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

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 64| Part 1| January 2008| Page m48
https://doi.org/10.1107/S160053680705742X

Tetra­kis(N,N-di­ethyl­carbamato)titanium(IV)

Nicholas A. Straessler,a M. Tyler Caudleb and Thomas L. Groyc*

aATK Launch Systems, Brigham City, UT 84302, USA, bBASF Catalysts LLC, Iselin, NJ 08830, USA, and cDepartment of Chemistry and Biochemistry, Arizona State University, Tempe, AZ 85287, USA
*Correspondence e-mail: tgroy@asu.edu

(Received 18 October 2007; accepted 9 November 2007; online 6 December 2007)

The mononuclear title compound, [Ti(C5H10NO2)4], is a rare example of an eight-coordinate TiIV compound in which all donor atoms are O atoms. The coordination geometry around TiIV is pseudo-dodeca­hedral and the O—C—O angles of the carbamate ligands are slightly compressed [range 115.3 (2)–116.7 (2)°], apparently on account of the high coordination number. One ethyl group is disordered over two positions; the site occupancy factors are 0.64 and 0.36.

Related literature

The pseudo-dodeca­hedral description of the coordination geometry is discussed in: Dell'Amico et al. (2000[Dell'Amico, D. B., Calderazzo, F., Ianelli, S., Labella, L., Marchetti, F. & Pelizzi, G. (2000). J. Chem. Soc. Dalton Trans. pp. 4339-4342.]). For related structures, see: Chisholm & Extine (1977b[Chisholm, M. H. & Extine, M. W. (1977b). J. Am. Chem. Soc. 99, 792-802.]); Dell'Amico et al. (2003[Dell'Amico, D. B., Calderazzo, F., Labella, L., Marchetti, F. & Pampaloni, G. (2003). Chem. Rev. 103, 3857-3897.]); McCowan et al. (2004[McCowan, C. S., Buss, C. E., Young, V. G. Jr, McDonnell, R. L. & Caudle, M. T. (2004). Acta Cryst. E60, m285-m287.]). Related synthesis details are given in: Calderazzo et al. (1991[Calderazzo, F., Ianelli, S., Pampaloni, G., Pelizzi, G. & Sperrle, M. (1991). J. Chem. Soc. Dalton Trans. pp. 693-698.]); Chisholm & Extine (1977a[Chisholm, M. H. & Extine, M. W. (1977a). J. Am. Chem. Soc. 99, 782-792.]).

[Scheme 1]

Experimental

Crystal data

  • [Ti(C5H10NO2)4]

  • Mr = 512.46

  • Monoclinic, P 21 /n

  • a = 13.9906 (9) Å

  • b = 11.7183 (8) Å

  • c = 17.7483 (12) Å

  • β = 112.494 (1)°

  • V = 2688.4 (3) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.37 mm−1

  • T = 263 (2) K

  • 0.23 × 0.18 × 0.14 mm
Data collection

  • Bruker SMART APEX CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2001[Bruker (2001). SADABS (Version 2.03), SAINT (Version 6.28A) and SMART (Version 5.625). Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.922, Tmax = 0.950

  • 21432 measured reflections

  • 4751 independent reflections

  • 3280 reflections with I > 2σ(I)

  • Rint = 0.052
Refinement

  • R[F2 > 2σ(F2)] = 0.044

  • wR(F2) = 0.114

  • S = 0.94

  • 4751 reflections

  • 313 parameters

  • 4 restraints

  • H-atom parameters constrained

  • Δρmax = 0.21 e Å−3

  • Δρmin = −0.25 e Å−3

Data collection: SMART (Bruker, 2001[Bruker (2001). SADABS (Version 2.03), SAINT (Version 6.28A) and SMART (Version 5.625). Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2001[Bruker (2001). SADABS (Version 2.03), SAINT (Version 6.28A) and SMART (Version 5.625). Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); molecular graphics: SHELXTL (Bruker, 1997[Bruker (1997). SHELXTL. Version 5.10. Bruker AXS Inc., Madison, Wisconsin, USA.]); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S160053680705742X/bi2252sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053680705742X/bi2252Isup2.hkl

checkCIF report


Comment top

Preparation of the title compound has been previously reported via direct reaction of Ti(NEt2)4 with CO2 (Chisholm & Extine, 1977a), and by a one-pot approach similar to that described herein but using a different solvent system (Calderazzo et al., 1991). In neither case was the compound structurally established by X-ray crystallography, although it was suggested to be mononuclear.

The coordination environment around the TiIV atom in the title compound consists of eight O atoms derived from the four bidentate carbamato ligands. The Ti—O bond distances are all similar, ranging between 2.0530 (15) and 2.1087 (16) Å, while the O—C—O angles of the carbamate ligands range from 115.3 (2) to 116.7 (2)°. These angles are considerably smaller than O—C—O angles in complexes having terminal η1 or µ1,3-bridging carbamato ligands, which tend to be greater than 120°, and they are small even when compared to other bidentate carbamato ligands (Dell'Amico et al., 2003; McCowan et al., 2004). The compressed O—C—O angles in the title compound are attributed in part to the high coordination number about the TiIV center, which has the effect of forcing the O atoms closer to one another.

Eight-coordinate TiIV compounds are rare, particularly in an environment consisting solely of O donor ligands (Dell'Amico et al., 2000). The title compound has a similar core structure to tetrakis(N,N-di-isopropylcarbamato)titanium(IV) (Dell'Amico et al., 2000), which together with the six-coordinate distorted octahedral compound bis(dimethylamido)bis(N,N-dimethylcarbamato)titanium(IV) (Chisholm & Extine, 1977b) are the only other crystallographically characterized mononuclear carbamato complexes of TiIV.

Related literature top

The pseudo-dodecahedral description of the coordination geometry is discussed in: Dell'Amico et al. (2000). For related structures, see: Chisholm & Extine (1977b); Dell'Amico et al. (2003); McCowan et al. (2004). Related synthesis details are given in: Calderazzo et al. (1991); Chisholm & Extine (1977a).

Experimental top

While stirring under an atmosphere of N2, 1.00 ml (9.12 mmol) of TiCl4 was added to approximately 70 ml of anhydrous THF in a Schlenk flask. A yellow solid formed that dissolved within several minutes. To the resulting bright yellow solution was added 7.50 ml (72.50 mmol) of anhydrous diethylamine. The mixture turned dark blue, almost black, in color. After ten minutes the flask was evacuated of all N2 and charged with 1 atm of anhydrous CO2 gas which caused the reaction mixture to turn yellow/orange and precipitate solid. After stirring overnight, solid white diethylammonium chloride was removed by filtration under N2. Approximately 30 ml freshly distilled n-hexane was added to the clear light yellow filtrate and the volume was reduced by slow evaporation under a stream of N2. This gave 2.85 g (61%) of pale yellow crystals suitable for X-ray analysis.

Refinement top

H atoms were positioned geometrically and allowed to ride with C—H = 0.96 Å, Uiso(H) = 1.5Ueq(C) for the methyl groups and C—H = 0.97 Å, Uiso(H) = 1.2Ueq(C) for the methylene groups. One ethyl group on the diethylcarbamate ligand containing N1A is disordered. Atoms C1D–C1E represent the majority component (site occupancy factor 0.639 (4)) and C1D'–C1E' represent the minority component (site occupancy factor 0.361 (4)). The components were refined with N—C and C—C bond lengths restrained to 1.46 (1) and 1.48 (1) Å, respectively, and with anisotropic displacement parameters constrained to be identical for the atom pairs C1D/C1D' and C1E/C1E'. Data were collected at 263 K because the crystals undergo what is believed to be a destructive phase transformation somewhere in the range 173–243 K.

Structure description top

Preparation of the title compound has been previously reported via direct reaction of Ti(NEt2)4 with CO2 (Chisholm & Extine, 1977a), and by a one-pot approach similar to that described herein but using a different solvent system (Calderazzo et al., 1991). In neither case was the compound structurally established by X-ray crystallography, although it was suggested to be mononuclear.

The coordination environment around the TiIV atom in the title compound consists of eight O atoms derived from the four bidentate carbamato ligands. The Ti—O bond distances are all similar, ranging between 2.0530 (15) and 2.1087 (16) Å, while the O—C—O angles of the carbamate ligands range from 115.3 (2) to 116.7 (2)°. These angles are considerably smaller than O—C—O angles in complexes having terminal η1 or µ1,3-bridging carbamato ligands, which tend to be greater than 120°, and they are small even when compared to other bidentate carbamato ligands (Dell'Amico et al., 2003; McCowan et al., 2004). The compressed O—C—O angles in the title compound are attributed in part to the high coordination number about the TiIV center, which has the effect of forcing the O atoms closer to one another.

Eight-coordinate TiIV compounds are rare, particularly in an environment consisting solely of O donor ligands (Dell'Amico et al., 2000). The title compound has a similar core structure to tetrakis(N,N-di-isopropylcarbamato)titanium(IV) (Dell'Amico et al., 2000), which together with the six-coordinate distorted octahedral compound bis(dimethylamido)bis(N,N-dimethylcarbamato)titanium(IV) (Chisholm & Extine, 1977b) are the only other crystallographically characterized mononuclear carbamato complexes of TiIV.

The pseudo-dodecahedral description of the coordination geometry is discussed in: Dell'Amico et al. (2000). For related structures, see: Chisholm & Extine (1977b); Dell'Amico et al. (2003); McCowan et al. (2004). Related synthesis details are given in: Calderazzo et al. (1991); Chisholm & Extine (1977a).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound with displacement ellipsoids shown at the 25% probability level. H atoms are omitted. Disorder of one ethyl group bonded to N1A is shown using C1D–C1E as the major component and C1D'–C1E' as the minor component.
Tetrakis(N,N-diethylcarbamato)titanium(IV) top
Crystal data top
[Ti(C5H10NO2)4]F(000) = 1096
Mr = 512.46Dx = 1.266 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 7268 reflections
a = 13.9906 (9) Åθ = 2.4–25.3°
b = 11.7183 (8) ŵ = 0.37 mm−1
c = 17.7483 (12) ÅT = 263 K
β = 112.494 (1)°Block, light-yellow
V = 2688.4 (3) Å30.23 × 0.18 × 0.14 mm
Z = 4
Data collection top
Bruker SMART APEX CCD
diffractometer		4751 independent reflections
Radiation source: fine-focus sealed tube3280 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.052
ω scanθmax = 25.0°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		h = −16→16
Tmin = 0.922, Tmax = 0.950k = −13→13
21432 measured reflectionsl = −21→21
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)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.114H-atom parameters constrained
S = 0.94 w = 1/[σ2(Fo2) + (0.062P)2]
where P = (Fo2 + 2Fc2)/3
4751 reflections(Δ/σ)max = 0.001
313 parametersΔρmax = 0.21 e Å−3
4 restraintsΔρmin = −0.25 e Å−3
Crystal data top
[Ti(C5H10NO2)4]V = 2688.4 (3) Å3
Mr = 512.46Z = 4
Monoclinic, P21/nMo Kα radiation
a = 13.9906 (9) ŵ = 0.37 mm−1
b = 11.7183 (8) ÅT = 263 K
c = 17.7483 (12) Å0.23 × 0.18 × 0.14 mm
β = 112.494 (1)°
Data collection top
Bruker SMART APEX CCD
diffractometer		4751 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		3280 reflections with I > 2σ(I)
Tmin = 0.922, Tmax = 0.950Rint = 0.052
21432 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0444 restraints
wR(F2) = 0.114H-atom parameters constrained
S = 0.94Δρmax = 0.21 e Å−3
4751 reflectionsΔρmin = −0.25 e Å−3
313 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)
Ti10.53057 (3)0.40515 (3)0.75825 (2)0.04645 (15)
C1A0.70112 (19)0.4099 (2)0.75016 (15)0.0550 (6)
C1B0.8487 (2)0.5285 (2)0.7645 (2)0.0790 (9)
H1B10.79990.58330.72940.095*
H1B20.90610.52280.74680.095*
C1C0.8880 (2)0.5717 (3)0.8500 (2)0.0964 (11)
H1C10.83150.57890.86770.145*
H1C20.91980.64500.85240.145*
H1C30.93810.51920.88490.145*
C1D0.8506 (4)0.3100 (4)0.7419 (3)0.0744 (17)0.639 (4)
H1D10.80110.24840.72140.089*0.639 (4)
H1D20.88280.32420.70310.089*0.639 (4)
C1E0.9301 (5)0.2802 (5)0.8232 (4)0.130 (2)0.639 (4)
H1E10.98220.33860.84020.195*0.639 (4)
H1E20.96150.20860.81970.195*0.639 (4)
H1E30.89800.27420.86210.195*0.639 (4)
C1D'0.8672 (7)0.3171 (8)0.7944 (6)0.0744 (17)0.361 (4)
H1DA0.91280.33640.84960.089*0.361 (4)
H1DB0.82640.25100.79610.089*0.361 (4)
C1E'0.9272 (10)0.2938 (9)0.7440 (7)0.130 (2)0.361 (4)
H1EA0.97330.23100.76690.195*0.361 (4)
H1EB0.96650.36020.74250.195*0.361 (4)
H1EC0.88090.27480.68960.195*0.361 (4)
N1A0.79773 (16)0.41651 (17)0.75455 (16)0.0756 (7)
O1A0.65588 (12)0.31632 (13)0.75096 (10)0.0585 (4)
O1B0.64677 (11)0.50028 (13)0.74517 (10)0.0549 (4)
C2A0.5985 (2)0.4936 (2)0.89342 (16)0.0617 (7)
C2B0.6239 (3)0.6631 (3)0.97834 (19)0.0927 (10)
H2B10.60570.70420.92730.111*
H2B20.68530.69811.01810.111*
C2C0.5377 (3)0.6704 (3)1.0072 (2)0.1165 (13)
H2C10.47620.63900.96660.175*
H2C20.52590.74891.01660.175*
H2C30.55530.62821.05700.175*
C2D0.7143 (3)0.4758 (3)1.03593 (18)0.1000 (11)
H2D10.69490.39601.02700.120*
H2D20.70480.50021.08480.120*
C2E0.8246 (3)0.4874 (5)1.0491 (3)0.171 (2)
H2E10.83470.46341.00090.257*
H2E20.86560.44071.09430.257*
H2E30.84530.56581.06050.257*
N2A0.64547 (18)0.5425 (2)0.96643 (13)0.0782 (7)
O2A0.61867 (13)0.39039 (15)0.88078 (10)0.0660 (5)
O2B0.53366 (13)0.54604 (14)0.83306 (10)0.0587 (4)
C3A0.4128 (2)0.2649 (2)0.77832 (14)0.0554 (6)
C3B0.2466 (2)0.2274 (3)0.78633 (19)0.0814 (9)
H3B10.25320.30530.80620.098*
H3B20.22710.17990.82290.098*
C3C0.1656 (3)0.2221 (3)0.7042 (2)0.1197 (13)
H3C10.18670.26530.66730.180*
H3C20.10260.25330.70500.180*
H3C30.15450.14400.68650.180*
C3D0.3691 (2)0.0673 (2)0.79305 (19)0.0792 (9)
H3D10.41570.05110.76560.095*
H3D20.30560.02520.76520.095*
C3F0.4174 (3)0.0266 (3)0.8796 (2)0.1360 (16)
H3F10.48000.06840.90770.204*
H3F20.4330−0.05320.88030.204*
H3F30.37010.03860.90630.204*
N3A0.34594 (17)0.18900 (18)0.78668 (13)0.0661 (6)
O3A0.49815 (13)0.23417 (13)0.77522 (10)0.0591 (4)
O3B0.39348 (12)0.37213 (14)0.77267 (10)0.0561 (4)
C4A0.42082 (17)0.4551 (2)0.61816 (14)0.0500 (6)
C4B0.3207 (2)0.5963 (2)0.51902 (16)0.0681 (7)
H4B10.32640.63670.56820.082*
H4B20.24780.59090.48460.082*
C4D0.3324 (3)0.3942 (3)0.47780 (17)0.0915 (10)
H4D10.37850.32930.49660.110*
H4D20.33980.42440.42940.110*
C4C0.3734 (3)0.6632 (3)0.4759 (2)0.1295 (15)
H4C10.44310.67910.51240.194*
H4C20.33710.73370.45720.194*
H4C30.37440.62040.43010.194*
C4E0.2238 (3)0.3556 (4)0.4564 (3)0.1613 (19)
H4E10.21740.32060.50320.242*
H4E20.20580.30130.41270.242*
H4E30.17810.42000.43970.242*
N4A0.36206 (16)0.48149 (18)0.54101 (12)0.0624 (6)
O4A0.46113 (12)0.35681 (14)0.63830 (9)0.0567 (4)
O4B0.43958 (11)0.52675 (12)0.67580 (9)0.0499 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ti10.0451 (3)0.0418 (3)0.0482 (3)0.00093 (18)0.01313 (19)−0.00154 (18)
C1A0.0531 (15)0.0437 (14)0.0666 (17)0.0018 (12)0.0210 (12)0.0013 (12)
C1B0.0607 (18)0.0499 (17)0.129 (3)−0.0032 (13)0.0386 (18)0.0121 (17)
C1C0.079 (2)0.062 (2)0.132 (3)−0.0101 (16)0.022 (2)0.0070 (19)
C1D0.049 (2)0.055 (2)0.110 (5)0.0029 (18)0.022 (3)−0.003 (3)
C1E0.131 (4)0.075 (3)0.150 (5)0.044 (3)0.015 (5)−0.008 (4)
C1D'0.049 (2)0.055 (2)0.110 (5)0.0029 (18)0.022 (3)−0.003 (3)
C1E'0.131 (4)0.075 (3)0.150 (5)0.044 (3)0.015 (5)−0.008 (4)
N1A0.0499 (13)0.0448 (13)0.136 (2)0.0011 (10)0.0398 (14)0.0025 (12)
O1A0.0495 (10)0.0411 (10)0.0844 (13)0.0000 (7)0.0250 (9)−0.0010 (8)
O1B0.0487 (9)0.0408 (9)0.0736 (11)0.0040 (7)0.0217 (8)0.0026 (8)
C2A0.0604 (16)0.0686 (18)0.0503 (16)−0.0084 (14)0.0147 (13)−0.0044 (14)
C2B0.104 (3)0.110 (3)0.060 (2)−0.039 (2)0.0262 (18)−0.0267 (18)
C2C0.123 (3)0.140 (4)0.094 (3)−0.022 (3)0.049 (2)−0.028 (2)
C2D0.096 (3)0.128 (3)0.0536 (19)−0.020 (2)0.0041 (17)0.0037 (18)
C2E0.080 (3)0.257 (6)0.140 (4)−0.016 (3)0.001 (3)0.071 (4)
N2A0.0854 (17)0.0863 (18)0.0474 (14)−0.0137 (14)0.0083 (12)−0.0113 (12)
O2A0.0680 (12)0.0646 (12)0.0520 (10)0.0045 (9)0.0080 (8)0.0042 (9)
O2B0.0616 (11)0.0568 (10)0.0489 (10)0.0036 (8)0.0112 (8)−0.0082 (8)
C3A0.0567 (16)0.0596 (17)0.0489 (15)−0.0058 (13)0.0192 (12)0.0004 (12)
C3B0.079 (2)0.087 (2)0.091 (2)−0.0163 (17)0.0456 (18)−0.0010 (17)
C3C0.073 (2)0.146 (4)0.128 (3)−0.014 (2)0.025 (2)−0.020 (3)
C3D0.088 (2)0.0605 (19)0.097 (2)−0.0171 (15)0.0442 (19)−0.0013 (16)
C3F0.199 (5)0.084 (3)0.110 (3)0.016 (3)0.043 (3)0.022 (2)
N3A0.0642 (14)0.0626 (14)0.0794 (16)−0.0077 (11)0.0361 (12)0.0024 (11)
O3A0.0544 (11)0.0472 (10)0.0761 (12)0.0012 (8)0.0255 (9)0.0055 (8)
O3B0.0538 (10)0.0522 (10)0.0634 (11)0.0003 (8)0.0235 (8)−0.0006 (8)
C4A0.0468 (14)0.0538 (15)0.0485 (15)−0.0024 (11)0.0173 (11)−0.0055 (12)
C4B0.0665 (17)0.0782 (19)0.0540 (16)0.0120 (14)0.0167 (13)0.0083 (14)
C4D0.109 (3)0.091 (2)0.0515 (18)0.0121 (19)0.0055 (16)−0.0182 (16)
C4C0.171 (4)0.113 (3)0.138 (4)0.013 (3)0.097 (3)0.040 (3)
C4E0.160 (4)0.156 (4)0.139 (4)−0.081 (4)0.024 (3)−0.062 (3)
N4A0.0682 (14)0.0642 (14)0.0449 (12)0.0067 (11)0.0104 (10)−0.0070 (10)
O4A0.0646 (11)0.0486 (10)0.0516 (10)0.0069 (8)0.0162 (8)−0.0081 (8)
O4B0.0540 (10)0.0455 (9)0.0456 (9)0.0024 (7)0.0139 (7)−0.0044 (7)
Geometric parameters (Å, º) top
Ti1—O4A2.0530 (15)C2D—N2A1.467 (3)
Ti1—O2A2.0561 (16)C2D—C2E1.477 (4)
Ti1—O1B2.0562 (15)C2D—H2D10.970
Ti1—O3B2.0663 (16)C2D—H2D20.970
Ti1—O1A2.0851 (16)C2E—H2E10.960
Ti1—O4B2.0897 (15)C2E—H2E20.960
Ti1—O3A2.1013 (16)C2E—H2E30.960
Ti1—O2B2.1087 (16)C3A—O3A1.269 (3)
C1A—O1A1.269 (3)C3A—O3B1.281 (3)
C1A—O1B1.287 (3)C3A—N3A1.339 (3)
C1A—N1A1.326 (3)C3B—N3A1.458 (3)
C1B—N1A1.471 (3)C3B—C3C1.466 (4)
C1B—C1C1.491 (4)C3B—H3B10.970
C1B—H1B10.970C3B—H3B20.970
C1B—H1B20.970C3C—H3C10.960
C1C—H1C10.960C3C—H3C20.960
C1C—H1C20.960C3C—H3C30.960
C1C—H1C30.960C3D—N3A1.457 (3)
C1D—C1E1.487 (7)C3D—C3F1.501 (4)
C1D—N1A1.511 (5)C3D—H3D10.970
C1D—H1D10.970C3D—H3D20.970
C1D—H1D20.970C3F—H3F10.960
C1E—H1E10.960C3F—H3F20.960
C1E—H1E20.960C3F—H3F30.960
C1E—H1E30.960C4A—O4B1.271 (3)
C1D'—C1E'1.468 (9)C4A—O4A1.272 (3)
C1D'—N1A1.508 (8)C4A—N4A1.336 (3)
C1D'—H1DA0.970C4B—N4A1.458 (3)
C1D'—H1DB0.970C4B—C4C1.475 (4)
C1E'—H1EA0.960C4B—H4B10.970
C1E'—H1EB0.960C4B—H4B20.970
C1E'—H1EC0.960C4D—N4A1.457 (3)
C2A—O2B1.267 (3)C4D—C4E1.488 (5)
C2A—O2A1.281 (3)C4D—H4D10.970
C2A—N2A1.337 (3)C4D—H4D20.970
C2B—N2A1.477 (4)C4C—H4C10.960
C2B—C2C1.481 (4)C4C—H4C20.960
C2B—H2B10.970C4C—H4C30.960
C2B—H2B20.970C4E—H4E10.960
C2C—H2C10.960C4E—H4E20.960
C2C—H2C20.960C4E—H4E30.960
C2C—H2C30.960
O4A—Ti1—O2A158.13 (7)H2C2—C2C—H2C3109.5
O4A—Ti1—O1B96.51 (7)N2A—C2D—C2E113.2 (3)
O2A—Ti1—O1B89.14 (7)N2A—C2D—H2D1108.9
O4A—Ti1—O3B89.05 (7)C2E—C2D—H2D1108.9
O2A—Ti1—O3B93.58 (7)N2A—C2D—H2D2108.9
O1B—Ti1—O3B157.96 (7)C2E—C2D—H2D2108.9
O4A—Ti1—O1A82.73 (6)H2D1—C2D—H2D2107.8
O2A—Ti1—O1A81.12 (7)C2D—C2E—H2E1109.5
O1B—Ti1—O1A62.86 (6)C2D—C2E—H2E2109.5
O3B—Ti1—O1A139.16 (7)H2E1—C2E—H2E2109.5
O4A—Ti1—O4B62.75 (6)C2D—C2E—H2E3109.5
O2A—Ti1—O4B139.12 (7)H2E1—C2E—H2E3109.5
O1B—Ti1—O4B81.22 (6)H2E2—C2E—H2E3109.5
O3B—Ti1—O4B82.46 (6)C2A—N2A—C2D120.5 (3)
O1A—Ti1—O4B126.75 (6)C2A—N2A—C2B119.8 (2)
O4A—Ti1—O3A80.97 (7)C2D—N2A—C2B119.6 (2)
O2A—Ti1—O3A80.98 (7)C2A—O2A—Ti191.30 (14)
O1B—Ti1—O3A139.15 (7)C2A—O2B—Ti189.34 (15)
O3B—Ti1—O3A62.76 (6)O3A—C3A—O3B116.7 (2)
O1A—Ti1—O3A76.44 (6)O3A—C3A—N3A121.7 (2)
O4B—Ti1—O3A130.05 (6)O3B—C3A—N3A121.6 (2)
O4A—Ti1—O2B139.16 (7)N3A—C3B—C3C111.3 (3)
O2A—Ti1—O2B62.63 (7)N3A—C3B—H3B1109.4
O1B—Ti1—O2B79.62 (6)C3C—C3B—H3B1109.4
O3B—Ti1—O2B82.25 (7)N3A—C3B—H3B2109.4
O1A—Ti1—O2B127.93 (6)C3C—C3B—H3B2109.4
O4B—Ti1—O2B76.54 (6)H3B1—C3B—H3B2108.0
O3A—Ti1—O2B127.58 (7)C3B—C3C—H3C1109.5
O1A—C1A—O1B115.3 (2)C3B—C3C—H3C2109.5
O1A—C1A—N1A123.5 (2)H3C1—C3C—H3C2109.5
O1B—C1A—N1A121.2 (2)C3B—C3C—H3C3109.5
N1A—C1B—C1C113.5 (2)H3C1—C3C—H3C3109.5
N1A—C1B—H1B1108.9H3C2—C3C—H3C3109.5
C1C—C1B—H1B1108.9N3A—C3D—C3F113.0 (3)
N1A—C1B—H1B2108.9N3A—C3D—H3D1109.0
C1C—C1B—H1B2108.9C3F—C3D—H3D1109.0
H1B1—C1B—H1B2107.7N3A—C3D—H3D2109.0
C1B—C1C—H1C1109.5C3F—C3D—H3D2109.0
C1B—C1C—H1C2109.5H3D1—C3D—H3D2107.8
H1C1—C1C—H1C2109.5C3D—C3F—H3F1109.5
C1B—C1C—H1C3109.5C3D—C3F—H3F2109.5
H1C1—C1C—H1C3109.5H3F1—C3F—H3F2109.5
H1C2—C1C—H1C3109.5C3D—C3F—H3F3109.5
C1E—C1D—N1A106.1 (4)H3F1—C3F—H3F3109.5
C1E—C1D—H1D1110.5H3F2—C3F—H3F3109.5
N1A—C1D—H1D1110.5C3A—N3A—C3D120.9 (2)
C1E—C1D—H1D2110.5C3A—N3A—C3B119.9 (2)
N1A—C1D—H1D2110.5C3D—N3A—C3B119.1 (2)
H1D1—C1D—H1D2108.7C3A—O3A—Ti189.66 (14)
C1E'—C1D'—N1A105.9 (7)C3A—O3B—Ti190.89 (14)
C1E'—C1D'—H1DA110.6O4B—C4A—O4A116.1 (2)
N1A—C1D'—H1DA110.6O4B—C4A—N4A121.9 (2)
C1E'—C1D'—H1DB110.5O4A—C4A—N4A122.0 (2)
N1A—C1D'—H1DB110.6N4A—C4B—C4C113.8 (2)
H1DA—C1D'—H1DB108.7N4A—C4B—H4B1108.8
C1D'—C1E'—H1EA109.5C4C—C4B—H4B1108.8
C1D'—C1E'—H1EB109.5N4A—C4B—H4B2108.8
H1EA—C1E'—H1EB109.5C4C—C4B—H4B2108.8
C1D'—C1E'—H1EC109.5H4B1—C4B—H4B2107.7
H1EA—C1E'—H1EC109.5N4A—C4D—C4E111.9 (3)
H1EB—C1E'—H1EC109.5N4A—C4D—H4D1109.2
C1A—N1A—C1B119.7 (2)C4E—C4D—H4D1109.2
C1A—N1A—C1D'116.2 (4)N4A—C4D—H4D2109.2
C1B—N1A—C1D'115.9 (5)C4E—C4D—H4D2109.2
C1A—N1A—C1D119.3 (3)H4D1—C4D—H4D2107.9
C1B—N1A—C1D120.8 (3)C4B—C4C—H4C1109.5
C1A—O1A—Ti190.24 (14)C4B—C4C—H4C2109.5
C1A—O1B—Ti191.02 (14)H4C1—C4C—H4C2109.5
O2B—C2A—O2A116.4 (2)C4B—C4C—H4C3109.5
O2B—C2A—N2A122.6 (3)H4C1—C4C—H4C3109.5
O2A—C2A—N2A121.0 (3)H4C2—C4C—H4C3109.5
N2A—C2B—C2C110.1 (3)C4D—C4E—H4E1109.5
N2A—C2B—H2B1109.6C4D—C4E—H4E2109.5
C2C—C2B—H2B1109.6H4E1—C4E—H4E2109.5
N2A—C2B—H2B2109.6C4D—C4E—H4E3109.5
C2C—C2B—H2B2109.6H4E1—C4E—H4E3109.5
H2B1—C2B—H2B2108.2H4E2—C4E—H4E3109.5
C2B—C2C—H2C1109.5C4A—N4A—C4D120.6 (2)
C2B—C2C—H2C2109.5C4A—N4A—C4B120.9 (2)
H2C1—C2C—H2C2109.5C4D—N4A—C4B118.4 (2)
C2B—C2C—H2C3109.5C4A—O4A—Ti191.41 (13)
H2C1—C2C—H2C3109.5C4A—O4B—Ti189.78 (13)

Experimental details

Crystal data
Chemical formula[Ti(C5H10NO2)4]
Mr512.46
Crystal system, space groupMonoclinic, P21/n
Temperature (K)263
a, b, c (Å)13.9906 (9), 11.7183 (8), 17.7483 (12)
β (°) 112.494 (1)
V (Å3)2688.4 (3)
Z4
Radiation typeMo Kα
µ (mm−1)0.37
Crystal size (mm)0.23 × 0.18 × 0.14
Data collection
DiffractometerBruker SMART APEX CCD
Absorption correctionMulti-scan
(SADABS; Bruker, 2001)
Tmin, Tmax0.922, 0.950
No. of measured, independent and
observed [I > 2σ(I)] reflections		21432, 4751, 3280
Rint0.052
(sin θ/λ)max (Å−1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.114, 0.94
No. of reflections4751
No. of parameters313
No. of restraints4
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.21, −0.25

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997).

 

Acknowledgements

The authors thank the National Science Foundation for its contribution toward the purchase of the single-crystal instrumentation used in this study through award No. CHE-9808440.

References

First citationBruker (1997). SHELXTL. Version 5.10. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
 First citationBruker (2001). SADABS (Version 2.03), SAINT (Version 6.28A) and SMART (Version 5.625). Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
 First citationCalderazzo, F., Ianelli, S., Pampaloni, G., Pelizzi, G. & Sperrle, M. (1991). J. Chem. Soc. Dalton Trans. pp. 693–698.  CSD CrossRef Web of Science Google Scholar
 First citationChisholm, M. H. & Extine, M. W. (1977a). J. Am. Chem. Soc. 99, 782–792.  CrossRef CAS Web of Science Google Scholar
 First citationChisholm, M. H. & Extine, M. W. (1977b). J. Am. Chem. Soc. 99, 792–802.  CSD CrossRef CAS Web of Science Google Scholar
 First citationDell'Amico, D. B., Calderazzo, F., Ianelli, S., Labella, L., Marchetti, F. & Pelizzi, G. (2000). J. Chem. Soc. Dalton Trans. pp. 4339–4342.  Web of Science CrossRef Google Scholar
 First citationDell'Amico, D. B., Calderazzo, F., Labella, L., Marchetti, F. & Pampaloni, G. (2003). Chem. Rev. 103, 3857–3897.  Web of Science CrossRef PubMed Google Scholar
 First citationMcCowan, C. S., Buss, C. E., Young, V. G. Jr, McDonnell, R. L. & Caudle, M. T. (2004). Acta Cryst. E60, m285–m287.  Web of Science CSD CrossRef IUCr Journals Google Scholar
 First citationSheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.  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.

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ISSN: 2056-9890
Volume 64| Part 1| January 2008| Page m48
https://doi.org/10.1107/S160053680705742X
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