Buy article online - an online subscription or single-article purchase is required to access this article.
The title complex, [Ti(C
5H
5)(C
2H
6N)
2Cl], exhibits two nearly planar dimethylamide groups oriented approximately perpendicular to each other. The Ti
cyclopentadienyl centroid vector lies nearly in the plane of one of the dimethylamide groups. Long-range contacts between Ti-Cl and cyclopentadienyl H-C groups give rise to geometric ordering in the extended solid.
Supporting information
CCDC reference: 786803
Data collection: SMART (Bruker, 2003); cell refinement: SMART (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalMaker (Palmer, 2005); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
Chlorido(
η5-cyclopentadienyl)bis(dimethylamido)titanium
top
Crystal data top
[Ti(C5H5)(C2H6N)2Cl] | F(000) = 496 |
Mr = 236.60 | Dx = 1.351 Mg m−3 |
Monoclinic, P21/n | Melting point: 336 K |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 9.3621 (9) Å | Cell parameters from 9781 reflections |
b = 11.0618 (10) Å | θ = 2.5–25.4° |
c = 11.5907 (11) Å | µ = 0.93 mm−1 |
β = 104.259 (1)° | T = 100 K |
V = 1163.37 (19) Å3 | Block, dark red |
Z = 4 | 0.20 × 0.20 × 0.20 mm |
Data collection top
Bruker SMART CCD area-detector diffractometer | 2133 independent reflections |
Radiation source: fine-focus sealed tube | 1960 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.035 |
φ and ω scans | θmax = 25.4°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −11→11 |
Tmin = 0.837, Tmax = 0.837 | k = −13→13 |
14937 measured reflections | l = −13→13 |
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)] = 0.025 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.064 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0284P)2 + 0.6046P] where P = (Fo2 + 2Fc2)/3 |
2133 reflections | (Δ/σ)max < 0.001 |
122 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
Special details top
Experimental. Data were collected on a single parallelepiped. The crystal was mounted on a
Cryoloop with Paratone-N oil. The crystal-to-detector distance was 60 mm and
exposure time was 10 s per frame using a scan width of 0.5°. |
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 | Uiso*/Ueq | |
Ti1 | 0.21237 (3) | 0.33216 (3) | 0.47002 (2) | 0.01448 (10) | |
Cl1 | 0.32843 (4) | 0.45489 (4) | 0.63118 (4) | 0.02238 (12) | |
N1 | 0.05397 (14) | 0.24969 (13) | 0.51023 (12) | 0.0188 (3) | |
N2 | 0.35083 (15) | 0.20437 (13) | 0.48327 (12) | 0.0180 (3) | |
C1 | 0.02702 (19) | 0.43809 (17) | 0.32309 (15) | 0.0259 (4) | |
H1A | −0.0758 | 0.4560 | 0.3287 | 0.031* | |
C2 | 0.07278 (19) | 0.33411 (16) | 0.27054 (15) | 0.0229 (4) | |
H2A | 0.0072 | 0.2676 | 0.2295 | 0.027* | |
C3 | 0.22210 (19) | 0.35011 (17) | 0.27068 (15) | 0.0247 (4) | |
H3A | 0.2802 | 0.2971 | 0.2292 | 0.030* | |
C4 | 0.2699 (2) | 0.46095 (17) | 0.32627 (16) | 0.0276 (4) | |
H4A | 0.3676 | 0.5000 | 0.3312 | 0.033* | |
C5 | 0.1480 (2) | 0.51503 (17) | 0.35797 (16) | 0.0296 (4) | |
H5A | 0.1464 | 0.5978 | 0.3923 | 0.036* | |
C6 | 0.1004 (2) | 0.20015 (17) | 0.63148 (15) | 0.0255 (4) | |
H6A | 0.0848 | 0.1125 | 0.6289 | 0.038* | |
H6B | 0.0421 | 0.2374 | 0.6816 | 0.038* | |
H6C | 0.2051 | 0.2176 | 0.6647 | 0.038* | |
C7 | −0.09587 (19) | 0.21187 (18) | 0.45330 (16) | 0.0265 (4) | |
H7A | −0.1594 | 0.2254 | 0.5078 | 0.040* | |
H7B | −0.0963 | 0.1258 | 0.4333 | 0.040* | |
H7C | −0.1328 | 0.2590 | 0.3805 | 0.040* | |
C8 | 0.32302 (19) | 0.07510 (15) | 0.48449 (16) | 0.0237 (4) | |
H8A | 0.3886 | 0.0389 | 0.5551 | 0.036* | |
H8B | 0.3415 | 0.0381 | 0.4127 | 0.036* | |
H8C | 0.2202 | 0.0612 | 0.4864 | 0.036* | |
C9 | 0.49634 (18) | 0.22941 (17) | 0.46392 (15) | 0.0233 (4) | |
H9A | 0.5722 | 0.1934 | 0.5285 | 0.035* | |
H9B | 0.5114 | 0.3170 | 0.4626 | 0.035* | |
H9C | 0.5031 | 0.1946 | 0.3877 | 0.035* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ti1 | 0.01332 (16) | 0.01598 (17) | 0.01359 (16) | 0.00148 (11) | 0.00225 (11) | 0.00040 (11) |
Cl1 | 0.0195 (2) | 0.0246 (2) | 0.0216 (2) | −0.00071 (16) | 0.00208 (16) | −0.00661 (16) |
N1 | 0.0170 (7) | 0.0210 (7) | 0.0179 (7) | −0.0004 (6) | 0.0035 (5) | −0.0002 (6) |
N2 | 0.0178 (7) | 0.0194 (7) | 0.0165 (7) | 0.0025 (6) | 0.0038 (5) | 0.0003 (6) |
C1 | 0.0220 (9) | 0.0341 (10) | 0.0197 (9) | 0.0114 (8) | 0.0015 (7) | 0.0091 (8) |
C2 | 0.0210 (9) | 0.0323 (10) | 0.0129 (8) | 0.0013 (7) | −0.0005 (7) | 0.0015 (7) |
C3 | 0.0225 (9) | 0.0377 (11) | 0.0140 (8) | 0.0075 (8) | 0.0049 (7) | 0.0064 (7) |
C4 | 0.0247 (9) | 0.0335 (10) | 0.0228 (9) | −0.0041 (8) | 0.0028 (7) | 0.0121 (8) |
C5 | 0.0400 (11) | 0.0210 (9) | 0.0254 (9) | 0.0071 (8) | 0.0034 (8) | 0.0088 (8) |
C6 | 0.0267 (9) | 0.0292 (10) | 0.0220 (9) | −0.0008 (8) | 0.0084 (7) | 0.0048 (8) |
C7 | 0.0201 (9) | 0.0322 (10) | 0.0277 (10) | −0.0073 (8) | 0.0064 (7) | −0.0038 (8) |
C8 | 0.0267 (9) | 0.0189 (9) | 0.0247 (9) | 0.0036 (7) | 0.0049 (7) | −0.0029 (7) |
C9 | 0.0172 (8) | 0.0313 (10) | 0.0216 (9) | 0.0062 (7) | 0.0054 (7) | 0.0037 (7) |
Geometric parameters (Å, º) top
Ti1—N1 | 1.8945 (14) | C3—C4 | 1.406 (3) |
Ti1—N2 | 1.8984 (14) | C3—H3A | 1.0000 |
Ti1—C3 | 2.3430 (17) | C4—C5 | 1.415 (3) |
Ti1—Cl1 | 2.3480 (5) | C4—H4A | 1.0000 |
Ti1—C4 | 2.3534 (17) | C5—H5A | 1.0000 |
Ti1—C2 | 2.3592 (17) | C6—H6A | 0.9800 |
Ti1—C5 | 2.3993 (18) | C6—H6B | 0.9800 |
Ti1—C1 | 2.4143 (16) | C6—H6C | 0.9800 |
N1—C7 | 1.457 (2) | C7—H7A | 0.9800 |
N1—C6 | 1.471 (2) | C7—H7B | 0.9800 |
N2—C8 | 1.454 (2) | C7—H7C | 0.9800 |
N2—C9 | 1.461 (2) | C8—H8A | 0.9800 |
C1—C5 | 1.395 (3) | C8—H8B | 0.9800 |
C1—C2 | 1.416 (3) | C8—H8C | 0.9800 |
C1—H1A | 1.0000 | C9—H9A | 0.9800 |
C2—C3 | 1.409 (2) | C9—H9B | 0.9800 |
C2—H2A | 1.0000 | C9—H9C | 0.9800 |
| | | |
N1—Ti1—N2 | 100.48 (6) | C1—C2—H2A | 125.9 |
N1—Ti1—C3 | 120.42 (6) | Ti1—C2—H2A | 125.9 |
N2—Ti1—C3 | 87.21 (6) | C4—C3—C2 | 108.30 (16) |
N1—Ti1—Cl1 | 108.64 (4) | C4—C3—Ti1 | 72.98 (10) |
N2—Ti1—Cl1 | 101.14 (4) | C2—C3—Ti1 | 73.20 (9) |
C3—Ti1—Cl1 | 127.79 (5) | C4—C3—H3A | 125.6 |
N1—Ti1—C4 | 142.68 (6) | C2—C3—H3A | 125.6 |
N2—Ti1—C4 | 103.72 (6) | Ti1—C3—H3A | 125.6 |
C3—Ti1—C4 | 34.84 (7) | C3—C4—C5 | 107.55 (16) |
Cl1—Ti1—C4 | 94.10 (5) | C3—C4—Ti1 | 72.18 (10) |
N1—Ti1—C2 | 88.12 (6) | C5—C4—Ti1 | 74.46 (10) |
N2—Ti1—C2 | 106.77 (6) | C3—C4—H4A | 125.9 |
C3—Ti1—C2 | 34.86 (6) | C5—C4—H4A | 125.9 |
Cl1—Ti1—C2 | 144.14 (5) | Ti1—C4—H4A | 125.9 |
C4—Ti1—C2 | 57.91 (6) | C1—C5—C4 | 108.43 (17) |
N1—Ti1—C5 | 115.58 (6) | C1—C5—Ti1 | 73.75 (10) |
N2—Ti1—C5 | 138.33 (6) | C4—C5—Ti1 | 70.92 (10) |
C3—Ti1—C5 | 57.34 (7) | C1—C5—H5A | 125.7 |
Cl1—Ti1—C5 | 87.04 (5) | C4—C5—H5A | 125.7 |
C4—Ti1—C5 | 34.62 (7) | Ti1—C5—H5A | 125.7 |
C2—Ti1—C5 | 57.12 (6) | N1—C6—H6A | 109.5 |
N1—Ti1—C1 | 86.39 (6) | N1—C6—H6B | 109.5 |
N2—Ti1—C1 | 140.92 (6) | H6A—C6—H6B | 109.5 |
C3—Ti1—C1 | 57.25 (6) | N1—C6—H6C | 109.5 |
Cl1—Ti1—C1 | 113.07 (5) | H6A—C6—H6C | 109.5 |
C4—Ti1—C1 | 57.10 (6) | H6B—C6—H6C | 109.5 |
C2—Ti1—C1 | 34.50 (6) | N1—C7—H7A | 109.5 |
C5—Ti1—C1 | 33.69 (6) | N1—C7—H7B | 109.5 |
C7—N1—C6 | 110.52 (13) | H7A—C7—H7B | 109.5 |
C7—N1—Ti1 | 138.73 (11) | N1—C7—H7C | 109.5 |
C6—N1—Ti1 | 110.47 (10) | H7A—C7—H7C | 109.5 |
C8—N2—C9 | 111.34 (14) | H7B—C7—H7C | 109.5 |
C8—N2—Ti1 | 127.78 (11) | N2—C8—H8A | 109.5 |
C9—N2—Ti1 | 119.37 (11) | N2—C8—H8B | 109.5 |
C5—C1—C2 | 108.07 (16) | H8A—C8—H8B | 109.5 |
C5—C1—Ti1 | 72.57 (10) | N2—C8—H8C | 109.5 |
C2—C1—Ti1 | 70.62 (9) | H8A—C8—H8C | 109.5 |
C5—C1—H1A | 125.9 | H8B—C8—H8C | 109.5 |
C2—C1—H1A | 125.9 | N2—C9—H9A | 109.5 |
Ti1—C1—H1A | 125.9 | N2—C9—H9B | 109.5 |
C3—C2—C1 | 107.62 (16) | H9A—C9—H9B | 109.5 |
C3—C2—Ti1 | 71.94 (9) | N2—C9—H9C | 109.5 |
C1—C2—Ti1 | 74.88 (10) | H9A—C9—H9C | 109.5 |
C3—C2—H2A | 125.9 | H9B—C9—H9C | 109.5 |
Mean structural parameters for CpTiClx(NR2)3-x complexes (Å, °) topComplex | (2) | (3) | (1a) | (1b) | (4) |
Ti—C | 2.314 | 2.345 | 2.374 | 2.378 | 2.377 |
Ti—N | | 1.864 | 1.896 | 1.899 | 1.897/2.055 |
Ti—Cl | 2.224 | 2.298 | 2.348 | 2.308 | |
Cl—Ti—Cl | 102.9 | 103.4 | | | |
Cl—Ti—N | | 106.1 | 104.9 | 104.2 | |
N—Ti—N | | | 100.5 | 99.5 | 102.6 |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
If you have already registered and are using a computer listed in your registration details, please email
support@iucr.org for assistance.