Bis[2-(benzyl­imino­meth­yl)pyrrol-1-ido-κ2N,N′]bis­(dimethyl­amido-κN)titanium(IV)

Chen, Z.; Liu, Y.; Li, Y.; Hu, B.

doi:10.1107/S1600536812014365

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Page m573

doi:10.1107/S1600536812014365

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Bis[2-(benzyliminomethyl)pyrrol-1-ido-κ²N,N′]bis(dimethylamido-κN)titanium(IV)

Zhou Chen,^a Yonglu Liu,^b Yahong Li ^a,^b ^* and Bin Hu ^a

^aQinghai Institute of Salt Lakes, Chinese Academy of Sciences, Xining 810008, People's Republic of China, and ^bKey Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, People's Republic of China
^*Correspondence e-mail: liyahong@suda.edu.cn

(Received 19 March 2012; accepted 3 April 2012; online 13 April 2012)

The mononuclear title complex, [Ti(C₂H₆N)₂(C₁₂H₁₁N₂)₂], was synthesized by the reaction of 1-phenyl-N-[(pyrrol-2-yl)methylidene]methanamine with Ti(NMe₂)₄. The Ti^IV atom is coordinated in a distorted octahedral geometry by four N atoms from two derivatized methanamine ligands and two N atoms from two dimethylamide ions. The dihedral angles between the pyrrole and phenyl rings in the bidentate ligands are 62.36 (9) and 78.32 (8)°. In the crystal, a weak π–π stacking interaction [centroid–centroid distance = 3.864 (2) Å] involving centrosymmetrically related molecules is observed.

Related literature

For the synthesis of N-[(pyrrol-2-yl)methylene]-1-phenylmethanamine, see: Brunner et al. (1998 ); Joly & Jacobsen (2004 ); La Regina et al. (2007 ). For the structures of related complexes, see: Li et al. (2008 ); Brunner et al. (2003 ); Simpson et al. (2004 ); Wansapura et al. (2003 ); Beer et al. (2003 ).

Experimental

Crystal data

[Ti(C₂H₆N)₂(C₁₂H₁₁N₂)₂]
M_r = 502.48
Triclinic, $[P \overline 1]$
a = 8.6363 (17) Å
b = 9.887 (2) Å
c = 16.666 (3) Å
α = 77.15 (3)°
β = 84.72 (3)°
γ = 71.82 (3)°
V = 1317.8 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.35 mm⁻¹
T = 293 K
0.25 × 0.23 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.917, T_max = 0.933
6581 measured reflections
4578 independent reflections
3886 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.121
S = 1.08
4578 reflections
320 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812014365/rz2726sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812014365/rz2726Isup2.hkl

checkCIF report

Comment top

The ligand N-[(pyrrol-2-yl)methylene]-1-phenylmethanamine can be synthesized by different methods (Brunner et al., 1998; Joly & Jacobsen, 2004; La Regina et al., 2007). This ligand has been used in the synthesis of a series of metal-organic complexes such as Ir(III) (Li et al., 2008), Rh(III) (Brunner et al., 2003), Pd(II) (Simpson et al., 2004), Cu(II) (Wansapura et al., 2003), Zn(II) and Ni(II) (Beer et al., 2003) by the reaction of the ligand with metal salts. Herein we report the synthesis and crystal structure of a titanium(IV) complex of this ligand.

The molecular structure of the mononuclear title complex is shown in Fig. 1. A distorted octahedral coordination geometry about the metal atom is provided by four nitrogen atoms from two N-[(pyrrol-2-yl)methylene]-1-phenylmethanamine ligands and two nitrogen atoms from two cis-arranged dimethylamino ions. In the bidentate ligands, the dihedral angles formed by the pyrrole and phenyl rings are 62.36 (9) and 78.32 (8)°. In the crystal structure, a weak π—π stacking interaction involving the C7–C12 phenyl rings of centrosymmetrically-related molecules with a centroid-to-centroid distance of 3.864 (2) Å is observed.

Related literature top

For the synthesis of N-[(pyrrol-2-yl)methylene]-1-phenylmethanamine, see: Brunner et al. (1998); Joly & Jacobsen (2004); La Regina et al. (2007). For the structures of related complexes, see: Li et al. (2008); Brunner et al. (2003); Simpson et al. (2004); Wansapura et al. (2003); Beer et al. (2003).

Experimental top

To a solution of Ti (NMe₂)₄ (0.112 g, 0.5 mmol) in THF (2 mL) was added N-((pyrrol-2-yl)methylene)-1 phenylmethanamine (0.184 g, 1 mmol) in THF (3 mL). After stirring at room temperature overnight, volatiles were removed in vacuo, resulting in an orange solid (0.236 g, yield 94 %). Single crystals suitable for X-ray diffraction were grown from a toluene/hexane (1:1 v/v) solution at -35°C.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound, with 30% probability displacement ellipsoids. H atoms have been omitted for clarity.

Bis[2-(benzyliminomethyl)pyrrol-1-ido- κ²N,N']bis(dimethylamido-κN)titanium(IV) top

Crystal data top

[Ti(C₂H₆N)₂(C₁₂H₁₁N₂)₂]	Z = 2
M_r = 502.48	F(000) = 532
Triclinic, P1	char
Hall symbol: -P 1	D_x = 1.266 Mg m⁻³
a = 8.6363 (17) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.887 (2) Å	Cell parameters from 5124 reflections
c = 16.666 (3) Å	θ = 2.4–27.7°
α = 77.15 (3)°	µ = 0.35 mm⁻¹
β = 84.72 (3)°	T = 293 K
γ = 71.82 (3)°	Block, yellow
V = 1317.8 (4) Å³	0.25 × 0.23 × 0.20 mm

Data collection top

Bruker APEXII CCD diffractometer	4578 independent reflections
Radiation source: fine-focus sealed tube	3886 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −10→9
T_min = 0.917, T_max = 0.933	k = −11→10
6581 measured reflections	l = −19→16

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.121	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0714P)² + 0.1031P] where P = (F_o² + 2F_c²)/3
4578 reflections	(Δ/σ)_max = 0.001
320 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

[Ti(C₂H₆N)₂(C₁₂H₁₁N₂)₂]	γ = 71.82 (3)°
M_r = 502.48	V = 1317.8 (4) Å³
Triclinic, P1	Z = 2
a = 8.6363 (17) Å	Mo Kα radiation
b = 9.887 (2) Å	µ = 0.35 mm⁻¹
c = 16.666 (3) Å	T = 293 K
α = 77.15 (3)°	0.25 × 0.23 × 0.20 mm
β = 84.72 (3)°

Data collection top

Bruker APEXII CCD diffractometer	4578 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	3886 reflections with I > 2σ(I)
T_min = 0.917, T_max = 0.933	R_int = 0.024
6581 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.121	H-atom parameters constrained
S = 1.08	Δρ_max = 0.32 e Å⁻³
4578 reflections	Δρ_min = −0.33 e Å⁻³
320 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

	x	y	z	U_iso*/U_eq
Ti	0.18544 (4)	0.26945 (3)	0.33887 (2)	0.02838 (14)
N1	0.0595 (2)	0.16019 (17)	0.28584 (11)	0.0320 (4)
N2	0.2912 (2)	0.27040 (17)	0.20770 (10)	0.0320 (4)
N4	0.0277 (2)	0.48183 (17)	0.26901 (10)	0.0304 (4)
N3	0.2968 (2)	0.42386 (17)	0.35233 (10)	0.0309 (4)
N5	0.3662 (2)	0.10471 (18)	0.37812 (11)	0.0359 (4)
N6	0.0465 (2)	0.27976 (18)	0.43391 (11)	0.0371 (4)
C7	0.3511 (3)	0.4759 (2)	0.10416 (13)	0.0347 (5)
C14	0.4206 (3)	0.5713 (2)	0.38831 (14)	0.0393 (5)
H14	0.4952	0.6017	0.4110	0.047*
C17	0.0711 (2)	0.5917 (2)	0.27540 (13)	0.0316 (5)
H17	0.0121	0.6853	0.2503	0.038*
C16	0.2107 (2)	0.5676 (2)	0.32156 (12)	0.0294 (4)
C19	−0.1969 (2)	0.6496 (2)	0.17407 (13)	0.0323 (5)
C4	0.1141 (3)	0.1328 (2)	0.20891 (13)	0.0330 (5)
C5	0.2381 (3)	0.1951 (2)	0.17016 (13)	0.0342 (5)
H5	0.2795	0.1808	0.1182	0.041*
C13	0.4227 (3)	0.4287 (2)	0.39300 (13)	0.0362 (5)
H13	0.5005	0.3473	0.4205	0.043*
C1	−0.0532 (3)	0.0895 (2)	0.30949 (15)	0.0401 (5)
H1	−0.1108	0.0885	0.3595	0.048*
C20	−0.3424 (3)	0.7220 (2)	0.20766 (14)	0.0397 (5)
H20	−0.3826	0.6768	0.2565	0.048*
C15	0.2844 (3)	0.6603 (2)	0.34270 (13)	0.0359 (5)
H15	0.2502	0.7614	0.3293	0.043*
C6	0.4175 (3)	0.3353 (2)	0.16516 (14)	0.0409 (5)
H6A	0.4937	0.2657	0.1365	0.049*
H6B	0.4776	0.3529	0.2062	0.049*
C2	−0.0721 (3)	0.0186 (2)	0.25006 (16)	0.0456 (6)
H2	−0.1427	−0.0367	0.2527	0.055*
C18	−0.1036 (3)	0.4969 (2)	0.21361 (15)	0.0417 (5)
H18A	−0.1803	0.4503	0.2448	0.050*
H18B	−0.0560	0.4440	0.1703	0.050*
C24	−0.1388 (3)	0.7203 (2)	0.10202 (14)	0.0420 (5)
H24	−0.0406	0.6732	0.0784	0.050*
C12	0.2948 (3)	0.4785 (3)	0.02883 (14)	0.0437 (6)
H12	0.2930	0.3922	0.0159	0.052*
C3	0.0349 (3)	0.0461 (2)	0.18578 (15)	0.0415 (5)
H3	0.0504	0.0128	0.1368	0.050*
C22	−0.3700 (3)	0.9295 (2)	0.09812 (16)	0.0488 (6)
H22	−0.4285	1.0230	0.0725	0.059*
C11	0.2411 (3)	0.6078 (3)	−0.02778 (14)	0.0480 (6)
H11	0.2027	0.6076	−0.0781	0.058*
C8	0.3535 (3)	0.6060 (2)	0.12081 (14)	0.0411 (5)
H8	0.3911	0.6069	0.1712	0.049*
C26	0.5335 (3)	0.0771 (3)	0.34638 (16)	0.0516 (6)
H26A	0.6071	0.0310	0.3911	0.077*
H26B	0.5518	0.1675	0.3196	0.077*
H26C	0.5518	0.0147	0.3076	0.077*
C10	0.2440 (3)	0.7364 (3)	−0.01045 (15)	0.0481 (6)
H10	0.2077	0.8232	−0.0486	0.058*
C28	−0.1310 (3)	0.3356 (3)	0.43669 (17)	0.0521 (6)
H28A	−0.1740	0.2694	0.4767	0.078*
H28B	−0.1723	0.3451	0.3835	0.078*
H28C	−0.1637	0.4289	0.4517	0.078*
C21	−0.4296 (3)	0.8609 (3)	0.16978 (16)	0.0494 (6)
H21	−0.5286	0.9081	0.1927	0.059*
C23	−0.2250 (3)	0.8598 (3)	0.06492 (15)	0.0507 (6)
H23	−0.1838	0.9065	0.0169	0.061*
C9	0.3010 (3)	0.7351 (3)	0.06378 (16)	0.0494 (6)
H9	0.3045	0.8214	0.0760	0.059*
C27	0.1122 (3)	0.2549 (3)	0.51480 (15)	0.0514 (6)
H27A	0.0806	0.3447	0.5339	0.077*
H27B	0.2289	0.2185	0.5116	0.077*
H27C	0.0705	0.1850	0.5525	0.077*
C25	0.3401 (3)	−0.0277 (2)	0.42785 (17)	0.0523 (6)
H25A	0.3585	−0.0990	0.3944	0.078*
H25B	0.2302	−0.0066	0.4494	0.078*
H25C	0.4146	−0.0648	0.4725	0.078*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ti	0.0237 (2)	0.0252 (2)	0.0335 (2)	−0.00713 (15)	−0.00057 (14)	−0.00083 (15)
N1	0.0292 (9)	0.0253 (8)	0.0399 (10)	−0.0091 (7)	0.0005 (7)	−0.0025 (7)
N2	0.0262 (9)	0.0274 (8)	0.0372 (9)	−0.0070 (7)	0.0035 (7)	0.0006 (7)
N4	0.0239 (9)	0.0276 (8)	0.0377 (9)	−0.0066 (7)	−0.0042 (7)	−0.0027 (7)
N3	0.0256 (9)	0.0301 (8)	0.0362 (9)	−0.0094 (7)	−0.0019 (7)	−0.0034 (7)
N5	0.0333 (10)	0.0314 (9)	0.0390 (10)	−0.0051 (7)	−0.0053 (8)	−0.0041 (7)
N6	0.0346 (10)	0.0323 (9)	0.0417 (10)	−0.0106 (8)	0.0048 (8)	−0.0036 (8)
C7	0.0294 (11)	0.0392 (11)	0.0359 (11)	−0.0150 (9)	0.0092 (9)	−0.0055 (9)
C14	0.0357 (13)	0.0491 (13)	0.0412 (12)	−0.0212 (10)	−0.0009 (10)	−0.0135 (10)
C17	0.0295 (11)	0.0238 (9)	0.0388 (11)	−0.0038 (8)	−0.0022 (9)	−0.0063 (8)
C16	0.0284 (11)	0.0293 (10)	0.0295 (10)	−0.0081 (8)	0.0014 (8)	−0.0055 (8)
C19	0.0280 (11)	0.0297 (10)	0.0397 (11)	−0.0088 (9)	−0.0087 (9)	−0.0048 (9)
C4	0.0310 (11)	0.0231 (9)	0.0406 (11)	−0.0034 (8)	−0.0017 (9)	−0.0041 (8)
C5	0.0320 (12)	0.0293 (10)	0.0346 (11)	−0.0031 (9)	0.0037 (9)	−0.0034 (9)
C13	0.0282 (11)	0.0407 (11)	0.0381 (11)	−0.0107 (9)	−0.0051 (9)	−0.0025 (9)
C1	0.0340 (12)	0.0320 (11)	0.0532 (13)	−0.0132 (9)	0.0050 (10)	−0.0044 (10)
C20	0.0345 (13)	0.0414 (12)	0.0406 (12)	−0.0122 (10)	0.0007 (9)	−0.0024 (10)
C15	0.0390 (13)	0.0340 (11)	0.0376 (11)	−0.0135 (9)	0.0010 (9)	−0.0099 (9)
C6	0.0291 (12)	0.0436 (12)	0.0463 (13)	−0.0133 (10)	0.0064 (10)	−0.0011 (10)
C2	0.0352 (13)	0.0329 (11)	0.0731 (17)	−0.0155 (10)	0.0012 (11)	−0.0132 (11)
C18	0.0368 (13)	0.0297 (11)	0.0583 (14)	−0.0097 (9)	−0.0198 (11)	−0.0014 (10)
C24	0.0363 (13)	0.0433 (12)	0.0456 (13)	−0.0113 (10)	0.0054 (10)	−0.0106 (10)
C12	0.0536 (15)	0.0445 (12)	0.0419 (13)	−0.0275 (11)	0.0040 (11)	−0.0110 (10)
C3	0.0397 (13)	0.0320 (11)	0.0529 (14)	−0.0067 (10)	−0.0047 (10)	−0.0135 (10)
C22	0.0508 (16)	0.0305 (11)	0.0593 (15)	−0.0058 (11)	−0.0192 (12)	0.0007 (11)
C11	0.0499 (15)	0.0611 (15)	0.0364 (12)	−0.0279 (12)	−0.0007 (10)	−0.0011 (11)
C8	0.0461 (14)	0.0471 (13)	0.0350 (12)	−0.0212 (11)	0.0086 (10)	−0.0117 (10)
C26	0.0335 (13)	0.0563 (15)	0.0520 (15)	0.0058 (11)	−0.0068 (11)	−0.0097 (12)
C10	0.0436 (14)	0.0430 (13)	0.0499 (14)	−0.0144 (11)	0.0071 (11)	0.0052 (11)
C28	0.0389 (14)	0.0562 (15)	0.0612 (16)	−0.0160 (12)	0.0146 (12)	−0.0160 (12)
C21	0.0310 (13)	0.0436 (13)	0.0650 (16)	0.0033 (10)	−0.0035 (11)	−0.0137 (12)
C23	0.0675 (18)	0.0457 (13)	0.0394 (13)	−0.0263 (13)	−0.0039 (12)	0.0049 (11)
C9	0.0580 (16)	0.0380 (12)	0.0550 (15)	−0.0216 (11)	0.0110 (12)	−0.0101 (11)
C27	0.0571 (17)	0.0521 (14)	0.0419 (13)	−0.0155 (12)	0.0052 (12)	−0.0072 (11)
C25	0.0592 (17)	0.0276 (11)	0.0680 (17)	−0.0105 (11)	−0.0166 (13)	−0.0034 (11)

Geometric parameters (Å, º) top

Ti—N6	1.8987 (18)	C20—H20	0.9300
Ti—N5	1.9091 (19)	C15—H15	0.9300
Ti—N3	2.1011 (17)	C6—H6A	0.9700
Ti—N1	2.1134 (19)	C6—H6B	0.9700
Ti—N4	2.2449 (19)	C2—C3	1.386 (3)
Ti—N2	2.2897 (18)	C2—H2	0.9300
N1—C1	1.350 (3)	C18—H18A	0.9700
N1—C4	1.379 (3)	C18—H18B	0.9700
N2—C5	1.277 (3)	C24—C23	1.380 (3)
N2—C6	1.482 (3)	C24—H24	0.9300
N4—C17	1.282 (3)	C12—C11	1.384 (3)
N4—C18	1.479 (3)	C12—H12	0.9300
N3—C13	1.351 (3)	C3—H3	0.9300
N3—C16	1.387 (3)	C22—C23	1.361 (4)
N5—C25	1.455 (3)	C22—C21	1.377 (4)
N5—C26	1.456 (3)	C22—H22	0.9300
N6—C27	1.451 (3)	C11—C10	1.373 (4)
N6—C28	1.459 (3)	C11—H11	0.9300
C7—C12	1.379 (3)	C8—C9	1.385 (3)
C7—C8	1.382 (3)	C8—H8	0.9300
C7—C6	1.508 (3)	C26—H26A	0.9600
C14—C13	1.389 (3)	C26—H26B	0.9600
C14—C15	1.399 (3)	C26—H26C	0.9600
C14—H14	0.9300	C10—C9	1.369 (4)
C17—C16	1.419 (3)	C10—H10	0.9300
C17—H17	0.9300	C28—H28A	0.9600
C16—C15	1.385 (3)	C28—H28B	0.9600
C19—C20	1.375 (3)	C28—H28C	0.9600
C19—C24	1.384 (3)	C21—H21	0.9300
C19—C18	1.504 (3)	C23—H23	0.9300
C4—C3	1.383 (3)	C9—H9	0.9300
C4—C5	1.432 (3)	C27—H27A	0.9600
C5—H5	0.9300	C27—H27B	0.9600
C13—H13	0.9300	C27—H27C	0.9600
C1—C2	1.381 (3)	C25—H25A	0.9600
C1—H1	0.9300	C25—H25B	0.9600
C20—C21	1.382 (3)	C25—H25C	0.9600

N6—Ti—N5	101.90 (8)	C7—C6—H6A	108.7
N6—Ti—N3	97.59 (8)	N2—C6—H6B	108.7
N5—Ti—N3	95.05 (7)	C7—C6—H6B	108.7
N6—Ti—N1	94.23 (8)	H6A—C6—H6B	107.6
N5—Ti—N1	97.39 (8)	C1—C2—C3	106.5 (2)
N3—Ti—N1	160.70 (7)	C1—C2—H2	126.8
N6—Ti—N4	92.44 (7)	C3—C2—H2	126.8
N5—Ti—N4	163.77 (7)	N4—C18—C19	116.14 (17)
N3—Ti—N4	75.34 (7)	N4—C18—H18A	108.3
N1—Ti—N4	89.00 (7)	C19—C18—H18A	108.3
N6—Ti—N2	165.25 (8)	N4—C18—H18B	108.3
N5—Ti—N2	89.27 (8)	C19—C18—H18B	108.3
N3—Ti—N2	90.90 (7)	H18A—C18—H18B	107.4
N1—Ti—N2	74.60 (7)	C23—C24—C19	120.7 (2)
N4—Ti—N2	78.01 (7)	C23—C24—H24	119.6
C1—N1—C4	105.19 (18)	C19—C24—H24	119.6
C1—N1—Ti	137.79 (16)	C7—C12—C11	120.8 (2)
C4—N1—Ti	116.42 (13)	C7—C12—H12	119.6
C5—N2—C6	117.90 (18)	C11—C12—H12	119.6
C5—N2—Ti	112.70 (13)	C4—C3—C2	106.4 (2)
C6—N2—Ti	129.23 (15)	C4—C3—H3	126.8
C17—N4—C18	121.51 (17)	C2—C3—H3	126.8
C17—N4—Ti	113.45 (14)	C23—C22—C21	119.7 (2)
C18—N4—Ti	124.76 (13)	C23—C22—H22	120.2
C13—N3—C16	105.68 (17)	C21—C22—H22	120.2
C13—N3—Ti	138.25 (14)	C10—C11—C12	120.7 (2)
C16—N3—Ti	115.35 (13)	C10—C11—H11	119.7
C25—N5—C26	110.80 (19)	C12—C11—H11	119.7
C25—N5—Ti	120.62 (16)	C7—C8—C9	121.1 (2)
C26—N5—Ti	126.40 (15)	C7—C8—H8	119.4
C27—N6—C28	110.83 (19)	C9—C8—H8	119.4
C27—N6—Ti	120.95 (16)	N5—C26—H26A	109.5
C28—N6—Ti	127.38 (16)	N5—C26—H26B	109.5
C12—C7—C8	117.9 (2)	H26A—C26—H26B	109.5
C12—C7—C6	121.7 (2)	N5—C26—H26C	109.5
C8—C7—C6	120.3 (2)	H26A—C26—H26C	109.5
C13—C14—C15	106.6 (2)	H26B—C26—H26C	109.5
C13—C14—H14	126.7	C9—C10—C11	119.1 (2)
C15—C14—H14	126.7	C9—C10—H10	120.5
N4—C17—C16	118.74 (18)	C11—C10—H10	120.5
N4—C17—H17	120.6	N6—C28—H28A	109.5
C16—C17—H17	120.6	N6—C28—H28B	109.5
C15—C16—N3	110.44 (18)	H28A—C28—H28B	109.5
C15—C16—C17	133.02 (19)	N6—C28—H28C	109.5
N3—C16—C17	116.54 (17)	H28A—C28—H28C	109.5
C20—C19—C24	118.36 (19)	H28B—C28—H28C	109.5
C20—C19—C18	121.14 (19)	C22—C21—C20	120.0 (2)
C24—C19—C18	120.5 (2)	C22—C21—H21	120.0
N1—C4—C3	110.47 (19)	C20—C21—H21	120.0
N1—C4—C5	116.31 (19)	C22—C23—C24	120.4 (2)
C3—C4—C5	133.2 (2)	C22—C23—H23	119.8
N2—C5—C4	119.35 (19)	C24—C23—H23	119.8
N2—C5—H5	120.3	C10—C9—C8	120.4 (2)
C4—C5—H5	120.3	C10—C9—H9	119.8
N3—C13—C14	111.09 (19)	C8—C9—H9	119.8
N3—C13—H13	124.5	N6—C27—H27A	109.5
C14—C13—H13	124.5	N6—C27—H27B	109.5
N1—C1—C2	111.5 (2)	H27A—C27—H27B	109.5
N1—C1—H1	124.3	N6—C27—H27C	109.5
C2—C1—H1	124.3	H27A—C27—H27C	109.5
C19—C20—C21	120.8 (2)	H27B—C27—H27C	109.5
C19—C20—H20	119.6	N5—C25—H25A	109.5
C21—C20—H20	119.6	N5—C25—H25B	109.5
C16—C15—C14	106.20 (18)	H25A—C25—H25B	109.5
C16—C15—H15	126.9	N5—C25—H25C	109.5
C14—C15—H15	126.9	H25A—C25—H25C	109.5
N2—C6—C7	114.20 (18)	H25B—C25—H25C	109.5
N2—C6—H6A	108.7

Experimental details

Crystal data
Chemical formula	[Ti(C₂H₆N)₂(C₁₂H₁₁N₂)₂]
M_r	502.48
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	8.6363 (17), 9.887 (2), 16.666 (3)
α, β, γ (°)	77.15 (3), 84.72 (3), 71.82 (3)
V (Å³)	1317.8 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.35
Crystal size (mm)	0.25 × 0.23 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.917, 0.933
No. of measured, independent and observed [I > 2σ(I)] reflections	6581, 4578, 3886
R_int	0.024

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.121, 1.08
No. of reflections	4578
No. of parameters	320
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.33

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

The authors acknowledge financial support by the Hundreds of Talents Program (2005012) of the CAS, the Natural Science Foundation of China (20872105), the Qinglan Project of Jiangsu Province (Bu109805) and the Open Project of the Key Laboratory for Magnetism and Magnetic Materials of the Ministry of Education of Lanzhou University (LZUMMM2010003).

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