Di-μ-oxido-bis-({2,2'-[ethane-1,2-diylbis(nitrilo-methanylyl-idene)]diphen-olato}titanium(IV)) chloro-form disolvate.

In the title structure, [Ti2(C16H16N2O2)2O2]·2CHCl3, the Ti atom is coordinated in a distorted octa-hedral geometry by the O,N,N',O' donor set of the salalen ligand and by two μ2-oxide O atoms, which bridge two Ti(salalen) fragments into a centrosymmetric dimeric unit. In the central Ti2(μ2-O)2 fragment, the metal-oxygen distances are significantly different [1.7962 (19) and 1.9292 (19) Å]. In the crystal, the chloro-form mol-ecule is anchored via an N-H⋯Cl and a bifurcated C-H⋯(O,O) hydrogen bond. Slipped π-π stacking [shortest C⋯C distance = 3.585 (4) Å] and C-H⋯π inter-actions contribute to the coherence of the structure.

Related literature

For general background to the chemistry affording the tetra­dentate salalen ligand, see: Matsumoto et al. (2005 ▶, 2007 ▶). For the crystal structure of a salalen complex, see: Taylor et al. (2006 ▶). For the structure of the parent titanium salen compound, see: Tsuchimoto (2001 ▶). For our previous work on titanium(IV) complexes with polydentate N,O-ligands, see: Zaitsev et al. (2006 ▶, 2008 ▶).

Experimental

Crystal data

[Ti2(C16H16N2O2)2O2]·2CHCl3

M = 903.15

Triclinic,

a = 10.237 (3) Å

b = 10.356 (3) Å

c = 10.936 (3) Å

α = 117.075 (4)°

β = 93.113 (4)°

γ = 110.463 (4)°

V = 935.0 (4) Å3

Z = 1

Mo Kα radiation

μ = 0.91 mm−1

T = 150 K

0.08 × 0.06 × 0.01 mm

Data collection

Bruker SMART APEXII diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.931, T max = 0.991

8213 measured reflections

3668 independent reflections

2761 reflections with I > 2σ(I)

R int = 0.037

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.092

S = 1.03

3668 reflections

238 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.41 e Å−3

Δρmin = −0.43 e Å−3

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

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536813029656/qk2062sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813029656/qk2062Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813029656/qk2062Isup3.mol

969061

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

[Ti2(C16H16N2O2)2O2]·2CHCl3	Z = 1
Mr = 903.15	F(000) = 460
Triclinic, P1	Dx = 1.604 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.237 (3) Å	Cell parameters from 1919 reflections
b = 10.356 (3) Å	θ = 2.2–25.7°
c = 10.936 (3) Å	µ = 0.91 mm−1
α = 117.075 (4)°	T = 150 K
β = 93.113 (4)°	Plate, light-yellow
γ = 110.463 (4)°	0.08 × 0.06 × 0.01 mm
V = 935.0 (4) Å3

Bruker SMART APEXII diffractometer	3668 independent reflections
Radiation source: fine-focus sealed tube	2761 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
ω scans	θmax = 26.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −12→12
Tmin = 0.931, Tmax = 0.991	k = −12→12
8213 measured reflections	l = −13→13

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)] = 0.041	Hydrogen site location: difference Fourier map
wR(F2) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0393P)2 + 0.3887P] where P = (Fo2 + 2Fc2)/3
3668 reflections	(Δ/σ)max < 0.001
238 parameters	Δρmax = 0.41 e Å−3
0 restraints	Δρmin = −0.43 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
Ti1	0.50658 (5)	0.65403 (6)	0.05634 (5)	0.01468 (14)
O1	0.6684 (2)	0.7828 (2)	0.21655 (19)	0.0185 (4)
O2	0.3932 (2)	0.7673 (2)	0.13984 (19)	0.0186 (4)
O3	0.4197 (2)	0.4842 (2)	0.07711 (19)	0.0179 (4)
N1	0.6242 (2)	0.8318 (3)	−0.0058 (2)	0.0166 (5)
N2	0.3580 (3)	0.5823 (3)	−0.1413 (3)	0.0198 (5)
H2	0.374 (3)	0.509 (4)	−0.198 (3)	0.030*
C11	0.7673 (3)	0.9337 (3)	0.2842 (3)	0.0166 (6)
C12	0.8403 (3)	1.0016 (3)	0.4247 (3)	0.0217 (6)
H12	0.8190	0.9395	0.4696	0.026*
C13	0.9432 (3)	1.1579 (4)	0.4998 (3)	0.0285 (7)
H13	0.9911	1.2026	0.5960	0.034*
C14	0.9772 (3)	1.2501 (4)	0.4359 (3)	0.0328 (8)
H14	1.0475	1.3578	0.4879	0.039*
C15	0.9077 (3)	1.1837 (4)	0.2962 (3)	0.0274 (7)
H15	0.9326	1.2463	0.2519	0.033*
C16	0.8012 (3)	1.0262 (3)	0.2176 (3)	0.0191 (6)
C17	0.7329 (3)	0.9660 (3)	0.0716 (3)	0.0186 (6)
H17	0.7713	1.0303	0.0308	0.022*
C18	0.5634 (3)	0.7824 (4)	−0.1528 (3)	0.0226 (7)
H18A	0.5968	0.7047	−0.2195	0.027*
H18B	0.5944	0.8762	−0.1659	0.027*
C21	0.2627 (3)	0.7615 (3)	0.1055 (3)	0.0190 (6)
C22	0.2212 (3)	0.8734 (4)	0.2051 (3)	0.0236 (7)
H22	0.2850	0.9515	0.2964	0.028*
C23	0.0879 (3)	0.8713 (4)	0.1718 (4)	0.0303 (8)
H23	0.0617	0.9490	0.2401	0.036*
C24	−0.0073 (3)	0.7581 (4)	0.0410 (4)	0.0323 (8)
H24	−0.0991	0.7565	0.0192	0.039*
C25	0.0326 (3)	0.6466 (4)	−0.0583 (3)	0.0268 (7)
H25	−0.0333	0.5679	−0.1484	0.032*
C26	0.1668 (3)	0.6469 (3)	−0.0294 (3)	0.0210 (6)
C27	0.2045 (3)	0.5213 (3)	−0.1398 (3)	0.0243 (7)
H27A	0.1818	0.4316	−0.1214	0.029*
H27B	0.1437	0.4789	−0.2346	0.029*
C28	0.4012 (3)	0.7066 (3)	−0.1807 (3)	0.0232 (7)
H28A	0.3675	0.7892	−0.1244	0.028*
H28B	0.3562	0.6586	−0.2825	0.028*
C1	0.4183 (3)	0.6758 (4)	0.4095 (3)	0.0325 (8)
H1	0.4220	0.6818	0.3210	0.039*
Cl1	0.26515 (9)	0.50389 (11)	0.37249 (10)	0.0455 (3)
Cl2	0.40908 (11)	0.84731 (11)	0.54051 (11)	0.0507 (3)
Cl3	0.57585 (8)	0.66277 (9)	0.46628 (8)	0.0301 (2)

	U11	U22	U33	U12	U13	U23
Ti1	0.0197 (3)	0.0154 (3)	0.0121 (3)	0.0095 (2)	0.0039 (2)	0.0078 (2)
O1	0.0219 (11)	0.0170 (10)	0.0174 (10)	0.0081 (9)	0.0017 (8)	0.0096 (9)
O2	0.0198 (11)	0.0202 (10)	0.0149 (10)	0.0119 (9)	0.0027 (8)	0.0059 (9)
O3	0.0226 (11)	0.0189 (10)	0.0172 (10)	0.0111 (9)	0.0089 (8)	0.0110 (9)
N1	0.0229 (13)	0.0180 (12)	0.0131 (12)	0.0119 (11)	0.0051 (10)	0.0085 (11)
N2	0.0263 (14)	0.0197 (13)	0.0166 (13)	0.0136 (12)	0.0053 (11)	0.0086 (11)
C11	0.0152 (14)	0.0162 (14)	0.0186 (15)	0.0091 (12)	0.0042 (12)	0.0072 (12)
C12	0.0233 (16)	0.0232 (16)	0.0188 (15)	0.0084 (13)	0.0025 (13)	0.0121 (13)
C13	0.0305 (18)	0.0246 (17)	0.0209 (16)	0.0071 (15)	−0.0028 (14)	0.0086 (14)
C14	0.0296 (19)	0.0222 (17)	0.0306 (19)	−0.0002 (15)	−0.0005 (15)	0.0101 (15)
C15	0.0301 (18)	0.0219 (16)	0.0273 (17)	0.0049 (14)	0.0054 (14)	0.0150 (14)
C16	0.0204 (15)	0.0196 (15)	0.0182 (15)	0.0107 (13)	0.0029 (12)	0.0088 (13)
C17	0.0230 (16)	0.0213 (16)	0.0189 (15)	0.0133 (14)	0.0091 (13)	0.0126 (13)
C18	0.0290 (17)	0.0245 (16)	0.0170 (15)	0.0103 (14)	0.0070 (13)	0.0131 (13)
C21	0.0198 (16)	0.0210 (15)	0.0254 (16)	0.0096 (13)	0.0081 (13)	0.0179 (14)
C22	0.0255 (17)	0.0278 (17)	0.0234 (16)	0.0147 (14)	0.0094 (13)	0.0148 (14)
C23	0.0337 (19)	0.043 (2)	0.0357 (19)	0.0273 (17)	0.0198 (16)	0.0273 (17)
C24	0.0239 (18)	0.053 (2)	0.043 (2)	0.0217 (17)	0.0167 (16)	0.0374 (19)
C25	0.0199 (16)	0.0364 (18)	0.0319 (18)	0.0100 (14)	0.0061 (14)	0.0246 (16)
C26	0.0228 (16)	0.0233 (16)	0.0232 (16)	0.0100 (14)	0.0069 (13)	0.0164 (14)
C27	0.0201 (16)	0.0229 (16)	0.0228 (16)	0.0049 (13)	−0.0041 (13)	0.0102 (14)
C28	0.0301 (17)	0.0268 (16)	0.0180 (15)	0.0137 (14)	0.0055 (13)	0.0143 (14)
C1	0.0328 (19)	0.053 (2)	0.0273 (18)	0.0241 (17)	0.0141 (15)	0.0276 (17)
Cl1	0.0276 (5)	0.0486 (6)	0.0434 (5)	0.0112 (4)	0.0027 (4)	0.0147 (5)
Cl2	0.0553 (6)	0.0449 (6)	0.0706 (7)	0.0339 (5)	0.0283 (5)	0.0328 (5)
Cl3	0.0289 (4)	0.0344 (5)	0.0295 (4)	0.0154 (4)	0.0090 (3)	0.0164 (4)

Ti1—O3	1.7962 (19)	C16—C17	1.447 (4)
Ti1—O1	1.8991 (19)	C17—H17	0.9500
Ti1—O2	1.9102 (19)	C18—C28	1.511 (4)
Ti1—O3i	1.9292 (19)	C18—H18A	0.9900
Ti1—N2	2.220 (2)	C18—H18B	0.9900
Ti1—N1	2.232 (2)	C21—C22	1.399 (4)
Ti1—Ti1i	2.7958 (12)	C21—C26	1.408 (4)
O1—C11	1.332 (3)	C22—C23	1.383 (4)
O2—C21	1.341 (3)	C22—H22	0.9500
O3—Ti1i	1.9292 (19)	C23—C24	1.376 (5)
N1—C17	1.277 (3)	C23—H23	0.9500
N1—C18	1.468 (3)	C24—C25	1.384 (4)
N2—C28	1.471 (4)	C24—H24	0.9500
N2—C27	1.479 (4)	C25—C26	1.392 (4)
N2—H2	0.81 (3)	C25—H25	0.9500
C11—C12	1.393 (4)	C26—C27	1.507 (4)
C11—C16	1.414 (4)	C27—H27A	0.9900
C12—C13	1.382 (4)	C27—H27B	0.9900
C12—H12	0.9500	C28—H28A	0.9900
C13—C14	1.386 (4)	C28—H28B	0.9900
C13—H13	0.9500	C1—Cl2	1.742 (3)
C14—C15	1.378 (4)	C1—Cl1	1.765 (3)
C14—H14	0.9500	C1—Cl3	1.767 (3)
C15—C16	1.403 (4)	C1—H1	1.0000
C15—H15	0.9500
O3—Ti1—O1	101.11 (8)	C15—C16—C11	118.5 (3)
O3—Ti1—O2	98.43 (9)	C15—C16—C17	118.2 (3)
O1—Ti1—O2	95.69 (8)	C11—C16—C17	123.4 (3)
O3—Ti1—O3i	82.80 (9)	N1—C17—C16	124.0 (3)
O1—Ti1—O3i	100.23 (8)	N1—C17—H17	118.0
O2—Ti1—O3i	163.49 (8)	C16—C17—H17	118.0
O3—Ti1—N2	100.65 (9)	N1—C18—C28	107.2 (2)
O1—Ti1—N2	158.23 (9)	N1—C18—H18A	110.3
O2—Ti1—N2	81.27 (9)	C28—C18—H18A	110.3
O3i—Ti1—N2	82.33 (9)	N1—C18—H18B	110.3
O3—Ti1—N1	168.80 (8)	C28—C18—H18B	110.3
O1—Ti1—N1	82.93 (8)	H18A—C18—H18B	108.5
O2—Ti1—N1	91.50 (8)	O2—C21—C22	119.4 (3)
O3i—Ti1—N1	86.21 (8)	O2—C21—C26	121.7 (3)
N2—Ti1—N1	75.64 (9)	C22—C21—C26	118.9 (3)
O3—Ti1—Ti1i	43.20 (6)	C23—C22—C21	120.6 (3)
O1—Ti1—Ti1i	104.27 (6)	C23—C22—H22	119.7
O2—Ti1—Ti1i	139.09 (7)	C21—C22—H22	119.7
O3i—Ti1—Ti1i	39.60 (5)	C24—C23—C22	120.8 (3)
N2—Ti1—Ti1i	91.53 (7)	C24—C23—H23	119.6
N1—Ti1—Ti1i	125.78 (6)	C22—C23—H23	119.6
C11—O1—Ti1	136.03 (17)	C23—C24—C25	119.2 (3)
C21—O2—Ti1	138.85 (18)	C23—C24—H24	120.4
Ti1—O3—Ti1i	97.20 (9)	C25—C24—H24	120.4
C17—N1—C18	119.5 (2)	C24—C25—C26	121.6 (3)
C17—N1—Ti1	127.32 (19)	C24—C25—H25	119.2
C18—N1—Ti1	113.18 (17)	C26—C25—H25	119.2
C28—N2—C27	113.9 (2)	C25—C26—C21	118.9 (3)
C28—N2—Ti1	112.28 (17)	C25—C26—C27	119.7 (3)
C27—N2—Ti1	112.94 (17)	C21—C26—C27	121.3 (2)
C28—N2—H2	107 (2)	N2—C27—C26	113.1 (2)
C27—N2—H2	109 (2)	N2—C27—H27A	109.0
Ti1—N2—H2	100 (2)	C26—C27—H27A	109.0
O1—C11—C12	118.7 (2)	N2—C27—H27B	109.0
O1—C11—C16	122.2 (2)	C26—C27—H27B	109.0
C12—C11—C16	119.1 (3)	H27A—C27—H27B	107.8
C13—C12—C11	120.9 (3)	N2—C28—C18	109.8 (2)
C13—C12—H12	119.5	N2—C28—H28A	109.7
C11—C12—H12	119.5	C18—C28—H28A	109.7
C12—C13—C14	120.5 (3)	N2—C28—H28B	109.7
C12—C13—H13	119.7	C18—C28—H28B	109.7
C14—C13—H13	119.7	H28A—C28—H28B	108.2
C15—C14—C13	119.2 (3)	Cl2—C1—Cl1	110.39 (17)
C15—C14—H14	120.4	Cl2—C1—Cl3	109.84 (18)
C13—C14—H14	120.4	Cl1—C1—Cl3	109.57 (18)
C14—C15—C16	121.7 (3)	Cl2—C1—H1	109.0
C14—C15—H15	119.2	Cl1—C1—H1	109.0
C16—C15—H15	119.2	Cl3—C1—H1	109.0

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···Cl3i	0.81 (3)	2.84 (3)	3.575 (3)	151 (3)
C1—H1···O2	1.00	2.55	3.506 (4)	160
C1—H1···O3	1.00	2.51	3.257 (4)	131
C17—H17···Cg2ii	0.95	2.81	3.754 (4)	174
C23—H23···Cg1iii	0.95	2.86	3.747 (4)	156

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C11–C16 and C21–C26 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯Cl3i	0.81 (3)	2.84 (3)	3.575 (3)	151 (3)
C1—H1⋯O2	1.00	2.55	3.506 (4)	160
C1—H1⋯O3	1.00	2.51	3.257 (4)	131
C17—H17⋯Cg2ii	0.95	2.81	3.754 (4)	174
C23—H23⋯Cg1iii	0.95	2.86	3.747 (4)	156

Symmetry codes: (i) ; (ii) ; (iii) .