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Acta Crystallogr Sect E Struct Rep Online. 2008 August 1; 64(Pt 8): m1029–m1030.
Published online 2008 July 16. doi:  10.1107/S1600536808021247
PMCID: PMC2961951

Bis{4,4′,6,6′-tetra­chloro-2,2′-[trans-(R,R)-cyclo­hexane-1,2-diylbis(imino­methyl­ene)]diphenolato-κ4 O,N,N′,O′}zirconium(IV)

Abstract

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 [triangle]); Illingsworth et al. (2002 [triangle]); Zhu et al. (2005 [triangle]). For related literature on salan-type complexes [salan = N,N′-ethyl­enebis(2-hydroxy­benz­yl)], see: García-Zarracino et al. (2002 [triangle]); Yeori et al. (2005 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-m1029-scheme1.jpg

Experimental

Crystal data

  • [Zr(C20H20Cl4N2O2)2]
  • M r = 1015.58
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-m1029-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.038
  • wR(F 2) = 0.068
  • S = 1.00
  • 11081 reflections
  • 527 parameters
  • 5 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.52 e Å−3
  • Δρmin = −0.37 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 5344 Friedel pairs
  • Flack parameter: −0.01 (3)

Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Selected geometric parameters (Å, °)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808021247/rz2233sup1.cif

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

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

Acknowledgments

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

supplementary crystallographic information

Comment

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).

Experimental

The title compound was crystallized from a 2 ml diethyl ether solution of Zr(OS-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.

Refinement

Hydrogen atoms on carbon atoms were included in calculated positions and were refined using a riding model, with C—H = 0.95-1.00 Å and Uiso(H) = 1.2 Ueq(C). Hydrogen atoms on nitrogen atoms were refined semifreely with the help of a distance restraint (N—H = 0.91 Å) and with Uiso(H) = 1.2 Ueq(N).

Figures

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.

Crystal data

[Zr(C20H20Cl4N2O2)2]F000 = 1032
Mr = 1015.58Dx = 1.570 Mg m3
Monoclinic, P21Mo Kα radiation λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 9891 reflections
a = 11.2570 (6) Åθ = 2.3–30.0º
b = 16.4848 (8) ŵ = 0.80 mm1
c = 12.7431 (6) ÅT = 125 (2) K
β = 114.6860 (10)ºBlock, colourless
V = 2148.62 (18) Å30.15 × 0.09 × 0.02 mm
Z = 2

Data collection

Bruker APEXII CCD diffractometer11081 independent reflections
Radiation source: fine-focus sealed tube9280 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.047
T = 125(2) Kθmax = 28.7º
[var phi] and ω scansθmin = 1.8º
Absorption correction: multi-scan(SADABS; Bruker, 2007)h = −15→15
Tmin = 0.890, Tmax = 0.984k = −22→22
29336 measured reflectionsl = −17→17

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.039  w = 1/[σ2(Fo2) + (0.024P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.068(Δ/σ)max < 0.001
S = 1.01Δρmax = 0.52 e Å3
11081 reflectionsΔρmin = −0.37 e Å3
527 parametersExtinction correction: none
5 restraintsAbsolute structure: Flack (1983), 5344 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: −0.01 (3)
Secondary atom site location: difference Fourier map

Special details

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)

xyzUiso*/Ueq
Zr0.21852 (2)0.025696 (16)0.24648 (2)0.01679 (6)
O110.06724 (19)−0.02645 (12)0.27759 (17)0.0217 (5)
O120.16648 (19)0.14816 (12)0.23235 (16)0.0209 (4)
O210.41628 (18)0.05315 (12)0.33466 (16)0.0220 (5)
O220.2219 (2)−0.07046 (12)0.14332 (17)0.0239 (5)
N110.0281 (2)0.03706 (14)0.06275 (19)0.0177 (5)
H110.023 (3)−0.0137 (12)0.037 (2)0.021*
N120.3180 (2)−0.08819 (15)0.3763 (2)0.0204 (5)
H120.252 (2)−0.1231 (16)0.362 (3)0.025*
N210.2823 (2)0.08477 (16)0.1011 (2)0.0192 (5)
H210.283 (3)0.1366 (11)0.120 (3)0.023*
N220.2551 (2)0.06397 (15)0.4425 (2)0.0197 (5)
H220.334 (2)0.0871 (17)0.470 (2)0.024*
Cl110.01552 (7)−0.17386 (5)0.38480 (6)0.02992 (19)
Cl120.09931 (8)−0.14904 (5)−0.08304 (6)0.03103 (19)
Cl21−0.45928 (8)−0.16006 (6)0.02610 (7)0.0382 (2)
Cl220.44983 (8)−0.38479 (5)0.12259 (7)0.03275 (19)
Cl310.85232 (8)0.22030 (5)0.29128 (7)0.0344 (2)
Cl320.23253 (9)0.43591 (5)0.52203 (8)0.0388 (2)
Cl410.60590 (7)0.12385 (5)0.55203 (6)0.02962 (18)
Cl420.22922 (8)0.29830 (5)0.13700 (7)0.03235 (19)
C11−0.0509 (3)−0.05738 (18)0.2207 (2)0.0195 (6)
C120.2697 (3)−0.14329 (18)0.1422 (2)0.0183 (6)
C21−0.0926 (3)−0.12690 (18)0.2586 (2)0.0211 (7)
C220.2245 (3)−0.18855 (18)0.0405 (2)0.0210 (6)
C31−0.2177 (3)−0.15817 (19)0.2006 (2)0.0246 (7)
H31A−0.2445−0.20460.22930.029*
C320.2770 (3)−0.26272 (18)0.0334 (2)0.0208 (6)
H32A0.2453−0.2922−0.03710.025*
C41−0.3018 (3)−0.12093 (19)0.1011 (3)0.0244 (7)
C420.3770 (3)−0.29308 (18)0.1317 (3)0.0222 (7)
C51−0.2648 (3)−0.05332 (19)0.0580 (3)0.0236 (7)
H51A−0.3239−0.0292−0.01210.028*
C520.4222 (3)−0.25144 (18)0.2346 (3)0.0214 (7)
H52A0.4900−0.27390.30150.026*
C61−0.1398 (3)−0.02071 (17)0.1184 (3)0.0194 (6)
C620.3691 (3)−0.17704 (18)0.2409 (2)0.0198 (6)
C71−0.0945 (3)0.05371 (17)0.0772 (3)0.0210 (7)
H71A−0.16370.07160.00250.025*
H71B−0.07880.09810.13380.025*
C720.4216 (3)−0.12984 (19)0.3524 (3)0.0251 (7)
H72A0.4700−0.16730.41690.030*
H72B0.4843−0.08870.34950.030*
C810.0454 (3)0.09205 (19)−0.0218 (2)0.0214 (7)
H81A0.04160.14940.00240.026*
C820.3656 (3)−0.06773 (18)0.5012 (2)0.0209 (6)
H82A0.4527−0.04080.52600.025*
C91−0.0596 (3)0.0805 (2)−0.1450 (2)0.0300 (8)
H91A−0.05920.0233−0.16860.036*
H91B−0.14660.0921−0.14660.036*
C920.3835 (3)−0.1424 (2)0.5775 (2)0.0296 (7)
H92A0.4472−0.17960.56780.036*
H92B0.2990−0.17140.55230.036*
C101−0.0371 (3)0.1360 (2)−0.2309 (3)0.0399 (10)
H10A−0.10390.1250−0.30990.048*
H10B−0.04590.1933−0.21210.048*
C1020.4318 (4)−0.1200 (2)0.7053 (3)0.0346 (8)
H10C0.4367−0.16950.75100.041*
H10D0.5207−0.09650.73330.041*
C1110.0985 (3)0.1222 (2)−0.2266 (3)0.0330 (8)
H11A0.11360.1607−0.27940.040*
H11B0.10420.0665−0.25300.040*
C1120.3401 (3)−0.0589 (2)0.7229 (3)0.0343 (8)
H11C0.3760−0.04210.80490.041*
H11D0.2537−0.08420.70300.041*
C1210.2032 (3)0.1340 (2)−0.1045 (3)0.0277 (7)
H12A0.20150.1909−0.08030.033*
H12B0.29030.1235−0.10340.033*
C1220.3248 (3)0.0153 (2)0.6464 (2)0.0268 (7)
H12C0.41070.04220.67020.032*
H12D0.26430.05430.65770.032*
C1310.1815 (3)0.07684 (19)−0.0196 (2)0.0210 (6)
H13A0.18390.0199−0.04550.025*
C1320.2722 (3)−0.00701 (17)0.5183 (2)0.0203 (6)
H13B0.1853−0.03390.49530.024*
C1410.4133 (3)0.05631 (19)0.1134 (2)0.0212 (6)
H14A0.42470.06990.04250.025*
H14B0.4186−0.00340.12270.025*
C1420.1574 (3)0.12355 (18)0.4452 (2)0.0219 (6)
H14C0.16190.12670.52430.026*
H14D0.06840.10540.39270.026*
C1510.5211 (3)0.09539 (18)0.2165 (2)0.0190 (6)
C1520.1832 (3)0.20643 (18)0.4083 (3)0.0207 (6)
C1610.6252 (3)0.13470 (18)0.2066 (3)0.0231 (7)
H16A0.62900.13820.13360.028*
C1620.1994 (3)0.27479 (19)0.4771 (3)0.0243 (7)
H16B0.19650.27010.55030.029*
C1710.7234 (3)0.16867 (18)0.3034 (3)0.0227 (7)
C1720.2197 (3)0.34961 (19)0.4383 (3)0.0264 (7)
C1810.7206 (3)0.16425 (18)0.4112 (3)0.0214 (6)
H18A0.78940.18640.47770.026*
C1820.2297 (3)0.35755 (19)0.3345 (3)0.0268 (7)
H18B0.24600.40900.30950.032*
C1920.2155 (3)0.28884 (19)0.2676 (2)0.0226 (7)
C1910.6144 (3)0.12660 (18)0.4186 (2)0.0212 (6)
C2010.5142 (3)0.09082 (17)0.3237 (2)0.0185 (6)
C2020.1886 (3)0.21253 (18)0.3006 (2)0.0185 (6)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Zr0.01607 (13)0.01881 (13)0.01375 (12)−0.00159 (13)0.00449 (10)−0.00096 (13)
O110.0170 (11)0.0270 (12)0.0191 (11)−0.0034 (9)0.0057 (9)0.0011 (9)
O120.0244 (11)0.0181 (11)0.0202 (11)−0.0019 (9)0.0092 (9)−0.0017 (9)
O210.0191 (11)0.0292 (12)0.0160 (10)−0.0038 (9)0.0056 (9)−0.0015 (8)
O220.0262 (11)0.0224 (11)0.0169 (10)0.0033 (9)0.0030 (9)−0.0027 (9)
N110.0180 (11)0.0157 (14)0.0185 (12)−0.0003 (10)0.0067 (9)−0.0002 (10)
N120.0198 (13)0.0215 (13)0.0160 (13)−0.0021 (10)0.0035 (11)−0.0017 (10)
N210.0180 (13)0.0216 (13)0.0164 (12)−0.0008 (11)0.0057 (10)−0.0019 (11)
N220.0189 (13)0.0218 (14)0.0188 (13)−0.0046 (10)0.0082 (11)−0.0023 (11)
Cl110.0262 (4)0.0322 (4)0.0247 (4)−0.0048 (3)0.0040 (3)0.0092 (3)
Cl120.0278 (4)0.0327 (4)0.0206 (4)0.0081 (3)−0.0017 (3)−0.0056 (3)
Cl210.0245 (4)0.0513 (6)0.0302 (5)−0.0175 (4)0.0028 (3)0.0061 (4)
Cl220.0401 (5)0.0262 (4)0.0280 (4)0.0121 (4)0.0103 (4)0.0001 (3)
Cl310.0229 (4)0.0460 (5)0.0328 (5)−0.0120 (4)0.0101 (4)0.0010 (4)
Cl320.0415 (5)0.0266 (4)0.0482 (6)−0.0051 (4)0.0188 (4)−0.0158 (4)
Cl410.0254 (4)0.0451 (5)0.0175 (4)−0.0067 (4)0.0080 (3)−0.0077 (3)
Cl420.0419 (5)0.0283 (4)0.0325 (5)−0.0046 (4)0.0211 (4)0.0028 (4)
C110.0208 (15)0.0200 (15)0.0180 (15)−0.0033 (12)0.0084 (13)−0.0026 (12)
C120.0173 (15)0.0204 (15)0.0171 (14)0.0018 (12)0.0071 (12)−0.0005 (12)
C210.0202 (16)0.0260 (17)0.0158 (15)0.0001 (13)0.0061 (13)0.0016 (12)
C220.0155 (14)0.0275 (17)0.0167 (15)0.0010 (12)0.0035 (12)0.0018 (13)
C310.0308 (17)0.0248 (17)0.0210 (16)−0.0056 (14)0.0136 (14)−0.0018 (13)
C320.0219 (16)0.0215 (16)0.0193 (15)−0.0026 (13)0.0088 (13)−0.0046 (13)
C410.0187 (16)0.0303 (18)0.0216 (16)−0.0068 (13)0.0058 (13)−0.0044 (14)
C420.0241 (16)0.0194 (16)0.0245 (16)0.0040 (13)0.0116 (14)0.0026 (13)
C510.0192 (15)0.0298 (18)0.0200 (15)−0.0005 (13)0.0065 (13)0.0001 (13)
C520.0204 (16)0.0249 (16)0.0168 (15)−0.0010 (13)0.0056 (13)0.0034 (13)
C610.0194 (15)0.0190 (16)0.0209 (16)−0.0006 (12)0.0094 (13)−0.0004 (12)
C620.0193 (15)0.0219 (16)0.0168 (14)0.0003 (12)0.0062 (12)−0.0001 (12)
C710.0157 (15)0.0219 (16)0.0217 (15)0.0018 (12)0.0040 (12)0.0011 (12)
C720.0230 (17)0.0247 (17)0.0228 (16)0.0042 (13)0.0048 (13)−0.0010 (13)
C810.0172 (15)0.0286 (17)0.0170 (15)−0.0004 (12)0.0059 (12)0.0037 (13)
C820.0225 (16)0.0240 (16)0.0130 (14)−0.0012 (13)0.0043 (12)−0.0006 (13)
C910.0165 (16)0.050 (2)0.0180 (16)0.0031 (15)0.0020 (13)0.0077 (15)
C920.039 (2)0.0280 (18)0.0163 (16)0.0026 (15)0.0064 (14)0.0046 (14)
C1010.0252 (18)0.070 (3)0.0229 (18)0.0049 (18)0.0084 (15)0.0179 (18)
C1020.041 (2)0.038 (2)0.0208 (17)0.0012 (16)0.0091 (16)0.0085 (15)
C1110.0260 (18)0.053 (2)0.0192 (17)−0.0008 (17)0.0081 (14)0.0090 (16)
C1120.041 (2)0.043 (2)0.0170 (16)0.0005 (17)0.0095 (15)0.0035 (15)
C1210.0235 (17)0.038 (2)0.0206 (16)−0.0022 (14)0.0083 (13)0.0055 (14)
C1220.0312 (16)0.0317 (19)0.0149 (14)−0.0029 (15)0.0071 (12)−0.0014 (14)
C1310.0178 (15)0.0281 (17)0.0148 (14)−0.0023 (13)0.0045 (12)−0.0008 (13)
C1320.0234 (16)0.0210 (15)0.0159 (15)−0.0027 (12)0.0077 (13)0.0019 (12)
C1410.0159 (14)0.0341 (17)0.0132 (14)−0.0016 (12)0.0056 (12)−0.0017 (12)
C1420.0239 (16)0.0243 (16)0.0184 (15)−0.0001 (13)0.0098 (13)−0.0018 (13)
C1510.0134 (14)0.0244 (16)0.0174 (15)−0.0006 (12)0.0045 (12)−0.0008 (12)
C1520.0161 (15)0.0218 (16)0.0239 (16)−0.0006 (12)0.0080 (13)−0.0001 (13)
C1610.0215 (16)0.0302 (18)0.0183 (15)0.0023 (13)0.0089 (13)0.0006 (13)
C1620.0191 (16)0.0272 (18)0.0264 (17)0.0005 (13)0.0094 (14)−0.0031 (14)
C1710.0162 (15)0.0236 (17)0.0272 (17)−0.0042 (13)0.0081 (13)0.0016 (13)
C1720.0202 (16)0.0270 (17)0.0290 (17)−0.0016 (14)0.0072 (13)−0.0102 (14)
C1810.0178 (15)0.0208 (15)0.0203 (15)−0.0005 (12)0.0026 (12)−0.0021 (13)
C1820.0228 (16)0.0199 (16)0.0354 (19)−0.0052 (13)0.0099 (14)−0.0017 (14)
C1920.0194 (15)0.0270 (17)0.0219 (16)−0.0008 (13)0.0089 (13)0.0014 (13)
C1910.0232 (16)0.0226 (16)0.0169 (14)0.0013 (13)0.0075 (12)0.0015 (13)
C2010.0161 (15)0.0189 (15)0.0195 (15)0.0022 (12)0.0064 (12)0.0012 (12)
C2020.0124 (14)0.0207 (16)0.0196 (15)−0.0014 (12)0.0039 (12)−0.0015 (12)

Geometric parameters (Å, °)

Zr—O222.070 (2)C81—C911.533 (4)
Zr—O212.0819 (19)C81—C1311.541 (4)
Zr—O112.088 (2)C81—H81A1.0000
Zr—O122.089 (2)C82—C921.529 (4)
Zr—N112.433 (2)C82—C1321.532 (4)
Zr—N222.439 (2)C82—H82A1.0000
Zr—N122.443 (2)C91—C1011.527 (4)
Zr—N212.451 (2)C91—H91A0.9900
O11—C111.322 (3)C91—H91B0.9900
O12—C2021.328 (3)C92—C1021.531 (4)
O21—C2011.323 (3)C92—H92A0.9900
O22—C121.318 (3)C92—H92B0.9900
N11—C811.482 (3)C101—C1111.521 (4)
N11—C711.492 (4)C101—H10A0.9900
N11—H110.892 (17)C101—H10B0.9900
N12—C821.491 (4)C102—C1121.524 (5)
N12—C721.491 (4)C102—H10C0.9900
N12—H120.900 (17)C102—H10D0.9900
N21—C1311.487 (3)C111—C1211.521 (4)
N21—C1411.492 (4)C111—H11A0.9900
N21—H210.885 (17)C111—H11B0.9900
N22—C1321.478 (4)C112—C1221.528 (4)
N22—C1421.486 (4)C112—H11C0.9900
N22—H220.896 (17)C112—H11D0.9900
Cl11—C211.741 (3)C121—C1311.529 (4)
Cl12—C221.742 (3)C121—H12A0.9900
Cl21—C411.749 (3)C121—H12B0.9900
Cl22—C421.746 (3)C122—C1321.530 (4)
Cl31—C1711.743 (3)C122—H12C0.9900
Cl32—C1721.748 (3)C122—H12D0.9900
Cl41—C1911.744 (3)C131—H13A1.0000
Cl42—C1921.742 (3)C132—H13B1.0000
C11—C211.399 (4)C141—C1511.511 (4)
C11—C611.406 (4)C141—H14A0.9900
C12—C221.395 (4)C141—H14B0.9900
C12—C621.403 (4)C142—C1521.512 (4)
C21—C311.388 (4)C142—H14C0.9900
C22—C321.377 (4)C142—H14D0.9900
C31—C411.371 (4)C151—C1611.391 (4)
C31—H31A0.9500C151—C2011.403 (4)
C32—C421.382 (4)C152—C1621.392 (4)
C32—H32A0.9500C152—C2021.403 (4)
C41—C511.381 (4)C161—C1711.385 (4)
C42—C521.376 (4)C161—H16A0.9500
C51—C611.399 (4)C162—C1721.383 (4)
C51—H51A0.9500C162—H16B0.9500
C52—C621.381 (4)C171—C1811.389 (4)
C52—H52A0.9500C172—C1821.379 (4)
C61—C711.505 (4)C181—C1911.385 (4)
C62—C721.507 (4)C181—H18A0.9500
C71—H71A0.9900C182—C1921.386 (4)
C71—H71B0.9900C182—H18B0.9500
C72—H72A0.9900C192—C2021.399 (4)
C72—H72B0.9900C191—C2011.393 (4)
O22—Zr—O21102.13 (8)C92—C82—C132110.5 (2)
O22—Zr—O1192.19 (8)N12—C82—H82A107.8
O21—Zr—O11139.47 (8)C92—C82—H82A107.8
O22—Zr—O12139.85 (8)C132—C82—H82A107.8
O21—Zr—O1291.98 (8)C101—C91—C81111.9 (3)
O11—Zr—O12101.11 (8)C101—C91—H91A109.2
O22—Zr—N1171.96 (8)C81—C91—H91A109.2
O21—Zr—N11144.73 (8)C101—C91—H91B109.2
O11—Zr—N1175.75 (7)C81—C91—H91B109.2
O12—Zr—N1174.93 (8)H91A—C91—H91B107.9
O22—Zr—N22143.96 (8)C82—C92—C102112.1 (3)
O21—Zr—N2272.90 (8)C82—C92—H92A109.2
O11—Zr—N2273.39 (8)C102—C92—H92A109.2
O12—Zr—N2276.09 (8)C82—C92—H92B109.2
N11—Zr—N22132.04 (8)C102—C92—H92B109.2
O22—Zr—N1273.55 (8)H92A—C92—H92B107.9
O21—Zr—N1273.57 (8)C111—C101—C91110.4 (3)
O11—Zr—N1274.61 (8)C111—C101—H10A109.6
O12—Zr—N12146.50 (8)C91—C101—H10A109.6
N11—Zr—N12132.94 (8)C111—C101—H10B109.6
N22—Zr—N1270.83 (8)C91—C101—H10B109.6
O22—Zr—N2174.65 (8)H10A—C101—H10B108.1
O21—Zr—N2174.74 (8)C112—C102—C92110.7 (3)
O11—Zr—N21145.76 (8)C112—C102—H10C109.5
O12—Zr—N2173.20 (8)C92—C102—H10C109.5
N11—Zr—N2170.16 (8)C112—C102—H10D109.5
N22—Zr—N21133.95 (8)C92—C102—H10D109.5
N12—Zr—N21128.39 (8)H10C—C102—H10D108.1
C11—O11—Zr140.16 (18)C101—C111—C121110.8 (3)
C202—O12—Zr138.32 (18)C101—C111—H11A109.5
C201—O21—Zr142.74 (18)C121—C111—H11A109.5
C12—O22—Zr145.11 (18)C101—C111—H11B109.5
C81—N11—C71112.7 (2)C121—C111—H11B109.5
C81—N11—Zr114.59 (16)H11A—C111—H11B108.1
C71—N11—Zr112.57 (16)C102—C112—C122109.8 (3)
C81—N11—H11109 (2)C102—C112—H11C109.7
C71—N11—H11107 (2)C122—C112—H11C109.7
Zr—N11—H11100.3 (19)C102—C112—H11D109.7
C82—N12—C72111.1 (2)C122—C112—H11D109.7
C82—N12—Zr114.07 (18)H11C—C112—H11D108.2
C72—N12—Zr113.07 (18)C111—C121—C131111.1 (3)
C82—N12—H12105 (2)C111—C121—H12A109.4
C72—N12—H12109 (2)C131—C121—H12A109.4
Zr—N12—H12105 (2)C111—C121—H12B109.4
C131—N21—C141112.0 (2)C131—C121—H12B109.4
C131—N21—Zr114.14 (17)H12A—C121—H12B108.0
C141—N21—Zr112.61 (17)C112—C122—C132112.3 (3)
C131—N21—H21106 (2)C112—C122—H12C109.2
C141—N21—H21112 (2)C132—C122—H12C109.2
Zr—N21—H2199 (2)C112—C122—H12D109.2
C132—N22—C142113.8 (2)C132—C122—H12D109.2
C132—N22—Zr112.64 (17)H12C—C122—H12D107.9
C142—N22—Zr112.62 (17)N21—C131—C121113.5 (2)
C132—N22—H22104 (2)N21—C131—C81109.1 (2)
C142—N22—H22110 (2)C121—C131—C81109.8 (2)
Zr—N22—H22103.1 (19)N21—C131—H13A108.1
O11—C11—C21122.1 (3)C121—C131—H13A108.1
O11—C11—C61120.4 (3)C81—C131—H13A108.1
C21—C11—C61117.5 (3)N22—C132—C122113.2 (2)
O22—C12—C22120.4 (2)N22—C132—C82109.5 (2)
O22—C12—C62121.9 (3)C122—C132—C82109.0 (2)
C22—C12—C62117.8 (3)N22—C132—H13B108.3
C31—C21—C11122.2 (3)C122—C132—H13B108.3
C31—C21—Cl11119.3 (2)C82—C132—H13B108.3
C11—C21—Cl11118.5 (2)N21—C141—C151110.9 (2)
C32—C22—C12122.4 (3)N21—C141—H14A109.5
C32—C22—Cl12118.7 (2)C151—C141—H14A109.5
C12—C22—Cl12118.9 (2)N21—C141—H14B109.5
C41—C31—C21118.8 (3)C151—C141—H14B109.5
C41—C31—H31A120.6H14A—C141—H14B108.0
C21—C31—H31A120.6N22—C142—C152110.5 (2)
C22—C32—C42118.1 (3)N22—C142—H14C109.5
C22—C32—H32A120.9C152—C142—H14C109.5
C42—C32—H32A120.9N22—C142—H14D109.5
C31—C41—C51121.5 (3)C152—C142—H14D109.5
C31—C41—Cl21119.4 (2)H14C—C142—H14D108.1
C51—C41—Cl21119.0 (2)C161—C151—C201120.3 (3)
C52—C42—C32121.3 (3)C161—C151—C141121.4 (3)
C52—C42—Cl22119.9 (2)C201—C151—C141118.3 (3)
C32—C42—Cl22118.7 (2)C162—C152—C202120.7 (3)
C41—C51—C61119.5 (3)C162—C152—C142121.8 (3)
C41—C51—H51A120.3C202—C152—C142117.5 (3)
C61—C51—H51A120.3C171—C161—C151119.8 (3)
C42—C52—C62120.1 (3)C171—C161—H16A120.1
C42—C52—H52A119.9C151—C161—H16A120.1
C62—C52—H52A119.9C172—C162—C152119.6 (3)
C51—C61—C11120.5 (3)C172—C162—H16B120.2
C51—C61—C71122.1 (3)C152—C162—H16B120.2
C11—C61—C71117.4 (3)C161—C171—C181121.3 (3)
C52—C62—C12120.2 (3)C161—C171—Cl31120.2 (2)
C52—C62—C72120.3 (3)C181—C171—Cl31118.5 (2)
C12—C62—C72119.5 (3)C182—C172—C162121.3 (3)
N11—C71—C61111.0 (2)C182—C172—Cl32119.3 (3)
N11—C71—H71A109.4C162—C172—Cl32119.4 (2)
C61—C71—H71A109.4C191—C181—C171117.9 (3)
N11—C71—H71B109.4C191—C181—H18A121.1
C61—C71—H71B109.4C171—C181—H18A121.1
H71A—C71—H71B108.0C172—C182—C192118.5 (3)
N12—C72—C62113.5 (2)C172—C182—H18B120.7
N12—C72—H72A108.9C192—C182—H18B120.7
C62—C72—H72A108.9C182—C192—C202122.3 (3)
N12—C72—H72B108.9C182—C192—Cl42118.8 (2)
C62—C72—H72B108.9C202—C192—Cl42118.9 (2)
H72A—C72—H72B107.7C181—C191—C201122.7 (3)
N11—C81—C91112.9 (2)C181—C191—Cl41118.6 (2)
N11—C81—C131108.6 (2)C201—C191—Cl41118.7 (2)
C91—C81—C131109.5 (2)O21—C201—C191121.1 (3)
N11—C81—H81A108.6O21—C201—C151121.0 (3)
C91—C81—H81A108.6C191—C201—C151117.9 (3)
C131—C81—H81A108.6O12—C202—C192121.8 (3)
N12—C82—C92113.0 (2)O12—C202—C152120.7 (3)
N12—C82—C132109.7 (2)C192—C202—C152117.5 (3)
O22—Zr—O11—C11−52.3 (3)Cl21—C41—C51—C61178.9 (2)
O21—Zr—O11—C11−163.9 (3)C32—C42—C52—C62−1.1 (5)
O12—Zr—O11—C1189.6 (3)Cl22—C42—C52—C62176.9 (2)
N11—Zr—O11—C1118.5 (3)C41—C51—C61—C111.6 (4)
N22—Zr—O11—C11161.3 (3)C41—C51—C61—C71−178.9 (3)
N12—Zr—O11—C11−124.6 (3)O11—C11—C61—C51180.0 (3)
N21—Zr—O11—C1113.2 (4)C21—C11—C61—C510.0 (4)
O22—Zr—O12—C202−162.5 (2)O11—C11—C61—C710.4 (4)
O21—Zr—O12—C202−50.9 (3)C21—C11—C61—C71−179.6 (3)
O11—Zr—O12—C20290.5 (3)C42—C52—C62—C12−0.5 (4)
N11—Zr—O12—C202162.3 (3)C42—C52—C62—C72−177.7 (3)
N22—Zr—O12—C20220.9 (3)O22—C12—C62—C52−176.0 (3)
N12—Zr—O12—C20211.6 (3)C22—C12—C62—C522.1 (4)
N21—Zr—O12—C202−124.3 (3)O22—C12—C62—C721.2 (4)
O22—Zr—O21—C20179.1 (3)C22—C12—C62—C72179.4 (3)
O11—Zr—O21—C201−172.8 (3)C81—N11—C71—C61155.0 (2)
O12—Zr—O21—C201−63.0 (3)Zr—N11—C71—C61−73.5 (2)
N11—Zr—O21—C2013.3 (4)C51—C61—C71—N11−123.8 (3)
N22—Zr—O21—C201−137.8 (3)C11—C61—C71—N1155.7 (3)
N12—Zr—O21—C201147.7 (3)C82—N12—C72—C62160.1 (2)
N21—Zr—O21—C2018.9 (3)Zr—N12—C72—C62−70.2 (3)
O21—Zr—O22—C1255.4 (3)C52—C62—C72—N12−140.9 (3)
O11—Zr—O22—C12−86.4 (3)C12—C62—C72—N1241.9 (4)
O12—Zr—O22—C12163.4 (3)C71—N11—C81—C91−65.0 (3)
N11—Zr—O22—C12−160.7 (3)Zr—N11—C81—C91164.5 (2)
N22—Zr—O22—C12−22.1 (4)C71—N11—C81—C131173.3 (2)
N12—Zr—O22—C12−13.2 (3)Zr—N11—C81—C13142.8 (3)
N21—Zr—O22—C12125.7 (3)C72—N12—C82—C92−70.5 (3)
O22—Zr—N11—C81−96.17 (19)Zr—N12—C82—C92160.3 (2)
O21—Zr—N11—C81−10.6 (3)C72—N12—C82—C132165.7 (2)
O11—Zr—N11—C81166.7 (2)Zr—N12—C82—C13236.5 (3)
O12—Zr—N11—C8160.78 (18)N11—C81—C91—C101−178.2 (3)
N22—Zr—N11—C81115.47 (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—C71133.25 (19)C81—C91—C101—C11156.4 (4)
O21—Zr—N11—C71−141.21 (17)C82—C92—C102—C11255.6 (4)
O11—Zr—N11—C7136.12 (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—C13157.8 (4)
N12—Zr—N11—C7188.5 (2)C102—C112—C122—C13258.2 (4)
N21—Zr—N11—C71−147.0 (2)C141—N21—C131—C121−67.6 (3)
O22—Zr—N12—C82175.8 (2)Zr—N21—C131—C121163.0 (2)
O21—Zr—N12—C8267.38 (19)C141—N21—C131—C81169.6 (2)
O11—Zr—N12—C82−87.2 (2)Zr—N21—C131—C8140.2 (3)
O12—Zr—N12—C82−0.3 (3)C111—C121—C131—N21179.1 (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—C82121.66 (19)C91—C81—C131—N21−177.7 (2)
O22—Zr—N12—C7247.57 (18)N11—C81—C131—C121−179.0 (2)
O21—Zr—N12—C72−60.81 (18)C91—C81—C131—C12157.3 (3)
O11—Zr—N12—C72144.6 (2)C142—N22—C132—C122−63.0 (3)
O12—Zr—N12—C72−128.47 (19)Zr—N22—C132—C122167.24 (19)
N11—Zr—N12—C7291.8 (2)C142—N22—C132—C82175.2 (2)
N22—Zr—N12—C72−138.0 (2)Zr—N22—C132—C8245.4 (3)
N21—Zr—N12—C72−6.5 (2)C112—C122—C132—N22179.3 (3)
O22—Zr—N21—C13162.43 (19)C112—C122—C132—C82−58.5 (3)
O21—Zr—N21—C131169.9 (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—C12256.5 (3)
N22—Zr—N21—C131−143.41 (18)C131—N21—C141—C151156.1 (2)
N12—Zr—N21—C131116.11 (19)Zr—N21—C141—C151−73.7 (3)
O22—Zr—N21—C141−66.70 (18)C132—N22—C142—C152156.8 (2)
O21—Zr—N21—C14140.80 (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—C141137.68 (19)N21—C141—C151—C20152.3 (4)
N11—Zr—N21—C141−142.7 (2)N22—C142—C152—C162−125.4 (3)
N22—Zr—N21—C14187.5 (2)N22—C142—C152—C20255.4 (3)
N12—Zr—N21—C141−13.0 (2)C201—C151—C161—C1710.7 (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—C1720.7 (4)
O11—Zr—N22—C13259.71 (18)C142—C152—C162—C172−178.5 (3)
O12—Zr—N22—C132166.0 (2)C151—C161—C171—C1810.2 (5)
N11—Zr—N22—C132111.77 (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—Cl32177.1 (2)
O22—Zr—N22—C142−140.67 (18)C161—C171—C181—C191−1.7 (5)
O21—Zr—N22—C142132.15 (19)Cl31—C171—C181—C191176.8 (2)
O11—Zr—N22—C142−70.68 (18)C162—C172—C182—C1921.7 (4)
O12—Zr—N22—C14235.64 (18)Cl32—C172—C182—C192−178.1 (2)
N11—Zr—N22—C142−18.6 (2)C172—C182—C192—C2021.5 (4)
N12—Zr—N22—C142−149.8 (2)C172—C182—C192—Cl42−179.5 (2)
N21—Zr—N22—C14284.9 (2)C171—C181—C191—C2012.5 (4)
Zr—O11—C11—C21139.5 (3)C171—C181—C191—Cl41−177.6 (2)
Zr—O11—C11—C61−40.5 (4)Zr—O21—C201—C191149.1 (2)
Zr—O22—C12—C22172.4 (2)Zr—O21—C201—C151−31.4 (5)
Zr—O22—C12—C62−9.4 (5)C181—C191—C201—O21177.9 (3)
O11—C11—C21—C31178.3 (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—C151178.4 (2)
C61—C11—C21—Cl11179.8 (2)C161—C151—C201—O21−179.5 (3)
O22—C12—C22—C32176.0 (3)C141—C151—C201—O210.2 (4)
C62—C12—C22—C32−2.3 (4)C161—C151—C201—C1910.0 (4)
O22—C12—C22—Cl12−2.8 (4)C141—C151—C201—C191179.6 (3)
C62—C12—C22—Cl12179.0 (2)Zr—O12—C202—C192137.0 (2)
C11—C21—C31—C411.9 (5)Zr—O12—C202—C152−44.3 (4)
Cl11—C21—C31—C41−179.7 (2)C182—C192—C202—O12175.4 (3)
C12—C22—C32—C420.7 (4)Cl42—C192—C202—O12−3.6 (4)
Cl12—C22—C32—C42179.4 (2)C182—C192—C202—C152−3.4 (4)
C21—C31—C41—C51−0.2 (5)Cl42—C192—C202—C152177.6 (2)
C21—C31—C41—Cl21179.4 (2)C162—C152—C202—O12−176.5 (3)
C22—C32—C42—C521.1 (4)C142—C152—C202—O122.7 (4)
C22—C32—C42—Cl22−177.0 (2)C162—C152—C202—C1922.3 (4)
C31—C41—C51—C61−1.5 (5)C142—C152—C202—C192−178.5 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N11—H11···O220.89 (2)2.28 (3)2.662 (3)105.7 (18)
N21—H21···O120.89 (2)2.32 (4)2.722 (4)108 (2)
N21—H21···Cl420.89 (2)2.76 (2)3.631 (3)166.8 (16)
N22—H22···O210.89 (2)2.34 (3)2.701 (4)104.1 (18)
C72—H72B···O210.992.443.024 (4)117
C132—H13B···O111.002.532.987 (3)108
C141—H14B···O220.992.583.137 (4)115
C51—H51A···Cl22i0.952.833.654 (3)146
C122—H12C···Cl22ii0.992.723.402 (3)126

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RZ2233).

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