metal-organic compounds Acta Crystallographica Section E
Structure Reports Online ISSN 1600-5368
Di-l-cyanido-1:2j2C:N,2:3j2N:Chexacyanido-1j3C,3j3C-tetrakis(1,10phenanthroline)-1j2N,N0 ;2j4N,N0 ;3j2N,N0 -1,3-dicobalt(III)-2-iron(II) tetrahydrate Ying Zhang,a Ai-Hua Yuan,a* Hu Zhou,a Ji-Xi Guob and Lang Liub a
School of Material Science and Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003, People’s Republic of China, and bInstitute of Applied Chemistry, Xinjiang University, Urumqi 830046, Xinjiang, People’s Republic of China Correspondence e-mail:
[email protected] Received 26 June 2009; accepted 29 July 2009 ˚; Key indicators: single-crystal X-ray study; T = 173 K; mean (C–C) = 0.003 A disorder in solvent or counterion; R factor = 0.031; wR factor = 0.079; data-toparameter ratio = 16.1.
Experimental Crystal data = 65.99 (3) ˚3 V = 2564.5 (12) A Z=2 Mo K radiation = 0.98 mm1 T = 173 K 0.74 0.56 0.33 mm
[Co2Fe(CN)8(C12H8N2)4]4H2O Mr = 1174.75 Triclinic, P1 ˚ a = 12.855 (3) A ˚ b = 14.006 (3) A ˚ c = 16.334 (3) A = 72.68 (3) = 82.54 (3)
Data collection
The hydrothermal reaction of CoCl26H2O, 1,10-phenanthroline (phen) and K3[Fe(CN)6] in deionized water yielded the title cyanide-bridged trinuclear cluster, [Co2Fe(CN)8(C12H8N2)4]4H2O or [{CoIII(phen)(CN)4}2{FeII(phen)2}]4H2O, which contains two CoIII centers and one FeII center linked by cyanide bridges. The combination of coordinative bonds, O—H N and O—H O hydrogen bonds and – stacking interactions [centroid–centroid distance = ˚ ] results in the stabilization of a supramolecular 3.630 (2) A structure. All uncoordinated water molecules are disordered. Thermogravimetric analysis reveals that the title complex loses the four crystal water molecules at about 333 K, then the anhydrous phase loses no further mass up to about 573 K, above which decomposition occurs.
Related literature For background to cyanide-bridged complexes, see: Rodrı´guez-Die´guez et al. (2007); Colacio et al. (2003, 2005); Chen et al. (2006); Ferlay et al. (1995); Ferna´ndez-Armas et al. (2007); Goodwin et al. (2008); He et al. (2005); Kosaka et al. (2009); Mao et al. (2005); Overgaard et al. (2004); Paredes-Garcı´a et al. (2006); Phillips et al. (2008); Reguera Balmaseda, del Castillo et al. (2008); Reguera, Balmaseda, Krap et al. (2008); Rodriguez et al. (2005); Xie et al. (2007); Yu et al. (2003). For related structures, see: Halbauer et al. (2008); Guo et al. (2007); Zhao et al. (2008); Brewer et al. (2007).
Acta Cryst. (2009). E65, m1033–m1034
Rigaku R-AXIS Spider diffractometer Absorption correction: multi-scan (ABSCOR; Higashi, 1995) Tmin = 0.555, Tmax = 0.755
41118 measured reflections 11723 independent reflections 10898 reflections with I > 2(I) Rint = 0.040
Refinement R[F 2 > 2(F 2)] = 0.031 wR(F 2) = 0.079 S = 1.03 11723 reflections
726 parameters H-atom parameters constrained ˚ 3 max = 0.44 e A ˚ 3 min = 0.70 e A
Table 1 ˚ , ). Selected geometric parameters (A Co1—C6 Co1—C7 Co1—C2 Co1—C8 Co1—N15 Co1—N16 Co2—C3 Co2—C4 Co2—C5 Co2—C1 Co2—N13 Co2—N14 Fe1—N2
doi:10.1107/S1600536809030165
1.8747 1.8779 1.8960 1.9076 1.9693 1.9762 1.8744 1.8822 1.8975 1.9044 1.9652 1.9665 2.0365
(16) (18) (16) (17) (13) (15) (17) (17) (17) (16) (15) (14) (14)
Fe1—N1 Fe1—N12 Fe1—N10 Fe1—N11 Fe1—N9 N1—C1 N2—C2 N3—C3 N4—C4 N5—C5 N6—C6 N7—C7 N8—C8
Zhang et al.
2.0464 (15) 2.0821 (15) 2.0845 (16) 2.0960 (16) 2.1067 (16) 1.144 (2) 1.144 (2) 1.147 (2) 1.147 (2) 1.149 (2) 1.148 (2) 1.156 (2) 1.146 (2)
m1033
metal-organic compounds Table 2 ˚ , ). Hydrogen-bond geometry (A D—H A
D—H
H A
D A
D—H A
O1—H1A N7 O1—H1B N3 O2—H2A N8i O2—H2B N4 O3A—H3A O2ii O3A—H3B O1 O3B—H3C O1 O3B—H3D O2ii O4A—H4A N6iii O4A—H4B N5 O4B—H4D N5
0.82 0.82 0.82 0.82 0.82 0.82 0.85 0.90 0.84 0.82 0.82
2.34 2.12 2.33 2.16 2.22 2.12 1.97 2.11 2.11 2.13 2.09
3.143 2.939 3.118 2.970 2.971 2.930 2.823 2.889 2.930 2.870 2.848
167 172 163 170 153 169 179 144 165 151 153
(2) (2) (3) (2) (3) (3) (16) (18) (6) (4) (4)
Symmetry codes: (i) x; y þ 1; z; (ii) x; y þ 2; z; (iii) x; y þ 1; z þ 1.
Data collection: RAPID-AUTO (Rigaku, 2004); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXL97.
The work was supported by the University Natural Science Foundation of China Jiangsu Province (No. 07KJB150030). Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: AT2833).
References Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Brewer, C. T., Brewer, G., Butcher, R. J., Carpenter, E. E., Schmiedekamp, A. M. & Viragh, C. (2007). Dalton Trans. pp. 295–298. Chen, X. B., Li, Y. Z. & You, X. Z. (2006). Appl. Organomet. Chem. 20, 305– 309. Colacio, E., Debdoubi, A., Kiveka¨s, R. & Rodrı´guez, A. (2005). Eur. J. Inorg. Chem. pp. 2860–2868.
m1034
Zhang et al.
[Co2Fe(CN)8(C12H8N2)4]4H2O
Colacio, E., Domı´nguez-Vera, J. M., Lloret, F., Moreno Sa´nchez, J. M., Kiveka¨s, R., Rodrı´guez, A. & Sillanpa¨a¨, R. (2003). Inorg. Chem. 42, 4209– 4214. Ferlay, S., Malleh, T., Ouake`s, R., Veillet, P. & Verdaguer, M. (1995). Nature (London), 378, 701–703. Ferna´ndez-Armas, S., Mesa, J. L., Pizarro, J. L., Arriortua, M. I. & Roji, T. (2007). Mater. Res. Bull. 42, 544–552. Goodwin, A. L., Calleja, M., Conterio, M. J., Dove, M. T., Evans, J. S. O., Keen, D. A., Peters, L. & Tucker, M. G. (2008). Science, 319, 794–797. Guo, Y., Feng, Y. H., Liu, Z. Q. & Liao, D. Z. (2007). J. Coord. Chem. 60, 2713– 2720. Halbauer, K., Go¨rls, H. & Imhof, W. (2008). Inorg. Chem. Commun. 11, 1177– 1180. He, X., Lu, C. Z., Yuan, D. Q., Chen, S. M. & Chen, J. T. (2005). Eur. J. Inorg. Chem. pp. 2181–2188. Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Kosaka, W., Imoto, K., Tsunobuchi, Y. & Ohkoshi, S. I. (2009). Inorg. Chem. 48, 4604–4606. Mao, H., Zhang, C., Xu, C., Zhang, H., Shen, X., Wu, B., Zhu, Y., Wu, Q. & Wang, H. (2005). Inorg. Chim. Acta, 358, 1934–1942. Overgaard, J., Rentschler, E., Timco, G. A. & Larsen, F. K. (2004). ChemPhysChem, 5, 1755–1761. Paredes-Garcı´a, V., Venegas-Yazigi, D., Latorre, R. O. & Spodine, E. (2006). Polyhedron, 25, 2026–2032. Phillips, A. E., Goodwin, A. L., Halder, G. J., Southon, P. D. & Kepert, C. J. (2008). Angew. Chem. Int. Ed. 47, 1396–1399. Reguera, L., Balmaseda, J., del Castillo, L. F. & Reguera, E. (2008). J. Phys. Chem. C, 112, 5589–5597. Reguera, L., Balmaseda, J., Krap, C. P. & Reguera, E. (2008). J. Phys. Chem. C, 112, 10490–10501. Rigaku (2004). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Rodriguez, A., Sakiyama, H., Masciocchi, N., Galli, S., Ga´lvez, N., Lloret, F. & Colacio, E. (2005). Inorg. Chem. 44, 8399–8406. Rodrı´guez-Die´guez, A., Kiveka¨s, R., Sakiyama, H., Debdoubi, A. & Colacio, E. (2007). Dalton Trans. pp. 2145–2149. Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Xie, L. H., Liu, S. X., Gao, C. Y., Cao, R., Cao, J. F., Sun, C. Y. & Su, Z. M. (2007). Inorg. Chem. 46, 7782–7788. Yu, J. H., Xu, J. Q., Yang, Q. X., Pan, L. Y., Wang, T. G., Lu¨, C. H. & Ma, T. H. (2003). J. Mol. Struct. 658, 1–7. Zhao, Y. G., Guo, D., Liu, Y., He, C. & Duan, C. Y. (2008). Chem. Commun. pp. 5725–5727.
Acta Cryst. (2009). E65, m1033–m1034
supplementary materials
supplementary materials Acta Cryst. (2009). E65, m1033-m1034
[ doi:10.1107/S1600536809030165 ]
Di- -cyanido-1:2 2C:N,2:3 2N:C-hexacyanido-1 3C,3 3C-tetrakis(1,10-phenanthroline)1 2N,N';2 4N,N';3 2N,N'-1,3-dicobalt(III)-2-iron(II) tetrahydrate Y. Zhang, A.-H. Yuan, H. Zhou, J.-X. Guo and L. Liu Comment Cyanide-bridged complexes have been investigated extensively over the past few years due to their excellent properties and potential applications, such as, high Tc molecular-based magnets (Ferlay et al., 1995; Kosaka et al., 2009), hydrogen storages (Reguera, Balmaseda & Krap et al., 2008; Reguera, Balmaseda & del Castillo et al., 2008), negative thermal expansion materials (Goodwin et al., 2008; Phillips et al., 2008), and so on. Increasing studies have shown that the hydrothermal reaction is a versatile and useful technique to prepare cyanide-bridged complexes, though the majority of synthetic procedures of cyanide-based systems still follow conventional solution routes. Recently, Colacio (Colacio et al., 2003; Rodriguez et al., 2005; Colacio et al., 2005; Rodríguez-Diéguez et al., 2007) and others (Yu et al., 2003; He et al., 2005; Mao et al., 2005; Chen et al., 2006) have shown that cyanide-bridged bimetallic complexes can also be assembled through hydrothermal reactions by using either [M(CN)6]3- (M = FeIII, CoIII) anions as a source of cyanide groups, which act as both reducing agents and bridging ligands. Bearing this in mind, we introduced CoCl2.6H2O, 1,10-phenanthroline (phen), and K3[Fe(CN)6] (or Na2[Fe(CN)5NO].2H2O) into the reaction in order to obtain a Co—Fe bimetallic monometallic complex. It is interesting that a novel cyanide-bridged trinuclear cluster [{CoIII(phen)(CN)4}2{FeII(phen)2}].4H2O, was obtained. It should be noted here that, to the best of our knowledge, the title complex is the first example of a trinuclear cluster prepared by hydrothermal method in the cyanide-based system. The asymmetric unit of the structure of the title complex is given in Fig. 1. Selected bond lengths and angles are listed in Table 1. Within the neutral [{CoIII(phen)(CN)4}2{FeII(phen)2}] unit, there are one FeII center and two CoIII centers, with {FeN6} and {CoN2C4} coordination environments, respectively. The Fe center is six-coordinate and adopts a distorted slightly octahedral geometry. Each Fe center is coordinated with two coordinated phen ligands and two bridging cyanide groups in a cis arrangement with the angle N1—Fe1—N2 = 89.63 (6)°. The dihedral angle between the planes of chelating phen ligands with the Fe1 atom is ca 85°. The mean basal plane is constructed by three N atoms (N9, N11, and N12) from two phen ligands and N1 atom from one bridging cyanide group, while the axial positions are occupied by N10 atom from one phen ligand and N2 atom of the other bridging cyanide group. The geometrical data of the [FeII(phen)2(CN)2] unit in the title complex are similar to those found for the [FeII(phen)2(CN)2] unit in the one-dimensional complex [Cu2FeII(CN)4(phen)3]n.0.5nH2O (He et al., 2005), the [FeII(bipy)2(CN)2] unit in the two-dimensional complex [FeII(bipy)2(CN)4Cu2] (Colacio et al., 2003), and three-dimensional complex [FeII(CN)4(phen)2Cu2] (Colacio et al., 2005). The CoIII centers (Co1 and Co2) are both coordinated by two N atoms from one phen ligand, one C atom from one bridging cyanide ligand, and three C atoms from three terminal cyanide ligands. For the CoIII centers, the basal plane is formed by two N atoms of one phen ligand and two C atoms of two terminal cyanide groups, while the axial sites are occupied
sup-1
supplementary materials by two C atoms of the other two cyanide groups. As in all other cyanide-bridged complexes, the M—C bond is much shorter than the M—N bond (Table 1). Furthermore, the Co—C—N angles are closed to be linear with the angles spanning from 171° to 179°, which are comparable with those observed for the complexes obtained by hydrothermal methods (Colacio et al., 2003; He et al., 2005; Mao et al., 2005; Colacio et al., 2005), based on [Fe(CN)6]3- as the building block. Thus, cyanide bridges connect one FeII atom to two CoIII atoms in cis arrangement, giving rise to a CoIII2FeII trinuclear cluster with a Fe1 ··· Co1 distance of 5.052 Å and a Fe1 ··· Co2 distance of 5.056 Å. It is noteworthy that the structure of the title complex is distinguished from that of cyanide-based mixed-valence CoII/CoIII complexes (Halbauer et al., 2008; Guo et al., 2007), and mixed-valence FeII/FeIII (Zhao et al., 2008; Overgaard et al., 2004; Brewer et al., 2007; Xie et al., 2007; Fernández-Armas et al., 2007; Paredes-García et al., 2006) complexes belonging to other systems. The crystallized water molecules are hydrogen-bonded to each other and terminal cyanide groups. The probable hydrogen bonding interactions are given in Table 2. In addition, weak face-to-face π-π interactions between the aromatic rings of adjacent phen ligands from neighboring trinuclear clusters also play important roles in the formation and stabilization of the three-dimensional supramolecular structure (Fig. 2). The distance between two adjacent aromatic ring center is ca 3.63 Å. The IR spectrum (Fig. 3) of the title complex exhibits two strong peaks at 2080 cm-1 and 2133 cm-1, and one weak peak at 2171 cm-1, which indicates the existence of different types of cyanide bridges in the structure. The lower frequencies at 2080 cm-1 and 2133 cm-1 are reasonably assigned to the terminal cyanide stretching vibrations, while the higher one of 2171 cm-1 confirms the presence of bridging cyanide groups. There is a broad band at the wavenumber range of 3700–2900 cm-1 ascribed to the O—H stretching absorption (νO—H) in H2O molecules. The IR spectrum exhibits characteristic strong bands of the coordinated phen ligands at 1638, 1521, 1425, 844, and 722 cm-1 (δC—H benzene ring). The bands at 1521, 1425 and 722 cm-1 are shifted from their positions for the free phen ligands (1503, 1420 and 737 cm-1), indicating nitrogen coordination. The IR feature has been confirmed by single-crystal X-ray crystallographic analysis. Thermogravimetric analysis (Fig. 4) is performed to study the thermal stability of the title complex, which shows the title complex loses four crystallized water molecules at above 333 K with a weight loss of 6.29% (Calc. 6.17%). The anhydrous phase loses no further mass up to about 573 K, above which thermal decomposition occurs. Experimental All starting reagents were of analytical grade quality, obtained from commercial sources and used without further purification. A mixture of CoCl2.6H2O (0.1071 g, 0.45 mmol), 1,10-phenanthroline (phen, 0.0892 g, 0.45 mmol), K3[Fe(CN)6] (0.1482 g, 0.45 mmol) in a molar ratio of 1:1:1 combined with 10 ml deionized water was stirred for 20 min at room temperature and then transferred into a 25 ml Teflon-lined stainless-steel vessel. The mixture was heated hydrothermally at 413 K for two days under autogenous pressure. Slow cooling of the resulting solution to room temperature afforded dark red, prism-shaped crystals suitable for single-crystal X-ray structure analysis. Yield: 30% (based on Fe). These crystals were separated, washed thoroughly with deionized water and finally with ethanol, and dried. Analysis calculated for C56H40N16O4Co2Fe: C 57.51, H 3.42, N 19.17%. Found: C 57.46, H 3.35, N 19.12%. EDS (energy dispersive spectrometer): Fe 32.33, Co 67.67. It is of interest that when working under the same hydrothermal conditions, except for using
sup-2
supplementary materials Na2[Fe(CN)5NO] instead of K3[Fe(CN)6] as the cyanide source, the same product was obtained (CCDC-732054). From the viewpoint of the mechanism of the formation of the title complex, it is reasonable that free cyanide groups from the dissociation of [Fe(CN)6]3- or [Fe(CN)5NO]2- might be responsible for the oxidation of the Co center from the original reduction state +II in the precursor CoCl2.6H2O to the oxidation state +III in the title complex. Refinement All non-H atoms were refined anisotropically. The C(H) atoms of the phen ligand were placed in calculated position (C—H = 0.95 Å) and refined using a riding model, with Uiso(H) = 1.2Ueq(C). The O(H) atoms of the water molecules were located in a difference Fourier map and refined as riding, with Uiso(H) = 1.5Ueq(O). O3 and O4 were both split into two positions (O3A and O3B, and O4A and O4B, respectively) with occupancy of 50% each.
Figures
Fig. 1. The asymmetric unit of the structure of the title complex showing 50% probability displacement ellipsoids. Water molecules have been omitted for clarity.
Fig. 2. Hydrogen-bonded supramolecular structure of the complex.
Fig. 3. IR spectrum of the title complex.
Fig. 4. Thermogravimetric curve of the title complex.
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supplementary materials Di-µ-cyanido-1:2κ2C:N,2:3κ2N:C- hexacyanido-1κ3C,3κ3C-tetrakis(1,10-phenanthroline)1κ2N,N';2κ4N,N';3κ2N,N'- 1,3-dicobalt(III)-2-iron(II) tetrahydrate Crystal data [Co2Fe(CN)8(C12H8N2)4]·4H2O1
Z=2
Mr = 1174.75
F000 = 1200
Triclinic, P1
Dx = 1.521 Mg m−3
Hall symbol: -P 1 a = 12.855 (3) Å b = 14.006 (3) Å
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 7618 reflections θ = 3.2–27.0º
c = 16.334 (3) Å
µ = 0.98 mm−1 T = 173 K Block, dark red 0.74 × 0.56 × 0.33 mm
α = 72.68 (3)º β = 82.54 (3)º γ = 65.99 (3)º V = 2564.5 (12) Å3
Data collection Rigaku R-AXIS Spider diffractometer Radiation source: fine-focus sealed tube
11723 independent reflections
Monochromator: graphite
10898 reflections with I > 2σ(I) Rint = 0.040
T = 153 K
θmax = 27.5º
φ and ω scans
θmin = 3.1º
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) Tmin = 0.555, Tmax = 0.755 41118 measured reflections
h = −16→16 k = −18→17 l = −21→21
Refinement Refinement on F2
Secondary atom site location: difference Fourier map
Least-squares matrix: full
Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.031
H-atom parameters constrained
wR(F2) = 0.079
w = 1/[σ2(Fo2) + (0.0331P)2 + 1.5388P]
where P = (Fo2 + 2Fc2)/3
S = 1.03
(Δ/σ)max = 0.001
11723 reflections
Δρmax = 0.44 e Å−3
726 parameters
Δρmin = −0.70 e Å−3
Primary atom site location: structure-invariant direct Extinction correction: none methods
sup-4
supplementary materials 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 Rfactors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) Co1 Co2 Fe1 N1 N2 N3 N4 N5 N6 N7 N8 N9 N10 N11 N12 N13 N14 N15 N16 C1 C2 C3 C4 C5 C6 C7 C8 C9 H9 C10 H10 C11 H11
x
y
z
Uiso*/Ueq
−0.124533 (16) 0.211367 (16) 0.272543 (16) 0.22567 (11) 0.11105 (11) −0.03701 (12) 0.27633 (15) 0.22982 (14) −0.15698 (12) −0.22187 (13) −0.35730 (13) 0.23205 (12) 0.42921 (12) 0.31060 (11) 0.33409 (11) 0.36947 (11) 0.17586 (10) −0.08549 (10) −0.05795 (11) 0.21160 (12) 0.02146 (13) 0.05769 (13) 0.25134 (14) 0.22034 (13) −0.14966 (13) −0.18567 (13) −0.27138 (14) 0.52910 (15) 0.5351 0.62613 (16) 0.6962 0.62013 (18) 0.6855
0.330081 (16) 0.613907 (16) 0.259948 (16) 0.40567 (11) 0.30592 (11) 0.73776 (12) 0.69837 (14) 0.80318 (13) 0.26931 (14) 0.57067 (12) 0.34691 (15) 0.19390 (12) 0.19929 (12) 0.13043 (11) 0.31894 (11) 0.52399 (10) 0.55913 (10) 0.35289 (10) 0.17536 (11) 0.48801 (13) 0.31837 (12) 0.69236 (12) 0.66576 (14) 0.73388 (13) 0.29636 (14) 0.47879 (14) 0.34141 (14) 0.19642 (15) 0.2178 0.16242 (16) 0.1614 0.13123 (15) 0.1089
0.192167 (12) 0.329103 (12) 0.270557 (12) 0.29752 (8) 0.23131 (8) 0.28215 (9) 0.14501 (10) 0.37282 (11) 0.38441 (9) 0.18027 (10) 0.15092 (10) 0.39825 (9) 0.33001 (10) 0.21731 (9) 0.15018 (8) 0.36591 (8) 0.45039 (8) 0.06914 (8) 0.19295 (8) 0.30657 (9) 0.21564 (9) 0.29917 (9) 0.21445 (10) 0.35471 (10) 0.31107 (10) 0.18580 (10) 0.16896 (10) 0.29379 (15) 0.2330 0.34347 (19) 0.3159 0.43026 (18) 0.4635
0.01867 (6) 0.01846 (5) 0.01544 (5) 0.0231 (3) 0.0225 (3) 0.0272 (3) 0.0416 (4) 0.0354 (3) 0.0357 (4) 0.0329 (3) 0.0377 (4) 0.0275 (3) 0.0288 (3) 0.0267 (3) 0.0235 (3) 0.0204 (2) 0.0184 (2) 0.0191 (2) 0.0213 (3) 0.0204 (3) 0.0203 (3) 0.0214 (3) 0.0269 (3) 0.0239 (3) 0.0250 (3) 0.0239 (3) 0.0253 (3) 0.0383 (4) 0.046* 0.0520 (6) 0.062* 0.0507 (6) 0.061*
Occ. (
