Bis{4,4′,6,6′-tetra­chloro-2,2′-[trans-(R,R)-cyclo­hexane-1,2-diylbis(imino­methyl­ene)]diphenolato-κ4O,N,N′,O′}zirconium(IV)

Shalumova, T.; Tanski, J.M.

doi:10.1107/S1600536808021247

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Pages m1029-m1030

doi:10.1107/S1600536808021247

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Bis{4,4′,6,6′-tetrachloro-2,2′-[trans-(R,R)-cyclohexane-1,2-diylbis(iminomethylene)]diphenolato-κ⁴O,N,N′,O′}zirconium(IV)

Tamila Shalumova ^a and Joseph M. Tanski ^a ^*

^aDepartment of Chemistry, Vassar College, Poughkeepsie, NY 12604, USA
^*Correspondence e-mail: jotanski@vassar.edu

(Received 3 July 2008; accepted 8 July 2008; online 16 July 2008)

The title mononuclear complex, [Zr(C₂₀H₂₀Cl₄N₂O₂)₂], was obtained by allowing hexane to diffuse into a diethyl ether solution of zirconium(IV) sec-butoxide and the enantiomerically pure tetradentate ligand N,N′-bis(3,5-dichloro-2-hydroxybenzyl)-trans-(R,R)-1,2-diaminocyclohexane. The metal centre is eight-coordinate and displays a distorted dodecahedral coordination environment with average Zr—O and Zr—N bond lengths of 2.082 (9) and 2.441 (8) Å, respectively. In the crystal structure, complex molecules are linked by intermolecular C—H⋯Cl hydrogen-bond interactions into zigzag chains running parallel to the [101] direction. C—H⋯O and N—H⋯O hydrogen bonds are also present.

Related literature

For examples of eight-coordinate zirconium complexes with related salen-type ligands (salen = N,N′-ethylenebis(salicylideneimine), see: Archer et al. (1979 ); Illingsworth et al. (2002 ); Zhu et al. (2005 ). For related literature on salan-type complexes [salan = N,N′-ethylenebis(2-hydroxybenzyl)], see: García-Zarracino et al. (2002 ); Yeori et al. (2005 ).

Experimental

Crystal data

[Zr(C₂₀H₂₀Cl₄N₂O₂)₂]
M_r = 1015.58
Monoclinic, P 2₁
a = 11.2570 (6) Å
b = 16.4848 (8) Å
c = 12.7431 (6) Å
β = 114.686 (1)°
V = 2148.62 (18) Å³
Z = 2
Mo Kα radiation
μ = 0.80 mm⁻¹
T = 125 (2) K
0.15 × 0.09 × 0.02 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.889, T_max = 0.984
29336 measured reflections
11081 independent reflections
9280 reflections with I > 2σ(I)
R_int = 0.047

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.068
S = 1.00
11081 reflections
527 parameters
5 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.52 e Å⁻³
Δρ_min = −0.37 e Å⁻³
Absolute structure: Flack (1983 ), 5344 Friedel pairs
Flack parameter: −0.01 (3)

Table 1
Selected geometric parameters (Å, °)

Zr—O22	2.070 (2)
Zr—O21	2.0819 (19)
Zr—O11	2.088 (2)
Zr—O12	2.089 (2)
Zr—N11	2.433 (2)
Zr—N22	2.439 (2)
Zr—N12	2.443 (2)
Zr—N21	2.451 (2)

O22—Zr—O21	102.13 (8)
O22—Zr—O11	92.19 (8)
O21—Zr—O11	139.47 (8)
O22—Zr—O12	139.85 (8)
O21—Zr—O12	91.98 (8)
O11—Zr—O12	101.11 (8)
N22—Zr—N12	70.83 (8)
N11—Zr—N21	70.16 (8)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N11—H11⋯O22	0.89 (2)	2.28 (3)	2.662 (3)	105.7 (18)
N21—H21⋯O12	0.89 (2)	2.32 (4)	2.722 (4)	108 (2)
N21—H21⋯Cl42	0.89 (2)	2.76 (2)	3.631 (3)	166.8 (16)
N22—H22⋯O21	0.89 (2)	2.34 (3)	2.701 (4)	104.1 (18)
C72—H72B⋯O21	0.99	2.44	3.024 (4)	117
C132—H13B⋯O11	1.00	2.53	2.987 (3)	108
C141—H14B⋯O22	0.99	2.58	3.137 (4)	115
C51—H51A⋯Cl22ⁱ	0.95	2.83	3.654 (3)	146
C122—H12C⋯Cl22ⁱⁱ	0.99	2.72	3.402 (3)	126
Symmetry codes: (i) $[-x, y+{\script{1\over 2}}, -z]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+1]$ .

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); 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 global, I. DOI: 10.1107/S1600536808021247/rz2233sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808021247/rz2233Isup2.hkl

checkCIF report

Comment top

Salcean type ligands (salcean = N,N'-bis(2-hydroxybenzyl)-1,2-diaminocyclohexane) may be obtained by reduction of the imine C=N bond of the more ubiquitous salcen type ligands (salcen = N,N'-bis(salicylidene)-1,2-diaminocyclohexane), a derivative of the general class of salen ligands (salen = N,N'-ethylenebis(salicylideneimine)) containing a cyclohexyldiamine backbone (Yeori et al., 2005). Whereas titanium(IV) alkoxides, Ti(OR)₄, coordinate one salcean ligand to yield complexes of the type [salcean]Ti(OR)₂ with the loss of two equivalents of alcohol (Yeori et al., 2005), two equivalents of salcean may displace all four alkoxides from a zirconium(IV) alkoxide, resulting in a distorted dodecahedral eight-coordinate bis(salcean)zirconium(IV) complex, as reported here. Although the structure of no other bis(salcean)zirconium(IV) complex has been reported, similar eight coordinate zirconium(IV) complexes with salen type ligands exhibiting a distorted dodecahedral coordination sphere are known (Archer et al., 1979; Illingsworth et al., 2001; Zhu et al., 2005).

The title compound (Fig. 1), was obtained by treating zirconium(IV) sec-butoxide with salcean(Cl)₄H₄ (salcean(Cl)₄H₄ = (N,N'-bis(3,5-dichloro-2-hydroxybenzyl)-trans-(R,R)-1,2-diamino-cyclohexane). The zirconium atom is eight-coordinate and exhibits a dodecahedral coordination geometry due to the attachment of two tetradentate salcean ligands with two O,N,N',O' donor atom sets. Each salcean ligand binds the metal center in a trans mer-mer fashion (García-Zarracino et al., 2002), with all four donor atoms nearly in a plane. The angle between the least-squares planes of the O,N,N',O' donor set of the ligands is 87.73 (5)°. The average Zr—O bond length is 2.082 (9) Å, while the average Zr—N bond length is 2.441 (8) Å. Notable bond lengths and angles are listed in Table 1. These bond lengths and angles are similar to those reported in the literature for related bis(salen)zirconium(IV) complexes (Archer et al., 1979; Zhu et al., 2005). The conformation of the complex is stabilized by intramolecular N—H···O, N—H···Cl and C—H···O hydrogen bonding interactions (Table 2). In the crystal structure, complex molecules are linked into zig-zag chains running parallel to the [101] direction by intermolecular C—H···Cl hydrogen bonds (Table 2).

Related literature top

For examples of eight-coordinate zirconium complexes with related salen type ligands (salen = N,N'-ethylenebis(salicylideneimine), see: Archer et al. (1979); Illingsworth et al. (2002); Zhu et al. (2005). For related literature on salan-type complexes (salan = N,N'-ethylenebis(2-hydroxybenzyl)), see: García-Zarracino et al. (2002); Yeori et al. (2005).

Experimental top

The title compound was crystallized from a 2 ml diethyl ether solution of Zr(O^S-2Bu)₄ (20 mg, 0.052 mmol) and N,N'-bis(3,5-dichloro-2-hydroxybenzyl)-trans-(R,R)-1,2-diaminocyclohexane (25 mg, 0.054 mmol), under a nitrogen atmosphere. Slow diffusion of hexanes into the solution allowed crystals to form as colourless parallelepipeds within two weeks.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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. A view of the title compound, with displacement ellipsoids shown at the 50% probability level. H atoms on carbon atoms have been omitted for clarity.

Bis{4,4',6,6'-tetrachloro-2,2'-[trans-(R,R)-cyclohexane-1,2- diylbis(iminomethylene)]diphenolato-κ⁴O,N,N',O'}zirconium(IV) top

Crystal data top

[Zr(C₂₀H₂₀Cl₄N₂O₂)₂]	F(000) = 1032
M_r = 1015.58	D_x = 1.570 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 9891 reflections
a = 11.2570 (6) Å	θ = 2.3–30.0°
b = 16.4848 (8) Å	µ = 0.80 mm⁻¹
c = 12.7431 (6) Å	T = 125 K
β = 114.686 (1)°	Block, colourless
V = 2148.62 (18) Å³	0.15 × 0.09 × 0.02 mm
Z = 2

Data collection top

Bruker APEXII CCD diffractometer	11081 independent reflections
Radiation source: fine-focus sealed tube	9280 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.047
ϕ and ω scans	θ_max = 28.7°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −15→15
T_min = 0.890, T_max = 0.984	k = −22→22
29336 measured reflections	l = −17→17

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.068	w = 1/[σ²(F_o²) + (0.024P)²] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
11081 reflections	Δρ_max = 0.52 e Å⁻³
527 parameters	Δρ_min = −0.37 e Å⁻³
5 restraints	Absolute structure: Flack (1983), 5344 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.01 (3)

Crystal data top

[Zr(C₂₀H₂₀Cl₄N₂O₂)₂]	V = 2148.62 (18) Å³
M_r = 1015.58	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 11.2570 (6) Å	µ = 0.80 mm⁻¹
b = 16.4848 (8) Å	T = 125 K
c = 12.7431 (6) Å	0.15 × 0.09 × 0.02 mm
β = 114.686 (1)°

Data collection top

Bruker APEXII CCD diffractometer	11081 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	9280 reflections with I > 2σ(I)
T_min = 0.890, T_max = 0.984	R_int = 0.047
29336 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.068	Δρ_max = 0.52 e Å⁻³
S = 1.01	Δρ_min = −0.37 e Å⁻³
11081 reflections	Absolute structure: Flack (1983), 5344 Friedel pairs
527 parameters	Absolute structure parameter: −0.01 (3)
5 restraints

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. EXTI refined to zero and was removed from the refinement.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Zr	0.21852 (2)	0.025696 (16)	0.24648 (2)	0.01679 (6)
O11	0.06724 (19)	−0.02645 (12)	0.27759 (17)	0.0217 (5)
O12	0.16648 (19)	0.14816 (12)	0.23235 (16)	0.0209 (4)
O21	0.41628 (18)	0.05315 (12)	0.33466 (16)	0.0220 (5)
O22	0.2219 (2)	−0.07046 (12)	0.14332 (17)	0.0239 (5)
N11	0.0281 (2)	0.03706 (14)	0.06275 (19)	0.0177 (5)
H11	0.023 (3)	−0.0137 (12)	0.037 (2)	0.021*
N12	0.3180 (2)	−0.08819 (15)	0.3763 (2)	0.0204 (5)
H12	0.252 (2)	−0.1231 (16)	0.362 (3)	0.025*
N21	0.2823 (2)	0.08477 (16)	0.1011 (2)	0.0192 (5)
H21	0.283 (3)	0.1366 (11)	0.120 (3)	0.023*
N22	0.2551 (2)	0.06397 (15)	0.4425 (2)	0.0197 (5)
H22	0.334 (2)	0.0871 (17)	0.470 (2)	0.024*
Cl11	0.01552 (7)	−0.17386 (5)	0.38480 (6)	0.02992 (19)
Cl12	0.09931 (8)	−0.14904 (5)	−0.08304 (6)	0.03103 (19)
Cl21	−0.45928 (8)	−0.16006 (6)	0.02610 (7)	0.0382 (2)
Cl22	0.44983 (8)	−0.38479 (5)	0.12259 (7)	0.03275 (19)
Cl31	0.85232 (8)	0.22030 (5)	0.29128 (7)	0.0344 (2)
Cl32	0.23253 (9)	0.43591 (5)	0.52203 (8)	0.0388 (2)
Cl41	0.60590 (7)	0.12385 (5)	0.55203 (6)	0.02962 (18)
Cl42	0.22922 (8)	0.29830 (5)	0.13700 (7)	0.03235 (19)
C11	−0.0509 (3)	−0.05738 (18)	0.2207 (2)	0.0195 (6)
C12	0.2697 (3)	−0.14329 (18)	0.1422 (2)	0.0183 (6)
C21	−0.0926 (3)	−0.12690 (18)	0.2586 (2)	0.0211 (7)
C22	0.2245 (3)	−0.18855 (18)	0.0405 (2)	0.0210 (6)
C31	−0.2177 (3)	−0.15817 (19)	0.2006 (2)	0.0246 (7)
H31A	−0.2445	−0.2046	0.2293	0.029*
C32	0.2770 (3)	−0.26272 (18)	0.0334 (2)	0.0208 (6)
H32A	0.2453	−0.2922	−0.0371	0.025*
C41	−0.3018 (3)	−0.12093 (19)	0.1011 (3)	0.0244 (7)
C42	0.3770 (3)	−0.29308 (18)	0.1317 (3)	0.0222 (7)
C51	−0.2648 (3)	−0.05332 (19)	0.0580 (3)	0.0236 (7)
H51A	−0.3239	−0.0292	−0.0121	0.028*
C52	0.4222 (3)	−0.25144 (18)	0.2346 (3)	0.0214 (7)
H52A	0.4900	−0.2739	0.3015	0.026*
C61	−0.1398 (3)	−0.02071 (17)	0.1184 (3)	0.0194 (6)
C62	0.3691 (3)	−0.17704 (18)	0.2409 (2)	0.0198 (6)
C71	−0.0945 (3)	0.05371 (17)	0.0772 (3)	0.0210 (7)
H71A	−0.1637	0.0716	0.0025	0.025*
H71B	−0.0788	0.0981	0.1338	0.025*
C72	0.4216 (3)	−0.12984 (19)	0.3524 (3)	0.0251 (7)
H72A	0.4700	−0.1673	0.4169	0.030*
H72B	0.4843	−0.0887	0.3495	0.030*
C81	0.0454 (3)	0.09205 (19)	−0.0218 (2)	0.0214 (7)
H81A	0.0416	0.1494	0.0024	0.026*
C82	0.3656 (3)	−0.06773 (18)	0.5012 (2)	0.0209 (6)
H82A	0.4527	−0.0408	0.5260	0.025*
C91	−0.0596 (3)	0.0805 (2)	−0.1450 (2)	0.0300 (8)
H91A	−0.0592	0.0233	−0.1686	0.036*
H91B	−0.1466	0.0921	−0.1466	0.036*
C92	0.3835 (3)	−0.1424 (2)	0.5775 (2)	0.0296 (7)
H92A	0.4472	−0.1796	0.5678	0.036*
H92B	0.2990	−0.1714	0.5523	0.036*
C101	−0.0371 (3)	0.1360 (2)	−0.2309 (3)	0.0399 (10)
H10A	−0.1039	0.1250	−0.3099	0.048*
H10B	−0.0459	0.1933	−0.2121	0.048*
C102	0.4318 (4)	−0.1200 (2)	0.7053 (3)	0.0346 (8)
H10C	0.4367	−0.1695	0.7510	0.041*
H10D	0.5207	−0.0965	0.7333	0.041*
C111	0.0985 (3)	0.1222 (2)	−0.2266 (3)	0.0330 (8)
H11A	0.1136	0.1607	−0.2794	0.040*
H11B	0.1042	0.0665	−0.2530	0.040*
C112	0.3401 (3)	−0.0589 (2)	0.7229 (3)	0.0343 (8)
H11C	0.3760	−0.0421	0.8049	0.041*
H11D	0.2537	−0.0842	0.7030	0.041*
C121	0.2032 (3)	0.1340 (2)	−0.1045 (3)	0.0277 (7)
H12A	0.2015	0.1909	−0.0803	0.033*
H12B	0.2903	0.1235	−0.1034	0.033*
C122	0.3248 (3)	0.0153 (2)	0.6464 (2)	0.0268 (7)
H12C	0.4107	0.0422	0.6702	0.032*
H12D	0.2643	0.0543	0.6577	0.032*
C131	0.1815 (3)	0.07684 (19)	−0.0196 (2)	0.0210 (6)
H13A	0.1839	0.0199	−0.0455	0.025*
C132	0.2722 (3)	−0.00701 (17)	0.5183 (2)	0.0203 (6)
H13B	0.1853	−0.0339	0.4953	0.024*
C141	0.4133 (3)	0.05631 (19)	0.1134 (2)	0.0212 (6)
H14A	0.4247	0.0699	0.0425	0.025*
H14B	0.4186	−0.0034	0.1227	0.025*
C142	0.1574 (3)	0.12355 (18)	0.4452 (2)	0.0219 (6)
H14C	0.1619	0.1267	0.5243	0.026*
H14D	0.0684	0.1054	0.3927	0.026*
C151	0.5211 (3)	0.09539 (18)	0.2165 (2)	0.0190 (6)
C152	0.1832 (3)	0.20643 (18)	0.4083 (3)	0.0207 (6)
C161	0.6252 (3)	0.13470 (18)	0.2066 (3)	0.0231 (7)
H16A	0.6290	0.1382	0.1336	0.028*
C162	0.1994 (3)	0.27479 (19)	0.4771 (3)	0.0243 (7)
H16B	0.1965	0.2701	0.5503	0.029*
C171	0.7234 (3)	0.16867 (18)	0.3034 (3)	0.0227 (7)
C172	0.2197 (3)	0.34961 (19)	0.4383 (3)	0.0264 (7)
C181	0.7206 (3)	0.16425 (18)	0.4112 (3)	0.0214 (6)
H18A	0.7894	0.1864	0.4777	0.026*
C182	0.2297 (3)	0.35755 (19)	0.3345 (3)	0.0268 (7)
H18B	0.2460	0.4090	0.3095	0.032*
C192	0.2155 (3)	0.28884 (19)	0.2676 (2)	0.0226 (7)
C191	0.6144 (3)	0.12660 (18)	0.4186 (2)	0.0212 (6)
C201	0.5142 (3)	0.09082 (17)	0.3237 (2)	0.0185 (6)
C202	0.1886 (3)	0.21253 (18)	0.3006 (2)	0.0185 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zr	0.01607 (13)	0.01881 (13)	0.01375 (12)	−0.00159 (13)	0.00449 (10)	−0.00096 (13)
O11	0.0170 (11)	0.0270 (12)	0.0191 (11)	−0.0034 (9)	0.0057 (9)	0.0011 (9)
O12	0.0244 (11)	0.0181 (11)	0.0202 (11)	−0.0019 (9)	0.0092 (9)	−0.0017 (9)
O21	0.0191 (11)	0.0292 (12)	0.0160 (10)	−0.0038 (9)	0.0056 (9)	−0.0015 (8)
O22	0.0262 (11)	0.0224 (11)	0.0169 (10)	0.0033 (9)	0.0030 (9)	−0.0027 (9)
N11	0.0180 (11)	0.0157 (14)	0.0185 (12)	−0.0003 (10)	0.0067 (9)	−0.0002 (10)
N12	0.0198 (13)	0.0215 (13)	0.0160 (13)	−0.0021 (10)	0.0035 (11)	−0.0017 (10)
N21	0.0180 (13)	0.0216 (13)	0.0164 (12)	−0.0008 (11)	0.0057 (10)	−0.0019 (11)
N22	0.0189 (13)	0.0218 (14)	0.0188 (13)	−0.0046 (10)	0.0082 (11)	−0.0023 (11)
Cl11	0.0262 (4)	0.0322 (4)	0.0247 (4)	−0.0048 (3)	0.0040 (3)	0.0092 (3)
Cl12	0.0278 (4)	0.0327 (4)	0.0206 (4)	0.0081 (3)	−0.0017 (3)	−0.0056 (3)
Cl21	0.0245 (4)	0.0513 (6)	0.0302 (5)	−0.0175 (4)	0.0028 (3)	0.0061 (4)
Cl22	0.0401 (5)	0.0262 (4)	0.0280 (4)	0.0121 (4)	0.0103 (4)	0.0001 (3)
Cl31	0.0229 (4)	0.0460 (5)	0.0328 (5)	−0.0120 (4)	0.0101 (4)	0.0010 (4)
Cl32	0.0415 (5)	0.0266 (4)	0.0482 (6)	−0.0051 (4)	0.0188 (4)	−0.0158 (4)
Cl41	0.0254 (4)	0.0451 (5)	0.0175 (4)	−0.0067 (4)	0.0080 (3)	−0.0077 (3)
Cl42	0.0419 (5)	0.0283 (4)	0.0325 (5)	−0.0046 (4)	0.0211 (4)	0.0028 (4)
C11	0.0208 (15)	0.0200 (15)	0.0180 (15)	−0.0033 (12)	0.0084 (13)	−0.0026 (12)
C12	0.0173 (15)	0.0204 (15)	0.0171 (14)	0.0018 (12)	0.0071 (12)	−0.0005 (12)
C21	0.0202 (16)	0.0260 (17)	0.0158 (15)	0.0001 (13)	0.0061 (13)	0.0016 (12)
C22	0.0155 (14)	0.0275 (17)	0.0167 (15)	0.0010 (12)	0.0035 (12)	0.0018 (13)
C31	0.0308 (17)	0.0248 (17)	0.0210 (16)	−0.0056 (14)	0.0136 (14)	−0.0018 (13)
C32	0.0219 (16)	0.0215 (16)	0.0193 (15)	−0.0026 (13)	0.0088 (13)	−0.0046 (13)
C41	0.0187 (16)	0.0303 (18)	0.0216 (16)	−0.0068 (13)	0.0058 (13)	−0.0044 (14)
C42	0.0241 (16)	0.0194 (16)	0.0245 (16)	0.0040 (13)	0.0116 (14)	0.0026 (13)
C51	0.0192 (15)	0.0298 (18)	0.0200 (15)	−0.0005 (13)	0.0065 (13)	0.0001 (13)
C52	0.0204 (16)	0.0249 (16)	0.0168 (15)	−0.0010 (13)	0.0056 (13)	0.0034 (13)
C61	0.0194 (15)	0.0190 (16)	0.0209 (16)	−0.0006 (12)	0.0094 (13)	−0.0004 (12)
C62	0.0193 (15)	0.0219 (16)	0.0168 (14)	0.0003 (12)	0.0062 (12)	−0.0001 (12)
C71	0.0157 (15)	0.0219 (16)	0.0217 (15)	0.0018 (12)	0.0040 (12)	0.0011 (12)
C72	0.0230 (17)	0.0247 (17)	0.0228 (16)	0.0042 (13)	0.0048 (13)	−0.0010 (13)
C81	0.0172 (15)	0.0286 (17)	0.0170 (15)	−0.0004 (12)	0.0059 (12)	0.0037 (13)
C82	0.0225 (16)	0.0240 (16)	0.0130 (14)	−0.0012 (13)	0.0043 (12)	−0.0006 (13)
C91	0.0165 (16)	0.050 (2)	0.0180 (16)	0.0031 (15)	0.0020 (13)	0.0077 (15)
C92	0.039 (2)	0.0280 (18)	0.0163 (16)	0.0026 (15)	0.0064 (14)	0.0046 (14)
C101	0.0252 (18)	0.070 (3)	0.0229 (18)	0.0049 (18)	0.0084 (15)	0.0179 (18)
C102	0.041 (2)	0.038 (2)	0.0208 (17)	0.0012 (16)	0.0091 (16)	0.0085 (15)
C111	0.0260 (18)	0.053 (2)	0.0192 (17)	−0.0008 (17)	0.0081 (14)	0.0090 (16)
C112	0.041 (2)	0.043 (2)	0.0170 (16)	0.0005 (17)	0.0095 (15)	0.0035 (15)
C121	0.0235 (17)	0.038 (2)	0.0206 (16)	−0.0022 (14)	0.0083 (13)	0.0055 (14)
C122	0.0312 (16)	0.0317 (19)	0.0149 (14)	−0.0029 (15)	0.0071 (12)	−0.0014 (14)
C131	0.0178 (15)	0.0281 (17)	0.0148 (14)	−0.0023 (13)	0.0045 (12)	−0.0008 (13)
C132	0.0234 (16)	0.0210 (15)	0.0159 (15)	−0.0027 (12)	0.0077 (13)	0.0019 (12)
C141	0.0159 (14)	0.0341 (17)	0.0132 (14)	−0.0016 (12)	0.0056 (12)	−0.0017 (12)
C142	0.0239 (16)	0.0243 (16)	0.0184 (15)	−0.0001 (13)	0.0098 (13)	−0.0018 (13)
C151	0.0134 (14)	0.0244 (16)	0.0174 (15)	−0.0006 (12)	0.0045 (12)	−0.0008 (12)
C152	0.0161 (15)	0.0218 (16)	0.0239 (16)	−0.0006 (12)	0.0080 (13)	−0.0001 (13)
C161	0.0215 (16)	0.0302 (18)	0.0183 (15)	0.0023 (13)	0.0089 (13)	0.0006 (13)
C162	0.0191 (16)	0.0272 (18)	0.0264 (17)	0.0005 (13)	0.0094 (14)	−0.0031 (14)
C171	0.0162 (15)	0.0236 (17)	0.0272 (17)	−0.0042 (13)	0.0081 (13)	0.0016 (13)
C172	0.0202 (16)	0.0270 (17)	0.0290 (17)	−0.0016 (14)	0.0072 (13)	−0.0102 (14)
C181	0.0178 (15)	0.0208 (15)	0.0203 (15)	−0.0005 (12)	0.0026 (12)	−0.0021 (13)
C182	0.0228 (16)	0.0199 (16)	0.0354 (19)	−0.0052 (13)	0.0099 (14)	−0.0017 (14)
C192	0.0194 (15)	0.0270 (17)	0.0219 (16)	−0.0008 (13)	0.0089 (13)	0.0014 (13)
C191	0.0232 (16)	0.0226 (16)	0.0169 (14)	0.0013 (13)	0.0075 (12)	0.0015 (13)
C201	0.0161 (15)	0.0189 (15)	0.0195 (15)	0.0022 (12)	0.0064 (12)	0.0012 (12)
C202	0.0124 (14)	0.0207 (16)	0.0196 (15)	−0.0014 (12)	0.0039 (12)	−0.0015 (12)

Geometric parameters (Å, º) top

Zr—O22	2.070 (2)	C81—C91	1.533 (4)
Zr—O21	2.0819 (19)	C81—C131	1.541 (4)
Zr—O11	2.088 (2)	C81—H81A	1.0000
Zr—O12	2.089 (2)	C82—C92	1.529 (4)
Zr—N11	2.433 (2)	C82—C132	1.532 (4)
Zr—N22	2.439 (2)	C82—H82A	1.0000
Zr—N12	2.443 (2)	C91—C101	1.527 (4)
Zr—N21	2.451 (2)	C91—H91A	0.9900
O11—C11	1.322 (3)	C91—H91B	0.9900
O12—C202	1.328 (3)	C92—C102	1.531 (4)
O21—C201	1.323 (3)	C92—H92A	0.9900
O22—C12	1.318 (3)	C92—H92B	0.9900
N11—C81	1.482 (3)	C101—C111	1.521 (4)
N11—C71	1.492 (4)	C101—H10A	0.9900
N11—H11	0.892 (17)	C101—H10B	0.9900
N12—C82	1.491 (4)	C102—C112	1.524 (5)
N12—C72	1.491 (4)	C102—H10C	0.9900
N12—H12	0.900 (17)	C102—H10D	0.9900
N21—C131	1.487 (3)	C111—C121	1.521 (4)
N21—C141	1.492 (4)	C111—H11A	0.9900
N21—H21	0.885 (17)	C111—H11B	0.9900
N22—C132	1.478 (4)	C112—C122	1.528 (4)
N22—C142	1.486 (4)	C112—H11C	0.9900
N22—H22	0.896 (17)	C112—H11D	0.9900
Cl11—C21	1.741 (3)	C121—C131	1.529 (4)
Cl12—C22	1.742 (3)	C121—H12A	0.9900
Cl21—C41	1.749 (3)	C121—H12B	0.9900
Cl22—C42	1.746 (3)	C122—C132	1.530 (4)
Cl31—C171	1.743 (3)	C122—H12C	0.9900
Cl32—C172	1.748 (3)	C122—H12D	0.9900
Cl41—C191	1.744 (3)	C131—H13A	1.0000
Cl42—C192	1.742 (3)	C132—H13B	1.0000
C11—C21	1.399 (4)	C141—C151	1.511 (4)
C11—C61	1.406 (4)	C141—H14A	0.9900
C12—C22	1.395 (4)	C141—H14B	0.9900
C12—C62	1.403 (4)	C142—C152	1.512 (4)
C21—C31	1.388 (4)	C142—H14C	0.9900
C22—C32	1.377 (4)	C142—H14D	0.9900
C31—C41	1.371 (4)	C151—C161	1.391 (4)
C31—H31A	0.9500	C151—C201	1.403 (4)
C32—C42	1.382 (4)	C152—C162	1.392 (4)
C32—H32A	0.9500	C152—C202	1.403 (4)
C41—C51	1.381 (4)	C161—C171	1.385 (4)
C42—C52	1.376 (4)	C161—H16A	0.9500
C51—C61	1.399 (4)	C162—C172	1.383 (4)
C51—H51A	0.9500	C162—H16B	0.9500
C52—C62	1.381 (4)	C171—C181	1.389 (4)
C52—H52A	0.9500	C172—C182	1.379 (4)
C61—C71	1.505 (4)	C181—C191	1.385 (4)
C62—C72	1.507 (4)	C181—H18A	0.9500
C71—H71A	0.9900	C182—C192	1.386 (4)
C71—H71B	0.9900	C182—H18B	0.9500
C72—H72A	0.9900	C192—C202	1.399 (4)
C72—H72B	0.9900	C191—C201	1.393 (4)

O22—Zr—O21	102.13 (8)	C92—C82—C132	110.5 (2)
O22—Zr—O11	92.19 (8)	N12—C82—H82A	107.8
O21—Zr—O11	139.47 (8)	C92—C82—H82A	107.8
O22—Zr—O12	139.85 (8)	C132—C82—H82A	107.8
O21—Zr—O12	91.98 (8)	C101—C91—C81	111.9 (3)
O11—Zr—O12	101.11 (8)	C101—C91—H91A	109.2
O22—Zr—N11	71.96 (8)	C81—C91—H91A	109.2
O21—Zr—N11	144.73 (8)	C101—C91—H91B	109.2
O11—Zr—N11	75.75 (7)	C81—C91—H91B	109.2
O12—Zr—N11	74.93 (8)	H91A—C91—H91B	107.9
O22—Zr—N22	143.96 (8)	C82—C92—C102	112.1 (3)
O21—Zr—N22	72.90 (8)	C82—C92—H92A	109.2
O11—Zr—N22	73.39 (8)	C102—C92—H92A	109.2
O12—Zr—N22	76.09 (8)	C82—C92—H92B	109.2
N11—Zr—N22	132.04 (8)	C102—C92—H92B	109.2
O22—Zr—N12	73.55 (8)	H92A—C92—H92B	107.9
O21—Zr—N12	73.57 (8)	C111—C101—C91	110.4 (3)
O11—Zr—N12	74.61 (8)	C111—C101—H10A	109.6
O12—Zr—N12	146.50 (8)	C91—C101—H10A	109.6
N11—Zr—N12	132.94 (8)	C111—C101—H10B	109.6
N22—Zr—N12	70.83 (8)	C91—C101—H10B	109.6
O22—Zr—N21	74.65 (8)	H10A—C101—H10B	108.1
O21—Zr—N21	74.74 (8)	C112—C102—C92	110.7 (3)
O11—Zr—N21	145.76 (8)	C112—C102—H10C	109.5
O12—Zr—N21	73.20 (8)	C92—C102—H10C	109.5
N11—Zr—N21	70.16 (8)	C112—C102—H10D	109.5
N22—Zr—N21	133.95 (8)	C92—C102—H10D	109.5
N12—Zr—N21	128.39 (8)	H10C—C102—H10D	108.1
C11—O11—Zr	140.16 (18)	C101—C111—C121	110.8 (3)
C202—O12—Zr	138.32 (18)	C101—C111—H11A	109.5
C201—O21—Zr	142.74 (18)	C121—C111—H11A	109.5
C12—O22—Zr	145.11 (18)	C101—C111—H11B	109.5
C81—N11—C71	112.7 (2)	C121—C111—H11B	109.5
C81—N11—Zr	114.59 (16)	H11A—C111—H11B	108.1
C71—N11—Zr	112.57 (16)	C102—C112—C122	109.8 (3)
C81—N11—H11	109 (2)	C102—C112—H11C	109.7
C71—N11—H11	107 (2)	C122—C112—H11C	109.7
Zr—N11—H11	100.3 (19)	C102—C112—H11D	109.7
C82—N12—C72	111.1 (2)	C122—C112—H11D	109.7
C82—N12—Zr	114.07 (18)	H11C—C112—H11D	108.2
C72—N12—Zr	113.07 (18)	C111—C121—C131	111.1 (3)
C82—N12—H12	105 (2)	C111—C121—H12A	109.4
C72—N12—H12	109 (2)	C131—C121—H12A	109.4
Zr—N12—H12	105 (2)	C111—C121—H12B	109.4
C131—N21—C141	112.0 (2)	C131—C121—H12B	109.4
C131—N21—Zr	114.14 (17)	H12A—C121—H12B	108.0
C141—N21—Zr	112.61 (17)	C112—C122—C132	112.3 (3)
C131—N21—H21	106 (2)	C112—C122—H12C	109.2
C141—N21—H21	112 (2)	C132—C122—H12C	109.2
Zr—N21—H21	99 (2)	C112—C122—H12D	109.2
C132—N22—C142	113.8 (2)	C132—C122—H12D	109.2
C132—N22—Zr	112.64 (17)	H12C—C122—H12D	107.9
C142—N22—Zr	112.62 (17)	N21—C131—C121	113.5 (2)
C132—N22—H22	104 (2)	N21—C131—C81	109.1 (2)
C142—N22—H22	110 (2)	C121—C131—C81	109.8 (2)
Zr—N22—H22	103.1 (19)	N21—C131—H13A	108.1
O11—C11—C21	122.1 (3)	C121—C131—H13A	108.1
O11—C11—C61	120.4 (3)	C81—C131—H13A	108.1
C21—C11—C61	117.5 (3)	N22—C132—C122	113.2 (2)
O22—C12—C22	120.4 (2)	N22—C132—C82	109.5 (2)
O22—C12—C62	121.9 (3)	C122—C132—C82	109.0 (2)
C22—C12—C62	117.8 (3)	N22—C132—H13B	108.3
C31—C21—C11	122.2 (3)	C122—C132—H13B	108.3
C31—C21—Cl11	119.3 (2)	C82—C132—H13B	108.3
C11—C21—Cl11	118.5 (2)	N21—C141—C151	110.9 (2)
C32—C22—C12	122.4 (3)	N21—C141—H14A	109.5
C32—C22—Cl12	118.7 (2)	C151—C141—H14A	109.5
C12—C22—Cl12	118.9 (2)	N21—C141—H14B	109.5
C41—C31—C21	118.8 (3)	C151—C141—H14B	109.5
C41—C31—H31A	120.6	H14A—C141—H14B	108.0
C21—C31—H31A	120.6	N22—C142—C152	110.5 (2)
C22—C32—C42	118.1 (3)	N22—C142—H14C	109.5
C22—C32—H32A	120.9	C152—C142—H14C	109.5
C42—C32—H32A	120.9	N22—C142—H14D	109.5
C31—C41—C51	121.5 (3)	C152—C142—H14D	109.5
C31—C41—Cl21	119.4 (2)	H14C—C142—H14D	108.1
C51—C41—Cl21	119.0 (2)	C161—C151—C201	120.3 (3)
C52—C42—C32	121.3 (3)	C161—C151—C141	121.4 (3)
C52—C42—Cl22	119.9 (2)	C201—C151—C141	118.3 (3)
C32—C42—Cl22	118.7 (2)	C162—C152—C202	120.7 (3)
C41—C51—C61	119.5 (3)	C162—C152—C142	121.8 (3)
C41—C51—H51A	120.3	C202—C152—C142	117.5 (3)
C61—C51—H51A	120.3	C171—C161—C151	119.8 (3)
C42—C52—C62	120.1 (3)	C171—C161—H16A	120.1
C42—C52—H52A	119.9	C151—C161—H16A	120.1
C62—C52—H52A	119.9	C172—C162—C152	119.6 (3)
C51—C61—C11	120.5 (3)	C172—C162—H16B	120.2
C51—C61—C71	122.1 (3)	C152—C162—H16B	120.2
C11—C61—C71	117.4 (3)	C161—C171—C181	121.3 (3)
C52—C62—C12	120.2 (3)	C161—C171—Cl31	120.2 (2)
C52—C62—C72	120.3 (3)	C181—C171—Cl31	118.5 (2)
C12—C62—C72	119.5 (3)	C182—C172—C162	121.3 (3)
N11—C71—C61	111.0 (2)	C182—C172—Cl32	119.3 (3)
N11—C71—H71A	109.4	C162—C172—Cl32	119.4 (2)
C61—C71—H71A	109.4	C191—C181—C171	117.9 (3)
N11—C71—H71B	109.4	C191—C181—H18A	121.1
C61—C71—H71B	109.4	C171—C181—H18A	121.1
H71A—C71—H71B	108.0	C172—C182—C192	118.5 (3)
N12—C72—C62	113.5 (2)	C172—C182—H18B	120.7
N12—C72—H72A	108.9	C192—C182—H18B	120.7
C62—C72—H72A	108.9	C182—C192—C202	122.3 (3)
N12—C72—H72B	108.9	C182—C192—Cl42	118.8 (2)
C62—C72—H72B	108.9	C202—C192—Cl42	118.9 (2)
H72A—C72—H72B	107.7	C181—C191—C201	122.7 (3)
N11—C81—C91	112.9 (2)	C181—C191—Cl41	118.6 (2)
N11—C81—C131	108.6 (2)	C201—C191—Cl41	118.7 (2)
C91—C81—C131	109.5 (2)	O21—C201—C191	121.1 (3)
N11—C81—H81A	108.6	O21—C201—C151	121.0 (3)
C91—C81—H81A	108.6	C191—C201—C151	117.9 (3)
C131—C81—H81A	108.6	O12—C202—C192	121.8 (3)
N12—C82—C92	113.0 (2)	O12—C202—C152	120.7 (3)
N12—C82—C132	109.7 (2)	C192—C202—C152	117.5 (3)

O22—Zr—O11—C11	−52.3 (3)	Cl21—C41—C51—C61	178.9 (2)
O21—Zr—O11—C11	−163.9 (3)	C32—C42—C52—C62	−1.1 (5)
O12—Zr—O11—C11	89.6 (3)	Cl22—C42—C52—C62	176.9 (2)
N11—Zr—O11—C11	18.5 (3)	C41—C51—C61—C11	1.6 (4)
N22—Zr—O11—C11	161.3 (3)	C41—C51—C61—C71	−178.9 (3)
N12—Zr—O11—C11	−124.6 (3)	O11—C11—C61—C51	180.0 (3)
N21—Zr—O11—C11	13.2 (4)	C21—C11—C61—C51	0.0 (4)
O22—Zr—O12—C202	−162.5 (2)	O11—C11—C61—C71	0.4 (4)
O21—Zr—O12—C202	−50.9 (3)	C21—C11—C61—C71	−179.6 (3)
O11—Zr—O12—C202	90.5 (3)	C42—C52—C62—C12	−0.5 (4)
N11—Zr—O12—C202	162.3 (3)	C42—C52—C62—C72	−177.7 (3)
N22—Zr—O12—C202	20.9 (3)	O22—C12—C62—C52	−176.0 (3)
N12—Zr—O12—C202	11.6 (3)	C22—C12—C62—C52	2.1 (4)
N21—Zr—O12—C202	−124.3 (3)	O22—C12—C62—C72	1.2 (4)
O22—Zr—O21—C201	79.1 (3)	C22—C12—C62—C72	179.4 (3)
O11—Zr—O21—C201	−172.8 (3)	C81—N11—C71—C61	155.0 (2)
O12—Zr—O21—C201	−63.0 (3)	Zr—N11—C71—C61	−73.5 (2)
N11—Zr—O21—C201	3.3 (4)	C51—C61—C71—N11	−123.8 (3)
N22—Zr—O21—C201	−137.8 (3)	C11—C61—C71—N11	55.7 (3)
N12—Zr—O21—C201	147.7 (3)	C82—N12—C72—C62	160.1 (2)
N21—Zr—O21—C201	8.9 (3)	Zr—N12—C72—C62	−70.2 (3)
O21—Zr—O22—C12	55.4 (3)	C52—C62—C72—N12	−140.9 (3)
O11—Zr—O22—C12	−86.4 (3)	C12—C62—C72—N12	41.9 (4)
O12—Zr—O22—C12	163.4 (3)	C71—N11—C81—C91	−65.0 (3)
N11—Zr—O22—C12	−160.7 (3)	Zr—N11—C81—C91	164.5 (2)
N22—Zr—O22—C12	−22.1 (4)	C71—N11—C81—C131	173.3 (2)
N12—Zr—O22—C12	−13.2 (3)	Zr—N11—C81—C131	42.8 (3)
N21—Zr—O22—C12	125.7 (3)	C72—N12—C82—C92	−70.5 (3)
O22—Zr—N11—C81	−96.17 (19)	Zr—N12—C82—C92	160.3 (2)
O21—Zr—N11—C81	−10.6 (3)	C72—N12—C82—C132	165.7 (2)
O11—Zr—N11—C81	166.7 (2)	Zr—N12—C82—C132	36.5 (3)
O12—Zr—N11—C81	60.78 (18)	N11—C81—C91—C101	−178.2 (3)
N22—Zr—N11—C81	115.47 (19)	C131—C81—C91—C101	−57.1 (4)
N12—Zr—N11—C81	−140.93 (18)	N12—C82—C92—C102	−179.7 (3)
N21—Zr—N11—C81	−16.45 (18)	C132—C82—C92—C102	−56.3 (4)
O22—Zr—N11—C71	133.25 (19)	C81—C91—C101—C111	56.4 (4)
O21—Zr—N11—C71	−141.21 (17)	C82—C92—C102—C112	55.6 (4)
O11—Zr—N11—C71	36.12 (17)	C91—C101—C111—C121	−55.9 (4)
O12—Zr—N11—C71	−69.80 (18)	C92—C102—C112—C122	−55.3 (4)
N22—Zr—N11—C71	−15.1 (2)	C101—C111—C121—C131	57.8 (4)
N12—Zr—N11—C71	88.5 (2)	C102—C112—C122—C132	58.2 (4)
N21—Zr—N11—C71	−147.0 (2)	C141—N21—C131—C121	−67.6 (3)
O22—Zr—N12—C82	175.8 (2)	Zr—N21—C131—C121	163.0 (2)
O21—Zr—N12—C82	67.38 (19)	C141—N21—C131—C81	169.6 (2)
O11—Zr—N12—C82	−87.2 (2)	Zr—N21—C131—C81	40.2 (3)
O12—Zr—N12—C82	−0.3 (3)	C111—C121—C131—N21	179.1 (3)
N11—Zr—N12—C82	−139.96 (18)	C111—C121—C131—C81	−58.4 (3)
N22—Zr—N12—C82	−9.79 (18)	N11—C81—C131—N21	−53.9 (3)
N21—Zr—N12—C82	121.66 (19)	C91—C81—C131—N21	−177.7 (2)
O22—Zr—N12—C72	47.57 (18)	N11—C81—C131—C121	−179.0 (2)
O21—Zr—N12—C72	−60.81 (18)	C91—C81—C131—C121	57.3 (3)
O11—Zr—N12—C72	144.6 (2)	C142—N22—C132—C122	−63.0 (3)
O12—Zr—N12—C72	−128.47 (19)	Zr—N22—C132—C122	167.24 (19)
N11—Zr—N12—C72	91.8 (2)	C142—N22—C132—C82	175.2 (2)
N22—Zr—N12—C72	−138.0 (2)	Zr—N22—C132—C82	45.4 (3)
N21—Zr—N12—C72	−6.5 (2)	C112—C122—C132—N22	179.3 (3)
O22—Zr—N21—C131	62.43 (19)	C112—C122—C132—C82	−58.5 (3)
O21—Zr—N21—C131	169.9 (2)	N12—C82—C132—N22	−53.9 (3)
O11—Zr—N21—C131	−8.1 (3)	C92—C82—C132—N22	−179.2 (2)
O12—Zr—N21—C131	−93.19 (19)	N12—C82—C132—C122	−178.3 (2)
N11—Zr—N21—C131	−13.55 (18)	C92—C82—C132—C122	56.5 (3)
N22—Zr—N21—C131	−143.41 (18)	C131—N21—C141—C151	156.1 (2)
N12—Zr—N21—C131	116.11 (19)	Zr—N21—C141—C151	−73.7 (3)
O22—Zr—N21—C141	−66.70 (18)	C132—N22—C142—C152	156.8 (2)
O21—Zr—N21—C141	40.80 (18)	Zr—N22—C142—C152	−73.4 (2)
O11—Zr—N21—C141	−137.25 (18)	N21—C141—C151—C161	−128.1 (3)
O12—Zr—N21—C141	137.68 (19)	N21—C141—C151—C201	52.3 (4)
N11—Zr—N21—C141	−142.7 (2)	N22—C142—C152—C162	−125.4 (3)
N22—Zr—N21—C141	87.5 (2)	N22—C142—C152—C202	55.4 (3)
N12—Zr—N21—C141	−13.0 (2)	C201—C151—C161—C171	0.7 (4)
O22—Zr—N22—C132	−10.3 (3)	C141—C151—C161—C171	−178.9 (3)
O21—Zr—N22—C132	−97.45 (19)	C202—C152—C162—C172	0.7 (4)
O11—Zr—N22—C132	59.71 (18)	C142—C152—C162—C172	−178.5 (3)
O12—Zr—N22—C132	166.0 (2)	C151—C161—C171—C181	0.2 (5)
N11—Zr—N22—C132	111.77 (19)	C151—C161—C171—Cl31	−178.4 (2)
N12—Zr—N22—C132	−19.36 (18)	C152—C162—C172—C182	−2.7 (5)
N21—Zr—N22—C132	−144.68 (18)	C152—C162—C172—Cl32	177.1 (2)
O22—Zr—N22—C142	−140.67 (18)	C161—C171—C181—C191	−1.7 (5)
O21—Zr—N22—C142	132.15 (19)	Cl31—C171—C181—C191	176.8 (2)
O11—Zr—N22—C142	−70.68 (18)	C162—C172—C182—C192	1.7 (4)
O12—Zr—N22—C142	35.64 (18)	Cl32—C172—C182—C192	−178.1 (2)
N11—Zr—N22—C142	−18.6 (2)	C172—C182—C192—C202	1.5 (4)
N12—Zr—N22—C142	−149.8 (2)	C172—C182—C192—Cl42	−179.5 (2)
N21—Zr—N22—C142	84.9 (2)	C171—C181—C191—C201	2.5 (4)
Zr—O11—C11—C21	139.5 (3)	C171—C181—C191—Cl41	−177.6 (2)
Zr—O11—C11—C61	−40.5 (4)	Zr—O21—C201—C191	149.1 (2)
Zr—O22—C12—C22	172.4 (2)	Zr—O21—C201—C151	−31.4 (5)
Zr—O22—C12—C62	−9.4 (5)	C181—C191—C201—O21	177.9 (3)
O11—C11—C21—C31	178.3 (3)	Cl41—C191—C201—O21	−2.1 (4)
C61—C11—C21—C31	−1.8 (4)	C181—C191—C201—C151	−1.6 (4)
O11—C11—C21—Cl11	−0.1 (4)	Cl41—C191—C201—C151	178.4 (2)
C61—C11—C21—Cl11	179.8 (2)	C161—C151—C201—O21	−179.5 (3)
O22—C12—C22—C32	176.0 (3)	C141—C151—C201—O21	0.2 (4)
C62—C12—C22—C32	−2.3 (4)	C161—C151—C201—C191	0.0 (4)
O22—C12—C22—Cl12	−2.8 (4)	C141—C151—C201—C191	179.6 (3)
C62—C12—C22—Cl12	179.0 (2)	Zr—O12—C202—C192	137.0 (2)
C11—C21—C31—C41	1.9 (5)	Zr—O12—C202—C152	−44.3 (4)
Cl11—C21—C31—C41	−179.7 (2)	C182—C192—C202—O12	175.4 (3)
C12—C22—C32—C42	0.7 (4)	Cl42—C192—C202—O12	−3.6 (4)
Cl12—C22—C32—C42	179.4 (2)	C182—C192—C202—C152	−3.4 (4)
C21—C31—C41—C51	−0.2 (5)	Cl42—C192—C202—C152	177.6 (2)
C21—C31—C41—Cl21	179.4 (2)	C162—C152—C202—O12	−176.5 (3)
C22—C32—C42—C52	1.1 (4)	C142—C152—C202—O12	2.7 (4)
C22—C32—C42—Cl22	−177.0 (2)	C162—C152—C202—C192	2.3 (4)
C31—C41—C51—C61	−1.5 (5)	C142—C152—C202—C192	−178.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11···O22	0.89 (2)	2.28 (3)	2.662 (3)	106 (2)
N21—H21···O12	0.89 (2)	2.32 (4)	2.722 (4)	108 (2)
N21—H21···Cl42	0.89 (2)	2.76 (2)	3.631 (3)	167 (2)
N22—H22···O21	0.89 (2)	2.34 (3)	2.701 (4)	104 (2)
C72—H72B···O21	0.99	2.44	3.024 (4)	117
C132—H13B···O11	1.00	2.53	2.987 (3)	108
C141—H14B···O22	0.99	2.58	3.137 (4)	115
C51—H51A···Cl22ⁱ	0.95	2.83	3.654 (3)	146
C122—H12C···Cl22ⁱⁱ	0.99	2.72	3.402 (3)	126

Symmetry codes: (i) −x, y+1/2, −z; (ii) −x+1, y+1/2, −z+1.

Experimental details

Crystal data
Chemical formula	[Zr(C₂₀H₂₀Cl₄N₂O₂)₂]
M_r	1015.58
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	125
a, b, c (Å)	11.2570 (6), 16.4848 (8), 12.7431 (6)
β (°)	114.686 (1)
V (Å³)	2148.62 (18)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.80
Crystal size (mm)	0.15 × 0.09 × 0.02

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.890, 0.984
No. of measured, independent and observed [I > 2σ(I)] reflections	29336, 11081, 9280
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.675

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.068, 1.01
No. of reflections	11081
No. of parameters	527
No. of restraints	5
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.52, −0.37
Absolute structure	Flack (1983), 5344 Friedel pairs
Absolute structure parameter	−0.01 (3)

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Zr—O22	2.070 (2)	Zr—N11	2.433 (2)
Zr—O21	2.0819 (19)	Zr—N22	2.439 (2)
Zr—O11	2.088 (2)	Zr—N12	2.443 (2)
Zr—O12	2.089 (2)	Zr—N21	2.451 (2)

O22—Zr—O21	102.13 (8)	O21—Zr—O12	91.98 (8)
O22—Zr—O11	92.19 (8)	O11—Zr—O12	101.11 (8)
O21—Zr—O11	139.47 (8)	N22—Zr—N12	70.83 (8)
O22—Zr—O12	139.85 (8)	N11—Zr—N21	70.16 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11···O22	0.89 (2)	2.28 (3)	2.662 (3)	105.7 (18)
N21—H21···O12	0.89 (2)	2.32 (4)	2.722 (4)	108 (2)
N21—H21···Cl42	0.89 (2)	2.76 (2)	3.631 (3)	166.8 (16)
N22—H22···O21	0.89 (2)	2.34 (3)	2.701 (4)	104.1 (18)
C72—H72B···O21	0.99	2.44	3.024 (4)	116.9
C132—H13B···O11	1.00	2.53	2.987 (3)	107.6
C141—H14B···O22	0.99	2.58	3.137 (4)	115.2
C51—H51A···Cl22ⁱ	0.95	2.83	3.654 (3)	146.0
C122—H12C···Cl22ⁱⁱ	0.99	2.72	3.402 (3)	126.1

Symmetry codes: (i) −x, y+1/2, −z; (ii) −x+1, y+1/2, −z+1.

Acknowledgements

This work was supported by Vassar College. X-ray facilities were provided by the US National Science Foundation (grant No. 0521237 to JMT).

References

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