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Acta Cryst. (2009). E65, m1531    [ doi:10.1107/S1600536809045796 ]

Di-[mu]-ethanolato-bis[diethanolato(2-methylquinolin-8-olato)titanium(IV)]

Y. Fazaeli, E. Najafi, M. M. Amini and H. R. Khavasi

Abstract top

In the centrosymmetric dinuclear title compound, [Ti2(C10H8NO)2(C2H5O)6], the Ti atom is bonded to an N,O-bidentate quinolin-8-olate ligand, two terminal ethanolate anions and two bridging ethanolate anions in a distorted TiNO5 octahedral geometry. An intramolecular C-H...O hydrogen bond occurs; in the crystal, intermolecular C-H...O interactions help to establish the packing.

Comment top

8-Hydroxyquinoline and its derivatives are reagents for the gravimetric analysis of metal ions and the crystal structures of a large number of metal 8-hydroxyquinolinates have been documented. However, for TiIV, only three 8-hydroxyquinolinates are known (Amini et al., 2004), (Birdet et al., 1973; Studd & Swallow, 1968). Recently, we have reported the structure of 2-methyl-8-hydroxyquinoline (Fazaeli et al., 2008). In continuation our work in preparation of 8-hydroxyquinoline derivatives of transition metal elements from corresponding alkoxides, here we report synthesis and characterization of the title compound, (I).

This molecule lie across crystallographic inversion centre and the assymetric unit therefore contains one-half of a molecule. The 8-hydroxy-2-methylquinolinate anion chelates to Ti in the triethanolate derivative; however, the coordination number is raised to six as two of the four ethanolate groups are bridging (Table 1) (Fig. 1).

Related literature top

For TiIV–8-hydroxyquinolinates, see: Amini et al. (2004); Birdet et al. (1973); Studd & Swallow (1968). For a related structure, see: Fazaeli et al. (2008).

Experimental top

Manipulations were carried out under nitrogen, using standard Schlenk techniques. TitaniumIV tetraethoxide was prepared from titaniumIV tetrapropoxide (Fluka) and dry ethanol by the alkoxide exchange method and it was puried by vacuum distillation. 8-Hydroxyquinoline (1.6 g, 10 mmol) was added to the reagent (2.28 g, 10 mmol) in toluene (10 ml). The mixture was stirred for a day and the solvent then removed under reduced pressure to furnish a yellow solid. The solid was crystallized from a dichloromethane n-hexane mixture to give yellow prisms of (I).

Refinement top

All H atoms were positioned geometrically, with C—H = 0.93 Å, 0.96Å and 0.97Å for aromatic, methyl and CH2 hydrogen atoms respectively and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA (Stoe & Cie, 2005); data reduction: X-RED (Stoe & Cie, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) with displacement ellipsoids drawn at the 30% probability level. Atoms with the suffix a are generated by (2–x, 2–y, –z).
Di-µ-ethanolato-bis[diethanolato(2-methylquinolin-8-olato)titanium(IV)] top
Crystal data top
[Ti2(C10H8NO)2(C2H5O)6]F(000) = 720
Mr = 682.51Dx = 1.354 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1633 reflections
a = 9.0497 (18) Åθ = 2.1–29.2°
b = 13.086 (3) ŵ = 0.53 mm−1
c = 14.189 (3) ÅT = 120 K
β = 95.21 (3)°Prism, yellow
V = 1673.4 (6) Å30.45 × 0.28 × 0.23 mm
Z = 2
Data collection top
Stoe IPDS II
diffractometer		4503 independent reflections
Radiation source: fine-focus sealed tube3540 reflections with I > 2σ(I)
graphiteRint = 0.099
Detector resolution: 0.15 mm pixels mm-1θmax = 29.2°, θmin = 2.1°
rotation method scansh = −12→12
Absorption correction: numerical
(X-SHAPE; Stoe & Cie, 2005)		k = −17→17
Tmin = 0.686, Tmax = 0.905l = −19→15
12962 measured reflections
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)] = 0.097Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.197H-atom parameters constrained
S = 1.14 w = 1/[σ2(Fo2) + (0.1579P)2 + 0.3709P]
where P = (Fo2 + 2Fc2)/3
4503 reflections(Δ/σ)max < 0.001
203 parametersΔρmax = 1.26 e Å−3
0 restraintsΔρmin = −1.14 e Å−3
Crystal data top
[Ti2(C10H8NO)2(C2H5O)6]V = 1673.4 (6) Å3
Mr = 682.51Z = 2
Monoclinic, P21/nMo Kα radiation
a = 9.0497 (18) ŵ = 0.53 mm−1
b = 13.086 (3) ÅT = 120 K
c = 14.189 (3) Å0.45 × 0.28 × 0.23 mm
β = 95.21 (3)°
Data collection top
Stoe IPDS II
diffractometer		4503 independent reflections
Absorption correction: numerical
(X-SHAPE; Stoe & Cie, 2005)		3540 reflections with I > 2σ(I)
Tmin = 0.686, Tmax = 0.905Rint = 0.099
12962 measured reflectionsθmax = 29.2°
Refinement top
R[F2 > 2σ(F2)] = 0.097H-atom parameters constrained
wR(F2) = 0.197Δρmax = 1.26 e Å−3
S = 1.14Δρmin = −1.14 e Å−3
4503 reflectionsAbsolute structure: ?
203 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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*/Ueq
C10.7281 (4)0.8994 (3)−0.1775 (3)0.0353 (7)
H1A0.67380.9058−0.12270.053*
H1B0.65980.8914−0.23290.053*
H1C0.78690.9596−0.18390.053*
C20.8274 (3)0.8079 (3)−0.1667 (2)0.0306 (7)
C30.8266 (4)0.7345 (3)−0.2396 (3)0.0354 (7)
H30.76500.7436−0.29500.042*
C40.9155 (4)0.6503 (3)−0.2294 (3)0.0349 (7)
H40.91650.6032−0.27840.042*
C51.0064 (4)0.6351 (3)−0.1439 (2)0.0310 (6)
C61.0989 (4)0.5492 (3)−0.1246 (3)0.0356 (7)
H61.10490.4985−0.17000.043*
C71.1805 (4)0.5410 (3)−0.0376 (3)0.0380 (8)
H71.24140.4844−0.02520.046*
C81.1734 (4)0.6166 (3)0.0329 (3)0.0349 (7)
H81.22980.60940.09070.042*
C91.0831 (4)0.7011 (3)0.0164 (2)0.0305 (7)
C100.9996 (3)0.7110 (3)−0.0735 (2)0.0284 (6)
C110.6511 (5)0.7812 (4)0.0572 (4)0.0516 (11)
H11A0.65600.7490−0.00400.062*
H11B0.55570.81490.05730.062*
C120.6658 (9)0.7025 (4)0.1327 (6)0.081 (2)
H12A0.76180.67100.13400.122*
H12B0.59030.65150.12020.122*
H12C0.65490.73400.19280.122*
C130.9606 (5)0.8822 (4)0.2620 (3)0.0431 (9)
H13A0.98890.81090.25850.052*
H13B0.85400.88530.26500.052*
C141.0373 (5)0.9294 (4)0.3496 (3)0.0512 (11)
H14A1.14270.92740.34620.077*
H14B1.01250.89180.40420.077*
H14C1.00570.99900.35470.077*
C151.2662 (4)0.9251 (3)−0.0154 (3)0.0347 (7)
H15A1.28250.86550.02490.042*
H15B1.34210.97500.00420.042*
C161.2818 (4)0.8944 (3)−0.1167 (3)0.0444 (9)
H16A1.20540.8464−0.13710.067*
H16B1.37720.8636−0.12100.067*
H16C1.27280.9539−0.15650.067*
N10.9147 (3)0.7980 (2)−0.0847 (2)0.0284 (6)
O11.0681 (3)0.7744 (2)0.07988 (17)0.0338 (5)
O20.7640 (3)0.8529 (2)0.07192 (19)0.0356 (6)
O30.9989 (3)0.9345 (2)0.17872 (19)0.0364 (6)
O41.1230 (2)0.96763 (19)−0.00251 (17)0.0302 (5)
Ti10.94929 (6)0.89765 (5)0.05650 (4)0.0280 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0283 (15)0.0410 (18)0.0341 (17)0.0002 (13)−0.0110 (13)0.0000 (13)
C20.0241 (13)0.0379 (16)0.0286 (15)−0.0053 (12)−0.0048 (11)0.0032 (12)
C30.0296 (15)0.0430 (18)0.0320 (17)−0.0047 (13)−0.0059 (12)0.0010 (14)
C40.0361 (16)0.0386 (18)0.0288 (16)−0.0035 (14)−0.0032 (13)−0.0046 (13)
C50.0260 (13)0.0359 (16)0.0312 (16)−0.0044 (12)0.0024 (11)0.0014 (13)
C60.0354 (16)0.0327 (16)0.0387 (18)0.0010 (13)0.0034 (14)−0.0022 (14)
C70.0332 (16)0.0360 (17)0.044 (2)0.0052 (14)0.0013 (14)0.0007 (15)
C80.0311 (15)0.0390 (18)0.0331 (17)0.0036 (13)−0.0055 (13)0.0010 (13)
C90.0254 (13)0.0358 (17)0.0293 (16)−0.0001 (12)−0.0031 (11)0.0016 (12)
C100.0237 (13)0.0350 (16)0.0258 (14)−0.0027 (12)−0.0007 (11)−0.0008 (12)
C110.0382 (19)0.061 (3)0.056 (3)−0.0186 (19)0.0044 (18)−0.009 (2)
C120.112 (5)0.039 (3)0.101 (5)−0.006 (3)0.055 (4)0.002 (3)
C130.0396 (18)0.060 (2)0.0292 (17)−0.0043 (17)0.0005 (14)0.0001 (16)
C140.045 (2)0.076 (3)0.0309 (19)0.013 (2)−0.0030 (16)−0.0061 (19)
C150.0218 (13)0.0404 (18)0.0420 (19)0.0031 (12)0.0028 (12)−0.0011 (14)
C160.0322 (17)0.056 (2)0.046 (2)−0.0024 (16)0.0101 (16)−0.0103 (18)
N10.0224 (11)0.0346 (14)0.0269 (13)−0.0025 (10)−0.0045 (10)0.0011 (10)
O10.0329 (11)0.0380 (13)0.0287 (12)0.0023 (10)−0.0073 (9)−0.0014 (9)
O20.0270 (11)0.0408 (14)0.0385 (13)−0.0043 (10)0.0009 (9)−0.0014 (10)
O30.0329 (12)0.0463 (15)0.0295 (12)−0.0052 (10)0.0000 (9)−0.0013 (10)
O40.0217 (9)0.0372 (12)0.0313 (12)0.0014 (9)0.0008 (8)−0.0026 (9)
Ti10.0224 (3)0.0344 (4)0.0264 (3)−0.0008 (2)−0.0020 (2)−0.0018 (2)
Geometric parameters (Å, °) top
C1—C21.496 (5)C12—H12A0.9600
C1—H1A0.9600C12—H12B0.9600
C1—H1B0.9600C12—H12C0.9600
C1—H1C0.9600C13—O31.435 (5)
C2—N11.352 (4)C13—C141.501 (6)
C2—C31.411 (5)C13—H13A0.9700
C3—C41.364 (5)C13—H13B0.9700
C3—H30.9300C14—H14A0.9600
C4—C51.417 (5)C14—H14B0.9600
C4—H40.9300C14—H14C0.9600
C5—C61.414 (5)C15—O41.438 (4)
C5—C101.414 (5)C15—C161.512 (6)
C6—C71.384 (5)C15—H15A0.9700
C6—H60.9300C15—H15B0.9700
C7—C81.412 (5)C16—H16A0.9600
C7—H70.9300C16—H16B0.9600
C8—C91.383 (5)C16—H16C0.9600
C8—H80.9300Ti1—N12.387 (3)
C9—O11.331 (4)Ti1—O11.950 (3)
C9—C101.428 (4)Ti1—O21.808 (3)
C10—N11.375 (4)Ti1—O31.817 (3)
C11—O21.389 (5)Ti1—O4i2.008 (3)
C11—C121.483 (9)Ti1—O42.061 (2)
C11—H11A0.9700Ti1—Ti1i3.2948 (13)
C11—H11B0.9700
C2—C1—H1A109.5C14—C13—H13A109.4
C2—C1—H1B109.5O3—C13—H13B109.4
H1A—C1—H1B109.5C14—C13—H13B109.4
C2—C1—H1C109.5H13A—C13—H13B108.0
H1A—C1—H1C109.5C13—C14—H14A109.5
H1B—C1—H1C109.5C13—C14—H14B109.5
N1—C2—C3121.9 (3)H14A—C14—H14B109.5
N1—C2—C1117.6 (3)C13—C14—H14C109.5
C3—C2—C1120.4 (3)H14A—C14—H14C109.5
C4—C3—C2120.6 (3)H14B—C14—H14C109.5
C4—C3—H3119.7O4—C15—C16112.8 (3)
C2—C3—H3119.7O4—C15—H15A109.0
C3—C4—C5119.6 (3)C16—C15—H15A109.0
C3—C4—H4120.2O4—C15—H15B109.0
C5—C4—H4120.2C16—C15—H15B109.0
C6—C5—C10119.0 (3)H15A—C15—H15B107.8
C6—C5—C4124.4 (3)C15—C16—H16A109.5
C10—C5—C4116.6 (3)C15—C16—H16B109.5
C7—C6—C5119.5 (3)H16A—C16—H16B109.5
C7—C6—H6120.2C15—C16—H16C109.5
C5—C6—H6120.2H16A—C16—H16C109.5
C6—C7—C8121.5 (3)H16B—C16—H16C109.5
C6—C7—H7119.2C2—N1—C10117.1 (3)
C8—C7—H7119.2C2—N1—Ti1133.8 (2)
C9—C8—C7120.3 (3)C10—N1—Ti1109.0 (2)
C9—C8—H8119.9C9—O1—Ti1124.7 (2)
C7—C8—H8119.9C11—O2—Ti1151.4 (3)
O1—C9—C8123.8 (3)C13—O3—Ti1127.0 (2)
O1—C9—C10117.4 (3)C15—O4—Ti1i123.9 (2)
C8—C9—C10118.7 (3)C15—O4—Ti1127.5 (2)
N1—C10—C5124.0 (3)Ti1i—O4—Ti1108.13 (10)
N1—C10—C9115.0 (3)O2—Ti1—O397.01 (12)
C5—C10—C9120.9 (3)O2—Ti1—O1102.40 (12)
O2—C11—C12110.1 (5)O3—Ti1—O188.43 (12)
O2—C11—H11A109.6O2—Ti1—O4i93.27 (11)
C12—C11—H11A109.6O3—Ti1—O4i100.06 (12)
O2—C11—H11B109.6O1—Ti1—O4i161.18 (11)
C12—C11—H11B109.6O2—Ti1—O4160.52 (12)
H11A—C11—H11B108.2O3—Ti1—O497.94 (11)
C11—C12—H12A109.5O1—Ti1—O490.44 (10)
C11—C12—H12B109.5O4i—Ti1—O471.87 (10)
H12A—C12—H12B109.5O2—Ti1—N182.66 (11)
C11—C12—H12C109.5O3—Ti1—N1161.53 (12)
H12A—C12—H12C109.5O1—Ti1—N173.70 (10)
H12B—C12—H12C109.5O4i—Ti1—N198.39 (10)
O3—C13—C14111.0 (4)O4—Ti1—N187.05 (10)
O3—C13—H13A109.4
N1—C2—C3—C4−0.2 (5)C11—O2—Ti1—N127.3 (6)
C1—C2—C3—C4−179.1 (3)C11—O2—Ti1—Ti1i115.5 (6)
C2—C3—C4—C51.7 (5)C13—O3—Ti1—O238.1 (3)
C3—C4—C5—C6177.8 (3)C13—O3—Ti1—O1−64.2 (3)
C3—C4—C5—C10−0.7 (5)C13—O3—Ti1—O4i132.7 (3)
C10—C5—C6—C70.1 (5)C13—O3—Ti1—O4−154.4 (3)
C4—C5—C6—C7−178.5 (4)C13—O3—Ti1—N1−49.7 (5)
C5—C6—C7—C80.2 (6)C13—O3—Ti1—Ti1i169.8 (3)
C6—C7—C8—C90.3 (6)C9—O1—Ti1—O281.3 (3)
C7—C8—C9—O1178.5 (3)C9—O1—Ti1—O3178.2 (3)
C7—C8—C9—C10−1.0 (5)C9—O1—Ti1—O4i−64.3 (4)
C6—C5—C10—N1179.4 (3)C9—O1—Ti1—O4−83.9 (3)
C4—C5—C10—N1−1.9 (5)C9—O1—Ti1—N12.9 (2)
C6—C5—C10—C9−0.8 (5)C9—O1—Ti1—Ti1i−79.3 (3)
C4—C5—C10—C9177.9 (3)C15—O4—Ti1—O2−130.7 (4)
O1—C9—C10—N11.5 (4)Ti1i—O4—Ti1—O241.8 (4)
C8—C9—C10—N1−178.9 (3)C15—O4—Ti1—O389.5 (3)
O1—C9—C10—C5−178.3 (3)Ti1i—O4—Ti1—O3−98.04 (13)
C8—C9—C10—C51.3 (5)C15—O4—Ti1—O11.0 (3)
C3—C2—N1—C10−2.3 (5)Ti1i—O4—Ti1—O1173.48 (12)
C1—C2—N1—C10176.6 (3)C15—O4—Ti1—O4i−172.5 (3)
C3—C2—N1—Ti1−178.5 (2)Ti1i—O4—Ti1—O4i0.0
C1—C2—N1—Ti10.5 (5)C15—O4—Ti1—N1−72.7 (3)
C5—C10—N1—C23.4 (5)Ti1i—O4—Ti1—N199.83 (12)
C9—C10—N1—C2−176.4 (3)C15—O4—Ti1—Ti1i−172.5 (3)
C5—C10—N1—Ti1−179.5 (3)C2—N1—Ti1—O269.3 (3)
C9—C10—N1—Ti10.7 (3)C10—N1—Ti1—O2−107.0 (2)
C8—C9—O1—Ti1176.8 (3)C2—N1—Ti1—O3159.5 (3)
C10—C9—O1—Ti1−3.6 (4)C10—N1—Ti1—O3−16.8 (4)
C12—C11—O2—Ti188.3 (7)C2—N1—Ti1—O1174.6 (3)
C14—C13—O3—Ti1173.2 (3)C10—N1—Ti1—O1−1.8 (2)
C16—C15—O4—Ti1i−67.7 (4)C2—N1—Ti1—O4i−22.9 (3)
C16—C15—O4—Ti1103.7 (3)C10—N1—Ti1—O4i160.7 (2)
C11—O2—Ti1—O3−134.1 (6)C2—N1—Ti1—O4−94.1 (3)
C11—O2—Ti1—O1−44.2 (6)C10—N1—Ti1—O489.6 (2)
C11—O2—Ti1—O4i125.3 (6)C2—N1—Ti1—Ti1i−59.2 (3)
C11—O2—Ti1—O485.9 (7)C10—N1—Ti1—Ti1i124.4 (2)
Symmetry codes: (i) −x+2, −y+2, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C15—H15A···O10.972.463.061 (5)120
C1—H1C···O3i0.962.383.292 (5)159
C3—H3···O1ii0.932.413.310 (5)163
Symmetry codes: (i) −x+2, −y+2, −z; (ii) x−1/2, −y+3/2, z−1/2.
Table 1
Selected geometric parameters (Å) top
Ti1—N12.387 (3)Ti1—O31.817 (3)
Ti1—O11.950 (3)Ti1—O4i2.008 (3)
Ti1—O21.808 (3)Ti1—O42.061 (2)
Symmetry codes: (i) −x+2, −y+2, −z.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C15—H15A···O10.972.463.061 (5)120
C1—H1C···O3i0.962.383.292 (5)159
C3—H3···O1ii0.932.413.310 (5)163
Symmetry codes: (i) −x+2, −y+2, −z; (ii) x−1/2, −y+3/2, z−1/2.
Acknowledgements top

We are grateful to Shahid Beheshti University for financial support.

references
References top

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