Crystal structure of dimethyl-1κ(2) C-bis(μ-4-methylphenolato-1:2κ(2) O:O)(N,N,N',N'-tetramethylethylenediamine-2κ(2) N,N')indium(III)lithium(I).

The mixed bimetallic title compound, [InLi(CH3)2(C7H7O)2(C6H16N2)] or [(tmeda)Li-μ-(4-MeC6H4O)2InMe2] (tmeda is N,N,N',N'-tetra-methyl-ethylenedi-amine), exhibits a four-membered LiO2In ring core via bridging 4-methyl-phenolate groups. The Li and In atoms are in distorted tetra-hedral N2O2 and C2O2 bonding environments, respectively. The Li atom is further chelated by a tmeda group, yielding a spiro-cyclic structure.

Related literature

For other bimetallic alkali–triel chalcogenolates, see: Niemeyer & Power (1997 ▸); Clegg et al. (1999 ▸); Muñoz et al. (2011 ▸, 2014 ▸); Uhl et al. (1994 ▸); Adonin et al. (2005 ▸); Soki et al. (2008 ▸); Normand et al. (2012 ▸). For metal-containing ligands, see Simmonds & Wright (2012 ▸). For organometallic precusors for indium tin oxide (ITO), see: Aksu & Driess (2009 ▸); Veith & Kunze (1991 ▸). For dimeric di­methyl­indium phenolates [Me2InOR]2, see: Briand et al. (2013 ▸, 2010 ▸); Beachley et al. (2003 ▸); Häusslein et al. (1999 ▸); Blake et al. (2011 ▸); Bradley et al. (1988 ▸); Trentler et al. (1997 ▸).

Experimental

Crystal data

[InLi(CH3)2(C7H7O)2(C6H16N2)]

M = 482.29

Monoclinic,

a = 9.0991 (8) Å

b = 16.4481 (15) Å

c = 16.4256 (15) Å

β = 91.956 (1)°

V = 2456.9 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.98 mm−1

T = 188 K

0.65 × 0.60 × 0.60 mm

Data collection

Bruker SMART1000/P4 diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2008a ▸) T min = 0.569, T max = 0.591

16648 measured reflections

5459 independent reflections

4921 reflections with I > 2σ(I)

R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.025

wR(F 2) = 0.067

S = 1.05

5459 reflections

261 parameters

H-atom parameters constrained

Δρmax = 0.56 e Å−3

Δρmin = −0.27 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, 2015 ▸); molecular graphics: DIAMOND (Brandenburg, 2012 ▸); software used to prepare material for publication: SHELXTL (Sheldrick, 2008b ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015023476/lh5799sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015023476/lh5799Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015023476/lh5799Isup4.cdx

Click here for additional data file.

I . DOI: 10.1107/S2056989015023476/lh5799fig1.tif

The mol­ecular structure of (I), with displacement ellipsoids drawn at the 50% probability level. H atoms have been omitted for clarity.

CCDC reference: 1440726

Additional supporting information: crystallographic information; 3D view; checkCIF report

[InLi(CH3)2(C7H7O)2(C6H16N2)]	F(000) = 1000
Mr = 482.29	Dx = 1.304 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.0991 (8) Å	Cell parameters from 5977 reflections
b = 16.4481 (15) Å	θ = 2.5–28.4°
c = 16.4256 (15) Å	µ = 0.98 mm−1
β = 91.956 (1)°	T = 188 K
V = 2456.9 (4) Å3	Irregular, colourless
Z = 4	0.65 × 0.60 × 0.60 mm

Bruker SMART1000/P4 diffractometer	5459 independent reflections
Radiation source: fine-focus sealed tube, K760	4921 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
φ and ω scans	θmax = 27.5°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	h = −11→11
Tmin = 0.569, Tmax = 0.591	k = −21→21
16648 measured reflections	l = −21→20

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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.067	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0318P)2 + 1.1193P] where P = (Fo2 + 2Fc2)/3
5459 reflections	(Δ/σ)max = 0.002
261 parameters	Δρmax = 0.56 e Å−3
0 restraints	Δρmin = −0.27 e Å−3

Experimental. Crystal decay was monitored by repeating the initial 50 frames at the end of the data collection and analyzing duplicate reflections

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.

	x	y	z	Uiso*/Ueq
In1	0.26596 (2)	0.05874 (2)	0.78772 (2)	0.03548 (6)
O1	0.37283 (15)	0.14787 (8)	0.71713 (8)	0.0396 (3)
O2	0.12094 (14)	0.16051 (8)	0.79780 (8)	0.0390 (3)
Li1	0.2425 (4)	0.2341 (2)	0.7385 (2)	0.0375 (7)
N1	0.3343 (2)	0.34149 (12)	0.79061 (12)	0.0511 (5)
N2	0.1764 (2)	0.30590 (12)	0.63874 (11)	0.0489 (4)
C1	0.3935 (4)	0.04698 (19)	0.89888 (16)	0.0686 (8)
H1A	0.4979	0.0543	0.8879	0.103*
H1B	0.3783	−0.0072	0.9220	0.103*
H1C	0.3628	0.0884	0.9376	0.103*
C2	0.1651 (2)	−0.02775 (13)	0.70346 (14)	0.0475 (5)
H2A	0.0581	−0.0208	0.7024	0.071*
H2B	0.1899	−0.0831	0.7211	0.071*
H2C	0.2016	−0.0185	0.6488	0.071*
C3	0.4953 (2)	0.12953 (11)	0.67653 (11)	0.0333 (4)
C4	0.6347 (2)	0.13756 (12)	0.71342 (11)	0.0382 (4)
H4	0.6443	0.1558	0.7682	0.046*
C5	0.7597 (2)	0.11910 (13)	0.67083 (12)	0.0408 (4)
H5	0.8537	0.1252	0.6971	0.049*
C6	0.7502 (2)	0.09210 (13)	0.59107 (12)	0.0415 (4)
C7	0.6121 (2)	0.08379 (13)	0.55467 (12)	0.0426 (5)
H7	0.6032	0.0653	0.4999	0.051*
C8	0.4854 (2)	0.10193 (12)	0.59630 (12)	0.0384 (4)
H8	0.3917	0.0955	0.5699	0.046*
C9	0.8866 (3)	0.06967 (18)	0.54574 (16)	0.0625 (7)
H9A	0.9076	0.0117	0.5534	0.094*
H9B	0.9702	0.1018	0.5669	0.094*
H9C	0.8702	0.0810	0.4876	0.094*
C10	0.0086 (2)	0.16495 (12)	0.84883 (11)	0.0334 (4)
C11	−0.0424 (2)	0.09752 (13)	0.89039 (13)	0.0415 (4)
H11	0.0019	0.0460	0.8824	0.050*
C12	−0.1578 (3)	0.10467 (14)	0.94352 (14)	0.0502 (5)
H12	−0.1910	0.0575	0.9708	0.060*
C13	−0.2252 (2)	0.17834 (15)	0.95769 (13)	0.0471 (5)
C14	−0.1765 (2)	0.24514 (14)	0.91485 (13)	0.0458 (5)
H14	−0.2227	0.2963	0.9220	0.055*
C15	−0.0617 (2)	0.23886 (13)	0.86159 (12)	0.0407 (4)
H15	−0.0305	0.2859	0.8333	0.049*
C16	−0.3460 (3)	0.18714 (19)	1.01892 (18)	0.0705 (8)
H16A	−0.4306	0.2151	0.9931	0.106*
H16B	−0.3090	0.2188	1.0658	0.106*
H16C	−0.3762	0.1331	1.0372	0.106*
C17	0.2618 (4)	0.37967 (17)	0.64916 (18)	0.0716 (8)
H17A	0.2149	0.4236	0.6164	0.086*
H17B	0.3615	0.3706	0.6285	0.086*
C18	0.2747 (4)	0.40580 (16)	0.7358 (2)	0.0719 (8)
H18A	0.3396	0.4540	0.7399	0.086*
H18B	0.1764	0.4221	0.7540	0.086*
C19	0.2068 (4)	0.2688 (2)	0.55914 (15)	0.0742 (8)
H19A	0.1775	0.3065	0.5154	0.111*
H19B	0.1509	0.2181	0.5528	0.111*
H19C	0.3121	0.2571	0.5565	0.111*
C20	0.0174 (3)	0.3218 (2)	0.64082 (18)	0.0748 (8)
H20A	−0.0056	0.3462	0.6933	0.112*
H20B	−0.0365	0.2705	0.6339	0.112*
H20C	−0.0115	0.3592	0.5967	0.112*
C21	0.4918 (3)	0.3336 (2)	0.7846 (3)	0.1069 (14)
H21A	0.5149	0.3171	0.7291	0.160*
H21B	0.5284	0.2924	0.8233	0.160*
H21C	0.5389	0.3859	0.7972	0.160*
C22	0.2953 (4)	0.3605 (2)	0.87428 (18)	0.0885 (10)
H22A	0.3377	0.3194	0.9114	0.133*
H22B	0.1881	0.3606	0.8781	0.133*
H22C	0.3341	0.4142	0.8894	0.133*

	U11	U22	U33	U12	U13	U23
In1	0.03663 (9)	0.03030 (8)	0.04007 (8)	−0.00028 (5)	0.00951 (6)	0.00208 (5)
O1	0.0382 (7)	0.0336 (7)	0.0480 (7)	0.0027 (6)	0.0178 (6)	0.0033 (6)
O2	0.0386 (7)	0.0350 (7)	0.0443 (7)	0.0027 (6)	0.0159 (6)	0.0039 (6)
Li1	0.0400 (17)	0.0319 (16)	0.0410 (16)	−0.0002 (13)	0.0065 (13)	0.0024 (13)
N1	0.0498 (11)	0.0399 (10)	0.0635 (12)	−0.0054 (8)	0.0004 (9)	−0.0099 (9)
N2	0.0563 (11)	0.0452 (10)	0.0454 (9)	0.0051 (9)	0.0050 (8)	0.0086 (8)
C1	0.0794 (19)	0.079 (2)	0.0467 (13)	0.0079 (15)	−0.0064 (13)	0.0139 (13)
C2	0.0454 (12)	0.0363 (11)	0.0613 (13)	−0.0092 (9)	0.0056 (10)	−0.0113 (10)
C3	0.0357 (9)	0.0257 (9)	0.0390 (9)	0.0004 (7)	0.0109 (7)	0.0026 (7)
C4	0.0403 (10)	0.0406 (10)	0.0338 (9)	0.0028 (8)	0.0047 (8)	−0.0026 (8)
C5	0.0340 (10)	0.0437 (11)	0.0449 (10)	0.0035 (8)	0.0025 (8)	0.0018 (9)
C6	0.0427 (11)	0.0387 (11)	0.0441 (10)	0.0097 (9)	0.0145 (9)	0.0038 (9)
C7	0.0524 (12)	0.0421 (11)	0.0337 (9)	0.0043 (9)	0.0078 (8)	−0.0047 (8)
C8	0.0375 (10)	0.0367 (10)	0.0411 (9)	−0.0021 (8)	0.0027 (8)	−0.0021 (8)
C9	0.0531 (14)	0.0774 (18)	0.0584 (14)	0.0221 (13)	0.0217 (12)	0.0033 (13)
C10	0.0319 (9)	0.0356 (10)	0.0329 (8)	−0.0025 (7)	0.0048 (7)	−0.0049 (7)
C11	0.0453 (11)	0.0326 (10)	0.0475 (10)	−0.0047 (8)	0.0158 (9)	−0.0079 (9)
C12	0.0567 (13)	0.0429 (12)	0.0525 (12)	−0.0154 (10)	0.0244 (10)	−0.0091 (10)
C13	0.0376 (10)	0.0536 (13)	0.0512 (11)	−0.0087 (9)	0.0145 (9)	−0.0189 (10)
C14	0.0381 (10)	0.0452 (12)	0.0546 (12)	0.0059 (9)	0.0073 (9)	−0.0123 (10)
C15	0.0388 (10)	0.0376 (10)	0.0461 (10)	0.0028 (8)	0.0073 (8)	−0.0001 (9)
C16	0.0580 (15)	0.0729 (18)	0.0832 (18)	−0.0151 (13)	0.0398 (14)	−0.0275 (15)
C17	0.093 (2)	0.0459 (14)	0.0762 (18)	−0.0046 (14)	0.0121 (16)	0.0229 (13)
C18	0.092 (2)	0.0334 (12)	0.091 (2)	−0.0066 (13)	0.0130 (17)	−0.0044 (13)
C19	0.100 (2)	0.077 (2)	0.0470 (13)	0.0161 (17)	0.0141 (14)	0.0074 (13)
C20	0.0626 (16)	0.100 (2)	0.0619 (15)	0.0196 (16)	−0.0017 (13)	0.0061 (16)
C21	0.0563 (18)	0.080 (2)	0.184 (4)	−0.0067 (16)	−0.005 (2)	−0.043 (3)
C22	0.117 (3)	0.085 (2)	0.0633 (17)	−0.023 (2)	−0.0025 (17)	−0.0287 (17)

In1—O1	2.1252 (13)	C9—H9B	0.9800
In1—C1	2.138 (3)	C9—H9C	0.9800
In1—O2	2.1414 (13)	C10—C11	1.391 (3)
In1—C2	2.167 (2)	C10—C15	1.393 (3)
O1—C3	1.352 (2)	C11—C12	1.393 (3)
O1—Li1	1.889 (4)	C11—H11	0.9500
O2—C10	1.346 (2)	C12—C13	1.382 (3)
O2—Li1	1.926 (3)	C12—H12	0.9500
Li1—N2	2.092 (4)	C13—C14	1.386 (3)
Li1—N1	2.122 (4)	C13—C16	1.522 (3)
N1—C21	1.446 (4)	C14—C15	1.389 (3)
N1—C22	1.465 (4)	C14—H14	0.9500
N1—C18	1.480 (4)	C15—H15	0.9500
N2—C17	1.448 (3)	C16—H16A	0.9800
N2—C20	1.471 (3)	C16—H16B	0.9800
N2—C19	1.478 (3)	C16—H16C	0.9800
C1—H1A	0.9800	C17—C18	1.487 (4)
C1—H1B	0.9800	C17—H17A	0.9900
C1—H1C	0.9800	C17—H17B	0.9900
C2—H2A	0.9800	C18—H18A	0.9900
C2—H2B	0.9800	C18—H18B	0.9900
C2—H2C	0.9800	C19—H19A	0.9800
C3—C4	1.393 (3)	C19—H19B	0.9800
C3—C8	1.394 (3)	C19—H19C	0.9800
C4—C5	1.389 (3)	C20—H20A	0.9800
C4—H4	0.9500	C20—H20B	0.9800
C5—C6	1.383 (3)	C20—H20C	0.9800
C5—H5	0.9500	C21—H21A	0.9800
C6—C7	1.380 (3)	C21—H21B	0.9800
C6—C9	1.514 (3)	C21—H21C	0.9800
C7—C8	1.392 (3)	C22—H22A	0.9800
C7—H7	0.9500	C22—H22B	0.9800
C8—H8	0.9500	C22—H22C	0.9800
C9—H9A	0.9800
O1—In1—C1	106.45 (10)	C6—C9—H9C	109.5
O1—In1—O2	78.32 (5)	H9A—C9—H9C	109.5
C1—In1—O2	108.82 (9)	H9B—C9—H9C	109.5
O1—In1—C2	107.23 (7)	O2—C10—C11	122.42 (17)
C1—In1—C2	133.76 (11)	O2—C10—C15	120.24 (17)
O2—In1—C2	108.30 (8)	C11—C10—C15	117.34 (17)
C3—O1—Li1	142.41 (15)	C10—C11—C12	120.8 (2)
C3—O1—In1	121.02 (11)	C10—C11—H11	119.6
Li1—O1—In1	96.57 (11)	C12—C11—H11	119.6
C10—O2—Li1	137.92 (16)	C13—C12—C11	121.9 (2)
C10—O2—In1	125.00 (12)	C13—C12—H12	119.1
Li1—O2—In1	94.94 (11)	C11—C12—H12	119.1
O1—Li1—O2	89.85 (15)	C12—C13—C14	117.28 (18)
O1—Li1—N2	116.35 (17)	C12—C13—C16	122.0 (2)
O2—Li1—N2	126.61 (19)	C14—C13—C16	120.7 (2)
O1—Li1—N1	117.30 (18)	C13—C14—C15	121.4 (2)
O2—Li1—N1	122.97 (18)	C13—C14—H14	119.3
N2—Li1—N1	86.82 (15)	C15—C14—H14	119.3
C21—N1—C22	110.9 (3)	C14—C15—C10	121.3 (2)
C21—N1—C18	111.5 (3)	C14—C15—H15	119.4
C22—N1—C18	108.8 (2)	C10—C15—H15	119.4
C21—N1—Li1	105.9 (2)	C13—C16—H16A	109.5
C22—N1—Li1	116.8 (2)	C13—C16—H16B	109.5
C18—N1—Li1	102.62 (18)	H16A—C16—H16B	109.5
C17—N2—C20	111.9 (2)	C13—C16—H16C	109.5
C17—N2—C19	109.5 (2)	H16A—C16—H16C	109.5
C20—N2—C19	107.9 (2)	H16B—C16—H16C	109.5
C17—N2—Li1	103.99 (18)	N2—C17—C18	112.3 (2)
C20—N2—Li1	109.79 (18)	N2—C17—H17A	109.1
C19—N2—Li1	113.73 (18)	C18—C17—H17A	109.1
In1—C1—H1A	109.5	N2—C17—H17B	109.1
In1—C1—H1B	109.5	C18—C17—H17B	109.1
H1A—C1—H1B	109.5	H17A—C17—H17B	107.9
In1—C1—H1C	109.5	N1—C18—C17	113.0 (2)
H1A—C1—H1C	109.5	N1—C18—H18A	109.0
H1B—C1—H1C	109.5	C17—C18—H18A	109.0
In1—C2—H2A	109.5	N1—C18—H18B	109.0
In1—C2—H2B	109.5	C17—C18—H18B	109.0
H2A—C2—H2B	109.5	H18A—C18—H18B	107.8
In1—C2—H2C	109.5	N2—C19—H19A	109.5
H2A—C2—H2C	109.5	N2—C19—H19B	109.5
H2B—C2—H2C	109.5	H19A—C19—H19B	109.5
O1—C3—C4	121.17 (17)	N2—C19—H19C	109.5
O1—C3—C8	120.74 (17)	H19A—C19—H19C	109.5
C4—C3—C8	118.09 (17)	H19B—C19—H19C	109.5
C5—C4—C3	120.61 (17)	N2—C20—H20A	109.5
C5—C4—H4	119.7	N2—C20—H20B	109.5
C3—C4—H4	119.7	H20A—C20—H20B	109.5
C6—C5—C4	121.43 (19)	N2—C20—H20C	109.5
C6—C5—H5	119.3	H20A—C20—H20C	109.5
C4—C5—H5	119.3	H20B—C20—H20C	109.5
C7—C6—C5	117.92 (18)	N1—C21—H21A	109.5
C7—C6—C9	120.8 (2)	N1—C21—H21B	109.5
C5—C6—C9	121.2 (2)	H21A—C21—H21B	109.5
C6—C7—C8	121.53 (18)	N1—C21—H21C	109.5
C6—C7—H7	119.2	H21A—C21—H21C	109.5
C8—C7—H7	119.2	H21B—C21—H21C	109.5
C7—C8—C3	120.41 (19)	N1—C22—H22A	109.5
C7—C8—H8	119.8	N1—C22—H22B	109.5
C3—C8—H8	119.8	H22A—C22—H22B	109.5
C6—C9—H9A	109.5	N1—C22—H22C	109.5
C6—C9—H9B	109.5	H22A—C22—H22C	109.5
H9A—C9—H9B	109.5	H22B—C22—H22C	109.5