![](/logos/buttonlogos/cross.png)
![](/logos/buttonlogos/cross.png)
metal-organic compounds
Di-μ-oxido-bis({2,2′-[ethane-1,2-diylbis(nitrilomethanylylidene)]diphenolato}titanium(IV)) chloroform disolvate
aDepartment of Chemistry, M.V. Lomonosov Moscow State University, Leninskie Gory 1/3, Moscow 119991, Russian Federation, and bInstitute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskii prosp. 31, Moscow 119991, Russian Federation
*Correspondence e-mail: churakov@igic.ras.ru.ru
In the title compound, [Ti2(C16H14N2O2)2O2]·2CHCl3, the TiIV atom in the centrosymmetric complex has a distorted octahedral N2O4 coordination environment and is linked via two μ2-oxido bridges into a dinuclear centrosymmetric complex, with a Ti⋯Ti separation of 2.7794 (8) Å. In the salen (N,N′-ethylenebis(salicylimine)) ligand, the two salicylimine units make a dihedral angle of 45.31 (5)°. The complex molecules are stacked parallel to [100], forming channels in which the solvent chloroform molecules are located. C—H⋯O hydrogen-bonding interactions between the complex molecules and the solvent molecules consolidate the crystal packing.
CCDC reference: 968536
Related literature
For general background to the chemistry of titanium complexes based on salen-type ligands, see: Gupta & Sutar (2008); Tsuchimoto (2001
). For our previous work on titanium(IV) complexes with polydentate N,O-chelating ligands, see: Zaitsev et al. (2006
, 2008
).
Experimental
Crystal data
|
|
Data collection: APEX2 (Bruker, 2008); cell SAINT (Bruker, 2008
); 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.
Supporting information
CCDC reference: 968536
10.1107/S1600536813029371/wm2780sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536813029371/wm2780Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536813029371/wm2780Isup3.mol
The title compound was obtained from reaction of equimolar amounts of Ti(O-iPr)4 and salen in chloroform as a solid which is insoluble in common organic solvents. The crystals suitable for X-Ray analysis crystallized from the reaction mixture.
All hydrogen atoms were placed in calculated positions and refined using a riding model with C—H = 1.00 Å and Uiso(H) = 1.2Ueq(C) for chloroform molecule; C—H = 0.99 Å and Uiso(H) = 1.2Ueq(C) for methylene groups; C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C) for sp2 carbon atoms.
Data collection: APEX2 (Bruker, 2008); cell
SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).[Ti2(C16H14N2O2)2O2]·2CHCl3 | F(000) = 912 |
Mr = 899.12 | Dx = 1.591 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 5413 reflections |
a = 8.8115 (10) Å | θ = 2.4–29.6° |
b = 11.4587 (13) Å | µ = 0.90 mm−1 |
c = 18.785 (2) Å | T = 150 K |
β = 98.226 (2)° | Block, colourless |
V = 1877.2 (4) Å3 | 0.25 × 0.08 × 0.06 mm |
Z = 2 |
Bruker APEXII CCD diffractometer | 3677 independent reflections |
Radiation source: fine-focus sealed tube | 3119 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
ω scans | θmax = 26.0°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −10→10 |
Tmin = 0.806, Tmax = 0.948 | k = −14→14 |
16236 measured reflections | l = −22→23 |
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)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.084 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0415P)2 + 1.1985P] where P = (Fo2 + 2Fc2)/3 |
3677 reflections | (Δ/σ)max = 0.001 |
235 parameters | Δρmax = 0.47 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
[Ti2(C16H14N2O2)2O2]·2CHCl3 | V = 1877.2 (4) Å3 |
Mr = 899.12 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.8115 (10) Å | µ = 0.90 mm−1 |
b = 11.4587 (13) Å | T = 150 K |
c = 18.785 (2) Å | 0.25 × 0.08 × 0.06 mm |
β = 98.226 (2)° |
Bruker APEXII CCD diffractometer | 3677 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | 3119 reflections with I > 2σ(I) |
Tmin = 0.806, Tmax = 0.948 | Rint = 0.028 |
16236 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | 0 restraints |
wR(F2) = 0.084 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.47 e Å−3 |
3677 reflections | Δρmin = −0.28 e Å−3 |
235 parameters |
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 | Uiso*/Ueq | ||
Ti1 | 0.55329 (4) | 0.89882 (3) | 0.471151 (19) | 0.02192 (11) | |
O3 | 0.38110 (15) | 0.94635 (12) | 0.50409 (7) | 0.0250 (3) | |
O1 | 0.44879 (16) | 0.76247 (12) | 0.42307 (7) | 0.0266 (3) | |
O2 | 0.66652 (16) | 0.81354 (14) | 0.54587 (8) | 0.0292 (3) | |
N1 | 0.50499 (19) | 0.96203 (15) | 0.36249 (9) | 0.0256 (4) | |
N2 | 0.77616 (19) | 0.89426 (14) | 0.42525 (9) | 0.0241 (4) | |
C11 | 0.3151 (2) | 0.76229 (18) | 0.38023 (11) | 0.0255 (4) | |
C12 | 0.2143 (3) | 0.6677 (2) | 0.38226 (12) | 0.0329 (5) | |
H12 | 0.2425 | 0.6046 | 0.4142 | 0.039* | |
C13 | 0.0748 (3) | 0.6657 (2) | 0.33826 (13) | 0.0374 (6) | |
H13 | 0.0062 | 0.6025 | 0.3413 | 0.045* | |
C14 | 0.0334 (3) | 0.7561 (2) | 0.28908 (12) | 0.0362 (5) | |
H14 | −0.0625 | 0.7540 | 0.2587 | 0.043* | |
C15 | 0.1313 (2) | 0.8470 (2) | 0.28506 (12) | 0.0328 (5) | |
H15 | 0.1036 | 0.9074 | 0.2510 | 0.039* | |
C16 | 0.2732 (2) | 0.85321 (19) | 0.33048 (11) | 0.0274 (5) | |
C17 | 0.3830 (2) | 0.94051 (19) | 0.31813 (12) | 0.0299 (5) | |
H17 | 0.3647 | 0.9847 | 0.2750 | 0.036* | |
C18 | 0.6317 (3) | 1.0275 (2) | 0.34028 (12) | 0.0317 (5) | |
H18A | 0.6505 | 1.0999 | 0.3690 | 0.038* | |
H18B | 0.6091 | 1.0487 | 0.2888 | 0.038* | |
C21 | 0.8128 (2) | 0.79353 (18) | 0.57183 (11) | 0.0267 (4) | |
C22 | 0.8487 (3) | 0.7483 (2) | 0.64094 (13) | 0.0370 (6) | |
H22 | 0.7693 | 0.7355 | 0.6693 | 0.044* | |
C23 | 0.9989 (3) | 0.7218 (2) | 0.66894 (13) | 0.0399 (6) | |
H23 | 1.0214 | 0.6916 | 0.7164 | 0.048* | |
C24 | 1.1163 (3) | 0.7389 (2) | 0.62846 (13) | 0.0360 (5) | |
H24 | 1.2185 | 0.7180 | 0.6472 | 0.043* | |
C25 | 1.0835 (2) | 0.78687 (19) | 0.56034 (12) | 0.0311 (5) | |
H25 | 1.1645 | 0.8006 | 0.5330 | 0.037* | |
C26 | 0.9329 (2) | 0.81553 (18) | 0.53108 (11) | 0.0248 (4) | |
C27 | 0.9073 (2) | 0.86562 (18) | 0.45940 (11) | 0.0251 (4) | |
H27 | 0.9946 | 0.8781 | 0.4360 | 0.030* | |
C28 | 0.7706 (2) | 0.9466 (2) | 0.35350 (11) | 0.0303 (5) | |
H28A | 0.7620 | 0.8846 | 0.3164 | 0.036* | |
H28B | 0.8657 | 0.9913 | 0.3507 | 0.036* | |
C1 | 0.6290 (3) | 0.54038 (19) | 0.40993 (12) | 0.0301 (5) | |
H1 | 0.5673 | 0.6049 | 0.4273 | 0.036* | |
Cl1 | 0.81195 (7) | 0.54170 (5) | 0.46134 (3) | 0.04022 (16) | |
Cl2 | 0.53362 (6) | 0.40740 (5) | 0.42008 (3) | 0.03615 (15) | |
Cl3 | 0.64366 (8) | 0.56598 (6) | 0.31832 (3) | 0.04712 (18) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ti1 | 0.01996 (19) | 0.0259 (2) | 0.02059 (19) | 0.00184 (14) | 0.00518 (14) | 0.00209 (14) |
O3 | 0.0203 (7) | 0.0296 (8) | 0.0263 (8) | −0.0016 (6) | 0.0078 (6) | −0.0015 (6) |
O1 | 0.0258 (7) | 0.0272 (8) | 0.0259 (8) | 0.0027 (6) | 0.0008 (6) | 0.0007 (6) |
O2 | 0.0211 (7) | 0.0387 (9) | 0.0284 (8) | 0.0015 (6) | 0.0051 (6) | 0.0092 (6) |
N1 | 0.0260 (9) | 0.0274 (9) | 0.0241 (9) | 0.0040 (7) | 0.0056 (7) | 0.0017 (7) |
N2 | 0.0263 (9) | 0.0240 (9) | 0.0231 (9) | 0.0030 (7) | 0.0078 (7) | 0.0001 (7) |
C11 | 0.0239 (10) | 0.0294 (11) | 0.0234 (10) | 0.0043 (8) | 0.0040 (8) | −0.0058 (8) |
C12 | 0.0357 (12) | 0.0347 (12) | 0.0282 (12) | −0.0003 (10) | 0.0047 (10) | −0.0015 (9) |
C13 | 0.0327 (12) | 0.0462 (14) | 0.0341 (13) | −0.0095 (11) | 0.0074 (10) | −0.0124 (11) |
C14 | 0.0254 (11) | 0.0503 (15) | 0.0311 (12) | 0.0020 (10) | −0.0017 (9) | −0.0127 (11) |
C15 | 0.0306 (12) | 0.0409 (13) | 0.0259 (11) | 0.0104 (10) | 0.0012 (9) | −0.0045 (10) |
C16 | 0.0269 (11) | 0.0331 (11) | 0.0226 (10) | 0.0058 (9) | 0.0047 (8) | −0.0036 (9) |
C17 | 0.0322 (12) | 0.0334 (12) | 0.0238 (11) | 0.0072 (9) | 0.0031 (9) | 0.0042 (9) |
C18 | 0.0347 (12) | 0.0344 (12) | 0.0273 (11) | 0.0004 (10) | 0.0087 (9) | 0.0088 (9) |
C21 | 0.0239 (10) | 0.0249 (11) | 0.0304 (11) | −0.0028 (8) | 0.0014 (9) | 0.0023 (8) |
C22 | 0.0295 (12) | 0.0474 (14) | 0.0341 (13) | −0.0033 (10) | 0.0046 (10) | 0.0141 (10) |
C23 | 0.0377 (13) | 0.0441 (14) | 0.0350 (13) | −0.0075 (11) | −0.0051 (10) | 0.0141 (11) |
C24 | 0.0240 (11) | 0.0355 (13) | 0.0453 (14) | −0.0017 (9) | −0.0059 (10) | 0.0028 (10) |
C25 | 0.0240 (11) | 0.0334 (12) | 0.0351 (12) | −0.0017 (9) | 0.0018 (9) | −0.0044 (10) |
C26 | 0.0246 (10) | 0.0223 (10) | 0.0275 (11) | −0.0019 (8) | 0.0038 (8) | −0.0032 (8) |
C27 | 0.0229 (10) | 0.0260 (10) | 0.0276 (11) | −0.0009 (8) | 0.0078 (8) | −0.0054 (8) |
C28 | 0.0296 (11) | 0.0376 (12) | 0.0260 (11) | 0.0025 (9) | 0.0115 (9) | 0.0028 (9) |
C1 | 0.0340 (12) | 0.0290 (11) | 0.0280 (11) | −0.0003 (9) | 0.0070 (9) | 0.0014 (9) |
Cl1 | 0.0384 (3) | 0.0407 (3) | 0.0393 (3) | −0.0079 (3) | −0.0021 (3) | 0.0001 (2) |
Cl2 | 0.0354 (3) | 0.0328 (3) | 0.0417 (3) | −0.0068 (2) | 0.0105 (2) | −0.0009 (2) |
Cl3 | 0.0518 (4) | 0.0621 (4) | 0.0276 (3) | −0.0147 (3) | 0.0063 (3) | 0.0046 (3) |
Ti1—O3 | 1.8029 (14) | C16—C17 | 1.433 (3) |
Ti1—O2 | 1.8760 (15) | C17—H17 | 0.9500 |
Ti1—O3i | 1.9029 (15) | C18—C28 | 1.527 (3) |
Ti1—O1 | 1.9664 (15) | C18—H18A | 0.9900 |
Ti1—N1 | 2.1502 (17) | C18—H18B | 0.9900 |
Ti1—N2 | 2.2555 (17) | C21—C22 | 1.391 (3) |
Ti1—Ti1i | 2.7794 (8) | C21—C26 | 1.415 (3) |
O3—Ti1i | 1.9029 (15) | C22—C23 | 1.386 (3) |
O1—C11 | 1.328 (2) | C22—H22 | 0.9500 |
O2—C21 | 1.331 (2) | C23—C24 | 1.382 (3) |
N1—C17 | 1.287 (3) | C23—H23 | 0.9500 |
N1—C18 | 1.455 (3) | C24—C25 | 1.384 (3) |
N2—C27 | 1.282 (3) | C24—H24 | 0.9500 |
N2—C28 | 1.470 (3) | C25—C26 | 1.401 (3) |
C11—C12 | 1.405 (3) | C25—H25 | 0.9500 |
C11—C16 | 1.413 (3) | C26—C27 | 1.451 (3) |
C12—C13 | 1.380 (3) | C27—H27 | 0.9500 |
C12—H12 | 0.9500 | C28—H28A | 0.9900 |
C13—C14 | 1.401 (4) | C28—H28B | 0.9900 |
C13—H13 | 0.9500 | C1—Cl1 | 1.756 (2) |
C14—C15 | 1.361 (3) | C1—Cl2 | 1.764 (2) |
C14—H14 | 0.9500 | C1—Cl3 | 1.768 (2) |
C15—C16 | 1.411 (3) | C1—H1 | 1.0000 |
C15—H15 | 0.9500 | ||
O3—Ti1—O2 | 106.51 (7) | N1—C17—C16 | 123.4 (2) |
O3—Ti1—O3i | 82.86 (6) | N1—C17—H17 | 118.3 |
O2—Ti1—O3i | 101.09 (7) | C16—C17—H17 | 118.3 |
O3—Ti1—O1 | 92.06 (6) | N1—C18—C28 | 105.69 (17) |
O2—Ti1—O1 | 95.38 (6) | N1—C18—H18A | 110.6 |
O3i—Ti1—O1 | 163.53 (6) | C28—C18—H18A | 110.6 |
O3—Ti1—N1 | 99.33 (7) | N1—C18—H18B | 110.6 |
O2—Ti1—N1 | 153.83 (7) | C28—C18—H18B | 110.6 |
O3i—Ti1—N1 | 85.98 (6) | H18A—C18—H18B | 108.7 |
O1—Ti1—N1 | 79.37 (6) | O2—C21—C22 | 119.04 (19) |
O3—Ti1—N2 | 163.69 (6) | O2—C21—C26 | 122.08 (19) |
O2—Ti1—N2 | 82.82 (6) | C22—C21—C26 | 118.87 (19) |
O3i—Ti1—N2 | 82.20 (6) | C23—C22—C21 | 120.9 (2) |
O1—Ti1—N2 | 100.49 (6) | C23—C22—H22 | 119.6 |
N1—Ti1—N2 | 73.13 (6) | C21—C22—H22 | 119.6 |
Ti1—O3—Ti1i | 97.15 (6) | C24—C23—C22 | 120.6 (2) |
C11—O1—Ti1 | 126.58 (13) | C24—C23—H23 | 119.7 |
C21—O2—Ti1 | 138.36 (13) | C22—C23—H23 | 119.7 |
C17—N1—C18 | 121.17 (18) | C23—C24—C25 | 119.4 (2) |
C17—N1—Ti1 | 125.73 (15) | C23—C24—H24 | 120.3 |
C18—N1—Ti1 | 112.97 (13) | C25—C24—H24 | 120.3 |
C27—N2—C28 | 118.22 (18) | C24—C25—C26 | 121.1 (2) |
C27—N2—Ti1 | 125.92 (14) | C24—C25—H25 | 119.5 |
C28—N2—Ti1 | 115.12 (13) | C26—C25—H25 | 119.5 |
O1—C11—C12 | 119.60 (19) | C25—C26—C21 | 119.08 (19) |
O1—C11—C16 | 121.65 (19) | C25—C26—C27 | 117.97 (19) |
C12—C11—C16 | 118.72 (19) | C21—C26—C27 | 122.94 (18) |
C13—C12—C11 | 120.6 (2) | N2—C27—C26 | 125.07 (19) |
C13—C12—H12 | 119.7 | N2—C27—H27 | 117.5 |
C11—C12—H12 | 119.7 | C26—C27—H27 | 117.5 |
C12—C13—C14 | 120.5 (2) | N2—C28—C18 | 108.51 (17) |
C12—C13—H13 | 119.7 | N2—C28—H28A | 110.0 |
C14—C13—H13 | 119.7 | C18—C28—H28A | 110.0 |
C15—C14—C13 | 119.7 (2) | N2—C28—H28B | 110.0 |
C15—C14—H14 | 120.2 | C18—C28—H28B | 110.0 |
C13—C14—H14 | 120.2 | H28A—C28—H28B | 108.4 |
C14—C15—C16 | 121.3 (2) | Cl1—C1—Cl2 | 111.23 (12) |
C14—C15—H15 | 119.4 | Cl1—C1—Cl3 | 110.17 (12) |
C16—C15—H15 | 119.4 | Cl2—C1—Cl3 | 110.53 (12) |
C15—C16—C11 | 119.2 (2) | Cl1—C1—H1 | 108.3 |
C15—C16—C17 | 119.8 (2) | Cl2—C1—H1 | 108.3 |
C11—C16—C17 | 120.21 (19) | Cl3—C1—H1 | 108.3 |
Symmetry code: (i) −x+1, −y+2, −z+1. |
Acknowledgements
This work was partially supported by a grant from the President of the Russian Federation to support the research of young Russian scientists and doctors (MD-3634.2012.3).
References
Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Gupta, K. C. & Sutar, A. K. (2008). Coord. Chem. Rev. 252, 1420–1450. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tsuchimoto, M. (2001). Bull. Chem. Soc. Jpn, 74, 2101–2105. Web of Science CSD CrossRef CAS Google Scholar
Zaitsev, K. V., Bermeshev, M. V., Samsonov, A. A., Oprunenko, J. F., Churakov, A. V., Howard, J. A. L., Karlov, S. S. & Zaitseva, G. S. (2008). New J. Chem. 32, 1415–1431. Web of Science CSD CrossRef CAS Google Scholar
Zaitsev, K. V., Karlov, S. S., Selina, A. A., Oprunenko, Yu. F., Churakov, A. V., Neumüller, B., Howard, J. A. K. & Zaitseva, G. S. (2006). Eur. J. Inorg. Chem. pp. 1987–1999. Web of Science CSD CrossRef Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
As a part of our investigation on the chemistry of titanium complexes based on tridentate or tetradentate ligands (Zaitsev et al., 2006, 2008) we obtained and studied the structure of the title compound, [Ti(O)(C16H14N2O2)]2 (or [Ti(O)(salen)]2) that crystallizes with two chloroform solvent molecules. For general background to the chemistry of titanium complexes based on salen-type ligands, see: Gupta & Sutar (2008).
The title salen complex is centrosymmetric. The Ti(IV) atoms are linked by µ2-oxido bridges and possess a distorted octahedral N2O4 coordination environment with cis interligand angles ranging from 82.20 (6) to 106.51 (7) °. In the central Ti2(µ2-O)2 fragment, the metal–oxygen distances are significantly different (1.8029 (14) and 1.9029 (15) Å). The opposite N–Ti bond lengths also vary by approximately 0.1 Å (2.1502 (17) and 2.2555 (17) Å). The same structural feature was previously reported for another solvatomorph of this complex (Tsuchimoto, 2001). In the ligand, the two salicylimine fragmets form a dihedral angle of 45.31 (5) ° (Fig. 1).
In the crystal, solvent chloroform molecule are linked via C—H···O hydrogen bonding interactions with the main molecule (Table 1). The solvent molecules fill channels spreading parallel to [100] (Fig. 2). The adjacent titanium complexes are connected by T-shaped C—H···π interactions. However, no π···π- stacking interactions are observed in this structure.