Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103022595/bm1541sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103022595/bm1541Isup2.hkl |
CCDC reference: 199378
A solution of tetrabutoxyzirconium (0.5 g, 1.19 mmole; 0.63 g of an 80% w/w solution in butanol) in CH2Cl2 (25 ml) was added dropwise to a solution of tris(2-hydroxy-3,5-dimethylbenzylamine) (0.95 g, 2.4 mmole) in CH2Cl2 (80 ml) and the mixture was stirred for 2 h. The colourless solid was filtered, washed with CH2Cl2 (30 ml) and dried in vacuo (yield 1.0 g, 98%). Analysis for C54H62N2O6Zr, found: C 69.83, H 7.05, N 3.03%; calculated: C 70.02, H 6.75, N 3.02%. Spectroscopic analysis: 1H NMR (400.13 MHz, CDCl3, δ, p.p.m.): 1.88 (s, 9H, 3Me), 2.10 (s, 9H, 3Me), 3.18 (b, 3H, 3CH), 4.67 (b, 3H, 3CH), 6.58 (d, 3JH—H = 1.76 Hz, 3H, 3Me-H), 6.74 (d, 3JH—H = 1.76 Hz, 3H, 3Me-H), 11.78, (b, 2H, 2NH); 13C{1H} NMR (100.6 MHz, CDCl3, δ, p.p.m.): 16.4 (Me), 20.3 (Me), 56.1 (CH2), 116.7 (o-C), 124.8 (o-C), 127.9 (C), 129.5 (C), 132.6 (C), 159.0 (ipso-C). Recrystallization of this product from dry chloroform in air gave colourless crystals of the CHCl3 solvate, (I) (yield: 1.28 g, 100%). Analysis for C56H64Cl6N2O6Zr, found: C 57.60, H 5.52, N 2.30%; calculated: C 57.73, H 5.54, N 2.40%.
All H atoms were included in calculated positions and refined using a riding model [Uiso(H) = 1.2Ueq(C) for CH2, with C—H = 0.99 Å, for aromatic CH, with C—H = 0.95 Å, and for chloroform atom H28, with C—H = 1.00 Å, and Uiso(H) = 1.5Ueq(C) for the Me H atom, with C—H = 0.98 Å], except for atom H1, which was located from a difference Fourier synthesis and refined with N—H = 0.845 Å.
Data collection: SMART (Siemens 1994); cell refinement: SMART; data reduction: SAINT (Siemens 1994); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, YEAR?); software used to prepare material for publication: SHELXL97.
| Fig. 1. A view of the molecular structure of (I), showing 50% probability displacement ellipsoids. H atoms have been omitted for clarity. Fig. 2. Caption required. |
[Zr(C27H31NO3)2]·2CHCl3 | F(000) = 1208 |
Mr = 1165.01 | Dx = 1.388 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 8192 reflections |
a = 11.3902 (2) Å | θ = 2–25° |
b = 13.9774 (1) Å | µ = 0.54 mm−1 |
c = 18.0502 (2) Å | T = 150 K |
β = 104.134 (1)° | Rectangular prism, colourless |
V = 2786.69 (6) Å3 | 0.40 × 0.24 × 0.18 mm |
Z = 2 |
Siemens SMART CCD area-detector diffractometer | 4880 independent reflections |
Radiation source: fine-focus sealed tube | 3907 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.045 |
ω scans | θmax = 25.1°, θmin = 1.8° |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | h = −13→13 |
Tmin = 0.814, Tmax = 0.910 | k = 0→16 |
14693 measured reflections | l = 0→21 |
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: inferred from neighbouring sites |
wR(F2) = 0.115 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.058P)2 + 2.019P] where P = (Fo2 + 2Fc2)/3 |
4880 reflections | (Δ/σ)max = 0.038 |
332 parameters | Δρmax = 0.95 e Å−3 |
0 restraints | Δρmin = −0.68 e Å−3 |
[Zr(C27H31NO3)2]·2CHCl3 | V = 2786.69 (6) Å3 |
Mr = 1165.01 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.3902 (2) Å | µ = 0.54 mm−1 |
b = 13.9774 (1) Å | T = 150 K |
c = 18.0502 (2) Å | 0.40 × 0.24 × 0.18 mm |
β = 104.134 (1)° |
Siemens SMART CCD area-detector diffractometer | 4880 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 3907 reflections with I > 2σ(I) |
Tmin = 0.814, Tmax = 0.910 | Rint = 0.045 |
14693 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.115 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.95 e Å−3 |
4880 reflections | Δρmin = −0.68 e Å−3 |
332 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Zr1 | 0.5000 | 0.5000 | 0.0000 | 0.02112 (12) | |
O1 | 0.63538 (17) | 0.49429 (13) | 0.09969 (11) | 0.0271 (4) | |
O2 | 0.49584 (17) | 0.64560 (13) | 0.01822 (11) | 0.0277 (4) | |
O3 | 0.37773 (17) | 0.48842 (13) | 0.06602 (11) | 0.0279 (4) | |
N1 | 0.50973 (19) | 0.62714 (15) | 0.17501 (13) | 0.0209 (5) | |
C1 | 0.5968 (2) | 0.5714 (2) | 0.23602 (15) | 0.0261 (6) | |
H1A | 0.6037 | 0.6030 | 0.2860 | 0.031* | |
H1B | 0.5641 | 0.5063 | 0.2391 | 0.031* | |
C2 | 0.7203 (2) | 0.56386 (18) | 0.22100 (15) | 0.0242 (6) | |
C3 | 0.7337 (2) | 0.52180 (19) | 0.15277 (15) | 0.0253 (6) | |
C4 | 0.8516 (3) | 0.5080 (2) | 0.14256 (17) | 0.0314 (6) | |
C5 | 0.9495 (3) | 0.5437 (2) | 0.19857 (18) | 0.0355 (7) | |
H5 | 1.0285 | 0.5372 | 0.1905 | 0.043* | |
C6 | 0.9376 (3) | 0.5879 (2) | 0.26499 (18) | 0.0338 (7) | |
C7 | 0.8216 (2) | 0.59609 (19) | 0.27597 (16) | 0.0274 (6) | |
H7 | 0.8107 | 0.6242 | 0.3218 | 0.033* | |
C8 | 0.8706 (3) | 0.4580 (3) | 0.07308 (19) | 0.0458 (8) | |
H8A | 0.8331 | 0.4953 | 0.0275 | 0.069* | |
H8B | 0.8335 | 0.3944 | 0.0693 | 0.069* | |
H8C | 0.9575 | 0.4516 | 0.0769 | 0.069* | |
C9 | 1.0456 (3) | 0.6272 (3) | 0.3234 (2) | 0.0488 (9) | |
H9A | 1.0879 | 0.5748 | 0.3549 | 0.073* | |
H9B | 1.0180 | 0.6738 | 0.3560 | 0.073* | |
H9C | 1.1009 | 0.6586 | 0.2970 | 0.073* | |
C10 | 0.5523 (2) | 0.72804 (19) | 0.16716 (15) | 0.0256 (6) | |
H10A | 0.5472 | 0.7651 | 0.2130 | 0.031* | |
H10B | 0.6383 | 0.7263 | 0.1651 | 0.031* | |
C11 | 0.4798 (2) | 0.77852 (19) | 0.09713 (15) | 0.0230 (5) | |
C12 | 0.4569 (2) | 0.73508 (18) | 0.02470 (15) | 0.0232 (6) | |
C13 | 0.3955 (2) | 0.78637 (19) | −0.04029 (15) | 0.0265 (6) | |
C14 | 0.3582 (3) | 0.8799 (2) | −0.03070 (16) | 0.0285 (6) | |
H14 | 0.3155 | 0.9142 | −0.0745 | 0.034* | |
C15 | 0.3808 (3) | 0.92497 (19) | 0.04009 (16) | 0.0285 (6) | |
C16 | 0.4416 (2) | 0.87291 (19) | 0.10361 (16) | 0.0259 (6) | |
H16 | 0.4577 | 0.9020 | 0.1526 | 0.031* | |
C17 | 0.3728 (3) | 0.7415 (2) | −0.11837 (16) | 0.0374 (7) | |
H17A | 0.3229 | 0.7846 | −0.1561 | 0.056* | |
H17B | 0.3304 | 0.6805 | −0.1183 | 0.056* | |
H17C | 0.4502 | 0.7303 | −0.1315 | 0.056* | |
C18 | 0.3390 (3) | 1.0272 (2) | 0.04710 (19) | 0.0426 (8) | |
H18A | 0.2929 | 1.0497 | −0.0030 | 0.064* | |
H18B | 0.4096 | 1.0685 | 0.0655 | 0.064* | |
H18C | 0.2874 | 1.0292 | 0.0833 | 0.064* | |
C19 | 0.3820 (2) | 0.62293 (19) | 0.18349 (16) | 0.0255 (6) | |
H19A | 0.3289 | 0.6580 | 0.1404 | 0.031* | |
H19B | 0.3780 | 0.6560 | 0.2313 | 0.031* | |
C20 | 0.3342 (2) | 0.52238 (19) | 0.18528 (16) | 0.0239 (6) | |
C21 | 0.3280 (2) | 0.4613 (2) | 0.12224 (15) | 0.0235 (6) | |
C22 | 0.2682 (2) | 0.3725 (2) | 0.11978 (17) | 0.0288 (6) | |
C23 | 0.2196 (2) | 0.3482 (2) | 0.18130 (18) | 0.0329 (7) | |
H23 | 0.1770 | 0.2895 | 0.1790 | 0.039* | |
C24 | 0.2302 (3) | 0.4051 (2) | 0.24538 (17) | 0.0316 (7) | |
C25 | 0.2881 (2) | 0.4930 (2) | 0.24632 (16) | 0.0280 (6) | |
H25 | 0.2963 | 0.5338 | 0.2894 | 0.034* | |
C26 | 0.2572 (3) | 0.3073 (2) | 0.05191 (19) | 0.0406 (8) | |
H26A | 0.3369 | 0.2809 | 0.0520 | 0.061* | |
H26B | 0.2263 | 0.3437 | 0.0048 | 0.061* | |
H26C | 0.2013 | 0.2550 | 0.0548 | 0.061* | |
C27 | 0.1775 (3) | 0.3743 (2) | 0.3111 (2) | 0.0465 (9) | |
H27A | 0.1036 | 0.4109 | 0.3097 | 0.070* | |
H27B | 0.2367 | 0.3861 | 0.3596 | 0.070* | |
H27C | 0.1580 | 0.3059 | 0.3064 | 0.070* | |
C28 | 0.1333 (3) | 0.8117 (2) | 0.0938 (2) | 0.0428 (8) | |
H28 | 0.2052 | 0.8135 | 0.0713 | 0.051* | |
Cl1 | 0.02686 (10) | 0.89636 (8) | 0.04580 (7) | 0.0707 (3) | |
Cl2 | 0.07125 (10) | 0.69675 (7) | 0.08120 (9) | 0.0800 (4) | |
Cl3 | 0.18107 (9) | 0.83990 (8) | 0.19055 (6) | 0.0608 (3) | |
H1 | 0.507 (2) | 0.6016 (19) | 0.1322 (16) | 0.016 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zr1 | 0.0221 (2) | 0.0208 (2) | 0.01944 (19) | 0.00095 (14) | 0.00306 (14) | −0.00211 (14) |
O1 | 0.0256 (10) | 0.0294 (10) | 0.0242 (9) | −0.0001 (8) | 0.0018 (8) | −0.0019 (8) |
O2 | 0.0298 (10) | 0.0244 (10) | 0.0278 (10) | 0.0036 (8) | 0.0049 (8) | −0.0025 (8) |
O3 | 0.0272 (10) | 0.0309 (11) | 0.0253 (10) | −0.0014 (8) | 0.0061 (8) | −0.0017 (8) |
N1 | 0.0202 (11) | 0.0230 (12) | 0.0186 (11) | 0.0003 (9) | 0.0030 (9) | −0.0013 (9) |
C1 | 0.0246 (14) | 0.0289 (14) | 0.0239 (14) | −0.0002 (11) | 0.0040 (11) | 0.0047 (11) |
C2 | 0.0219 (13) | 0.0201 (13) | 0.0279 (14) | 0.0020 (10) | 0.0008 (11) | 0.0037 (11) |
C3 | 0.0221 (14) | 0.0257 (14) | 0.0244 (14) | 0.0016 (11) | −0.0013 (11) | 0.0030 (11) |
C4 | 0.0261 (15) | 0.0383 (16) | 0.0291 (15) | 0.0066 (13) | 0.0053 (12) | 0.0051 (13) |
C5 | 0.0203 (14) | 0.0436 (18) | 0.0406 (17) | 0.0048 (13) | 0.0037 (13) | 0.0068 (15) |
C6 | 0.0251 (15) | 0.0304 (16) | 0.0403 (17) | −0.0007 (12) | −0.0027 (13) | 0.0042 (13) |
C7 | 0.0282 (15) | 0.0253 (14) | 0.0255 (14) | 0.0016 (11) | 0.0001 (11) | 0.0006 (11) |
C8 | 0.0340 (18) | 0.064 (2) | 0.0398 (18) | 0.0144 (17) | 0.0101 (14) | −0.0025 (17) |
C9 | 0.0269 (17) | 0.054 (2) | 0.057 (2) | −0.0029 (15) | −0.0047 (15) | −0.0072 (18) |
C10 | 0.0240 (14) | 0.0223 (13) | 0.0284 (14) | −0.0042 (11) | 0.0022 (11) | −0.0025 (11) |
C11 | 0.0186 (13) | 0.0249 (13) | 0.0256 (13) | −0.0029 (10) | 0.0054 (10) | 0.0006 (11) |
C12 | 0.0197 (13) | 0.0206 (13) | 0.0292 (14) | −0.0017 (10) | 0.0060 (11) | −0.0005 (11) |
C13 | 0.0269 (14) | 0.0242 (14) | 0.0274 (14) | 0.0002 (11) | 0.0044 (11) | 0.0006 (12) |
C14 | 0.0272 (15) | 0.0283 (15) | 0.0286 (14) | 0.0043 (12) | 0.0038 (12) | 0.0062 (12) |
C15 | 0.0277 (15) | 0.0255 (14) | 0.0328 (15) | 0.0013 (11) | 0.0086 (12) | −0.0003 (12) |
C16 | 0.0248 (14) | 0.0262 (14) | 0.0263 (14) | −0.0012 (11) | 0.0058 (11) | −0.0040 (12) |
C17 | 0.0506 (19) | 0.0327 (16) | 0.0259 (15) | 0.0071 (14) | 0.0038 (13) | 0.0018 (13) |
C18 | 0.055 (2) | 0.0324 (16) | 0.0381 (18) | 0.0115 (15) | 0.0070 (15) | −0.0020 (14) |
C19 | 0.0206 (13) | 0.0261 (14) | 0.0313 (14) | 0.0027 (11) | 0.0090 (11) | −0.0015 (12) |
C20 | 0.0148 (12) | 0.0277 (14) | 0.0284 (14) | 0.0040 (10) | 0.0038 (10) | 0.0006 (11) |
C21 | 0.0154 (13) | 0.0274 (13) | 0.0272 (14) | 0.0030 (11) | 0.0040 (10) | 0.0033 (11) |
C22 | 0.0191 (13) | 0.0263 (14) | 0.0390 (16) | 0.0011 (11) | 0.0033 (12) | −0.0002 (12) |
C23 | 0.0214 (14) | 0.0264 (15) | 0.0508 (19) | 0.0019 (11) | 0.0090 (13) | 0.0092 (13) |
C24 | 0.0226 (14) | 0.0344 (16) | 0.0402 (17) | 0.0087 (12) | 0.0120 (13) | 0.0086 (14) |
C25 | 0.0213 (14) | 0.0337 (15) | 0.0302 (14) | 0.0065 (12) | 0.0087 (11) | 0.0020 (12) |
C26 | 0.0369 (18) | 0.0354 (17) | 0.0483 (19) | −0.0079 (14) | 0.0083 (15) | −0.0102 (15) |
C27 | 0.045 (2) | 0.0422 (19) | 0.061 (2) | 0.0050 (15) | 0.0311 (18) | 0.0118 (17) |
C28 | 0.0363 (18) | 0.0401 (18) | 0.052 (2) | 0.0066 (15) | 0.0118 (15) | 0.0047 (16) |
Cl1 | 0.0697 (7) | 0.0652 (7) | 0.0746 (7) | 0.0233 (5) | 0.0123 (5) | 0.0325 (6) |
Cl2 | 0.0520 (6) | 0.0440 (6) | 0.1264 (10) | −0.0070 (4) | −0.0121 (6) | −0.0067 (6) |
Cl3 | 0.0613 (6) | 0.0692 (6) | 0.0497 (5) | 0.0150 (5) | 0.0097 (4) | −0.0101 (5) |
Zr1—O1 | 2.066 (2) | C10—C11 | 1.506 (4) |
Zr1—O2 | 2.064 (2) | C11—C16 | 1.403 (4) |
Zr1—O3 | 2.049 (2) | C11—C12 | 1.407 (4) |
Zr1—H1 | 2.76 (3) | C12—C13 | 1.406 (4) |
O1—C3 | 1.340 (3) | C13—C14 | 1.399 (4) |
O1—H1 | 2.27 (3) | C13—C17 | 1.506 (4) |
O2—C12 | 1.342 (3) | C14—C15 | 1.391 (4) |
O2—H1 | 2.12 (3) | C15—C16 | 1.391 (4) |
O3—C21 | 1.333 (3) | C15—C18 | 1.521 (4) |
O3—H1 | 2.29 (3) | C19—C20 | 1.511 (4) |
N1—C19 | 1.501 (3) | C20—C25 | 1.393 (4) |
N1—C1 | 1.506 (3) | C20—C21 | 1.411 (4) |
N1—C10 | 1.509 (3) | C21—C22 | 1.410 (4) |
C1—C2 | 1.500 (4) | C22—C23 | 1.398 (4) |
C2—C7 | 1.400 (4) | C22—C26 | 1.507 (4) |
C2—C3 | 1.406 (4) | C23—C24 | 1.384 (4) |
C3—C4 | 1.413 (4) | C24—C25 | 1.392 (4) |
C4—C5 | 1.402 (4) | C24—C27 | 1.517 (4) |
C4—C8 | 1.497 (4) | C28—Cl1 | 1.764 (3) |
C5—C6 | 1.385 (4) | C28—Cl2 | 1.747 (3) |
C6—C7 | 1.388 (4) | C28—Cl3 | 1.742 (4) |
C6—C9 | 1.515 (4) | ||
O1—Zr1—O2 | 86.60 (7) | C11—C10—N1 | 113.2 (2) |
O1—Zr1—O3 | 87.66 (8) | C16—C11—C12 | 119.5 (2) |
O2—Zr1—O3 | 86.56 (7) | C16—C11—C10 | 119.2 (2) |
O1—Zr1—H1 | 53.8 (5) | C12—C11—C10 | 121.1 (2) |
O2—Zr1—H1 | 49.6 (6) | O2—C12—C13 | 120.7 (2) |
O3—Zr1—H1 | 54.5 (6) | O2—C12—C11 | 119.5 (2) |
C3—O1—Zr1 | 158.04 (17) | C13—C12—C11 | 119.8 (2) |
C3—O1—H1 | 96.0 (7) | C14—C13—C12 | 118.5 (2) |
Zr1—O1—H1 | 79.0 (7) | C14—C13—C17 | 121.1 (2) |
C12—O2—Zr1 | 162.56 (17) | C12—C13—C17 | 120.3 (2) |
C12—O2—H1 | 97.4 (8) | C15—C14—C13 | 122.9 (3) |
Zr1—O2—H1 | 82.6 (8) | C14—C15—C16 | 117.6 (2) |
C21—O3—Zr1 | 160.29 (18) | C14—C15—C18 | 120.7 (3) |
C21—O3—H1 | 98.0 (7) | C16—C15—C18 | 121.7 (3) |
Zr1—O3—H1 | 78.8 (7) | C15—C16—C11 | 121.7 (3) |
C19—N1—C1 | 112.7 (2) | N1—C19—C20 | 113.7 (2) |
C19—N1—C10 | 112.8 (2) | C25—C20—C21 | 120.3 (2) |
C1—N1—C10 | 112.5 (2) | C25—C20—C19 | 119.9 (2) |
C2—C1—N1 | 112.5 (2) | C21—C20—C19 | 119.6 (2) |
C7—C2—C3 | 120.6 (3) | O3—C21—C20 | 119.7 (2) |
C7—C2—C1 | 119.7 (2) | O3—C21—C22 | 121.2 (2) |
C3—C2—C1 | 119.7 (2) | C20—C21—C22 | 119.1 (2) |
O1—C3—C2 | 119.7 (2) | C23—C22—C21 | 118.0 (3) |
O1—C3—C4 | 121.5 (2) | C23—C22—C26 | 121.9 (3) |
C2—C3—C4 | 118.8 (2) | C21—C22—C26 | 120.1 (3) |
C5—C4—C3 | 118.1 (3) | C24—C23—C22 | 123.6 (3) |
C5—C4—C8 | 121.2 (3) | C23—C24—C25 | 117.5 (3) |
C3—C4—C8 | 120.6 (3) | C23—C24—C27 | 121.3 (3) |
C6—C5—C4 | 123.6 (3) | C25—C24—C27 | 121.2 (3) |
C5—C6—C7 | 117.3 (3) | C24—C25—C20 | 121.3 (3) |
C5—C6—C9 | 122.0 (3) | Cl3—C28—Cl2 | 110.9 (2) |
C7—C6—C9 | 120.7 (3) | Cl3—C28—Cl1 | 110.45 (18) |
C6—C7—C2 | 121.4 (3) | Cl2—C28—Cl1 | 110.18 (19) |
Experimental details
Crystal data | |
Chemical formula | [Zr(C27H31NO3)2]·2CHCl3 |
Mr | 1165.01 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 150 |
a, b, c (Å) | 11.3902 (2), 13.9774 (1), 18.0502 (2) |
β (°) | 104.134 (1) |
V (Å3) | 2786.69 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.54 |
Crystal size (mm) | 0.40 × 0.24 × 0.18 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.814, 0.910 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14693, 4880, 3907 |
Rint | 0.045 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.115, 1.04 |
No. of reflections | 4880 |
No. of parameters | 332 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.95, −0.68 |
Computer programs: SMART (Siemens 1994), SMART, SAINT (Siemens 1994), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, YEAR?), SHELXL97.
Zr1—O1 | 2.066 (2) | O1—H1 | 2.27 (3) |
Zr1—O2 | 2.064 (2) | O2—C12 | 1.342 (3) |
Zr1—O3 | 2.049 (2) | O2—H1 | 2.12 (3) |
Zr1—H1 | 2.76 (3) | O3—C21 | 1.333 (3) |
O1—C3 | 1.340 (3) | O3—H1 | 2.29 (3) |
O1—Zr1—O2 | 86.60 (7) | C3—O1—Zr1 | 158.04 (17) |
O1—Zr1—O3 | 87.66 (8) | C12—O2—Zr1 | 162.56 (17) |
O2—Zr1—O3 | 86.56 (7) | C21—O3—Zr1 | 160.29 (18) |
O1—Zr1—H1 | 53.8 (5) | C19—N1—C1 | 112.7 (2) |
O2—Zr1—H1 | 49.6 (6) | C19—N1—C10 | 112.8 (2) |
O3—Zr1—H1 | 54.5 (6) | C1—N1—C10 | 112.5 (2) |
When two equivalents of tris(2-hydroxy-3,5-dimethylbenzyl)amine, {N[N(YOH)3]} (Y is?), are added to [Zr(OnBu)4] in CH2Cl2, a colourless air-stable precipitate appears in the solution after ca 10 min. Analytical data are consistent with two tris(phenoxide) ligands and one Zr atom. The complex is insoluble in CH2Cl2 but readily dissolves in CHCl3 and was crystallized from the latter solvent as the chloroform disolvate, (I). \sch
The structural arrangement in (I) is shown in Fig. 1. The Zr atom lies on a centre of symmetry surrounded by a distorted octahedral arrangement of six similar phenoxy O atoms, suggesting that this part of the complex has an overall formal charge of 2-, as might be expected for a [Zr(OAr)6]2− dianion. However, whereas [ZrCl6]2− is well known (e.g. [NMe4]2[ZrCl6]; Morss et al., 1991), [Zr(OAr)6]2− is apparently not, the nearest equivalent being [Zr(SAr)6]2− (Friese et al., 2000). The alternative, whereby one of the phenoxy ligands in each ligand is protonated, is inconsistent with the observed 1H NMR spectrum, which shows a symmetrical complex. Inspection of the difference map in the vicinity of the donor O atoms also failed to show signs of any protonation. However, a potential site for the extra H atom was detected near the N atom of each ligand, giving the N atom a positive charge and thus maintaining charge balance. A similar structure has recently been reported for the zwitterion moiety when crystallized with toluene molecules of crystallization (Davidson et al., 2003).
The Zr—O bond lengths in (I) [2.066 (2), 2.064 (2) and 2.049 (2) Å] are similar to those found in phenoxide complexes where the O → Zr π donation is also spread over several O atom donors, e.g. in [Zr(O—C6H4NO2-4)(acac)3], where the phenoxide Zr—O bond length is 2.045 (3) Å (Dinger & Scott, 2001)}, and in the toluene analogue of (I) (Davidson et al., 2003), where corresponding values of 2.058 (2), 2.064 (2) and 2.057 (2) Å are observed. The Zr—O—C bond angles of 158.0 (2), 162.6 (2) and 160.3 (2)° do not differ greatly from those observed in [Ti(OCHMe2)(N(YO)3)] [Ti—O—C bond angles 164.4 (6)°; Kol et al., 2001] or in the toluene solvate of (I) [Zr—O—C bond angles 157.2 (2), 154.5 (2) and 160.0 (2)°; Davidson et al., 2003]. The N-bound H atom is trapped in a cage-like arrangement, at distances of 2.27, 2.12 and 2.29 Å from atoms O1, O2 and O3, respectively, such approaches being indicative of H···O hydrogen bonding. The H atom points directly at the Zr [Zr···H—N 174 (2)°] at a distance of 2.76 (3) Å. The Zr···N separation is 3.603 (2) Å.
A further feature of the structure of (I) is the two chloroform molecules found associated with each Zr complex. In this respect the current structure differs from that of the recently reported zwitterion with toluene solvate (Davidson et al., 2003). The H atom of each chloroform points directly at one of the benzene rings of each phenoxide moiety, approaching its C atoms at 2.70, 2.74, 2.98, 3.09, 3.32 and 3.36 Å. The H···ring-centroid distance is 2.71 Å. A survey of the Cambridge Structural Database (Version?; Allen, 2002) shows that a similar feature has been previously crystallographically characterized, but only in a few phenoxide complexes (Sudbrake & Vahrenkamp, 2001, and references therein). There is NMR evidence for such an interaction in solution (Nishio et al., 1995). This weak hydrogen-bond interaction provides a possible explanation as to why the complex is soluble in CHCl3 but is almost completely insoluble in CH2Cl2.
From the coeditor: AUTHOR: the datanames such as _diffrn_reflns_limit_h_min refer to the data as measured, not the unique fraction. Please supply the correct range.