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metal-organic compounds
{Bis(3,5-Di-tert-butyl-2-oxidobenzyl)[2-(N,N-dimethylamino)ethyl]amine-κ4N,N′,O,O′}zinc(II) and {bis(3-tert-butyl-5-methyl-2-oxidobenzyl)[2-(N,N-dimethylamino)ethyl]amine-κ4N,N′,O,O′}(tetrahdyrofuran)zinc(II)
aSchool of Chemical Sciences and Pharmacy, University of East Anglia, Norwich NR4 7TJ, England
*Correspondence e-mail: joseph.wright@uea.ac.uk
The title zinc(II) complexes, [Zn(C34H54N2O2)], (II), and [Zn(C28H42N2O2)(C4H8O)], (III)
, were obtained as monomeric 1:1 complexes, in contrast with the calcium complexes supported by the same ligand class. Complex (II)
crystallizes with two independent molecules in the which have similar geometric parameters. The donor atoms in (II)
form a distorted trigonal–pyramidal arrangement around the zinc centre. Complex (III)
contains a coordinated tetrahydrofuran molecule, resulting in a five-coordinate trigonal–bipyramidal arrangement around the Zn atom. The electron density provided by the coordination of this tetrahydrofuran molecule elongates the Zn—O and Zn—N bonds by approximately 0.07 and 0.10 Å, respectively, in comparison with (II)
. Neither (II)
nor (III)
is active as an ∊-caprolactone polymerization catalyst. The data presented here demonstrate that Zn may bind both an ONNO ligand and an additional oxygen-based ligand. The lack of activity is thus not due to steric hinderance at the metal atom.
Comment
The use of biodegradable polymers is of increasing interest, with environmental factors being a key driving force (Drumright et al., 2000). A principle route to these materials is the of ∊-caprolactone (CL) (systematic name: oxepan-2-one) or lactide (LA) (systematic name: 3,6-dimethyl-1,4-dioxane-2,5-dione) to give polyesters. Both of these monomers are readily available from corn, and so are themselves renewable (O'Keefe et al., 2001
; Dechy-Cabaret et al., 2004
). In order to control the physical properties and of these polyesters, a variety of main-group and transition metal complexes have attracted attention.
The syntheses of a number of catalysts for CL and LA polymerization based on substituted aminobis(2-hydroxyarylmethyl) (ONNO) ligand systems have recently been
reported (Sarazin et al., 2006![Sarazin, Y., Howard, R. H., Hughes, D. L., Humphrey, S. M. & Bochmann, M. (2006). Dalton Trans. pp. 340-350. [Sarazin, Y., Howard, R. H., Hughes, D. L., Humphrey, S. M. & Bochmann, M. (2006). Dalton Trans. pp. 340-350.]](../../../../../../logos/arrows/c_arr.gif)
![Tshuva, E. Y., Goldberg, I., Kol, M. & Goldschmidt, Z. (2001a). Inorg. Chem. 40, 4263-4270. [Tshuva, E. Y., Goldberg, I., Kol, M. & Goldschmidt, Z. (2001a). Inorg. Chem. 40, 4263-4270.]](../../../../../../logos/arrows/c_arr.gif)
![Tshuva, E. Y., Goldberg, I., Kol, M. & Goldschmidt, Z. (2001b). Chem. Commun. pp. 2120-2121. [Tshuva, E. Y., Goldberg, I., Kol, M. & Goldschmidt, Z. (2001b). Chem. Commun. pp. 2120-2121.]](../../../../../../logos/arrows/c_arr.gif)
![Tshuva, E. Y., Groysman, S., Goldberg, I., Kol, M. & Goldschmidt, Z. (2002). Organometallics, 21, 662-670. [Tshuva, E. Y., Groysman, S., Goldberg, I., Kol, M. & Goldschmidt, Z. (2002). Organometallics, 21, 662-670.]](../../../../../../logos/arrows/c_arr.gif)
![Groysman, S., Goldberg, I., Kol, M., Genizi, E. & Goldschmidt, Z. (2003). Inorg. Chim. Acta, 345, 137-144. [Groysman, S., Goldberg, I., Kol, M., Genizi, E. & Goldschmidt, Z. (2003). Inorg. Chim. Acta, 345, 137-144.]](../../../../../../logos/arrows/c_arr.gif)
![Sarazin, Y., Howard, R. H., Hughes, D. L., Humphrey, S. M. & Bochmann, M. (2006). Dalton Trans. pp. 340-350. [Sarazin, Y., Howard, R. H., Hughes, D. L., Humphrey, S. M. & Bochmann, M. (2006). Dalton Trans. pp. 340-350.]](../../../../../../logos/arrows/c_arr.gif)
![[link]](../../../../../../logos/arrows/c_arr.gif)
![[link]](../../../../../../logos/arrows/c_arr.gif)
![Atkins, P. W., Overton, T., Rourke, J., Weller, M. & Armstrong, F. (2006). Shriver & Atkins Inorganic Chemistry, 4th ed. Oxford University Press. [Atkins, P. W., Overton, T., Rourke, J., Weller, M. & Armstrong, F. (2006). Shriver & Atkins Inorganic Chemistry, 4th ed. Oxford University Press.]](../../../../../../logos/arrows/c_arr.gif)
![[link]](../../../../../../logos/arrows/c_arr.gif)
![[link]](../../../../../../logos/arrows/c_arr.gif)
Complex (II) crystallizes in the triclinic P
, with two independent molecules in the (Fig. 1
). Table 1
highlights the bond lengths and angles around the metal centre. It can be seen that the two independent molecules exhibit similar geometric values. The metal–donor distances in (II)
(Table 1
) are similar to those in the previously reported monomeric titanium complex, (V). The M—O distances in (II)
fall close to those in (V) [1.9034 (15) and 1.9009 (15) Å], consistent with the similar ionic radii of the central atoms. However, the M—N distances are much longer in the titanium complex [2.400 (2) and 2.335 (2) Å] than in (II)
. In contrast, the dimeric calcium complex, (IV), exhibits significantly longer (non-bridging) M—O distances [2.1842 (16) and 2.1817 (16) Å] than (II)
. The M—N distances are again significantly shorter in (II)
than in (IV) [2.4981 (19)–2.552 (2) Å]. The donor atoms form a distorted trigonal–pyramidal arrangement around the Zn atom, which lies 0.205 (1) Å from mean plane of the O and N atoms which form the base of the pyramid. The Naxial—Zn—donor angles demonstrate the distortion of the molecule from ideal geometry, with the two O atoms bent away from the Zn—Naxial bond.
Complex (III) is trigonal–bipyramidal, with the fifth coordination site occupied by a tetrahydrofuran (THF) molecule (Fig. 2
). The change of R group from tert-butyl to methyl is remote from the metal centre, and so it is reasonable to compare the geometry of (III)
with that seen in (II)
. As expected, the additional electron density donated by the THF molecule results in the elongation of the metal–donor bond lengths in (III)
compared with (II)
(Tables 1
and 2
). The Zn—O bonds are lengthened by approximately 0.07 Å, whilst the Zn—N bonds are extended by approximately 0.1 Å. The geometry of the ONNO ligand at the metal centre is similar to that in (II)
, although the metal atom is displaced by only 0.0185 (16) Å from the mean plane of the equatorial donors.
Neither complex (II) nor (III)
is active in the polymerization of LA or CL, in contrast with (IV). The structures presented in this report demonstrate the ability of the metal centre to bind both the ONNO ligand and an additional oxygen-based ligand. The lack of polymerization activity cannot, therefore, be due to steric protection of the Lewis acidic site.
![]() | Figure 1 The two independent molecules of (II) ![]() |
![]() | Figure 2 A representation of (III) ![]() |
Experimental
The ligands (Ia) (Tshuva et al., 2001a
) and (Ib)
(Sarazin et al., 2006
) were produced according to literature methods, as was complex (II)
(Sarazin et al., 2006
). Crystals of (II)
suitable for X-ray diffraction were grown from a light petroleum–diethyl ether (1:3 v/v) solution at 268 K. Complex (III)
was prepared by a method analogous to that used to produce (II)
. Reaction of Zn[N(SiMe3)2]2 (0.97 g, 2.5 mmol) and (Ib) (1.1 g, 2.5 mmol) in light petroleum (30 ml) gave a white solid. 1H NMR (300 MHz, C6D6): δ 7.31 (d, 2H, Ar), 6.60 (d, 2H, Ar), 3.76 (s, 1H, Ar–CH2), 3.72 (s, 1H, Ar–CH2), 3.07 (d, 1H, Ar–CH2), 3.03 (s, 1H, Ar–CH2), 2.34 (s, 6H, 2 × MeAr), 2.04 (t, 1H, N–CH2–CH2–N), 1.76 (s, 18H, tBu), 1.59 (t, 1H, N–CH2–CH2–N), 1.49 (s, 6H, NMe2); 13C NMR (75MHz, C6D6): δ 164.9 (C–O), 138.7 (CAr), 130.5 (CAr), 128.9(CAr), 123.0 (CAr), 122.9 (CAr), 60.1 (Ar–CH2), 59.4 (N–CH2), 46.5 (N–CH2), 41.8 [N(CH3)2], 35.8 [C(CH3)3], 30.2 [C(CH3)3], 22.9 (Ar–CH3). Crystals of (III)
suitable for X-ray diffraction were grown from a tetrahydrofuran–light petroleum–diethyl ether solution (1:1:3 v/v/v) at 268 K.
Compound (II)![[link]](../../../../../../logos/arrows/c_arr.gif)
Crystal data
|
Refinement
|
|
Compound (III)![[link]](../../../../../../logos/arrows/c_arr.gif)
Crystal data
|
Refinement
|
|
All H atoms were refined using a riding model, with C—H = 0.98–0.99 Å and Uiso(H) = 1.5 or 1.2 times Ueq(C). Methyl H atoms were positioned using residual electron density (HFIX 137). One tert-butyl group of (II) (central atom C112, and methyl atoms C113, C114 and C115) was found to be disordered and was freely refined over two positions. This gave a final occupancy of 0.853 (3) for the major position (shown in Fig. 2
). The central atom-to-methyl bonds were restrained to a distance of 1.55 Å for all of the disordered C atoms (DFIX 1.55 0.02). A second tert-butyl group (central atom C127, and methyl atoms C128, C129 and C130) showed evidence of disorder, particularly in the displacement parameters for atom C129. However, this could not be successfully modelled.
For both compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2003); cell CrysAlis RED; data reduction: CrysAlis RED; program(s) used to solve structure: SIR92 (Altomare et al., 1993
); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997
); molecular graphics: ORTEP-3 (Farrugia, 1997
); software used to prepare material for publication: SHELXL97, PLATON (Spek, 2003
), WinGX (Farrugia, 1999
) and enCIFer (Allen et al., 2004
).
Supporting information
10.1107/S0108270106018695/fg3023sup1.cif
contains datablocks global, II, III. DOI:Structure factors: contains datablock II. DOI: 10.1107/S0108270106018695/fg3023IIsup2.hkl
Structure factors: contains datablock III. DOI: 10.1107/S0108270106018695/fg3023IIIsup3.hkl
The ligands (Ia) (Tshuva et al., 2001a) and (Ib) (Sarazin et al., 2006) were produced by the literature methods, as was complex (II) (Sarazin et al., 2006). Crystals of (II) suitable for X-ray diffraction were grown from a 1:3 light petroleum—diethyl ether solution at 268 K. Complex (III) was prepared by a method analogous to that used to produce (II). Reaction of Zn[N(SiMe3)2]2 (0.97 g, 2.5 mmol) and (Ib) (1.1 g, 2.5 mmol) in light petroleum (30 ml) gave a white solid. Spectroscopic analysis: 1H NMR (300 MHz, C6D6, δ, p.p.m.): 7.31 (d, 2H, Ar), 6.60 (d, 2H, Ar), 3.76 (s, 1H, Ar—CH2), 3.72 (s, 1H, Ar—CH2), 3.07 (d, 1H, Ar—CH2), 3.03 (s, 1H, Ar—CH2), 2.34 (s, 6H, 2 × MeAr), 2.04 (t, 1H, N—CH2—CH2—N), 1.76 (s, 18H, tBu), 1.59 (t, 1H, N—CH2—CH2—N), 1.49 (s, 6H, NMe2); 13C NMR (75 MHz, C6D6, δ, p.p.m.): 164.9 (C—O), 138.7 (CAr), 130.5 (CAr), 128.9(CAr), 123.0 (CAr), 122.9 (CAr), 60.1 (Ar—CH2), 59.4 (N—CH2), 46.5 (N—CH2), 41.8 [N(CH3)2], 35.8 [C(CH3)3], 30.2 [C(CH3)3], 22.9 (Ar—CH3). Crystals of (III) suitable for X-ray diffraction were grown from a 1:1:3 tetrahydrofuran–light petroleum–diethyl ether solution at 268 K.
All H atoms were refined using a riding model, using the default SHELXL97 parameters (Sheldrick, 1997) (C—H = 0.98–0.99 Å Please check added text) and with Uiso(H) = 1.5 or 1.2 times Ueq(C). Methyl H atoms were positioned using residual electron denisty (HFIX 137). One tBu group of (II) (central atom C112, and methyl atoms C113, C114 and C115) was found to be disordered, and was freely refined over two positions. This gave a final occupancy of 0.853 (3) in the major position (shown in Fig. 2). The central atom—methyl bonds were restrained to a distance of 1.55 Å for all of the disordered C atoms (DFIX 1.55 0.02). A second tBu group (central atom C127, and methyl atoms C128, C129 and C130) showed evidence for disorder, particularly in the displacement parameters for C129. However, this could not be successfully modelled.
For both compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2003); cell
CrysAlis RED; data reduction: CrysAlis RED; program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97, PLATON (Spek, 2003), WinGX (Farrugia, 1999) and enCIFer (Allen et al., 2004).[Zn(C34H54N2O2)] | Z = 4 |
Mr = 588.16 | F(000) = 1272 |
Triclinic, P1 | Dx = 1.160 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 12.9275 (12) Å | Cell parameters from 15277 reflections |
b = 14.0002 (13) Å | θ = 3.7–27.6° |
c = 19.6729 (14) Å | µ = 0.76 mm−1 |
α = 100.747 (7)° | T = 140 K |
β = 102.467 (7)° | Plate, colourless |
γ = 96.879 (8)° | 0.20 × 0.08 × 0.02 mm |
V = 3367.8 (5) Å3 |
Oxford Xcalibur3 CCD area-detector diffractometer | 15272 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 8001 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.076 |
Detector resolution: 16.0050 pixels mm-1 | θmax = 27.6°, θmin = 3.7° |
Thin slice ϕ and ω scans | h = −16→16 |
Absorption correction: multi-scan (ABSPACK; Oxford Diffraction, 2003) | k = −18→18 |
Tmin = 0.925, Tmax = 0.983 | l = −25→25 |
42426 measured reflections |
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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.071 | H-atom parameters constrained |
S = 0.79 | w = 1/[σ2(Fo2) + (0.0243P)2] where P = (Fo2 + 2Fc2)/3 |
15272 reflections | (Δ/σ)max = 0.001 |
744 parameters | Δρmax = 0.45 e Å−3 |
12 restraints | Δρmin = −0.43 e Å−3 |
[Zn(C34H54N2O2)] | γ = 96.879 (8)° |
Mr = 588.16 | V = 3367.8 (5) Å3 |
Triclinic, P1 | Z = 4 |
a = 12.9275 (12) Å | Mo Kα radiation |
b = 14.0002 (13) Å | µ = 0.76 mm−1 |
c = 19.6729 (14) Å | T = 140 K |
α = 100.747 (7)° | 0.20 × 0.08 × 0.02 mm |
β = 102.467 (7)° |
Oxford Xcalibur3 CCD area-detector diffractometer | 15272 independent reflections |
Absorption correction: multi-scan (ABSPACK; Oxford Diffraction, 2003) | 8001 reflections with I > 2σ(I) |
Tmin = 0.925, Tmax = 0.983 | Rint = 0.076 |
42426 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 12 restraints |
wR(F2) = 0.071 | H-atom parameters constrained |
S = 0.79 | Δρmax = 0.45 e Å−3 |
15272 reflections | Δρmin = −0.43 e Å−3 |
744 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. |
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 > 2σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Zn1 | 0.21611 (2) | 0.06073 (2) | 0.826370 (15) | 0.02147 (8) | |
Zn2 | 0.83543 (2) | 0.48447 (2) | 0.314827 (15) | 0.02080 (8) | |
C101 | 0.32137 (19) | 0.01416 (17) | 0.71210 (13) | 0.0256 (6) | |
H10A | 0.3196 | −0.0032 | 0.6607 | 0.031* | |
H10B | 0.3589 | −0.0332 | 0.7354 | 0.031* | |
C102 | 0.38484 (19) | 0.11712 (16) | 0.74353 (12) | 0.0207 (6) | |
C103 | 0.40703 (19) | 0.15618 (17) | 0.81766 (12) | 0.0197 (6) | |
C104 | 0.47591 (19) | 0.24934 (17) | 0.84629 (12) | 0.0206 (6) | |
C105 | 0.51285 (19) | 0.29836 (17) | 0.79840 (12) | 0.0226 (6) | |
H105 | 0.5580 | 0.3606 | 0.8174 | 0.027* | |
C106 | 0.48846 (19) | 0.26283 (17) | 0.72477 (12) | 0.0217 (6) | |
C107 | 0.42495 (19) | 0.17083 (18) | 0.69919 (13) | 0.0236 (6) | |
H107 | 0.4080 | 0.1431 | 0.6494 | 0.028* | |
C108 | 0.50685 (19) | 0.29201 (17) | 0.92665 (12) | 0.0234 (6) | |
C109 | 0.5824 (2) | 0.39143 (19) | 0.94640 (13) | 0.0383 (8) | |
H10C | 0.6475 | 0.3832 | 0.9296 | 0.057* | |
H10D | 0.6018 | 0.4153 | 0.9983 | 0.057* | |
H10E | 0.5461 | 0.4392 | 0.9239 | 0.057* | |
C110 | 0.5659 (2) | 0.22020 (18) | 0.96521 (13) | 0.0289 (6) | |
H11A | 0.5181 | 0.1569 | 0.9557 | 0.043* | |
H11B | 0.5871 | 0.2481 | 1.0167 | 0.043* | |
H11C | 0.6302 | 0.2101 | 0.9477 | 0.043* | |
C111 | 0.4072 (2) | 0.30963 (18) | 0.95451 (13) | 0.0292 (6) | |
H11D | 0.3715 | 0.3569 | 0.9310 | 0.044* | |
H11E | 0.4289 | 0.3360 | 1.0062 | 0.044* | |
H11F | 0.3575 | 0.2472 | 0.9441 | 0.044* | |
C112 | 0.5324 (2) | 0.32285 (19) | 0.67592 (13) | 0.0280 (6) | |
C113 | 0.6569 (2) | 0.3308 (2) | 0.69166 (18) | 0.0364 (9) | 0.853 (3) |
H11G | 0.6848 | 0.3703 | 0.6613 | 0.055* | 0.853 (3) |
H11H | 0.6755 | 0.2646 | 0.6817 | 0.055* | 0.853 (3) |
H11I | 0.6887 | 0.3625 | 0.7419 | 0.055* | 0.853 (3) |
C114 | 0.4844 (3) | 0.2784 (2) | 0.59823 (15) | 0.0395 (10) | 0.853 (3) |
H11J | 0.5099 | 0.3221 | 0.5695 | 0.059* | 0.853 (3) |
H11K | 0.4059 | 0.2702 | 0.5887 | 0.059* | 0.853 (3) |
H11L | 0.5062 | 0.2140 | 0.5857 | 0.059* | 0.853 (3) |
C115 | 0.5075 (3) | 0.4286 (2) | 0.69173 (16) | 0.0291 (8) | 0.853 (3) |
H11M | 0.5390 | 0.4594 | 0.7422 | 0.044* | 0.853 (3) |
H11N | 0.4295 | 0.4264 | 0.6811 | 0.044* | 0.853 (3) |
H11O | 0.5382 | 0.4672 | 0.6619 | 0.044* | 0.853 (3) |
C313 | 0.5950 (15) | 0.2543 (12) | 0.6328 (10) | 0.0364 (9) | 0.147 (3) |
H33A | 0.6275 | 0.2905 | 0.6024 | 0.055* | 0.147 (3) |
H33B | 0.5450 | 0.1960 | 0.6030 | 0.055* | 0.147 (3) |
H33C | 0.6515 | 0.2338 | 0.6661 | 0.055* | 0.147 (3) |
C314 | 0.4328 (14) | 0.3315 (15) | 0.6112 (9) | 0.0395 (10) | 0.147 (3) |
H34A | 0.3956 | 0.3847 | 0.6282 | 0.059* | 0.147 (3) |
H34B | 0.3824 | 0.2691 | 0.5955 | 0.059* | 0.147 (3) |
H34C | 0.4609 | 0.3460 | 0.5711 | 0.059* | 0.147 (3) |
C315 | 0.5887 (15) | 0.4250 (10) | 0.7067 (9) | 0.0291 (8) | 0.147 (3) |
H35A | 0.6010 | 0.4570 | 0.6683 | 0.044* | 0.147 (3) |
H35B | 0.6578 | 0.4242 | 0.7389 | 0.044* | 0.147 (3) |
H35C | 0.5446 | 0.4615 | 0.7334 | 0.044* | 0.147 (3) |
C116 | 0.1446 (2) | 0.06182 (18) | 0.67715 (13) | 0.0265 (6) | |
H11P | 0.1351 | 0.0317 | 0.6260 | 0.032* | |
H11Q | 0.1854 | 0.1293 | 0.6865 | 0.032* | |
C117 | 0.0354 (2) | 0.06885 (17) | 0.69117 (13) | 0.0244 (6) | |
C118 | 0.02346 (19) | 0.11206 (16) | 0.75938 (13) | 0.0220 (6) | |
C119 | −0.0807 (2) | 0.12601 (17) | 0.76780 (14) | 0.0252 (6) | |
C120 | −0.1674 (2) | 0.09147 (18) | 0.70836 (14) | 0.0303 (7) | |
H120 | −0.2371 | 0.0997 | 0.7141 | 0.036* | |
C121 | −0.1581 (2) | 0.04578 (18) | 0.64143 (15) | 0.0343 (7) | |
C122 | −0.0556 (2) | 0.03642 (17) | 0.63422 (14) | 0.0320 (7) | |
H122 | −0.0465 | 0.0068 | 0.5888 | 0.038* | |
C123 | −0.0975 (2) | 0.17830 (18) | 0.83949 (14) | 0.0287 (6) | |
C124 | −0.0317 (2) | 0.28366 (17) | 0.86243 (13) | 0.0291 (6) | |
H12A | −0.0569 | 0.3217 | 0.8269 | 0.044* | |
H12B | 0.0445 | 0.2802 | 0.8660 | 0.044* | |
H12C | −0.0411 | 0.3159 | 0.9089 | 0.044* | |
C125 | −0.0624 (2) | 0.11926 (18) | 0.89690 (13) | 0.0350 (7) | |
H12D | −0.0791 | 0.1498 | 0.9414 | 0.053* | |
H12E | 0.0151 | 0.1192 | 0.9052 | 0.053* | |
H12F | −0.1009 | 0.0513 | 0.8806 | 0.053* | |
C126 | −0.2150 (2) | 0.1888 (2) | 0.83663 (16) | 0.0469 (8) | |
H12G | −0.2391 | 0.2288 | 0.8022 | 0.070* | |
H12H | −0.2211 | 0.2211 | 0.8840 | 0.070* | |
H12I | −0.2598 | 0.1234 | 0.8219 | 0.070* | |
C127 | −0.2555 (2) | 0.0094 (2) | 0.57674 (16) | 0.0462 (9) | |
C128 | −0.2519 (3) | 0.0781 (3) | 0.52605 (17) | 0.0745 (12) | |
H12J | −0.1844 | 0.0790 | 0.5110 | 0.112* | |
H12K | −0.2564 | 0.1448 | 0.5502 | 0.112* | |
H12L | −0.3126 | 0.0550 | 0.4841 | 0.112* | |
C129 | −0.2536 (3) | −0.0951 (2) | 0.5405 (2) | 0.124 (2) | |
H12M | −0.3182 | −0.1190 | 0.5014 | 0.186* | |
H12N | −0.2518 | −0.1373 | 0.5751 | 0.186* | |
H12O | −0.1897 | −0.0970 | 0.5214 | 0.186* | |
C130 | −0.3631 (3) | 0.0113 (3) | 0.59868 (19) | 0.0814 (13) | |
H13D | −0.4228 | −0.0151 | 0.5566 | 0.122* | |
H13E | −0.3684 | 0.0794 | 0.6193 | 0.122* | |
H13F | −0.3663 | −0.0290 | 0.6341 | 0.122* | |
C131 | 0.1584 (2) | −0.10094 (16) | 0.70662 (13) | 0.0268 (6) | |
H13G | 0.1793 | −0.1393 | 0.6655 | 0.032* | |
H13H | 0.0793 | −0.1060 | 0.6943 | 0.032* | |
C132 | 0.1933 (2) | −0.14385 (17) | 0.77191 (13) | 0.0283 (6) | |
H13I | 0.1544 | −0.2121 | 0.7629 | 0.034* | |
H13J | 0.2712 | −0.1464 | 0.7806 | 0.034* | |
C133 | 0.2350 (2) | −0.10487 (19) | 0.90182 (14) | 0.0432 (8) | |
H13K | 0.2154 | −0.1746 | 0.9020 | 0.065* | |
H13L | 0.2206 | −0.0638 | 0.9438 | 0.065* | |
H13M | 0.3116 | −0.0905 | 0.9031 | 0.065* | |
C134 | 0.0546 (2) | −0.10599 (18) | 0.83519 (15) | 0.0370 (7) | |
H13N | 0.0347 | −0.1768 | 0.8320 | 0.056* | |
H13O | 0.0113 | −0.0874 | 0.7938 | 0.056* | |
H13P | 0.0416 | −0.0688 | 0.8790 | 0.056* | |
C201 | 0.65527 (17) | 0.45778 (17) | 0.19360 (12) | 0.0197 (6) | |
H20A | 0.6241 | 0.4415 | 0.1414 | 0.024* | |
H20B | 0.6323 | 0.5197 | 0.2136 | 0.024* | |
C202 | 0.61032 (17) | 0.37572 (16) | 0.22537 (12) | 0.0174 (5) | |
C203 | 0.63793 (18) | 0.38410 (17) | 0.29998 (13) | 0.0196 (6) | |
C204 | 0.59083 (19) | 0.30878 (17) | 0.32866 (12) | 0.0204 (6) | |
C205 | 0.51772 (18) | 0.23105 (17) | 0.28150 (12) | 0.0211 (6) | |
H205 | 0.4863 | 0.1807 | 0.3007 | 0.025* | |
C206 | 0.48736 (18) | 0.22222 (17) | 0.20753 (12) | 0.0202 (6) | |
C207 | 0.53645 (18) | 0.29562 (16) | 0.18092 (12) | 0.0183 (6) | |
H207 | 0.5193 | 0.2913 | 0.1309 | 0.022* | |
C208 | 0.6194 (2) | 0.31407 (18) | 0.40947 (12) | 0.0242 (6) | |
C209 | 0.5605 (2) | 0.22461 (18) | 0.42853 (13) | 0.0348 (7) | |
H20C | 0.5832 | 0.2291 | 0.4800 | 0.052* | |
H20D | 0.5778 | 0.1639 | 0.4030 | 0.052* | |
H20E | 0.4828 | 0.2237 | 0.4147 | 0.052* | |
C210 | 0.5884 (2) | 0.40755 (17) | 0.44889 (13) | 0.0266 (6) | |
H21A | 0.5103 | 0.4042 | 0.4346 | 0.040* | |
H21B | 0.6241 | 0.4656 | 0.4368 | 0.040* | |
H21C | 0.6108 | 0.4126 | 0.5005 | 0.040* | |
C211 | 0.7409 (2) | 0.31509 (19) | 0.43651 (13) | 0.0328 (7) | |
H21D | 0.7814 | 0.3722 | 0.4262 | 0.049* | |
H21E | 0.7602 | 0.2544 | 0.4124 | 0.049* | |
H21F | 0.7583 | 0.3193 | 0.4881 | 0.049* | |
C212 | 0.40207 (19) | 0.13512 (17) | 0.16153 (13) | 0.0235 (6) | |
C213 | 0.29744 (19) | 0.13683 (18) | 0.18712 (14) | 0.0298 (7) | |
H21G | 0.2733 | 0.2002 | 0.1849 | 0.045* | |
H21H | 0.3107 | 0.1282 | 0.2364 | 0.045* | |
H21I | 0.2418 | 0.0832 | 0.1563 | 0.045* | |
C214 | 0.3769 (2) | 0.13907 (18) | 0.08281 (12) | 0.0313 (7) | |
H21J | 0.3544 | 0.2022 | 0.0773 | 0.047* | |
H21K | 0.3190 | 0.0849 | 0.0558 | 0.047* | |
H21L | 0.4413 | 0.1327 | 0.0647 | 0.047* | |
C215 | 0.4407 (2) | 0.03678 (17) | 0.16800 (14) | 0.0324 (7) | |
H21M | 0.3852 | −0.0180 | 0.1386 | 0.049* | |
H21N | 0.4546 | 0.0311 | 0.2179 | 0.049* | |
H21O | 0.5070 | 0.0345 | 0.1516 | 0.049* | |
C216 | 0.81327 (18) | 0.39133 (17) | 0.16733 (13) | 0.0206 (6) | |
H21P | 0.7934 | 0.3919 | 0.1159 | 0.025* | |
H21Q | 0.7753 | 0.3290 | 0.1735 | 0.025* | |
C217 | 0.93294 (18) | 0.39221 (16) | 0.18959 (12) | 0.0184 (6) | |
C218 | 0.98275 (18) | 0.38766 (16) | 0.26066 (12) | 0.0191 (5) | |
C219 | 1.09358 (19) | 0.38057 (16) | 0.27772 (12) | 0.0204 (6) | |
C220 | 1.14985 (19) | 0.38320 (16) | 0.22483 (13) | 0.0226 (6) | |
H220 | 1.2243 | 0.3796 | 0.2367 | 0.027* | |
C221 | 1.10328 (19) | 0.39089 (16) | 0.15538 (13) | 0.0204 (6) | |
C222 | 0.99400 (18) | 0.39491 (16) | 0.13988 (13) | 0.0208 (6) | |
H222 | 0.9596 | 0.3997 | 0.0931 | 0.025* | |
C223 | 1.14889 (19) | 0.36973 (18) | 0.35306 (13) | 0.0239 (6) | |
C224 | 1.0919 (2) | 0.27716 (18) | 0.37025 (13) | 0.0309 (7) | |
H22A | 1.1264 | 0.2719 | 0.4186 | 0.046* | |
H22B | 1.0969 | 0.2184 | 0.3359 | 0.046* | |
H22C | 1.0161 | 0.2823 | 0.3671 | 0.046* | |
C225 | 1.1460 (2) | 0.46093 (18) | 0.40904 (13) | 0.0332 (7) | |
H22D | 1.1842 | 0.4545 | 0.4563 | 0.050* | |
H22E | 1.0712 | 0.4666 | 0.4091 | 0.050* | |
H22F | 1.1807 | 0.5200 | 0.3976 | 0.050* | |
C226 | 1.2677 (2) | 0.3587 (2) | 0.35992 (14) | 0.0369 (7) | |
H22G | 1.3070 | 0.4176 | 0.3511 | 0.055* | |
H22H | 1.2724 | 0.3006 | 0.3249 | 0.055* | |
H22I | 1.2993 | 0.3507 | 0.4081 | 0.055* | |
C227 | 1.16632 (19) | 0.38907 (18) | 0.09749 (13) | 0.0244 (6) | |
C228 | 1.1392 (2) | 0.4676 (2) | 0.05450 (14) | 0.0376 (7) | |
H22J | 1.1578 | 0.5330 | 0.0866 | 0.056* | |
H22K | 1.0622 | 0.4546 | 0.0315 | 0.056* | |
H22L | 1.1803 | 0.4655 | 0.0180 | 0.056* | |
C229 | 1.1350 (2) | 0.28661 (18) | 0.04725 (14) | 0.0334 (7) | |
H22M | 1.1747 | 0.2838 | 0.0100 | 0.050* | |
H22N | 1.0577 | 0.2743 | 0.0252 | 0.050* | |
H22O | 1.1526 | 0.2363 | 0.0745 | 0.050* | |
C230 | 1.28785 (19) | 0.40901 (18) | 0.12852 (13) | 0.0292 (6) | |
H23A | 1.3085 | 0.4733 | 0.1620 | 0.044* | |
H23B | 1.3245 | 0.4091 | 0.0898 | 0.044* | |
H23C | 1.3085 | 0.3574 | 0.1537 | 0.044* | |
C231 | 0.81672 (19) | 0.57145 (16) | 0.19410 (12) | 0.0212 (6) | |
H23D | 0.7678 | 0.5844 | 0.1519 | 0.025* | |
H23E | 0.8883 | 0.5696 | 0.1840 | 0.025* | |
C232 | 0.8256 (2) | 0.65388 (17) | 0.25868 (13) | 0.0260 (6) | |
H23F | 0.8586 | 0.7169 | 0.2504 | 0.031* | |
H23G | 0.7529 | 0.6609 | 0.2653 | 0.031* | |
C233 | 0.8727 (2) | 0.69441 (19) | 0.38847 (14) | 0.0426 (8) | |
H23H | 0.9161 | 0.6795 | 0.4314 | 0.064* | |
H23I | 0.7964 | 0.6806 | 0.3881 | 0.064* | |
H23J | 0.8926 | 0.7642 | 0.3884 | 0.064* | |
C234 | 1.0084 (2) | 0.65339 (19) | 0.32612 (15) | 0.0352 (7) | |
H23K | 1.0274 | 0.7217 | 0.3223 | 0.053* | |
H23L | 1.0234 | 0.6086 | 0.2861 | 0.053* | |
H23M | 1.0511 | 0.6436 | 0.3711 | 0.053* | |
N101 | 0.20907 (16) | 0.00364 (13) | 0.72052 (10) | 0.0218 (5) | |
N102 | 0.17089 (17) | −0.08316 (14) | 0.83635 (11) | 0.0284 (5) | |
N201 | 0.77509 (15) | 0.47478 (13) | 0.20724 (10) | 0.0187 (5) | |
N202 | 0.89223 (16) | 0.63242 (14) | 0.32436 (11) | 0.0253 (5) | |
O101 | 0.36577 (12) | 0.10567 (11) | 0.86029 (8) | 0.0227 (4) | |
O102 | 0.10972 (13) | 0.14260 (11) | 0.81524 (8) | 0.0224 (4) | |
O201 | 0.70621 (12) | 0.46305 (11) | 0.34334 (8) | 0.0216 (4) | |
O202 | 0.92543 (12) | 0.38776 (11) | 0.31033 (8) | 0.0213 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.02403 (18) | 0.01658 (17) | 0.02199 (18) | 0.00116 (13) | 0.00418 (14) | 0.00286 (13) |
Zn2 | 0.01902 (17) | 0.01911 (17) | 0.02331 (18) | 0.00040 (13) | 0.00428 (14) | 0.00509 (14) |
C101 | 0.0316 (16) | 0.0234 (14) | 0.0220 (15) | 0.0048 (12) | 0.0091 (12) | 0.0020 (12) |
C102 | 0.0234 (14) | 0.0159 (13) | 0.0202 (14) | 0.0009 (10) | 0.0052 (11) | −0.0010 (11) |
C103 | 0.0212 (14) | 0.0181 (13) | 0.0221 (14) | 0.0055 (11) | 0.0072 (11) | 0.0063 (11) |
C104 | 0.0223 (14) | 0.0194 (13) | 0.0205 (14) | 0.0031 (11) | 0.0077 (11) | 0.0026 (11) |
C105 | 0.0228 (14) | 0.0216 (14) | 0.0214 (14) | −0.0011 (11) | 0.0073 (11) | 0.0006 (11) |
C106 | 0.0222 (14) | 0.0230 (14) | 0.0207 (14) | 0.0020 (11) | 0.0088 (11) | 0.0038 (11) |
C107 | 0.0283 (15) | 0.0251 (15) | 0.0180 (14) | 0.0054 (12) | 0.0080 (12) | 0.0031 (12) |
C108 | 0.0242 (15) | 0.0241 (14) | 0.0200 (14) | −0.0011 (11) | 0.0072 (11) | 0.0016 (11) |
C109 | 0.0476 (19) | 0.0385 (17) | 0.0196 (15) | −0.0116 (14) | 0.0086 (14) | −0.0047 (13) |
C110 | 0.0255 (15) | 0.0381 (16) | 0.0216 (15) | 0.0052 (12) | 0.0061 (12) | 0.0030 (12) |
C111 | 0.0354 (16) | 0.0302 (15) | 0.0233 (15) | 0.0106 (12) | 0.0102 (13) | 0.0027 (12) |
C112 | 0.0324 (17) | 0.0293 (16) | 0.0256 (16) | 0.0021 (13) | 0.0163 (13) | 0.0057 (13) |
C113 | 0.036 (2) | 0.036 (2) | 0.047 (2) | 0.0081 (16) | 0.0238 (17) | 0.0160 (17) |
C114 | 0.058 (3) | 0.038 (2) | 0.0239 (18) | −0.0050 (17) | 0.0205 (17) | 0.0051 (16) |
C115 | 0.033 (2) | 0.0315 (18) | 0.0257 (18) | 0.0038 (16) | 0.0101 (16) | 0.0115 (15) |
C313 | 0.036 (2) | 0.036 (2) | 0.047 (2) | 0.0081 (16) | 0.0238 (17) | 0.0160 (17) |
C314 | 0.058 (3) | 0.038 (2) | 0.0239 (18) | −0.0050 (17) | 0.0205 (17) | 0.0051 (16) |
C315 | 0.033 (2) | 0.0315 (18) | 0.0257 (18) | 0.0038 (16) | 0.0101 (16) | 0.0115 (15) |
C116 | 0.0376 (17) | 0.0189 (14) | 0.0199 (15) | 0.0036 (12) | 0.0029 (12) | 0.0025 (11) |
C117 | 0.0277 (15) | 0.0182 (14) | 0.0245 (15) | 0.0002 (11) | 0.0005 (12) | 0.0066 (12) |
C118 | 0.0239 (15) | 0.0126 (13) | 0.0245 (15) | −0.0016 (11) | −0.0020 (12) | 0.0035 (11) |
C119 | 0.0248 (15) | 0.0158 (14) | 0.0320 (16) | −0.0018 (11) | 0.0019 (13) | 0.0073 (12) |
C120 | 0.0234 (15) | 0.0258 (15) | 0.0381 (18) | 0.0021 (12) | −0.0021 (13) | 0.0107 (13) |
C121 | 0.0341 (18) | 0.0194 (15) | 0.0397 (18) | −0.0009 (12) | −0.0121 (14) | 0.0101 (13) |
C122 | 0.0471 (19) | 0.0180 (14) | 0.0219 (15) | 0.0033 (13) | −0.0068 (14) | 0.0016 (12) |
C123 | 0.0230 (15) | 0.0281 (15) | 0.0356 (17) | 0.0009 (12) | 0.0078 (13) | 0.0095 (13) |
C124 | 0.0297 (16) | 0.0254 (15) | 0.0334 (16) | 0.0054 (12) | 0.0111 (13) | 0.0046 (12) |
C125 | 0.0386 (18) | 0.0273 (15) | 0.0356 (17) | −0.0075 (13) | 0.0090 (14) | 0.0065 (13) |
C126 | 0.0276 (17) | 0.061 (2) | 0.053 (2) | 0.0051 (15) | 0.0159 (15) | 0.0110 (17) |
C127 | 0.044 (2) | 0.0327 (18) | 0.044 (2) | 0.0073 (14) | −0.0230 (16) | 0.0030 (15) |
C128 | 0.072 (3) | 0.092 (3) | 0.047 (2) | 0.013 (2) | −0.0203 (19) | 0.022 (2) |
C129 | 0.106 (4) | 0.047 (2) | 0.137 (4) | 0.028 (2) | −0.097 (3) | −0.044 (2) |
C130 | 0.040 (2) | 0.096 (3) | 0.081 (3) | −0.012 (2) | −0.028 (2) | 0.017 (2) |
C131 | 0.0363 (16) | 0.0140 (13) | 0.0268 (15) | −0.0003 (11) | 0.0080 (13) | −0.0011 (11) |
C132 | 0.0294 (16) | 0.0169 (14) | 0.0357 (17) | 0.0005 (12) | 0.0047 (13) | 0.0043 (12) |
C133 | 0.063 (2) | 0.0321 (17) | 0.0344 (18) | 0.0113 (15) | 0.0057 (16) | 0.0128 (14) |
C134 | 0.0449 (19) | 0.0196 (15) | 0.0480 (19) | −0.0029 (13) | 0.0193 (15) | 0.0067 (13) |
C201 | 0.0160 (13) | 0.0223 (14) | 0.0203 (14) | 0.0023 (10) | 0.0040 (11) | 0.0049 (11) |
C202 | 0.0133 (13) | 0.0180 (13) | 0.0216 (14) | 0.0017 (10) | 0.0054 (10) | 0.0052 (11) |
C203 | 0.0162 (13) | 0.0191 (13) | 0.0232 (14) | 0.0041 (10) | 0.0049 (11) | 0.0029 (11) |
C204 | 0.0212 (14) | 0.0189 (13) | 0.0226 (14) | 0.0047 (11) | 0.0074 (11) | 0.0047 (11) |
C205 | 0.0205 (14) | 0.0189 (13) | 0.0269 (15) | 0.0007 (11) | 0.0105 (11) | 0.0086 (11) |
C206 | 0.0177 (14) | 0.0190 (14) | 0.0223 (14) | 0.0008 (11) | 0.0045 (11) | 0.0024 (11) |
C207 | 0.0172 (13) | 0.0214 (14) | 0.0168 (13) | 0.0041 (11) | 0.0057 (11) | 0.0030 (11) |
C208 | 0.0287 (15) | 0.0243 (14) | 0.0193 (14) | 0.0035 (12) | 0.0063 (12) | 0.0040 (11) |
C209 | 0.0546 (19) | 0.0272 (15) | 0.0233 (15) | 0.0024 (14) | 0.0131 (14) | 0.0062 (12) |
C210 | 0.0256 (15) | 0.0306 (15) | 0.0254 (15) | 0.0034 (12) | 0.0097 (12) | 0.0074 (12) |
C211 | 0.0394 (17) | 0.0366 (16) | 0.0222 (15) | 0.0130 (13) | 0.0048 (13) | 0.0051 (13) |
C212 | 0.0216 (14) | 0.0208 (14) | 0.0247 (15) | −0.0018 (11) | 0.0050 (12) | 0.0009 (12) |
C213 | 0.0226 (15) | 0.0290 (15) | 0.0349 (17) | −0.0020 (12) | 0.0069 (13) | 0.0038 (13) |
C214 | 0.0250 (15) | 0.0331 (16) | 0.0276 (16) | −0.0082 (12) | 0.0025 (12) | −0.0007 (13) |
C215 | 0.0275 (16) | 0.0222 (15) | 0.0405 (18) | −0.0020 (12) | 0.0043 (14) | −0.0018 (13) |
C216 | 0.0201 (14) | 0.0173 (13) | 0.0239 (15) | 0.0021 (11) | 0.0043 (11) | 0.0051 (11) |
C217 | 0.0145 (13) | 0.0156 (13) | 0.0242 (14) | 0.0023 (10) | 0.0033 (11) | 0.0040 (11) |
C218 | 0.0186 (13) | 0.0126 (12) | 0.0247 (14) | −0.0019 (10) | 0.0046 (11) | 0.0047 (11) |
C219 | 0.0186 (14) | 0.0162 (13) | 0.0236 (14) | 0.0007 (10) | 0.0008 (11) | 0.0038 (11) |
C220 | 0.0134 (13) | 0.0209 (14) | 0.0315 (16) | 0.0013 (11) | 0.0031 (11) | 0.0043 (12) |
C221 | 0.0181 (14) | 0.0173 (13) | 0.0244 (15) | 0.0024 (10) | 0.0040 (11) | 0.0026 (11) |
C222 | 0.0207 (14) | 0.0183 (13) | 0.0211 (14) | 0.0020 (10) | 0.0019 (11) | 0.0031 (11) |
C223 | 0.0206 (14) | 0.0264 (15) | 0.0224 (15) | 0.0032 (11) | 0.0006 (11) | 0.0053 (12) |
C224 | 0.0271 (15) | 0.0319 (16) | 0.0344 (17) | 0.0054 (12) | 0.0021 (13) | 0.0148 (13) |
C225 | 0.0321 (17) | 0.0360 (17) | 0.0249 (16) | 0.0051 (13) | −0.0041 (13) | 0.0038 (13) |
C226 | 0.0241 (16) | 0.0526 (19) | 0.0328 (17) | 0.0080 (13) | −0.0027 (13) | 0.0164 (15) |
C227 | 0.0198 (14) | 0.0288 (15) | 0.0256 (15) | 0.0065 (11) | 0.0074 (12) | 0.0044 (12) |
C228 | 0.0306 (17) | 0.0501 (19) | 0.0449 (18) | 0.0155 (14) | 0.0183 (14) | 0.0260 (15) |
C229 | 0.0264 (16) | 0.0391 (17) | 0.0303 (16) | 0.0045 (13) | 0.0053 (13) | −0.0009 (13) |
C230 | 0.0255 (15) | 0.0310 (15) | 0.0318 (16) | 0.0046 (12) | 0.0112 (12) | 0.0039 (12) |
C231 | 0.0198 (14) | 0.0170 (13) | 0.0278 (15) | 0.0001 (10) | 0.0067 (11) | 0.0085 (11) |
C232 | 0.0228 (15) | 0.0170 (14) | 0.0383 (17) | 0.0009 (11) | 0.0066 (12) | 0.0088 (12) |
C233 | 0.058 (2) | 0.0310 (17) | 0.0339 (18) | 0.0070 (15) | 0.0071 (16) | 0.0011 (14) |
C234 | 0.0300 (17) | 0.0260 (16) | 0.0448 (19) | −0.0059 (13) | 0.0010 (14) | 0.0122 (14) |
N101 | 0.0259 (12) | 0.0134 (11) | 0.0244 (12) | 0.0010 (9) | 0.0053 (10) | 0.0023 (9) |
N102 | 0.0332 (14) | 0.0221 (12) | 0.0272 (13) | 0.0009 (10) | 0.0025 (11) | 0.0069 (10) |
N201 | 0.0161 (11) | 0.0133 (10) | 0.0259 (12) | 0.0006 (8) | 0.0039 (9) | 0.0050 (9) |
N202 | 0.0265 (13) | 0.0183 (12) | 0.0282 (13) | −0.0003 (9) | 0.0048 (10) | 0.0024 (10) |
O101 | 0.0233 (10) | 0.0241 (9) | 0.0192 (9) | 0.0002 (7) | 0.0032 (8) | 0.0056 (8) |
O102 | 0.0216 (10) | 0.0204 (9) | 0.0214 (10) | 0.0027 (7) | 0.0005 (8) | 0.0009 (8) |
O201 | 0.0201 (9) | 0.0190 (9) | 0.0221 (10) | −0.0033 (7) | 0.0052 (8) | 0.0000 (7) |
O202 | 0.0211 (10) | 0.0227 (9) | 0.0236 (10) | 0.0038 (7) | 0.0072 (8) | 0.0112 (8) |
Zn1—O101 | 1.8918 (15) | C132—H13I | 0.9900 |
Zn1—O102 | 1.8960 (17) | C132—H13J | 0.9900 |
Zn1—N101 | 2.065 (2) | C133—N102 | 1.478 (3) |
Zn1—N102 | 2.0864 (19) | C133—H13K | 0.9800 |
Zn2—O201 | 1.8821 (16) | C133—H13L | 0.9800 |
Zn2—O202 | 1.8899 (17) | C133—H13M | 0.9800 |
Zn2—N201 | 2.0643 (18) | C134—N102 | 1.493 (3) |
Zn2—N202 | 2.0727 (19) | C134—H13N | 0.9800 |
C101—N101 | 1.490 (3) | C134—H13O | 0.9800 |
C101—C102 | 1.516 (3) | C134—H13P | 0.9800 |
C101—H10A | 0.9900 | C201—N201 | 1.495 (3) |
C101—H10B | 0.9900 | C201—C202 | 1.521 (3) |
C102—C107 | 1.394 (3) | C201—H20A | 0.9900 |
C102—C103 | 1.412 (3) | C201—H20B | 0.9900 |
C103—O101 | 1.346 (2) | C202—C207 | 1.397 (3) |
C103—C104 | 1.429 (3) | C202—C203 | 1.412 (3) |
C104—C105 | 1.394 (3) | C203—O201 | 1.348 (3) |
C104—C108 | 1.528 (3) | C203—C204 | 1.420 (3) |
C105—C106 | 1.393 (3) | C204—C205 | 1.392 (3) |
C105—H105 | 0.9500 | C204—C208 | 1.538 (3) |
C106—C107 | 1.383 (3) | C205—C206 | 1.401 (3) |
C106—C112 | 1.541 (3) | C205—H205 | 0.9500 |
C107—H107 | 0.9500 | C206—C207 | 1.386 (3) |
C108—C111 | 1.534 (3) | C206—C212 | 1.535 (3) |
C108—C109 | 1.533 (3) | C207—H207 | 0.9500 |
C108—C110 | 1.545 (3) | C208—C210 | 1.535 (3) |
C109—H10C | 0.9800 | C208—C209 | 1.536 (3) |
C109—H10D | 0.9800 | C208—C211 | 1.543 (3) |
C109—H10E | 0.9800 | C209—H20C | 0.9800 |
C110—H11A | 0.9800 | C209—H20D | 0.9800 |
C110—H11B | 0.9800 | C209—H20E | 0.9800 |
C110—H11C | 0.9800 | C210—H21A | 0.9800 |
C111—H11D | 0.9800 | C210—H21B | 0.9800 |
C111—H11E | 0.9800 | C210—H21C | 0.9800 |
C111—H11F | 0.9800 | C211—H21D | 0.9800 |
C112—C315 | 1.476 (13) | C211—H21E | 0.9800 |
C112—C114 | 1.500 (4) | C211—H21F | 0.9800 |
C112—C115 | 1.542 (4) | C212—C214 | 1.525 (3) |
C112—C113 | 1.558 (4) | C212—C215 | 1.537 (3) |
C112—C313 | 1.573 (14) | C212—C213 | 1.543 (3) |
C112—C314 | 1.638 (14) | C213—H21G | 0.9800 |
C113—H11G | 0.9800 | C213—H21H | 0.9800 |
C113—H11H | 0.9800 | C213—H21I | 0.9800 |
C113—H11I | 0.9800 | C214—H21J | 0.9800 |
C114—H11J | 0.9800 | C214—H21K | 0.9800 |
C114—H11K | 0.9800 | C214—H21L | 0.9800 |
C114—H11L | 0.9800 | C215—H21M | 0.9800 |
C115—H11M | 0.9800 | C215—H21N | 0.9800 |
C115—H11N | 0.9800 | C215—H21O | 0.9800 |
C115—H11O | 0.9800 | C216—N201 | 1.479 (3) |
C313—H33A | 0.9800 | C216—C217 | 1.512 (3) |
C313—H33B | 0.9800 | C216—H21P | 0.9900 |
C313—H33C | 0.9800 | C216—H21Q | 0.9900 |
C314—H34A | 0.9800 | C217—C222 | 1.386 (3) |
C314—H34B | 0.9800 | C217—C218 | 1.424 (3) |
C314—H34C | 0.9800 | C218—O202 | 1.348 (3) |
C315—H35A | 0.9800 | C218—C219 | 1.419 (3) |
C315—H35B | 0.9800 | C219—C220 | 1.396 (3) |
C315—H35C | 0.9800 | C219—C223 | 1.544 (3) |
C116—N101 | 1.484 (3) | C220—C221 | 1.399 (3) |
C116—C117 | 1.506 (4) | C220—H220 | 0.9500 |
C116—H11P | 0.9900 | C221—C222 | 1.390 (3) |
C116—H11Q | 0.9900 | C221—C227 | 1.535 (3) |
C117—C122 | 1.400 (3) | C222—H222 | 0.9500 |
C117—C118 | 1.414 (3) | C223—C225 | 1.533 (3) |
C118—O102 | 1.347 (3) | C223—C226 | 1.542 (3) |
C118—C119 | 1.424 (3) | C223—C224 | 1.543 (3) |
C119—C120 | 1.397 (3) | C224—H22A | 0.9800 |
C119—C123 | 1.535 (4) | C224—H22B | 0.9800 |
C120—C121 | 1.389 (4) | C224—H22C | 0.9800 |
C120—H120 | 0.9500 | C225—H22D | 0.9800 |
C121—C122 | 1.382 (4) | C225—H22E | 0.9800 |
C121—C127 | 1.542 (3) | C225—H22F | 0.9800 |
C122—H122 | 0.9500 | C226—H22G | 0.9800 |
C123—C126 | 1.533 (4) | C226—H22H | 0.9800 |
C123—C125 | 1.543 (3) | C226—H22I | 0.9800 |
C123—C124 | 1.545 (3) | C227—C230 | 1.529 (3) |
C124—H12A | 0.9800 | C227—C228 | 1.536 (3) |
C124—H12B | 0.9800 | C227—C229 | 1.536 (3) |
C124—H12C | 0.9800 | C228—H22J | 0.9800 |
C125—H12D | 0.9800 | C228—H22K | 0.9800 |
C125—H12E | 0.9800 | C228—H22L | 0.9800 |
C125—H12F | 0.9800 | C229—H22M | 0.9800 |
C126—H12G | 0.9800 | C229—H22N | 0.9800 |
C126—H12H | 0.9800 | C229—H22O | 0.9800 |
C126—H12I | 0.9800 | C230—H23A | 0.9800 |
C127—C129 | 1.509 (4) | C230—H23B | 0.9800 |
C127—C128 | 1.513 (4) | C230—H23C | 0.9800 |
C127—C130 | 1.545 (5) | C231—N201 | 1.485 (2) |
C128—H12J | 0.9800 | C231—C232 | 1.522 (3) |
C128—H12K | 0.9800 | C231—H23D | 0.9900 |
C128—H12L | 0.9800 | C231—H23E | 0.9900 |
C129—H12M | 0.9800 | C232—N202 | 1.493 (3) |
C129—H12N | 0.9800 | C232—H23F | 0.9900 |
C129—H12O | 0.9800 | C232—H23G | 0.9900 |
C130—H13D | 0.9800 | C233—N202 | 1.480 (3) |
C130—H13E | 0.9800 | C233—H23H | 0.9800 |
C130—H13F | 0.9800 | C233—H23I | 0.9800 |
C131—N101 | 1.480 (3) | C233—H23J | 0.9800 |
C131—C132 | 1.522 (3) | C234—N202 | 1.487 (3) |
C131—H13G | 0.9900 | C234—H23K | 0.9800 |
C131—H13H | 0.9900 | C234—H23L | 0.9800 |
C132—N102 | 1.493 (3) | C234—H23M | 0.9800 |
O101—Zn1—O102 | 125.35 (7) | N201—C201—H20A | 108.8 |
O101—Zn1—N101 | 99.58 (7) | C202—C201—H20A | 108.8 |
O102—Zn1—N101 | 99.77 (7) | N201—C201—H20B | 108.8 |
O101—Zn1—N102 | 112.76 (7) | C202—C201—H20B | 108.8 |
O102—Zn1—N102 | 118.59 (8) | H20A—C201—H20B | 107.7 |
N101—Zn1—N102 | 87.81 (8) | C207—C202—C203 | 120.41 (19) |
O201—Zn2—O202 | 121.39 (7) | C207—C202—C201 | 119.6 (2) |
O201—Zn2—N201 | 99.95 (7) | C203—C202—C201 | 119.85 (19) |
O202—Zn2—N201 | 99.80 (7) | O201—C203—C202 | 120.64 (19) |
O201—Zn2—N202 | 113.08 (8) | O201—C203—C204 | 120.6 (2) |
O202—Zn2—N202 | 122.20 (8) | C202—C203—C204 | 118.8 (2) |
N201—Zn2—N202 | 88.07 (7) | C205—C204—C203 | 117.9 (2) |
N101—C101—C102 | 113.5 (2) | C205—C204—C208 | 121.4 (2) |
N101—C101—H10A | 108.9 | C203—C204—C208 | 120.7 (2) |
C102—C101—H10A | 108.9 | C204—C205—C206 | 124.3 (2) |
N101—C101—H10B | 108.9 | C204—C205—H205 | 117.9 |
C102—C101—H10B | 108.9 | C206—C205—H205 | 117.9 |
H10A—C101—H10B | 107.7 | C207—C206—C205 | 116.5 (2) |
C107—C102—C103 | 120.4 (2) | C207—C206—C212 | 124.2 (2) |
C107—C102—C101 | 119.5 (2) | C205—C206—C212 | 119.29 (19) |
C103—C102—C101 | 120.0 (2) | C206—C207—C202 | 122.1 (2) |
O101—C103—C102 | 120.5 (2) | C206—C207—H207 | 119.0 |
O101—C103—C104 | 121.1 (2) | C202—C207—H207 | 119.0 |
C102—C103—C104 | 118.4 (2) | C210—C208—C209 | 108.1 (2) |
C105—C104—C103 | 117.6 (2) | C210—C208—C204 | 109.91 (19) |
C105—C104—C108 | 122.2 (2) | C209—C208—C204 | 111.91 (19) |
C103—C104—C108 | 120.25 (19) | C210—C208—C211 | 109.6 (2) |
C106—C105—C104 | 124.9 (2) | C209—C208—C211 | 107.1 (2) |
C106—C105—H105 | 117.6 | C204—C208—C211 | 110.2 (2) |
C104—C105—H105 | 117.6 | C208—C209—H20C | 109.5 |
C107—C106—C105 | 116.0 (2) | C208—C209—H20D | 109.5 |
C107—C106—C112 | 122.8 (2) | H20C—C209—H20D | 109.5 |
C105—C106—C112 | 121.1 (2) | C208—C209—H20E | 109.5 |
C106—C107—C102 | 122.6 (2) | H20C—C209—H20E | 109.5 |
C106—C107—H107 | 118.7 | H20D—C209—H20E | 109.5 |
C102—C107—H107 | 118.7 | C208—C210—H21A | 109.5 |
C104—C108—C111 | 110.94 (19) | C208—C210—H21B | 109.5 |
C104—C108—C109 | 112.04 (19) | H21A—C210—H21B | 109.5 |
C111—C108—C109 | 106.9 (2) | C208—C210—H21C | 109.5 |
C104—C108—C110 | 109.4 (2) | H21A—C210—H21C | 109.5 |
C111—C108—C110 | 109.88 (19) | H21B—C210—H21C | 109.5 |
C109—C108—C110 | 107.6 (2) | C208—C211—H21D | 109.5 |
C108—C109—H10C | 109.5 | C208—C211—H21E | 109.5 |
C108—C109—H10D | 109.5 | H21D—C211—H21E | 109.5 |
H10C—C109—H10D | 109.5 | C208—C211—H21F | 109.5 |
C108—C109—H10E | 109.5 | H21D—C211—H21F | 109.5 |
H10C—C109—H10E | 109.5 | H21E—C211—H21F | 109.5 |
H10D—C109—H10E | 109.5 | C214—C212—C206 | 112.00 (18) |
C108—C110—H11A | 109.5 | C214—C212—C215 | 107.8 (2) |
C108—C110—H11B | 109.5 | C206—C212—C215 | 110.6 (2) |
H11A—C110—H11B | 109.5 | C214—C212—C213 | 108.4 (2) |
C108—C110—H11C | 109.5 | C206—C212—C213 | 109.4 (2) |
H11A—C110—H11C | 109.5 | C215—C212—C213 | 108.62 (19) |
H11B—C110—H11C | 109.5 | C212—C213—H21G | 109.5 |
C108—C111—H11D | 109.5 | C212—C213—H21H | 109.5 |
C108—C111—H11E | 109.5 | H21G—C213—H21H | 109.5 |
H11D—C111—H11E | 109.5 | C212—C213—H21I | 109.5 |
C108—C111—H11F | 109.5 | H21G—C213—H21I | 109.5 |
H11D—C111—H11F | 109.5 | H21H—C213—H21I | 109.5 |
H11E—C111—H11F | 109.5 | C212—C214—H21J | 109.5 |
C114—C112—C115 | 108.0 (2) | C212—C214—H21K | 109.5 |
C315—C112—C106 | 118.9 (7) | H21J—C214—H21K | 109.5 |
C114—C112—C106 | 112.5 (2) | C212—C214—H21L | 109.5 |
C115—C112—C106 | 109.8 (2) | H21J—C214—H21L | 109.5 |
C114—C112—C113 | 109.3 (3) | H21K—C214—H21L | 109.5 |
C115—C112—C113 | 107.4 (2) | C212—C215—H21M | 109.5 |
C106—C112—C113 | 109.7 (2) | C212—C215—H21N | 109.5 |
C315—C112—C313 | 115.3 (10) | H21M—C215—H21N | 109.5 |
C106—C112—C313 | 106.4 (6) | C212—C215—H21O | 109.5 |
C315—C112—C314 | 105.1 (10) | H21M—C215—H21O | 109.5 |
C106—C112—C314 | 109.1 (7) | H21N—C215—H21O | 109.5 |
C313—C112—C314 | 100.3 (11) | N201—C216—C217 | 114.68 (19) |
C112—C113—H11G | 109.5 | N201—C216—H21P | 108.6 |
C112—C113—H11H | 109.5 | C217—C216—H21P | 108.6 |
C112—C113—H11I | 109.5 | N201—C216—H21Q | 108.6 |
C112—C114—H11J | 109.5 | C217—C216—H21Q | 108.6 |
C112—C114—H11K | 109.5 | H21P—C216—H21Q | 107.6 |
C112—C114—H11L | 109.5 | C222—C217—C218 | 119.8 (2) |
C112—C115—H11M | 109.5 | C222—C217—C216 | 119.6 (2) |
C112—C115—H11N | 109.5 | C218—C217—C216 | 120.5 (2) |
C112—C115—H11O | 109.5 | O202—C218—C219 | 120.6 (2) |
C112—C313—H33A | 109.5 | O202—C218—C217 | 120.8 (2) |
C112—C313—H33B | 109.5 | C219—C218—C217 | 118.6 (2) |
H33A—C313—H33B | 109.5 | C220—C219—C218 | 118.3 (2) |
C112—C313—H33C | 109.5 | C220—C219—C223 | 121.6 (2) |
H33A—C313—H33C | 109.5 | C218—C219—C223 | 120.1 (2) |
H33B—C313—H33C | 109.5 | C219—C220—C221 | 124.0 (2) |
C112—C314—H34A | 109.5 | C219—C220—H220 | 118.0 |
C112—C314—H34B | 109.5 | C221—C220—H220 | 118.0 |
H34A—C314—H34B | 109.5 | C222—C221—C220 | 116.2 (2) |
C112—C314—H34C | 109.5 | C222—C221—C227 | 121.0 (2) |
H34A—C314—H34C | 109.5 | C220—C221—C227 | 122.7 (2) |
H34B—C314—H34C | 109.5 | C217—C222—C221 | 123.0 (2) |
C112—C315—H35A | 109.5 | C217—C222—H222 | 118.5 |
C112—C315—H35B | 109.5 | C221—C222—H222 | 118.5 |
H35A—C315—H35B | 109.5 | C225—C223—C226 | 107.4 (2) |
C112—C315—H35C | 109.5 | C225—C223—C224 | 109.4 (2) |
H35A—C315—H35C | 109.5 | C226—C223—C224 | 107.3 (2) |
H35B—C315—H35C | 109.5 | C225—C223—C219 | 110.3 (2) |
N101—C116—C117 | 114.7 (2) | C226—C223—C219 | 112.2 (2) |
N101—C116—H11P | 108.6 | C224—C223—C219 | 110.14 (18) |
C117—C116—H11P | 108.6 | C223—C224—H22A | 109.5 |
N101—C116—H11Q | 108.6 | C223—C224—H22B | 109.5 |
C117—C116—H11Q | 108.6 | H22A—C224—H22B | 109.5 |
H11P—C116—H11Q | 107.6 | C223—C224—H22C | 109.5 |
C122—C117—C118 | 119.5 (3) | H22A—C224—H22C | 109.5 |
C122—C117—C116 | 118.8 (2) | H22B—C224—H22C | 109.5 |
C118—C117—C116 | 121.5 (2) | C223—C225—H22D | 109.5 |
O102—C118—C117 | 120.6 (2) | C223—C225—H22E | 109.5 |
O102—C118—C119 | 120.3 (2) | H22D—C225—H22E | 109.5 |
C117—C118—C119 | 119.1 (2) | C223—C225—H22F | 109.5 |
C120—C119—C118 | 117.8 (2) | H22D—C225—H22F | 109.5 |
C120—C119—C123 | 120.9 (2) | H22E—C225—H22F | 109.5 |
C118—C119—C123 | 121.3 (2) | C223—C226—H22G | 109.5 |
C121—C120—C119 | 124.2 (3) | C223—C226—H22H | 109.5 |
C121—C120—H120 | 117.9 | H22G—C226—H22H | 109.5 |
C119—C120—H120 | 117.9 | C223—C226—H22I | 109.5 |
C122—C121—C120 | 116.7 (2) | H22G—C226—H22I | 109.5 |
C122—C121—C127 | 120.4 (3) | H22H—C226—H22I | 109.5 |
C120—C121—C127 | 122.8 (3) | C230—C227—C228 | 107.4 (2) |
C121—C122—C117 | 122.6 (3) | C230—C227—C229 | 108.7 (2) |
C121—C122—H122 | 118.7 | C228—C227—C229 | 109.3 (2) |
C117—C122—H122 | 118.7 | C230—C227—C221 | 112.47 (19) |
C126—C123—C119 | 113.1 (2) | C228—C227—C221 | 110.7 (2) |
C126—C123—C125 | 107.1 (2) | C229—C227—C221 | 108.19 (19) |
C119—C123—C125 | 109.9 (2) | C227—C228—H22J | 109.5 |
C126—C123—C124 | 106.8 (2) | C227—C228—H22K | 109.5 |
C119—C123—C124 | 109.94 (19) | H22J—C228—H22K | 109.5 |
C125—C123—C124 | 109.9 (2) | C227—C228—H22L | 109.5 |
C123—C124—H12A | 109.5 | H22J—C228—H22L | 109.5 |
C123—C124—H12B | 109.5 | H22K—C228—H22L | 109.5 |
H12A—C124—H12B | 109.5 | C227—C229—H22M | 109.5 |
C123—C124—H12C | 109.5 | C227—C229—H22N | 109.5 |
H12A—C124—H12C | 109.5 | H22M—C229—H22N | 109.5 |
H12B—C124—H12C | 109.5 | C227—C229—H22O | 109.5 |
C123—C125—H12D | 109.5 | H22M—C229—H22O | 109.5 |
C123—C125—H12E | 109.5 | H22N—C229—H22O | 109.5 |
H12D—C125—H12E | 109.5 | C227—C230—H23A | 109.5 |
C123—C125—H12F | 109.5 | C227—C230—H23B | 109.5 |
H12D—C125—H12F | 109.5 | H23A—C230—H23B | 109.5 |
H12E—C125—H12F | 109.5 | C227—C230—H23C | 109.5 |
C123—C126—H12G | 109.5 | H23A—C230—H23C | 109.5 |
C123—C126—H12H | 109.5 | H23B—C230—H23C | 109.5 |
H12G—C126—H12H | 109.5 | N201—C231—C232 | 110.62 (18) |
C123—C126—H12I | 109.5 | N201—C231—H23D | 109.5 |
H12G—C126—H12I | 109.5 | C232—C231—H23D | 109.5 |
H12H—C126—H12I | 109.5 | N201—C231—H23E | 109.5 |
C129—C127—C128 | 111.1 (3) | C232—C231—H23E | 109.5 |
C129—C127—C121 | 110.1 (2) | H23D—C231—H23E | 108.1 |
C128—C127—C121 | 108.6 (2) | N202—C232—C231 | 110.71 (19) |
C129—C127—C130 | 108.0 (3) | N202—C232—H23F | 109.5 |
C128—C127—C130 | 107.1 (3) | C231—C232—H23F | 109.5 |
C121—C127—C130 | 111.9 (3) | N202—C232—H23G | 109.5 |
C127—C128—H12J | 109.5 | C231—C232—H23G | 109.5 |
C127—C128—H12K | 109.5 | H23F—C232—H23G | 108.1 |
H12J—C128—H12K | 109.5 | N202—C233—H23H | 109.5 |
C127—C128—H12L | 109.5 | N202—C233—H23I | 109.5 |
H12J—C128—H12L | 109.5 | H23H—C233—H23I | 109.5 |
H12K—C128—H12L | 109.5 | N202—C233—H23J | 109.5 |
C127—C129—H12M | 109.5 | H23H—C233—H23J | 109.5 |
C127—C129—H12N | 109.5 | H23I—C233—H23J | 109.5 |
H12M—C129—H12N | 109.5 | N202—C234—H23K | 109.5 |
C127—C129—H12O | 109.5 | N202—C234—H23L | 109.5 |
H12M—C129—H12O | 109.5 | H23K—C234—H23L | 109.5 |
H12N—C129—H12O | 109.5 | N202—C234—H23M | 109.5 |
C127—C130—H13D | 109.5 | H23K—C234—H23M | 109.5 |
C127—C130—H13E | 109.5 | H23L—C234—H23M | 109.5 |
H13D—C130—H13E | 109.5 | C131—N101—C116 | 112.97 (18) |
C127—C130—H13F | 109.5 | C131—N101—C101 | 112.12 (19) |
H13D—C130—H13F | 109.5 | C116—N101—C101 | 110.95 (18) |
H13E—C130—H13F | 109.5 | C131—N101—Zn1 | 105.41 (13) |
N101—C131—C132 | 110.62 (19) | C116—N101—Zn1 | 107.63 (15) |
N101—C131—H13G | 109.5 | C101—N101—Zn1 | 107.36 (14) |
C132—C131—H13G | 109.5 | C133—N102—C134 | 108.6 (2) |
N101—C131—H13H | 109.5 | C133—N102—C132 | 110.2 (2) |
C132—C131—H13H | 109.5 | C134—N102—C132 | 110.09 (19) |
H13G—C131—H13H | 108.1 | C133—N102—Zn1 | 112.54 (15) |
N102—C132—C131 | 111.0 (2) | C134—N102—Zn1 | 112.60 (16) |
N102—C132—H13I | 109.4 | C132—N102—Zn1 | 102.73 (14) |
C131—C132—H13I | 109.4 | C216—N201—C231 | 112.96 (18) |
N102—C132—H13J | 109.4 | C216—N201—C201 | 111.35 (17) |
C131—C132—H13J | 109.4 | C231—N201—C201 | 111.65 (17) |
H13I—C132—H13J | 108.0 | C216—N201—Zn2 | 108.05 (14) |
N102—C133—H13K | 109.5 | C231—N201—Zn2 | 105.30 (13) |
N102—C133—H13L | 109.5 | C201—N201—Zn2 | 107.10 (14) |
H13K—C133—H13L | 109.5 | C233—N202—C234 | 108.8 (2) |
N102—C133—H13M | 109.5 | C233—N202—C232 | 109.8 (2) |
H13K—C133—H13M | 109.5 | C234—N202—C232 | 110.57 (19) |
H13L—C133—H13M | 109.5 | C233—N202—Zn2 | 111.58 (15) |
N102—C134—H13N | 109.5 | C234—N202—Zn2 | 113.50 (16) |
N102—C134—H13O | 109.5 | C232—N202—Zn2 | 102.38 (13) |
H13N—C134—H13O | 109.5 | C103—O101—Zn1 | 113.05 (13) |
N102—C134—H13P | 109.5 | C118—O102—Zn1 | 118.15 (15) |
H13N—C134—H13P | 109.5 | C203—O201—Zn2 | 111.79 (14) |
H13O—C134—H13P | 109.5 | C218—O202—Zn2 | 115.18 (13) |
N201—C201—C202 | 113.91 (18) | ||
N101—C101—C102—C107 | −118.9 (2) | C217—C218—C219—C220 | 3.1 (3) |
N101—C101—C102—C103 | 63.9 (3) | O202—C218—C219—C223 | 1.8 (3) |
C107—C102—C103—O101 | 178.1 (2) | C217—C218—C219—C223 | −176.6 (2) |
C101—C102—C103—O101 | −4.8 (3) | C218—C219—C220—C221 | −1.0 (3) |
C107—C102—C103—C104 | −3.2 (3) | C223—C219—C220—C221 | 178.7 (2) |
C101—C102—C103—C104 | 173.9 (2) | C219—C220—C221—C222 | −0.7 (3) |
O101—C103—C104—C105 | −178.2 (2) | C219—C220—C221—C227 | −177.3 (2) |
C102—C103—C104—C105 | 3.1 (3) | C218—C217—C222—C221 | 1.7 (3) |
O101—C103—C104—C108 | 1.9 (3) | C216—C217—C222—C221 | −176.7 (2) |
C102—C103—C104—C108 | −176.8 (2) | C220—C221—C222—C217 | 0.4 (3) |
C103—C104—C105—C106 | −0.7 (4) | C227—C221—C222—C217 | 177.0 (2) |
C108—C104—C105—C106 | 179.3 (2) | C220—C219—C223—C225 | 117.5 (3) |
C104—C105—C106—C107 | −1.7 (4) | C218—C219—C223—C225 | −62.8 (3) |
C104—C105—C106—C112 | 179.5 (2) | C220—C219—C223—C226 | −2.2 (3) |
C105—C106—C107—C102 | 1.6 (4) | C218—C219—C223—C226 | 177.5 (2) |
C112—C106—C107—C102 | −179.6 (2) | C220—C219—C223—C224 | −121.7 (2) |
C103—C102—C107—C106 | 0.8 (4) | C218—C219—C223—C224 | 58.0 (3) |
C101—C102—C107—C106 | −176.3 (2) | C222—C221—C227—C230 | 166.5 (2) |
C105—C104—C108—C111 | 118.6 (2) | C220—C221—C227—C230 | −17.1 (3) |
C103—C104—C108—C111 | −61.5 (3) | C222—C221—C227—C228 | 46.3 (3) |
C105—C104—C108—C109 | −0.8 (3) | C220—C221—C227—C228 | −137.3 (2) |
C103—C104—C108—C109 | 179.1 (2) | C222—C221—C227—C229 | −73.4 (3) |
C105—C104—C108—C110 | −120.0 (2) | C220—C221—C227—C229 | 103.0 (2) |
C103—C104—C108—C110 | 59.9 (3) | N201—C231—C232—N202 | 54.9 (2) |
C107—C106—C112—C315 | 172.9 (9) | C132—C131—N101—C116 | −152.8 (2) |
C105—C106—C112—C315 | −8.4 (10) | C132—C131—N101—C101 | 80.9 (3) |
C107—C106—C112—C114 | 9.4 (4) | C132—C131—N101—Zn1 | −35.6 (2) |
C105—C106—C112—C114 | −171.9 (3) | C117—C116—N101—C131 | 62.4 (3) |
C107—C106—C112—C115 | 129.7 (3) | C117—C116—N101—C101 | −170.7 (2) |
C105—C106—C112—C115 | −51.5 (3) | C117—C116—N101—Zn1 | −53.5 (2) |
C107—C106—C112—C113 | −112.5 (3) | C102—C101—N101—C131 | −165.37 (18) |
C105—C106—C112—C113 | 66.2 (3) | C102—C101—N101—C116 | 67.3 (2) |
C107—C106—C112—C313 | −55.0 (8) | C102—C101—N101—Zn1 | −50.1 (2) |
C105—C106—C112—C313 | 123.8 (8) | O101—Zn1—N101—C131 | 122.62 (14) |
C107—C106—C112—C314 | 52.4 (9) | O102—Zn1—N101—C131 | −108.74 (15) |
C105—C106—C112—C314 | −128.8 (9) | N102—Zn1—N101—C131 | 9.91 (15) |
N101—C116—C117—C122 | −122.9 (2) | O101—Zn1—N101—C116 | −116.56 (14) |
N101—C116—C117—C118 | 60.5 (3) | O102—Zn1—N101—C116 | 12.08 (15) |
C122—C117—C118—O102 | 179.09 (19) | N102—Zn1—N101—C116 | 130.73 (15) |
C116—C117—C118—O102 | −4.4 (3) | O101—Zn1—N101—C101 | 2.93 (15) |
C122—C117—C118—C119 | −3.0 (3) | O102—Zn1—N101—C101 | 131.57 (14) |
C116—C117—C118—C119 | 173.5 (2) | N102—Zn1—N101—C101 | −109.78 (15) |
O102—C118—C119—C120 | −178.99 (19) | C131—C132—N102—C133 | −161.6 (2) |
C117—C118—C119—C120 | 3.1 (3) | C131—C132—N102—C134 | 78.6 (2) |
O102—C118—C119—C123 | 1.7 (3) | C131—C132—N102—Zn1 | −41.5 (2) |
C117—C118—C119—C123 | −176.2 (2) | O101—Zn1—N102—C133 | 36.1 (2) |
C118—C119—C120—C121 | −1.0 (3) | O102—Zn1—N102—C133 | −124.49 (19) |
C123—C119—C120—C121 | 178.3 (2) | N101—Zn1—N102—C133 | 135.6 (2) |
C119—C120—C121—C122 | −1.2 (4) | O101—Zn1—N102—C134 | 159.25 (15) |
C119—C120—C121—C127 | −179.4 (2) | O102—Zn1—N102—C134 | −1.34 (19) |
C120—C121—C122—C117 | 1.4 (4) | N101—Zn1—N102—C134 | −101.28 (17) |
C127—C121—C122—C117 | 179.6 (2) | O101—Zn1—N102—C132 | −82.36 (15) |
C118—C117—C122—C121 | 0.7 (3) | O102—Zn1—N102—C132 | 117.05 (15) |
C116—C117—C122—C121 | −175.9 (2) | N101—Zn1—N102—C132 | 17.11 (15) |
C120—C119—C123—C126 | −1.2 (3) | C217—C216—N201—C231 | 65.6 (2) |
C118—C119—C123—C126 | 178.1 (2) | C217—C216—N201—C201 | −167.82 (18) |
C120—C119—C123—C125 | 118.4 (2) | C217—C216—N201—Zn2 | −50.5 (2) |
C118—C119—C123—C125 | −62.3 (3) | C232—C231—N201—C216 | −151.28 (19) |
C120—C119—C123—C124 | −120.5 (2) | C232—C231—N201—C201 | 82.3 (2) |
C118—C119—C123—C124 | 58.8 (3) | C232—C231—N201—Zn2 | −33.6 (2) |
C122—C121—C127—C129 | 50.7 (4) | C202—C201—N201—C216 | 69.0 (2) |
C120—C121—C127—C129 | −131.2 (3) | C202—C201—N201—C231 | −163.70 (19) |
C122—C121—C127—C128 | −71.2 (3) | C202—C201—N201—Zn2 | −48.9 (2) |
C120—C121—C127—C128 | 106.9 (3) | O201—Zn2—N201—C216 | −118.55 (13) |
C122—C121—C127—C130 | 170.8 (3) | O202—Zn2—N201—C216 | 5.99 (14) |
C120—C121—C127—C130 | −11.1 (4) | N202—Zn2—N201—C216 | 128.35 (14) |
N101—C131—C132—N102 | 54.8 (3) | O201—Zn2—N201—C231 | 120.49 (14) |
N201—C201—C202—C207 | −122.2 (2) | O202—Zn2—N201—C231 | −114.98 (14) |
N201—C201—C202—C203 | 62.0 (3) | N202—Zn2—N201—C231 | 7.39 (15) |
C207—C202—C203—O201 | −177.6 (2) | O201—Zn2—N201—C201 | 1.52 (15) |
C201—C202—C203—O201 | −1.8 (3) | O202—Zn2—N201—C201 | 126.05 (14) |
C207—C202—C203—C204 | 1.2 (3) | N202—Zn2—N201—C201 | −111.59 (15) |
C201—C202—C203—C204 | 177.0 (2) | C231—C232—N202—C233 | −162.33 (19) |
O201—C203—C204—C205 | 177.5 (2) | C231—C232—N202—C234 | 77.5 (2) |
C202—C203—C204—C205 | −1.3 (3) | C231—C232—N202—Zn2 | −43.7 (2) |
O201—C203—C204—C208 | −1.9 (3) | O201—Zn2—N202—C233 | 37.09 (18) |
C202—C203—C204—C208 | 179.3 (2) | O202—Zn2—N202—C233 | −122.54 (17) |
C203—C204—C205—C206 | −0.1 (4) | N201—Zn2—N202—C233 | 137.09 (17) |
C208—C204—C205—C206 | 179.4 (2) | O201—Zn2—N202—C234 | 160.49 (15) |
C204—C205—C206—C207 | 1.5 (4) | O202—Zn2—N202—C234 | 0.86 (19) |
C204—C205—C206—C212 | −177.3 (2) | N201—Zn2—N202—C234 | −99.52 (17) |
C205—C206—C207—C202 | −1.6 (4) | O201—Zn2—N202—C232 | −80.33 (16) |
C212—C206—C207—C202 | 177.2 (2) | O202—Zn2—N202—C232 | 120.04 (15) |
C203—C202—C207—C206 | 0.3 (4) | N201—Zn2—N202—C232 | 19.67 (15) |
C201—C202—C207—C206 | −175.5 (2) | C102—C103—O101—Zn1 | −49.8 (3) |
C205—C204—C208—C210 | −118.9 (2) | C104—C103—O101—Zn1 | 131.49 (19) |
C203—C204—C208—C210 | 60.6 (3) | O102—Zn1—O101—C103 | −63.10 (18) |
C205—C204—C208—C209 | 1.3 (3) | N101—Zn1—O101—C103 | 46.21 (16) |
C203—C204—C208—C209 | −179.3 (2) | N102—Zn1—O101—C103 | 137.86 (16) |
C205—C204—C208—C211 | 120.3 (2) | C117—C118—O102—Zn1 | −42.2 (2) |
C203—C204—C208—C211 | −60.3 (3) | C119—C118—O102—Zn1 | 139.94 (18) |
C207—C206—C212—C214 | −0.4 (3) | O101—Zn1—O102—C118 | 143.80 (15) |
C205—C206—C212—C214 | 178.4 (2) | N101—Zn1—O102—C118 | 34.58 (16) |
C207—C206—C212—C215 | 119.8 (3) | N102—Zn1—O102—C118 | −58.27 (17) |
C205—C206—C212—C215 | −61.4 (3) | C202—C203—O201—Zn2 | −52.7 (3) |
C207—C206—C212—C213 | −120.6 (3) | C204—C203—O201—Zn2 | 128.5 (2) |
C205—C206—C212—C213 | 58.1 (3) | O202—Zn2—O201—C203 | −59.93 (16) |
N201—C216—C217—C222 | −120.8 (2) | N201—Zn2—O201—C203 | 48.10 (15) |
N201—C216—C217—C218 | 60.9 (3) | N202—Zn2—O201—C203 | 140.25 (14) |
C222—C217—C218—O202 | 178.1 (2) | C219—C218—O202—Zn2 | 134.45 (18) |
C216—C217—C218—O202 | −3.5 (3) | C217—C218—O202—Zn2 | −47.1 (2) |
C222—C217—C218—C219 | −3.4 (3) | O201—Zn2—O202—C218 | 149.80 (14) |
C216—C217—C218—C219 | 174.9 (2) | N201—Zn2—O202—C218 | 41.69 (15) |
O202—C218—C219—C220 | −178.5 (2) | N202—Zn2—O202—C218 | −52.23 (17) |
[Zn(C28H42N2O2)(C4H8O)] | F(000) = 1240 |
Mr = 576.11 | Dx = 1.235 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 33137 reflections |
a = 13.669 (3) Å | θ = 3.5–27.8° |
b = 17.476 (4) Å | µ = 0.83 mm−1 |
c = 12.989 (4) Å | T = 140 K |
β = 93.14 (2)° | Block, light yellow |
V = 3098.1 (14) Å3 | 0.06 × 0.06 × 0.02 mm |
Z = 4 |
Oxford Xcalibur3 CCD area-detector diffractometer | 7121 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 2308 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.195 |
Detector resolution: 16.0050 pixels mm-1 | θmax = 27.8°, θmin = 3.5° |
Thin slice ϕ and ω scans | h = −17→17 |
Absorption correction: multi-scan (ABSPACK; Oxford Diffraction, 2003) | k = −22→22 |
Tmin = 0.801, Tmax = 0.984 | l = −17→17 |
33137 measured reflections |
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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.073 | H-atom parameters constrained |
S = 0.68 | w = 1/[σ2(Fo2) + (0.0123P)2] where P = (Fo2 + 2Fc2)/3 |
7121 reflections | (Δ/σ)max = 0.001 |
353 parameters | Δρmax = 0.37 e Å−3 |
0 restraints | Δρmin = −0.49 e Å−3 |
[Zn(C28H42N2O2)(C4H8O)] | V = 3098.1 (14) Å3 |
Mr = 576.11 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.669 (3) Å | µ = 0.83 mm−1 |
b = 17.476 (4) Å | T = 140 K |
c = 12.989 (4) Å | 0.06 × 0.06 × 0.02 mm |
β = 93.14 (2)° |
Oxford Xcalibur3 CCD area-detector diffractometer | 7121 independent reflections |
Absorption correction: multi-scan (ABSPACK; Oxford Diffraction, 2003) | 2308 reflections with I > 2σ(I) |
Tmin = 0.801, Tmax = 0.984 | Rint = 0.195 |
33137 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.073 | H-atom parameters constrained |
S = 0.68 | Δρmax = 0.37 e Å−3 |
7121 reflections | Δρmin = −0.49 e Å−3 |
353 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. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Zn1 | 0.22744 (3) | 0.61170 (3) | 0.54949 (4) | 0.02396 (13) | |
C101 | 0.1033 (2) | 0.4792 (2) | 0.6099 (3) | 0.0253 (11) | |
H10A | 0.0811 | 0.4750 | 0.5363 | 0.030* | |
H10B | 0.0946 | 0.4284 | 0.6420 | 0.030* | |
C102 | 0.0392 (3) | 0.5365 (2) | 0.6613 (3) | 0.0214 (10) | |
C103 | 0.0319 (2) | 0.6109 (3) | 0.6210 (3) | 0.0207 (9) | |
C104 | −0.0403 (3) | 0.6613 (2) | 0.6631 (3) | 0.0223 (10) | |
C105 | −0.0899 (2) | 0.6363 (2) | 0.7476 (3) | 0.0265 (11) | |
H105 | −0.1354 | 0.6701 | 0.7764 | 0.032* | |
C106 | −0.0765 (3) | 0.5643 (2) | 0.7922 (3) | 0.0256 (11) | |
C107 | −0.0114 (3) | 0.5146 (2) | 0.7466 (3) | 0.0295 (11) | |
H107 | −0.0016 | 0.4647 | 0.7744 | 0.035* | |
C108 | −0.0585 (3) | 0.7421 (2) | 0.6183 (3) | 0.0247 (11) | |
C109 | −0.1424 (3) | 0.7858 (2) | 0.6676 (3) | 0.0430 (13) | |
H10C | −0.2035 | 0.7567 | 0.6573 | 0.064* | |
H10D | −0.1504 | 0.8362 | 0.6352 | 0.064* | |
H10E | −0.1266 | 0.7921 | 0.7416 | 0.064* | |
C110 | −0.0869 (2) | 0.7375 (2) | 0.5015 (3) | 0.0332 (12) | |
H11A | −0.0364 | 0.7091 | 0.4667 | 0.050* | |
H11B | −0.0923 | 0.7893 | 0.4729 | 0.050* | |
H11C | −0.1499 | 0.7111 | 0.4909 | 0.050* | |
C111 | 0.0355 (3) | 0.7915 (2) | 0.6355 (3) | 0.0358 (12) | |
H11D | 0.0488 | 0.8001 | 0.7095 | 0.054* | |
H11E | 0.0259 | 0.8408 | 0.6004 | 0.054* | |
H11F | 0.0912 | 0.7648 | 0.6073 | 0.054* | |
C112 | −0.1278 (3) | 0.5405 (2) | 0.8888 (3) | 0.0404 (13) | |
H11G | −0.0856 | 0.5524 | 0.9502 | 0.061* | |
H11H | −0.1410 | 0.4854 | 0.8864 | 0.061* | |
H11I | −0.1897 | 0.5685 | 0.8919 | 0.061* | |
C116 | 0.2477 (2) | 0.5003 (2) | 0.7264 (3) | 0.0238 (10) | |
H11J | 0.2407 | 0.4482 | 0.7551 | 0.029* | |
H11K | 0.2055 | 0.5350 | 0.7649 | 0.029* | |
C117 | 0.3533 (3) | 0.5255 (2) | 0.7448 (3) | 0.0203 (10) | |
C118 | 0.3853 (2) | 0.5982 (2) | 0.7136 (3) | 0.0239 (11) | |
C119 | 0.4821 (2) | 0.6238 (2) | 0.7508 (3) | 0.0223 (10) | |
C120 | 0.5386 (3) | 0.5738 (2) | 0.8123 (3) | 0.0251 (11) | |
H120 | 0.6016 | 0.5908 | 0.8370 | 0.030* | |
C121 | 0.5098 (3) | 0.5005 (2) | 0.8406 (3) | 0.0240 (10) | |
C122 | 0.4153 (3) | 0.4777 (2) | 0.8068 (3) | 0.0261 (11) | |
H122 | 0.3923 | 0.4288 | 0.8262 | 0.031* | |
C123 | 0.5177 (3) | 0.7050 (2) | 0.7271 (3) | 0.0252 (11) | |
C124 | 0.4451 (2) | 0.7647 (2) | 0.7650 (3) | 0.0316 (12) | |
H12A | 0.3808 | 0.7570 | 0.7294 | 0.047* | |
H12B | 0.4689 | 0.8162 | 0.7503 | 0.047* | |
H12C | 0.4393 | 0.7589 | 0.8395 | 0.047* | |
C125 | 0.5299 (2) | 0.7143 (2) | 0.6099 (3) | 0.0310 (12) | |
H12D | 0.5813 | 0.6796 | 0.5883 | 0.047* | |
H12E | 0.5482 | 0.7672 | 0.5951 | 0.047* | |
H12F | 0.4680 | 0.7019 | 0.5720 | 0.047* | |
C126 | 0.6184 (2) | 0.7233 (2) | 0.7830 (3) | 0.0375 (13) | |
H12G | 0.6130 | 0.7190 | 0.8577 | 0.056* | |
H12H | 0.6382 | 0.7755 | 0.7658 | 0.056* | |
H12I | 0.6676 | 0.6870 | 0.7607 | 0.056* | |
C127 | 0.5753 (2) | 0.4501 (2) | 0.9102 (3) | 0.0338 (12) | |
H12J | 0.6120 | 0.4150 | 0.8679 | 0.051* | |
H12K | 0.5349 | 0.4206 | 0.9560 | 0.051* | |
H12L | 0.6212 | 0.4822 | 0.9515 | 0.051* | |
C131 | 0.2679 (2) | 0.4449 (2) | 0.5555 (3) | 0.0280 (11) | |
H13I | 0.2420 | 0.3926 | 0.5642 | 0.034* | |
H13J | 0.3376 | 0.4452 | 0.5807 | 0.034* | |
C132 | 0.2601 (3) | 0.4663 (2) | 0.4442 (3) | 0.0281 (11) | |
H13K | 0.3028 | 0.4322 | 0.4057 | 0.034* | |
H13L | 0.1918 | 0.4583 | 0.4170 | 0.034* | |
C133 | 0.2600 (2) | 0.5684 (2) | 0.3200 (3) | 0.0364 (12) | |
H13P | 0.2875 | 0.5316 | 0.2725 | 0.055* | |
H13Q | 0.2850 | 0.6197 | 0.3060 | 0.055* | |
H13R | 0.1884 | 0.5683 | 0.3102 | 0.055* | |
C134 | 0.3991 (2) | 0.5550 (2) | 0.4403 (3) | 0.0352 (12) | |
H13M | 0.4304 | 0.5226 | 0.3900 | 0.053* | |
H13N | 0.4208 | 0.5391 | 0.5102 | 0.053* | |
H13O | 0.4175 | 0.6085 | 0.4298 | 0.053* | |
C135 | 0.1758 (3) | 0.7394 (2) | 0.3759 (3) | 0.0362 (12) | |
H13A | 0.1162 | 0.7076 | 0.3796 | 0.043* | |
H13B | 0.2045 | 0.7303 | 0.3086 | 0.043* | |
C136 | 0.1512 (3) | 0.8229 (2) | 0.3880 (3) | 0.0380 (13) | |
H13C | 0.0942 | 0.8295 | 0.4311 | 0.046* | |
H13D | 0.1365 | 0.8473 | 0.3201 | 0.046* | |
C137 | 0.2433 (2) | 0.8563 (2) | 0.4406 (3) | 0.0340 (12) | |
H13E | 0.2908 | 0.8717 | 0.3896 | 0.041* | |
H13F | 0.2280 | 0.9010 | 0.4836 | 0.041* | |
C138 | 0.2821 (3) | 0.7908 (2) | 0.5060 (3) | 0.0315 (12) | |
H13G | 0.3546 | 0.7913 | 0.5098 | 0.038* | |
H13H | 0.2596 | 0.7957 | 0.5769 | 0.038* | |
N101 | 0.21178 (19) | 0.49954 (17) | 0.6170 (2) | 0.0202 (8) | |
N102 | 0.2883 (2) | 0.54682 (17) | 0.4261 (2) | 0.0231 (9) | |
O101 | 0.08671 (15) | 0.63419 (13) | 0.54433 (19) | 0.0262 (7) | |
O102 | 0.32714 (16) | 0.64392 (13) | 0.65463 (19) | 0.0268 (7) | |
O103 | 0.24679 (16) | 0.72042 (15) | 0.4607 (2) | 0.0295 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0181 (2) | 0.0245 (3) | 0.0287 (3) | −0.0006 (3) | −0.00329 (19) | −0.0010 (3) |
C101 | 0.022 (2) | 0.018 (3) | 0.036 (3) | −0.005 (2) | −0.007 (2) | 0.002 (2) |
C102 | 0.018 (2) | 0.019 (3) | 0.027 (3) | −0.003 (2) | −0.003 (2) | −0.005 (2) |
C103 | 0.020 (2) | 0.020 (2) | 0.022 (3) | −0.004 (2) | −0.0040 (18) | −0.003 (3) |
C104 | 0.018 (2) | 0.023 (3) | 0.026 (3) | 0.001 (2) | −0.003 (2) | −0.001 (2) |
C105 | 0.019 (2) | 0.031 (3) | 0.030 (3) | 0.000 (2) | 0.002 (2) | −0.006 (2) |
C106 | 0.023 (2) | 0.026 (3) | 0.027 (3) | −0.011 (2) | −0.002 (2) | 0.003 (2) |
C107 | 0.024 (2) | 0.026 (3) | 0.039 (3) | −0.005 (2) | −0.001 (2) | 0.006 (2) |
C108 | 0.018 (2) | 0.027 (3) | 0.029 (3) | 0.006 (2) | 0.008 (2) | 0.002 (2) |
C109 | 0.042 (3) | 0.033 (3) | 0.055 (4) | 0.009 (2) | 0.010 (2) | 0.004 (3) |
C110 | 0.026 (2) | 0.030 (3) | 0.043 (3) | −0.005 (2) | −0.007 (2) | 0.002 (2) |
C111 | 0.035 (3) | 0.029 (3) | 0.042 (3) | −0.002 (2) | −0.006 (2) | −0.006 (2) |
C112 | 0.030 (3) | 0.052 (3) | 0.038 (3) | −0.006 (2) | −0.001 (2) | 0.001 (3) |
C116 | 0.021 (2) | 0.020 (3) | 0.030 (3) | −0.0033 (19) | −0.002 (2) | 0.000 (2) |
C117 | 0.014 (2) | 0.024 (3) | 0.022 (3) | 0.000 (2) | −0.0004 (19) | 0.000 (2) |
C118 | 0.020 (2) | 0.028 (3) | 0.023 (3) | 0.004 (2) | −0.0033 (19) | 0.001 (2) |
C119 | 0.019 (2) | 0.028 (3) | 0.020 (2) | 0.004 (2) | 0.0011 (18) | 0.003 (2) |
C120 | 0.019 (2) | 0.026 (3) | 0.029 (3) | 0.002 (2) | −0.006 (2) | −0.004 (2) |
C121 | 0.021 (2) | 0.030 (3) | 0.021 (3) | 0.005 (2) | −0.001 (2) | 0.003 (2) |
C122 | 0.029 (3) | 0.020 (3) | 0.030 (3) | −0.005 (2) | 0.004 (2) | 0.003 (2) |
C123 | 0.019 (2) | 0.028 (3) | 0.028 (3) | −0.002 (2) | −0.006 (2) | 0.001 (2) |
C124 | 0.029 (2) | 0.030 (3) | 0.035 (3) | −0.006 (2) | −0.006 (2) | −0.006 (2) |
C125 | 0.021 (2) | 0.030 (3) | 0.042 (3) | 0.001 (2) | 0.003 (2) | 0.001 (2) |
C126 | 0.016 (2) | 0.047 (3) | 0.049 (3) | −0.008 (2) | −0.007 (2) | 0.010 (3) |
C127 | 0.026 (2) | 0.032 (3) | 0.042 (3) | 0.006 (2) | −0.005 (2) | 0.006 (2) |
C131 | 0.017 (2) | 0.023 (3) | 0.044 (3) | −0.004 (2) | −0.005 (2) | −0.004 (2) |
C132 | 0.023 (2) | 0.031 (3) | 0.030 (3) | 0.005 (2) | −0.003 (2) | 0.002 (3) |
C133 | 0.030 (2) | 0.035 (3) | 0.044 (3) | −0.009 (2) | 0.000 (2) | −0.006 (2) |
C134 | 0.025 (2) | 0.039 (3) | 0.042 (3) | 0.005 (2) | 0.000 (2) | −0.008 (2) |
C135 | 0.033 (3) | 0.048 (3) | 0.027 (3) | −0.004 (2) | −0.009 (2) | 0.003 (3) |
C136 | 0.031 (3) | 0.041 (3) | 0.041 (3) | −0.001 (2) | −0.008 (2) | 0.013 (3) |
C137 | 0.030 (3) | 0.029 (3) | 0.043 (3) | −0.004 (2) | −0.007 (2) | 0.004 (2) |
C138 | 0.028 (3) | 0.032 (3) | 0.034 (3) | 0.002 (2) | −0.004 (2) | 0.003 (3) |
N101 | 0.0116 (17) | 0.025 (2) | 0.024 (2) | −0.0014 (16) | −0.0028 (15) | −0.0080 (18) |
N102 | 0.024 (2) | 0.017 (2) | 0.027 (3) | −0.0112 (16) | −0.0055 (17) | −0.0003 (17) |
O101 | 0.0175 (14) | 0.035 (2) | 0.0258 (18) | 0.0036 (13) | 0.0026 (12) | 0.0045 (14) |
O102 | 0.0221 (15) | 0.0262 (18) | 0.0309 (19) | −0.0008 (13) | −0.0102 (13) | 0.0015 (14) |
O103 | 0.0271 (17) | 0.0294 (19) | 0.030 (2) | −0.0073 (14) | −0.0117 (14) | 0.0005 (17) |
Zn1—O102 | 1.958 (2) | C121—C122 | 1.399 (4) |
Zn1—O101 | 1.961 (2) | C121—C127 | 1.518 (4) |
Zn1—N101 | 2.163 (3) | C122—H122 | 0.9500 |
Zn1—N102 | 2.166 (3) | C123—C124 | 1.540 (5) |
Zn1—O103 | 2.246 (3) | C123—C125 | 1.550 (5) |
C101—C102 | 1.510 (5) | C123—C126 | 1.554 (4) |
C101—N101 | 1.523 (4) | C124—H12A | 0.9800 |
C101—H10A | 0.9900 | C124—H12B | 0.9800 |
C101—H10B | 0.9900 | C124—H12C | 0.9800 |
C102—C107 | 1.392 (5) | C125—H12D | 0.9800 |
C102—C103 | 1.404 (5) | C125—H12E | 0.9800 |
C103—O101 | 1.342 (4) | C125—H12F | 0.9800 |
C103—C104 | 1.451 (5) | C126—H12G | 0.9800 |
C104—C105 | 1.393 (5) | C126—H12H | 0.9800 |
C104—C108 | 1.542 (5) | C126—H12I | 0.9800 |
C105—C106 | 1.393 (5) | C127—H12J | 0.9800 |
C105—H105 | 0.9500 | C127—H12K | 0.9800 |
C106—C107 | 1.398 (5) | C127—H12L | 0.9800 |
C106—C112 | 1.529 (5) | C131—N101 | 1.484 (4) |
C107—H107 | 0.9500 | C131—C132 | 1.492 (5) |
C108—C109 | 1.546 (4) | C131—H13I | 0.9900 |
C108—C110 | 1.547 (5) | C131—H13J | 0.9900 |
C108—C111 | 1.555 (4) | C132—N102 | 1.481 (4) |
C109—H10C | 0.9800 | C132—H13K | 0.9900 |
C109—H10D | 0.9800 | C132—H13L | 0.9900 |
C109—H10E | 0.9800 | C133—N102 | 1.461 (4) |
C110—H11A | 0.9800 | C133—H13P | 0.9800 |
C110—H11B | 0.9800 | C133—H13Q | 0.9800 |
C110—H11C | 0.9800 | C133—H13R | 0.9800 |
C111—H11D | 0.9800 | C134—N102 | 1.522 (4) |
C111—H11E | 0.9800 | C134—H13M | 0.9800 |
C111—H11F | 0.9800 | C134—H13N | 0.9800 |
C112—H11G | 0.9800 | C134—H13O | 0.9800 |
C112—H11H | 0.9800 | C135—O103 | 1.466 (4) |
C112—H11I | 0.9800 | C135—C136 | 1.508 (5) |
C116—N101 | 1.478 (4) | C135—H13A | 0.9900 |
C116—C117 | 1.515 (4) | C135—H13B | 0.9900 |
C116—H11J | 0.9900 | C136—C137 | 1.516 (4) |
C116—H11K | 0.9900 | C136—H13C | 0.9900 |
C117—C118 | 1.411 (5) | C136—H13D | 0.9900 |
C117—C122 | 1.411 (5) | C137—C138 | 1.504 (4) |
C118—O102 | 1.337 (4) | C137—H13E | 0.9900 |
C118—C119 | 1.454 (4) | C137—H13F | 0.9900 |
C119—C120 | 1.389 (5) | C138—O103 | 1.436 (4) |
C119—C123 | 1.538 (5) | C138—H13G | 0.9900 |
C120—C121 | 1.395 (5) | C138—H13H | 0.9900 |
C120—H120 | 0.9500 | ||
O102—Zn1—O101 | 127.59 (10) | C124—C123—C126 | 106.4 (3) |
O102—Zn1—N101 | 93.35 (11) | C125—C123—C126 | 107.3 (3) |
O101—Zn1—N101 | 94.41 (10) | C123—C124—H12A | 109.5 |
O102—Zn1—N102 | 112.67 (11) | C123—C124—H12B | 109.5 |
O101—Zn1—N102 | 119.71 (11) | H12A—C124—H12B | 109.5 |
N101—Zn1—N102 | 82.88 (12) | C123—C124—H12C | 109.5 |
O102—Zn1—O103 | 91.02 (10) | H12A—C124—H12C | 109.5 |
O101—Zn1—O103 | 87.46 (9) | H12B—C124—H12C | 109.5 |
N101—Zn1—O103 | 172.77 (11) | C123—C125—H12D | 109.5 |
N102—Zn1—O103 | 90.13 (11) | C123—C125—H12E | 109.5 |
C102—C101—N101 | 113.9 (3) | H12D—C125—H12E | 109.5 |
C102—C101—H10A | 108.8 | C123—C125—H12F | 109.5 |
N101—C101—H10A | 108.8 | H12D—C125—H12F | 109.5 |
C102—C101—H10B | 108.8 | H12E—C125—H12F | 109.5 |
N101—C101—H10B | 108.8 | C123—C126—H12G | 109.5 |
H10A—C101—H10B | 107.7 | C123—C126—H12H | 109.5 |
C107—C102—C103 | 121.6 (4) | H12G—C126—H12H | 109.5 |
C107—C102—C101 | 119.7 (4) | C123—C126—H12I | 109.5 |
C103—C102—C101 | 118.7 (4) | H12G—C126—H12I | 109.5 |
O101—C103—C102 | 121.7 (4) | H12H—C126—H12I | 109.5 |
O101—C103—C104 | 121.0 (4) | C121—C127—H12J | 109.5 |
C102—C103—C104 | 117.3 (4) | C121—C127—H12K | 109.5 |
C105—C104—C103 | 118.5 (4) | H12J—C127—H12K | 109.5 |
C105—C104—C108 | 120.6 (4) | C121—C127—H12L | 109.5 |
C103—C104—C108 | 120.9 (4) | H12J—C127—H12L | 109.5 |
C104—C105—C106 | 123.6 (4) | H12K—C127—H12L | 109.5 |
C104—C105—H105 | 118.2 | N101—C131—C132 | 110.4 (3) |
C106—C105—H105 | 118.2 | N101—C131—H13I | 109.6 |
C105—C106—C107 | 117.2 (4) | C132—C131—H13I | 109.6 |
C105—C106—C112 | 122.1 (4) | N101—C131—H13J | 109.6 |
C107—C106—C112 | 120.7 (4) | C132—C131—H13J | 109.6 |
C102—C107—C106 | 121.5 (4) | H13I—C131—H13J | 108.1 |
C102—C107—H107 | 119.3 | N102—C132—C131 | 112.7 (3) |
C106—C107—H107 | 119.3 | N102—C132—H13K | 109.0 |
C104—C108—C109 | 113.8 (3) | C131—C132—H13K | 109.0 |
C104—C108—C110 | 110.4 (3) | N102—C132—H13L | 109.0 |
C109—C108—C110 | 106.3 (3) | C131—C132—H13L | 109.0 |
C104—C108—C111 | 109.8 (3) | H13K—C132—H13L | 107.8 |
C109—C108—C111 | 107.0 (3) | N102—C133—H13P | 109.5 |
C110—C108—C111 | 109.3 (3) | N102—C133—H13Q | 109.5 |
C108—C109—H10C | 109.5 | H13P—C133—H13Q | 109.5 |
C108—C109—H10D | 109.5 | N102—C133—H13R | 109.5 |
H10C—C109—H10D | 109.5 | H13P—C133—H13R | 109.5 |
C108—C109—H10E | 109.5 | H13Q—C133—H13R | 109.5 |
H10C—C109—H10E | 109.5 | N102—C134—H13M | 109.5 |
H10D—C109—H10E | 109.5 | N102—C134—H13N | 109.5 |
C108—C110—H11A | 109.5 | H13M—C134—H13N | 109.5 |
C108—C110—H11B | 109.5 | N102—C134—H13O | 109.5 |
H11A—C110—H11B | 109.5 | H13M—C134—H13O | 109.5 |
C108—C110—H11C | 109.5 | H13N—C134—H13O | 109.5 |
H11A—C110—H11C | 109.5 | O103—C135—C136 | 106.5 (3) |
H11B—C110—H11C | 109.5 | O103—C135—H13A | 110.4 |
C108—C111—H11D | 109.5 | C136—C135—H13A | 110.4 |
C108—C111—H11E | 109.5 | O103—C135—H13B | 110.4 |
H11D—C111—H11E | 109.5 | C136—C135—H13B | 110.4 |
C108—C111—H11F | 109.5 | H13A—C135—H13B | 108.6 |
H11D—C111—H11F | 109.5 | C135—C136—C137 | 103.5 (3) |
H11E—C111—H11F | 109.5 | C135—C136—H13C | 111.1 |
C106—C112—H11G | 109.5 | C137—C136—H13C | 111.1 |
C106—C112—H11H | 109.5 | C135—C136—H13D | 111.1 |
H11G—C112—H11H | 109.5 | C137—C136—H13D | 111.1 |
C106—C112—H11I | 109.5 | H13C—C136—H13D | 109.0 |
H11G—C112—H11I | 109.5 | C138—C137—C136 | 102.8 (3) |
H11H—C112—H11I | 109.5 | C138—C137—H13E | 111.2 |
N101—C116—C117 | 114.7 (3) | C136—C137—H13E | 111.2 |
N101—C116—H11J | 108.6 | C138—C137—H13F | 111.2 |
C117—C116—H11J | 108.6 | C136—C137—H13F | 111.2 |
N101—C116—H11K | 108.6 | H13E—C137—H13F | 109.1 |
C117—C116—H11K | 108.6 | O103—C138—C137 | 108.6 (3) |
H11J—C116—H11K | 107.6 | O103—C138—H13G | 110.0 |
C118—C117—C122 | 120.7 (3) | C137—C138—H13G | 110.0 |
C118—C117—C116 | 121.6 (3) | O103—C138—H13H | 110.0 |
C122—C117—C116 | 117.1 (3) | C137—C138—H13H | 110.0 |
O102—C118—C117 | 121.2 (3) | H13G—C138—H13H | 108.3 |
O102—C118—C119 | 120.6 (4) | C116—N101—C131 | 111.7 (3) |
C117—C118—C119 | 118.1 (4) | C116—N101—C101 | 109.3 (3) |
C120—C119—C118 | 117.7 (4) | C131—N101—C101 | 110.3 (3) |
C120—C119—C123 | 121.6 (3) | C116—N101—Zn1 | 110.3 (2) |
C118—C119—C123 | 120.6 (3) | C131—N101—Zn1 | 107.4 (2) |
C119—C120—C121 | 125.0 (3) | C101—N101—Zn1 | 107.7 (2) |
C119—C120—H120 | 117.5 | C133—N102—C132 | 109.7 (3) |
C121—C120—H120 | 117.5 | C133—N102—C134 | 107.5 (3) |
C120—C121—C122 | 116.5 (4) | C132—N102—C134 | 109.6 (3) |
C120—C121—C127 | 121.6 (3) | C133—N102—Zn1 | 118.0 (2) |
C122—C121—C127 | 121.7 (4) | C132—N102—Zn1 | 105.4 (2) |
C121—C122—C117 | 121.8 (4) | C134—N102—Zn1 | 106.4 (2) |
C121—C122—H122 | 119.1 | C103—O101—Zn1 | 120.1 (2) |
C117—C122—H122 | 119.1 | C118—O102—Zn1 | 126.6 (2) |
C119—C123—C124 | 110.2 (3) | C138—O103—C135 | 107.9 (3) |
C119—C123—C125 | 110.2 (3) | C138—O103—Zn1 | 124.1 (2) |
C124—C123—C125 | 110.4 (3) | C135—O103—Zn1 | 119.1 (2) |
C119—C123—C126 | 112.3 (3) | ||
N101—C101—C102—C107 | −115.4 (4) | C117—C116—N101—Zn1 | −57.5 (3) |
N101—C101—C102—C103 | 65.0 (4) | C132—C131—N101—C116 | −157.3 (3) |
C107—C102—C103—O101 | 174.4 (3) | C132—C131—N101—C101 | 80.9 (4) |
C101—C102—C103—O101 | −6.1 (5) | C132—C131—N101—Zn1 | −36.3 (3) |
C107—C102—C103—C104 | −7.8 (5) | C102—C101—N101—C116 | 62.7 (4) |
C101—C102—C103—C104 | 171.8 (3) | C102—C101—N101—C131 | −174.1 (3) |
O101—C103—C104—C105 | −175.3 (3) | C102—C101—N101—Zn1 | −57.1 (3) |
C102—C103—C104—C105 | 6.8 (5) | O102—Zn1—N101—C116 | 20.8 (2) |
O101—C103—C104—C108 | 2.2 (5) | O101—Zn1—N101—C116 | −107.3 (2) |
C102—C103—C104—C108 | −175.7 (3) | N102—Zn1—N101—C116 | 133.3 (2) |
C103—C104—C105—C106 | −2.1 (6) | O102—Zn1—N101—C131 | −101.0 (2) |
C108—C104—C105—C106 | −179.6 (3) | O101—Zn1—N101—C131 | 130.8 (2) |
C104—C105—C106—C107 | −2.0 (6) | N102—Zn1—N101—C131 | 11.4 (2) |
C104—C105—C106—C112 | 176.3 (3) | O102—Zn1—N101—C101 | 140.1 (2) |
C103—C102—C107—C106 | 3.8 (6) | O101—Zn1—N101—C101 | 12.0 (2) |
C101—C102—C107—C106 | −175.7 (3) | N102—Zn1—N101—C101 | −107.4 (2) |
C105—C106—C107—C102 | 1.2 (6) | C131—C132—N102—C133 | −168.3 (3) |
C112—C106—C107—C102 | −177.1 (3) | C131—C132—N102—C134 | 73.9 (4) |
C105—C104—C108—C109 | −6.4 (5) | C131—C132—N102—Zn1 | −40.2 (3) |
C103—C104—C108—C109 | 176.2 (3) | O102—Zn1—N102—C133 | −131.6 (2) |
C105—C104—C108—C110 | −125.8 (4) | O101—Zn1—N102—C133 | 46.7 (3) |
C103—C104—C108—C110 | 56.8 (4) | N101—Zn1—N102—C133 | 137.7 (2) |
C105—C104—C108—C111 | 113.6 (4) | O103—Zn1—N102—C133 | −40.5 (2) |
C103—C104—C108—C111 | −63.8 (4) | O102—Zn1—N102—C132 | 105.5 (2) |
N101—C116—C117—C118 | 59.3 (5) | O101—Zn1—N102—C132 | −76.2 (3) |
N101—C116—C117—C122 | −129.2 (4) | N101—Zn1—N102—C132 | 14.8 (2) |
C122—C117—C118—O102 | 179.9 (3) | O103—Zn1—N102—C132 | −163.4 (2) |
C116—C117—C118—O102 | −8.9 (6) | O102—Zn1—N102—C134 | −10.9 (3) |
C122—C117—C118—C119 | −2.7 (5) | O101—Zn1—N102—C134 | 167.4 (2) |
C116—C117—C118—C119 | 168.5 (3) | N101—Zn1—N102—C134 | −101.5 (2) |
O102—C118—C119—C120 | 179.5 (3) | O103—Zn1—N102—C134 | 80.3 (2) |
C117—C118—C119—C120 | 2.1 (5) | C102—C103—O101—Zn1 | −45.9 (4) |
O102—C118—C119—C123 | 2.6 (5) | C104—C103—O101—Zn1 | 136.3 (3) |
C117—C118—C119—C123 | −174.8 (3) | O102—Zn1—O101—C103 | −60.3 (3) |
C118—C119—C120—C121 | 0.4 (6) | N101—Zn1—O101—C103 | 37.4 (3) |
C123—C119—C120—C121 | 177.3 (4) | N102—Zn1—O101—C103 | 121.7 (3) |
C119—C120—C121—C122 | −2.4 (6) | O103—Zn1—O101—C103 | −149.6 (3) |
C119—C120—C121—C127 | −178.6 (4) | C117—C118—O102—Zn1 | −31.9 (5) |
C120—C121—C122—C117 | 1.8 (6) | C119—C118—O102—Zn1 | 150.7 (3) |
C127—C121—C122—C117 | 178.0 (4) | O101—Zn1—O102—C118 | 120.9 (3) |
C118—C117—C122—C121 | 0.7 (6) | N101—Zn1—O102—C118 | 22.7 (3) |
C116—C117—C122—C121 | −170.9 (3) | N102—Zn1—O102—C118 | −61.0 (3) |
C120—C119—C123—C124 | −120.8 (4) | O103—Zn1—O102—C118 | −151.5 (3) |
C118—C119—C123—C124 | 56.0 (5) | C137—C138—O103—C135 | −7.5 (4) |
C120—C119—C123—C125 | 117.1 (4) | C137—C138—O103—Zn1 | −154.2 (2) |
C118—C119—C123—C125 | −66.1 (4) | C136—C135—O103—C138 | −13.5 (4) |
C120—C119—C123—C126 | −2.5 (5) | C136—C135—O103—Zn1 | 135.2 (2) |
C118—C119—C123—C126 | 174.3 (3) | O102—Zn1—O103—C138 | −25.4 (3) |
N101—C131—C132—N102 | 53.6 (4) | O101—Zn1—O103—C138 | 102.2 (3) |
O103—C135—C136—C137 | 28.7 (4) | N102—Zn1—O103—C138 | −138.1 (3) |
C135—C136—C137—C138 | −32.1 (4) | O102—Zn1—O103—C135 | −168.8 (3) |
C136—C137—C138—O103 | 25.1 (4) | O101—Zn1—O103—C135 | −41.2 (3) |
C117—C116—N101—C131 | 61.9 (4) | N102—Zn1—O103—C135 | 78.6 (3) |
C117—C116—N101—C101 | −175.8 (3) |
Experimental details
(II) | (III) | |
Crystal data | ||
Chemical formula | [Zn(C34H54N2O2)] | [Zn(C28H42N2O2)(C4H8O)] |
Mr | 588.16 | 576.11 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21/c |
Temperature (K) | 140 | 140 |
a, b, c (Å) | 12.9275 (12), 14.0002 (13), 19.6729 (14) | 13.669 (3), 17.476 (4), 12.989 (4) |
α, β, γ (°) | 100.747 (7), 102.467 (7), 96.879 (8) | 90, 93.14 (2), 90 |
V (Å3) | 3367.8 (5) | 3098.1 (14) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.76 | 0.83 |
Crystal size (mm) | 0.20 × 0.08 × 0.02 | 0.06 × 0.06 × 0.02 |
Data collection | ||
Diffractometer | Oxford Xcalibur3 CCD area-detector diffractometer | Oxford Xcalibur3 CCD area-detector diffractometer |
Absorption correction | Multi-scan (ABSPACK; Oxford Diffraction, 2003) | Multi-scan (ABSPACK; Oxford Diffraction, 2003) |
Tmin, Tmax | 0.925, 0.983 | 0.801, 0.984 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 42426, 15272, 8001 | 33137, 7121, 2308 |
Rint | 0.076 | 0.195 |
(sin θ/λ)max (Å−1) | 0.652 | 0.656 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.071, 0.79 | 0.049, 0.073, 0.68 |
No. of reflections | 15272 | 7121 |
No. of parameters | 744 | 353 |
No. of restraints | 12 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.45, −0.43 | 0.37, −0.49 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2003), CrysAlis RED, SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97, PLATON (Spek, 2003), WinGX (Farrugia, 1999) and enCIFer (Allen et al., 2004).
Zn1—O101 | 1.8918 (15) | Zn2—O201 | 1.8821 (16) |
Zn1—O102 | 1.8960 (17) | Zn2—O202 | 1.8899 (17) |
Zn1—N101 | 2.065 (2) | Zn2—N201 | 2.0643 (18) |
Zn1—N102 | 2.0864 (19) | Zn2—N202 | 2.0727 (19) |
O101—Zn1—O102 | 125.35 (7) | O201—Zn2—O202 | 121.39 (7) |
O101—Zn1—N101 | 99.58 (7) | O201—Zn2—N201 | 99.95 (7) |
O102—Zn1—N101 | 99.77 (7) | O202—Zn2—N201 | 99.80 (7) |
O101—Zn1—N102 | 112.76 (7) | O201—Zn2—N202 | 113.08 (8) |
O102—Zn1—N102 | 118.59 (8) | O202—Zn2—N202 | 122.20 (8) |
N101—Zn1—N102 | 87.81 (8) | N201—Zn2—N202 | 88.07 (7) |
Zn1—O102 | 1.958 (2) | Zn1—N102 | 2.166 (3) |
Zn1—O101 | 1.961 (2) | Zn1—O103 | 2.246 (3) |
Zn1—N101 | 2.163 (3) | ||
O102—Zn1—O101 | 127.59 (10) | N101—Zn1—N102 | 82.88 (12) |
O102—Zn1—N101 | 93.35 (11) | O102—Zn1—O103 | 91.02 (10) |
O101—Zn1—N101 | 94.41 (10) | O101—Zn1—O103 | 87.46 (9) |
O102—Zn1—N102 | 112.67 (11) | N101—Zn1—O103 | 172.77 (11) |
O101—Zn1—N102 | 119.71 (11) | N102—Zn1—O103 | 90.13 (11) |
Acknowledgements
RHH and JAW thank the EPSRC for funding.
References
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The use of biodegradable polymers is of increasing interest, with environmental factors being a key driving force (Drumright et al., 2000). A principle route to these materials is the ring-opening polymerization of ε-caprolactone (CL) (systematic name: oxepan-2-one) or lactide (LA) (systematic name: 3,6-dimethyl-[1,4]dioxane-2,5-dione) (Fig. 1) to give polyesters. Both of these monomers are readily available from corn, and so are themselves renewable (O'Keefe et al., 2001; Dechy-Cabaret et al., 2004). In order to control the physical properties and tacticity of these polyesters, a variety of main-group and transition metal complexes have attracted attention.
The synthesis of a number of catalysts for CL and LA polymerization based on substituted amino-bis(2-hydroxyarylmethyl) (ONNO) ligand systems has recently been reported (Sarazin et al., 2006). The first complexes of this class of ligands were those of group IV metals; in particular, the titanium, hafnium and zirconium benzyl complexes were structurally characterized and observed to be highly active in the polymerization of α-olefins (Tshuva et al., 2001a,b; Tshuva et al., 2002; Groysman et al., 2003). Although Sarazin et al. (2006) reported solution data on the magnesium, calcium, titanium and zinc complexes of the ONNO ligand (Ia) (R = tBu), only the calcium [(IV)] and titanium [(V)] systems were structurally characterized. The calcium system was found to form a dimeric complex, both in the solid state and in solution. The solid-state structure showed one Ca···H agostic bond at each metal centre (Ca···H distances of 2.31 and 2.41 Å), resulting in distorted octahedral geometry at both Ca atoms. On the other hand, the titanium system was found to be monomeric and six coordinate, with two coordination sites occupied by iPrO− groups. Equally, solution NMR data for the zinc system, (II), suggested a similar monomeric 1:1 structure. This is in line with the ionic radii of the metal ions, with calcium significantly larger than either titanium or zinc (Ca2+ 1.14 Å, Zn2+ 0.88 Å, Ti4+ 0.75 Å; Atkins et al., 2006). The monomeric nature of the zinc–ONNO complex, (II), has now been established by X-ray analysis. The related complex, (III), bearing a less bulky ONNO ligand, has also been synthesized and characterized for the first time.
Complex (II) crystallizes in the triclinic spacegroup P1, with two independent molecules in the asymmetric unit (Fig. 2). Table 1 highlights the bond lengths and angles around the metal centre. It can be seen that the two independent molecules exhibit similar geometric values. The metal–donor distances in (II) (Table 1) are similar to those in the previously reported monomeric titanium complex, (V). The M—O distances in (II) fall close to those in (V) [1.9034 (15) and 1.9009 (15) Å], consistent with the similar ionic radii of the central atoms. However, the M—N distances are much longer in the titanium complex [2.400 (2) and 2.335 (2) Å] than in (II). In contrast, the dimeric calcium complex, (IV), exhibits significantly longer (non-bridging) M—O [2.1842 (16) and 2.1817 (16) Å] distances than (II). The M—N distances are again significantly shorter in (II) than in (IV) [2.4981 (19)–2.552 (2) Å]. The donor atoms form a distorted trigonal–pyramidal arrangement around the Zn. The Zn atom is 0.205 (1) Å from mean plane of the O and N atoms which form the base of the pyramid. The Naxial—Zn—donor angles demonstrate the distortion of the molecule from ideal geometry, with the two O atoms bent away from the Zn—Naxial bond.
Complex (III) is trigonal–bipyramidal, with the fifth coordination site occupied by a tetrahydrofuran (THF) molecule (Fig. 3). The change of R group from tBu to methyl is remote from the metal centre, and so it is reasonable to compare the geometry of (III) with that seen in (II). As would be expected, the additional electron density donated by the THF molecule results in the elongation of the metal—donor bond lengths in (III) compared with complex (II) (Table 1 and Table 2). The Zn—O bonds are lengthened by approximately 0.07 Å, whilst the Zn—N bonds are extended by approximately 0.1 Å. The geometry of the ONNO ligand at the metal centre is similar to that in (II), although the metal is displaced by only 0.0185 (16) Å from the mean plane of the equatorial donors.
Neither complex (II) nor complex (III) is active in the polymerization of LA or CL, in contrast with (IV). The structures presented in this report demonstrate the ability of the metal centre to bind both the ONNO ligand and an additional oxygen-based ligand. The lack of polymerization activity cannot, therefore, be due to steric protection of the Lewis acidic site.