 (14)	0.000 (2)	−0.0018 (17)
C3	0.0177 (19)	0.0139 (15)	0.0179 (17)	0.0038 (13)	0.0005 (15)	0.0001 (14)
C4	0.019 (2)	0.0132 (15)	0.0214 (17)	0.0010 (14)	−0.0015 (16)	−0.0011 (14)
O5	0.0193 (15)	0.0251 (13)	0.0333 (17)	−0.0004 (11)	−0.0037 (13)	−0.0135 (13)
O6	0.0213 (15)	0.0324 (15)	0.0369 (19)	0.0024 (12)	0.0032 (14)	−0.0131 (14)
O7	0.0224 (13)	0.0229 (12)	0.0217 (14)	−0.0042 (10)	−0.0032 (11)	0.0066 (10)
O8	0.0180 (13)	0.0273 (15)	0.0239 (15)	−0.0057 (11)	−0.0039 (13)	0.0084 (12)
C5	0.031 (3)	0.080 (4)	0.049 (4)	−0.020 (2)	0.006 (3)	−0.016 (3)
N1	0.028 (2)	0.074 (3)	0.049 (3)	−0.006 (2)	−0.011 (2)	−0.001 (2)
OW1	0.026 (2)	0.086 (4)	0.039 (4)	0.024 (2)	0.000	0.000
OW2	0.084 (4)	0.067 (4)	0.055 (4)	0.013 (4)	−0.002 (5)	−0.006 (4)
OW3	0.083 (3)	0.146 (4)	0.072 (3)	0.016 (3)	−0.030 (3)	−0.045 (3)

In1—O5ⁱ	2.168 (3)	C4—O8	1.270 (5)
In1—O3	2.185 (3)	O5—In1ⁱⁱⁱ	2.168 (3)
In1—O1	2.196 (3)	O6—In1ⁱⁱⁱ	2.370 (3)
In1—O8ⁱⁱ	2.230 (3)	O7—In1^iv	2.327 (3)
In1—O7ⁱⁱ	2.327 (3)	O8—In1^iv	2.230 (3)
In1—O4	2.331 (3)	C5—N1	1.480 (8)
In1—O6ⁱ	2.370 (3)	C5—C5^v	1.492 (12)
In1—O2	2.423 (3)	C5—H5C	0.9700
O1—C1	1.242 (5)	C5—H5A	0.9700
O2—C2	1.248 (6)	N1—H1A	0.8900
O3—C3	1.253 (5)	N1—H1B	0.8900
O4—C4	1.235 (5)	N1—H1C	0.8900
C1—O5	1.260 (6)	OW1—HW1A	0.8500
C1—C2	1.522 (6)	OW2—HW2B	0.8502
C2—O6	1.250 (6)	OW2—HW2A	0.8500
C3—O7	1.243 (4)	OW3—HW3B	0.8498
C3—C4	1.539 (5)	OW3—HW3A	0.8500

O5ⁱ—In1—O3	140.63 (11)	C4—O4—In1	114.7 (2)
O5ⁱ—In1—O1	111.52 (10)	O1—C1—O5	123.2 (4)
O3—In1—O1	86.60 (12)	O1—C1—C2	118.2 (4)
O5ⁱ—In1—O8ⁱⁱ	92.22 (11)	O5—C1—C2	118.7 (4)
O3—In1—O8ⁱⁱ	96.82 (11)	O2—C2—O6	128.6 (4)
O1—In1—O8ⁱⁱ	137.63 (10)	O2—C2—C1	115.8 (4)
O5ⁱ—In1—O7ⁱⁱ	144.54 (11)	O6—C2—C1	115.5 (4)
O3—In1—O7ⁱⁱ	74.02 (11)	O7—C3—O3	125.5 (4)
O1—In1—O7ⁱⁱ	68.82 (10)	O7—C3—C4	117.2 (3)
O8ⁱⁱ—In1—O7ⁱⁱ	71.65 (10)	O3—C3—C4	117.3 (3)
O5ⁱ—In1—O4	72.66 (9)	O4—C4—O8	127.0 (4)
O3—In1—O4	72.43 (9)	O4—C4—C3	116.8 (3)
O1—In1—O4	142.91 (10)	O8—C4—C3	116.1 (3)
O8ⁱⁱ—In1—O4	76.46 (10)	C1—O5—In1ⁱⁱⁱ	119.2 (3)
O7ⁱⁱ—In1—O4	129.79 (9)	C2—O6—In1ⁱⁱⁱ	114.5 (3)
O5ⁱ—In1—O6ⁱ	71.78 (10)	C3—O7—In1^iv	115.0 (2)
O3—In1—O6ⁱ	147.56 (11)	C4—O8—In1^iv	118.0 (3)
O1—In1—O6ⁱ	75.75 (11)	N1—C5—C5^v	114.0 (4)
O8ⁱⁱ—In1—O6ⁱ	79.52 (11)	N1—C5—H5C	108.7
O7ⁱⁱ—In1—O6ⁱ	74.28 (10)	C5^v—C5—H5C	108.7
O4—In1—O6ⁱ	135.78 (10)	N1—C5—H5A	108.7
O5ⁱ—In1—O2	74.70 (10)	C5^v—C5—H5A	108.7
O3—In1—O2	79.93 (11)	H5C—C5—H5A	107.6
O1—In1—O2	69.90 (11)	C5—N1—H1A	109.5
O8ⁱⁱ—In1—O2	152.36 (10)	C5—N1—H1B	109.5
O7ⁱⁱ—In1—O2	131.86 (10)	H1A—N1—H1B	109.5
O4—In1—O2	76.41 (9)	C5—N1—H1C	109.5
O6ⁱ—In1—O2	117.54 (10)	H1A—N1—H1C	109.5
C1—O1—In1	121.4 (3)	H1B—N1—H1C	109.5
C2—O2—In1	114.5 (3)	HW2B—OW2—HW2A	109.8
C3—O3—In1	118.7 (2)	HW3B—OW3—HW3A	109.8

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···OW1^vi	0.89	2.35	2.880 (8)	118
N1—H1B···O7^iv	0.89	2.47	2.956 (5)	115
N1—H1B···OW3	0.89	2.21	2.825 (8)	126
N1—H1C···O4^vi	0.89	2.44	3.140 (6)	136
N1—H1C···O5ⁱⁱⁱ	0.89	2.38	3.166 (5)	147
OW1—HW1A···O2^v	0.85	2.04	2.889 (5)	180
OW2—HW2B···O1ⁱⁱⁱ	0.85	2.46	3.241 (15)	153
OW2—HW2A···O3	0.85	2.39	3.12 (3)	145
OW3—HW3B···O8^vii	0.85	2.19	2.870 (6)	137
OW3—HW3A···O7	0.85	2.26	2.971 (7)	141
OW3—HW3A···O3^iv	0.85	2.40	2.962 (6)	124

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1C⋯OW1ⁱ	0.89	2.35	2.880 (8)	118
N1—H1B⋯O7ⁱⁱ	0.89	2.47	2.956 (5)	115
N1—H1B⋯OW3	0.89	2.21	2.825 (8)	126
N1—H1C⋯O4ⁱ	0.89	2.44	3.140 (6)	136
N1—H1C⋯O5ⁱⁱⁱ	0.89	2.38	3.166 (5)	147
OW1—HW1A⋯O2^iv	0.85	2.04	2.889 (5)	180
OW2—HW2B⋯O1ⁱⁱⁱ	0.85	2.46	3.241 (15)	153
OW2—HW2A⋯O3	0.85	2.39	3.12 (3)	145
OW3—HW3B⋯O8^v	0.85	2.19	2.870 (6)	137
OW3—HW3A⋯O7	0.85	2.26	2.971 (7)	141
OW3—HW3A⋯O3ⁱⁱ	0.85	2.40	2.962 (6)	124

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .

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