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Acta Crystallographica Section E: Structure Reports Online logoLink to Acta Crystallographica Section E: Structure Reports Online
. 2011 Apr 7;67(Pt 5):m549–m550. doi: 10.1107/S1600536811012396

{2-[(η5-Cyclo­penta­dien­yl)diphenyl­meth­yl]-1H-imidazolido-κN}bis­(N,N-diethyl­amido)­titanium(IV)

Xianfeng Cai a,‡, Yingying Xu a, Wanli Nie a,*, Maxim V Borzov a
PMCID: PMC3089115  PMID: 21754286

Abstract

The chemically achiral title mol­ecule, [Ti(C4H10N)2(C21H16N2)], crystallizes in the chiral space group P21. All three N atoms coordinating to the TiIV atom adopt planar environments [sums of valence angles = 359.5 (6), 360.0 (7) and 360.0 (6)°], which is indicative of pπ–dπ donation from all of these N atoms to the metal and, thus, of the formal 18 e− nature of the complex. The overall coordination about the TiIV atom is distorted tetra­hedral, assuming the cyclo­penta­dienyl ring occupies one coordination site. The Ti—Nimidazole amide-type bond is longer by approximately 0.16 Å than the other two Ti—Namide bonds.

Related literature

For structural parameters of η5-CpTi-tris­(sec-amido)-type complexes, see: Rhodes et al. (2002 ▶); Li et al. (2003 ▶); Seo et al. (2001 ▶); Kunz et al. (2001 ▶, 2002 ▶); Carpenetti et al. (1996 ▶); Bertolasi et al. (2007 ▶); Wu et al. (2006 ▶); Cano et al. (2005 ▶); Martin et al. (1994 ▶). For two related TiIV complexes, see: Wang et al. (2009 ▶). For the structural parameters of 1H-imidazol(in)-2-yl side-chain functionalized cyclo­penta­dienes and their Li, Ti, and Zr complexes, see: Krut’ko et al. (2006 ▶); Nie et al. (2008 ▶); Sun et al. (2009 ▶, 2010 ▶); Ge et al. (2010 ▶). For synthetic details, see: Curtis & Brown (1980 ▶); Bürger & Dämmen (1974 ▶); Bradley & Thomas (1960 ▶); Chajara & Ottosson (2004 ▶); Armarego & Perrin (1997 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶).graphic file with name e-67-0m549-scheme1.jpg

Experimental

Crystal data

  • [Ti(C4H10N)2(C21H16N2)]

  • M r = 488.52

  • Monoclinic, Inline graphic

  • a = 8.6495 (6) Å

  • b = 17.9486 (12) Å

  • c = 9.1130 (6) Å

  • β = 110.603 (1)°

  • V = 1324.27 (15) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.35 mm−1

  • T = 296 K

  • 0.35 × 0.23 × 0.08 mm

Data collection

  • Bruker SMART APEXII diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.888, T max = 0.973

  • 7145 measured reflections

  • 4906 independent reflections

  • 4031 reflections with I > 2σ(I)

  • R int = 0.022

Refinement

  • R[F 2 > 2σ(F 2)] = 0.040

  • wR(F 2) = 0.102

  • S = 0.99

  • 4906 reflections

  • 311 parameters

  • 1 restraint

  • H-atom parameters constrained

  • Δρmax = 0.21 e Å−3

  • Δρmin = −0.21 e Å−3

  • Absolute structure: Flack (1983 ▶), 2209 Friedel pairs

  • Flack parameter: 0.02 (3)

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

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811012396/wm2469sup1.cif

e-67-0m549-sup1.cif (43.8KB, cif)

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811012396/wm2469Isup2.hkl

e-67-0m549-Isup2.hkl (249.9KB, hkl)

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

Financial support from the National Natural Science Foundation of China (project Nos. 20702041 and 21072157) and the Shaanxi Province Administration of Foreign Experts Bureau Foundation (grant No. 20106100079) is gratefully acknowledged. The authors are grateful to Mr Wang Minchang and Mr Su Pengfei (Xi’an Modern Chemistry Research Institute) for their help in carrying out the NMR spectroscopy and X-ray diffraction experiments.

supplementary crystallographic information

Comment

Cyclopentadienes (Cp-s) with pendant 1H-imidazol(in)-2-yl side-chain functional groups, their mono- and di-Li salts, and group 4 transition metal complexes of general type [η5-Cp-(C1 or C2)-imidazol(in)e)-κN]-MIVLn [M = Ti, Zr; Ln = Cl3, (NR2)2] have been described previously (Krut'ko et al., 2006; Nie et al., 2008; Sun et al., 2009; Wang et al., 2009; Ge et al., 2010; Sun et al., 2010). The present contribution reports the structural investigation of the closest analogue of two TiIV 18e- (η5-Cp)tris(sec-amido)- type complexes described recently by Wang et al. (2009).

The title complex, [Ti(C4H10N)2(C21H16N2)], (I), was prepared by treatment of 2-[(cyclopentadienyl)diphenylmethyl]-1H-imidazole, C21H18N2, (II), with Ti(NEt2)4 in toluene by an analogy to what described in Wang et al. (2009) (see Experimental for more details). Of interest, despite its molecule is chemically achiral, (I) crystallizes in the chiral space group P21. The TiIV is in a distorted tetrahedral environment (assuming the Cp-ring occupies one coordination site), with all three N-atoms coordinating to the Ti-centre adopting planar environments [valent angles sums 359.5 (6), 360.0 (7), and 360.0 (6)°, respectively] what is indicative of the pπ–dπ donation from all of these N-atoms to the metal and, thus, of the formal 18e- nature of the complex. The Ti—Nimidazole amido-type bond is approximately by 0.16 Å longer than the other two Ti—N amido-bonds, presumably due to the ridgid bridge constraint and/or certain electronic effects (e.g. involvment of the Nimidazolep-AO into the aromatic system of the heterocycle ring).

The bond lengths and angles at the Ti atom are close to those reported by Wang et al. (2009). The distance of the r.m.s. plane (PL1) of the Cp ring (C11–C15) to the Ti atom is 2.057 Å. The Ti atom only slightly deviates from the r.m.s. plane (PL2) of the imidazole C1/N1/C2/C3/N2 ring by 0.201 (5) Å, with the PL1–PL2 angle being 101.58 (14)°.

Analysis of the Cambridge Structural Database (version 5.27, release: May 2009) (Allen, 2002) reveals 16 structurally characterized Ti complexes of similar η5-CpTi-tris(sec-amido) types (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). Noteworthy, that except of η5-Cp*-Ti(NMe2)3 (Martin et al., 1994) all these complexes as in case of compound (I) contain, at least, one amido-functionality linked to the Cp-ring with a flexible bridge.

Experimental

All operations were performed under Ar atmosphere in conventional glassware or in all-sealed evacuated glass vessels with application of a high-vacuum line (the residual pressure of non-condensable gases within 1.5–1.0×10 -3 Torr; 1 Torr = 133 Pa). 5-(Diphenylmethylidene)cyclopenta-1,3-diene (6,6-diphenylfulvene) was prepared as described by Chajara & Ottosson (2004). Ti(NEt2)4 was prepared as described earlier by Bürger & Dämmen (1974); Bradley & Thomas (1960). 1-Diethoxymethyl-1H-imidazole and its 2-lithiated derivative were prepared as described by Curtis & Brown (1980). All other chemicals were commercially available and purified by conventional methods (Armarego & Perrin, 1997). Solvents were purified by distillation over sodium benzophenoneketyl (diethyl ether, THF), Na—K alloy (toluene, hexane, benzene), and CaH2 (chloroform). The deuterated solvent (C6D6) was dried similarly. Compound (I) was prepared in a full analogy to what was described by Wang et al. (2009). The NMR spectra were recorded on a Varian INOVA-400 instrument. For 1H spectrum, the TMS (δH = 0.00 and δC = 0.0) resonance was used as an internal reference standard. 1H NMR (298 K, C6D6): δ = 0.70 (virt. t, an X-part of an ABX3 spin system, 12 H, 3JAX = 3JBX = 6.7 Hz, NCH2CH3), 3.12, 3.46 (both virt. dq, an AB-part of an ABX3 spin system, 4 H + 4H, 3JAX = 3JBX = 6.7 Hz, 2JAB = 14.0 Hz, NCH2CH3), 5.74 (unresolved m, 4 H, CH in Cp), 7.04, 7.15, 7.86 (all m, p-, m-, and o-CH in Ph, in respective order), 7.21, 7.55 (an AB spin system, 1 H + 1 H, 2JAB = 1.2 Hz, imidazole ring protons).

A crystal of (I) suitable for X-ray diffraction analysis was picked up from the isolated material and mounted inside a Lindemann glass capillary (diameter 0.5 mm; N2-filled glove-box).

Refinement

H atoms were treated as riding atoms with distances C—H = 0.96 (CH3), 0.97 (CH2), 0.93 Å (CArH), and Uiso(H) = 1.5 Ueq(C), 1.2 Ueq(C), and 1.2 Ueq(C), respectively.

Figures

Fig. 1.

Fig. 1.

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The molecule of compound (I) in the asymmetric unit with the labelling scheme. Displacement ellipsoids are shown at the 50% probability level. All H atoms have been omitted for clarity.

Crystal data

[Ti(C4H10N)2(C21H16N2)] F(000) = 520
Mr = 488.52 Dx = 1.225 Mg m−3
Monoclinic, P21 Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb Cell parameters from 5258 reflections
a = 8.6495 (6) Å θ = 2.6–28.2°
b = 17.9486 (12) Å µ = 0.35 mm−1
c = 9.1130 (6) Å T = 296 K
β = 110.603 (1)° Block, brown
V = 1324.27 (15) Å3 0.35 × 0.23 × 0.08 mm
Z = 2
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Data collection

Bruker SMART APEXII diffractometer 4906 independent reflections
Radiation source: fine-focus sealed tube 4031 reflections with I > 2σ(I)
graphite Rint = 0.022
Detector resolution: 8.333 pixels mm-1 θmax = 26.0°, θmin = 2.3°
φ and ω scans h = −8→10
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) k = −22→22
Tmin = 0.888, Tmax = 0.973 l = −11→9
7145 measured reflections
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Refinement

Refinement on F2 Secondary atom site location: difference Fourier map
Least-squares matrix: full Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040 H-atom parameters constrained
wR(F2) = 0.102 w = 1/[σ2(Fo2) + (0.0594P)2] where P = (Fo2 + 2Fc2)/3
S = 0.99 (Δ/σ)max < 0.001
4906 reflections Δρmax = 0.21 e Å−3
311 parameters Δρmin = −0.21 e Å−3
1 restraint Absolute structure: Flack (1983), 2209 Friedel pairs
Primary atom site location: structure-invariant direct methods Flack parameter: 0.02 (3)
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Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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.
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Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

x y z Uiso*/Ueq
Ti1 0.80413 (5) 0.23594 (2) 0.88291 (5) 0.03379 (13)
N1 0.5871 (3) 0.24357 (15) 0.9268 (3) 0.0402 (5)
N2 0.3929 (3) 0.21126 (16) 1.0254 (4) 0.0546 (8)
N3 0.7642 (3) 0.23863 (19) 0.6661 (3) 0.0484 (5)
N4 0.8943 (3) 0.33169 (14) 0.9552 (3) 0.0423 (6)
C1 0.5246 (3) 0.19024 (16) 0.9950 (4) 0.0371 (6)
C2 0.4852 (4) 0.30452 (18) 0.9156 (4) 0.0514 (9)
H2 0.4947 0.3511 0.8747 0.062*
C3 0.3696 (5) 0.2835 (2) 0.9755 (5) 0.0592 (10)
H3 0.2854 0.3140 0.9818 0.071*
C4 0.5952 (3) 0.11126 (15) 1.0097 (3) 0.0347 (6)
C11 0.7649 (3) 0.12130 (15) 0.9937 (3) 0.0354 (6)
C12 0.8975 (3) 0.15962 (18) 1.1051 (4) 0.0433 (7)
H12 0.8977 0.1779 1.2007 0.052*
C13 1.0270 (4) 0.1656 (2) 1.0498 (4) 0.0547 (9)
H13 1.1282 0.1885 1.1008 0.066*
C14 0.9777 (4) 0.13112 (19) 0.9038 (5) 0.0572 (10)
H14 1.0407 0.1274 0.8399 0.069*
C15 0.8150 (4) 0.10237 (16) 0.8682 (4) 0.0455 (8)
H15 0.7537 0.0761 0.7787 0.055*
C21 0.6162 (3) 0.07332 (17) 1.1669 (3) 0.0390 (7)
C22 0.7484 (4) 0.0259 (2) 1.2372 (4) 0.0585 (9)
H22 0.8285 0.0199 1.1918 0.070*
C23 0.7638 (6) −0.0125 (3) 1.3726 (5) 0.0729 (13)
H23 0.8511 −0.0455 1.4150 0.087*
C24 0.6505 (5) −0.0021 (2) 1.4449 (4) 0.0674 (11)
H24 0.6626 −0.0266 1.5382 0.081*
C25 0.5211 (5) 0.0442 (2) 1.3793 (4) 0.0667 (11)
H25 0.4436 0.0510 1.4275 0.080*
C26 0.5025 (4) 0.0819 (2) 1.2406 (4) 0.0519 (8)
H26 0.4123 0.1132 1.1969 0.062*
C31 0.4818 (3) 0.06271 (16) 0.8743 (3) 0.0371 (6)
C32 0.5116 (4) −0.01293 (19) 0.8684 (4) 0.0516 (8)
H32 0.6011 −0.0342 0.9466 0.062*
C33 0.4118 (5) −0.0571 (2) 0.7495 (4) 0.0639 (10)
H33 0.4340 −0.1078 0.7485 0.077*
C34 0.2792 (5) −0.0267 (2) 0.6321 (5) 0.0609 (11)
H34 0.2116 −0.0565 0.5514 0.073*
C35 0.2480 (5) 0.0478 (2) 0.6356 (4) 0.0611 (9)
H35 0.1584 0.0688 0.5570 0.073*
C36 0.3485 (4) 0.09227 (19) 0.7552 (4) 0.0492 (8)
H36 0.3259 0.1429 0.7555 0.059*
C41 0.8291 (5) 0.2021 (2) 0.5546 (5) 0.0678 (10)
H41A 0.7439 0.2014 0.4514 0.081*
H41B 0.8578 0.1509 0.5870 0.081*
C42 0.9794 (5) 0.2417 (4) 0.5458 (5) 0.0835 (12)
H42A 1.0255 0.2134 0.4818 0.125*
H42B 1.0600 0.2467 0.6493 0.125*
H42C 0.9482 0.2902 0.5006 0.125*
C43 0.6389 (5) 0.2954 (2) 0.5932 (5) 0.0649 (10)
H43A 0.6786 0.3270 0.5276 0.078*
H43B 0.6253 0.3264 0.6749 0.078*
C44 0.4723 (6) 0.2641 (3) 0.4946 (6) 0.0979 (16)
H44A 0.4842 0.2335 0.4128 0.147*
H44B 0.3977 0.3043 0.4490 0.147*
H44C 0.4293 0.2347 0.5594 0.147*
C51 0.9457 (4) 0.38919 (18) 0.8705 (4) 0.0523 (8)
H51A 0.9370 0.3696 0.7686 0.063*
H51B 1.0612 0.4004 0.9268 0.063*
C52 0.8487 (5) 0.4608 (2) 0.8464 (6) 0.0828 (13)
H52A 0.8870 0.4945 0.7848 0.124*
H52B 0.8637 0.4830 0.9463 0.124*
H52C 0.7336 0.4504 0.7927 0.124*
C53 0.9123 (5) 0.3530 (2) 1.1150 (5) 0.0635 (10)
H53A 0.8673 0.3134 1.1605 0.076*
H53B 0.8463 0.3973 1.1103 0.076*
C54 1.0848 (7) 0.3683 (4) 1.2218 (6) 0.1085 (19)
H54A 1.1261 0.4116 1.1858 0.163*
H54B 1.1535 0.3263 1.2223 0.163*
H54C 1.0856 0.3770 1.3261 0.163*
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Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23
Ti1 0.0344 (2) 0.0293 (2) 0.0416 (2) 0.0000 (2) 0.01819 (18) 0.0026 (3)
N1 0.0359 (10) 0.0304 (13) 0.0572 (14) 0.0000 (12) 0.0199 (10) −0.0029 (14)
N2 0.0435 (14) 0.0494 (18) 0.084 (2) 0.0053 (11) 0.0391 (15) −0.0057 (14)
N3 0.0594 (13) 0.0446 (14) 0.0430 (12) −0.0077 (17) 0.0203 (10) −0.0006 (16)
N4 0.0415 (14) 0.0349 (14) 0.0521 (16) −0.0049 (11) 0.0186 (13) −0.0021 (12)
C1 0.0321 (14) 0.0349 (17) 0.0459 (17) −0.0004 (12) 0.0156 (13) −0.0050 (13)
C2 0.0457 (18) 0.0329 (18) 0.077 (3) 0.0088 (14) 0.0237 (18) −0.0003 (16)
C3 0.0466 (19) 0.047 (2) 0.092 (3) 0.0143 (16) 0.035 (2) −0.0057 (19)
C4 0.0321 (14) 0.0338 (15) 0.0425 (16) −0.0008 (11) 0.0186 (12) 0.0008 (12)
C11 0.0349 (14) 0.0314 (15) 0.0456 (17) 0.0049 (11) 0.0212 (13) 0.0080 (12)
C12 0.0340 (15) 0.0463 (18) 0.0485 (17) 0.0035 (14) 0.0133 (13) 0.0138 (15)
C13 0.0332 (15) 0.054 (2) 0.078 (2) 0.0061 (15) 0.0215 (16) 0.024 (2)
C14 0.0511 (19) 0.045 (2) 0.095 (3) 0.0150 (16) 0.050 (2) 0.0195 (19)
C15 0.0584 (19) 0.0292 (16) 0.065 (2) 0.0063 (14) 0.0414 (17) 0.0053 (14)
C21 0.0392 (15) 0.0381 (16) 0.0440 (17) −0.0108 (13) 0.0199 (13) −0.0018 (13)
C22 0.060 (2) 0.061 (2) 0.065 (2) 0.0084 (18) 0.0344 (19) 0.0193 (18)
C23 0.071 (3) 0.078 (3) 0.067 (3) 0.002 (2) 0.022 (2) 0.033 (2)
C24 0.078 (3) 0.075 (3) 0.049 (2) −0.017 (2) 0.022 (2) 0.0128 (19)
C25 0.074 (3) 0.083 (3) 0.059 (2) −0.024 (2) 0.042 (2) −0.005 (2)
C26 0.0480 (18) 0.064 (2) 0.0507 (19) −0.0111 (16) 0.0264 (16) −0.0032 (16)
C31 0.0409 (15) 0.0345 (16) 0.0434 (16) −0.0025 (12) 0.0242 (13) 0.0002 (12)
C32 0.063 (2) 0.0382 (18) 0.053 (2) 0.0042 (15) 0.0196 (17) 0.0009 (15)
C33 0.085 (3) 0.043 (2) 0.063 (2) −0.0104 (19) 0.025 (2) −0.0089 (18)
C34 0.062 (2) 0.065 (3) 0.057 (2) −0.018 (2) 0.023 (2) −0.019 (2)
C35 0.0541 (19) 0.066 (3) 0.057 (2) 0.0007 (18) 0.0109 (17) −0.0064 (19)
C36 0.0462 (17) 0.0469 (19) 0.0514 (19) 0.0036 (15) 0.0131 (15) 0.0002 (16)
C41 0.085 (3) 0.070 (2) 0.054 (2) −0.007 (2) 0.032 (2) −0.0125 (18)
C42 0.093 (3) 0.101 (3) 0.077 (2) −0.017 (3) 0.055 (2) −0.005 (3)
C43 0.078 (2) 0.052 (2) 0.058 (2) −0.0039 (19) 0.0161 (19) 0.0087 (18)
C44 0.074 (3) 0.113 (4) 0.081 (3) 0.001 (3) −0.005 (2) 0.008 (3)
C51 0.0487 (18) 0.0391 (18) 0.066 (2) −0.0058 (15) 0.0161 (17) 0.0060 (16)
C52 0.074 (3) 0.045 (2) 0.118 (4) 0.005 (2) 0.019 (3) 0.016 (2)
C53 0.071 (3) 0.060 (2) 0.065 (2) −0.016 (2) 0.030 (2) −0.014 (2)
C54 0.093 (4) 0.151 (6) 0.067 (3) −0.030 (3) 0.009 (3) −0.030 (3)
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Geometric parameters (Å, °)

Ti1—N3 1.883 (2) C24—H24 0.9300
Ti1—N4 1.906 (2) C25—C26 1.392 (5)
Ti1—N1 2.057 (2) C25—H25 0.9300
Ti1—C12 2.341 (3) C26—H26 0.9300
Ti1—C13 2.358 (3) C31—C36 1.381 (4)
Ti1—C11 2.368 (3) C31—C32 1.386 (4)
Ti1—C14 2.372 (3) C32—C33 1.375 (5)
Ti1—C15 2.405 (3) C32—H32 0.9300
N1—C1 1.353 (4) C33—C34 1.377 (6)
N1—C2 1.386 (4) C33—H33 0.9300
N2—C1 1.318 (4) C34—C35 1.368 (5)
N2—C3 1.365 (5) C34—H34 0.9300
N3—C43 1.465 (5) C35—C36 1.383 (5)
N3—C41 1.476 (4) C35—H35 0.9300
N4—C51 1.450 (4) C36—H36 0.9300
N4—C53 1.460 (5) C41—C42 1.508 (6)
C1—C4 1.531 (4) C41—H41A 0.9700
C2—C3 1.351 (5) C41—H41B 0.9700
C2—H2 0.9300 C42—H42A 0.9600
C3—H3 0.9300 C42—H42B 0.9600
C4—C11 1.536 (4) C42—H42C 0.9600
C4—C21 1.539 (4) C43—C44 1.512 (6)
C4—C31 1.547 (4) C43—H43A 0.9700
C11—C15 1.399 (4) C43—H43B 0.9700
C11—C12 1.414 (4) C44—H44A 0.9600
C12—C13 1.385 (4) C44—H44B 0.9600
C12—H12 0.9300 C44—H44C 0.9600
C13—C14 1.391 (5) C51—C52 1.508 (5)
C13—H13 0.9300 C51—H51A 0.9700
C14—C15 1.425 (5) C51—H51B 0.9700
C14—H14 0.9300 C52—H52A 0.9600
C15—H15 0.9300 C52—H52B 0.9600
C21—C26 1.380 (4) C52—H52C 0.9600
C21—C22 1.388 (5) C53—C54 1.492 (6)
C22—C23 1.378 (5) C53—H53A 0.9700
C22—H22 0.9300 C53—H53B 0.9700
C23—C24 1.373 (6) C54—H54A 0.9600
C23—H23 0.9300 C54—H54B 0.9600
C24—C25 1.353 (6) C54—H54C 0.9600
N3—Ti1—N4 103.96 (13) C26—C21—C4 122.2 (3)
N3—Ti1—N1 111.06 (10) C22—C21—C4 120.6 (3)
N4—Ti1—N1 99.38 (10) C23—C22—C21 121.6 (3)
N3—Ti1—C12 143.42 (14) C23—C22—H22 119.2
N4—Ti1—C12 104.71 (12) C21—C22—H22 119.2
N1—Ti1—C12 86.06 (10) C24—C23—C22 120.1 (4)
N3—Ti1—C13 119.81 (13) C24—C23—H23 119.9
N4—Ti1—C13 96.74 (13) C22—C23—H23 119.9
N1—Ti1—C13 120.34 (11) C25—C24—C23 119.3 (4)
C12—Ti1—C13 34.29 (11) C25—C24—H24 120.3
N3—Ti1—C11 117.95 (13) C23—C24—H24 120.3
N4—Ti1—C11 137.59 (11) C24—C25—C26 120.9 (4)
N1—Ti1—C11 72.40 (10) C24—C25—H25 119.5
C12—Ti1—C11 34.94 (11) C26—C25—H25 119.5
C13—Ti1—C11 57.80 (10) C21—C26—C25 120.8 (4)
N3—Ti1—C14 88.97 (14) C21—C26—H26 119.6
N4—Ti1—C14 121.12 (12) C25—C26—H26 119.6
N1—Ti1—C14 129.20 (11) C36—C31—C32 117.4 (3)
C12—Ti1—C14 56.66 (13) C36—C31—C4 122.0 (3)
C13—Ti1—C14 34.21 (13) C32—C31—C4 120.5 (3)
C11—Ti1—C14 57.19 (10) C33—C32—C31 121.5 (3)
N3—Ti1—C15 87.91 (13) C33—C32—H32 119.3
N4—Ti1—C15 153.99 (12) C31—C32—H32 119.3
N1—Ti1—C15 97.66 (10) C32—C33—C34 120.3 (4)
C12—Ti1—C15 57.06 (12) C32—C33—H33 119.9
C13—Ti1—C15 57.54 (13) C34—C33—H33 119.9
C11—Ti1—C15 34.08 (9) C35—C34—C33 119.1 (4)
C14—Ti1—C15 34.70 (11) C35—C34—H34 120.4
C1—N1—C2 104.2 (2) C33—C34—H34 120.4
C1—N1—Ti1 125.6 (2) C34—C35—C36 120.5 (4)
C2—N1—Ti1 129.7 (2) C34—C35—H35 119.7
C1—N2—C3 103.8 (3) C36—C35—H35 119.7
C43—N3—C41 113.4 (3) C31—C36—C35 121.1 (3)
C43—N3—Ti1 109.1 (2) C31—C36—H36 119.4
C41—N3—Ti1 137.5 (3) C35—C36—H36 119.4
C51—N4—C53 113.6 (3) N3—C41—C42 111.8 (3)
C51—N4—Ti1 128.5 (2) N3—C41—H41A 109.3
C53—N4—Ti1 117.9 (2) C42—C41—H41A 109.3
N2—C1—N1 114.1 (3) N3—C41—H41B 109.3
N2—C1—C4 126.5 (3) C42—C41—H41B 109.3
N1—C1—C4 118.9 (2) H41A—C41—H41B 107.9
C3—C2—N1 106.9 (3) C41—C42—H42A 109.5
C3—C2—H2 126.5 C41—C42—H42B 109.5
N1—C2—H2 126.5 H42A—C42—H42B 109.5
C2—C3—N2 110.9 (3) C41—C42—H42C 109.5
C2—C3—H3 124.6 H42A—C42—H42C 109.5
N2—C3—H3 124.6 H42B—C42—H42C 109.5
C1—C4—C11 104.4 (2) N3—C43—C44 114.1 (4)
C1—C4—C21 113.8 (2) N3—C43—H43A 108.7
C11—C4—C21 109.7 (2) C44—C43—H43A 108.7
C1—C4—C31 109.3 (2) N3—C43—H43B 108.7
C11—C4—C31 110.5 (2) C44—C43—H43B 108.7
C21—C4—C31 109.1 (2) H43A—C43—H43B 107.6
C15—C11—C12 107.4 (3) C43—C44—H44A 109.5
C15—C11—C4 129.0 (3) C43—C44—H44B 109.5
C12—C11—C4 123.3 (3) H44A—C44—H44B 109.5
C15—C11—Ti1 74.39 (16) C43—C44—H44C 109.5
C12—C11—Ti1 71.46 (16) H44A—C44—H44C 109.5
C4—C11—Ti1 115.30 (17) H44B—C44—H44C 109.5
C13—C12—C11 109.4 (3) N4—C51—C52 115.1 (3)
C13—C12—Ti1 73.52 (18) N4—C51—H51A 108.5
C11—C12—Ti1 73.60 (16) C52—C51—H51A 108.5
C13—C12—H12 125.3 N4—C51—H51B 108.5
C11—C12—H12 125.3 C52—C51—H51B 108.5
Ti1—C12—H12 119.3 H51A—C51—H51B 107.5
C12—C13—C14 107.3 (3) C51—C52—H52A 109.5
C12—C13—Ti1 72.19 (17) C51—C52—H52B 109.5
C14—C13—Ti1 73.47 (18) H52A—C52—H52B 109.5
C12—C13—H13 126.3 C51—C52—H52C 109.5
C14—C13—H13 126.3 H52A—C52—H52C 109.5
Ti1—C13—H13 119.9 H52B—C52—H52C 109.5
C13—C14—C15 109.0 (3) N4—C53—C54 115.5 (4)
C13—C14—Ti1 72.32 (19) N4—C53—H53A 108.4
C15—C14—Ti1 73.90 (17) C54—C53—H53A 108.4
C13—C14—H14 125.5 N4—C53—H53B 108.4
C15—C14—H14 125.5 C54—C53—H53B 108.4
Ti1—C14—H14 120.0 H53A—C53—H53B 107.5
C11—C15—C14 106.9 (3) C53—C54—H54A 109.5
C11—C15—Ti1 71.53 (16) C53—C54—H54B 109.5
C14—C15—Ti1 71.40 (18) H54A—C54—H54B 109.5
C11—C15—H15 126.6 C53—C54—H54C 109.5
C14—C15—H15 126.6 H54A—C54—H54C 109.5
Ti1—C15—H15 122.3 H54B—C54—H54C 109.5
C26—C21—C22 117.2 (3)
N3—Ti1—N1—C1 116.2 (3) C14—Ti1—C12—C13 37.6 (2)
N4—Ti1—N1—C1 −134.7 (2) C15—Ti1—C12—C13 79.3 (2)
C12—Ti1—N1—C1 −30.5 (3) N3—Ti1—C12—C11 −56.3 (2)
C13—Ti1—N1—C1 −31.2 (3) N4—Ti1—C12—C11 163.17 (17)
C11—Ti1—N1—C1 2.4 (2) N1—Ti1—C12—C11 64.50 (17)
C14—Ti1—N1—C1 9.4 (3) C13—Ti1—C12—C11 −116.6 (3)
C15—Ti1—N1—C1 25.5 (3) C14—Ti1—C12—C11 −79.0 (2)
N3—Ti1—N1—C2 −73.5 (3) C15—Ti1—C12—C11 −37.26 (16)
N4—Ti1—N1—C2 35.5 (3) C11—C12—C13—C14 −0.2 (4)
C12—Ti1—N1—C2 139.8 (3) Ti1—C12—C13—C14 −65.6 (2)
C13—Ti1—N1—C2 139.1 (3) C11—C12—C13—Ti1 65.4 (2)
C11—Ti1—N1—C2 172.6 (3) N3—Ti1—C13—C12 −143.4 (2)
C14—Ti1—N1—C2 179.7 (3) N4—Ti1—C13—C12 106.3 (2)
C15—Ti1—N1—C2 −164.2 (3) N1—Ti1—C13—C12 1.3 (3)
N4—Ti1—N3—C43 −64.0 (2) C11—Ti1—C13—C12 −37.2 (2)
N1—Ti1—N3—C43 42.0 (3) C14—Ti1—C13—C12 −115.0 (3)
C12—Ti1—N3—C43 155.3 (2) C15—Ti1—C13—C12 −77.8 (2)
C13—Ti1—N3—C43 −170.4 (2) N3—Ti1—C13—C14 −28.4 (2)
C11—Ti1—N3—C43 122.6 (2) N4—Ti1—C13—C14 −138.76 (19)
C14—Ti1—N3—C43 174.1 (3) N1—Ti1—C13—C14 116.21 (19)
C15—Ti1—N3—C43 139.4 (2) C12—Ti1—C13—C14 115.0 (3)
N4—Ti1—N3—C41 112.6 (4) C11—Ti1—C13—C14 77.7 (2)
N1—Ti1—N3—C41 −141.4 (3) C15—Ti1—C13—C14 37.12 (18)
C12—Ti1—N3—C41 −28.1 (4) C12—C13—C14—C15 −0.6 (4)
C13—Ti1—N3—C41 6.2 (4) Ti1—C13—C14—C15 −65.3 (2)
C11—Ti1—N3—C41 −60.8 (4) C12—C13—C14—Ti1 64.7 (2)
C14—Ti1—N3—C41 −9.3 (4) N3—Ti1—C14—C13 155.6 (2)
C15—Ti1—N3—C41 −44.0 (4) N4—Ti1—C14—C13 49.9 (2)
N3—Ti1—N4—C51 −9.0 (3) N1—Ti1—C14—C13 −87.7 (2)
N1—Ti1—N4—C51 −123.6 (3) C12—Ti1—C14—C13 −37.70 (19)
C12—Ti1—N4—C51 148.1 (3) C11—Ti1—C14—C13 −79.7 (2)
C13—Ti1—N4—C51 114.1 (3) C15—Ti1—C14—C13 −116.6 (3)
C11—Ti1—N4—C51 162.3 (2) N3—Ti1—C14—C15 −87.8 (2)
C14—Ti1—N4—C51 88.4 (3) N4—Ti1—C14—C15 166.45 (19)
C15—Ti1—N4—C51 106.1 (3) N1—Ti1—C14—C15 28.9 (3)
N3—Ti1—N4—C53 169.3 (3) C12—Ti1—C14—C15 78.9 (2)
N1—Ti1—N4—C53 54.7 (3) C13—Ti1—C14—C15 116.6 (3)
C12—Ti1—N4—C53 −33.6 (3) C11—Ti1—C14—C15 36.88 (18)
C13—Ti1—N4—C53 −67.6 (3) C12—C11—C15—C14 −1.2 (3)
C11—Ti1—N4—C53 −19.4 (3) C4—C11—C15—C14 173.2 (3)
C14—Ti1—N4—C53 −93.3 (3) Ti1—C11—C15—C14 63.1 (2)
C15—Ti1—N4—C53 −75.6 (3) C12—C11—C15—Ti1 −64.3 (2)
C3—N2—C1—N1 −0.9 (4) C4—C11—C15—Ti1 110.2 (3)
C3—N2—C1—C4 −172.4 (3) C13—C14—C15—C11 1.2 (4)
C2—N1—C1—N2 1.0 (4) Ti1—C14—C15—C11 −63.2 (2)
Ti1—N1—C1—N2 173.3 (2) C13—C14—C15—Ti1 64.3 (2)
C2—N1—C1—C4 173.2 (2) N3—Ti1—C15—C11 −152.97 (19)
Ti1—N1—C1—C4 −14.5 (4) N4—Ti1—C15—C11 88.6 (3)
C1—N1—C2—C3 −0.6 (4) N1—Ti1—C15—C11 −42.0 (2)
Ti1—N1—C2—C3 −172.5 (2) C12—Ti1—C15—C11 38.23 (17)
N1—C2—C3—N2 0.2 (5) C13—Ti1—C15—C11 79.2 (2)
C1—N2—C3—C2 0.4 (4) C14—Ti1—C15—C11 115.8 (3)
N2—C1—C4—C11 −168.7 (3) N3—Ti1—C15—C14 91.2 (2)
N1—C1—C4—C11 20.1 (3) N4—Ti1—C15—C14 −27.2 (4)
N2—C1—C4—C21 −49.1 (4) N1—Ti1—C15—C14 −157.8 (2)
N1—C1—C4—C21 139.7 (3) C12—Ti1—C15—C14 −77.6 (2)
N2—C1—C4—C31 73.1 (4) C13—Ti1—C15—C14 −36.6 (2)
N1—C1—C4—C31 −98.1 (3) C11—Ti1—C15—C14 −115.8 (3)
C1—C4—C11—C15 −107.5 (3) C1—C4—C21—C26 38.4 (4)
C21—C4—C11—C15 130.2 (3) C11—C4—C21—C26 154.9 (3)
C31—C4—C11—C15 9.9 (4) C31—C4—C21—C26 −84.0 (3)
C1—C4—C11—C12 66.2 (3) C1—C4—C21—C22 −144.5 (3)
C21—C4—C11—C12 −56.1 (3) C11—C4—C21—C22 −28.0 (4)
C31—C4—C11—C12 −176.4 (3) C31—C4—C21—C22 93.1 (3)
C1—C4—C11—Ti1 −17.5 (3) C26—C21—C22—C23 1.5 (6)
C21—C4—C11—Ti1 −139.78 (19) C4—C21—C22—C23 −175.7 (4)
C31—C4—C11—Ti1 99.9 (2) C21—C22—C23—C24 −2.6 (7)
N3—Ti1—C11—C15 30.9 (2) C22—C23—C24—C25 2.1 (7)
N4—Ti1—C11—C15 −139.5 (2) C23—C24—C25—C26 −0.7 (6)
N1—Ti1—C11—C15 135.9 (2) C22—C21—C26—C25 0.0 (5)
C12—Ti1—C11—C15 −114.9 (3) C4—C21—C26—C25 177.1 (3)
C13—Ti1—C11—C15 −78.4 (2) C24—C25—C26—C21 −0.4 (6)
C14—Ti1—C11—C15 −37.6 (2) C1—C4—C31—C36 5.5 (4)
N3—Ti1—C11—C12 145.87 (18) C11—C4—C31—C36 −108.9 (3)
N4—Ti1—C11—C12 −24.5 (2) C21—C4—C31—C36 130.5 (3)
N1—Ti1—C11—C12 −109.15 (18) C1—C4—C31—C32 −174.7 (3)
C13—Ti1—C11—C12 36.54 (19) C11—C4—C31—C32 71.0 (3)
C14—Ti1—C11—C12 77.4 (2) C21—C4—C31—C32 −49.7 (3)
C15—Ti1—C11—C12 114.9 (3) C36—C31—C32—C33 −0.5 (5)
N3—Ti1—C11—C4 −95.3 (2) C4—C31—C32—C33 179.6 (3)
N4—Ti1—C11—C4 94.3 (2) C31—C32—C33—C34 0.4 (6)
N1—Ti1—C11—C4 9.69 (19) C32—C33—C34—C35 −0.2 (6)
C12—Ti1—C11—C4 118.8 (3) C33—C34—C35—C36 0.2 (6)
C13—Ti1—C11—C4 155.4 (3) C32—C31—C36—C35 0.5 (5)
C14—Ti1—C11—C4 −163.8 (3) C4—C31—C36—C35 −179.6 (3)
C15—Ti1—C11—C4 −126.2 (3) C34—C35—C36—C31 −0.4 (6)
C15—C11—C12—C13 0.9 (3) C43—N3—C41—C42 91.0 (4)
C4—C11—C12—C13 −174.0 (3) Ti1—N3—C41—C42 −85.5 (5)
Ti1—C11—C12—C13 −65.4 (2) C41—N3—C43—C44 74.6 (4)
C15—C11—C12—Ti1 66.3 (2) Ti1—N3—C43—C44 −107.9 (4)
C4—C11—C12—Ti1 −108.6 (2) C53—N4—C51—C52 −62.0 (4)
N3—Ti1—C12—C13 60.3 (3) Ti1—N4—C51—C52 116.3 (3)
N4—Ti1—C12—C13 −80.2 (2) C51—N4—C53—C54 −62.7 (5)
N1—Ti1—C12—C13 −178.9 (2) Ti1—N4—C53—C54 118.7 (4)
C11—Ti1—C12—C13 116.6 (3)
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Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: WM2469).

References

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Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811012396/wm2469sup1.cif

e-67-0m549-sup1.cif (43.8KB, cif)

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811012396/wm2469Isup2.hkl

e-67-0m549-Isup2.hkl (249.9KB, hkl)

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography

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