catena-Poly[bis­[dimeth­yl(pyridine-κN)indium(III)]-μ4-benzene-1,3-diolato-bis­[di­methyl­indium(III)]-μ4-benzene-1,3-diolato]

Glen G Briand; Andreas Decken; Marshall R Hoey

doi:10.1107/S1600536813028985

. 2013 Oct 26;69(Pt 11):m622. doi: 10.1107/S1600536813028985

catena-Poly[bis[dimethyl(pyridine-κN)indium(III)]-μ₄-benzene-1,3-diolato-bis[dimethylindium(III)]-μ₄-benzene-1,3-diolato]

Glen G Briand ^a,^*, Andreas Decken ^b, Marshall R Hoey ^a

PMCID: PMC3884271 PMID: 24454047

Abstract

The title compound, [In₂(CH₃)₄(C₆H₄O₂)(C₅H₅N)] or [{(CH₃)₂In}(1,3-O₂C₆H₄){In(CH₃)₂(py)}]_n, (py = pyridine) contains two crystallographically unique In^III ions which are in distorted tetrahedral C₂O₂ and distorted trigonal-bipyramidal C₂O₂N coordination environments. The In^III coordination centers are bridged head-to-head via In—O bonds, yielding four-membered In₂O₂ rings and zigzag polymeric chains along [001].

Related literature

For background to dimethylindium aryloxides, see: Briand et al. (2010 ▶); Beachley et al. (2003 ▶); Hausslein et al. (1999 ▶); Blake et al. (2011 ▶); Bradley et al. (1988 ▶); Trentler et al. (1997 ▶). For dimethylindium compounds with bidentate imine-alkoxide ligands, see: Hu et al. (1999 ▶); Wu et al. (1999 ▶); Pal et al. (2013 ▶); Lewinski et al. (2003 ▶); Ghoshal et al. (2007 ▶). graphic file with name e-69-0m622-scheme1.jpg

Experimental

Crystal data

[In₂(CH₃)₄(C₆H₄O₂)(C₅H₅N)]
M _r = 476.97
Monoclinic,
a = 9.1584 (17) Å
b = 14.075 (3) Å
c = 13.856 (3) Å
β = 90.106 (3)°
V = 1786.1 (6) Å³
Z = 4
Mo Kα radiation
μ = 2.58 mm⁻¹
T = 188 K
0.20 × 0.03 × 0.03 mm

Data collection

Bruker P4/SMART 1000 diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a ▶) T _min = 0.626, T _max = 0.938
12064 measured reflections
3967 independent reflections
2885 reflections with I > 2σ(I)
R _int = 0.039

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.087
S = 1.16
3967 reflections
185 parameters
H-atom parameters constrained
Δρ_max = 1.02 e Å⁻³
Δρ_min = −0.72 e Å⁻³

Data collection: SMART (Bruker, 1999 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008b ▶); molecular graphics: DIAMOND (Brandenburg, 2012 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008b ▶).

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536813028985/lh5663sup1.cif

e-69-0m622-sup1.cif^{(373.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813028985/lh5663Isup2.hkl

e-69-0m622-Isup2.hkl^{(217.7KB, hkl)}

Click here for additional data file.^{(4KB, cdx)}

Supplementary material file. DOI: 10.1107/S1600536813028985/lh5663Isup3.cdx

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This work was supported by the Natural Sciences and Engineering Research Council of Canada, the New Brunswick Innovation Foundation, the Canadian Foundation for Innovation and Mount Allison University.

supplementary crystallographic information

1. Comment

Dimethylindium aryloxides [Me₂InOR]₂ form dimeric structures in the solid state via intermolecular In—O coordinate bonding interactions (Briand et al., 2010; Beachley et al., 2003; Hausslein et al., 1999; Blake et al., 2011; Bradley et al., 1988; Trentler et al., 1997). These structures feature distorted tetrahedral geometries at In, distorted trigonal planar or slightly pyramidal geometries at O, and symmetric near planar In₂O₂ ring cores. Substitution of monodentate alkoxide (–OR) ligands with bidentate imine-alkoxide ligands additionally results in an intramolecular In—N coordination, yielding distorted trigonal bipyramidal In centres and asymmetric In₂O₂ rings (Hu et al., 1999; Wu et al., 1999; Pal et al., 2013; Lewinski et al., 2003; Ghoshal et al., 2007). The molecular structure of (I) (Fig. 1) shows two crystallographically unique In atoms. In addition to the In1—O1 bond, In1 exhibits an intermolecular In1—O1ⁱ interaction. This results in a distorted tetrahedral C₂O₂ bonding environment for indium [C1—In1—C2 = 144.3 (3), O1—In1—O1ⁱ = 73.87 (14)°] and a symmetric In₂O₂ ring structure [In1—O1 = 2.172 (3), In1—O1ⁱ = 2.174 (3) Å]. Similarly, In2 is coordinated to two methyl C atoms [C3 and C4] and two aryloxide O atoms [O2 and O2ⁱⁱ], but is is also coordinated by the N atom of a pyridine molecule [2.486 (4) Å]. This results in a distorted trigonal bypyramidal C₂O₂N bonding environment for In, with the two methyl C atoms and a bridging O atom in equatorial positions [C3—In2—C4 = 142.5 (2), C3—In2—O2ⁱⁱ = 107.8 (2), C4—In2—O2ⁱⁱ = 109.25 (19)°], and the pyridine N atom and a bridging O atom in axial positions [O2—In2—N1 = 156.63 (13)°]. The axial In2—O2 bond distance [2.330 (3) Å] is longer than the equatorial In2—O2ⁱⁱ bond distance [2.152 (3) Å], presumably as a result of the trans influence of the pyridine N atom, resulting in an asymmetric In₂O₂ ring. The two unique In₂O₂ rings are bridged by the 1,3-benzenediolate phenyl ring, giving a zigzag polymeric structure along [001] (Fig. 2).

2. Experimental

Under an atmosphere of dinitrogen, InMe₃ (0.250 g, 1.56 mmol) was dissolved in diethyl ether (10 ml). Pyridine (0.125 g, 1.56 mmol) was added and the solution stirred for 30 min. Resorcinol (0.088 g, 0.78 mmol) was then added and the reaction mixture stirred for an additional 1 h. The reaction was then filtered and the filtrate allowed to sit at 296K. After 1 d, the solution was filtered to yield colourless crystals of [Me₂In(1,3-O₂C₆H₄)InMe₂(py)]_∞ (0.122 g, 0.256 mmol, 33%). Anal. Calc. for C₁₅H₂₁In₂NO₂: C, 37.77; H, 4.44; N, 2.94. Found: C, 38.32; H, 4.47; N, 2.88. F T—IR (ATR, cm^-1): 618 w, 698 s, 748 m, 772 w, 829 w, 844 w, 968 s, 1003 w, 1034 w, 1142 s, 1171 s, 1213 w, 1249 m, 1299 m, 1427 w, 1441 w, 1482 m, 1467 m, 1573 s, 2283 w, 2475 w, 2881 m, 3004 m. FT-Raman (cm^-1): 487 vs [ν_sym (Me—In—Me)], 524 w [ν_asym (Me—In—Me)], 994 m, 1034 m, 1159 m, 1305 w, 1586 w, 2920 m, 2982 w, 3064 m.