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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 73| Part 2| February 2017| Pages 122-126
https://doi.org/10.1107/S2056989016019964

Crystal structures of a novel NNN pincer ligand and its dinuclear titanium(IV) alkoxide pincer complex

CROSSMARK_Color_square_no_text.svg
Jakub Pedziwiatr,a Ion Ghiviriga,a Khalil A. Abbouda* and Adam S. Veigea

aDepartment of Chemistry, Center for Catalysis, University of Florida, Gainesville, FL 32611, USA
*Correspondence e-mail: abboud@chem.ufl.edu

Edited by A. J. Lough, University of Toronto, Canada (Received 26 August 2016; accepted 15 December 2016; online 6 January 2017)

This report describes a synthetic protocols and the crystal structures involving a novel pincer-type H3[NNN] ligand, namely di-μ-bromido-μ-{2-(2,2-di­methylpropanimido­yl)-N-[2-(2,2-di­methyl­propanimido­yl)-4-methyl­phen­yl]-4-methylaniline}-bis­[(diethyl ether)lithium], [Li2Br2(C24H33N3)(C4H10O)2] (1) and a dinuclear metal complex, namely di-μ-bromido-2:3κ4Br:Br-bis­{2-(2,2-di­methylpropanimido­yl)-N-[2-(2,2-di­methyl­propanimido­yl)-4-methyl­phen­yl]-4-methylaniline}-1κ3N,N′,N′′;4κ3N,N′,N′′-tetra-μ-iso­propano­lato-1:2κ4O:O;3:4κ4O:O-diiso­propano­lato-1κO,4κO-2,3-dilithium-1,4-dititanium, [Li2Ti2Br2(C24H32N3)2(C3H7O)6] or {[NHNNH]Ti(OiPr)3(LiBr)2}2 (2). Complex 1, which sits on a twofold rotation axis, is a rare example of a pincer-type ligand which bears ketimine side arms. A unique feature of complex 1 is that the ketimine N atoms have an LiBr(Et2O) fragment bonded to them, with the Li atom adopting a distorted tetra­hedral geometry. This particular fragment creates an LiBr bridge between the two ketimine sidearms, which leads to a cage-type appearance of the ligand. Complex 2 consists of the previously described ligand and a TiIV metal atom in an octa­hedral environment, and is located on an inversion center. Complex 2 crystallizes as a dinuclear species with the metal atoms being bridged by an LiBr entity [the Br atoms are disordered and refined in two positions with their site occupation factors refining to 0.674 (12)/0.372 (12)], and the Li cation being bonded to the isopropoxide O atoms (Li having a tetra­hedral coordination as in 1). The organic ligand of compound 2 exhibits disorder in its periphery groups; isopropyl and tert-butyl groups (occupation factors fixed at 0.6/0.4). The novel [NNN]H3 pincer-type ligand was characterized by multinuclear and multidimensional NMR, HRMS and X-ray crystallography. The dinuclear metal complex 2 was characterized by X-ray crystallography. Although each structure exhibits donor N—H groups, no hydrogen bonding is found in either one, perhaps due to the bulky groups around them. One of the ethyl groups of the ether ligand of 1 is disordered and refined in two parts with site-occupation factors of 0.812 (8) and 0.188 (8). One and a half toluene solvent mol­ecules are also present in the asymmetric unit of 2. The toluene mol­ecules were significantly disordered and could not be modeled properly, thus SQUEEZE [Spek (2015[Spek, A. L. (2015). Acta Cryst. C71, 9-18.]). Acta Cryst. C71, 9–18] was used to remove their contributions to the overall intensity data.

CCDC references: 1523135; 1523134

Similar articles

1. Chemical context

Pincer ligands occupy the meridional coordination sites on a metal ion and were first introduced by Moulton and Shaw in 1976. In the original system, the pincer ligand 2,6-bis[(di-t-butyl­phosphino)meth­yl]phenyl binds to the late transition metals Ni, Pd, Pt, Rh, and Ir through the deprotonated aromatic carbon and the pendant –PR2 side arms (R = t-but­yl) (Moulton & Shaw, 1976[Moulton, C. J. & Shaw, B. L. (1976). J. Chem. Soc. Dalton Trans. pp. 1020-1024.]). Under the HSAB theory, this particular arrangement can be viewed as a soft–hard–soft coordination mode. Since this discovery, the library of tridentate ligands that exhibit this unique meridional coord­in­ation of a metal atom has been extended not only by additional monoanionic pincer and pincer-type ligands, but as well by numerous neutral, dianionic and trianionic pincer-type ligands (Van Koten, 2013[Van Koten, G. (2013). Top. Organomet. Chem. 40, 1-20.]; Gunanathan & Milstein, 2011[Gunanathan, C. & Milstein, D. (2011). Acc. Chem. Res. 44, 588-602.]; O'Reilly & Veige, 2014[O'Reilly, M. E. & Veige, A. S. (2014). Chem. Soc. Rev. 43, 6325-6369.]). Recent advances in the chemistry of metal complexes supported by trianionic pincer and pincer-type ligands which exhibit a unique hard–hard–hard binding mode (Sarkar et al., 2008[Sarkar, S., Carlson, A. R., Veige, M. K., Falkowski, J. M., Abboud, K. A. & Veige, A. S. (2008). J. Am. Chem. Soc. 130, 1116-1117.]) highlight their potential for applications as catalysts in polymerizations (McGowan et al., 2013[McGowan, K. P., O'Reilly, M. E., Ghiviriga, I., Abboud, K. A. & Veige, A. S. (2013). Chem. Sci. 4, 1145-1155.]), alkene isomerizations (McGowan et al., 2011[McGowan, K. P., Abboud, K. A. & Veige, A. S. (2011). Organometallics, 30, 4949-4957.]), and as catalytic group or atom-transfer reagents (O'Reilly et al., 2009[O'Reilly, M. E., Falkowski, J. M., Ramachandran, V., Pati, M., Abboud, K. A., Dalal, N. S., Gray, T. G. & Veige, A. S. (2009). Inorg. Chem. 48, 10901-10903.]).

[Scheme 1]

Monoanionic di­aryl­amino [NNN] ligands with imine functionality on the flanking side arms were reported in 1978 by Black and Rothnie (Black & Rothnie, 1978[Black, D. St. C. & Rothnie, N. E. (1978). Tetrahedron Lett. 19, 2835-2836.]), and are gaining inter­est as evidenced by newly introduced systems in recent years. In the present work, we introduce a protocol for the synthesis and characterization of a novel [NNN]H3 pincer-type ligand that involves the addition of a nitrile to an ar­yl–lithium salt, a protocol described by Parham and coworkers (Parham et al., 1978[Parham, W. E., Bradsher, C. K. & Hunt, D. A. (1978). J. Org. Chem. 43, 1606-1607.]).

2. Structural commentary

Ketimine ligands typically possess a bulky group (such as tBu) on their N atoms. The ligand moiety of 1 (Fig. 1[link]) is unique in that it contains a proton in the terminal position. The complete molecule of 1 is located about a twofold rotation axis. The coordinated Li atoms exhibit an N2—Li2 bond length of 2.065 (7) Å and a N3—Li1 bond length of 2.065 (7) Å. The two lithium ions are both bridged by two bromides with an Li1—Br1 bond length of 2.504 (6) Å and an Li—Br1(−x + 1, y, −z + [{1\over 2}]) bond length of 2.531 (7) Å. Furthermore, both coordinated lithium ions carry a bound Et2O solvent mol­ecule, each with an Li—O bond length of 1.961 (7) Å. The short C=N bond length of 1.277 (4) Å is comparable to reported C=N bond lengths. For instance the C=N bond length in furazan is 1.29 Å (Allen et al., 1987[Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1-S19.]).

[Figure 1]
Figure 1
The mol­ecular structure of [NNN]H3 (1), with C-bound H atoms and minor components of disorder removed for clarity. Symmetry code: (A) −x + 1, y, −z + [{1\over 2}].

Similar to its solid-state structure, 1 exhibits C2 symmetry in solution. The 1H NMR spectrum in CDCl3 (see Supporting information) exhibits a singlet at 2.26 ppm attributable to the methyl groups on the aryl backbone of the ligand framework. Another characteristic singlet that appears at 1.20 ppm has three times the intensity of the backbone CH3 and is attrib­utable to the tert-butyl CH3 protons residing on each ligand arm. Furthermore, the 1H NMR spectrum exhibits a quartet at 3.48 ppm and a triplet at 1.20 ppm, both signals can be assigned to the –CH2 and –CH3 groups of bound Et2O. The central backbone N—H resonates as a singlet at 5.32 ppm, and the ketimine N—H protons resonate at 9.42 ppm. 1H–15N gHMBC indirect detection demonstrates that the central nitro­gen resonates at 77.00 ppm. In contrast, the chemical shifts of the ketimine nitro­gen atoms are not observable. Furthermore, in a NOESY1D experiment the tert-butyl CH3 groups show an nOe with the Et2O –CH3 group when irradiated selectively at 1.28 ppm. From the occurrence of this nOe, it can be concluded that one Et2O mol­ecule is bonded to every lithium atom.

In the solid state, complex 2 is located on an inversion center (Figs. 2[link] and 3[link]) and the TiIV core exhibits a slightly distorted octa­hedral environment. The N2—Ti bond length of 2.069 (2) Å confirms that the central pincer nitro­gen atom is deprotonated. The slightly elongated N1—Ti and N3—Ti bonds of 2.136 (3) and 2.130 (3) Å are indicative of an L-type bonding of the ket-mine nitro­gen atoms. The bond lengths and the fact that the titanium metal atom is coordinated by three isopropoxide ligands supports the claim that the [NNN] ligand within 2 must be monoanionic with both ketimine N—H protons still present. The Ti—O1, Ti—O2 and Ti—O3 bond lengths are 1.805 (2), 1.901 (2) and 1.934 (2) Å, respectively. The increase in bond length between Ti—O2 and Ti—O3 in comparison to Ti—O1 is attributed to the coordination of Li to O2 and O3. While the O3—Ti—O1 bond angle of 173.58 (9)° deviates slightly from the optimal angle of 180°, the angle N1—Ti—N3 is 160.94 (11)°. This distortion is due to the short bond length that can be found in a C=N bond. The dinuclear complex also exhibits four disordered regions. The isopropyl groups on C25, C28, C31 and the tert-butyl group on C21 are all disordered and were refined in two parts. The bridging Br ligands are also disordered and were refined in two parts; namely Br1 and Br2.

[Figure 2]
Figure 2
The mol­ecular structure of the dinuclear {[NHNNH]Ti(OiPr)3(LiBr)2}2 complex (2), with all hydrogen atoms bound to C atoms removed for clarity. Symmetry code: (A) −x, −y + 1, −z + 1.
[Figure 3]
Figure 3
The mol­ecular structure of one half of the {[NHNNH]Ti(OiPr)3(LiBr)2}2 dimer (2)with hydrogen atoms removed for clarity.

3. Experimental

Unless specified otherwise, all manipulations were performed under an inert atmosphere using standard Schlenk or glovebox techniques. Glassware was pre-dried in an oven before use. Pentane, toluene, and diethyl ether (Et2O) were dried using a GlassContours drying column. Chloro­from-d1 (Cambridge Isotopes) was dried over anhydrous CaCl2; vacuum transferred, passed over a plug of basic alumina, and stored over 4 Å mol­ecular sieves. Di-p-tolyl­amine, nBuLi (2.5 M in hexa­nes), titanium(IV)isopropoxide, and HCl (1 M in Et2O) were purchased from Sigma Aldrich and used as received. Tri­methyl­aceto­nitrile was vacuum distilled and freeze pump thawed prior to use. Bis(2-bromo-4-methyl­phen­yl)amine was prepared by literature methods (Corey et al., 2010[Corey, J. Y., Trankler, K. A., Braddock-Wilking, J. & Rath, N. P. (2010). Organometallics, 29, 5708-5713.]).

3.1. Synthesis and crystallization of title compound 1

In a nitro­gen-filled glove-box, a glass vial was charged with bis­(2-bromo-4-methyl­phen­yl)amine (0.125 g, 0.35 mmol), 3.0 mL of Et2O. 3.1 eq. nBuLi (2.5 M in hexa­nes) (0.44 mL, 1.1 mmol) was added dropwise to a stirring solution of bis­(2-bromo-4-methyl­phen­yl)amine. The reaction mixture color changed from colorless to yellow. After stirring for 120 min, pivalo­nitrile was added dropwise, resulting in a color change from yellow to orange. After an additional 180 min of stirring, excess HCl (1 M in Et2O) was added dropwise, resulting in a color change from orange to yellow and the formation of a white microcrystalline powder. The pale-yellow solution was filtered through Celite™. The volatiles in the resulting filtrate were removed in vacuo and the oily residue was triturated three times (3 × 2 mL) with pentane. Single crystals were obtained by cooling a concentrated toluene solution of 1 to 238 K. Yield: 0.091 g (0.14 mmol, 41%). 1H NMR (500 MHz, CDCl3, 298 K): δ = 1.20 (t, 12H, CH3(Et2O)2), 1.28 (s, 18H, CH3(C4H9)2), 2.26 (s, 6H, –CH3), 3.48 [q, 8H, CH2(Et2O)2], 6.79 (s, 2H, Ar-H), 6.96 (dd, 4H, Ar-H,) ppm. 1H–13C gHMBC NMR (500 MHz, CDCl3, 298 K): δ(ppm) = 15.3 [s, CH3(Et2O) C], 20.2 (s, CH3), 28.1 [s, CH3(C4H9)], 40.9 [s, –C–(C4H9)], 65.8 [s, CH2(Et2O) C], 119.8 (s, Ar C), 127.6 (s, Ar C), 129.5 (s, Ar C), 129.7 (s, Ar C), 132.3 (s, Ar C), 137.3 (s, Ar C) and 190.6 (s, N=C); HRMS calculated (found) for C24H33N3 (M+) 364.2747 (364.2755).

3.2. Synthesis and crystallization of title compound 2

In a nitro­gen-filled glove-box, a glass vial was charged with [NNN]H3(LiBr)2 (1) (0.075 g, 0.118 mmol), and 3 mL of Et2O. 1.1 eq. Ti(OiPr)4 (38.5 µL, 0.130 mmol) was added dropwise to a stirring solution of 1. The reaction mixture changed color instantaneously from yellow to dark red. After stirring for 120 min, the dark-red solution was filtered through Celite™. The volatiles in the resulting filtrate were removed in vacuo and the resulting oily residue was washed three times (3 × 2 mL) with pentane. Single crystals were obtained by preparing a concentrated solution of the oily complex 2 in toluene and cooling it for two weeks at 238 K. Yield: 0.107 g (0.081 mmol, 69%).

4. Refinement details complex 1

Crystal data, data collection and structure refinement details are summarized in Table 1[link]. The non-H atoms were refined with anisotropic displacement parameters and all of the H atoms were calculated in idealized positions (C—H = 0.93/1.00 Å) and refined riding on their parent atoms with Uiso(H)= 1.2/1.5Ueq(C), except for the –N—H hydrogen atoms which were obtained from a difference Fourier map and refined freely. The dimer complex is located on a twofold rotation axis of symmetry and thus only a half is contained in the asymmetric unit. One ethyl group of the Li-coordinating ether ligand is disordered and was refined in two parts (C15–C16/C15′–C16′). Their site-occupation factors dependently refined to 0.812 (8) and 0.188 (8), for the major and minor parts, respectively.

Table 1
Experimental details

  1 2
Crystal data
Chemical formula [Li2Br2(C24H33N3)(C4H10O)2] [Li2Ti2Br2(C24H32N3)2(C3H7O)6]·1.5C7H8
Mr 685.47 1761.71
Crystal system, space group Orthorhombic, Pbcn Triclinic, P[\overline{1}]
Temperature (K) 100 100
a, b, c (Å) 11.8301 (7), 22.3946 (13), 13.4254 (8) 12.2546 (3), 12.7240 (3), 15.9477 (5)
α, β, γ (°) 90, 90, 90 75.8613 (15), 68.0449 (15), 83.2200 (17)
V (Å3) 3556.8 (4) 2235.49 (11)
Z 4 1
Radiation type Mo Kα Cu Kα
μ (mm−1) 2.31 3.00
Crystal size (mm) 0.15 × 0.13 × 0.06 0.25 × 0.20 × 0.04
 
Data collection
Diffractometer Bruker APEXII DUO Bruker APEXII DUO
Absorption correction Analytical [based on measured indexed crystal faces (SHELXTL; Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.])] Analytical [based on measured indexed crystal faces (SHELXTL; Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.])]
Tmin, Tmax 0.758, 0.891 0.667, 0.890
No. of measured, independent and observed [I > 2σ(I)] reflections 45357, 4096, 3116 30419, 7594, 6139
Rint 0.050 0.083
(sin θ/λ)max (Å−1) 0.650 0.595
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.052, 0.140, 1.03 0.058, 0.172, 1.10
No. of reflections 4096 7594
No. of parameters 189 386
No. of restraints 3 324
H-atom treatment H atoms treated by a mixture of independent and constrained refinement H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3) 1.01, −0.79 0.72, −0.43
Computer programs: APEX2 and SAINT (Bruker, 2008[Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXT2013 (Sheldrick, 2015a[Sheldrick, G. M. (2015a). Acta Cryst. A71, 3-8.]), SHELXTL2014 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), SHELXL2013 (Sheldrick, 2015b[Sheldrick, G. M. (2015b). Acta Cryst. C71, 3-8.]) and DIAMOND (Brandenburg, 2014[Brandenburg, K. (2014). DIAMOND. Crystal Impact GbR, Bonn, Germany.]).

4.1. Refinement details complex 2

The non-H atoms were refined with anisotropic displacement parameters and all of the H atoms were calculated in idealized positions (C—H = 0.93/1.00 Å) and refined riding on their parent atoms with Uiso(H)= 1.2/1.5Ueq(C), except for the –N—H hydrogen atoms which were obtained from a difference-Fourier map and refined freely. The Ti dimer is located on an inversion center and thus a half dimer is present in the asymmetric unit. One and a half toluene solvent mol­ecules are also present in the asymmetric unit. The half toluene mol­ecule is disordered around inversion symmetry while the one in a general position is disordered in two parts. The toluene mol­ecules were significantly disordered and could not be modeled properly, thus SQUEEZE (Spek, 2015[Spek, A. L. (2015). Acta Cryst. C71, 9-18.]), a part of the PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]) package of crystallographic software, was used to calculate the solvents' disorder areas and remove their contributions to the overall intensity data. The disordered solvents area is centered around the 0.0, 0.0, 0.0 position and showing an estimated total of 151 electrons and a void volume of 586 Å3. The dimer also exhibits four disordered regions. The isopropyl groups on C25, C28, C31 and the t-butyl group on C21 are all disordered and were refined in two parts with their site occupation factors fixed to 0.6/0.4 in the final refinement model. The bridging Br ligands are also disordered and refined in two parts, Br1 and Br2, to values of 0.674 (12) and 0.326 (12), respectively. The –N—H hydrogen atoms were obtained from a difference-Fourier map and refined freely.

Supporting information

CCDC references: 1523135; 1523134

Crystal structure: contains datablocks 1, 2. DOI: https://doi.org/10.1107/S2056989016019964/lh5823sup1.cif

Structure factors: contains datablock 1. DOI: https://doi.org/10.1107/S2056989016019964/lh58231sup2.hkl

Structure factors: contains datablock 2. DOI: https://doi.org/10.1107/S2056989016019964/lh58232sup3.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989016019964/lh5823sup4.pdf

checkCIF report


Computing details top

For both compounds, data collection: APEX2 (Bruker, 2008); cell refinement: APEX2 (Bruker, 2008); data reduction: SAINT (Bruker, 2008). Program(s) used to solve structure: SHELXT2013 (Sheldrick, 2015a) for (1); SHELXTL2014 (Sheldrick, 2008) for (2). Program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015b) for (1); SHELXTL2014 (Sheldrick, 2008) for (2). Molecular graphics: DIAMOND (Brandenburg, 2014) for (1); SHELXTL2014 (Sheldrick, 2008) for (2). Software used to prepare material for publication: SHELXL2013 (Sheldrick, 2015b) for (1); SHELXTL2014 (Sheldrick, 2008) for (2).

(1) Di-µ-bromido-µ-{2-(2,2-dimethylpropanimidoyl)-N-[2-(2,2-dimethylpropanimidoyl)-4-methylphenyl]-4-methylaniline}-bis[(diethyl ether)lithium] top
Crystal data top
[Li2Br2(C24H33N3)(C4H10O)2]Dx = 1.280 Mg m−3
Mr = 685.47Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, PbcnCell parameters from 9991 reflections
a = 11.8301 (7) Åθ = 2.0–28.0°
b = 22.3946 (13) ŵ = 2.31 mm−1
c = 13.4254 (8) ÅT = 100 K
V = 3556.8 (4) Å3Platelets, orange
Z = 40.15 × 0.13 × 0.06 mm
F(000) = 1432
Data collection top
Bruker APEXII DUO
diffractometer		3116 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.050
phi and ω scansθmax = 27.5°, θmin = 1.8°
Absorption correction: analytical
[based on measured indexed crystal faces (SHELXTL; Sheldrick, 2008)]		h = −14→15
Tmin = 0.758, Tmax = 0.891k = −29→28
45357 measured reflectionsl = −17→17
4096 independent 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)] = 0.052Hydrogen site location: mixed
wR(F2) = 0.140H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 1/[σ2(Fo2) + (0.0691P)2 + 7.3069P]
where P = (Fo2 + 2Fc2)/3
4096 reflections(Δ/σ)max < 0.001
189 parametersΔρmax = 1.01 e Å−3
3 restraintsΔρmin = −0.79 e Å−3
Special details top

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. All H atoms were positioned geometrically ( C—H = 0.93/1.00 Å) and allowed to ride with Uiso(H)= 1.2/1.5Ueq(C). Methyl ones were allowed to rotate around the corresponding C—C.

The dimer complex is located on a 2-fold rotation axis of symmetry thus only a half is contained in the asymmetric unit. One ethyl group of the Li coordinated ether ligand is disordered and was refined in two parts (C15-C16/C15'-C16'). Their site occupation factors dependently refined to 0.812 (8) and 0.188 (8) for the major and minor parts, respectively. The nitrogen protons were obtained from a Difference Fourier map and refined freely.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Br10.61932 (3)0.39333 (2)0.34805 (3)0.03136 (14)
O10.6756 (3)0.44324 (13)0.0817 (2)0.0480 (8)
N10.50000.1968 (2)0.25000.0340 (12)
H10.50000.226 (2)0.25000.014 (15)*
Li10.5936 (6)0.3850 (3)0.1634 (4)0.0299 (13)
N20.6013 (3)0.29847 (13)0.1107 (2)0.0236 (6)
H20.529 (3)0.2921 (16)0.095 (3)0.020 (9)*
C10.5220 (3)0.16765 (15)0.1599 (2)0.0273 (8)
C20.4665 (4)0.11449 (16)0.1360 (3)0.0358 (9)
H2A0.41540.09740.18260.043*
C30.4844 (3)0.08642 (16)0.0463 (3)0.0317 (8)
H3A0.44630.05000.03260.038*
C40.5571 (3)0.11027 (14)−0.0246 (2)0.0223 (7)
C50.6128 (3)0.16289 (14)−0.0011 (2)0.0190 (6)
H5A0.66280.1799−0.04860.023*
C60.5978 (3)0.19165 (14)0.0902 (2)0.0189 (6)
C70.6566 (3)0.24952 (15)0.1137 (2)0.0198 (6)
C80.7805 (3)0.24912 (17)0.1459 (2)0.0284 (8)
C90.8530 (3)0.2188 (2)0.0673 (4)0.0504 (13)
H9A0.84750.24090.00450.076*
H9B0.82630.17780.05720.076*
H9C0.93190.21810.08950.076*
C100.7884 (4)0.2155 (2)0.2453 (4)0.0553 (13)
H10A0.74130.23550.29510.083*
H10B0.86710.21500.26800.083*
H10C0.76190.17440.23620.083*
C110.8247 (4)0.3122 (2)0.1619 (3)0.0431 (10)
H11A0.82190.33420.09890.065*
H11B0.90290.31040.18570.065*
H11C0.77770.33260.21150.065*
C120.5736 (3)0.07978 (16)−0.1236 (2)0.0270 (7)
H12A0.62730.1027−0.16390.041*
H12B0.50100.0773−0.15850.041*
H12C0.60330.0394−0.11270.041*
C130.6566 (4)0.4554 (2)−0.0192 (3)0.0449 (11)
H13A0.72720.4705−0.04980.054*
H13B0.59840.4870−0.02530.054*
C140.6196 (5)0.4029 (2)−0.0716 (3)0.0563 (13)
H14A0.60780.4127−0.14200.084*
H14B0.54860.3886−0.04260.084*
H14C0.67740.3717−0.06600.084*
C150.7467 (5)0.4866 (3)0.1318 (4)0.0477 (14)*0.812 (8)
H15A0.77580.46930.19470.057*0.812 (8)
H15B0.81220.49660.08910.057*0.812 (8)
C160.6824 (7)0.5401 (4)0.1531 (6)0.081 (2)*0.812 (8)
H16A0.73100.56930.18670.121*0.812 (8)
H16B0.61840.53010.19640.121*0.812 (8)
H16C0.65420.55720.09070.121*0.812 (8)
C15'0.6749 (17)0.5051 (3)0.1147 (12)0.0477 (14)*0.188 (8)
H15C0.67050.53100.05510.057*0.188 (8)
H15D0.60530.51180.15410.057*0.188 (8)
C16'0.771 (2)0.5238 (17)0.174 (2)0.081 (2)*0.188 (8)
H16D0.76210.56600.19180.121*0.188 (8)
H16E0.84040.51860.13520.121*0.188 (8)
H16F0.77470.49960.23460.121*0.188 (8)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0324 (2)0.0367 (2)0.02499 (19)−0.00523 (16)−0.00689 (14)0.00029 (15)
O10.075 (2)0.0360 (16)0.0331 (14)−0.0292 (16)−0.0057 (15)0.0070 (12)
N10.059 (3)0.018 (2)0.025 (2)0.0000.023 (2)0.000
Li10.039 (3)0.024 (3)0.027 (3)−0.005 (3)−0.001 (3)−0.001 (2)
N20.0241 (16)0.0225 (14)0.0240 (14)−0.0015 (12)0.0002 (12)−0.0004 (11)
C10.037 (2)0.0225 (16)0.0228 (16)0.0012 (14)0.0149 (15)0.0016 (13)
C20.047 (2)0.0276 (19)0.033 (2)−0.0091 (17)0.0263 (17)−0.0012 (15)
C30.040 (2)0.0206 (16)0.0347 (19)−0.0075 (16)0.0144 (17)−0.0003 (15)
C40.0249 (17)0.0229 (16)0.0192 (15)0.0017 (14)0.0034 (13)0.0011 (13)
C50.0180 (15)0.0220 (15)0.0169 (14)0.0003 (13)0.0029 (12)0.0052 (12)
C60.0188 (16)0.0184 (15)0.0195 (14)0.0012 (12)0.0065 (12)0.0027 (12)
C70.0238 (16)0.0248 (16)0.0109 (12)0.0002 (14)0.0053 (12)−0.0001 (12)
C80.0256 (18)0.0340 (19)0.0256 (17)0.0025 (15)−0.0007 (14)−0.0076 (15)
C90.0213 (19)0.075 (3)0.055 (3)0.009 (2)−0.0015 (18)−0.036 (2)
C100.053 (3)0.066 (3)0.046 (3)−0.011 (3)−0.022 (2)0.019 (2)
C110.027 (2)0.041 (2)0.061 (3)−0.0044 (18)−0.0027 (19)−0.014 (2)
C120.0327 (19)0.0269 (18)0.0215 (16)−0.0048 (15)0.0036 (14)−0.0025 (14)
C130.046 (2)0.049 (3)0.040 (2)−0.001 (2)0.0007 (19)0.019 (2)
C140.079 (4)0.062 (3)0.028 (2)0.000 (3)0.002 (2)0.003 (2)
Geometric parameters (Å, º) top
Br1—Li12.504 (6)C9—H9B0.9800
Br1—Li1i2.531 (7)C9—H9C0.9800
O1—C131.400 (5)C10—H10A0.9800
O1—C151.450 (6)C10—H10B0.9800
O1—C15'1.454 (8)C10—H10C0.9800
O1—Li11.961 (7)C11—H11A0.9800
N1—C1i1.399 (4)C11—H11B0.9800
N1—C11.399 (4)C11—H11C0.9800
N1—H10.66 (5)C12—H12A0.9800
Li1—N22.065 (7)C12—H12B0.9800
Li1—Br1i2.531 (7)C12—H12C0.9800
Li1—Li1i3.211 (13)C13—C141.438 (7)
N2—C71.277 (4)C13—H13A0.9900
N2—H20.89 (4)C13—H13B0.9900
C1—C21.397 (5)C14—H14A0.9800
C1—C61.404 (4)C14—H14B0.9800
C2—C31.375 (5)C14—H14C0.9800
C2—H2A0.9500C15—C161.449 (9)
C3—C41.390 (5)C15—H15A0.9900
C3—H3A0.9500C15—H15B0.9900
C4—C51.387 (5)C16—H16A0.9800
C4—C121.506 (4)C16—H16B0.9800
C5—C61.395 (4)C16—H16C0.9800
C5—H5A0.9500C15'—C16'1.448 (10)
C6—C71.504 (4)C15'—H15C0.9900
C7—C81.528 (5)C15'—H15D0.9900
C8—C91.520 (5)C16'—H16D0.9800
C8—C111.521 (6)C16'—H16E0.9800
C8—C101.535 (6)C16'—H16F0.9800
C9—H9A0.9800
Li1—Br1—Li1i79.3 (2)C8—C10—H10A109.5
C13—O1—C15114.3 (3)C8—C10—H10B109.5
C13—O1—C15'96.2 (7)H10A—C10—H10B109.5
C13—O1—Li1126.3 (3)C8—C10—H10C109.5
C15—O1—Li1118.2 (3)H10A—C10—H10C109.5
C15'—O1—Li1117.3 (5)H10B—C10—H10C109.5
C1i—N1—C1124.3 (4)C8—C11—H11A109.5
C1i—N1—H1117.8 (2)C8—C11—H11B109.5
C1—N1—H1117.8 (2)H11A—C11—H11B109.5
O1—Li1—N2114.2 (3)C8—C11—H11C109.5
O1—Li1—Br1116.4 (3)H11A—C11—H11C109.5
N2—Li1—Br1113.8 (3)H11B—C11—H11C109.5
O1—Li1—Br1i114.2 (3)C4—C12—H12A109.5
N2—Li1—Br1i95.3 (3)C4—C12—H12B109.5
Br1—Li1—Br1i100.1 (2)H12A—C12—H12B109.5
O1—Li1—Li1i138.3 (2)C4—C12—H12C109.5
N2—Li1—Li1i106.2 (2)H12A—C12—H12C109.5
Br1—Li1—Li1i50.74 (16)H12B—C12—H12C109.5
Br1i—Li1—Li1i50.01 (19)O1—C13—C14111.3 (4)
C7—N2—Li1144.9 (3)O1—C13—H13A109.4
C7—N2—H2111 (2)C14—C13—H13A109.4
Li1—N2—H2101 (2)O1—C13—H13B109.4
C2—C1—N1120.6 (3)C14—C13—H13B109.4
C2—C1—C6118.2 (3)H13A—C13—H13B108.0
N1—C1—C6121.1 (3)C13—C14—H14A109.5
C3—C2—C1121.2 (3)C13—C14—H14B109.5
C3—C2—H2A119.4H14A—C14—H14B109.5
C1—C2—H2A119.4C13—C14—H14C109.5
C2—C3—C4121.3 (3)H14A—C14—H14C109.5
C2—C3—H3A119.3H14B—C14—H14C109.5
C4—C3—H3A119.3C16—C15—O1109.9 (5)
C5—C4—C3117.7 (3)C16—C15—H15A109.7
C5—C4—C12121.6 (3)O1—C15—H15A109.7
C3—C4—C12120.7 (3)C16—C15—H15B109.7
C4—C5—C6122.2 (3)O1—C15—H15B109.7
C4—C5—H5A118.9H15A—C15—H15B108.2
C6—C5—H5A118.9C15—C16—H16A109.5
C5—C6—C1119.4 (3)C15—C16—H16B109.5
C5—C6—C7121.6 (3)H16A—C16—H16B109.5
C1—C6—C7119.0 (3)C15—C16—H16C109.5
N2—C7—C6119.8 (3)H16A—C16—H16C109.5
N2—C7—C8120.3 (3)H16B—C16—H16C109.5
C6—C7—C8119.8 (3)C16'—C15'—O1116 (2)
C9—C8—C11108.6 (3)C16'—C15'—H15C108.3
C9—C8—C7110.3 (3)O1—C15'—H15C108.3
C11—C8—C7111.4 (3)C16'—C15'—H15D108.3
C9—C8—C10110.5 (4)O1—C15'—H15D108.3
C11—C8—C10108.2 (3)H15C—C15'—H15D107.4
C7—C8—C10107.9 (3)C15'—C16'—H16D109.5
C8—C9—H9A109.5C15'—C16'—H16E109.5
C8—C9—H9B109.5H16D—C16'—H16E109.5
H9A—C9—H9B109.5C15'—C16'—H16F109.5
C8—C9—H9C109.5H16D—C16'—H16F109.5
H9A—C9—H9C109.5H16E—C16'—H16F109.5
H9B—C9—H9C109.5
Symmetry code: (i) −x+1, y, −z+1/2.
(2) Di-µ-bromido-2:3κ4Br:Br-bis{2-(2,2-dimethylpropanimidoyl)-N-[2-(2,2-dimethylpropanimidoyl)-4-methylphenyl]-4-methylaniline}-1κ3N,N',N'';4κ3N,N',N''-tetra-µ-isopropanolato-1:2κ4O:O;3:4κ4O:O-diisopropanolato-1κO,4κO-2,3-dilithium-1,4-dititanium top
Crystal data top
[Li2Ti2Br2(C24H32N3)2(C3H7O)6]·1.5C7H8Z = 1
Mr = 1761.71F(000) = 860
Triclinic, P1Dx = 1.309 Mg m−3
a = 12.2546 (3) ÅCu Kα radiation, λ = 1.54178 Å
b = 12.7240 (3) ÅCell parameters from 16469 reflections
c = 15.9477 (5) Åθ = 2.0–28.0°
α = 75.8613 (15)°µ = 3.00 mm−1
β = 68.0449 (15)°T = 100 K
γ = 83.2200 (17)°Plates, orange
V = 2235.49 (11) Å30.25 × 0.20 × 0.04 mm
Data collection top
Bruker APEXII DUO
diffractometer		6139 reflections with I > 2σ(I)
Radiation source: IµS microsourceRint = 0.083
phi and ω scansθmax = 66.5°, θmin = 3.1°
Absorption correction: analytical
[based on measured indexed crystal faces (SHELXTL2014; Sheldrick, 2008)]		h = −14→14
Tmin = 0.667, Tmax = 0.890k = −15→14
30419 measured reflectionsl = −18→18
7594 independent 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)] = 0.058Hydrogen site location: mixed
wR(F2) = 0.172H atoms treated by a mixture of independent and constrained refinement
S = 1.10 w = 1/[σ2(Fo2) + (0.1092P)2 + 0.3301P]
where P = (Fo2 + 2Fc2)/3
7594 reflections(Δ/σ)max = 0.005
386 parametersΔρmax = 0.72 e Å−3
324 restraintsΔρmin = −0.43 e Å−3
Special details top

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. All H atoms were positioned geometrically ( C—H = 0.93/1.00 Å) and allowed to ride with Uiso(H)= 1.2/1.5Ueq(C). Methyl ones were allowed to rotate around the corresponding C—C.

The asymmetric unit consists of the Ti dimer and one and a half toluene solvent molecules. The half toluene molecule is disordered around inversion symmetry while the one in general position is disordered in two parts. The toluene molecules were disordered and could not be modelled properly, thus program SQUEEZE, a part of the PLATON package of crystallographic software, was used to calculate the solvent disorder area and remove its contribution to the overall intensity data. The dimer also exhibits four disordered regions. The isopropyl groups on C25, C28, C31 and the t-butyl group on C21 are all disordered and each was refined in two parts. In each disordered case, the site occupation factors of the major and minor parts were fixed (only in the final cycle of refinement) to 0.6 and 0.4, respectively. The bridging Br ligand is also disordered and was refined in two parts, Br1 and Br2, with their site occupation factors refining to 0.68 (1) and 0.32 (1), respectively.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ti1−0.29130 (4)0.27167 (4)0.60831 (4)0.03250 (17)
Li1−0.0775 (5)0.3916 (4)0.5292 (4)0.0430 (11)
Br10.13740 (19)0.41263 (16)0.4542 (4)0.0495 (6)0.674 (12)
Br20.1396 (4)0.4153 (4)0.4281 (4)0.0495 (6)0.326 (12)
O1−0.4149 (2)0.27962 (18)0.57128 (16)0.0442 (5)
O2−0.1909 (2)0.34242 (17)0.48909 (15)0.0430 (5)
O3−0.15594 (17)0.27994 (15)0.64078 (14)0.0342 (4)
N1−0.3643 (2)0.39751 (19)0.68255 (18)0.0357 (5)
H1−0.323 (4)0.448 (4)0.664 (3)0.048 (11)*
N2−0.3823 (2)0.17604 (18)0.73599 (17)0.0343 (5)
N3−0.2387 (2)0.1146 (2)0.5799 (2)0.0414 (6)
H3−0.230 (4)0.116 (4)0.518 (4)0.077 (15)*
C1−0.4601 (3)0.4005 (2)0.7516 (2)0.0386 (6)
C2−0.5434 (3)0.3118 (2)0.7792 (2)0.0374 (6)
C3−0.5012 (3)0.2035 (2)0.7759 (2)0.0366 (6)
C4−0.5854 (3)0.1220 (3)0.8087 (2)0.0442 (7)
H4A−0.55940.04830.81120.053*
C5−0.7044 (3)0.1470 (3)0.8371 (3)0.0511 (8)
H5A−0.75860.09020.85850.061*
C6−0.7471 (3)0.2539 (3)0.8352 (3)0.0505 (8)
C7−0.6653 (3)0.3340 (3)0.8077 (2)0.0423 (7)
H7A−0.69290.40690.80810.051*
C8−0.8773 (3)0.2820 (3)0.8636 (3)0.0628 (11)
H8A−0.89020.34860.82160.094*
H8B−0.90750.29320.92710.094*
H8C−0.91870.22260.86040.094*
C9−0.4886 (3)0.4914 (3)0.8066 (2)0.0448 (7)
C10−0.3744 (4)0.5333 (3)0.8038 (3)0.0597 (10)
H10A−0.39350.59060.83890.089*
H10B−0.32520.56260.73930.089*
H10C−0.33160.47350.83120.089*
C11−0.5520 (5)0.5852 (3)0.7634 (3)0.0677 (11)
H11A−0.57040.64240.79860.102*
H11B−0.62510.56020.76430.102*
H11C−0.50150.61400.69920.102*
C12−0.5613 (3)0.4498 (3)0.9095 (3)0.0545 (8)
H12A−0.56980.50690.94330.082*
H12B−0.52110.38610.93500.082*
H12C−0.63930.43000.91580.082*
C13−0.2379 (3)0.0185 (2)0.6279 (2)0.0453 (7)
C14−0.2662 (3)0.0043 (2)0.7277 (3)0.0467 (8)
C15−0.3413 (3)0.0789 (2)0.7780 (2)0.0409 (7)
C16−0.3732 (3)0.0539 (3)0.8745 (3)0.0482 (8)
H16A−0.42550.10220.90920.058*
C17−0.3313 (3)−0.0384 (3)0.9212 (3)0.0587 (9)
H17A−0.3539−0.05190.98660.070*
C18−0.2549 (4)−0.1125 (3)0.8715 (3)0.0649 (11)
C19−0.2254 (4)−0.0897 (3)0.7786 (3)0.062 (1)
H19A−0.1742−0.13960.74510.074*
C20−0.2074 (5)−0.2153 (4)0.9223 (4)0.0935 (18)
H20A−0.1799−0.26830.88280.140*
H20B−0.2703−0.24650.98000.140*
H20C−0.1419−0.19680.93660.140*
C21−0.2161 (5)−0.0767 (5)0.5729 (5)0.0342 (16)*0.6
C22−0.2181 (5)−0.0386 (6)0.4752 (5)0.0452 (15)*0.6
H22A−0.15680.01450.43870.068*0.6
H22B−0.2035−0.10090.44590.068*0.6
H22C−0.2952−0.00500.47800.068*0.6
C23−0.3127 (5)−0.1588 (5)0.6266 (5)0.0413 (13)*0.6
H23A−0.3138−0.18500.69000.062*0.6
H23B−0.3890−0.12430.62810.062*0.6
H23C−0.2974−0.22010.59610.062*0.6
C24−0.0911 (5)−0.1281 (5)0.5622 (5)0.0447 (16)*0.6
H24A−0.0320−0.07260.52740.067*0.6
H24B−0.0864−0.15750.62360.067*0.6
H24C−0.0762−0.18670.52880.067*0.6
C21'−0.2093 (8)−0.0880 (8)0.5985 (8)0.039 (3)*0.4
C22'−0.2132 (10)−0.0623 (10)0.5063 (10)0.057 (3)*0.4
H22D−0.1953−0.12810.48130.085*0.4
H22E−0.2920−0.03400.50870.085*0.4
H22F−0.1550−0.00760.46630.085*0.4
C23'−0.3044 (8)−0.1723 (8)0.6603 (8)0.046 (2)*0.4
H23D−0.3032−0.19090.72330.070*0.4
H23E−0.3820−0.14160.66160.070*0.4
H23F−0.2880−0.23770.63500.070*0.4
C24'−0.0853 (8)−0.1383 (7)0.5917 (8)0.041 (2)*0.4
H24D−0.0798−0.15670.65340.061*0.4
H24E−0.0726−0.20420.56730.061*0.4
H24F−0.0252−0.08600.55020.061*0.4
C25−0.5266 (4)0.2636 (4)0.5714 (4)0.0730 (12)
H25A−0.58600.27840.63080.088*0.6
H25B−0.58220.23280.63510.088*0.4
C26−0.5319 (8)0.1375 (7)0.5749 (6)0.080 (2)*0.6
H26A−0.60870.12260.57510.119*0.6
H26B−0.46950.11840.52040.119*0.6
H26C−0.52080.09430.63120.119*0.6
C27−0.5598 (10)0.3282 (9)0.4990 (7)0.094 (3)*0.6
H27A−0.63890.30940.50700.140*0.6
H27B−0.55980.40490.50020.140*0.6
H27C−0.50380.31530.43950.140*0.6
C26'−0.5114 (13)0.1940 (12)0.5077 (10)0.081 (3)*0.4
H26D−0.58830.18170.50670.122*0.4
H26E−0.46050.22900.44540.122*0.4
H26F−0.47520.12440.52800.122*0.4
C27'−0.5690 (13)0.3826 (11)0.5299 (10)0.080 (3)*0.4
H27D−0.64720.37900.52750.120*0.4
H27E−0.57260.43180.56960.120*0.4
H27F−0.51310.40950.46730.120*0.4
C28−0.2138 (4)0.3758 (4)0.4047 (3)0.0673 (11)
H28A−0.29830.40060.42150.081*0.6
H28B−0.29920.36220.42310.081*0.4
C29−0.1426 (6)0.4698 (6)0.3430 (5)0.0556 (15)*0.6
H29A−0.15990.49100.28580.083*0.6
H29B−0.16200.53060.37420.083*0.6
H29C−0.05880.45000.32800.083*0.6
C30−0.1992 (7)0.2844 (6)0.3591 (5)0.0548 (16)*0.6
H30A−0.21550.31000.30160.082*0.6
H30B−0.11830.25490.34470.082*0.6
H30C−0.25410.22770.40060.082*0.6
C29'−0.2041 (18)0.4866 (16)0.3691 (13)0.108 (5)*0.4
H29D−0.25220.52540.41740.163*0.4
H29E−0.12160.50610.34810.163*0.4
H29F−0.23150.50670.31680.163*0.4
C30'−0.153 (2)0.297 (2)0.3506 (18)0.138 (9)*0.4
H30D−0.17220.22430.38880.206*0.4
H30E−0.17810.30760.29740.206*0.4
H30F−0.06820.30700.32870.206*0.4
C31−0.1278 (3)0.2505 (3)0.7214 (3)0.0579 (9)
H31A−0.20220.22700.77440.069*0.6
H31B−0.16980.18220.75900.069*0.4
C32−0.0894 (5)0.3535 (5)0.7367 (4)0.0479 (13)*0.6
H32A−0.06930.33520.79270.072*0.6
H32B−0.02060.38290.68320.072*0.6
H32C−0.15410.40790.74410.072*0.6
C33−0.0448 (6)0.1628 (5)0.7214 (5)0.0565 (15)*0.6
H33A−0.02970.14710.77950.085*0.6
H33B−0.07610.09860.71570.085*0.6
H33C0.02890.18220.66910.085*0.6
C32'−0.1373 (16)0.3123 (15)0.7800 (12)0.102 (5)*0.4
H32D−0.11140.27040.82990.153*0.4
H32E−0.08800.37550.74700.153*0.4
H32F−0.21960.33640.80630.153*0.4
C33'0.0222 (12)0.2159 (12)0.6785 (10)0.082 (3)*0.4
H33D0.03650.16970.63420.123*0.4
H33E0.06740.28190.64740.123*0.4
H33F0.04680.17650.72980.123*0.4
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ti10.0346 (3)0.0216 (3)0.0388 (3)−0.0095 (2)−0.0098 (2)−0.00359 (19)
Li10.037 (2)0.029 (2)0.055 (3)−0.007 (2)−0.006 (2)−0.007 (2)
Br10.0345 (2)0.0240 (2)0.0692 (16)−0.00711 (16)0.0107 (7)−0.0167 (6)
Br20.0345 (2)0.0240 (2)0.0692 (16)−0.00711 (16)0.0107 (7)−0.0167 (6)
O10.0448 (11)0.0411 (11)0.0506 (13)−0.0091 (10)−0.021 (1)−0.0069 (9)
O20.0516 (12)0.0342 (11)0.0392 (11)−0.0132 (10)−0.0142 (9)0.0018 (8)
O30.0362 (10)0.0279 (9)0.0375 (11)−0.0094 (8)−0.0087 (8)−0.0086 (8)
N10.0343 (12)0.0220 (11)0.0448 (14)−0.0098 (10)−0.0079 (10)−0.0023 (9)
N20.0338 (11)0.0207 (10)0.0434 (13)−0.0067 (9)−0.0096 (10)−0.0024 (9)
N30.0393 (13)0.0314 (12)0.0506 (16)−0.0099 (11)−0.0088 (11)−0.0114 (11)
C10.0405 (15)0.0246 (13)0.0480 (17)−0.0044 (12)−0.0152 (13)−0.0025 (11)
C20.0337 (14)0.0293 (14)0.0447 (17)−0.0089 (11)−0.0116 (12)0.0001 (11)
C30.0372 (14)0.0274 (13)0.0424 (16)−0.0060 (12)−0.0146 (12)0.0004 (11)
C40.0380 (15)0.0301 (15)0.057 (2)−0.0088 (13)−0.0144 (13)0.0033 (13)
C50.0410 (16)0.0331 (15)0.071 (2)−0.0157 (13)−0.0179 (15)0.0068 (14)
C60.0363 (16)0.0429 (17)0.067 (2)−0.0073 (14)−0.0194 (15)0.0023 (15)
C70.0401 (15)0.0307 (14)0.0508 (19)−0.0024 (12)−0.0154 (13)−0.0002 (12)
C80.0398 (17)0.050 (2)0.092 (3)−0.0052 (16)−0.0266 (18)0.0032 (19)
C90.0468 (16)0.0322 (15)0.0541 (19)−0.0002 (13)−0.0143 (14)−0.0133 (13)
C100.058 (2)0.052 (2)0.069 (2)−0.0137 (17)−0.0106 (17)−0.0277 (18)
C110.088 (3)0.0331 (17)0.083 (3)0.0070 (19)−0.032 (2)−0.0171 (17)
C120.0490 (18)0.055 (2)0.060 (2)−0.0027 (16)−0.0139 (16)−0.0229 (16)
C130.0368 (15)0.0298 (14)0.0609 (19)−0.0103 (13)−0.0053 (14)−0.0099 (13)
C140.0394 (15)0.0252 (14)0.064 (2)−0.0077 (13)−0.0091 (14)−0.0015 (13)
C150.0362 (14)0.0275 (13)0.0525 (18)−0.0112 (12)−0.0121 (13)0.0017 (12)
C160.0413 (16)0.0406 (16)0.0558 (19)−0.0089 (14)−0.0157 (14)0.0026 (13)
C170.0489 (19)0.054 (2)0.055 (2)−0.0084 (16)−0.0140 (16)0.0157 (16)
C180.052 (2)0.0435 (19)0.076 (2)0.0017 (17)−0.0137 (18)0.0132 (17)
C190.053 (2)0.0329 (17)0.078 (2)0.0023 (16)−0.0109 (17)0.0074 (16)
C200.081 (3)0.066 (3)0.099 (4)0.007 (3)−0.023 (3)0.025 (3)
C250.053 (2)0.091 (3)0.095 (3)−0.001 (2)−0.039 (2)−0.035 (3)
C280.080 (3)0.065 (2)0.051 (2)−0.018 (2)−0.027 (2)0.0107 (18)
C310.054 (2)0.068 (2)0.053 (2)−0.0237 (19)−0.0206 (16)−0.0049 (17)
Geometric parameters (Å, º) top
Ti1—O11.805 (2)C22—H22C0.9800
Ti1—O21.901 (2)C23—H23A0.9800
Ti1—O31.934 (2)C23—H23B0.9800
Ti1—N22.069 (2)C23—H23C0.9800
Ti1—N32.130 (3)C24—H24A0.9800
Ti1—N12.136 (3)C24—H24B0.9800
Ti1—Li12.885 (5)C24—H24C0.9800
Li1—O21.950 (6)C21'—C22'1.444 (16)
Li1—O31.979 (5)C21'—C23'1.549 (14)
Li1—Br12.468 (6)C21'—C24'1.553 (13)
Li1—Br22.551 (7)C22'—H22D0.9800
Li1—Br1i2.561 (5)C22'—H22E0.9800
Li1—Br2i2.658 (7)C22'—H22F0.9800
Li1—Li1i3.276 (10)C23'—H23D0.9800
Br1—Li1i2.561 (5)C23'—H23E0.9800
Br2—Li1i2.658 (7)C23'—H23F0.9800
O1—C251.406 (5)C24'—H24D0.9800
O2—C281.430 (5)C24'—H24E0.9800
O3—C311.406 (4)C24'—H24F0.9800
N1—C11.279 (4)C25—C271.408 (11)
N1—H10.79 (5)C25—C26'1.453 (14)
N2—C151.389 (4)C25—C261.601 (10)
N2—C31.394 (4)C25—C27'1.607 (14)
N3—C131.276 (4)C25—H25A1.0000
N3—H30.94 (5)C25—H25B1.0000
C1—C21.484 (4)C26—H26A0.9800
C1—C91.550 (4)C26—H26B0.9800
C2—C71.404 (4)C26—H26C0.9800
C2—C31.420 (4)C27—H27A0.9800
C3—C41.414 (4)C27—H27B0.9800
C4—C51.379 (5)C27—H27C0.9800
C4—H4A0.9500C26'—H26D0.9800
C5—C61.396 (5)C26'—H26E0.9800
C5—H5A0.9500C26'—H26F0.9800
C6—C71.390 (5)C27'—H27D0.9800
C6—C81.511 (5)C27'—H27E0.9800
C7—H7A0.9500C27'—H27F0.9800
C8—H8A0.9800C28—C29'1.39 (2)
C8—H8B0.9800C28—C30'1.43 (3)
C8—H8C0.9800C28—C301.477 (9)
C9—C111.511 (5)C28—C291.480 (8)
C9—C121.536 (5)C28—H28A1.0000
C9—C101.536 (5)C28—H28B1.0000
C10—H10A0.9800C29—H29A0.9800
C10—H10B0.9800C29—H29B0.9800
C10—H10C0.9800C29—H29C0.9800
C11—H11A0.9800C30—H30A0.9800
C11—H11B0.9800C30—H30B0.9800
C11—H11C0.9800C30—H30C0.9800
C12—H12A0.9800C29'—H29D0.9800
C12—H12B0.9800C29'—H29E0.9800
C12—H12C0.9800C29'—H29F0.9800
C13—C141.465 (5)C30'—H30D0.9800
C13—C21'1.501 (10)C30'—H30E0.9800
C13—C211.604 (7)C30'—H30F0.9800
C14—C151.416 (5)C31—C32'1.326 (17)
C14—C191.424 (5)C31—C331.419 (8)
C15—C161.402 (5)C31—C321.545 (7)
C16—C171.383 (5)C31—C33'1.749 (14)
C16—H16A0.9500C31—H31A1.0000
C17—C181.413 (6)C31—H31B1.0000
C17—H17A0.9500C32—H32A0.9800
C18—C191.352 (6)C32—H32B0.9800
C18—C201.536 (5)C32—H32C0.9800
C19—H19A0.9500C33—H33A0.9800
C20—H20A0.9800C33—H33B0.9800
C20—H20B0.9800C33—H33C0.9800
C20—H20C0.9800C32'—H32D0.9800
C21—C231.524 (8)C32'—H32E0.9800
C21—C221.524 (9)C32'—H32F0.9800
C21—C241.558 (8)C33'—H33D0.9800
C22—H22A0.9800C33'—H33E0.9800
C22—H22B0.9800C33'—H33F0.9800
O1—Ti1—O292.8 (1)C24—C21—C13108.3 (5)
O1—Ti1—O3173.58 (9)C21—C22—H22A109.5
O2—Ti1—O382.72 (9)C21—C22—H22B109.5
O1—Ti1—N291.72 (10)H22A—C22—H22B109.5
O2—Ti1—N2171.56 (10)C21—C22—H22C109.5
O3—Ti1—N293.31 (9)H22A—C22—H22C109.5
O1—Ti1—N392.29 (11)H22B—C22—H22C109.5
O2—Ti1—N392.89 (10)C21—C23—H23A109.5
O3—Ti1—N392.52 (10)C21—C23—H23B109.5
N2—Ti1—N379.8 (1)H23A—C23—H23B109.5
O1—Ti1—N192.3 (1)C21—C23—H23C109.5
O2—Ti1—N1105.35 (10)H23A—C23—H23C109.5
O3—Ti1—N184.51 (9)H23B—C23—H23C109.5
N2—Ti1—N181.58 (9)C21—C24—H24A109.5
N3—Ti1—N1160.94 (11)C21—C24—H24B109.5
O1—Ti1—Li1131.18 (14)H24A—C24—H24B109.5
O2—Ti1—Li142.14 (14)C21—C24—H24C109.5
O3—Ti1—Li143.13 (13)H24A—C24—H24C109.5
N2—Ti1—Li1135.69 (14)H24B—C24—H24C109.5
N3—Ti1—Li1105.04 (13)C22'—C21'—C13103.8 (8)
N1—Ti1—Li185.61 (13)C22'—C21'—C23'108.1 (9)
O2—Li1—O380.3 (2)C13—C21'—C23'111.5 (7)
O2—Li1—Br1131.2 (3)C22'—C21'—C24'107.5 (9)
O3—Li1—Br1125.0 (3)C13—C21'—C24'115.7 (8)
O2—Li1—Br2122.9 (3)C23'—C21'—C24'109.7 (8)
O3—Li1—Br2130.7 (3)C21'—C22'—H22D109.5
Br1—Li1—Br28.92 (14)C21'—C22'—H22E109.5
O2—Li1—Br1i106.9 (3)H22D—C22'—H22E109.5
O3—Li1—Br1i114.7 (3)C21'—C22'—H22F109.5
Br1—Li1—Br1i98.70 (18)H22D—C22'—H22F109.5
Br2—Li1—Br1i100.0 (2)H22E—C22'—H22F109.5
O2—Li1—Br2i111.8 (3)C21'—C23'—H23D109.5
O3—Li1—Br2i107.9 (3)C21'—C23'—H23E109.5
Br1—Li1—Br2i99.5 (2)H23D—C23'—H23E109.5
Br2—Li1—Br2i102.1 (2)C21'—C23'—H23F109.5
Br1i—Li1—Br2i8.51 (13)H23D—C23'—H23F109.5
O2—Li1—Ti140.86 (11)H23E—C23'—H23F109.5
O3—Li1—Ti141.91 (11)C21'—C24'—H24D109.5
Br1—Li1—Ti1154.6 (2)C21'—C24'—H24E109.5
Br2—Li1—Ti1152.1 (2)H24D—C24'—H24E109.5
Br1i—Li1—Ti1106.67 (18)C21'—C24'—H24F109.5
Br2i—Li1—Ti1105.5 (2)H24D—C24'—H24F109.5
O2—Li1—Li1i136.3 (3)H24E—C24'—H24F109.5
O3—Li1—Li1i139.3 (4)O1—C25—C27117.4 (6)
Br1—Li1—Li1i50.58 (15)O1—C25—C26'108.0 (7)
Br2—Li1—Li1i52.49 (17)O1—C25—C26106.6 (4)
Br1i—Li1—Li1i48.12 (14)C27—C25—C26110.8 (6)
Br2i—Li1—Li1i49.59 (17)O1—C25—C27'103.9 (6)
Ti1—Li1—Li1i154.8 (3)C26'—C25—C27'108.9 (8)
Li1—Br1—Li1i81.30 (18)O1—C25—H25A107.2
Li1—Br2—Li1i77.9 (2)C27—C25—H25A107.2
C25—O1—Ti1161.1 (3)C26—C25—H25A107.2
C28—O2—Ti1129.1 (2)O1—C25—H25B111.9
C28—O2—Li1131.4 (3)C26'—C25—H25B111.9
Ti1—O2—Li197.00 (19)C27'—C25—H25B111.9
C31—O3—Ti1136.7 (2)C25—C26—H26A109.5
C31—O3—Li1125.9 (3)C25—C26—H26B109.5
Ti1—O3—Li194.95 (19)H26A—C26—H26B109.5
C1—N1—Ti1129.6 (2)C25—C26—H26C109.5
C1—N1—H1118 (3)H26A—C26—H26C109.5
Ti1—N1—H1112 (3)H26B—C26—H26C109.5
C15—N2—C3117.2 (2)C25—C27—H27A109.5
C15—N2—Ti1125.9 (2)C25—C27—H27B109.5
C3—N2—Ti1116.09 (18)H27A—C27—H27B109.5
C13—N3—Ti1135.9 (3)C25—C27—H27C109.5
C13—N3—H3113 (3)H27A—C27—H27C109.5
Ti1—N3—H3109 (3)H27B—C27—H27C109.5
N1—C1—C2117.6 (3)C25—C26'—H26D109.5
N1—C1—C9121.9 (3)C25—C26'—H26E109.5
C2—C1—C9120.5 (3)H26D—C26'—H26E109.5
C7—C2—C3119.0 (3)C25—C26'—H26F109.5
C7—C2—C1120.5 (3)H26D—C26'—H26F109.5
C3—C2—C1120.6 (3)H26E—C26'—H26F109.5
N2—C3—C4119.2 (3)C25—C27'—H27D109.5
N2—C3—C2123.0 (3)C25—C27'—H27E109.5
C4—C3—C2117.6 (3)H27D—C27'—H27E109.5
C5—C4—C3121.5 (3)C25—C27'—H27F109.5
C5—C4—H4A119.3H27D—C27'—H27F109.5
C3—C4—H4A119.3H27E—C27'—H27F109.5
C4—C5—C6121.5 (3)C29'—C28—C30'122.7 (14)
C4—C5—H5A119.3C29'—C28—O2112.7 (9)
C6—C5—H5A119.3C30'—C28—O2105.7 (11)
C7—C6—C5117.4 (3)O2—C28—C30111.6 (4)
C7—C6—C8120.9 (3)O2—C28—C29111.1 (4)
C5—C6—C8121.7 (3)C30—C28—C29112.8 (5)
C6—C7—C2122.8 (3)O2—C28—H28A107.0
C6—C7—H7A118.6C30—C28—H28A107.0
C2—C7—H7A118.6C29—C28—H28A107.0
C6—C8—H8A109.5C29'—C28—H28B104.7
C6—C8—H8B109.5C30'—C28—H28B104.7
H8A—C8—H8B109.5O2—C28—H28B104.7
C6—C8—H8C109.5C28—C29—H29A109.5
H8A—C8—H8C109.5C28—C29—H29B109.5
H8B—C8—H8C109.5H29A—C29—H29B109.5
C11—C9—C12110.9 (3)C28—C29—H29C109.5
C11—C9—C10108.1 (3)H29A—C29—H29C109.5
C12—C9—C10106.1 (3)H29B—C29—H29C109.5
C11—C9—C1109.6 (3)C28—C30—H30A109.5
C12—C9—C1111.7 (3)C28—C30—H30B109.5
C10—C9—C1110.2 (3)H30A—C30—H30B109.5
C9—C10—H10A109.5C28—C30—H30C109.5
C9—C10—H10B109.5H30A—C30—H30C109.5
H10A—C10—H10B109.5H30B—C30—H30C109.5
C9—C10—H10C109.5C28—C29'—H29D109.5
H10A—C10—H10C109.5C28—C29'—H29E109.5
H10B—C10—H10C109.5H29D—C29'—H29E109.5
C9—C11—H11A109.5C28—C29'—H29F109.5
C9—C11—H11B109.5H29D—C29'—H29F109.5
H11A—C11—H11B109.5H29E—C29'—H29F109.5
C9—C11—H11C109.5C28—C30'—H30D109.5
H11A—C11—H11C109.5C28—C30'—H30E109.5
H11B—C11—H11C109.5H30D—C30'—H30E109.5
C9—C12—H12A109.5C28—C30'—H30F109.5
C9—C12—H12B109.5H30D—C30'—H30F109.5
H12A—C12—H12B109.5H30E—C30'—H30F109.5
C9—C12—H12C109.5C32'—C31—O3127.3 (8)
H12A—C12—H12C109.5O3—C31—C33114.2 (4)
H12B—C12—H12C109.5O3—C31—C32107.8 (4)
N3—C13—C14118.2 (3)C33—C31—C32113.1 (4)
N3—C13—C21'130.1 (5)C32'—C31—C33'104.6 (10)
C14—C13—C21'111.7 (5)O3—C31—C33'102.7 (5)
N3—C13—C21115.5 (4)O3—C31—H31A107.1
C14—C13—C21126.1 (4)C33—C31—H31A107.1
C15—C14—C19117.6 (4)C32—C31—H31A107.1
C15—C14—C13121.6 (3)C32'—C31—H31B106.9
C19—C14—C13120.6 (3)O3—C31—H31B106.9
N2—C15—C16118.9 (3)C33'—C31—H31B106.9
N2—C15—C14123.1 (3)C31—C32—H32A109.5
C16—C15—C14118.0 (3)C31—C32—H32B109.5
C17—C16—C15122.5 (4)H32A—C32—H32B109.5
C17—C16—H16A118.8C31—C32—H32C109.5
C15—C16—H16A118.8H32A—C32—H32C109.5
C16—C17—C18120.0 (4)H32B—C32—H32C109.5
C16—C17—H17A120.0C31—C33—H33A109.5
C18—C17—H17A120.0C31—C33—H33B109.5
C19—C18—C17117.8 (3)H33A—C33—H33B109.5
C19—C18—C20121.6 (4)C31—C33—H33C109.5
C17—C18—C20120.6 (4)H33A—C33—H33C109.5
C18—C19—C14124.1 (4)H33B—C33—H33C109.5
C18—C19—H19A117.9C31—C32'—H32D109.5
C14—C19—H19A117.9C31—C32'—H32E109.5
C18—C20—H20A109.5H32D—C32'—H32E109.5
C18—C20—H20B109.5C31—C32'—H32F109.5
H20A—C20—H20B109.5H32D—C32'—H32F109.5
C18—C20—H20C109.5H32E—C32'—H32F109.5
H20A—C20—H20C109.5C31—C33'—H33D109.5
H20B—C20—H20C109.5C31—C33'—H33E109.5
C23—C21—C22107.4 (6)H33D—C33'—H33E109.5
C23—C21—C24112.3 (5)C31—C33'—H33F109.5
C22—C21—C24106.1 (5)H33D—C33'—H33F109.5
C23—C21—C13108.6 (5)H33E—C33'—H33F109.5
C22—C21—C13114.2 (5)
Symmetry code: (i) −x, −y+1, −z+1.
 

Acknowledgements

ASV thanks the University of Florida and the National Science Foundation for financial support of this project (CHE-1265993). KAA thanks the University of Florida and the National Science Foundation (CHE-0821346) for funding the purchase of X-ray equipment. This material is based upon work supported by the National Science Foundation CHE-1265993 and CHE-1565654.

Funding information

Funding for this research was provided by: National Science Foundation (award No. CHE-0821346, CHE-1265993 and CHE-1565654).

References

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ISSN: 2056-9890
Volume 73| Part 2| February 2017| Pages 122-126
https://doi.org/10.1107/S2056989016019964
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