Low temperature redetermination of the structure of [Ni(CO)(η5 C5H5)]2

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Acta Crystallographica Section E Structure Reports

Online

ISSN 1600-5368

Low temperature redetermination

of the structure of [Ni(CO)(

g

5

-C5H5)]2

Cameron Evans* and Louis J. Farrugia

Department of Chemistry, University Of Glasgow, Joseph Black Building, University Avenue, Glasgow G12 8QQ, Scotland

Correspondence e-mail: [email protected]

Key indicators Single-crystal X-ray study T= 115 K

Mean(C±C) = 0.003 AÊ Disorder in main residue Rfactor = 0.024 wRfactor = 0.065

Data-to-parameter ratio = 20.4

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2003 International Union of Crystallography

The crystal structure of [Ni(CO)(5_-C

5H5)]2 has been redetermined at 115 K. The low temperature data provide a more precise structure solution and indicate the presence of a minor degree of disorder in the material. There are two molecules in the asymmetric unit.

Comment

The structure of [Ni(CO)(5_-C

5H5)]2, (I), has been determined previously on two separate occasions, both at room tempera-ture (Byers & Dahl, 1980; Madachet al., 1980). The advances made in crystallographic techniques since this time allowed for a redetermination of the structure at lower temperature with a signi®cant increase in the quality of the structure solution.

As previously reported, there are two independent mol-ecules in the asymmetric unit (Fig. 1). The NiÐNi distances [2.3691 (3) and 2.3575 (3) AÊ for Ni1ÐNi2 and Ni3ÐNi4 respectively] are greater than those previously reported [2.3627 (9) and 2.3510 (9) AÊ (Byers & Dahl, 1980); 2.361 (2) and 2.348 (2) AÊ (Madachet al., 1980)], though the remaining bond parameters of the molecules display no signi®cant differences. Both molecules possess non-planar Ni2(CO)2 units, analogous to that found for Co2(CO)8(Sumner et al., 1964; Leung & Coppens, 1983), with the5_-C

5H5rings tilted in the opposite direction. The angle between the 5_-C

5H5 and NiC2planes ranges from 80.33 (6) to 82.56 (7)across the two molecules.

A minor component of disorder was noted from difference maps and the positions of the Ni atoms in this component identi®ed. Re®nement indicated the extent of the disorder to be approximately 1%, with the NiÐNi distances in the minor component [2.32 (2) and 2.34 (2) AÊ for Ni1aÐNi2a and Ni3aÐNi4a respectively] similar to those in the main struc-ture. The positions of the Ni atoms in the minor component of the disorder are related to those of the major component by a translation of 6.3±6.4 AÊ along thecaxis of the unit cell (Fig. 2). The possibility that this electron density is a result of twinning rather than disorder was examined using the ROTAX

program (Cooper et al., 2002) to test for the presence of a twofold axis, though none was identi®ed. Similarly, the set comprising the weakest 655 re¯ections provided a mean scale

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factorK(K= meanFo2/meanFc2) of 1.87, lower than generally observed for a genuine twinned structure. There was no evidence for twinning from the diffraction pattern.

Experimental

[Ni(CO)(5_-C

5H5)]2was obtained from a commercial source (Sigma±

Aldrich Ltd). Crystals suitable for structural determination were obtained from a concentrated hexane solution at 253 K. Contrary to previous reports, all crystals obtained through sublimation displayed evidence of twinning and were disregarded.

Crystal data

C12H10Ni2O2 Mr= 303.62 Triclinic,P1 a= 7.7498 (1) AÊ b= 10.8752 (1) AÊ c= 13.4942 (2) AÊ

= 76.776 (1) = 81.112 (1) = 78.449 (1)

V= 1077.65 (2) AÊ3

Z= 4

Dx= 1.871 Mg mÿ3 MoKradiation

Cell parameters from 133537 re¯ections

= 1±35.0 = 3.47 mmÿ1 T= 115 (2) K Prism, black

0.400.280.15 mm

Data collection

Nonius KappaCCD diffractometer

!and'scans

Absorption correction: multi-scan (Blessing, 1995)

Tmin= 0.264,Tmax= 0.594 84232 measured re¯ections 6276 independent re¯ections

5839 re¯ections withI> 2(I) Rint= 0.071

max= 30 h=ÿ10!10 k=ÿ15!15 l=ÿ18!18

Re®nement

Re®nement onF2 R[F2_{> 2}₍_F2_{)] = 0.025} wR(F2_{) = 0.065} S= 1.10 6276 re¯ections 307 parameters

H-atom parameters constrained

w= 1/[2₍_F

o2) + (0.0315P)2 + 0.5418P]

whereP= (Fo2+ 2Fc2)/3 (/)max= 0.001

max= 0.62 e AÊÿ3 min=ÿ0.64 e AÊÿ3

Extinction correction:SHELXL Extinction coef®cient: 0.0030 (4)

All H atoms were placed in calculated positions (Uiso= 1.2Ueqof

the C atom to which they were attached) using a riding model. The Ni atoms of the minor component of the disorder were identi®ed from difference maps and re®ned using isotropic displacement parameters. Data collection:COLLECT(Nonius, 1997±2000); cell re®nement:

HKL SCALEPACK(Otwinowski & Minor, 1997); data reduction:

HKL DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to re®ne structure:SHELXL97 (Sheldrick, 1997); molecular graphics:ORTEP-3 for Windows(Farrugia, 1997); soft-ware used to prepare material for publication:WinGX publication routines (Farrugia, 1999).

CE thanks the New Zealand Foundation for Research, Science and Technology for a Postdoctoral Research Fellow-ship (Contract No. UOGX0201).

References

Blessing, R. H. (1995).Acta Cryst.A51, 33±38.

Byers, L. R. & Dahl, L. F. (1980).Inorg. Chem.19, 680±692.

Cooper, R. I., Gould, R. O., Parsons, S. & Watkin, D. J. (2002).J. Appl. Cryst. 35, 168±174.

Farrugia, L. J. (1997).J. Appl. Cryst.30, 565. Farrugia, L. J. (1999).J. Appl. Cryst.32, 837.

Leung, P. C. & Coppens, P. (1983).Acta Cryst.B39, 535.

Madach, T., Fischer, K. & Vahrenkamp, H. (1980).Chem. Ber.113, 3235±3244. Nonius (1997±2000).COLLECT. Nonius BV, Delft, Netherlands.

Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, edited by C. W. Carter Jr and R. M. Sweet, Part A, pp. 307±326. New York: Academic Press.

Sheldrick, G. M. (1997).SHELXL97. University of GoÈttingen, Germany. Sumner, G. G., Klug, H. P. & Alexander, L. E. (1964).Acta Cryst.17, 732.

Acta Cryst.(2003). E59, m510±m511 Evans and Farrugia C₁₂H₁₀Ni₂O₂

m511

metal-organic papers

Figure 1

View of the two molecules in the asymmetric unit, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level, with H atoms represented by circles of arbitrary size. The minor component of the disorder has been omitted

Figure 2

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supporting information

Acta Cryst. (2003). E59, m510–m511 [doi:10.1107/S1600536803012984]

Low temperature redetermination of the structure of [Ni(CO)(

η

5

-C

5

H

5

)]

2

Cameron Evans and Louis J. Farrugia

S1. Comment

The structure of [Ni(CO)(η5_-C

5H5)]2 had been determined previously on two separate occassions, both at room

temperature (Byers & Dahl, 1980; Madach et al., 1980). The advances made in crystallographic techniques since this time allowed for a redetermination of the structure at lower temperature with a significant increase in the quality of the

structural solution.

As previously reported, there are two independent molecules within the asymmetric unit (Figure 1). The Ni—Ni

distances [2.3691 (3) and 2.3575 (3) Å for Ni(1)—Ni(2) and Ni(3)—Ni(4) respectively] are greater than those previously

reported [2.3627 (9) and 2.3510 (9) Å Byers & Dahl, 1980; 2.361 (2) and 2.348 (2) Å Madach et al., 1980] though the remaining bond parameters of the molecules display no significant differences. Both molecules possess non-planar

Ni2(CO)2 units, analogous to that found for Co2(CO)8 (Sumner et al., 1964; Leung & Coppens, 1983), with the η5-C5H5

rings tilted in the opposite direction. The angle between the η5_-C

5H5 and NiC2 planes ranges from 80.3–82.6° across the

two molecules.

A minor component of disorder was noted from difference maps and the positions of the nickel atoms in this component

identified. Refinement indicated the extent of the disorder to be approximately 1% with the Ni—Ni distances in the minor

component [2.32 (2) and 2.34 (2) Å for Ni(1a)—Ni(2a) and Ni(3a)—Ni(4a) respectively] similar to those in the main

structure. The positions of the nickel atoms in the minor component of the disorder appear related to those of the major

component by a translation of 6.3–6.4 Å along the c axis of the unit cell (Figure 2). The possibility that this electron density was a result of twinning rather than disorder was examined using the ROTAX program (Cooper et al., 2002) to test for the presence of a 2-fold axis though none was identified. Similarly, the set comprising the weakest 655 reflections

provided a K-factor of 1.87, lower than generally observed for a genuine twinned structure. There was also no evidence

from the diffraction pattern observed for a twinned crystal.

S2. Experimental

[Ni(CO)(η5_-C

5H5)]2 was obtained from a commercial source. Crystals suitable for structural determination were obtained

from a concentrated hexane solution at −20°C. Contrary to previous reports, all crystals obtained through sublimation

displayed evidence of twinning and were disregarded.

S3. Refinement

All H atoms were placed in calculated positions (Uiso 1.2 times that of the carbon to which they were attached) using a

riding model. The nickel atoms of the minor component of the disorder were identified from difference maps and refined

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supporting information

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[image:4.610.125.483.72.317.2]

Acta Cryst. (2003). E59, m510–m511

Figure 1

View of the two molecules in the asymmetric unit showing the atom-labelling scheme. Ellipsoids are drawn at the 50%

probability level with H atoms represented by circles of arbitrary size. The minor component of the disorder has been

omitted

Figure 2

View of the unit cell indicating the positions of the nickel atoms in both components of the disorder.

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Crystal data

C12H10Ni2O2

Mr = 303.62 Triclinic, P1 Hall symbol: -P 1

a = 7.7498 (1) Å

b = 10.8752 (1) Å

c = 13.4942 (2) Å

α = 76.776 (1)°

β = 81.112 (1)°

γ = 78.449 (1)°

V = 1077.65 (2) Å3

[image:4.610.119.485.385.564.2]

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F(000) = 616

Dx = 1.871 Mg m−3

Mo Kα radiation, λ = 0.71073 Å

Cell parameters from 133537 reflections

θ = 1–35.0°

µ = 3.47 mm−1

T = 115 K Prism, black

0.40 × 0.28 × 0.15 mm

Data collection

KappaCCD diffractometer

Radiation source: Enraf Nonius FR590 Graphite monochromator

CCD rotation images, thick slices scans Absorption correction: multi-scan

(Blessing, 1995)

Tmin = 0.264, Tmax = 0.594

84232 measured reflections 6276 independent reflections 5839 reflections with I > 2σ(I)

Rint = 0.071

θmax = 30°, θmin = 1.6°

h = −10→10

k = −15→15

l = −18→18

Refinement

Refinement on F2

Least-squares matrix: full

R[F2_{> 2}_σ₍_F2_{)] = 0.025}

wR(F2_{) = 0.065}

S = 1.10 6276 reflections 307 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained

w = 1/[σ2₍_F

o2) + (0.0315P)2 + 0.5418P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max = 0.001

Δρmax = 0.62 e Å−3

Δρmin = −0.64 e Å−3

Extinction correction: SHELXL, Fc*_{=kFc[1+0.001xFc}2_λ3_/sin(2_θ_)]-1/4

Extinction coefficient: 0.0030 (4)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2_{against ALL reflections. The weighted}_R_-factor_wR_{and goodness of fit}_S_{are based on}_F2_,

conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of}_F2_>_σ₍_F2_{) is used}

only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2

are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

x y z Uiso*/Ueq Occ. (<1)

Ni1 0.22846 (2) 0.276719 (17) 0.470339 (13) 0.01510 (5) 0.9893 (6) Ni2 0.40518 (2) 0.403569 (17) 0.345001 (14) 0.01549 (5) 0.9893 (6) O1 0.60220 (15) 0.19174 (12) 0.47306 (10) 0.0311 (3)

O2 0.07454 (16) 0.38667 (13) 0.28323 (9) 0.0298 (3) C1 0.47518 (19) 0.25718 (14) 0.44374 (12) 0.0206 (3) C2 0.18366 (19) 0.36542 (14) 0.33737 (11) 0.0195 (3) C11 −0.0354 (2) 0.29308 (17) 0.54332 (12) 0.0263 (3)

H11 −0.1305 0.356 0.5172 0.032*

C12 0.0722 (2) 0.30539 (15) 0.61484 (12) 0.0235 (3)

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supporting information

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Acta Cryst. (2003). E59, m510–m511

C13 0.2022 (2) 0.19308 (15) 0.62888 (11) 0.0228 (3)

H13 0.2961 0.177 0.6703 0.027*

C14 0.1690 (2) 0.10783 (16) 0.57036 (12) 0.0253 (3)

H14 0.234 0.0244 0.5681 0.03*

C15 0.0229 (2) 0.16948 (18) 0.51673 (13) 0.0286 (3)

H15 −0.0278 0.1356 0.4713 0.034*

C21 0.6220 (2) 0.50014 (17) 0.33382 (14) 0.0298 (4)

H21 0.7019 0.481 0.3842 0.036*

C22 0.4677 (2) 0.59468 (15) 0.32982 (13) 0.0255 (3)

H22 0.4281 0.6529 0.3747 0.031*

C23 0.3834 (2) 0.58662 (15) 0.24689 (12) 0.0241 (3)

H23 0.2734 0.6362 0.2281 0.029*

C24 0.4904 (2) 0.49164 (16) 0.19554 (13) 0.0280 (3)

H24 0.466 0.469 0.1358 0.034*

C25 0.6380 (2) 0.43782 (17) 0.24927 (15) 0.0314 (4)

H25 0.7315 0.3721 0.2326 0.038*

Ni3 0.27696 (2) 0.106655 (17) 0.154043 (14) 0.01574 (5) 0.9893 (6) Ni4 0.08613 (2) 0.231899 (18) 0.034791 (14) 0.01724 (5) 0.9893 (6) O3 0.41294 (16) 0.32257 (12) 0.02415 (10) 0.0314 (3)

O4 −0.09044 (16) 0.13918 (14) 0.23367 (10) 0.0365 (3) C3 0.3095 (2) 0.25505 (14) 0.05641 (11) 0.0203 (3) C4 0.0303 (2) 0.15367 (15) 0.17137 (12) 0.0230 (3) C31 0.5362 (2) −0.00498 (16) 0.14873 (13) 0.0267 (3)

H31 0.6244 0.0058 0.0916 0.032*

C32 0.5029 (2) 0.06396 (16) 0.23048 (15) 0.0322 (4)

H32 0.566 0.1273 0.2377 0.039*

C33 0.3605 (3) 0.02107 (17) 0.29782 (13) 0.0311 (4)

H33 0.3109 0.0493 0.3594 0.037*

C34 0.3030 (2) −0.07296 (15) 0.25739 (12) 0.0257 (3)

H34 0.2057 −0.1156 0.2861 0.031*

C35 0.4162 (2) −0.09125 (14) 0.16744 (12) 0.0235 (3)

H35 0.412 −0.1511 0.1268 0.028*

C41 0.0077 (2) 0.38819 (16) −0.08238 (12) 0.0261 (3)

H41 0.0409 0.4699 −0.0918 0.031*

C42 −0.1419 (2) 0.34940 (19) −0.02176 (13) 0.0316 (4)

H42 −0.2292 0.3996 0.017 0.038*

C43 −0.1397 (2) 0.2193 (2) −0.02877 (15) 0.0379 (4)

H43 −0.2236 0.167 0.0067 0.045*

C44 0.0096 (3) 0.18205 (18) −0.09793 (15) 0.0362 (4)

H44 0.0402 0.1025 −0.1196 0.043*

C45 0.1028 (2) 0.28468 (18) −0.12799 (12) 0.0282 (3)

H45 0.2114 0.2853 −0.1716 0.034*

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Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

Ni1 0.01393 (9) 0.01538 (9) 0.01476 (9) −0.00276 (6) −0.00137 (6) −0.00058 (6) Ni2 0.01394 (9) 0.01544 (9) 0.01568 (9) −0.00304 (6) −0.00117 (6) −0.00022 (6) O1 0.0190 (5) 0.0299 (6) 0.0369 (7) 0.0010 (4) −0.0059 (5) 0.0058 (5) O2 0.0258 (6) 0.0370 (7) 0.0259 (6) −0.0102 (5) −0.0106 (5) 0.0043 (5) C1 0.0180 (6) 0.0195 (6) 0.0223 (7) −0.0032 (5) −0.0015 (5) −0.0010 (5) C2 0.0186 (6) 0.0206 (6) 0.0187 (6) −0.0052 (5) −0.0021 (5) −0.0008 (5) C11 0.0156 (6) 0.0338 (8) 0.0233 (7) −0.0028 (6) 0.0015 (5) 0.0029 (6) C12 0.0247 (7) 0.0230 (7) 0.0194 (7) −0.0018 (6) 0.0032 (5) −0.0033 (5) C13 0.0245 (7) 0.0250 (7) 0.0155 (6) −0.0022 (6) −0.0020 (5) 0.0006 (5) C14 0.0308 (8) 0.0178 (7) 0.0232 (7) −0.0068 (6) 0.0050 (6) 0.0009 (6) C15 0.0265 (8) 0.0363 (9) 0.0262 (8) −0.0191 (7) 0.0020 (6) −0.0042 (7) C21 0.0231 (7) 0.0316 (8) 0.0332 (8) −0.0137 (6) −0.0083 (6) 0.0075 (7) C22 0.0304 (8) 0.0206 (7) 0.0265 (7) −0.0106 (6) 0.0002 (6) −0.0036 (6) C23 0.0235 (7) 0.0194 (7) 0.0260 (7) −0.0058 (5) −0.0039 (6) 0.0046 (6) C24 0.0355 (8) 0.0274 (8) 0.0201 (7) −0.0122 (7) 0.0032 (6) −0.0013 (6) C25 0.0206 (7) 0.0248 (8) 0.0410 (9) −0.0043 (6) 0.0110 (7) −0.0002 (7) Ni3 0.01522 (9) 0.01507 (9) 0.01543 (9) −0.00127 (6) −0.00317 (6) −0.00030 (6) Ni4 0.01623 (9) 0.01686 (9) 0.01767 (9) −0.00220 (7) −0.00520 (7) 0.00006 (7) O3 0.0285 (6) 0.0321 (6) 0.0325 (6) −0.0144 (5) −0.0092 (5) 0.0075 (5) O4 0.0211 (6) 0.0423 (7) 0.0340 (7) −0.0008 (5) 0.0045 (5) 0.0077 (6) C3 0.0197 (6) 0.0207 (7) 0.0195 (6) −0.0037 (5) −0.0054 (5) 0.0002 (5) C4 0.0195 (6) 0.0216 (7) 0.0243 (7) −0.0007 (5) −0.0037 (5) 0.0011 (5) C31 0.0176 (6) 0.0238 (7) 0.0319 (8) 0.0007 (5) −0.0011 (6) 0.0031 (6) C32 0.0315 (8) 0.0234 (8) 0.0444 (10) −0.0011 (6) −0.0241 (8) −0.0026 (7) C33 0.0433 (10) 0.0270 (8) 0.0185 (7) 0.0100 (7) −0.0117 (7) −0.0040 (6) C34 0.0256 (7) 0.0205 (7) 0.0238 (7) −0.0005 (6) −0.0002 (6) 0.0054 (6) C35 0.0275 (7) 0.0167 (6) 0.0240 (7) 0.0011 (5) −0.0054 (6) −0.0025 (5) C41 0.0340 (8) 0.0224 (7) 0.0211 (7) −0.0021 (6) −0.0122 (6) 0.0008 (6) C42 0.0236 (7) 0.0421 (10) 0.0232 (7) 0.0079 (7) −0.0084 (6) −0.0028 (7) C43 0.0302 (9) 0.0455 (11) 0.0382 (10) −0.0182 (8) −0.0198 (8) 0.0115 (8) C44 0.0477 (11) 0.0265 (8) 0.0407 (10) 0.0003 (7) −0.0273 (8) −0.0107 (7) C45 0.0277 (8) 0.0385 (9) 0.0176 (7) −0.0006 (7) −0.0072 (6) −0.0053 (6)

Geometric parameters (Å, º)

Ni1—C1 1.8681 (15) Ni3—C4 1.8696 (15)

Ni1—C2 1.8807 (15) Ni3—C32 2.0879 (16)

Ni1—C15 2.0956 (15) Ni3—C33 2.0905 (16)

Ni1—C14 2.1023 (16) Ni3—C34 2.1176 (15)

Ni1—C13 2.1202 (15) Ni3—C31 2.1295 (15)

Ni1—C11 2.1205 (15) Ni3—C35 2.1867 (15)

Ni1—C12 2.1825 (15) Ni3—Ni4 2.3575 (3)

Ni1—Ni2 2.3691 (3) Ni4—C4 1.8685 (16)

Ni2—C2 1.8679 (15) Ni4—C3 1.8733 (15)

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supporting information

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Acta Cryst. (2003). E59, m510–m511

Ni2—C24 2.0925 (16) Ni4—C41 2.1006 (15)

Ni2—C25 2.0957 (16) Ni4—C43 2.1049 (17)

Ni2—C23 2.1149 (15) Ni4—C45 2.1299 (16)

Ni2—C21 2.1224 (16) Ni4—C44 2.1806 (17)

Ni2—C22 2.1848 (15) O3—C3 1.1632 (19)

O1—C1 1.1589 (19) O4—C4 1.1672 (19)

O2—C2 1.1566 (18) C31—C35 1.406 (2)

C11—C12 1.413 (2) C31—C32 1.435 (3)

C11—C15 1.438 (3) C31—H31 0.95

C11—H11 0.95 C32—C33 1.401 (3)

C12—C13 1.416 (2) C32—H32 0.95

C12—H12 0.95 C33—C34 1.433 (3)

C13—C14 1.429 (2) C33—H33 0.95

C13—H13 0.95 C34—C35 1.412 (2)

C14—C15 1.408 (2) C34—H34 0.95

C14—H14 0.95 C35—H35 0.95

C15—H15 0.95 C41—C42 1.391 (2)

C21—C22 1.411 (2) C41—C45 1.426 (2)

C21—C25 1.433 (3) C41—H41 0.95

C21—H21 0.95 C42—C43 1.436 (3)

C22—C23 1.407 (2) C42—H42 0.95

C22—H22 0.95 C43—C44 1.423 (3)

C23—C24 1.429 (2) C43—H43 0.95

C23—H23 0.95 C44—C45 1.399 (3)

C24—C25 1.404 (3) C44—H44 0.95

C24—H24 0.95 C45—H45 0.95

C25—H25 0.95 Ni1A—Ni2A 2.32 (2)

Ni3—C3 1.8685 (15) Ni3A—Ni4A 2.34 (2)

C1—Ni1—C2 95.61 (6) C3—Ni3—C4 93.72 (7)

C1—Ni1—C15 141.48 (7) C3—Ni3—C32 103.64 (7) C2—Ni1—C15 103.16 (7) C4—Ni3—C32 143.36 (8) C1—Ni1—C14 107.02 (7) C3—Ni3—C33 135.63 (7) C2—Ni1—C14 136.92 (7) C4—Ni3—C33 108.03 (7) C15—Ni1—C14 39.19 (7) C32—Ni3—C33 39.19 (8) C1—Ni1—C13 100.01 (6) C3—Ni3—C34 167.00 (6) C2—Ni1—C13 164.09 (6) C4—Ni3—C34 99.25 (6) C15—Ni1—C13 65.90 (7) C32—Ni3—C34 66.03 (7) C14—Ni1—C13 39.57 (7) C33—Ni3—C34 39.82 (7) C1—Ni1—C11 163.84 (7) C3—Ni3—C31 102.22 (6)

C2—Ni1—C11 99.15 (6) C4—Ni3—C31 162.05 (7)

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C13—Ni1—C12 38.38 (6) C34—Ni3—C35 38.26 (6) C11—Ni1—C12 38.31 (6) C31—Ni3—C35 38.00 (6)

C1—Ni1—Ni2 50.82 (5) C3—Ni3—Ni4 51.04 (5)

C2—Ni1—Ni2 50.56 (4) C4—Ni3—Ni4 50.88 (5)

C15—Ni1—Ni2 152.70 (5) C32—Ni3—Ni4 154.58 (5) C14—Ni1—Ni2 155.60 (5) C33—Ni3—Ni4 157.47 (5) C13—Ni1—Ni2 141.38 (5) C34—Ni3—Ni4 139.31 (5) C11—Ni1—Ni2 138.33 (5) C31—Ni3—Ni4 136.82 (5) C12—Ni1—Ni2 133.39 (4) C35—Ni3—Ni4 130.50 (4)

C2—Ni2—C1 95.85 (6) C4—Ni4—C3 93.59 (7)

C2—Ni2—C24 105.03 (7) C4—Ni4—C42 109.41 (7) C1—Ni2—C24 139.17 (7) C3—Ni4—C42 136.44 (7) C2—Ni2—C25 139.33 (7) C4—Ni4—C41 144.21 (7) C1—Ni2—C25 105.10 (7) C3—Ni4—C41 104.05 (7) C24—Ni2—C25 39.17 (7) C42—Ni4—C41 38.70 (7)

C2—Ni2—C23 99.29 (6) C4—Ni4—C43 100.68 (7)

C1—Ni2—C23 164.11 (7) C3—Ni4—C43 165.45 (7) C24—Ni2—C23 39.69 (7) C42—Ni4—C43 39.94 (8) C25—Ni2—C23 65.79 (6) C41—Ni4—C43 65.51 (7) C2—Ni2—C21 163.55 (7) C4—Ni4—C45 163.26 (7)

C1—Ni2—C21 99.77 (7) C3—Ni4—C45 100.65 (7)

C24—Ni2—C21 65.75 (7) C42—Ni4—C45 65.50 (7) C25—Ni2—C21 39.71 (8) C41—Ni4—C45 39.39 (7) C23—Ni2—C21 64.75 (6) C43—Ni4—C45 64.81 (7) C2—Ni2—C22 126.19 (6) C4—Ni4—C44 125.46 (8) C1—Ni2—C22 126.88 (7) C3—Ni4—C44 128.61 (8) C24—Ni2—C22 65.23 (6) C42—Ni4—C44 65.57 (7) C25—Ni2—C22 65.29 (7) C41—Ni4—C44 64.83 (7) C23—Ni2—C22 38.16 (6) C43—Ni4—C44 38.74 (8) C21—Ni2—C22 38.22 (7) C45—Ni4—C44 37.85 (7)

C2—Ni2—Ni1 51.04 (4) C4—Ni4—Ni3 50.92 (5)

C1—Ni2—Ni1 50.61 (5) C3—Ni4—Ni3 50.86 (5)

C24—Ni2—Ni1 154.52 (5) C42—Ni4—Ni3 159.27 (5) C25—Ni2—Ni1 154.30 (5) C41—Ni4—Ni3 154.88 (5) C23—Ni2—Ni1 139.85 (4) C43—Ni4—Ni3 139.25 (5) C21—Ni2—Ni1 139.65 (5) C45—Ni4—Ni3 135.24 (5) C22—Ni2—Ni1 133.18 (4) C44—Ni4—Ni3 128.75 (5) O1—C1—Ni1 140.83 (13) O3—C3—Ni3 141.24 (13) O1—C1—Ni2 140.60 (13) O3—C3—Ni4 140.61 (12)

Ni1—C1—Ni2 78.56 (6) Ni3—C3—Ni4 78.11 (6)

O2—C2—Ni2 141.60 (12) O4—C4—Ni4 141.57 (13) O2—C2—Ni1 139.97 (12) O4—C4—Ni3 140.22 (13)

Ni2—C2—Ni1 78.39 (6) Ni4—C4—Ni3 78.20 (6)

C12—C11—C15 108.60 (14) C35—C31—C32 108.43 (15) C12—C11—Ni1 73.22 (9) C35—C31—Ni3 73.20 (9) C15—C11—Ni1 69.13 (9) C32—C31—Ni3 68.56 (9)

C12—C11—H11 125.7 C35—C31—H31 125.8

(10)

supporting information

sup-8

Acta Cryst. (2003). E59, m510–m511

Ni1—C11—H11 123.5 Ni3—C31—H31 124

C11—C12—H12 126.4 C33—C32—H32 126.2

C13—C12—H12 126.4 C31—C32—H32 126.2

Ni1—C12—H12 128.3 Ni3—C32—H32 123.3

C12—C13—H13 125.6 C32—C33—H33 126.1

C14—C13—H13 125.6 C34—C33—H33 126.1

Ni1—C13—H13 123.2 Ni3—C33—H33 124.1

C15—C14—H14 126.1 C35—C34—H34 125.9

C13—C14—H14 126.1 C33—C34—H34 125.9

Ni1—C14—H14 124.5 Ni3—C34—H34 123.1

C14—C15—H15 126.3 C31—C35—H35 126.1

C11—C15—H15 126.3 C34—C35—H35 126.1

Ni1—C15—H15 123.7 Ni3—C35—H35 128.4

C22—C21—H21 125.7 C42—C41—H41 125.7

C25—C21—H21 125.7 C45—C41—H41 125.7

Ni2—C21—H21 123.5 Ni4—C41—H41 123.9

C23—C22—H22 126.4 C41—C42—H42 126.4

C21—C22—H22 126.4 C43—C42—H42 126.4

Ni2—C22—H22 128.4 Ni4—C42—H42 124.2

C22—C23—H23 125.6 C44—C43—H43 125.8

C24—C23—H23 125.6 C42—C43—H43 125.8

Ni2—C23—H23 123.1 Ni4—C43—H43 122.5

C25—C24—H24 126.2 C45—C44—H44 126.5

(11)

Ni2—C24—H24 123.9 Ni4—C44—H44 128.2 C24—C25—C21 107.52 (15) C44—C45—C41 108.71 (16) C24—C25—Ni2 70.29 (9) C44—C45—Ni4 73.04 (10) C21—C25—Ni2 71.15 (9) C41—C45—Ni4 69.19 (9)

C24—C25—H25 126.2 C44—C45—H45 125.6

C21—C25—H25 126.2 C41—C45—H45 125.6