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Achiral {2-[2-(η5-cyclo­penta­dien­yl)-2-methyl­prop­yl]-1H-imid­azolyl-κN1}bis­(N,N-diethyl­amido-κN)titanium(IV), [Ti(C4H10N)2(C12H14N2)], (I), and closely related racemic (SR)-{2-[(η5-cyclo­penta­dien­yl)(phen­yl)meth­yl]-1H-imidazol­yl-κN1}bis­(N,N-diethyl­amido-κN)titanium(IV), [Ti(C4H10N)2(C15H12N2)], (II), have been prepared by direct reactions of Ti(NEt2)4 and the corresponding 1H-imidazol-2-yl side-chain functionalized cyclo­penta­dienes. In compound (II), there are two crystallographically independent mol­ecules of very similar geometries connected by a noncrystallographic pseudosymmetry operation akin to a 21 screw axis. All Ti-ligating N atoms in both (I) and (II) are in planar environments, which is indicative of an additional N→Ti pπ–dπ donation. This fact and the 18ē nature of both (I) and (II) are additionally supported by quantum chemical single-point density functional theory (DFT) computations.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010902112X/bg3099sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827010902112X/bg3099Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827010902112X/bg3099IIsup3.hkl
Contains datablock II

CCDC references: 742229; 742230

Comment top

1H-Imidazol(-olin)-2-yl side-chain functionalized cyclopentadienes were introduced as ligands into the organometallic chemistry of the Group 4 transition metals not long ago (Krut'ko et al., 2006; Nie et al., 2008). However, in all of the Ti (and Zr) complexes described in these papers, the imidazole(-oline) part of the ligands possesses Me groups at the N1 atoms and the M—N bonds are, actually, coordination ones. The present contribution reports the details of preparation and molecular structures of two first `geometry-constrained' Ti(+4) 18ē η5-Cp-tris(sec-amido)-type complexes derived from 1H-imidazol-2-yl side-chain functionalized cyclopentadienes, achiral {2-[2-(η5-cyclopenta-2,4-dienyl)-2-methylpropyl]-1H-imidazolyl-κN}bis(N,N-diethylamido-κN)titanium(+4), (C12H14N2)Ti(NEt2)2, (I), and the closely related rac-{2-[(η5-cyclopenta-2,4-dienyl)(phenyl)methyl]-1H-imidazolyl-κN}bis(N,N-diethylamido-κN)titanium(+4), (C15H12N2)Ti(NEt2)2, (II).

Complexes (I) and (II) have been prepared by direct reactions of Ti(NEt2)4 and corresponding 1H-imidazol-2-yl side-chain functionalized cyclopentadienes (see Scheme 1). Both (I) and (II) crystallize in centrosymmetric space groups (P21/n and P1, respectively).

In compound (II) there are two crystallographically independent molecules, (IIA) and (IIB), of very similar geometries, connected by a noncrystallographic pseudosymmetry operation (see below). Ellipsoid plots for molecules of (I) and (II) are presented in Figs. 1 and 2, respectively.

The principal geometric parameters for (I), (IIA) and (IIB) are rather similar (see Table 1 and supplementary material). The coordination polyhedra of the Ti atoms in all cases are distorted tetrahedra (assuming that each Cp ring occupies one coordination place). N atoms ligating to Ti atoms are all in planar environments (see Table 2). The same concerns [is true of?] head-of-bridge imidazole fragment atoms C1, Cp-ring atom C11, and Ph-ring atom C41 [in (II)] [see Table 2; here and throughout the text atoms are named as for compound (I); for atom names in molecules (IIA) and (IIB), appending of an appropriate suffix A or B is assumed]. Imidazole and Cp rings are all nearly planar; Ti1—PL1 [PL = ?] distances in all moieties are approximately identical (see Table 3). The C and Ti atoms C4 and Ti1 deviate slightly from the imidazole ring planes PL2 [PL2 = ?] (see Table 3). Of interest, in all moieties of the question, Ti1 atoms deviate considerably from the bisectrices [bisectors?] of the outer C21—N3—C23 and C31—N4—C33 angles (see Table 1). Also noteworthy is the fact that the imidazole fragments in (I), (IIA) and (IIB) exhibit distinctly alternating single and double bonds (compare the C1—N1, C2—N1, C3—N2 bond lengths with the C1—N2 and C2—C3 ones; see Table 1). Thus, the N1 atom should be `honestly' assigned an amido-type nature.

The presence of an additional CH2 group in the hydrocarbon linkage of (I) causes certain differences in its structure compared with that of (II). Thus, while in (II) the bridging C4 atoms deviate from the PL1 towards the Ti1 atoms side, the related C atom C5 in (I) is shifted outwards [towards?] the metal centre side (see Table 3). In comparison with (II), the imidazole fragment plane PL2 in (I) is more declined from the norm of PL1 [compare the dihedral PL1–PL2 angle of 62.58 (8)° in (I) with 77.52 (8) and 75.03 (8)° in (IIA) and (IIB)]. The greater rigidity of the C1 linkage in (II) than the C2 linkage in (I) also results in a different positioning of the Ti1 atoms with respect to the C1—N1—C2 outer angle bisetrices [bisectors?] (compare the C1—N1—Ti1 and C2—N1—Ti1 angles in Table 1). The same `C2-linkage effect' brings the methyl-group C atom C7 in (I) nearly into the PL1 plane [torsion angle C7—C5—C11—C12 -3.7 (3)°].

As was mentioned above, molecules (IIA) and (IIB) [for convenience, forms of the same chirality (S-) were chosen] are connected by a noncrystallographic pseudosymmetry. Thus, rotation of a molecule (IIA) around the axis X1AX1B [passes through the middle of the Ti1A–Ti1B segment, angles with a, b and c axes 71.4, 1.1, and 88.4°, respectively] by 179.4° followed by translation (–0.003, -0.282, -0.004) [fractional crystallographic coordinates; angles with a, b and c axes 71.6, 1.1, and 88.3°, respectively] results in a nearly complete overlap of the image with the molecule (IIB) [mean squared deviation 0.05 (1) Å2 (all atoms included)]. This symmetry transformation is very close to a one-step rotation around a 21 screw axis nearly parallel to the b axis of the unit cell with a period close to a quarter of the b axis length (see Fig. 2).

Analysis of the Cambridge Structural Database (CSD; version 5.27, release February 2009; Allen, 2002) reveals 16 structurally characterized Ti complexes of the similar η5-CpTi-tris(sec-amido) type (22 independent fragments) (Rhodes et al., 2002; Li et al., 2003; Seo et al., 2001; Kunz et al., 2002; Carpenetti et al., 1996; Kunz et al., 2001; Bertolasi et al., 2007; Wu et al., 2006; Cano et al., 2005; Martin et al., 1994). It is noteworthy that, except η5-Cp*-Ti(NMe2)3 (Martin et al., 1994), all these complexes, as in the case of compounds (I) and (II), contain at least one amido functionality linked to the Cp ring with a flexible bridge. Distances and angles around the Ti centre in (I) and (II) are all within the ranges reported previously.

In all the fragments mentioned above, except the Ti complex reported by Cano et al. (2005), the amido-N atom environments are planar and these N atoms are usually treated as sp2-hybridized ones. The question upon the electron count at the Ti atom and the ability of an N-heterocyclic system to participate in an NTi pπ-dπ-donation was discussed in an earlier work (Seo et al., 2001), where the structure of a close η5-Cp–Ti-(sec-amido)3-type counterpart of complexes (I) and (II) derived from a (pyrrol-2-yl)methyl side-chain functionalized cyclopentadiene, [2-[(η5-cyclopenta-2,4-dienyl)methyl]-1H-pyrrolyl-κN]bis(N,N-dimethylamido-κN)titanium(+4), (III), was reported. The main features of the metal centre environment in (I), (II) and (III) are very similar, with the environments of all amido-N atoms in (III) also being planar. However, as far as the Ti1—N1 bond in (III) is about 0.16 Å longer than other Ti—N bonds [the same is true for (I) and (II)], Seo et al. (2001) considered complex (III) to be formally a 16ē one, suggesting that the aromatic heterocycle moiety be exclusively a σ-, but not a π-donor, only on the basis of a noticeable, but non-critical Ti1—N1 bond elongation.

To clarify the question, we performed single-point DFT computations for the experimentally established geometries of (I) and (IIA) (for details, see Experimental). The HOMO orbitals (π-binding, 2 knot surfaces) in both (I) and (IIA) are fully located at the imidazole rings. Two next by energy MO-s (HOMO–1 and HOMO–2) in both (I) and (IIA) are evidently responsible for the pπ-dπ-donation from the NEt2 groups towards the metal centre. However, in the case of (I), the HOMO–3 through HOMO–6 orbitals all exhibit distinct pπ-dπ overlap of the N1 and Ti1 AO-s, with the knot surface passing through Ti1 and N1 atom centres being present in all of these cases. Lower orbitals in (I) (HOMO–7, HOMO–9, HOMO–10, and HOMO–12) provide σ-binding of all three amido-type moieties to the central atom. A similar situation is observed in the case of (IIA). Taking all this into consideration, there is no doubt about the presence of the pπ-dπ-donation to the titanium centre from all of the adjacent N atoms in both (I) and (II) [and, surely, in (III)], and all of these complexes would rather be treated as 18ē ones.

In solution, compound (I) exhibits fluxional behaviour. NMR data (see Experimental) in both C6D6 and THF-d8 are indicative of the pseudo-Cs symmetry for (I) at ambient temperature. This fluxional behaviour is rather typical for the class of compounds to which complex (I) belongs (see, for example, Krut'ko et al.,1996a,b, 1998, 2003, 2004, 2005, 2006; Nie et al., 2008) and is, actually, a degenerate interconversion of the Ti1—C11—C5—C4—C1—N1—(Ti1) six-membered pseudo-metallacycle. The `remains' of this flexibility, of interest, are also noticeable even in the solid state, where this interconversion is `frozen' and (I) is presented by two enantiomorphic conformers. The thermal ellipsoids of (C13, C14) and (C12, C15) are all `stretched' in directions close to the Cp-ring plane, with the length of the maximal principal axes of C13 and C14 being considerably greater than that of C12 and C15. This may be interpreted assuming that in the `geometry constrained ' (I) the Cp ring is involved in a `slipping' movement over the Ti1 atom and may be best described as a rotational vibration of the whole Cp ring around an axis approximately normal to the Cp plane and crossing it close to atom C5.

Experimental top

All operations were performed in all-sealed evacuated glass vessels with application of the high-vacuum line (the residual pressure of non-condensable gases within the range 1.5–1.0 ×10 -3 Torr; 1 Torr = 133.322 Pa). Ti(NEt2)4 was prepared as described earlier (Bürger & Dämmen, 1974; Bradley & Thomas, 1960). 2-{[Cyclopenta-1,3-dien-1(or 2)-yl]phenylmethyl}- and 2-{2-[cyclopenta-1,3-dien-1(or 2)-yl]2 methylpropyl}-1H-imidazoles, (IV) and (V), respectively, were prepared as described in Wang et al. (2009). Toluene and hexane were purified by distillation from over a Na—K alloy. C6D6 was dried similarly. THF-d8 was kept with disodium benzophenone ketyl. Both THF-d8 and C6D6 were transferred into NMR sample tubes on a high-vacuum line by trapping their vapours with liquid N2. NMR spectra were recorded on a Varian INOVA-400 instrument. For 1H and 13C{1H} NMR spectra, the residual proton resonances of the d-solvents [δH = 7.15 and δC = 128.0 (C6D6); δH = 1.73 and δC = 25.3 (THF-d8)] were used as internal reference standards.

General procedure. The solutions of equimolar amounts of Ti(NEt2)4 and cyclopentadiene (IV) or (IV)[V]? in toluene (20 ml) were mixed and heated in a water bath (353 K) for 8 h. The reaction mixture was then concentrated till dryness (by trapping of the volatile components into an adjacent vessel cooled with liquid N2) and extracted with hexane (6 × 40 ml). Pure (I) and (II) were obtained by recrystallization from hot hexane (50 ml).

Compound (I) was prepared from Ti(NEt2)4 (0.984 g, 2.6 mmol) and (V) (0.496 g, 2.6 mmol). Orange crystals were obtained in a yield of 0.478 g (50%). Compound (II) was prepared from Ti(NEt2)4 (1.110 g, 3.3 mmol) and cyclopentadiene (IV) (0.739 g, 3.3 mmol). Well formed yellow crystals were obtained in a yield of 0.816 g (60%).

Single crystals of (I) and (II) suitable for X-ray diffraction analyses were picked up directly from the isolated materials (N2-filled glove-box) and mounted inside Lindemann glass capillaries (diameter 0.5 mm).

Details of the quantum chemical computation. The single-point DFT calculations for (I) and (IIA) were performed using the hybrid RB3LYP functional and the valency-split 6–31+G(d,p) basis set with added diffuse and polarization functions [program package Gaussian 03 W (Frisch et al., 2003)]. Tight criteria on the self-consistent field convergence were applied. The wavefunctions were checked for stability. All additional computational materials not included in the body of the paper are available from the authors on request.

Refinement top

Non-H atoms were refined anisotropically. H atoms were treated as riding atoms with distances C—H = 0.96 (CH3), 0.97 (CH2), 0.93 (CArH) Å, and Uiso(H) = 1.5 Ueq(C), 1.2 Ueq(C), and 1.2 Ueq(C), respectively. The components of the anisotropic displacements of atoms C13, C14 along the C13—C14 bond in (I), C13A, C14A along the C13A—C14A bond in (II), and N4A,C31A along the N4A—C31A bond in (II) were restrained to be the same, with standard uncertainties of 0.002, 0.01 and 0.005 Å2, respectively. The components of the anisotropic displacements of Ph-ring C atoms C42 through C46 [both molecules (IIA) and (IIB)] along the 1–2 and 1–3 directions were restrained to be the same, with a standard uncertainty of 0.01 Å2.

Computing details top

For both compounds, data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009).

Figures top
[Figure 1] Fig. 1. Elipsoid plot for compound (I). Thermal ellipsoids are shown at the 50% probability level. All H atoms are omitted for clarity.
[Figure 2] Fig. 2. Elipsoid plot for compound (II). Crystallographically independent molecules (IIA) (top) and (IIB) (bottom) are shown (both S enantiomers). Thermal ellipsoids are shown at the 50% probability level. All H atoms are omitted for clarity. Both molecules have been oriented in a similar way to demonstrate their similarity.
[Figure 3] Fig. 3. Noncrystallographic pseudo-symmetry in (II). Prospective view of the unit cell along the direction of the a axis. For clarity, non-H atoms are drawn as circles; all H atoms are omitted. Ph-ring C atoms are eclipsed. Clockwise rotation of crystallographically independent molecule (IIA) around axis X1AX1B by 179.4° followed by translation along vector X1AX1B results in a nearly complete overlap of the image (depicted with dashed lines) and molecule (IIB). Parameters of the symmetrical transformation were optimized to minimize the sum of squared deviations of the image and molecule (IIB) atoms (all atoms were considered; no weigh[t?]ing scheme was applied).
(I) {2-[2-(η5-cyclopentadienyl)-2-methylpropyl]-1H-imidazolyl- κN}bis(N,N-diethylamido-κN)titanium(IV) top
Crystal data top
[Ti(C4H10N)2(C12H14N2)]F(000) = 816
Mr = 378.41Dx = 1.157 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 4438 reflections
a = 13.729 (3) Åθ = 2.4–27.1°
b = 14.829 (3) ŵ = 0.40 mm1
c = 10.679 (2) ÅT = 293 K
β = 92.749 (3)°Block, orange
V = 2171.7 (8) Å30.36 × 0.27 × 0.14 mm
Z = 4
Data collection top
Bruker SMART APEXII
diffractometer
4213 independent reflections
Radiation source: fine-focus sealed tube3287 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.030
Detector resolution: 8.333 pixels mm-1θmax = 26.0°, θmin = 2.0°
ϕ and ω scansh = 1516
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
k = 1218
Tmin = 0.868, Tmax = 0.946l = 1213
11087 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)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.106H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0601P)2 + 0.1364P]
where P = (Fo2 + 2Fc2)/3
4213 reflections(Δ/σ)max < 0.001
232 parametersΔρmax = 0.30 e Å3
1 restraintΔρmin = 0.23 e Å3
Crystal data top
[Ti(C4H10N)2(C12H14N2)]V = 2171.7 (8) Å3
Mr = 378.41Z = 4
Monoclinic, P21/nMo Kα radiation
a = 13.729 (3) ŵ = 0.40 mm1
b = 14.829 (3) ÅT = 293 K
c = 10.679 (2) Å0.36 × 0.27 × 0.14 mm
β = 92.749 (3)°
Data collection top
Bruker SMART APEXII
diffractometer
4213 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
3287 reflections with I > 2σ(I)
Tmin = 0.868, Tmax = 0.946Rint = 0.030
11087 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0371 restraint
wR(F2) = 0.106H-atom parameters constrained
S = 1.04Δρmax = 0.30 e Å3
4213 reflectionsΔρmin = 0.23 e Å3
232 parameters
Special details top

Experimental. Compound (I) 1H NMR (C6D6, 293 K): δ = 0.69 (t, 12 H, 1JCH = 126 Hz, X part of degenerate ABX3 spin system, 3JAX = 3JBX = 7.0 Hz, NCH2CH3), 1.14 [s, 6 H, 1JCH = 126 Hz, C(CH3)2], 2.93 (s, CH2 in bridge), 3.13 (dq, A part of degenerate ABX3 spin system, 4 H, 3JAX = 3JBX = 7.0 Hz, 2JAB = 13.8 Hz, NCH2CH3), 3.70 (dq, B part of degenerate ABX3 spin system, 4 H, 3JAX = 3JBX = 7.0 Hz, 2JAB = 13.8 Hz, NCH2CH3), 5.75, 5.88 (both m, 2 H + 2 H, CH in Cp), 7.25, 7.37 (AB spin system, 1 H + 1H, 3JAB =1.1 Hz, imidazole ring protons). All signals are noticeably broadened. 13C{1H} NMR (C6D6, 293 K): δ = 14.37 (NCH2CH3), 28.87 [C(CH3)2], 35.13 (CH2 in the bridge), 47.32 [C(CH3)2], 47.71 (NCH2CH3), 109.86, 111.91 (CH in Cp), 127.60, 127.85 (CH in imidazole, overlap with C6D6), 140.58 (C in Cp), 152.16 (C in imidazole). 1H NMR (THF-d8, 293 K): δ = 0.87 (t, 12 H, X part of degenerate ABX3 spin system, 3JAX = 3JBX = 7.0 Hz, NCH2CH3), 1.15 [s, 6 H, C(CH3)2], 2.69 (s, CH2 in bridge), 3.41 (dq, A part of degenerate ABX3 spin system, 4 H, 3JAX = 3JBX = 7.0 Hz, 2JAB = 13.8 Hz, NCH2CH3), 3.97 (dq, B part of degenerate ABX3 spin system, 4 H, 3JAX = 3JBX = 7.0 Hz, 2JAB = 13.8 Hz, NCH2CH3), 6.09, 6.29 (both m, 2 H + 2 H, CH in Cp), 6.59, 7.03 (AB spin system, 1 H + 1H, 3JAB =1.1 Hz, imidazole ring protons). 13C{1H} NMR (THF-d8, 293 K): δ = 14.58 (NCH2CH3), 29.06 [C(CH3)2], 35.67 (CH2 in the bridge), 47.60 [C(CH3)2], 48.27 (NCH2CH3), 110.87, 112.81 (CH in Cp), 127.06, 127.96 (CH in imidazole), 141.17 (C in Cp), 152.35 (C in imidazole).

Compound (II) 1H NMR (C6D6, 293 K): δ = 0.70, 0.77 (both t, 6 H + 6 H, X parts of two different degenerate ABX3 spin system, all 3JAX = 3JBX = 7.0 Hz, NCH2CH3), 3.06, 3.76 and 3.26, 3.33 (all dq, AB parts of two different degenerate ABX3 spin system, each 2 H, 3JAX = 3JBX = 7.0 Hz, 2JAB = 14.0 Hz, NCH2CH3), 5.63 (s, 1 H, CHPh), 5.64, 5.65, 5.76, 5.82 (all virt. q, all 1 H, all 3J all 4J 2.7 Hz, CH in Cp), 7.08, 7.17, 7.30 (all m, p-, m-, and o-CH in Ph, in respective order), 7.19, 7.50 (unresolved AB spin system, 1 H + 1H, imidazole ring protons). 13C{1H} NMR (C6D6, 293 K): δ = 14.94, 15.15 (NCH2CH3), 46.84 (CHPh), 46.95, 47.17 (NCH2CH3), 109.02, 109.42, 115.13 (CH in Cp, signal at 115.13 of double intensity in respect to that at 109.02), 124.69, 126.67 (CH in imidazole), 137.56 (C in Ph), 143.00 (C in Cp), 168.74 (C in imidazole).

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ti10.20201 (2)0.17894 (2)0.82210 (2)0.03600 (12)
N10.30133 (10)0.23004 (10)0.70280 (13)0.0407 (3)
N20.39726 (13)0.24827 (14)0.54004 (17)0.0654 (5)
N30.26794 (12)0.08156 (11)0.90385 (13)0.0484 (4)
N40.20551 (11)0.27110 (10)0.94566 (13)0.0437 (4)
C10.32101 (14)0.20583 (14)0.58286 (17)0.0475 (5)
C20.37294 (13)0.29263 (13)0.73589 (18)0.0483 (5)
H20.38040.32250.81230.058*
C30.42982 (15)0.30248 (16)0.6374 (2)0.0620 (6)
H30.48350.34060.63570.074*
C40.26376 (15)0.13682 (15)0.50932 (17)0.0562 (5)
H4B0.27490.07840.54820.067*
H4A0.28800.13400.42560.067*
C50.15332 (15)0.15448 (14)0.49859 (16)0.0481 (5)
C60.1051 (2)0.08192 (18)0.4138 (2)0.0748 (7)
H6B0.03570.09050.40960.112*
H6C0.12010.02330.44770.112*
H6A0.12930.08660.33120.112*
C70.13310 (19)0.24679 (16)0.43998 (19)0.0671 (6)
H7A0.16210.25000.36010.101*
H7C0.16050.29290.49410.101*
H7B0.06400.25570.42880.101*
C110.11083 (13)0.14761 (13)0.62719 (16)0.0433 (4)
C120.06339 (14)0.21587 (16)0.69302 (18)0.0542 (5)
H120.05480.27530.66680.065*
C130.03135 (15)0.1789 (2)0.8049 (2)0.0698 (6)
H130.00320.20910.86490.084*
C140.06038 (17)0.0892 (2)0.8099 (2)0.0711 (6)
H140.04960.04920.87480.085*
C150.10857 (15)0.06939 (15)0.70107 (17)0.0555 (5)
H150.13480.01370.68090.067*
C210.36998 (16)0.10456 (15)0.93963 (19)0.0585 (5)
H21B0.38490.08351.02440.070*
H21A0.37690.16970.93970.070*
C220.44324 (19)0.06457 (19)0.8538 (3)0.0811 (7)
H22A0.43280.08930.77110.122*
H22B0.43530.00030.85050.122*
H22C0.50810.07880.88530.122*
C230.2450 (2)0.01144 (15)0.9399 (2)0.0697 (7)
H23B0.30210.04900.93060.084*
H23A0.19330.03440.88360.084*
C240.2134 (3)0.0183 (2)1.0741 (2)0.0992 (10)
H24A0.15670.01861.08380.149*
H24C0.26530.00221.13050.149*
H24B0.19810.07991.09270.149*
C310.17698 (16)0.36277 (14)0.9065 (2)0.0568 (5)
H31A0.16520.36280.81630.068*
H31B0.23160.40280.92560.068*
C320.08743 (19)0.40166 (19)0.9658 (3)0.0907 (9)
H32B0.07030.45800.92640.136*
H32C0.10160.41131.05370.136*
H32A0.03400.36020.95470.136*
C330.22177 (17)0.26019 (16)1.08120 (17)0.0605 (6)
H33A0.23840.19771.09870.073*
H33B0.16130.27311.12110.073*
C340.3014 (2)0.3199 (2)1.1393 (2)0.0911 (9)
H34A0.35810.31661.09010.137*
H34C0.31780.29991.22310.137*
H34B0.27870.38111.14130.137*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ti10.03580 (19)0.0409 (2)0.03155 (17)0.00546 (14)0.00385 (12)0.00089 (12)
N10.0360 (8)0.0447 (9)0.0420 (8)0.0001 (7)0.0071 (6)0.0055 (6)
N20.0480 (11)0.0861 (15)0.0641 (11)0.0022 (10)0.0246 (9)0.0104 (10)
N30.0621 (10)0.0395 (9)0.0434 (8)0.0032 (8)0.0004 (7)0.0049 (7)
N40.0444 (9)0.0460 (9)0.0411 (8)0.0063 (7)0.0067 (6)0.0043 (6)
C10.0398 (10)0.0566 (12)0.0474 (10)0.0103 (9)0.0139 (8)0.0067 (8)
C20.0378 (10)0.0487 (11)0.0586 (11)0.0026 (8)0.0040 (8)0.0070 (9)
C30.0382 (11)0.0664 (15)0.0828 (16)0.0084 (10)0.0161 (10)0.0136 (12)
C40.0604 (13)0.0648 (14)0.0446 (10)0.0095 (11)0.0160 (9)0.0079 (9)
C50.0541 (12)0.0548 (12)0.0353 (9)0.0022 (9)0.0024 (8)0.0036 (8)
C60.0906 (18)0.0834 (17)0.0500 (12)0.0073 (15)0.0017 (11)0.0205 (12)
C70.0763 (16)0.0735 (15)0.0507 (12)0.0061 (13)0.0052 (11)0.0135 (11)
C110.0355 (9)0.0552 (11)0.0390 (9)0.0031 (8)0.0015 (7)0.0060 (8)
C120.0361 (10)0.0750 (14)0.0511 (11)0.0085 (10)0.0016 (8)0.0139 (10)
C130.0337 (11)0.1243 (18)0.0522 (12)0.0109 (12)0.0108 (9)0.0218 (13)
C140.0592 (14)0.1009 (16)0.0540 (12)0.0408 (13)0.0097 (10)0.0009 (12)
C150.0579 (13)0.0598 (13)0.0482 (10)0.0226 (10)0.0020 (9)0.0041 (9)
C210.0652 (14)0.0499 (12)0.0587 (12)0.0040 (10)0.0131 (10)0.0061 (9)
C220.0635 (16)0.0728 (17)0.106 (2)0.0179 (13)0.0032 (14)0.0031 (15)
C230.0998 (19)0.0427 (12)0.0669 (13)0.0082 (12)0.0076 (12)0.0118 (10)
C240.147 (3)0.084 (2)0.0682 (16)0.0214 (19)0.0162 (16)0.0298 (14)
C310.0561 (13)0.0489 (12)0.0663 (13)0.0039 (10)0.0141 (10)0.0044 (10)
C320.0722 (18)0.0692 (17)0.134 (2)0.0126 (14)0.0351 (17)0.0000 (16)
C330.0679 (14)0.0714 (15)0.0422 (10)0.0077 (12)0.0046 (9)0.0097 (9)
C340.0821 (19)0.121 (3)0.0689 (15)0.0206 (17)0.0075 (13)0.0298 (15)
Geometric parameters (Å, º) top
Ti1—N31.8950 (16)C11—C121.409 (3)
Ti1—N41.8988 (15)C12—C131.404 (3)
Ti1—N12.0551 (14)C12—H120.9300
Ti1—C132.341 (2)C13—C141.388 (4)
Ti1—C142.355 (2)C13—H130.9300
Ti1—C122.360 (2)C14—C151.396 (3)
Ti1—C152.4075 (19)C14—H140.9300
Ti1—C112.4219 (17)C15—H150.9300
N1—C11.370 (2)C21—C221.514 (3)
N1—C21.385 (2)C21—H21B0.9700
N2—C11.322 (3)C21—H21A0.9700
N2—C31.372 (3)C22—H22A0.9600
N3—C231.470 (3)C22—H22B0.9600
N3—C211.474 (3)C22—H22C0.9600
N4—C331.463 (2)C23—C241.520 (3)
N4—C311.470 (3)C23—H23B0.9700
C1—C41.491 (3)C23—H23A0.9700
C2—C31.347 (3)C24—H24A0.9600
C2—H20.9300C24—H24C0.9600
C3—H30.9300C24—H24B0.9600
C4—C51.537 (3)C31—C321.523 (3)
C4—H4B0.9700C31—H31A0.9700
C4—H4A0.9700C31—H31B0.9700
C5—C111.521 (2)C32—H32B0.9600
C5—C71.525 (3)C32—H32C0.9600
C5—C61.536 (3)C32—H32A0.9600
C6—H6B0.9600C33—C341.516 (3)
C6—H6C0.9600C33—H33A0.9700
C6—H6A0.9600C33—H33B0.9700
C7—H7A0.9600C34—H34A0.9600
C7—H7C0.9600C34—H34C0.9600
C7—H7B0.9600C34—H34B0.9600
C11—C151.404 (3)
N3—Ti1—N4103.45 (7)C12—C11—C5127.49 (19)
N3—Ti1—N1104.48 (7)C15—C11—Ti172.54 (10)
N4—Ti1—N199.79 (6)C12—C11—Ti170.47 (10)
N3—Ti1—C13119.34 (9)C5—C11—Ti1123.94 (12)
N4—Ti1—C1392.68 (8)C13—C12—C11108.4 (2)
N1—Ti1—C13129.99 (7)C13—C12—Ti171.90 (12)
N3—Ti1—C1488.27 (9)C11—C12—Ti175.27 (11)
N4—Ti1—C14116.00 (8)C13—C12—H12125.8
N1—Ti1—C14138.15 (7)C11—C12—H12125.8
C13—Ti1—C1434.39 (9)Ti1—C12—H12118.9
N3—Ti1—C12143.12 (8)C14—C13—C12107.8 (2)
N4—Ti1—C12103.40 (7)C14—C13—Ti173.32 (13)
N1—Ti1—C1295.32 (7)C12—C13—Ti173.35 (11)
C13—Ti1—C1234.75 (8)C14—C13—H13126.1
C14—Ti1—C1257.20 (9)C12—C13—H13126.1
N3—Ti1—C1587.91 (8)Ti1—C13—H13119.1
N4—Ti1—C15148.63 (7)C13—C14—C15108.4 (2)
N1—Ti1—C15105.56 (6)C13—C14—Ti172.29 (13)
C13—Ti1—C1556.78 (8)C15—C14—Ti175.04 (12)
C14—Ti1—C1534.07 (7)C13—C14—H14125.8
C12—Ti1—C1556.57 (8)C15—C14—H14125.8
N3—Ti1—C11117.75 (7)Ti1—C14—H14118.7
N4—Ti1—C11136.90 (7)C14—C15—C11108.5 (2)
N1—Ti1—C1182.47 (6)C14—C15—Ti170.88 (12)
C13—Ti1—C1157.21 (7)C11—C15—Ti173.66 (11)
C14—Ti1—C1156.82 (7)C14—C15—H15125.7
C12—Ti1—C1134.25 (7)C11—C15—H15125.7
C15—Ti1—C1133.80 (7)Ti1—C15—H15121.4
C1—N1—C2104.17 (15)N3—C21—C22113.77 (18)
C1—N1—Ti1130.51 (13)N3—C21—H21B108.8
C2—N1—Ti1124.94 (12)C22—C21—H21B108.8
C1—N2—C3104.55 (17)N3—C21—H21A108.8
C23—N3—C21111.22 (17)C22—C21—H21A108.8
C23—N3—Ti1137.05 (16)H21B—C21—H21A107.7
C21—N3—Ti1111.72 (12)C21—C22—H22A109.5
C33—N4—C31114.18 (16)C21—C22—H22B109.5
C33—N4—Ti1127.27 (14)H22A—C22—H22B109.5
C31—N4—Ti1118.07 (12)C21—C22—H22C109.5
N2—C1—N1113.19 (19)H22A—C22—H22C109.5
N2—C1—C4123.42 (17)H22B—C22—H22C109.5
N1—C1—C4123.37 (16)N3—C23—C24112.6 (2)
C3—C2—N1107.72 (18)N3—C23—H23B109.1
C3—C2—H2126.1C24—C23—H23B109.1
N1—C2—H2126.1N3—C23—H23A109.1
C2—C3—N2110.36 (19)C24—C23—H23A109.1
C2—C3—H3124.8H23B—C23—H23A107.8
N2—C3—H3124.8C23—C24—H24A109.5
C1—C4—C5114.55 (16)C23—C24—H24C109.5
C1—C4—H4B108.6C23—C24—H24B109.5
C5—C4—H4B108.6N4—C31—C32116.20 (18)
C1—C4—H4A108.6N4—C31—H31A108.2
C5—C4—H4A108.6C32—C31—H31A108.2
H4B—C4—H4A107.6N4—C31—H31B108.2
C11—C5—C7111.13 (17)C32—C31—H31B108.2
C11—C5—C6108.19 (17)H31A—C31—H31B107.4
C7—C5—C6108.78 (18)C31—C32—H32B109.5
C11—C5—C4109.93 (15)C31—C32—H32C109.5
C7—C5—C4110.05 (18)H32B—C32—H32C109.5
C6—C5—C4108.70 (17)C31—C32—H32A109.5
C5—C6—H6B109.5H32B—C32—H32A109.5
C5—C6—H6C109.5H32C—C32—H32A109.5
H6B—C6—H6C109.5N4—C33—C34114.4 (2)
C5—C6—H6A109.5N4—C33—H33A108.7
H6B—C6—H6A109.5C34—C33—H33A108.7
H6C—C6—H6A109.5N4—C33—H33B108.7
C5—C7—H7A109.5C34—C33—H33B108.7
C5—C7—H7C109.5H33A—C33—H33B107.6
H7A—C7—H7C109.5C33—C34—H34A109.5
C5—C7—H7B109.5C33—C34—H34C109.5
H7A—C7—H7B109.5H34A—C34—H34C109.5
H7C—C7—H7B109.5C33—C34—H34B109.5
C15—C11—C12106.85 (18)H34A—C34—H34B109.5
C15—C11—C5125.62 (18)H34C—C34—H34B109.5
N3—Ti1—N1—C186.68 (16)N1—Ti1—C11—C511.54 (16)
N4—Ti1—N1—C1166.55 (16)C13—Ti1—C11—C5160.5 (2)
C13—Ti1—N1—C164.63 (19)C14—Ti1—C11—C5158.3 (2)
C14—Ti1—N1—C117.3 (2)C12—Ti1—C11—C5122.7 (2)
C12—Ti1—N1—C161.94 (17)C15—Ti1—C11—C5121.6 (2)
C15—Ti1—N1—C15.20 (17)C15—C11—C12—C130.9 (2)
C11—Ti1—N1—C130.12 (16)C5—C11—C12—C13176.87 (18)
N3—Ti1—N1—C285.11 (15)Ti1—C11—C12—C1364.81 (14)
N4—Ti1—N1—C221.66 (16)C15—C11—C12—Ti163.89 (13)
C13—Ti1—N1—C2123.58 (16)C5—C11—C12—Ti1118.33 (18)
C14—Ti1—N1—C2170.91 (16)N3—Ti1—C12—C1360.74 (19)
C12—Ti1—N1—C2126.27 (15)N4—Ti1—C12—C1374.99 (15)
C15—Ti1—N1—C2176.99 (15)N1—Ti1—C12—C13176.39 (15)
C11—Ti1—N1—C2158.09 (15)C14—Ti1—C12—C1337.51 (14)
N4—Ti1—N3—C23119.0 (2)C15—Ti1—C12—C1378.46 (16)
N1—Ti1—N3—C23136.94 (19)C11—Ti1—C12—C13115.4 (2)
C13—Ti1—N3—C2318.1 (2)N3—Ti1—C12—C1154.63 (17)
C14—Ti1—N3—C232.7 (2)N4—Ti1—C12—C11169.65 (12)
C12—Ti1—N3—C2316.7 (3)N1—Ti1—C12—C1168.24 (13)
C15—Ti1—N3—C2331.4 (2)C13—Ti1—C12—C11115.4 (2)
C11—Ti1—N3—C2347.9 (2)C14—Ti1—C12—C1177.86 (14)
N4—Ti1—N3—C2161.96 (13)C15—Ti1—C12—C1136.91 (11)
N1—Ti1—N3—C2142.07 (14)C11—C12—C13—C141.3 (2)
C13—Ti1—N3—C21162.89 (12)Ti1—C12—C13—C1465.75 (15)
C14—Ti1—N3—C21178.30 (14)C11—C12—C13—Ti167.03 (14)
C12—Ti1—N3—C21162.33 (12)N3—Ti1—C13—C1428.06 (15)
C15—Ti1—N3—C21147.61 (13)N4—Ti1—C13—C14135.13 (13)
C11—Ti1—N3—C21131.09 (13)N1—Ti1—C13—C14119.72 (14)
N3—Ti1—N4—C3319.86 (17)C12—Ti1—C13—C14115.03 (19)
N1—Ti1—N4—C33127.45 (16)C15—Ti1—C13—C1437.23 (12)
C13—Ti1—N4—C33101.17 (17)C11—Ti1—C13—C1477.80 (13)
C14—Ti1—N4—C3374.85 (18)N3—Ti1—C13—C12143.09 (14)
C12—Ti1—N4—C33134.62 (16)N4—Ti1—C13—C12109.85 (14)
C15—Ti1—N4—C3388.8 (2)N1—Ti1—C13—C124.69 (19)
C11—Ti1—N4—C33143.14 (15)C14—Ti1—C13—C12115.03 (19)
N3—Ti1—N4—C31168.59 (13)C15—Ti1—C13—C1277.79 (14)
N1—Ti1—N4—C3160.99 (14)C11—Ti1—C13—C1237.23 (13)
C13—Ti1—N4—C3170.38 (14)C12—C13—C14—C151.2 (2)
C14—Ti1—N4—C3196.71 (15)Ti1—C13—C14—C1566.92 (15)
C12—Ti1—N4—C3136.93 (14)C12—C13—C14—Ti165.76 (14)
C15—Ti1—N4—C3182.72 (18)N3—Ti1—C14—C13155.78 (13)
C11—Ti1—N4—C3128.42 (17)N4—Ti1—C14—C1351.64 (15)
C3—N2—C1—N10.6 (2)N1—Ti1—C14—C1394.27 (16)
C3—N2—C1—C4177.90 (19)C12—Ti1—C14—C1337.92 (12)
C2—N1—C1—N20.4 (2)C15—Ti1—C14—C13115.4 (2)
Ti1—N1—C1—N2173.50 (14)C11—Ti1—C14—C1379.03 (14)
C2—N1—C1—C4178.06 (18)N3—Ti1—C14—C1588.84 (16)
Ti1—N1—C1—C45.0 (3)N4—Ti1—C14—C15167.03 (14)
C1—N1—C2—C30.1 (2)N1—Ti1—C14—C1521.1 (2)
Ti1—N1—C2—C3173.65 (14)C13—Ti1—C14—C15115.4 (2)
N1—C2—C3—N20.3 (2)C12—Ti1—C14—C1577.47 (15)
C1—N2—C3—C20.5 (3)C11—Ti1—C14—C1536.36 (13)
N2—C1—C4—C5127.2 (2)C13—C14—C15—C110.6 (2)
N1—C1—C4—C554.5 (3)Ti1—C14—C15—C1164.51 (14)
C1—C4—C5—C1165.4 (2)C13—C14—C15—Ti165.11 (16)
C1—C4—C5—C757.3 (2)C12—C11—C15—C140.2 (2)
C1—C4—C5—C6176.36 (17)C5—C11—C15—C14177.63 (18)
C7—C5—C11—C15173.74 (19)Ti1—C11—C15—C1462.72 (14)
C6—C5—C11—C1554.4 (3)C12—C11—C15—Ti162.52 (13)
C4—C5—C11—C1564.2 (2)C5—C11—C15—Ti1119.64 (18)
C7—C5—C11—C123.6 (3)N3—Ti1—C15—C1489.99 (16)
C6—C5—C11—C12123.0 (2)N4—Ti1—C15—C1422.8 (2)
C4—C5—C11—C12118.4 (2)N1—Ti1—C15—C14165.55 (16)
C7—C5—C11—Ti194.13 (19)C13—Ti1—C15—C1437.59 (15)
C6—C5—C11—Ti1146.51 (16)C12—Ti1—C15—C1479.48 (17)
C4—C5—C11—Ti128.0 (2)C11—Ti1—C15—C14116.9 (2)
N3—Ti1—C11—C1530.71 (14)N3—Ti1—C15—C11153.11 (12)
N4—Ti1—C11—C15130.55 (13)N4—Ti1—C15—C1194.09 (15)
N1—Ti1—C11—C15133.15 (13)N1—Ti1—C15—C1148.66 (13)
C13—Ti1—C11—C1577.93 (14)C13—Ti1—C15—C1179.30 (14)
C14—Ti1—C11—C1536.66 (14)C14—Ti1—C15—C11116.9 (2)
C12—Ti1—C11—C15115.72 (18)C12—Ti1—C15—C1137.42 (11)
N3—Ti1—C11—C12146.43 (13)C23—N3—C21—C2276.6 (2)
N4—Ti1—C11—C1214.83 (16)Ti1—N3—C21—C22102.69 (19)
N1—Ti1—C11—C12111.13 (13)C21—N3—C23—C2486.2 (3)
C13—Ti1—C11—C1237.79 (14)Ti1—N3—C23—C2494.8 (3)
C14—Ti1—C11—C1279.06 (15)C33—N4—C31—C3255.6 (3)
C15—Ti1—C11—C12115.72 (18)Ti1—N4—C31—C32117.0 (2)
N3—Ti1—C11—C590.91 (17)C31—N4—C33—C3460.0 (3)
N4—Ti1—C11—C5107.84 (16)Ti1—N4—C33—C34128.2 (2)
(II) (SR)-{2-[(η5-cyclopentadienyl)(phenyl)methyl]-1H- imidazolyl-κN}bis(N,N-diethylamido- κN)titanium(IV) top
Crystal data top
[Ti(C4H10N)2(C15H12N2)]Z = 4
Mr = 412.43F(000) = 880
Triclinic, P1Dx = 1.166 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 9.7472 (15) ÅCell parameters from 3373 reflections
b = 14.469 (2) Åθ = 2.3–24.0°
c = 18.006 (3) ŵ = 0.38 mm1
α = 89.362 (2)°T = 293 K
β = 76.965 (2)°Block, yellow
γ = 72.161 (2)°0.40 × 0.29 × 0.17 mm
V = 2350.4 (6) Å3
Data collection top
Bruker SMART APEX
diffractometer
8157 independent reflections
Radiation source: fine-focus sealed tube5573 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.022
Detector resolution: 8.333 pixels mm-1θmax = 25.0°, θmin = 1.9°
ϕ and ω scansh = 1111
Absorption correction: multi-scan
(SADABS; Sheldrick,1996)
k = 1717
Tmin = 0.863, Tmax = 0.939l = 1721
11818 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041H-atom parameters constrained
wR(F2) = 0.116 w = 1/[σ2(Fo2) + (0.0633P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max = 0.001
8157 reflectionsΔρmax = 0.23 e Å3
506 parametersΔρmin = 0.27 e Å3
16 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0036 (6)
Crystal data top
[Ti(C4H10N)2(C15H12N2)]γ = 72.161 (2)°
Mr = 412.43V = 2350.4 (6) Å3
Triclinic, P1Z = 4
a = 9.7472 (15) ÅMo Kα radiation
b = 14.469 (2) ŵ = 0.38 mm1
c = 18.006 (3) ÅT = 293 K
α = 89.362 (2)°0.40 × 0.29 × 0.17 mm
β = 76.965 (2)°
Data collection top
Bruker SMART APEX
diffractometer
8157 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick,1996)
5573 reflections with I > 2σ(I)
Tmin = 0.863, Tmax = 0.939Rint = 0.022
11818 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.04116 restraints
wR(F2) = 0.116H-atom parameters constrained
S = 1.00Δρmax = 0.23 e Å3
8157 reflectionsΔρmin = 0.27 e Å3
506 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*/Ueq
Ti1A0.15633 (4)0.67894 (3)0.61786 (2)0.04333 (14)
N1A0.0134 (2)0.61844 (13)0.63052 (10)0.0480 (5)
C1A0.0083 (2)0.52369 (16)0.60921 (12)0.0453 (5)
C2A0.1602 (3)0.65071 (19)0.66906 (14)0.0596 (7)
H2A0.21180.71320.69100.072*
C3A0.2164 (3)0.5761 (2)0.66958 (15)0.0636 (7)
H3A0.31350.57930.69250.076*
N2A0.1091 (2)0.49460 (15)0.63130 (12)0.0585 (5)
C4A0.1567 (2)0.46302 (16)0.56185 (13)0.0471 (6)
H4A0.14180.44540.51250.057*
C11A0.2568 (2)0.52667 (15)0.54695 (12)0.0460 (6)
C12A0.3610 (2)0.53300 (16)0.58772 (13)0.0489 (6)
H12A0.39180.49210.62500.059*
C13A0.4103 (3)0.61179 (18)0.56239 (15)0.0556 (6)
H13A0.47760.63330.58090.067*
C14A0.3413 (3)0.65219 (18)0.50479 (15)0.0605 (7)
H14A0.35550.70490.47760.073*
C15A0.2467 (3)0.60014 (17)0.49464 (13)0.0539 (6)
H15A0.18750.61200.45950.065*
C41A0.2247 (3)0.36973 (16)0.59696 (15)0.0532 (6)
C42A0.2175 (3)0.3661 (2)0.67390 (17)0.0688 (7)
H42A0.16400.42140.70600.083*
C43A0.2886 (4)0.2813 (3)0.7049 (2)0.0951 (10)
H43A0.28450.28030.75700.114*
C44A0.3645 (4)0.1992 (3)0.6580 (3)0.1152 (15)
H44A0.41110.14210.67850.138*
C45A0.3725 (4)0.2005 (2)0.5817 (3)0.1111 (14)
H45A0.42530.14450.55020.133*
C46A0.3014 (3)0.28568 (19)0.55042 (19)0.0805 (9)
H46A0.30560.28600.49830.097*
N3A0.2005 (2)0.68298 (12)0.71425 (10)0.0465 (5)
C23A0.3274 (3)0.64985 (18)0.74900 (15)0.0620 (7)
H23A0.40750.60220.71390.074*
H23B0.29980.61770.79500.074*
C24A0.3826 (4)0.7304 (2)0.76918 (19)0.0918 (10)
H24C0.46440.70410.79270.138*
H24B0.30420.77780.80410.138*
H24A0.41460.76070.72370.138*
C21A0.0612 (3)0.73064 (17)0.77058 (14)0.0570 (7)
H21A0.01380.76410.74370.068*
H21B0.07670.77920.80170.068*
C22A0.0041 (4)0.6604 (2)0.82266 (16)0.0882 (10)
H22C0.08820.69540.85680.132*
H22B0.07520.62970.85170.132*
H22A0.01080.61170.79230.132*
N4A0.0746 (2)0.81233 (14)0.59961 (11)0.0590 (6)
C33A0.0962 (3)0.89538 (18)0.63562 (17)0.0777 (9)
H33B0.09040.88520.68940.093*
H33A0.01640.95360.63180.093*
C34A0.2436 (4)0.9115 (2)0.6001 (2)0.1176 (13)
H34C0.25100.96680.62600.176*
H34A0.24940.92300.54710.176*
H34B0.32330.85490.60500.176*
C31A0.0142 (4)0.8369 (2)0.53199 (17)0.0904 (10)
H31A0.03140.77740.50210.109*
H31B0.06700.87600.50080.109*
C32A0.1491 (4)0.8917 (3)0.5507 (2)0.1224 (14)
H32A0.18170.90620.50420.184*
H32C0.16700.95130.57960.184*
H32B0.20260.85270.58010.184*
Ti1B0.81277 (4)0.24648 (3)0.88912 (2)0.04305 (14)
N1B0.9843 (2)0.11871 (13)0.87309 (11)0.0487 (5)
C1B0.9676 (3)0.03174 (15)0.89605 (13)0.0467 (6)
C2B1.1310 (3)0.09459 (18)0.83527 (15)0.0629 (7)
H2B1.17930.13740.81190.075*
C3B1.1924 (3)0.00230 (19)0.83805 (16)0.0689 (8)
H3B1.29130.03660.81710.083*
N2B1.0886 (2)0.04326 (14)0.87609 (12)0.0607 (6)
C4B0.8187 (3)0.02712 (15)0.93926 (13)0.0491 (6)
H4B0.83080.00500.98660.059*
C11B0.7182 (3)0.13064 (16)0.95992 (13)0.0486 (6)
C12B0.6083 (3)0.18375 (17)0.92398 (15)0.0557 (6)
H12B0.57260.15870.88770.067*
C13B0.5608 (3)0.28188 (18)0.95202 (16)0.0634 (7)
H13B0.49020.33300.93670.076*
C14B0.6389 (3)0.28832 (18)1.00703 (15)0.0636 (7)
H14B0.62810.34441.03550.076*
C15B0.7357 (3)0.19627 (17)1.01187 (13)0.0539 (6)
H15B0.80110.18061.04390.065*
C41B0.7533 (3)0.02936 (16)0.89457 (15)0.0541 (7)
C42B0.7662 (3)0.0204 (2)0.81773 (17)0.0704 (8)
H42B0.82090.01790.79240.084*
C43B0.6993 (3)0.0673 (3)0.7771 (2)0.0955 (11)
H43B0.70850.06000.72500.115*
C44B0.6206 (4)0.1236 (3)0.8135 (3)0.1136 (15)
H44B0.57620.15550.78630.136*
C45B0.6064 (4)0.1338 (3)0.8888 (3)0.1188 (16)
H45B0.55130.17230.91350.143*
C46B0.6733 (3)0.0873 (2)0.93018 (19)0.0878 (10)
H46B0.66390.09550.98220.105*
N3B0.7603 (2)0.27211 (13)0.79519 (11)0.0530 (5)
C23B0.6289 (3)0.2912 (2)0.76384 (18)0.0759 (8)
H23D0.55080.27630.80110.091*
H23C0.65260.24840.71850.091*
C24B0.5730 (4)0.3952 (3)0.7434 (3)0.1442 (19)
H24D0.48800.40370.72240.216*
H24E0.64960.41020.70640.216*
H24F0.54580.43780.78840.216*
C21B0.8963 (3)0.26727 (19)0.73643 (14)0.0645 (7)
H21D0.97420.26750.76170.077*
H21C0.87690.32510.70770.077*
C22B0.9510 (4)0.1775 (2)0.68094 (16)0.0978 (11)
H22E1.03550.18070.64270.147*
H22D0.87350.17550.65690.147*
H22F0.97850.12000.70840.147*
N4B0.8981 (2)0.34462 (14)0.90524 (12)0.0558 (5)
C33B0.8724 (3)0.43813 (18)0.87006 (17)0.0747 (8)
H33C0.86750.42840.81760.090*
H33D0.95630.46130.86890.090*
C34B0.7325 (4)0.5155 (2)0.9107 (2)0.1150 (13)
H34E0.72130.57400.88390.172*
H34F0.73850.52830.96190.172*
H34D0.64870.49320.91220.172*
C31B0.9688 (4)0.3404 (2)0.96917 (17)0.0833 (9)
H31C0.95540.28630.99920.100*
H31D0.91950.39961.00170.100*
C32B1.1326 (4)0.3284 (3)0.9451 (2)0.1199 (14)
H32F1.17090.32920.98970.180*
H32E1.14730.38080.91450.180*
H32D1.18350.26760.91590.180*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ti1A0.0454 (3)0.0406 (2)0.0416 (3)0.01206 (18)0.00720 (19)0.00146 (17)
N1A0.0420 (11)0.0496 (11)0.0506 (12)0.0119 (9)0.0101 (9)0.0026 (9)
C1A0.0487 (14)0.0505 (13)0.0415 (13)0.0171 (11)0.0176 (11)0.0047 (10)
C2A0.0422 (14)0.0621 (15)0.0670 (17)0.0083 (12)0.0085 (13)0.0043 (13)
C3A0.0426 (14)0.0776 (18)0.0704 (18)0.0182 (13)0.0138 (13)0.0075 (14)
N2A0.0498 (12)0.0660 (13)0.0665 (14)0.0248 (11)0.0176 (11)0.0070 (11)
C4A0.0516 (14)0.0501 (13)0.0430 (13)0.0194 (11)0.0125 (11)0.0042 (10)
C11A0.0469 (14)0.0474 (12)0.0382 (13)0.0130 (10)0.0006 (11)0.0077 (10)
C12A0.0420 (13)0.0465 (13)0.0515 (14)0.0080 (10)0.0049 (11)0.0065 (11)
C13A0.0453 (14)0.0592 (15)0.0595 (16)0.0198 (12)0.0011 (12)0.0121 (12)
C14A0.0671 (17)0.0545 (14)0.0539 (16)0.0267 (13)0.0088 (14)0.0044 (12)
C15A0.0646 (16)0.0565 (14)0.0372 (13)0.0199 (12)0.0033 (12)0.0018 (11)
C41A0.0471 (14)0.0492 (13)0.0666 (17)0.0211 (11)0.0112 (13)0.0040 (12)
C42A0.0652 (18)0.0715 (18)0.077 (2)0.0258 (14)0.0260 (16)0.0172 (15)
C43A0.087 (2)0.101 (3)0.118 (3)0.044 (2)0.046 (2)0.051 (2)
C44A0.072 (2)0.081 (2)0.195 (4)0.0247 (19)0.037 (3)0.058 (3)
C45A0.085 (2)0.0525 (18)0.171 (4)0.0120 (16)0.007 (3)0.005 (2)
C46A0.075 (2)0.0537 (16)0.102 (2)0.0226 (14)0.0057 (17)0.0054 (15)
N3A0.0484 (11)0.0438 (10)0.0453 (11)0.0094 (8)0.0137 (9)0.0033 (8)
C23A0.0622 (17)0.0611 (15)0.0630 (17)0.0129 (13)0.0236 (14)0.0030 (13)
C24A0.085 (2)0.086 (2)0.112 (3)0.0204 (17)0.047 (2)0.0270 (19)
C21A0.0548 (15)0.0602 (15)0.0503 (15)0.0094 (12)0.0124 (12)0.0075 (12)
C22A0.089 (2)0.115 (3)0.0521 (18)0.0277 (19)0.0048 (16)0.0147 (17)
N4A0.0760 (15)0.0477 (11)0.0485 (12)0.0125 (10)0.0146 (11)0.0060 (9)
C33A0.101 (2)0.0446 (14)0.082 (2)0.0215 (15)0.0128 (18)0.0002 (13)
C34A0.139 (3)0.084 (2)0.141 (3)0.060 (2)0.021 (3)0.013 (2)
C31A0.130 (3)0.0660 (18)0.0630 (19)0.0068 (19)0.0302 (19)0.0149 (15)
C32A0.143 (4)0.103 (3)0.115 (3)0.005 (3)0.079 (3)0.013 (2)
Ti1B0.0437 (3)0.0393 (2)0.0441 (3)0.00882 (17)0.01200 (19)0.00310 (17)
N1B0.0419 (11)0.0469 (11)0.0538 (12)0.0085 (8)0.0117 (9)0.0071 (9)
C1B0.0502 (14)0.0431 (12)0.0464 (14)0.0090 (10)0.0184 (11)0.0032 (10)
C2B0.0444 (15)0.0608 (16)0.0779 (19)0.0136 (12)0.0070 (13)0.0055 (13)
C3B0.0422 (15)0.0627 (17)0.090 (2)0.0036 (13)0.0095 (14)0.0086 (15)
N2B0.0523 (13)0.0469 (11)0.0760 (15)0.0037 (10)0.0174 (11)0.0007 (10)
C4B0.0570 (15)0.0442 (12)0.0439 (13)0.0136 (11)0.0110 (11)0.0102 (10)
C11B0.0481 (14)0.0476 (13)0.0433 (13)0.0123 (11)0.0009 (11)0.0053 (11)
C12B0.0465 (14)0.0553 (14)0.0628 (17)0.0146 (12)0.0096 (13)0.0046 (12)
C13B0.0468 (15)0.0582 (15)0.0726 (19)0.0048 (12)0.0050 (14)0.0030 (13)
C14B0.0649 (17)0.0538 (15)0.0587 (17)0.0130 (13)0.0055 (14)0.0069 (12)
C15B0.0592 (16)0.0553 (14)0.0402 (14)0.0128 (12)0.0050 (12)0.0025 (11)
C41B0.0458 (14)0.0463 (13)0.0644 (17)0.0166 (11)0.0024 (12)0.0040 (12)
C42B0.0697 (19)0.0771 (18)0.072 (2)0.0347 (15)0.0140 (15)0.0034 (15)
C43B0.074 (2)0.116 (3)0.098 (3)0.034 (2)0.0147 (19)0.039 (2)
C44B0.0510 (19)0.113 (3)0.166 (4)0.0312 (18)0.008 (2)0.078 (3)
C45B0.084 (3)0.093 (2)0.168 (4)0.059 (2)0.038 (3)0.044 (3)
C46B0.088 (2)0.0731 (19)0.091 (2)0.0409 (17)0.0234 (18)0.0128 (16)
N3B0.0581 (13)0.0515 (11)0.0572 (13)0.0183 (10)0.0278 (11)0.0144 (9)
C23B0.085 (2)0.0792 (19)0.085 (2)0.0335 (16)0.0542 (18)0.0285 (16)
C24B0.130 (3)0.114 (3)0.240 (5)0.049 (3)0.135 (4)0.100 (3)
C21B0.0800 (19)0.0663 (16)0.0542 (16)0.0276 (14)0.0239 (14)0.0182 (13)
C22B0.125 (3)0.112 (3)0.0551 (19)0.046 (2)0.0056 (19)0.0161 (17)
N4B0.0618 (13)0.0561 (12)0.0551 (13)0.0234 (10)0.0179 (11)0.0008 (10)
C33B0.086 (2)0.0543 (16)0.085 (2)0.0277 (15)0.0142 (17)0.0001 (14)
C34B0.115 (3)0.0562 (19)0.154 (4)0.0103 (18)0.013 (3)0.012 (2)
C31B0.098 (2)0.101 (2)0.069 (2)0.0491 (19)0.0301 (18)0.0025 (17)
C32B0.101 (3)0.173 (4)0.120 (3)0.073 (3)0.053 (2)0.006 (3)
Geometric parameters (Å, º) top
Ti1A—N3A1.8857 (19)Ti1B—N3B1.876 (2)
Ti1A—N4A1.905 (2)Ti1B—N4B1.906 (2)
Ti1A—N1A2.0655 (19)Ti1B—N1B2.0485 (18)
Ti1A—C14A2.341 (2)Ti1B—C14B2.350 (2)
Ti1A—C13A2.346 (2)Ti1B—C15B2.351 (2)
Ti1A—C15A2.358 (2)Ti1B—C13B2.359 (2)
Ti1A—C11A2.371 (2)Ti1B—C11B2.378 (2)
Ti1A—C12A2.385 (2)Ti1B—C12B2.392 (2)
N1A—C1A1.367 (3)N1B—C1B1.365 (3)
N1A—C2A1.377 (3)N1B—C2B1.375 (3)
C1A—N2A1.316 (3)C1B—N2B1.316 (3)
C1A—C4A1.507 (3)C1B—C4B1.505 (3)
C2A—C3A1.351 (3)C2B—C3B1.351 (3)
C2A—H2A0.9300C2B—H2B0.9300
C3A—N2A1.377 (3)C3B—N2B1.374 (3)
C3A—H3A0.9300C3B—H3B0.9300
C4A—C41A1.511 (3)C4B—C41B1.513 (3)
C4A—C11A1.517 (3)C4B—C11B1.514 (3)
C4A—H4A0.9800C4B—H4B0.9800
C11A—C12A1.405 (3)C11B—C12B1.398 (3)
C11A—C15A1.408 (3)C11B—C15B1.413 (3)
C12A—C13A1.401 (3)C12B—C13B1.412 (3)
C12A—H12A0.9300C12B—H12B0.9300
C13A—C14A1.390 (4)C13B—C14B1.399 (4)
C13A—H13A0.9300C13B—H13B0.9300
C14A—C15A1.398 (3)C14B—C15B1.392 (3)
C14A—H14A0.9300C14B—H14B0.9300
C15A—H15A0.9300C15B—H15B0.9300
C41A—C42A1.372 (4)C41B—C42B1.369 (4)
C41A—C46A1.387 (3)C41B—C46B1.372 (3)
C42A—C43A1.391 (4)C42B—C43B1.385 (4)
C42A—H42A0.9300C42B—H42B0.9300
C43A—C44A1.368 (5)C43B—C44B1.352 (5)
C43A—H43A0.9300C43B—H43B0.9300
C44A—C45A1.358 (5)C44B—C45B1.343 (5)
C44A—H44A0.9300C44B—H44B0.9300
C45A—C46A1.398 (5)C45B—C46B1.390 (5)
C45A—H45A0.9300C45B—H45B0.9300
C46A—H46A0.9300C46B—H46B0.9300
N3A—C23A1.460 (3)N3B—C23B1.464 (3)
N3A—C21A1.472 (3)N3B—C21B1.481 (3)
C23A—C24A1.504 (4)C23B—C24B1.507 (4)
C23A—H23A0.9700C23B—H23D0.9700
C23A—H23B0.9700C23B—H23C0.9700
C24A—H24C0.9600C24B—H24D0.9600
C24A—H24B0.9600C24B—H24E0.9600
C24A—H24A0.9600C24B—H24F0.9600
C21A—C22A1.521 (4)C21B—C22B1.527 (4)
C21A—H21A0.9700C21B—H21D0.9700
C21A—H21B0.9700C21B—H21C0.9700
C22A—H22C0.9600C22B—H22E0.9600
C22A—H22B0.9600C22B—H22D0.9600
C22A—H22A0.9600C22B—H22F0.9600
N4A—C31A1.463 (3)N4B—C31B1.461 (3)
N4A—C33A1.464 (3)N4B—C33B1.463 (3)
C33A—C34A1.521 (4)C33B—C34B1.510 (4)
C33A—H33B0.9700C33B—H33C0.9700
C33A—H33A0.9700C33B—H33D0.9700
C34A—H34C0.9600C34B—H34E0.9600
C34A—H34A0.9600C34B—H34F0.9600
C34A—H34B0.9600C34B—H34D0.9600
C31A—C32A1.505 (5)C31B—C32B1.512 (4)
C31A—H31A0.9700C31B—H31C0.9700
C31A—H31B0.9700C31B—H31D0.9700
C32A—H32A0.9600C32B—H32F0.9600
C32A—H32C0.9600C32B—H32E0.9600
C32A—H32B0.9600C32B—H32D0.9600
N3A—Ti1A—N4A103.96 (8)N3B—Ti1B—N4B104.47 (9)
N3A—Ti1A—N1A107.24 (8)N3B—Ti1B—N1B107.31 (8)
N4A—Ti1A—N1A106.57 (9)N4B—Ti1B—N1B105.11 (8)
N3A—Ti1A—C14A121.40 (9)N3B—Ti1B—C14B122.80 (10)
N4A—Ti1A—C14A92.10 (9)N4B—Ti1B—C14B92.47 (9)
N1A—Ti1A—C14A121.46 (8)N1B—Ti1B—C14B120.31 (9)
N3A—Ti1A—C13A89.43 (9)N3B—Ti1B—C15B143.41 (9)
N4A—Ti1A—C13A114.31 (9)N4B—Ti1B—C15B104.58 (9)
N1A—Ti1A—C13A130.34 (8)N1B—Ti1B—C15B85.92 (8)
C14A—Ti1A—C13A34.49 (9)C14B—Ti1B—C15B34.44 (8)
N3A—Ti1A—C15A143.35 (9)N3B—Ti1B—C13B90.36 (10)
N4A—Ti1A—C15A103.97 (9)N4B—Ti1B—C13B114.34 (9)
N1A—Ti1A—C15A86.84 (8)N1B—Ti1B—C13B130.91 (8)
C14A—Ti1A—C15A34.62 (8)C14B—Ti1B—C13B34.55 (9)
C13A—Ti1A—C15A57.43 (9)C15B—Ti1B—C13B57.36 (10)
N3A—Ti1A—C11A116.29 (8)N3B—Ti1B—C11B115.31 (9)
N4A—Ti1A—C11A138.05 (9)N4B—Ti1B—C11B138.82 (9)
N1A—Ti1A—C11A73.33 (7)N1B—Ti1B—C11B73.63 (8)
C14A—Ti1A—C11A57.62 (8)C14B—Ti1B—C11B57.60 (8)
C13A—Ti1A—C11A57.56 (8)C15B—Ti1B—C11B34.78 (8)
C15A—Ti1A—C11A34.65 (8)C13B—Ti1B—C11B57.53 (8)
N3A—Ti1A—C12A86.97 (8)N3B—Ti1B—C12B86.89 (9)
N4A—Ti1A—C12A147.81 (9)N4B—Ti1B—C12B148.03 (9)
N1A—Ti1A—C12A98.57 (7)N1B—Ti1B—C12B99.57 (8)
C14A—Ti1A—C12A57.14 (9)C14B—Ti1B—C12B57.13 (9)
C13A—Ti1A—C12A34.45 (8)C15B—Ti1B—C12B56.93 (9)
C15A—Ti1A—C12A57.09 (9)C13B—Ti1B—C12B34.56 (8)
C11A—Ti1A—C12A34.35 (8)C11B—Ti1B—C12B34.08 (8)
C1A—N1A—C2A103.30 (18)C1B—N1B—C2B103.65 (18)
C1A—N1A—Ti1A123.42 (14)C1B—N1B—Ti1B123.51 (15)
C2A—N1A—Ti1A132.59 (15)C2B—N1B—Ti1B132.66 (16)
N2A—C1A—N1A114.6 (2)N2B—C1B—N1B114.6 (2)
N2A—C1A—C4A125.6 (2)N2B—C1B—C4B125.3 (2)
N1A—C1A—C4A119.77 (19)N1B—C1B—C4B120.08 (19)
C3A—C2A—N1A108.3 (2)C3B—C2B—N1B107.8 (2)
C3A—C2A—H2A125.8C3B—C2B—H2B126.1
N1A—C2A—H2A125.8N1B—C2B—H2B126.1
C2A—C3A—N2A110.2 (2)C2B—C3B—N2B110.7 (2)
C2A—C3A—H3A124.9C2B—C3B—H3B124.7
N2A—C3A—H3A124.9N2B—C3B—H3B124.7
C1A—N2A—C3A103.6 (2)C1B—N2B—C3B103.3 (2)
C1A—C4A—C41A113.66 (19)C1B—C4B—C41B112.62 (18)
C1A—C4A—C11A107.73 (17)C1B—C4B—C11B107.49 (18)
C41A—C4A—C11A112.37 (19)C41B—C4B—C11B111.5 (2)
C1A—C4A—H4A107.6C1B—C4B—H4B108.4
C41A—C4A—H4A107.6C41B—C4B—H4B108.4
C11A—C4A—H4A107.6C11B—C4B—H4B108.4
C12A—C11A—C15A107.4 (2)C12B—C11B—C15B107.1 (2)
C12A—C11A—C4A127.6 (2)C12B—C11B—C4B127.3 (2)
C15A—C11A—C4A124.6 (2)C15B—C11B—C4B124.9 (2)
C12A—C11A—Ti1A73.39 (12)C12B—C11B—Ti1B73.51 (13)
C15A—C11A—Ti1A72.17 (12)C15B—C11B—Ti1B71.58 (13)
C4A—C11A—Ti1A113.95 (13)C4B—C11B—Ti1B112.84 (14)
C13A—C12A—C11A108.1 (2)C11B—C12B—C13B108.5 (2)
C13A—C12A—Ti1A71.24 (13)C11B—C12B—Ti1B72.41 (14)
C11A—C12A—Ti1A72.26 (12)C13B—C12B—Ti1B71.46 (14)
C13A—C12A—H12A126.0C11B—C12B—H12B125.8
C11A—C12A—H12A126.0C13B—C12B—H12B125.8
Ti1A—C12A—H12A122.2Ti1B—C12B—H12B122.0
C14A—C13A—C12A108.2 (2)C14B—C13B—C12B107.6 (2)
C14A—C13A—Ti1A72.55 (14)C14B—C13B—Ti1B72.36 (14)
C12A—C13A—Ti1A74.31 (13)C12B—C13B—Ti1B73.98 (14)
C14A—C13A—H13A125.9C14B—C13B—H13B126.2
C12A—C13A—H13A125.9C12B—C13B—H13B126.2
Ti1A—C13A—H13A119.1Ti1B—C13B—H13B119.4
C13A—C14A—C15A108.3 (2)C15B—C14B—C13B108.2 (2)
C13A—C14A—Ti1A72.95 (14)C15B—C14B—Ti1B72.81 (13)
C15A—C14A—Ti1A73.35 (13)C13B—C14B—Ti1B73.09 (14)
C13A—C14A—H14A125.8C15B—C14B—H14B125.9
C15A—C14A—H14A125.8C13B—C14B—H14B125.9
Ti1A—C14A—H14A119.7Ti1B—C14B—H14B120.0
C14A—C15A—C11A108.0 (2)C14B—C15B—C11B108.6 (2)
C14A—C15A—Ti1A72.03 (13)C14B—C15B—Ti1B72.75 (14)
C11A—C15A—Ti1A73.18 (12)C11B—C15B—Ti1B73.65 (13)
C14A—C15A—H15A126.0C14B—C15B—H15B125.7
C11A—C15A—H15A126.0C11B—C15B—H15B125.7
Ti1A—C15A—H15A120.6Ti1B—C15B—H15B119.7
C42A—C41A—C46A118.5 (3)C42B—C41B—C46B118.0 (3)
C42A—C41A—C4A121.9 (2)C42B—C41B—C4B120.7 (2)
C46A—C41A—C4A119.6 (3)C46B—C41B—C4B121.2 (3)
C41A—C42A—C43A121.3 (3)C41B—C42B—C43B121.2 (3)
C41A—C42A—H42A119.3C41B—C42B—H42B119.4
C43A—C42A—H42A119.3C43B—C42B—H42B119.4
C44A—C43A—C42A119.4 (4)C44B—C43B—C42B119.7 (4)
C44A—C43A—H43A120.3C44B—C43B—H43B120.2
C42A—C43A—H43A120.3C42B—C43B—H43B120.2
C45A—C44A—C43A120.6 (4)C45B—C44B—C43B120.3 (3)
C45A—C44A—H44A119.7C45B—C44B—H44B119.8
C43A—C44A—H44A119.7C43B—C44B—H44B119.8
C44A—C45A—C46A120.1 (4)C44B—C45B—C46B120.5 (3)
C44A—C45A—H45A119.9C44B—C45B—H45B119.8
C46A—C45A—H45A119.9C46B—C45B—H45B119.8
C41A—C46A—C45A120.1 (3)C41B—C46B—C45B120.3 (3)
C41A—C46A—H46A119.9C41B—C46B—H46B119.9
C45A—C46A—H46A119.9C45B—C46B—H46B119.9
C23A—N3A—C21A112.53 (19)C23B—N3B—C21B113.0 (2)
C23A—N3A—Ti1A139.26 (16)C23B—N3B—Ti1B138.91 (18)
C21A—N3A—Ti1A108.13 (15)C21B—N3B—Ti1B108.05 (15)
N3A—C23A—C24A113.7 (2)N3B—C23B—C24B112.6 (2)
N3A—C23A—H23A108.8N3B—C23B—H23D109.1
C24A—C23A—H23A108.8C24B—C23B—H23D109.1
N3A—C23A—H23B108.8N3B—C23B—H23C109.1
C24A—C23A—H23B108.8C24B—C23B—H23C109.1
H23A—C23A—H23B107.7H23D—C23B—H23C107.8
C23A—C24A—H24C109.5C23B—C24B—H24D109.5
C23A—C24A—H24B109.5C23B—C24B—H24E109.5
H24C—C24A—H24B109.5H24D—C24B—H24E109.5
C23A—C24A—H24A109.5C23B—C24B—H24F109.5
H24C—C24A—H24A109.5H24D—C24B—H24F109.5
H24B—C24A—H24A109.5H24E—C24B—H24F109.5
N3A—C21A—C22A113.5 (2)N3B—C21B—C22B113.6 (2)
N3A—C21A—H21A108.9N3B—C21B—H21D108.8
C22A—C21A—H21A108.9C22B—C21B—H21D108.8
N3A—C21A—H21B108.9N3B—C21B—H21C108.8
C22A—C21A—H21B108.9C22B—C21B—H21C108.8
H21A—C21A—H21B107.7H21D—C21B—H21C107.7
C21A—C22A—H22C109.5C21B—C22B—H22E109.5
C21A—C22A—H22B109.5C21B—C22B—H22D109.5
H22C—C22A—H22B109.5H22E—C22B—H22D109.5
C21A—C22A—H22A109.5C21B—C22B—H22F109.5
H22C—C22A—H22A109.5H22E—C22B—H22F109.5
H22B—C22A—H22A109.5H22D—C22B—H22F109.5
C31A—N4A—C33A113.0 (2)C31B—N4B—C33B113.1 (2)
C31A—N4A—Ti1A119.10 (17)C31B—N4B—Ti1B119.78 (17)
C33A—N4A—Ti1A126.21 (19)C33B—N4B—Ti1B125.64 (18)
N4A—C33A—C34A113.4 (2)N4B—C33B—C34B114.0 (2)
N4A—C33A—H33B108.9N4B—C33B—H33C108.8
C34A—C33A—H33B108.9C34B—C33B—H33C108.8
N4A—C33A—H33A108.9N4B—C33B—H33D108.8
C34A—C33A—H33A108.9C34B—C33B—H33D108.8
H33B—C33A—H33A107.7H33C—C33B—H33D107.7
C33A—C34A—H34C109.5C33B—C34B—H34E109.5
C33A—C34A—H34A109.5C33B—C34B—H34F109.5
H34C—C34A—H34A109.5H34E—C34B—H34F109.5
C33A—C34A—H34B109.5C33B—C34B—H34D109.5
H34C—C34A—H34B109.5H34E—C34B—H34D109.5
H34A—C34A—H34B109.5H34F—C34B—H34D109.5
N4A—C31A—C32A113.5 (3)N4B—C31B—C32B113.8 (3)
N4A—C31A—H31A108.9N4B—C31B—H31C108.8
C32A—C31A—H31A108.9C32B—C31B—H31C108.8
N4A—C31A—H31B108.9N4B—C31B—H31D108.8
C32A—C31A—H31B108.9C32B—C31B—H31D108.8
H31A—C31A—H31B107.7H31C—C31B—H31D107.7
C31A—C32A—H32A109.5C31B—C32B—H32F109.5
C31A—C32A—H32C109.5C31B—C32B—H32E109.5
H32A—C32A—H32C109.5H32F—C32B—H32E109.5
C31A—C32A—H32B109.5C31B—C32B—H32D109.5
H32A—C32A—H32B109.5H32F—C32B—H32D109.5
H32C—C32A—H32B109.5H32E—C32B—H32D109.5
N3A—Ti1A—N1A—C1A101.01 (18)N3B—Ti1B—N1B—C1B102.55 (19)
N4A—Ti1A—N1A—C1A148.14 (17)N4B—Ti1B—N1B—C1B146.64 (18)
C14A—Ti1A—N1A—C1A45.0 (2)C14B—Ti1B—N1B—C1B44.5 (2)
C13A—Ti1A—N1A—C1A3.4 (2)C15B—Ti1B—N1B—C1B42.63 (19)
C15A—Ti1A—N1A—C1A44.50 (18)C13B—Ti1B—N1B—C1B3.6 (2)
C11A—Ti1A—N1A—C1A12.01 (17)C11B—Ti1B—N1B—C1B9.48 (18)
C12A—Ti1A—N1A—C1A11.54 (19)C12B—Ti1B—N1B—C1B12.85 (19)
N3A—Ti1A—N1A—C2A67.8 (2)N3B—Ti1B—N1B—C2B71.8 (2)
N4A—Ti1A—N1A—C2A43.0 (2)N4B—Ti1B—N1B—C2B39.0 (2)
C14A—Ti1A—N1A—C2A146.1 (2)C14B—Ti1B—N1B—C2B141.1 (2)
C13A—Ti1A—N1A—C2A172.3 (2)C15B—Ti1B—N1B—C2B143.0 (2)
C15A—Ti1A—N1A—C2A146.7 (2)C13B—Ti1B—N1B—C2B178.0 (2)
C11A—Ti1A—N1A—C2A179.1 (2)C11B—Ti1B—N1B—C2B176.2 (2)
C12A—Ti1A—N1A—C2A157.3 (2)C12B—Ti1B—N1B—C2B161.5 (2)
C2A—N1A—C1A—N2A0.6 (3)C2B—N1B—C1B—N2B0.2 (3)
Ti1A—N1A—C1A—N2A170.94 (16)Ti1B—N1B—C1B—N2B175.57 (16)
C2A—N1A—C1A—C4A177.4 (2)C2B—N1B—C1B—C4B179.1 (2)
Ti1A—N1A—C1A—C4A11.1 (3)Ti1B—N1B—C1B—C4B3.4 (3)
C1A—N1A—C2A—C3A0.7 (3)C1B—N1B—C2B—C3B0.4 (3)
Ti1A—N1A—C2A—C3A169.80 (18)Ti1B—N1B—C2B—C3B175.59 (18)
N1A—C2A—C3A—N2A0.5 (3)N1B—C2B—C3B—N2B0.9 (3)
N1A—C1A—N2A—C3A0.4 (3)N1B—C1B—N2B—C3B0.7 (3)
C4A—C1A—N2A—C3A177.5 (2)C4B—C1B—N2B—C3B179.5 (2)
C2A—C3A—N2A—C1A0.1 (3)C2B—C3B—N2B—C1B0.9 (3)
N2A—C1A—C4A—C41A57.3 (3)N2B—C1B—C4B—C41B65.0 (3)
N1A—C1A—C4A—C41A124.9 (2)N1B—C1B—C4B—C41B113.8 (2)
N2A—C1A—C4A—C11A177.5 (2)N2B—C1B—C4B—C11B171.8 (2)
N1A—C1A—C4A—C11A0.3 (3)N1B—C1B—C4B—C11B9.4 (3)
C1A—C4A—C11A—C12A96.2 (2)C1B—C4B—C11B—C12B101.8 (3)
C41A—C4A—C11A—C12A29.8 (3)C41B—C4B—C11B—C12B22.0 (3)
C1A—C4A—C11A—C15A75.0 (3)C1B—C4B—C11B—C15B67.3 (3)
C41A—C4A—C11A—C15A159.0 (2)C41B—C4B—C11B—C15B168.9 (2)
C1A—C4A—C11A—Ti1A9.2 (2)C1B—C4B—C11B—Ti1B15.6 (2)
C41A—C4A—C11A—Ti1A116.75 (18)C41B—C4B—C11B—Ti1B108.26 (19)
N3A—Ti1A—C11A—C12A34.19 (15)N3B—Ti1B—C11B—C12B36.25 (16)
N4A—Ti1A—C11A—C12A128.00 (16)N4B—Ti1B—C11B—C12B127.56 (16)
N1A—Ti1A—C11A—C12A135.56 (14)N1B—Ti1B—C11B—C12B138.03 (15)
C14A—Ti1A—C11A—C12A77.83 (15)C14B—Ti1B—C11B—C12B77.93 (16)
C13A—Ti1A—C11A—C12A36.71 (14)C15B—Ti1B—C11B—C12B114.9 (2)
C15A—Ti1A—C11A—C12A115.0 (2)C13B—Ti1B—C11B—C12B36.73 (15)
N3A—Ti1A—C11A—C15A149.23 (15)N3B—Ti1B—C11B—C15B151.17 (14)
N4A—Ti1A—C11A—C15A13.0 (2)N4B—Ti1B—C11B—C15B12.6 (2)
N1A—Ti1A—C11A—C15A109.40 (16)N1B—Ti1B—C11B—C15B107.04 (15)
C14A—Ti1A—C11A—C15A37.21 (15)C14B—Ti1B—C11B—C15B36.99 (15)
C13A—Ti1A—C11A—C15A78.33 (16)C13B—Ti1B—C11B—C15B78.19 (16)
C12A—Ti1A—C11A—C15A115.0 (2)C12B—Ti1B—C11B—C15B114.9 (2)
N3A—Ti1A—C11A—C4A90.16 (18)N3B—Ti1B—C11B—C4B87.93 (19)
N4A—Ti1A—C11A—C4A107.65 (18)N4B—Ti1B—C11B—C4B108.25 (18)
N1A—Ti1A—C11A—C4A11.21 (16)N1B—Ti1B—C11B—C4B13.85 (16)
C14A—Ti1A—C11A—C4A157.8 (2)C14B—Ti1B—C11B—C4B157.9 (2)
C13A—Ti1A—C11A—C4A161.1 (2)C15B—Ti1B—C11B—C4B120.9 (2)
C15A—Ti1A—C11A—C4A120.6 (2)C13B—Ti1B—C11B—C4B160.9 (2)
C12A—Ti1A—C11A—C4A124.3 (2)C12B—Ti1B—C11B—C4B124.2 (2)
C15A—C11A—C12A—C13A2.0 (2)C15B—C11B—C12B—C13B1.4 (3)
C4A—C11A—C12A—C13A170.4 (2)C4B—C11B—C12B—C13B169.2 (2)
Ti1A—C11A—C12A—C13A62.65 (15)Ti1B—C11B—C12B—C13B62.76 (17)
C15A—C11A—C12A—Ti1A64.65 (15)C15B—C11B—C12B—Ti1B64.17 (15)
C4A—C11A—C12A—Ti1A107.8 (2)C4B—C11B—C12B—Ti1B106.5 (2)
N3A—Ti1A—C12A—C13A93.41 (16)N3B—Ti1B—C12B—C11B147.63 (15)
N4A—Ti1A—C12A—C13A18.3 (3)N4B—Ti1B—C12B—C11B99.7 (2)
N1A—Ti1A—C12A—C13A159.61 (15)N1B—Ti1B—C12B—C11B40.59 (15)
C14A—Ti1A—C12A—C13A37.54 (15)C14B—Ti1B—C12B—C11B79.44 (16)
C15A—Ti1A—C12A—C13A79.04 (16)C15B—Ti1B—C12B—C11B38.12 (13)
C11A—Ti1A—C12A—C13A116.9 (2)C13B—Ti1B—C12B—C11B117.2 (2)
N3A—Ti1A—C12A—C11A149.70 (14)N3B—Ti1B—C12B—C13B95.17 (17)
N4A—Ti1A—C12A—C11A98.62 (19)N4B—Ti1B—C12B—C13B17.5 (3)
N1A—Ti1A—C12A—C11A42.71 (14)N1B—Ti1B—C12B—C13B157.79 (16)
C14A—Ti1A—C12A—C11A79.35 (15)C14B—Ti1B—C12B—C13B37.76 (15)
C13A—Ti1A—C12A—C11A116.9 (2)C15B—Ti1B—C12B—C13B79.09 (17)
C15A—Ti1A—C12A—C11A37.85 (13)C11B—Ti1B—C12B—C13B117.2 (2)
C11A—C12A—C13A—C14A1.9 (2)C11B—C12B—C13B—C14B1.7 (3)
Ti1A—C12A—C13A—C14A65.17 (16)Ti1B—C12B—C13B—C14B65.05 (17)
C11A—C12A—C13A—Ti1A63.31 (15)C11B—C12B—C13B—Ti1B63.37 (17)
N3A—Ti1A—C13A—C14A159.19 (15)N3B—Ti1B—C13B—C14B161.10 (15)
N4A—Ti1A—C13A—C14A54.11 (17)N4B—Ti1B—C13B—C14B55.01 (17)
N1A—Ti1A—C13A—C14A88.46 (17)N1B—Ti1B—C13B—C14B85.37 (17)
C15A—Ti1A—C13A—C14A37.38 (14)C15B—Ti1B—C13B—C14B37.18 (14)
C11A—Ti1A—C13A—C14A78.73 (15)C11B—Ti1B—C13B—C14B78.71 (16)
C12A—Ti1A—C13A—C14A115.3 (2)C12B—Ti1B—C13B—C14B114.9 (2)
N3A—Ti1A—C13A—C12A85.48 (15)N3B—Ti1B—C13B—C12B83.98 (17)
N4A—Ti1A—C13A—C12A169.44 (15)N4B—Ti1B—C13B—C12B169.93 (16)
N1A—Ti1A—C13A—C12A26.9 (2)N1B—Ti1B—C13B—C12B29.5 (2)
C14A—Ti1A—C13A—C12A115.3 (2)C14B—Ti1B—C13B—C12B114.9 (2)
C15A—Ti1A—C13A—C12A77.96 (15)C15B—Ti1B—C13B—C12B77.73 (17)
C11A—Ti1A—C13A—C12A36.61 (14)C11B—Ti1B—C13B—C12B36.20 (15)
C12A—C13A—C14A—C15A1.0 (3)C12B—C13B—C14B—C15B1.3 (3)
Ti1A—C13A—C14A—C15A65.34 (16)Ti1B—C13B—C14B—C15B64.84 (17)
C12A—C13A—C14A—Ti1A66.33 (15)C12B—C13B—C14B—Ti1B66.13 (17)
N3A—Ti1A—C14A—C13A24.60 (17)N3B—Ti1B—C14B—C15B138.52 (16)
N4A—Ti1A—C14A—C13A132.37 (15)N4B—Ti1B—C14B—C15B112.49 (17)
N1A—Ti1A—C14A—C13A116.71 (15)N1B—Ti1B—C14B—C15B3.4 (2)
C15A—Ti1A—C14A—C13A115.8 (2)C13B—Ti1B—C14B—C15B115.9 (2)
C11A—Ti1A—C14A—C13A78.54 (16)C11B—Ti1B—C14B—C15B37.36 (15)
C12A—Ti1A—C14A—C13A37.49 (14)C12B—Ti1B—C14B—C15B78.08 (17)
N3A—Ti1A—C14A—C15A140.38 (15)N3B—Ti1B—C14B—C13B22.66 (18)
N4A—Ti1A—C14A—C15A111.85 (17)N4B—Ti1B—C14B—C13B131.65 (16)
N1A—Ti1A—C14A—C15A0.9 (2)N1B—Ti1B—C14B—C13B119.24 (15)
C13A—Ti1A—C14A—C15A115.8 (2)C15B—Ti1B—C14B—C13B115.9 (2)
C11A—Ti1A—C14A—C15A37.24 (15)C11B—Ti1B—C14B—C13B78.49 (16)
C12A—Ti1A—C14A—C15A78.29 (16)C12B—Ti1B—C14B—C13B37.77 (15)
C13A—C14A—C15A—C11A0.3 (3)C13B—C14B—C15B—C11B0.4 (3)
Ti1A—C14A—C15A—C11A64.82 (15)Ti1B—C14B—C15B—C11B65.44 (16)
C13A—C14A—C15A—Ti1A65.08 (16)C13B—C14B—C15B—Ti1B65.01 (17)
C12A—C11A—C15A—C14A1.4 (2)C12B—C11B—C15B—C14B0.6 (3)
C4A—C11A—C15A—C14A171.30 (19)C4B—C11B—C15B—C14B170.3 (2)
Ti1A—C11A—C15A—C14A64.07 (15)Ti1B—C11B—C15B—C14B64.86 (17)
C12A—C11A—C15A—Ti1A65.46 (14)C12B—C11B—C15B—Ti1B65.47 (16)
C4A—C11A—C15A—Ti1A107.23 (19)C4B—C11B—C15B—Ti1B105.5 (2)
N3A—Ti1A—C15A—C14A65.8 (2)N3B—Ti1B—C15B—C14B69.1 (2)
N4A—Ti1A—C15A—C14A72.91 (18)N4B—Ti1B—C15B—C14B72.51 (18)
N1A—Ti1A—C15A—C14A179.21 (17)N1B—Ti1B—C15B—C14B177.07 (17)
C13A—Ti1A—C15A—C14A37.24 (15)C13B—Ti1B—C15B—C14B37.31 (15)
C11A—Ti1A—C15A—C14A116.0 (2)C11B—Ti1B—C15B—C14B116.1 (2)
C12A—Ti1A—C15A—C14A78.46 (17)C12B—Ti1B—C15B—C14B78.73 (17)
N3A—Ti1A—C15A—C11A50.2 (2)N3B—Ti1B—C15B—C11B47.0 (2)
N4A—Ti1A—C15A—C11A171.11 (14)N4B—Ti1B—C15B—C11B171.44 (14)
N1A—Ti1A—C15A—C11A64.81 (15)N1B—Ti1B—C15B—C11B66.88 (14)
C14A—Ti1A—C15A—C11A116.0 (2)C14B—Ti1B—C15B—C11B116.1 (2)
C13A—Ti1A—C15A—C11A78.74 (16)C13B—Ti1B—C15B—C11B78.74 (16)
C12A—Ti1A—C15A—C11A37.52 (13)C12B—Ti1B—C15B—C11B37.33 (13)
C1A—C4A—C41A—C42A40.3 (3)C1B—C4B—C41B—C42B39.8 (3)
C11A—C4A—C41A—C42A82.4 (3)C11B—C4B—C41B—C42B81.1 (3)
C1A—C4A—C41A—C46A142.0 (2)C1B—C4B—C41B—C46B143.3 (2)
C11A—C4A—C41A—C46A95.3 (3)C11B—C4B—C41B—C46B95.7 (3)
C46A—C41A—C42A—C43A1.8 (4)C46B—C41B—C42B—C43B0.8 (4)
C4A—C41A—C42A—C43A175.9 (2)C4B—C41B—C42B—C43B176.2 (2)
C41A—C42A—C43A—C44A1.4 (5)C41B—C42B—C43B—C44B0.5 (5)
C42A—C43A—C44A—C45A0.9 (6)C42B—C43B—C44B—C45B0.4 (5)
C43A—C44A—C45A—C46A0.7 (6)C43B—C44B—C45B—C46B0.6 (6)
C42A—C41A—C46A—C45A1.7 (4)C42B—C41B—C46B—C45B1.0 (4)
C4A—C41A—C46A—C45A176.1 (3)C4B—C41B—C46B—C45B176.0 (3)
C44A—C45A—C46A—C41A1.2 (5)C44B—C45B—C46B—C41B0.9 (5)
N4A—Ti1A—N3A—C23A122.6 (2)N4B—Ti1B—N3B—C23B124.2 (2)
N1A—Ti1A—N3A—C23A124.8 (2)N1B—Ti1B—N3B—C23B124.6 (2)
C14A—Ti1A—N3A—C23A21.3 (3)C14B—Ti1B—N3B—C23B21.5 (3)
C13A—Ti1A—N3A—C23A7.6 (2)C15B—Ti1B—N3B—C23B17.4 (3)
C15A—Ti1A—N3A—C23A16.1 (3)C13B—Ti1B—N3B—C23B8.9 (3)
C11A—Ti1A—N3A—C23A45.3 (3)C11B—Ti1B—N3B—C23B44.9 (3)
C12A—Ti1A—N3A—C23A26.8 (2)C12B—Ti1B—N3B—C23B25.5 (2)
N4A—Ti1A—N3A—C21A60.96 (16)N4B—Ti1B—N3B—C21B58.86 (16)
N1A—Ti1A—N3A—C21A51.68 (15)N1B—Ti1B—N3B—C21B52.39 (16)
C14A—Ti1A—N3A—C21A162.26 (14)C14B—Ti1B—N3B—C21B161.52 (14)
C13A—Ti1A—N3A—C21A175.90 (15)C15B—Ti1B—N3B—C21B159.54 (14)
C15A—Ti1A—N3A—C21A160.37 (14)C13B—Ti1B—N3B—C21B174.15 (15)
C11A—Ti1A—N3A—C21A131.21 (14)C11B—Ti1B—N3B—C21B132.07 (14)
C12A—Ti1A—N3A—C21A149.72 (15)C12B—Ti1B—N3B—C21B151.45 (15)
C21A—N3A—C23A—C24A76.5 (3)C21B—N3B—C23B—C24B74.0 (3)
Ti1A—N3A—C23A—C24A107.2 (3)Ti1B—N3B—C23B—C24B109.1 (3)
C23A—N3A—C21A—C22A71.7 (3)C23B—N3B—C21B—C22B69.7 (3)
Ti1A—N3A—C21A—C22A105.9 (2)Ti1B—N3B—C21B—C22B108.1 (2)
N3A—Ti1A—N4A—C31A174.3 (2)N3B—Ti1B—N4B—C31B172.52 (19)
N1A—Ti1A—N4A—C31A61.2 (2)N1B—Ti1B—N4B—C31B59.7 (2)
C14A—Ti1A—N4A—C31A62.5 (2)C14B—Ti1B—N4B—C31B62.6 (2)
C13A—Ti1A—N4A—C31A89.9 (2)C15B—Ti1B—N4B—C31B30.0 (2)
C15A—Ti1A—N4A—C31A29.6 (2)C13B—Ti1B—N4B—C31B90.4 (2)
C11A—Ti1A—N4A—C31A22.1 (3)C11B—Ti1B—N4B—C31B22.6 (2)
C12A—Ti1A—N4A—C31A78.6 (3)C12B—Ti1B—N4B—C31B79.6 (3)
N3A—Ti1A—N4A—C33A21.5 (2)N3B—Ti1B—N4B—C33B22.1 (2)
N1A—Ti1A—N4A—C33A134.6 (2)N1B—Ti1B—N4B—C33B134.94 (19)
C14A—Ti1A—N4A—C33A101.6 (2)C14B—Ti1B—N4B—C33B102.7 (2)
C13A—Ti1A—N4A—C33A74.3 (2)C15B—Ti1B—N4B—C33B135.4 (2)
C15A—Ti1A—N4A—C33A134.5 (2)C13B—Ti1B—N4B—C33B75.0 (2)
C11A—Ti1A—N4A—C33A142.1 (2)C11B—Ti1B—N4B—C33B142.80 (19)
C12A—Ti1A—N4A—C33A85.5 (3)C12B—Ti1B—N4B—C33B85.8 (3)
C31A—N4A—C33A—C34A85.1 (3)C31B—N4B—C33B—C34B83.2 (3)
Ti1A—N4A—C33A—C34A79.9 (3)Ti1B—N4B—C33B—C34B83.0 (3)
C33A—N4A—C31A—C32A76.4 (3)C33B—N4B—C31B—C32B75.8 (3)
Ti1A—N4A—C31A—C32A117.4 (3)Ti1B—N4B—C31B—C32B117.1 (3)

Experimental details

(I)(II)
Crystal data
Chemical formula[Ti(C4H10N)2(C12H14N2)][Ti(C4H10N)2(C15H12N2)]
Mr378.41412.43
Crystal system, space groupMonoclinic, P21/nTriclinic, P1
Temperature (K)293293
a, b, c (Å)13.729 (3), 14.829 (3), 10.679 (2)9.7472 (15), 14.469 (2), 18.006 (3)
α, β, γ (°)90, 92.749 (3), 9089.362 (2), 76.965 (2), 72.161 (2)
V3)2171.7 (8)2350.4 (6)
Z44
Radiation typeMo KαMo Kα
µ (mm1)0.400.38
Crystal size (mm)0.36 × 0.27 × 0.140.40 × 0.29 × 0.17
Data collection
DiffractometerBruker SMART APEXII
diffractometer
Bruker SMART APEX
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Multi-scan
(SADABS; Sheldrick,1996)
Tmin, Tmax0.868, 0.9460.863, 0.939
No. of measured, independent and
observed [I > 2σ(I)] reflections
11087, 4213, 3287 11818, 8157, 5573
Rint0.0300.022
(sin θ/λ)max1)0.6170.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.106, 1.04 0.041, 0.116, 1.00
No. of reflections42138157
No. of parameters232506
No. of restraints116
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.30, 0.230.23, 0.27

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009).

Selected geometric parameters (Å, °) for (I), (IIA) and (IIB). top
(I)(IIA)(IIB)
Ti1—N12.0551 (14)2.0655 (19)2.0485 (18)
Ti1—N31.8950 (16)1.8857 (19)1.876 (2)
Ti1—N41.8988 (15)1.905 (2)1.906 (2)
N1—C11.370 (2)1.367 (3)1.365 (3)
N1—C21.385 (2)1.377 (3)1.375 (3)
N2—C11.322 (3)1.316 (3)1.316 (3)
N2—C31.372 (3)1.377 (3)1.374 (3)
C2—C31.347 (3)1.351 (3)1.351 (3)
N3—Ti1—N4103.45 (7)103.96 (8)104.47 (9)
N3—Ti1—N1104.48 (7)107.24 (8)107.31 (8)
N4—Ti1—N199.79 (6)106.57 (9)105.11 (8)
C1—N1—C2104.17 (15)103.30 (18)103.65 (18)
C1—N1—Ti1130.51 (13)123.42 (14)123.51 (15)
C2—N1—Ti1124.94 (12)132.59 (15)132.66 (16)
C23—N3—C21111.22 (17)112.53 (19)113.0 (2)
C23—N3—Ti1137.05 (16)139.26 (16)138.91 (18)
C21—N3—Ti1111.72 (12)108.13 (15)108.05 (15)
C33—N4—C31114.18 (16)113.0 (2)113.1 (2)
C33—N4—Ti1127.27 (14)126.21 (19)125.64 (18)
C31—N4—Ti1118.07 (12)119.10 (17)119.78 (17)
For atom names in (IIA) and (IIB), suffixes A or B should be appended, respectively.
Sums of the valence angles (°) at atoms in planar environments for (I), (IIA) and (IIB). top
(I)(IIA)(IIB)
N1359.6 (4)359.3 (5)359.8 (5)
N3360.0 (5)359.9 (5)360.0 (5)
N4359.5 (4)358.3 (6)358.5 (6)
C1360.0 (5)360.0 (6)360.0 (6)
C11360.0 (6)359.5 (6)359.3 (6)
C41359.9 (8)359.9 (8)
For atom names in (IIA) and (IIB), suffixes A or B should be appended, respectively.
R.m.s. planes and atom deviations (Å) for (I), (IIA) and (IIB). top
(I)(IIA)(IIB)
PL1a0.0070 (13)0.0111 (13)0.008 (2)
PL2a0.0031 (13)0.003 (2)0.005 (2)
Ti1—PL12.0555 (10)2.0370 (10)2.0427 (11)
Ti1—PL20.181 (3)0.272 (4)0.122 (4)
C4(or C5)—PL1-0.061 (3)0.200 (4)0.220 (4)
C4—PL20.046 (4)-0.058 (4)0.013 (4)
PL1 denotes the C11–C15 Cp ring r.m.s. plane and PL2 the imidazole N1/C1/N2/C2/C3 r.m.s. plane. For atom names in (IIA) and (IIB), suffixes A or B should be appended, respectively. Note: (a) Maximum deviations of the r.m.s. plane forming atoms.
 

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