Bis[2-(benzyl-imino-meth-yl)pyrrol-1-ido-κ(2)N,N']bis-(dimethyl-amido-κN)titanium(IV).

The mononuclear title complex, [Ti(C(2)H(6)N)(2)(C(12)H(11)N(2))(2)], was synthesized by the reaction of 1-phenyl-N-[(pyrrol-2-yl)methyl-idene]methanamine with Ti(NMe(2))(4). The Ti(IV) atom is coordinated in a distorted octa-hedral geometry by four N atoms from two derivatized methanamine ligands and two N atoms from two dimethyl-amide 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 inter-action [centroid-centroid distance = 3.864 (2) Å] involving centrosymmetrically related mol-ecules 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 = 502.48

Triclinic,

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[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.121

S = 1.08

4578 reflections

320 parameters

H-atom parameters constrained

Δρmax = 0.32 e Å−3

Δρmin = −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.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812014365/rz2726sup1.cif

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

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

[Ti(C2H6N)2(C12H11N2)2]	Z = 2
Mr = 502.48	F(000) = 532
Triclinic, P1	char
Hall symbol: -P 1	Dx = 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

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

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(Fo2) + (0.0714P)2 + 0.1031P] where P = (Fo2 + 2Fc2)/3
4578 reflections	(Δ/σ)max = 0.001
320 parameters	Δρmax = 0.32 e Å−3
0 restraints	Δρmin = −0.33 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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