Crystal structure and com­putational study of an oxo-bridged bis-titanium(III) com­plex

Bloomfield, H.R.; Hollett, J.W.; Ritch, J.S.

doi:10.1107/S2053229621006094

Crystal structure and computational study of an oxo-bridged bis-titanium(III) complex

H. R. Bloomfield, J. W. Hollett and J. S. Ritch

The solid-state structure of the new compound μ-oxido-bis[dichloridotris(tetrahydrofuran-κO)titanium(III)], [Ti₂Cl₄O(C₄H₈O)₆], at 150 K has been determined. The crystal has monoclinic (C2/c) symmetry and the complex features C₂ symmetry about the bridging O atom. Positional disorder is evident in one of the three tetrahydrofuran environments. A post-Hartree–Fock computational analysis indicates that the complex has nearly degenerate triplet and singlet spin states, with the former favoured slightly by ca 2 kJ mol⁻¹.

Keywords: titanium(III); bimetallic complex; coordination compound; crystal structure; computational modelling.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229621006094/dg3018sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229621006094/dg3018Isup2.hkl Contains datablock I
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229621006094/dg3018Isup3.cml Supplementary material

CCDC reference: 2089304

Computing details top

Data collection: SAINT (Bruker, 2016); cell refinement: APEX2 (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT2018 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

µ-Oxido-bis[dichloridotris(tetrahydrofuran-κO)titanium(III)] top

Crystal data top

[Ti₂Cl₄O(C₄H₈O)₆]	F(000) = 1440
M_r = 686.22	D_x = 1.421 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 19.1347 (5) Å	Cell parameters from 9986 reflections
b = 9.1227 (3) Å	θ = 2.5–29.6°
c = 18.7937 (5) Å	µ = 0.87 mm⁻¹
β = 102.092 (2)°	T = 150 K
V = 3207.84 (16) Å³	Block, clear light red
Z = 4	0.33 × 0.33 × 0.28 mm

Data collection top

Bruker APEXII CCD diffractometer	3244 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.068
Absorption correction: numerical (SADABS; Bruker, 2016)	θ_max = 29.6°, θ_min = 2.5°
T_min = 0.562, T_max = 0.678	h = −21→25
25791 measured reflections	k = −11→12
4461 independent reflections	l = −25→26

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.073	w = 1/[σ²(F_o²) + 30.5697P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.138	(Δ/σ)_max = 0.001
S = 1.13	Δρ_max = 0.57 e Å⁻³
4461 reflections	Δρ_min = −0.41 e Å⁻³
182 parameters	Extinction correction: SHELXT2018 (Sheldrick, 2015a), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
10 restraints	Extinction coefficient: 0.00039 (7)

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ti1	0.43130 (4)	0.55202 (7)	0.66762 (4)	0.01715 (16)
Cl1	0.48830 (5)	0.37747 (11)	0.59944 (5)	0.0254 (2)
Cl2	0.35094 (6)	0.72586 (11)	0.70921 (6)	0.0283 (2)
O1	0.500000	0.5536 (5)	0.750000	0.0249 (8)
O2	0.37164 (15)	0.3758 (3)	0.70116 (15)	0.0231 (6)
O3	0.34579 (14)	0.5523 (4)	0.56683 (14)	0.0277 (6)
C1	0.3783 (3)	0.2223 (5)	0.6840 (3)	0.0441 (13)
H1A	0.428225	0.188668	0.700561	0.052*
H1B	0.363459	0.205566	0.630934	0.052*
C2	0.3295 (3)	0.1431 (6)	0.7241 (3)	0.0481 (14)
H2A	0.344622	0.040137	0.734186	0.057*
H2B	0.279355	0.145037	0.696499	0.057*
C3	0.3384 (2)	0.2311 (5)	0.7932 (3)	0.0324 (10)
H3A	0.383188	0.204980	0.827718	0.038*
H3B	0.297459	0.216653	0.817106	0.038*
C4	0.3409 (2)	0.3859 (5)	0.7659 (2)	0.0278 (9)
H4A	0.292234	0.428372	0.753550	0.033*
H4B	0.371007	0.448157	0.803364	0.033*
C5	0.3560 (2)	0.5794 (5)	0.4940 (2)	0.0325 (10)
H5A	0.403410	0.544106	0.488285	0.038*
H5B	0.352068	0.685421	0.482495	0.038*
C6	0.2973 (3)	0.4953 (7)	0.4456 (3)	0.0513 (15)
H6A	0.283008	0.542792	0.397404	0.061*
H6B	0.312242	0.393259	0.438912	0.061*
C7	0.2381 (3)	0.4994 (9)	0.4857 (3)	0.0617 (18)
H7A	0.205144	0.581543	0.468189	0.074*
H7B	0.210670	0.406647	0.478715	0.074*
C8	0.2718 (2)	0.5198 (7)	0.5631 (3)	0.0475 (14)
H8A	0.248572	0.601541	0.584008	0.056*
H8B	0.266981	0.429577	0.590949	0.056*
O4A	0.47581 (15)	0.7265 (3)	0.61486 (16)	0.0256 (6)	0.305 (10)
C9A	0.4666 (11)	0.8798 (15)	0.6335 (10)	0.037 (2)	0.305 (10)
H9AA	0.490493	0.901398	0.684430	0.044*	0.305 (10)
H9AB	0.415424	0.906631	0.625989	0.044*	0.305 (10)
C10A	0.5028 (10)	0.9567 (17)	0.5800 (12)	0.046 (2)	0.305 (10)
H10A	0.471578	0.958661	0.530799	0.055*	0.305 (10)
H10B	0.515873	1.058390	0.595679	0.055*	0.305 (10)
C11A	0.5679 (11)	0.866 (3)	0.5809 (18)	0.038 (3)	0.305 (10)
H11A	0.607203	0.893953	0.621795	0.045*	0.305 (10)
H11B	0.584567	0.875524	0.534694	0.045*	0.305 (10)
C12A	0.5431 (12)	0.711 (2)	0.591 (2)	0.023 (2)	0.305 (10)
H12A	0.535634	0.656542	0.543999	0.027*	0.305 (10)
H12B	0.578690	0.657804	0.627323	0.027*	0.305 (10)
O4B	0.47581 (15)	0.7265 (3)	0.61486 (16)	0.0256 (6)	0.695 (10)
C9B	0.4520 (4)	0.8769 (7)	0.6009 (5)	0.037 (2)	0.695 (10)
H9BA	0.414616	0.902429	0.628045	0.044*	0.695 (10)
H9BB	0.433408	0.893978	0.548355	0.044*	0.695 (10)
C10B	0.5197 (4)	0.9630 (8)	0.6284 (6)	0.046 (2)	0.695 (10)
H10C	0.516303	1.062613	0.607030	0.055*	0.695 (10)
H10D	0.530015	0.971064	0.682082	0.055*	0.695 (10)
C11B	0.5756 (5)	0.8740 (11)	0.6031 (6)	0.038 (3)	0.695 (10)
H11C	0.622887	0.886866	0.636076	0.045*	0.695 (10)
H11D	0.579341	0.902179	0.553189	0.045*	0.695 (10)
C12B	0.5498 (4)	0.7179 (10)	0.6051 (7)	0.023 (2)	0.695 (10)
H12C	0.551874	0.666786	0.559096	0.027*	0.695 (10)
H12D	0.579946	0.663704	0.645962	0.027*	0.695 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ti1	0.0167 (3)	0.0163 (3)	0.0178 (3)	0.0004 (3)	0.0021 (2)	−0.0008 (3)
Cl1	0.0277 (5)	0.0219 (5)	0.0287 (5)	0.0048 (4)	0.0107 (4)	−0.0014 (4)
Cl2	0.0296 (5)	0.0248 (5)	0.0323 (5)	0.0067 (4)	0.0103 (4)	−0.0038 (4)
O1	0.022 (2)	0.028 (2)	0.0226 (19)	0.000	0.0002 (15)	0.000
O2	0.0273 (15)	0.0185 (14)	0.0259 (14)	−0.0053 (11)	0.0108 (12)	−0.0033 (11)
O3	0.0183 (14)	0.0435 (18)	0.0207 (14)	0.0014 (13)	0.0033 (11)	−0.0041 (13)
C1	0.068 (4)	0.021 (2)	0.055 (3)	−0.010 (2)	0.040 (3)	−0.012 (2)
C2	0.059 (4)	0.027 (3)	0.065 (4)	−0.014 (2)	0.028 (3)	−0.007 (2)
C3	0.031 (2)	0.031 (2)	0.035 (2)	−0.0086 (19)	0.0091 (19)	0.0018 (19)
C4	0.032 (2)	0.029 (2)	0.027 (2)	−0.0024 (18)	0.0164 (18)	−0.0025 (17)
C5	0.032 (2)	0.040 (3)	0.024 (2)	0.002 (2)	0.0020 (17)	0.0023 (19)
C6	0.048 (3)	0.078 (4)	0.026 (2)	−0.019 (3)	0.004 (2)	−0.011 (3)
C7	0.034 (3)	0.105 (5)	0.043 (3)	−0.012 (3)	0.000 (2)	−0.017 (3)
C8	0.017 (2)	0.089 (4)	0.034 (3)	−0.007 (2)	0.0015 (18)	−0.008 (3)
O4A	0.0231 (15)	0.0179 (14)	0.0363 (17)	−0.0006 (11)	0.0075 (12)	0.0034 (12)
C9A	0.031 (4)	0.020 (3)	0.060 (6)	0.009 (2)	0.012 (4)	0.017 (4)
C10A	0.046 (4)	0.021 (3)	0.070 (6)	−0.004 (3)	0.013 (4)	0.000 (4)
C11A	0.037 (3)	0.030 (3)	0.050 (8)	−0.005 (2)	0.017 (4)	0.012 (4)
C12A	0.024 (3)	0.029 (2)	0.016 (6)	−0.001 (2)	0.007 (3)	−0.004 (3)
O4B	0.0231 (15)	0.0179 (14)	0.0363 (17)	−0.0006 (11)	0.0075 (12)	0.0034 (12)
C9B	0.031 (4)	0.020 (3)	0.060 (6)	0.009 (2)	0.012 (4)	0.017 (4)
C10B	0.046 (4)	0.021 (3)	0.070 (6)	−0.004 (3)	0.013 (4)	0.000 (4)
C11B	0.037 (3)	0.030 (3)	0.050 (8)	−0.005 (2)	0.017 (4)	0.012 (4)
C12B	0.024 (3)	0.029 (2)	0.016 (6)	−0.001 (2)	0.007 (3)	−0.004 (3)

Geometric parameters (Å, º) top

Ti1—Cl1	2.4398 (12)	C7—C8	1.474 (7)
Ti1—Cl2	2.4482 (12)	C8—H8A	0.9900
Ti1—O1	1.8091 (7)	C8—H8B	0.9900
Ti1—O2	2.142 (3)	O4A—C9A	1.462 (14)
Ti1—O3	2.229 (3)	O4A—C12A	1.460 (14)
Ti1—O4A	2.144 (3)	C9A—H9AA	0.9900
Ti1—O4B	2.144 (3)	C9A—H9AB	0.9900
O2—C1	1.448 (5)	C9A—C10A	1.509 (16)
O2—C4	1.462 (4)	C10A—H10A	0.9900
O3—C5	1.444 (5)	C10A—H10B	0.9900
O3—C8	1.434 (5)	C10A—C11A	1.496 (16)
C1—H1A	0.9900	C11A—H11A	0.9900
C1—H1B	0.9900	C11A—H11B	0.9900
C1—C2	1.502 (7)	C11A—C12A	1.511 (15)
C2—H2A	0.9900	C12A—H12A	0.9900
C2—H2B	0.9900	C12A—H12B	0.9900
C2—C3	1.505 (7)	O4B—C9B	1.452 (7)
C3—H3A	0.9900	O4B—C12B	1.468 (7)
C3—H3B	0.9900	C9B—H9BA	0.9900
C3—C4	1.506 (6)	C9B—H9BB	0.9900
C4—H4A	0.9900	C9B—C10B	1.510 (9)
C4—H4B	0.9900	C10B—H10C	0.9900
C5—H5A	0.9900	C10B—H10D	0.9900
C5—H5B	0.9900	C10B—C11B	1.497 (9)
C5—C6	1.499 (6)	C11B—H11C	0.9900
C6—H6A	0.9900	C11B—H11D	0.9900
C6—H6B	0.9900	C11B—C12B	1.510 (8)
C6—C7	1.487 (7)	C12B—H12C	0.9900
C7—H7A	0.9900	C12B—H12D	0.9900
C7—H7B	0.9900

Cl1—Ti1—Cl2	165.98 (5)	H7A—C7—H7B	108.7
O1—Ti1—Cl1	97.47 (9)	C8—C7—C6	106.3 (4)
O1—Ti1—Cl2	96.55 (9)	C8—C7—H7A	110.5
O1—Ti1—O2	95.20 (13)	C8—C7—H7B	110.5
O1—Ti1—O3	179.21 (13)	O3—C8—C7	107.3 (4)
O1—Ti1—O4A	95.86 (13)	O3—C8—H8A	110.3
O1—Ti1—O4B	95.86 (13)	O3—C8—H8B	110.3
O2—Ti1—Cl1	89.38 (8)	C7—C8—H8A	110.3
O2—Ti1—Cl2	89.04 (8)	C7—C8—H8B	110.3
O2—Ti1—O3	84.79 (11)	H8A—C8—H8B	108.5
O2—Ti1—O4A	168.93 (11)	C9A—O4A—Ti1	121.3 (7)
O2—Ti1—O4B	168.93 (11)	C12A—O4A—Ti1	122.3 (10)
O3—Ti1—Cl1	83.32 (8)	C12A—O4A—C9A	109.1 (11)
O3—Ti1—Cl2	82.67 (8)	O4A—C9A—H9AA	111.6
O4A—Ti1—Cl1	88.68 (8)	O4A—C9A—H9AB	111.6
O4A—Ti1—Cl2	90.21 (8)	O4A—C9A—C10A	100.9 (11)
O4A—Ti1—O3	84.16 (11)	H9AA—C9A—H9AB	109.4
O4B—Ti1—Cl1	88.68 (8)	C10A—C9A—H9AA	111.6
O4B—Ti1—Cl2	90.21 (8)	C10A—C9A—H9AB	111.6
O4B—Ti1—O3	84.16 (11)	C9A—C10A—H10A	111.1
Ti1—O1—Ti1ⁱ	179.1 (3)	C9A—C10A—H10B	111.1
C1—O2—Ti1	125.7 (2)	H10A—C10A—H10B	109.0
C1—O2—C4	108.4 (3)	C11A—C10A—C9A	103.4 (13)
C4—O2—Ti1	122.0 (2)	C11A—C10A—H10A	111.1
C5—O3—Ti1	125.8 (2)	C11A—C10A—H10B	111.1
C8—O3—Ti1	125.6 (3)	C10A—C11A—H11A	111.0
C8—O3—C5	108.5 (3)	C10A—C11A—H11B	111.0
O2—C1—H1A	110.7	C10A—C11A—C12A	103.7 (13)
O2—C1—H1B	110.7	H11A—C11A—H11B	109.0
O2—C1—C2	105.1 (4)	C12A—C11A—H11A	111.0
H1A—C1—H1B	108.8	C12A—C11A—H11B	111.0
C2—C1—H1A	110.7	O4A—C12A—C11A	105.5 (12)
C2—C1—H1B	110.7	O4A—C12A—H12A	110.6
C1—C2—H2A	111.4	O4A—C12A—H12B	110.6
C1—C2—H2B	111.4	C11A—C12A—H12A	110.6
C1—C2—C3	101.9 (4)	C11A—C12A—H12B	110.6
H2A—C2—H2B	109.3	H12A—C12A—H12B	108.8
C3—C2—H2A	111.4	C9B—O4B—Ti1	130.2 (4)
C3—C2—H2B	111.4	C9B—O4B—C12B	107.6 (5)
C2—C3—H3A	111.3	C12B—O4B—Ti1	120.4 (4)
C2—C3—H3B	111.3	O4B—C9B—H9BA	111.3
C2—C3—C4	102.3 (4)	O4B—C9B—H9BB	111.3
H3A—C3—H3B	109.2	O4B—C9B—C10B	102.5 (5)
C4—C3—H3A	111.3	H9BA—C9B—H9BB	109.2
C4—C3—H3B	111.3	C10B—C9B—H9BA	111.3
O2—C4—C3	105.7 (3)	C10B—C9B—H9BB	111.3
O2—C4—H4A	110.6	C9B—C10B—H10C	111.1
O2—C4—H4B	110.6	C9B—C10B—H10D	111.1
C3—C4—H4A	110.6	H10C—C10B—H10D	109.1
C3—C4—H4B	110.6	C11B—C10B—C9B	103.2 (6)
H4A—C4—H4B	108.7	C11B—C10B—H10C	111.1
O3—C5—H5A	110.8	C11B—C10B—H10D	111.1
O3—C5—H5B	110.8	C10B—C11B—H11C	110.9
O3—C5—C6	104.7 (4)	C10B—C11B—H11D	110.9
H5A—C5—H5B	108.9	C10B—C11B—C12B	104.2 (6)
C6—C5—H5A	110.8	H11C—C11B—H11D	108.9
C6—C5—H5B	110.8	C12B—C11B—H11C	110.9
C5—C6—H6A	111.1	C12B—C11B—H11D	110.9
C5—C6—H6B	111.1	O4B—C12B—C11B	106.3 (6)
H6A—C6—H6B	109.0	O4B—C12B—H12C	110.5
C7—C6—C5	103.5 (4)	O4B—C12B—H12D	110.5
C7—C6—H6A	111.1	C11B—C12B—H12C	110.5
C7—C6—H6B	111.1	C11B—C12B—H12D	110.5
C6—C7—H7A	110.5	H12C—C12B—H12D	108.7
C6—C7—H7B	110.5

Symmetry code: (i) −x+1, y, −z+3/2.

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Crystal structure and com­putational study of an oxo-bridged bis-titanium(III) com­plex

Supporting information

Crystal structure and computational study of an oxo-bridged bis-titanium(III) complex