Bis(μ-2-hy­droxy­methyl-2-methyl­propane-1,3-diolato)bis­[di­chlorido­titanium(IV)] diethyl ether disolvate

Nielson, A.J.; Shen, C.; Waters, J.M.

doi:10.1107/S1600536813031504

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 12| December 2013| Pages m676-m677

doi:10.1107/S1600536813031504

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Bis(μ-2-hydroxymethyl-2-methylpropane-1,3-diolato)bis[dichloridotitanium(IV)] diethyl ether disolvate

Alastair J. Nielson,^a ^* Chaohong Shen ^b ‡ and Joyce M. Waters ^a

^aChemistry, Institute of Natural and Mathematical Sciences, Massey University at Albany, PO Box 102904 North Shore Mail Centre, Auckland, New Zealand, and ^bChemistry, Institute of Fundamental Sciences, Massey University at Albany, PO Box 102904 North, Shore Mail Centre, Auckland, New Zealand
^*Correspondence e-mail: a.j.nielson@massey.ac.nz

(Received 7 November 2013; accepted 19 November 2013; online 23 November 2013)

The title complex, [Ti₂Cl₄{CH₃C(CH₂O)₂(CH₂OH)}₂], lies across a centre of symmetry with a diethyl ether solvent molecule hydrogen bonded to the –CH₂OH groups on either side of it. The Ti^IV atom is coordinated in a distorted octahedral geometry by a tripodal ligand and two terminal chloride atoms. There are three coordination modes for the tripodal ligand distinguishable on the basis of their very different Ti—O bond lengths. For the terminal alkoxo ligand, the Ti—O distance is 1.760 (1) Å, the asymmetric bridge system has Ti—O bond lengths of 1.911 (1) and 2.048 (1) Å. The Ti—O bond length for the alcohol O atom is the longest at 2.148 (1) Å.

CCDC reference: 972604

Related literature

For general background to Ti—O and Ti—Cl bonds, see: Gau et al. (1996 ); Wu et al. (1996 ). For closely related structures, see: Talbot-Eeckelaers et al. (2006 ); Chang et al. (1993 ); Salta & Zubieta (1997 ); Chen et al. (1997 ). For cluster compounds of this ligand type, see: Boyle et al. (1995 ); Delmont et al. (2000 ); Liu et al. (1990 ).

Experimental

Crystal data

[Ti₂Cl₄(C₅H₁₀O₃)₂]·2C₄H₁₀O
M_r = 622.10
Triclinic, $[P \overline 1]$
a = 7.9617 (3) Å
b = 9.6379 (4) Å
c = 10.5783 (5) Å
α = 71.351 (1)°
β = 82.023 (1)°
γ = 66.757 (1)°
V = 706.60 (5) Å³
Z = 1
Mo Kα radiation
μ = 0.98 mm⁻¹
T = 150 K
0.26 × 0.24 × 0.10 mm

Data collection

Siemens SMART CCD diffractometer
Absorption correction: multi-scan (Blessing, 1995 ) T_min = 0.766, T_max = 0.892
6510 measured reflections
2661 independent reflections
2417 reflections with I > 2σ(I)
R_int = 0.015

Refinement

R[F² > 2σ(F²)] = 0.022
wR(F²) = 0.061
S = 1.04
2661 reflections
152 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O11	0.74 (2)	1.89 (2)	2.6233 (14)	168 (2)

Data collection: SMART (Siemens, 1995 ); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: SHELXL97.

Supporting information

CCDC reference: 972604

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813031504/hg5360sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813031504/hg5360Isup2.hkl

checkCIF report

Comment top

Transition metal complexes that arise from the tris-hydroxymethyl ethane ligand CH₃C(CH₂OH)₃ are not widely reported in the literature. Structures identified by X-ray crystallography include the triply deprotonated form in cluster compounds of molybdenum and tungsten (Liu et al. 1990; Delmont et al. 2000) and dimeric and cluster compounds of chromium (Talbot-Eeckelaers et al. 2006), the doubly deprotonated form in dimeric vanadium-oxo complexes (Chang et al. 1993; Salta & Zubieta 1997) and the fully protonated form in monomeric yttrium complexes (Chen et al. 1997). For titanium only µ3–O and µ2–O coordination modes have been identified (Boyle et al. 1995).

When TiCl₄ in diethyl ether was reacted with a mixture of CH₃C(CH₂OSiMe₃)₃ and CH₃C(CH₂OSiMe₃)₂(CH₂OH) we obtained a small amount of colourless crystals analysing as TiCl₂[(OCH₂)₂(HOCH₂)CCH₃]. 0.5 diethyl ether. One crystal was characterized by X-ray crystallography. The structure consists of a centrosymmetric dimer made up of two [(OCH₂)₂(HOCH₂)CCH₃] ligands forming a tripodal bridging system across two titanium atoms each of which also contain two terminal chloro ligands. One tripodal ligand is positioned above the two Ti atoms and out towards the rear of the molecule and the other is below and out the front with the two related by an inversion centre. The distorted octahedral geometry about Ti is made from one arm of a terminal alkoxo ligand (O2), another from an alcohol ligand (O3) and a third arm from the bridging alkoxo atoms (O1 and O1ⁱ). These latter each lie in trans-positions to the two cis-related chloro ligands.

For the terminal alkoxo ligand the Ti–O2 distance is 1.760 (1) Å which is indicative of strong π-bonding (see later). The asymmetric bridge system has Ti–O bond lengths of 1.991 (1) and 2.048 (7) Å and the Ti–Cl bonds trans to these bridging O atoms also show differences in length, 2.3184 (4) Å for Ti–Cl1 which is trans to the longer Ti–O1 and 2.3292 (4) Å for Ti–Cl2 which lies trans to the shorter Ti–O1ⁱ bond. The Ti–O bond length for the alcohol oxygen (Ti–O3) is the longest at 2.148 (1) Å. The strongly π-bonded terminal alkoxo ligand O atoms (O2, O2ⁱ) lie trans to the weak dative bonds made by the alcohol ligand O atoms (O3ⁱ, O3).

The overall coordination geometry and deprotonation features of the two ligands are identical with that found in the vanadium (v) complex {V₂O₂Cl₂([(OCH₂)₂(HOCH₂)CCH₃]₂} (Chang et al. 1993; Salta & Zubieta 1997). In {M₂O₄[(OCH₂)₃CCH₃]₂}^2- (M = Mo, W) all three arms of the tripod are deprotonated (Liu et al. 1990; Delmont et al. 2000). Single deprotonation occurs in {Cr₂Cl₄([(OCH₂)HOCH₂)₂(CEt]₂} (Talbot-Eeckelaers et al. 2006).

The Ti–O bond lengths in the present complex reflect the various coordination modes in the molecule. The Ti–O1 bond lengths [1.991 (1) and 2.048 (1) Å] show the asymmetric nature of the bridging system across the two Ti atoms. The short Ti–O2 bond length [1.760 (1) Å] is associated with an alkoxo ligand. In comparison, terminal alkoxo ligand Ti–O bond lengths range from 1.702 (4) to 1.742 (6) Å in a variety of iso-propoxo Ti complexes (Gau et al. 1996). The dative nature of the alcohol ligand is shown by the longer Ti–O3 bond length [2.148 (1) Å] in the present complex being slightly longer than observed for isopropyl alcohol ligated to titanium [bond lengths 2.087 (4) and 2.093 (4) Å] (Wu et al. 1996). The Ti–Cl1 and Ti–Cl2 bond lengths [2.3184 (4) and 2.3292 (4) Å] do not differ significantly from each other and are typical of Ti–Cl bonds observed elsewhere. (Gau et al. 1996; Wu et al. 1996).

The strong π-donor nature of the alkoxo ligand oxygen is shown by the way other coordinated atoms push away from it [O2–Ti–O1, 86.71 (4); O2–Ti–O1ⁱ, 101.78 (5); O–2–Ti–Cl1, 97.18 (4); O2–Ti–Cl2, 93.95 (4)°]. For the dative Ti–O bond all the associated O3ⁱ–Ti–Y angles are 90° or below [range 80.17 (4) to 90.02 (3)°]. The bond angle associated with the bridging Ti–O1–Tiⁱ system [103.17 (4)°] does not differ significantly from comparable angles observed in other complexes. In this regard, it is noted that all known complexes have an alkoxo ligand making up the bridging system. The largest terminal Ti–O–C bond angle is associated with the alkoxo ligand [alkoxo Ti–O2–C3 angle 138.33 (9)° cf. alcohol Tiⁱ–O3–C4 angle 126.66 (9)°]. To accommodate the coordination mode of the various oxygen ligands across the two Ti atoms, the O–C–C bond angles of the tripod [range, 112.4 (1) to 113.3 (1)°] are slightly greater than the ideal tetrahedral angle.

Related literature top

For general background to Ti—O and Ti—Cl bonds, see: Gau et al. (1996); Wu et al. (1996). For closely related structures, see: Talbot-Eeckelaers et al. (2006); Chang et al. (1993); Salta & Zubieta (1997); Chen et al. (1997). For cluster compounds of this ligand type, see: Boyle et al. (1995); Delmont et al. (2000); Liu et al. (1990).

Experimental top

Using normal bench-top techniques for air-sensitive compounds, TiCl₄ (1.25 g, 6.59 mmol) was cooled to dry-ice temperature and diethyl ether (50 ml) chilled to -20 °C was added. The mixture was warmed to room temperature, heated until all the yellow solid had dissolved and 1,1,1-tris(hydroxymethyl)ethane (2.2 g, 6.6 mmol) in diethyl ether (50 ml) was added to the rapidly stirred solution whereupon a dense colourless precipitate was formed. The mixture was refluxed for 3 h, cooled to room temperature and the remaining solid allowed to settle and the solution was filtered. The volume was reduced to ca 30 ml and the solution stood at -20 ° C whereupon a mass of crystalline colourless material was deposited. Found: C, 31.06; H, 6.15%. C₁₄H₃₀Cl₄O₆Ti₂ (i.e. C₁₀H₂₀Cl₄O₆Ti₂.diethyl ether) requires C, 31.61; H, 5.69%. A crystal was chosen from the mass and the X-ray crystal structure obtained. This molecule corresponded to C₁₀H₂₀Cl₄O₆Ti₂.bis-diethyl ether.

Computing details top

Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. ORTEP diagram of molecule, at the 50% probability level, showing the numbering system. Symmetry code: (i) -x + 1, -y + 1, -z + 1.

Bis(µ-2-hydroxymethyl-2-methylpropane-1,3-diolato)bis[dichloridotitanium(IV)] diethyl ether disolvate top

Crystal data top

[Ti₂Cl₄(C₅H₁₀O₃)₂]·2C₄H₁₀O	Z = 1
M_r = 622.10	F(000) = 324
Triclinic, P1	D_x = 1.462 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.9617 (3) Å	Cell parameters from 5595 reflections
b = 9.6379 (4) Å	θ = 2–25°
c = 10.5783 (5) Å	µ = 0.98 mm⁻¹
α = 71.351 (1)°	T = 150 K
β = 82.023 (1)°	Plate, colourless
γ = 66.757 (1)°	0.26 × 0.24 × 0.10 mm
V = 706.60 (5) Å³

Data collection top

Siemens SMART CCD diffractometer	2661 independent reflections
Radiation source: fine-focus sealed tube	2417 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.015
Area detector ω scans	θ_max = 25.7°, θ_min = 2.0°
Absorption correction: multi-scan (Blessing, 1995)	h = −9→9
T_min = 0.766, T_max = 0.892	k = −10→11
6510 measured reflections	l = 0→12

Refinement top

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)] = 0.022	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.061	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0325P)² + 0.2355P] where P = (F_o² + 2F_c²)/3
2661 reflections	(Δ/σ)_max < 0.001
152 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

[Ti₂Cl₄(C₅H₁₀O₃)₂]·2C₄H₁₀O	γ = 66.757 (1)°
M_r = 622.10	V = 706.60 (5) Å³
Triclinic, P1	Z = 1
a = 7.9617 (3) Å	Mo Kα radiation
b = 9.6379 (4) Å	µ = 0.98 mm⁻¹
c = 10.5783 (5) Å	T = 150 K
α = 71.351 (1)°	0.26 × 0.24 × 0.10 mm
β = 82.023 (1)°

Data collection top

Siemens SMART CCD diffractometer	2661 independent reflections
Absorption correction: multi-scan (Blessing, 1995)	2417 reflections with I > 2σ(I)
T_min = 0.766, T_max = 0.892	R_int = 0.015
6510 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.022	0 restraints
wR(F²) = 0.061	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.31 e Å⁻³
2661 reflections	Δρ_min = −0.27 e Å⁻³
152 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
Ti	0.58094 (3)	0.61520 (3)	0.39188 (2)	0.01725 (9)
Cl1	0.74357 (5)	0.59557 (5)	0.19464 (4)	0.02805 (11)
Cl2	0.47954 (5)	0.88725 (4)	0.35265 (4)	0.02495 (10)
O1	0.43149 (13)	0.59722 (11)	0.56614 (9)	0.0177 (2)
O2	0.76654 (13)	0.57443 (12)	0.48899 (10)	0.0217 (2)
O3	0.66826 (14)	0.32177 (13)	0.70683 (10)	0.0197 (2)
C1	0.4634 (2)	0.65978 (17)	0.66438 (14)	0.0209 (3)
H1A	0.3764	0.6490	0.7400	0.025*
H1B	0.4384	0.7737	0.6237	0.025*
C2	0.6586 (2)	0.57709 (17)	0.71785 (15)	0.0211 (3)
C3	0.7972 (2)	0.60351 (19)	0.60594 (15)	0.0248 (3)
H3A	0.7897	0.7137	0.5832	0.030*
H3B	0.9221	0.5328	0.6382	0.030*
H3	0.721 (3)	0.236 (3)	0.737 (2)	0.038 (6)*
C4	0.6997 (2)	0.40296 (17)	0.78961 (15)	0.0227 (3)
H4A	0.8288	0.3514	0.8178	0.027*
H4B	0.6216	0.3934	0.8709	0.027*
C5	0.6733 (2)	0.65305 (19)	0.82181 (16)	0.0296 (4)
H5A	0.5924	0.6323	0.8981	0.044*
H5B	0.6371	0.7672	0.7813	0.044*
H5C	0.7997	0.6079	0.8522	0.044*
O11	0.89033 (14)	0.03405 (12)	0.82316 (10)	0.0220 (2)
C11	0.7018 (2)	0.0355 (2)	1.01998 (16)	0.0309 (4)
H11A	0.7672	0.0891	1.0464	0.046*
H11B	0.6635	−0.0316	1.0999	0.046*
H11C	0.5939	0.1143	0.9687	0.046*
C12	0.8258 (2)	−0.06469 (18)	0.93561 (16)	0.0276 (3)
H12A	0.9306	−0.1496	0.9889	0.033*
H12B	0.7584	−0.1142	0.9041	0.033*
C13	1.0030 (2)	−0.0498 (2)	0.73231 (17)	0.0305 (4)
H13A	0.9318	−0.0910	0.6945	0.037*
H13B	1.1090	−0.1401	0.7797	0.037*
C14	1.0679 (2)	0.0633 (2)	0.62220 (18)	0.0375 (4)
H14A	0.9624	0.1497	0.5732	0.056*
H14B	1.1492	0.0074	0.5610	0.056*
H14C	1.1343	0.1064	0.6609	0.056*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ti	0.01564 (14)	0.01876 (14)	0.01493 (14)	−0.00583 (10)	0.00015 (10)	−0.00266 (10)
Cl1	0.0258 (2)	0.0379 (2)	0.01864 (19)	−0.01292 (16)	0.00543 (15)	−0.00699 (16)
Cl2	0.0292 (2)	0.01963 (18)	0.0251 (2)	−0.01055 (15)	−0.00415 (15)	−0.00208 (14)
O1	0.0167 (5)	0.0178 (5)	0.0160 (5)	−0.0040 (4)	0.0002 (4)	−0.0047 (4)
O2	0.0178 (5)	0.0266 (5)	0.0192 (5)	−0.0073 (4)	−0.0004 (4)	−0.0058 (4)
O3	0.0222 (5)	0.0149 (5)	0.0202 (5)	−0.0041 (4)	−0.0047 (4)	−0.0046 (4)
C1	0.0239 (7)	0.0196 (7)	0.0181 (7)	−0.0051 (6)	0.0006 (6)	−0.0084 (6)
C2	0.0241 (7)	0.0200 (7)	0.0196 (7)	−0.0070 (6)	−0.0026 (6)	−0.0070 (6)
C3	0.0248 (8)	0.0308 (8)	0.0221 (8)	−0.0129 (6)	−0.0025 (6)	−0.0078 (6)
C4	0.0273 (8)	0.0217 (7)	0.0188 (7)	−0.0074 (6)	−0.0051 (6)	−0.0057 (6)
C5	0.0405 (9)	0.0274 (8)	0.0245 (8)	−0.0122 (7)	−0.0050 (7)	−0.0108 (7)
O11	0.0222 (5)	0.0197 (5)	0.0201 (5)	−0.0051 (4)	0.0000 (4)	−0.0042 (4)
C11	0.0341 (9)	0.0376 (9)	0.0224 (8)	−0.0189 (8)	0.0021 (7)	−0.0046 (7)
C12	0.0321 (9)	0.0237 (8)	0.0244 (8)	−0.0124 (7)	−0.0032 (7)	0.0002 (6)
C13	0.0270 (8)	0.0294 (8)	0.0296 (9)	−0.0014 (7)	−0.0008 (7)	−0.0130 (7)
C14	0.0289 (9)	0.0492 (11)	0.0312 (9)	−0.0110 (8)	0.0069 (7)	−0.0151 (8)

Geometric parameters (Å, º) top

Ti—O2	1.7601 (10)	C3—H3B	0.9900
Ti—O1ⁱ	1.9911 (10)	C4—H4A	0.9900
Ti—O1	2.0478 (10)	C4—H4B	0.9900
Ti—O3ⁱ	2.1481 (11)	C5—H5A	0.9800
Ti—Cl1	2.3184 (4)	C5—H5B	0.9800
Ti—Cl2	2.3292 (4)	C5—H5C	0.9800
Ti—Tiⁱ	3.1649 (5)	O11—C13	1.4374 (19)
O1—C1	1.4501 (17)	O11—C12	1.4413 (18)
O1—Tiⁱ	1.9911 (10)	C11—C12	1.502 (2)
O2—C3	1.4243 (18)	C11—H11A	0.9800
O3—C4	1.4473 (18)	C11—H11B	0.9800
O3—Tiⁱ	2.1481 (11)	C11—H11C	0.9800
O3—H3	0.74 (2)	C12—H12A	0.9900
C1—C2	1.533 (2)	C12—H12B	0.9900
C1—H1A	0.9900	C13—C14	1.509 (3)
C1—H1B	0.9900	C13—H13A	0.9900
C2—C4	1.523 (2)	C13—H13B	0.9900
C2—C3	1.533 (2)	C14—H14A	0.9800
C2—C5	1.542 (2)	C14—H14B	0.9800
C3—H3A	0.9900	C14—H14C	0.9800

O2—Ti—O1ⁱ	101.78 (5)	C2—C3—H3A	109.1
O2—Ti—O1	86.71 (4)	O2—C3—H3B	109.1
O1ⁱ—Ti—O1	76.83 (4)	C2—C3—H3B	109.1
O2—Ti—O3ⁱ	172.39 (5)	H3A—C3—H3B	107.9
O1ⁱ—Ti—O3ⁱ	80.17 (4)	O3—C4—C2	112.55 (12)
O1—Ti—O3ⁱ	86.59 (4)	O3—C4—H4A	109.1
O2—Ti—Cl1	97.18 (4)	C2—C4—H4A	109.1
O1ⁱ—Ti—Cl1	93.21 (3)	O3—C4—H4B	109.1
O1—Ti—Cl1	169.89 (3)	C2—C4—H4B	109.1
O3ⁱ—Ti—Cl1	90.02 (3)	H4A—C4—H4B	107.8
O2—Ti—Cl2	93.95 (4)	C2—C5—H5A	109.5
O1ⁱ—Ti—Cl2	158.75 (3)	C2—C5—H5B	109.5
O1—Ti—Cl2	90.05 (3)	H5A—C5—H5B	109.5
O3ⁱ—Ti—Cl2	82.46 (3)	C2—C5—H5C	109.5
Cl1—Ti—Cl2	98.956 (16)	H5A—C5—H5C	109.5
O2—Ti—Tiⁱ	95.24 (4)	H5B—C5—H5C	109.5
O1ⁱ—Ti—Tiⁱ	39.05 (3)	C13—O11—C12	112.91 (12)
O1—Ti—Tiⁱ	37.78 (3)	C12—C11—H11A	109.5
O3ⁱ—Ti—Tiⁱ	81.61 (3)	C12—C11—H11B	109.5
Cl1—Ti—Tiⁱ	132.238 (18)	H11A—C11—H11B	109.5
Cl2—Ti—Tiⁱ	125.940 (16)	C12—C11—H11C	109.5
C1—O1—Tiⁱ	124.13 (8)	H11A—C11—H11C	109.5
C1—O1—Ti	118.13 (8)	H11B—C11—H11C	109.5
Tiⁱ—O1—Ti	103.17 (4)	O11—C12—C11	108.69 (13)
C3—O2—Ti	138.33 (9)	O11—C12—H12A	110.0
C4—O3—Tiⁱ	126.66 (9)	C11—C12—H12A	110.0
C4—O3—H3	106.5 (16)	O11—C12—H12B	110.0
Tiⁱ—O3—H3	117.1 (16)	C11—C12—H12B	110.0
O1—C1—C2	113.32 (11)	H12A—C12—H12B	108.3
O1—C1—H1A	108.9	O11—C13—C14	108.13 (14)
C2—C1—H1A	108.9	O11—C13—H13A	110.1
O1—C1—H1B	108.9	C14—C13—H13A	110.1
C2—C1—H1B	108.9	O11—C13—H13B	110.1
H1A—C1—H1B	107.7	C14—C13—H13B	110.1
C4—C2—C1	110.95 (12)	H13A—C13—H13B	108.4
C4—C2—C3	112.76 (13)	C13—C14—H14A	109.5
C1—C2—C3	110.72 (12)	C13—C14—H14B	109.5
C4—C2—C5	107.06 (12)	H14A—C14—H14B	109.5
C1—C2—C5	108.02 (12)	C13—C14—H14C	109.5
C3—C2—C5	107.07 (13)	H14A—C14—H14C	109.5
O2—C3—C2	112.41 (12)	H14B—C14—H14C	109.5
O2—C3—H3A	109.1

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O11	0.74 (2)	1.89 (2)	2.6233 (14)	168 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O11	0.74 (2)	1.89 (2)	2.6233 (14)	168 (2)

Footnotes

‡Former address.

Acknowledgements

We are grateful to Massey University for the award of a Post-Doctoral Fellowship to CS, and to Ms T. Groutso of the University of Auckland for the data collection.

References

Blessing, R. H. (1995). Acta Cryst. A51, 33–38. CrossRef CAS Web of Science IUCr Journals Google Scholar
Boyle, T. J., Schwartz, R. W., Doedens, R. J. & Ziller, J. W. (1995). Inorg. Chem. 34, 1110–1120. CSD CrossRef CAS Web of Science Google Scholar
Chang, Y., Chen, Q., Khan, M. I., Salta, J. & Zubieta, J. (1993). J . Chem. Soc. Chem. Commun. pp. 1872–1874. CrossRef Web of Science Google Scholar
Chen, Q., Chang, Y. D. & Zubieta, J. (1997). Inorg, Chim. Acta, 258, 257–262. Google Scholar
Delmont, R., Proust, A., Robert, F., Herson, P. & Gourzerh, P. (2000). Chimie, 3, 147–155. CAS Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Gau, H.-M., Lee, C.-S., Lin, C.-C. & Jiang, M.-K. (1996). J. Am. Chem. Soc. 118, 2936–2941. CSD CrossRef CAS Web of Science Google Scholar
Liu, S., Ma, L., McGowty, D. & Zubieta, J. (1990). Polyhedron, 9, 1541–1553. CSD CrossRef CAS Web of Science Google Scholar
Salta, J. & Zubieta, J. (1997). Inorg. Chim. Acta, 257, 83–88. CSD CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1995). SAINT and SMART. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar
Talbot-Eeckelaers, C. E., Rajaraman, G., Cano, J., Aromí, G., Ruiz, E. & Brechin, E. K. (2006). Eur. J. Inorg. Chem. pp. 3382–3392. Google Scholar
Wu, Y.-T., Ho, Y.-C., Lin, C.-C. & Gau, H.-M. (1996). Inorg. Chem. 35, 5948–5952. CSD CrossRef CAS Web of Science Google Scholar

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