metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

Bis{2,2′-[methyl­aza­nediylbis(methyl­ene)]bis­­(4,6-di­methyl­phenolato)-κ3O,N,O′}titanium(IV) toluene sesquisolvate

aDepartment of Chemistry, Chungbuk National University, Cheongju, Chungbuk 361-763, Republic of Korea
*Correspondence e-mail: ykim@chungbuk.ac.kr

(Received 24 January 2013; accepted 13 March 2013; online 20 March 2013)

The title compound, [Ti(C19H23NO2)2]·1.5C7H8, crystallizes with one titanium complex mol­ecule per asymmetric unit together with one and a half toluene mol­ecules. The TiIV atom is coordinated by two fully deprotonated O,N,O′-tridentate phen­oxy­amine ligands in a distorted octa­hedral environment. Within this arrangement the O atoms occupy the equatorial sites and the N atoms the axial sites. One of the toluene mol­ecules is disordered over two sets of sites in a 0.628 (18):0.372 (18) ratio.

Related literature

For other compounds of titanium with tri- and tetra­dentate ligands, see: Mun et al. (2010[Mun, S.-D., Kim, S. H., Lee, J., Kim, H.-J., Do, Y. & Kim, Y. (2010). Polyhedron, 29, 379-383.]); Chmura et al. (2006[Chmura, A. J. H., Davidson, M. G., Jones, M. D., Lunn, M. D. & Mahon, M. F. (2006). Dalton Trans. pp. 887-889.]); Hong et al. (2008[Hong, Y., Mun, S.-D., Lee, J., Do, Y. & Kim, Y. (2008). J. Organomet. Chem. 693, 1945-1951.]); Kim et al. (2009[Kim, S. H., Lee, J., Kim, D. J., Moon, J. H., Yoon, S. W., Oh, H. J., Ko, Y. S., Do, Y. & Kim, Y. (2009). J. Organomet. Chem. 694, 3409-3417.], 2011[Kim, J. H., Yoon, S., Mun, S.-D., Kim, S. H., Lee, J., Chung, Y., Kwon, S. H., Lee, K. S., Lee, C. & Kim, Y. (2011). J. Organomet. Chem. 696, 1729-1735.], 2012[Kim, S. H., Kim, D. J., Go, M. J., Ko, Y. S., Lee, J. & Kim, Y. (2012). Dalton Trans. 41, 11619-11626.]); Lee et al. (2007[Lee, J., Kim, Y. & Do, Y. (2007). Inorg. Chem. 46, 7701-7703.], 2008[Lee, J., Hong, Y., Kim, J. H., Kim, S. H., Do, Y., Shin, Y. K. & Kim, Y. (2008). J. Organomet. Chem. 693, 3715-3721.]).

[Scheme 1]

Experimental

Crystal data
  • [Ti(C19H23NO2)2]·1.5C7H8

  • Mr = 780.34

  • Triclinic, [P \overline 1]

  • a = 12.053 (2) Å

  • b = 13.374 (3) Å

  • c = 14.511 (3) Å

  • α = 102.02 (3)°

  • β = 112.07 (3)°

  • γ = 93.04 (3)°

  • V = 2097.8 (7) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.25 mm−1

  • T = 173 K

  • 0.50 × 0.25 × 0.14 mm

Data collection
  • Bruker SMART CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2004[Bruker (2004). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.83, Tmax = 0.96

  • 12545 measured reflections

  • 7019 independent reflections

  • 5111 reflections with I > 2σ(I)

  • Rint = 0.029

Refinement
  • R[F2 > 2σ(F2)] = 0.072

  • wR(F2) = 0.223

  • S = 1.02

  • 7019 reflections

  • 582 parameters

  • 6 restraints

  • H-atom parameters constrained

  • Δρmax = 0.76 e Å−3

  • Δρmin = −0.37 e Å−3

Data collection: SMART (Bruker, 2004[Bruker (2004). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2004[Bruker (2004). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]); software used to prepare material for publication: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]).

Supporting information


Comment top

Titanium complexes containing tridentate or tetradentate ligands have attracted considerable attention in the fields of organometallic catalysis. Recently, we have reported the various kinds of titanium complexes containing these ligands (Hong et al. 2008, Kim et al. 2012, Kim et al. 2011, Kim et al. 2009, Mun et al. 2010, Lee et al. 2008, Lee et al. 2007). In addition, the similar structure of the title complex with four methylene chloride molecules in the monoclinic unit was reported in the literature (Chmura et al., 2006); however, crystallographic data and parameters for the title compound were quite different from those of the previously reported literature (Chmura et al., 2006). Herein, we report the X-ray structure of the title compound. In the title compound (Fig. 1), Ti atom is coordinated by he two fully deprotonated tridentate ligands N-methyl-N,N-bis(2-oxy-3,5-dimethylbenzyl)amine with 1.5 molecules of toluene in the asymmetric unit. To remove the disorders of toluene molecules, we tried to solve the structure with space group, P1. However, the result was unsuccessful. The coordination geometry around the central Ti atom is close to octahedron.

Related literature top

For other compounds of titanium with tri- and tetradentate ligands, see: Mun et al. (2010); Chmura et al. (2006); Hong et al. (2008); Kim et al. (2009, 2011, 2012); Lee et al. (2007, 2008).

Experimental top

The title compound could be synthesized in 92% yield (1.18 g) via slow addition of Ti(O-iPr)4 (0.568 g, 2 mmol) in 10 mL toluene to N-methyl-N,N-bis(2-hydroxy-3,5-dimethylbenzyl)amine (1.20 g, 4 mmol) in 40 mL toluene. The crystal was obtained by slow evaporation of solvent in a refrigerator.

Refinement top

The quality of the crystal used was poor but we were unable to grow a better crystal. We tried refining the structure in the space group P1 to see if this removed the disorder, but this was unsuccessful since it gave non-positive definite atomic displacement parameters. The poor quality of the crystal and the difficulty in clearly resolving the disorder explains the large value of the weighted agreement index.

The disordered toluene molecule was modeled by splitting the atoms into two components (C41—C47 and C51—C57), the site occupation factors of which refined in a ratio of 0.628 (18):0.372 (18). Due to the large thermal parameters, the atomic displacement factor of C57 atom was held fixed. H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93–0.97 Å and with Uiso(H) = 1.2 (1.5 for methyl groups) times Ueq(C). One hydrogen atom in C41 position can not be located in the disordered toluene molecule.

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are omitted for clarity. Both positions of the toluene molecule are shown disordered around the center of symmetry.
Bis{2,2'-[methylazanediylbis(methylene)]bis(4,6-dimethylphenolato)-κ3O,N,O'}titanium(IV) toluene sesquisolvate top
Crystal data top
[Ti(C19H23NO2)2]·1.5C7H8Z = 2
Mr = 780.34F(000) = 833
Triclinic, P1Dx = 1.235 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 12.053 (2) ÅCell parameters from 7019 reflections
b = 13.374 (3) Åθ = 1.6–24.7°
c = 14.511 (3) ŵ = 0.25 mm1
α = 102.02 (3)°T = 173 K
β = 112.07 (3)°Plate, orange
γ = 93.04 (3)°0.5 × 0.25 × 0.14 mm
V = 2097.8 (7) Å3
Data collection top
Bruker SMART CCD area-detector
diffractometer
7019 independent reflections
Radiation source: fine-focus sealed tube5111 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.029
phi and ω scansθmax = 24.7°, θmin = 1.6°
Absorption correction: multi-scan
(SADABS; Bruker, 2004)
h = 1414
Tmin = 0.83, Tmax = 0.96k = 1515
12545 measured reflectionsl = 1617
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.072Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.223H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.0838P)2 + 8.6517P]
where P = (Fo2 + 2Fc2)/3
7019 reflections(Δ/σ)max = 0.001
582 parametersΔρmax = 0.76 e Å3
6 restraintsΔρmin = 0.37 e Å3
Crystal data top
[Ti(C19H23NO2)2]·1.5C7H8γ = 93.04 (3)°
Mr = 780.34V = 2097.8 (7) Å3
Triclinic, P1Z = 2
a = 12.053 (2) ÅMo Kα radiation
b = 13.374 (3) ŵ = 0.25 mm1
c = 14.511 (3) ÅT = 173 K
α = 102.02 (3)°0.5 × 0.25 × 0.14 mm
β = 112.07 (3)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
7019 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2004)
5111 reflections with I > 2σ(I)
Tmin = 0.83, Tmax = 0.96Rint = 0.029
12545 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0726 restraints
wR(F2) = 0.223H-atom parameters constrained
S = 1.02Δρmax = 0.76 e Å3
7019 reflectionsΔρmin = 0.37 e Å3
582 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
xyzUiso*/UeqOcc. (<1)
Ti10.94677 (8)0.78673 (6)0.72763 (7)0.0252 (2)
N11.0610 (3)0.9160 (3)0.7095 (3)0.0258 (9)
N20.8283 (4)0.6581 (3)0.7396 (3)0.0275 (9)
O10.8214 (3)0.8631 (3)0.6767 (3)0.0317 (8)
O21.0927 (3)0.7329 (3)0.7771 (3)0.0359 (9)
O30.9085 (3)0.6993 (3)0.5968 (3)0.0375 (9)
O40.9677 (3)0.8483 (2)0.8632 (2)0.0312 (8)
C10.7967 (4)0.9475 (4)0.6414 (3)0.0271 (10)
C20.6873 (4)0.9851 (4)0.6311 (4)0.0311 (11)
C30.5956 (5)0.9261 (5)0.6540 (5)0.0438 (14)
H3A0.52540.96040.64180.066*
H3B0.62980.92280.72440.066*
H3C0.57310.85740.61030.066*
C40.6664 (5)1.0739 (4)0.5947 (4)0.0344 (12)
H40.59371.09890.58660.041*
C50.7496 (5)1.1268 (4)0.5699 (4)0.0313 (11)
C60.7247 (5)1.2233 (4)0.5318 (5)0.0443 (14)
H6A0.78961.27840.57440.066*
H6B0.65021.24260.53450.066*
H6C0.71851.21050.46230.066*
C70.8569 (4)1.0866 (4)0.5807 (4)0.0290 (11)
H70.91411.12050.56480.035*
C80.8808 (4)0.9972 (4)0.6145 (3)0.0259 (10)
C90.9900 (4)0.9480 (4)0.6142 (4)0.0297 (11)
H9A0.96370.88750.55680.036*
H9B1.04320.99630.60250.036*
C101.1006 (4)1.0068 (4)0.7986 (4)0.0296 (11)
H10A1.14501.06080.78650.044*
H10B1.15140.98750.85920.044*
H10C1.03101.03100.80790.044*
C111.1688 (4)0.8766 (4)0.6956 (4)0.0297 (11)
H11A1.21140.92960.67950.036*
H11B1.14110.81700.63730.036*
C121.2561 (4)0.8462 (4)0.7872 (4)0.0294 (11)
C131.3776 (5)0.8833 (4)0.8314 (4)0.0378 (13)
H131.40720.93260.80640.045*
C141.4576 (5)0.8495 (4)0.9121 (4)0.0394 (13)
C151.5912 (5)0.8890 (5)0.9577 (5)0.0574 (18)
H15A1.62940.86871.02070.086*
H15B1.60300.96300.97110.086*
H15C1.62610.86050.91030.086*
C161.4098 (5)0.7746 (4)0.9461 (4)0.0400 (13)
H161.46200.75121.00040.048*
C171.2885 (5)0.7331 (4)0.9035 (4)0.0369 (13)
C181.2388 (6)0.6491 (5)0.9379 (5)0.0499 (16)
H18A1.30430.62420.98520.075*
H18B1.19290.59330.87940.075*
H18C1.18730.67600.97100.075*
C191.2112 (5)0.7705 (4)0.8222 (4)0.0310 (11)
C200.8330 (5)0.6163 (4)0.5304 (4)0.0301 (11)
C210.8512 (5)0.5705 (4)0.4415 (4)0.0354 (12)
C220.9541 (6)0.6143 (5)0.4224 (4)0.0448 (14)
H22A0.95270.57490.35850.067*
H22B1.02880.61150.47710.067*
H22C0.94720.68480.41930.067*
C230.7690 (5)0.4852 (4)0.3731 (4)0.0357 (12)
H230.77940.45500.31370.043*
C240.6713 (5)0.4426 (4)0.3895 (4)0.0348 (12)
C250.5840 (5)0.3506 (4)0.3124 (4)0.0454 (14)
H25A0.54380.31620.34560.068*
H25B0.62750.30370.28450.068*
H25C0.52510.37350.25810.068*
C260.6599 (5)0.4878 (4)0.4799 (4)0.0337 (12)
H260.59850.45920.49480.040*
C270.7373 (5)0.5742 (4)0.5487 (4)0.0299 (11)
C280.7169 (5)0.6265 (4)0.6435 (4)0.0314 (11)
H28A0.67920.68740.63090.038*
H28B0.66070.57980.65360.038*
C290.8925 (5)0.5682 (4)0.7575 (4)0.0352 (12)
H29A0.83800.51280.75700.053*
H29B0.95980.58750.82290.053*
H29C0.92120.54590.70430.053*
C300.7875 (4)0.6935 (4)0.8250 (4)0.0306 (11)
H30A0.74190.75030.81160.037*
H30B0.73340.63750.82530.037*
C310.8885 (4)0.7281 (4)0.9288 (4)0.0293 (11)
C320.8961 (5)0.6846 (4)1.0083 (4)0.0348 (12)
H320.83920.62880.99720.042*
C330.9879 (5)0.7228 (4)1.1055 (4)0.0361 (12)
C340.9934 (6)0.6776 (5)1.1945 (4)0.0502 (15)
H34A1.07620.67411.23550.075*
H34B0.94800.60941.16850.075*
H34C0.95960.72071.23570.075*
C351.0725 (5)0.8038 (4)1.1196 (4)0.0320 (11)
H351.13350.82961.18460.038*
C361.0708 (5)0.8492 (4)1.0406 (4)0.0295 (11)
C371.1644 (5)0.9370 (4)1.0572 (4)0.0414 (13)
H37A1.21150.91471.01820.062*
H37B1.21640.95891.12870.062*
H37C1.12510.99351.03520.062*
C380.9765 (5)0.8091 (4)0.9438 (4)0.0284 (11)
C410.3393 (13)0.6314 (13)0.2349 (12)0.060 (4)0.628 (18)
H41A0.27240.66270.24250.090*0.628 (18)
H41B0.35730.58000.27370.090*0.628 (18)
H41C0.31860.59950.16380.090*0.628 (18)
C420.4496 (11)0.7138 (8)0.2742 (8)0.038 (3)0.628 (18)
C430.558 (4)0.712 (3)0.363 (3)0.056 (10)0.628 (18)
H430.56290.65810.39530.068*0.628 (18)
C440.6493 (12)0.7890 (9)0.3965 (11)0.060 (4)0.628 (18)
H440.71600.79170.45660.072*0.628 (18)
C450.6473 (16)0.8630 (10)0.3456 (13)0.077 (5)0.628 (18)
H450.71310.91510.37160.093*0.628 (18)
C460.5523 (19)0.8639 (13)0.2574 (14)0.084 (7)0.628 (18)
H460.55510.91190.22000.101*0.628 (18)
C470.450 (2)0.7896 (14)0.2252 (16)0.044 (5)0.628 (18)
H470.38110.79240.16900.052*0.628 (18)
C510.720 (3)0.829 (2)0.362 (2)0.075 (7)0.372 (18)
H51A0.77020.79230.40750.113*0.372 (18)
H51B0.72520.89910.39850.113*0.372 (18)
H51C0.74630.82940.30700.113*0.372 (18)
C520.5938 (17)0.7787 (14)0.3187 (14)0.047 (6)0.372 (18)
C530.510 (3)0.813 (3)0.238 (3)0.049 (10)0.372 (18)
H530.53370.86910.21670.058*0.372 (18)
C540.395 (3)0.764 (3)0.192 (2)0.052 (9)0.372 (18)
H540.34060.78300.13540.062*0.372 (18)
C550.356 (3)0.6849 (19)0.226 (2)0.056 (6)0.372 (18)
H550.27620.65310.19450.067*0.372 (18)
C560.437 (2)0.6543 (19)0.3067 (18)0.064 (7)0.372 (18)
H560.41440.60040.33050.076*0.372 (18)
C570.547 (5)0.704 (4)0.349 (4)0.035 (12)0.372 (18)
H570.59990.68630.40690.042*0.372 (18)
C610.6733 (13)0.6495 (13)0.1397 (12)0.071 (4)0.50
H61A0.63620.69370.17730.106*0.50
H61B0.71180.68970.10950.106*0.50
H61C0.73250.61800.18550.106*0.50
C620.5915 (9)0.5786 (8)0.0683 (8)0.092 (3)
C630.5316 (11)0.5130 (9)0.1048 (8)0.095 (3)
H630.55340.52170.17490.114*
C640.4435 (9)0.4383 (8)0.0378 (7)0.083 (3)
H640.40390.39580.06260.099*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ti10.0311 (5)0.0249 (4)0.0234 (5)0.0041 (4)0.0141 (4)0.0079 (3)
N10.028 (2)0.030 (2)0.024 (2)0.0085 (17)0.0123 (18)0.0095 (17)
N20.036 (2)0.030 (2)0.020 (2)0.0053 (18)0.0147 (18)0.0073 (17)
O10.0305 (19)0.0367 (19)0.034 (2)0.0059 (15)0.0142 (16)0.0171 (16)
O20.041 (2)0.0318 (19)0.045 (2)0.0120 (16)0.0227 (19)0.0181 (17)
O30.049 (2)0.037 (2)0.029 (2)0.0059 (17)0.0225 (18)0.0030 (16)
O40.046 (2)0.0262 (17)0.0214 (18)0.0005 (15)0.0134 (16)0.0060 (14)
C10.028 (3)0.031 (3)0.017 (2)0.002 (2)0.005 (2)0.004 (2)
C20.028 (3)0.044 (3)0.019 (2)0.004 (2)0.006 (2)0.009 (2)
C30.026 (3)0.067 (4)0.043 (3)0.009 (3)0.010 (3)0.028 (3)
C40.027 (3)0.049 (3)0.029 (3)0.015 (2)0.008 (2)0.016 (2)
C50.033 (3)0.035 (3)0.023 (3)0.010 (2)0.005 (2)0.010 (2)
C60.046 (3)0.049 (3)0.048 (4)0.022 (3)0.021 (3)0.026 (3)
C70.032 (3)0.032 (3)0.023 (3)0.004 (2)0.011 (2)0.007 (2)
C80.028 (3)0.031 (3)0.019 (2)0.004 (2)0.010 (2)0.007 (2)
C90.034 (3)0.035 (3)0.028 (3)0.009 (2)0.017 (2)0.015 (2)
C100.030 (3)0.029 (3)0.031 (3)0.002 (2)0.013 (2)0.009 (2)
C110.030 (3)0.033 (3)0.034 (3)0.008 (2)0.018 (2)0.012 (2)
C120.032 (3)0.033 (3)0.030 (3)0.013 (2)0.018 (2)0.009 (2)
C130.041 (3)0.033 (3)0.042 (3)0.012 (2)0.019 (3)0.006 (2)
C140.038 (3)0.038 (3)0.039 (3)0.016 (2)0.016 (3)0.002 (3)
C150.042 (4)0.060 (4)0.053 (4)0.015 (3)0.007 (3)0.001 (3)
C160.040 (3)0.051 (3)0.028 (3)0.026 (3)0.011 (2)0.008 (2)
C170.049 (3)0.038 (3)0.037 (3)0.024 (3)0.027 (3)0.015 (2)
C180.054 (4)0.059 (4)0.057 (4)0.029 (3)0.032 (3)0.033 (3)
C190.036 (3)0.034 (3)0.028 (3)0.015 (2)0.017 (2)0.009 (2)
C200.041 (3)0.026 (2)0.025 (3)0.009 (2)0.015 (2)0.008 (2)
C210.051 (3)0.034 (3)0.027 (3)0.015 (2)0.018 (3)0.012 (2)
C220.060 (4)0.051 (3)0.032 (3)0.013 (3)0.027 (3)0.009 (3)
C230.049 (3)0.038 (3)0.019 (3)0.018 (3)0.012 (2)0.004 (2)
C240.050 (3)0.027 (3)0.025 (3)0.012 (2)0.011 (2)0.006 (2)
C250.052 (4)0.044 (3)0.032 (3)0.007 (3)0.012 (3)0.000 (3)
C260.042 (3)0.028 (3)0.029 (3)0.005 (2)0.013 (2)0.005 (2)
C270.043 (3)0.030 (3)0.018 (2)0.006 (2)0.013 (2)0.006 (2)
C280.039 (3)0.033 (3)0.023 (3)0.002 (2)0.015 (2)0.005 (2)
C290.047 (3)0.029 (3)0.037 (3)0.006 (2)0.023 (3)0.010 (2)
C300.031 (3)0.038 (3)0.024 (3)0.002 (2)0.016 (2)0.003 (2)
C310.031 (3)0.035 (3)0.027 (3)0.008 (2)0.016 (2)0.009 (2)
C320.041 (3)0.038 (3)0.029 (3)0.001 (2)0.018 (2)0.008 (2)
C330.040 (3)0.046 (3)0.026 (3)0.010 (3)0.015 (2)0.014 (2)
C340.061 (4)0.057 (4)0.033 (3)0.004 (3)0.013 (3)0.023 (3)
C350.032 (3)0.039 (3)0.023 (3)0.011 (2)0.009 (2)0.005 (2)
C360.035 (3)0.031 (3)0.027 (3)0.009 (2)0.017 (2)0.005 (2)
C370.047 (3)0.045 (3)0.027 (3)0.004 (3)0.014 (3)0.001 (2)
C380.036 (3)0.031 (3)0.023 (3)0.011 (2)0.016 (2)0.007 (2)
C410.051 (8)0.061 (9)0.061 (9)0.013 (8)0.024 (7)0.005 (8)
C420.046 (8)0.035 (6)0.041 (6)0.001 (5)0.025 (6)0.009 (5)
C430.085 (18)0.055 (16)0.021 (10)0.021 (12)0.006 (10)0.016 (9)
C440.056 (8)0.059 (8)0.043 (8)0.003 (6)0.004 (6)0.003 (6)
C450.077 (11)0.036 (8)0.095 (12)0.023 (7)0.024 (10)0.009 (7)
C460.117 (17)0.066 (10)0.071 (11)0.036 (9)0.036 (11)0.033 (9)
C470.060 (17)0.035 (9)0.034 (9)0.006 (12)0.014 (11)0.014 (7)
C510.080 (18)0.062 (15)0.077 (16)0.001 (13)0.030 (15)0.010 (12)
C520.057 (12)0.054 (12)0.032 (12)0.020 (9)0.018 (10)0.012 (8)
C530.05 (2)0.07 (2)0.06 (2)0.02 (2)0.04 (2)0.05 (2)
C540.05 (2)0.07 (2)0.034 (15)0.025 (16)0.011 (12)0.007 (12)
C550.058 (17)0.043 (14)0.070 (15)0.006 (14)0.036 (14)0.002 (13)
C560.071 (18)0.063 (14)0.077 (17)0.019 (13)0.047 (15)0.022 (13)
C570.038 (14)0.033 (14)0.033 (15)0.000 (8)0.013 (10)0.006 (8)
C610.049 (8)0.099 (12)0.065 (10)0.029 (9)0.020 (8)0.021 (9)
C620.094 (7)0.103 (7)0.084 (7)0.074 (6)0.033 (6)0.020 (6)
C630.137 (9)0.111 (8)0.074 (6)0.093 (7)0.061 (7)0.043 (6)
C640.104 (7)0.106 (7)0.061 (5)0.072 (6)0.042 (5)0.037 (5)
Geometric parameters (Å, º) top
Ti1—O11.873 (3)C25—H25B0.9600
Ti1—O21.879 (4)C25—H25C0.9600
Ti1—O41.882 (3)C26—C271.381 (7)
Ti1—O31.882 (4)C26—H260.9300
Ti1—N22.254 (4)C27—C281.521 (6)
Ti1—N12.272 (4)C28—H28A0.9700
N1—C101.482 (6)C28—H28B0.9700
N1—C91.491 (6)C29—H29A0.9600
N1—C111.494 (6)C29—H29B0.9600
N2—C291.479 (6)C29—H29C0.9600
N2—C281.488 (6)C30—C311.496 (7)
N2—C301.496 (6)C30—H30A0.9700
O1—C11.337 (6)C30—H30B0.9700
O2—C191.343 (6)C31—C321.372 (7)
O3—C201.334 (6)C31—C381.398 (7)
O4—C381.349 (6)C32—C331.394 (7)
C1—C81.398 (7)C32—H320.9300
C1—C21.403 (7)C33—C351.375 (8)
C2—C41.394 (7)C33—C341.516 (7)
C2—C31.498 (7)C34—H34A0.9600
C3—H3A0.9600C34—H34B0.9600
C3—H3B0.9600C34—H34C0.9600
C3—H3C0.9600C35—C361.399 (7)
C4—C51.392 (7)C35—H350.9300
C4—H40.9300C36—C381.405 (7)
C5—C71.394 (7)C36—C371.499 (7)
C5—C61.509 (7)C37—H37A0.9600
C6—H6A0.9600C37—H37B0.9600
C6—H6B0.9600C37—H37C0.9600
C6—H6C0.9600C41—C421.523 (18)
C7—C81.389 (7)C41—H41A0.9600
C7—H70.9300C41—H41B0.9600
C8—C91.504 (6)C41—H41C0.9600
C9—H9A0.9700C42—C471.35 (2)
C9—H9B0.9700C42—C431.45 (4)
C10—H10A0.9600C43—C441.34 (4)
C10—H10B0.9600C43—H430.9300
C10—H10C0.9600C44—C451.35 (2)
C11—C121.502 (7)C44—H440.9300
C11—H11A0.9700C45—C461.36 (2)
C11—H11B0.9700C45—H450.9300
C12—C131.374 (7)C46—C471.40 (2)
C12—C191.393 (7)C46—H460.9300
C13—C141.387 (8)C47—H470.9300
C13—H130.9300C51—C521.47 (3)
C14—C161.392 (8)C51—H51A0.9600
C14—C151.508 (8)C51—H51B0.9600
C15—H15A0.9600C51—H51C0.9600
C15—H15B0.9600C52—C571.34 (5)
C15—H15C0.9600C52—C531.41 (3)
C16—C171.385 (8)C53—C541.36 (4)
C16—H160.9300C53—H530.9300
C17—C191.407 (7)C54—C551.39 (5)
C17—C181.503 (8)C54—H540.9300
C18—H18A0.9600C55—C561.37 (4)
C18—H18B0.9600C55—H550.9300
C18—H18C0.9600C56—C571.31 (6)
C20—C271.393 (7)C56—H560.9300
C20—C211.409 (7)C57—H570.9300
C21—C231.392 (8)C61—C621.292 (17)
C21—C221.485 (8)C61—H61A0.9600
C22—H22A0.9600C61—H61B0.9600
C22—H22B0.9600C61—H61C0.9600
C22—H22C0.9600C62—C64i1.399 (12)
C23—C241.401 (8)C62—C631.408 (14)
C23—H230.9300C63—C641.334 (13)
C24—C261.386 (7)C63—H630.9300
C24—C251.509 (8)C64—C62i1.399 (12)
C25—H25A0.9600C64—H640.9300
O1—Ti1—O2168.10 (15)C27—C26—H26119.1
O1—Ti1—O490.78 (15)C24—C26—H26119.1
O2—Ti1—O490.01 (16)C26—C27—C20120.3 (5)
O1—Ti1—O392.34 (17)C26—C27—C28120.5 (5)
O2—Ti1—O389.53 (17)C20—C27—C28119.2 (4)
O4—Ti1—O3167.03 (15)N2—C28—C27114.9 (4)
O1—Ti1—N295.28 (15)N2—C28—H28A108.6
O2—Ti1—N296.62 (15)C27—C28—H28A108.6
O4—Ti1—N285.06 (15)N2—C28—H28B108.6
O3—Ti1—N282.12 (15)C27—C28—H28B108.6
O1—Ti1—N183.29 (14)H28A—C28—H28B107.5
O2—Ti1—N184.82 (15)C31—C30—N2114.1 (4)
O4—Ti1—N196.52 (15)C31—C30—H30A108.7
O3—Ti1—N196.34 (15)N2—C30—H30A108.7
N2—Ti1—N1177.87 (15)C31—C30—H30B108.7
C10—N1—C9109.4 (4)N2—C30—H30B108.7
C10—N1—C11109.9 (4)H30A—C30—H30B107.6
C9—N1—C11106.6 (3)C32—C31—C38119.9 (5)
C10—N1—Ti1112.1 (3)C32—C31—C30122.7 (5)
C9—N1—Ti1109.4 (3)C38—C31—C30117.4 (4)
C11—N1—Ti1109.4 (3)C31—C32—C33120.9 (5)
C29—N2—C28110.0 (4)C31—C32—H32119.5
C29—N2—C30108.6 (4)C33—C32—H32119.5
C28—N2—C30106.5 (4)C35—C33—C32118.5 (5)
C29—N2—Ti1111.4 (3)C35—C33—C34120.5 (5)
C28—N2—Ti1109.1 (3)C32—C33—C34121.0 (5)
C30—N2—Ti1111.1 (3)C33—C35—C36122.9 (5)
C1—O1—Ti1142.9 (3)C33—C35—H35118.6
C19—O2—Ti1136.5 (3)C36—C35—H35118.6
C20—O3—Ti1141.8 (3)C35—C36—C38117.0 (5)
C38—O4—Ti1132.7 (3)C35—C36—C37122.2 (5)
O1—C1—C8119.2 (4)C38—C36—C37120.8 (4)
O1—C1—C2120.2 (4)O4—C38—C31118.3 (4)
C8—C1—C2120.6 (4)O4—C38—C36121.1 (4)
C4—C2—C1117.9 (5)C31—C38—C36120.7 (4)
C4—C2—C3122.8 (5)C47—C42—C43118.3 (19)
C1—C2—C3119.3 (5)C47—C42—C41120.4 (15)
C5—C4—C2123.0 (5)C43—C42—C41121.2 (19)
C5—C4—H4118.5C44—C43—C42118 (3)
C2—C4—H4118.5C44—C43—H43120.8
C4—C5—C7117.4 (4)C42—C43—H43120.8
C4—C5—C6121.6 (5)C43—C44—C45121.7 (19)
C7—C5—C6121.0 (5)C43—C44—H44119.2
C8—C7—C5121.8 (5)C45—C44—H44119.2
C8—C7—H7119.1C44—C45—C46122.3 (15)
C5—C7—H7119.1C44—C45—H45118.9
C7—C8—C1119.3 (4)C46—C45—H45118.9
C7—C8—C9121.1 (4)C45—C46—C47117.4 (17)
C1—C8—C9119.3 (4)C45—C46—H46121.3
N1—C9—C8115.6 (4)C47—C46—H46121.3
N1—C9—H9A108.4C42—C47—C46121.5 (18)
C8—C9—H9A108.4C42—C47—H47119.2
N1—C9—H9B108.4C46—C47—H47119.2
C8—C9—H9B108.4C52—C51—H51A109.5
H9A—C9—H9B107.4C52—C51—H51B109.5
N1—C11—C12114.4 (4)H51A—C51—H51B109.5
N1—C11—H11A108.7C52—C51—H51C109.5
C12—C11—H11A108.7H51A—C51—H51C109.5
N1—C11—H11B108.7H51B—C51—H51C109.5
C12—C11—H11B108.7C57—C52—C53116 (3)
H11A—C11—H11B107.6C57—C52—C51127 (3)
C13—C12—C19119.5 (5)C53—C52—C51117 (2)
C13—C12—C11123.1 (5)C54—C53—C52118 (3)
C19—C12—C11117.1 (4)C54—C53—H53120.8
C12—C13—C14122.0 (5)C52—C53—H53120.8
C12—C13—H13119.0C53—C54—C55122 (3)
C14—C13—H13119.0C53—C54—H54119.1
C13—C14—C16117.1 (5)C55—C54—H54119.1
C13—C14—C15121.2 (6)C56—C55—C54119 (3)
C16—C14—C15121.7 (5)C56—C55—H55120.3
C17—C16—C14123.5 (5)C54—C55—H55120.3
C17—C16—H16118.3C57—C56—C55117 (4)
C14—C16—H16118.3C57—C56—H56121.5
C16—C17—C19117.2 (5)C55—C56—H56121.5
C16—C17—C18123.0 (5)C56—C57—C52128 (5)
C19—C17—C18119.8 (5)C56—C57—H57116.2
O2—C19—C12119.2 (4)C52—C57—H57116.2
O2—C19—C17120.1 (5)C62—C61—H61A109.5
C12—C19—C17120.7 (5)C62—C61—H61B109.5
O3—C20—C27120.6 (4)H61A—C61—H61B109.5
O3—C20—C21119.5 (5)C62—C61—H61C109.5
C27—C20—C21120.0 (5)H61A—C61—H61C109.5
C23—C21—C20117.7 (5)H61B—C61—H61C109.5
C23—C21—C22122.2 (5)C61—C62—C64i127.7 (14)
C20—C21—C22120.1 (5)C61—C62—C63114.1 (12)
C21—C23—C24123.2 (5)C64i—C62—C63118.2 (10)
C21—C23—H23118.4C64—C63—C62119.4 (9)
C24—C23—H23118.4C64—C63—H63120.3
C26—C24—C23117.0 (5)C62—C63—H63120.3
C26—C24—C25121.9 (5)C63—C64—C62i122.4 (10)
C23—C24—C25121.1 (5)C63—C64—H64118.8
C27—C26—C24121.8 (5)C62i—C64—H64118.8
Symmetry code: (i) x+1, y+1, z.

Experimental details

Crystal data
Chemical formula[Ti(C19H23NO2)2]·1.5C7H8
Mr780.34
Crystal system, space groupTriclinic, P1
Temperature (K)173
a, b, c (Å)12.053 (2), 13.374 (3), 14.511 (3)
α, β, γ (°)102.02 (3), 112.07 (3), 93.04 (3)
V3)2097.8 (7)
Z2
Radiation typeMo Kα
µ (mm1)0.25
Crystal size (mm)0.5 × 0.25 × 0.14
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2004)
Tmin, Tmax0.83, 0.96
No. of measured, independent and
observed [I > 2σ(I)] reflections
12545, 7019, 5111
Rint0.029
(sin θ/λ)max1)0.588
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.072, 0.223, 1.02
No. of reflections7019
No. of parameters582
No. of restraints6
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.76, 0.37

Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), SHELXTL (Sheldrick, 2008).

 

Acknowledgements

This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MEST) (No. 2010–0023904).

References

First citationBruker (2004). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationChmura, A. J. H., Davidson, M. G., Jones, M. D., Lunn, M. D. & Mahon, M. F. (2006). Dalton Trans. pp. 887–889.  Web of Science CSD CrossRef
First citationFarrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854.  Web of Science CrossRef CAS IUCr Journals
First citationHong, Y., Mun, S.-D., Lee, J., Do, Y. & Kim, Y. (2008). J. Organomet. Chem. 693, 1945–1951.  Web of Science CSD CrossRef CAS
First citationKim, S. H., Kim, D. J., Go, M. J., Ko, Y. S., Lee, J. & Kim, Y. (2012). Dalton Trans. 41, 11619–11626.  Web of Science CSD CrossRef CAS PubMed
First citationKim, S. H., Lee, J., Kim, D. J., Moon, J. H., Yoon, S. W., Oh, H. J., Ko, Y. S., Do, Y. & Kim, Y. (2009). J. Organomet. Chem. 694, 3409–3417.  Web of Science CSD CrossRef CAS
First citationKim, J. H., Yoon, S., Mun, S.-D., Kim, S. H., Lee, J., Chung, Y., Kwon, S. H., Lee, K. S., Lee, C. & Kim, Y. (2011). J. Organomet. Chem. 696, 1729–1735.  Web of Science CSD CrossRef CAS
First citationLee, J., Hong, Y., Kim, J. H., Kim, S. H., Do, Y., Shin, Y. K. & Kim, Y. (2008). J. Organomet. Chem. 693, 3715–3721.  Web of Science CSD CrossRef CAS
First citationLee, J., Kim, Y. & Do, Y. (2007). Inorg. Chem. 46, 7701–7703.  Web of Science CSD CrossRef PubMed CAS
First citationMun, S.-D., Kim, S. H., Lee, J., Kim, H.-J., Do, Y. & Kim, Y. (2010). Polyhedron, 29, 379–383.  Web of Science CSD CrossRef CAS
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals

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.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds