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Acta Cryst. (2000). C56, 551-553
https://doi.org/10.1107/S0108270100001670
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Bimetallic assemblies, [Ni(en)2]3[M(CN)6]2·3H2O (en = H2NCH2CH2NH2; M = Fe, Co)

J. Eriksen, A. Hazell, A. Jensen, J. Jepsen and R. D. Poulsen
The reaction between tris(ethyl­enedi­amine)­nickel(II) cations and hexa­cyanometallate(III) anions (M = Fe, Co) yields ordered bimetallic assemblies, catena-poly­[[tris­(ethyl­enedi­amine)­nickel-bis([mu]-hexa­cyano­iron-N,N')] trihydrate] and catena-poly­[[tris­(ethyl­enedi­amine)­nickel-bis([mu]-hexa­cyano­cobalt-N,N')] trihydrate], [{Ni(C2H8N2)2}3{M(CN)6}2]·3H2O, in which both cis and trans [Ni(en)2] and [M(CN)6] moieties are linked to give S-shaped Ni-NC-M-CN-Ni-NC-M-CN-Ni units which are cross­linked to give ribbons parallel to the b axis. The two compounds are isomorphous with mean metal-ligand distances Fe-C = 1.940 (3), Co-C = 1.844 (3) and Ni-N = 2.102 (2) Å for the iron, and 2.105 (3) Å for the cobalt compound. These compounds appear to be identical with those formulated as [Ni(en)2]3[M(CN)6]2·2H2O [Ohba, Maruona, Okawa, Enoki & Latour (1994). J. Am. Chem. Soc. 116, 11566-11567; Ohba, Fukita & Okawa (1997). J. Chem. Soc. Dalton Trans. pp. 1733-1737] which were indexed on a smaller unit cell and described as disordered.
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Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100001670/os1101sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100001670/os1101Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100001670/os1101IIsup3.hkl
Contains datablock II

Comment top

Hexacyanometalate ions [M(CN6)]n- have been shown (Dunbar & Heintz, 1997, and references therein) to act as building blocks to provide bimetallic assemblies exhibiting spontaneous magnetization. Kou et al. (1998) have reported the synthesis of a 2:1 compound [Ni(en)2]2[Fe(CN)6]NO3·3H2O which they obtained from the reaction between [Ni(en)3](NO3)2 (en = ethylenediamine) and K3[Fe(CN)6] but they were unable to obtain crystals suitable for X-ray diffraction. Our attempts at repeating their synthesis has yielded crystals which diffracted well but were found to be [Ni(en)2]3[Fe(CN)6]2·3H2O, (I). \sch

This compound contains both cis and trans [Ni(en)2]2+ cations linked by [Fe(CN)6]3- anions (Fig. 1) via cyanide bridges to give S-shaped Ni—NC—Fe—CN—Ni—NC—Fe—CN—Ni units which are cross-linked by the terminal cis-Ni(en)2 to give ribbons running along the b axis (Fig. 2). Fe—C distances vary from 1.929 (2) to 1.960 (2) Å with a mean value of 1.941 (3) Å, Ni—N distances from 2.071 (2) to 2.122 (2) Å mean value 2.102 (3) Å, C—N (cyanide) from 1.147 (2) to 1.157 (2) Å mean value 1.152 (1) Å, C—N (ethlylene diamine) 1.475 (3) to 1.488 (3) Å mean value 1.480 (1) Å, C—C 1.509 (3) to 1.522 (3) Å mean 1.518 (2) Å. The uncertainties given for the mean values are the sample standard deviations of the mean. Repeating the synthesis with an excess of Ni(NO3)2 still gave the 3:2 compound.

The structure is remarkably similar to that described by Ohba et al. (1994) for [Ni(en)2]3[Fe(CN)6]2·2H2O except that we found a unit cell twice as large as theirs, the small cell being obtained from ours by the transformation (1,0,0,1, 1/2,1,0, 1/2,0), and we believe the two compounds to be identical. We also found three waters of crystallization instead of two. Doubling the cell removes the apparent disorder of the trans Ni(en)2 moiety which had previously been observed and explains the very anisotropic displacement parameters previously observed for one of the monodentate cyanide groups. The analogous Co(CN)6 compound was described by Ohba et al. (1997) as being isomorphous with the Fe(CN)6 compound. We have prepared the cobalt compound and find that it too should be described on the the doubled unit cell, i.e. it is isomorphous with (I) and should be formulated as [Ni(en)2]3[Co(CN)6]2·3H2O, (II).

Co—C distances vary from 1.884 (3) to 1.917 (3) Å with a mean value of 1.899 (3) Å, Ni—N distances from 2.077 (2) to 2.128 (2) Å mean value 2.105 (3) Å, C—N (cyanide) from 1.143 (4) to 1.159 (3) Å mean value 1.151 (1) Å, C—N (ethlylene diamine) 1.476 (4) to 1.486 (4) Å mean value 1.481 (1) Å, C—C 1.507 (4) to 1.523 (4) Å mean 1.514 (2) Å. For both structures there is a wide spread in the values obtained for the Ni—N distances, for each cis-Ni(en)2 moiety one of the Ni—N(cyanide) bonds is short, 2.086 (2) and 2.072 (2) Å for the iron and 2.088 (2) and 2.077 (2) Å for the cobalt complex. The Ni—N(cyanide) distances for the trans-Ni(en)2 are also short. The curvature of the S-shaped fragments is achieved largely through the relatively large deviations from linearity at the nitrogen atoms of the cyanide groups, the Ni—N—C angles are in the range 149.7 (2)–154.4 (2)° for the iron compound and 149.9 (2)–154.6((2)° for the cobalt compound. Similar values are also found in Ni(en)2Ni(CN)4 (Černac et al., 1988) and in Ni(en)2Ni(CN)4·2.18H2O (Černac et al., 1990) a structure which also contains both cis and trans Ni(en)2 moities. The Ni—N—C—M groups linking the S's are closer to linearity with Ni—N—C angles of 168.1 (2) and 168.6 (2) and 168.0 (2) and 169.1 (2)° for the iron and for the cobalt complexes, and it is for these cross linkeages that the shortest Ni—N bonds occur. As expected (Sharpe, 1981) the CN stretching frequencies are slightly lower for the iron than for the cobalt compound. We could not however observe any significant difference in the C—N bond distances.

Experimental top

[Ni(en)2]3[Fe(CN)6]2·3H2O, (I): K3Fe(CN)6 (0.825 g, 2.5 mmol) was added to Ni(NO3)2·6H2O (1.454 g, 5 mmol) and ethylenediamine (0.901 mg 15 mmol) in water (100 ml), the colour changed from violet to yellow and then brown. Black crystals appeared after 3–4 d. IR spectra, KBr disc, recorded on a Perkin Elmer FT—IR spectrometer showed ν(CN) 2106, 2128, 2153 cm-1. [Ni(en)2]3[Co(CN)6]23.H2O, (II): as for (I) except that K3Fe(CN)6 was replaced by K3Co(CN)6, the solution remained violet and violet crystals appeared after a few days. IR spectra, KBr disc ν(CN) 2118, 2141, 2164 cm-1.

Refinement top

The crystals were cooled to 100 K by a stream of dry nitrogen produced by an Oxford Cryostream cooler (1986).

Computing details top

For both compounds, data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT. Program(s) used to solve structure: SIR97 (Cascarano et al., 1996) and KRYSTAL (Hazell, 1995)' for (I); SIR97 (Cascarano et al., 1996) and KRYSTAL (Hazell, 1995) for (II). Program(s) used to refine structure: modified ORFLS (1962) and KRYSTAL for (I); modified ORFLS(1962) and KRYSTAL for (II). For both compounds, molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and KRYSTAL; software used to prepare material for publication: KRYSTAL.

Figures top
[Figure 1] Fig. 1. View of (I) showing the labelling of the non-H atoms. Displacement ellipsoids are shown at 50% probability levels; H atoms are omitted [symmetry codes: (i) 1 - x, 2 - y, -z; (ii) 1 - x, 1 - y, -z; (iii) x, 1 + y, z].
[Figure 2] Fig. 2. The structure as viewed parallel to the a axis. The cell chosen by Ohba et al. is shown as b' and c'.
(I) insert name here top
Crystal data top
[{Ni(C2H8N2)2}3{Fe(CN)6}2]·3H2O]Z = 2
Mr = 1014.72F(000) = 1052.0
Triclinic, P1Dx = 1.591 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 9.6424 (9) ÅCell parameters from 8192 reflections
b = 14.861 (2) Åθ = 2.3–30.4°
c = 17.021 (2) ŵ = 2.04 mm−1
α = 107.604 (3)°T = 120 K
β = 101.474 (2)°Block, black
γ = 106.528 (2)°0.40 × 0.20 × 0.20 mm
V = 2117.6 (4) Å3
Data collection top
Siemens SMART CCD
diffractometer		10994 independent reflections
Radiation source: x-ray tube7683 reflections with I > 3σ(I)
Graphite monochromatorRint = 0.017
ω rotation scans with narrow framesθmax = 29.0°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −9→13
Tmin = 0.505, Tmax = 0.650k = −20→20
19479 measured reflectionsl = −23→23
Refinement top
Refinement on F0 constraints
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.0241/{[σcs(F2) + 1.03F2]1/2-|F|}2
wR(F2) = 0.033(Δ/σ)max = 0.002
S = 1.14Δρmax = 0.52 (7) e Å−3
7456 reflectionsΔρmin = −0.37 (7) e Å−3
509 parametersExtinction correction: B-C type 1 Lorentzian isotropic Becker and Coppens (1974)
0 restraintsExtinction coefficient: 19 (4)
Crystal data top
[{Ni(C2H8N2)2}3{Fe(CN)6}2]·3H2O]γ = 106.528 (2)°
Mr = 1014.72V = 2117.6 (4) Å3
Triclinic, P1Z = 2
a = 9.6424 (9) ÅMo Kα radiation
b = 14.861 (2) ŵ = 2.04 mm−1
c = 17.021 (2) ÅT = 120 K
α = 107.604 (3)°0.40 × 0.20 × 0.20 mm
β = 101.474 (2)°
Data collection top
Siemens SMART CCD
diffractometer		10994 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		7683 reflections with I > 3σ(I)
Tmin = 0.505, Tmax = 0.650Rint = 0.017
19479 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0240 restraints
wR(F2) = 0.033H-atom parameters constrained
S = 1.14Δρmax = 0.52 (7) e Å−3
7456 reflectionsΔρmin = −0.37 (7) e Å−3
509 parameters
Special details top

Refinement. Sfls: F calc weight full matrix

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ni10.23657 (3)0.67917 (2)0.37010 (2)0.0097 (2)
Ni20.23658 (3)0.18374 (2)0.37655 (2)0.0096 (2)
Ni30.500001.000000.000000.0113 (2)
Ni40.500000.500000.000000.0114 (2)
Fe10.51533 (3)0.94423 (2)0.27531 (2)0.0089 (2)
Fe20.51459 (3)0.43636 (2)0.27145 (2)0.0091 (2)
N10.3703 (2)0.1012 (1)0.3413 (1)0.015 (1)
N20.3977 (2)0.8146 (1)0.3770 (1)0.014 (1)
N30.2006 (2)0.8134 (1)0.1372 (1)0.019 (1)
N40.7101 (2)0.8190 (1)0.2173 (1)0.021 (1)
N50.5747 (2)1.0102 (1)0.1268 (1)0.015 (1)
N60.8111 (2)1.1039 (1)0.4163 (1)0.017 (1)
N70.2279 (2)0.2759 (1)0.1228 (1)0.024 (1)
N80.6880 (2)0.3000 (1)0.1983 (1)0.021 (1)
N90.5548 (2)0.5211 (1)0.1305 (1)0.017 (1)
N100.8103 (2)0.5991 (1)0.4110 (1)0.017 (1)
N110.3689 (2)0.5937 (1)0.3358 (1)0.015 (1)
N120.3986 (2)0.3176 (1)0.3811 (1)0.014 (1)
N130.0857 (2)0.5432 (1)0.3680 (1)0.013 (1)
N140.3191 (2)0.7094 (1)0.5041 (1)0.014 (1)
N150.0855 (2)0.7558 (1)0.3902 (1)0.014 (1)
N160.1253 (2)0.6457 (1)0.2390 (1)0.015 (1)
N170.0877 (2)0.0468 (1)0.3746 (1)0.014 (1)
N180.3199 (2)0.2135 (1)0.5106 (1)0.013 (1)
N190.0875 (2)0.2610 (1)0.3979 (1)0.013 (1)
N200.1215 (2)0.1489 (1)0.2454 (1)0.014 (1)
N210.6080 (2)0.8993 (1)−0.0449 (1)0.017 (1)
N220.7103 (2)1.1114 (1)0.0210 (1)0.015 (1)
N230.2888 (2)0.5135 (1)0.0008 (1)0.018 (1)
N240.5718 (2)0.6578 (1)0.0311 (1)0.017 (1)
C10.4221 (2)1.0418 (1)0.3157 (1)0.012 (1)
C20.4502 (2)0.8694 (1)0.3459 (1)0.012 (1)
C30.3198 (2)0.8587 (1)0.1879 (1)0.013 (1)
C40.6313 (2)0.8603 (1)0.2391 (1)0.015 (1)
C50.5613 (2)0.9939 (1)0.1872 (1)0.013 (1)
C60.7016 (2)1.0421 (1)0.3643 (1)0.013 (1)
C70.3324 (2)0.3367 (1)0.1796 (1)0.016 (1)
C80.6236 (2)0.3487 (1)0.2286 (1)0.015 (1)
C90.5498 (2)0.4956 (1)0.1874 (1)0.013 (1)
C100.6995 (2)0.5367 (1)0.3597 (1)0.012 (1)
C110.4183 (2)0.5326 (1)0.3115 (1)0.013 (1)
C120.4516 (2)0.3666 (1)0.3457 (1)0.012 (1)
C130.1535 (2)0.5320 (1)0.4489 (1)0.015 (1)
C140.2068 (2)0.6343 (1)0.5230 (1)0.015 (1)
C150.0299 (2)0.7730 (2)0.3106 (1)0.017 (1)
C16−0.0090 (2)0.6751 (2)0.2335 (1)0.019 (1)
C170.1581 (2)0.0351 (1)0.4544 (1)0.016 (1)
C180.2098 (2)0.1370 (2)0.5292 (1)0.015 (1)
C190.0359 (2)0.2812 (1)0.3195 (1)0.016 (1)
C20−0.0066 (2)0.1847 (2)0.2407 (1)0.019 (1)
C210.7450 (2)0.9580 (2)−0.0610 (1)0.019 (1)
C220.8211 (2)1.0603 (2)0.0138 (1)0.020 (1)
C230.3232 (3)0.6220 (2)0.0523 (1)0.022 (1)
C240.4357 (3)0.6860 (2)0.0220 (1)0.021 (1)
O10.9345 (2)0.4272 (1)0.1522 (1)0.049 (1)
O20.0379 (2)0.3366 (1)0.0188 (1)0.026 (1)
O3−0.0298 (2)−0.0836 (1)0.1653 (1)0.037 (1)
H1a1.00000.41290.18260.050*
H1b0.86510.38330.16300.050*
H2a−0.04000.2800−0.02000.050*
H2b0.08000.30000.04000.050*
H3a−0.1000−0.12000.18000.050*
H3b0.0160−0.12490.14830.050*
HN13a−0.01140.54720.36610.016*
HN13b0.07540.48710.31880.016*
HN14a0.41520.70260.51730.016*
HN14b0.32920.77630.53770.016*
HN15a0.00210.71560.40170.017*
HN15b0.13710.81900.43790.017*
HN16a0.19300.68260.21620.018*
HN16b0.09390.57500.20650.018*
HN17a0.0764−0.00890.32490.017*
HN17b−0.00920.05060.37400.017*
HN18a0.32820.27980.54430.016*
HN18b0.41700.20800.52370.016*
HN19a0.13900.32330.44670.015*
HN19b0.00260.22030.40790.015*
HN20a0.08380.07750.21420.017*
HN20b0.19010.18160.22060.017*
HN21a0.63740.8733−0.00240.021*
HN21b0.54120.8447−0.09710.021*
HN22a0.70131.1405−0.02150.017*
HN22b0.74261.16320.07710.017*
HN23a0.22630.4945−0.05680.022*
HN23b0.23850.47170.02690.022*
HN24a0.63800.69310.08900.020*
HN24b0.62370.6750−0.00740.020*
H13a0.07940.48250.45880.018*
H13b0.23740.51160.44440.018*
H14a0.25290.63000.57580.018*
H14b0.12260.65430.52780.018*
H15a−0.05830.78940.31110.020*
H15b0.10680.82690.30730.020*
H16a−0.03620.68570.18110.022*
H16b−0.09170.62280.23450.022*
H17a0.24300.01610.44910.019*
H17b0.0858−0.01560.46420.019*
H18a0.12470.15570.53440.018*
H18b0.25700.13250.58170.018*
H19a0.11550.33460.31730.020*
H19b−0.05030.29990.32050.020*
H20a−0.09370.13390.23970.022*
H20b−0.02840.19830.18950.022*
H21a0.81320.9228−0.06420.023*
H21b0.71580.9671−0.11390.023*
H22a0.90611.10080.00370.024*
H22b0.85451.05090.06610.024*
H23a0.23240.63610.04360.026*
H23b0.36590.63670.11210.026*
H24a0.46430.75580.05650.025*
H24b0.39090.6739−0.03700.025*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0102 (1)0.0094 (1)0.0106 (1)0.0041 (1)0.0039 (1)0.0045 (1)
Ni20.0104 (1)0.0096 (1)0.0100 (1)0.0044 (1)0.0038 (1)0.0045 (1)
Ni30.0147 (2)0.0111 (2)0.0086 (2)0.0042 (1)0.0043 (1)0.0046 (1)
Ni40.0161 (2)0.0108 (2)0.0089 (2)0.0054 (1)0.0052 (1)0.0048 (1)
Fe10.0098 (2)0.0096 (1)0.0081 (1)0.0040 (1)0.0030 (1)0.0040 (1)
Fe20.0104 (2)0.0094 (1)0.0083 (1)0.0040 (1)0.0032 (1)0.0040 (1)
N20.013 (1)0.014 (1)0.014 (1)0.004 (1)0.003 (1)0.006 (1)
N30.017 (1)0.020 (1)0.017 (1)0.005 (1)0.004 (1)0.007 (1)
N40.021 (1)0.024 (1)0.017 (1)0.012 (1)0.003 (1)0.004 (1)
N50.015 (1)0.017 (1)0.012 (1)0.005 (1)0.004 (1)0.006 (1)
N60.017 (1)0.019 (1)0.015 (1)0.007 (1)0.006 (1)0.004 (1)
N70.026 (1)0.018 (1)0.021 (1)0.003 (1)−0.002 (1)0.006 (1)
N80.023 (1)0.022 (1)0.021 (1)0.013 (1)0.008 (1)0.008 (1)
N90.023 (1)0.015 (1)0.013 (1)0.008 (1)0.006 (1)0.005 (1)
N100.014 (1)0.019 (1)0.016 (1)0.006 (1)0.005 (1)0.004 (1)
N110.014 (1)0.015 (1)0.017 (1)0.006 (1)0.007 (1)0.008 (1)
N10.015 (1)0.015 (1)0.016 (1)0.007 (1)0.007 (1)0.007 (1)
N120.014 (1)0.013 (1)0.015 (1)0.005 (1)0.004 (1)0.006 (1)
N130.013 (1)0.012 (1)0.015 (1)0.005 (1)0.004 (1)0.005 (1)
N140.012 (1)0.014 (1)0.015 (1)0.004 (1)0.004 (1)0.006 (1)
N150.015 (1)0.014 (1)0.012 (1)0.007 (1)0.003 (1)0.005 (1)
N160.017 (1)0.013 (1)0.013 (1)0.005 (1)0.005 (1)0.004 (1)
N170.015 (1)0.013 (1)0.016 (1)0.006 (1)0.006 (1)0.006 (1)
N180.013 (1)0.015 (1)0.013 (1)0.005 (1)0.004 (1)0.006 (1)
N190.014 (1)0.013 (1)0.011 (1)0.006 (1)0.004 (1)0.004 (1)
N200.017 (1)0.012 (1)0.012 (1)0.006 (1)0.004 (1)0.004 (1)
N210.021 (1)0.013 (1)0.016 (1)0.006 (1)0.005 (1)0.004 (1)
N220.016 (1)0.014 (1)0.013 (1)0.005 (1)0.004 (1)0.006 (1)
N230.020 (1)0.017 (1)0.019 (1)0.006 (1)0.008 (1)0.007 (1)
N240.022 (1)0.015 (1)0.013 (1)0.008 (1)0.006 (1)0.006 (1)
C10.009 (1)0.014 (1)0.011 (1)0.002 (1)0.002 (1)0.005 (1)
C20.010 (1)0.013 (1)0.011 (1)0.004 (1)0.001 (1)0.003 (1)
C30.018 (1)0.013 (1)0.012 (1)0.008 (1)0.007 (1)0.007 (1)
C40.014 (1)0.016 (1)0.013 (1)0.006 (1)0.003 (1)0.006 (1)
C50.010 (1)0.013 (1)0.013 (1)0.004 (1)0.002 (1)0.004 (1)
C60.015 (1)0.015 (1)0.012 (1)0.008 (1)0.006 (1)0.007 (1)
C70.019 (1)0.016 (1)0.016 (1)0.008 (1)0.006 (1)0.010 (1)
C80.017 (1)0.014 (1)0.013 (1)0.005 (1)0.003 (1)0.006 (1)
C90.014 (1)0.011 (1)0.012 (1)0.004 (1)0.004 (1)0.002 (1)
C100.014 (1)0.015 (1)0.012 (1)0.008 (1)0.007 (1)0.007 (1)
C110.012 (1)0.015 (1)0.012 (1)0.003 (1)0.004 (1)0.007 (1)
C120.011 (1)0.012 (1)0.010 (1)0.005 (1)0.001 (1)0.003 (1)
C130.016 (1)0.014 (1)0.020 (1)0.006 (1)0.009 (1)0.010 (1)
C140.016 (1)0.017 (1)0.015 (1)0.007 (1)0.007 (1)0.010 (1)
C150.019 (1)0.020 (1)0.017 (1)0.011 (1)0.005 (1)0.010 (1)
C160.017 (1)0.021 (1)0.015 (1)0.006 (1)0.000 (1)0.006 (1)
C170.017 (1)0.015 (1)0.021 (1)0.007 (1)0.009 (1)0.011 (1)
C180.014 (1)0.019 (1)0.016 (1)0.006 (1)0.007 (1)0.010 (1)
C190.018 (1)0.017 (1)0.015 (1)0.010 (1)0.004 (1)0.006 (1)
C200.018 (1)0.020 (1)0.014 (1)0.009 (1)−0.001 (1)0.003 (1)
C210.019 (1)0.021 (1)0.018 (1)0.009 (1)0.008 (1)0.007 (1)
C220.017 (1)0.020 (1)0.019 (1)0.006 (1)0.004 (1)0.007 (1)
C230.025 (1)0.021 (1)0.020 (1)0.013 (1)0.007 (1)0.004 (1)
C240.029 (1)0.017 (1)0.018 (1)0.012 (1)0.005 (1)0.007 (1)
O10.044 (1)0.027 (1)0.053 (1)−0.005 (1)0.024 (1)−0.003 (1)
O20.024 (1)0.023 (1)0.025 (1)0.006 (1)−0.001 (1)0.007 (1)
O30.037 (1)0.018 (1)0.055 (1)0.009 (1)0.026 (1)0.007 (1)
Geometric parameters (Å, º) top
Fe1—C11.941 (2)C13—C141.519 (3)
Fe1—C21.946 (2)C15—C161.523 (3)
Fe1—C31.939 (2)C17—C181.522 (3)
Fe1—C41.947 (2)C19—C201.518 (3)
Fe1—C51.934 (2)C21—C221.514 (3)
Fe1—C61.933 (2)C23—C241.509 (3)
Fe2—C71.937 (2)N13—HN13a0.950
Fe2—C81.960 (2)N13—HN13b0.950
Fe2—C91.929 (2)N14—HN14b0.950
Fe2—C101.930 (2)N14—HN14a0.950
Fe2—C111.947 (2)N15—HN15a0.950
Fe2—C121.945 (2)N15—HN15b0.950
Ni1—N22.117 (2)N16—HN16b0.950
Ni1—N112.086 (2)N16—HN16a0.950
Ni1—N132.113 (2)N17—HN17a0.950
Ni1—N142.120 (2)N17—HN17b0.950
Ni1—N152.107 (2)N18—HN18a0.950
Ni1—N162.110 (2)N18—HN18b0.950
Ni2—N12.071 (2)N19—HN19b0.950
Ni2—N122.119 (2)N19—HN19a0.950
Ni2—N172.117 (2)N20—HN20a0.950
Ni2—N182.122 (2)N20—HN20b0.950
Ni2—N192.100 (2)N21—HN21b0.950
Ni2—N202.115 (2)N21—HN21a0.950
Ni3—N52.079 (2)N22—HN22a0.950
Ni3—N5i2.079 (2)N22—HN22b0.950
Ni3—N212.103 (2)N23—HN23a0.950
Ni3—N21i2.103 (2)N23—HN23b0.950
Ni3—N222.104 (2)N24—HN24a0.950
Ni3—N22i2.104 (2)N24—HN24b0.950
Ni4—N92.081 (2)C13—H13a0.950
Ni4—N9ii2.081 (2)C13—H13b0.950
Ni4—N232.105 (2)C14—H14b0.950
Ni4—N23ii2.105 (2)C14—H14a0.950
Ni4—N242.107 (2)C15—H15a0.950
Ni4—N24ii2.107 (2)C15—H15b0.950
N1—C1iii1.150 (3)C16—H16b0.950
N2—C21.155 (2)C16—H16a0.950
N3—C31.154 (3)C17—H17a0.950
N4—C41.153 (3)C17—H17b0.950
N5—C51.147 (2)C18—H18a0.950
N6—C61.152 (3)C18—H18b0.950
N7—C71.155 (3)C19—H19a0.950
N8—C81.153 (3)C19—H19b0.950
N9—C91.146 (2)C20—H20a0.950
N10—C101.157 (3)C20—H20b0.950
N11—C111.149 (3)C21—H21b0.950
N12—C121.154 (2)C21—H21a0.950
N13—C131.481 (2)C22—H22b0.950
N14—C141.479 (2)C22—H22a0.950
N15—C151.478 (2)C23—H23a0.950
N16—C161.475 (3)C23—H23b0.950
N17—C171.476 (3)C24—H24a0.950
N18—C181.479 (2)C24—H24b0.950
N19—C191.477 (2)O1—H1a0.851
N20—C201.476 (3)O1—H1b0.884
N21—C211.488 (3)O2—H2b0.881
N22—C221.480 (3)O2—H2a0.902
N23—C231.485 (3)O3—H3b0.868
N24—C241.480 (3)O3—H3a0.869
C1—Fe1—C293.67 (8)Ni3—N21—C21107.1 (1)
C1—Fe1—C387.13 (8)Ni3—N22—C22107.1 (1)
C1—Fe1—C4173.17 (8)Ni4—N23—C23106.2 (1)
C1—Fe1—C592.74 (8)Ni4—N24—C24108.4 (1)
C1—Fe1—C686.53 (8)N13—C13—C14107.8 (2)
C2—Fe1—C386.78 (8)N14—C14—C13108.2 (2)
C2—Fe1—C490.34 (8)N15—C15—C16107.5 (2)
C2—Fe1—C5169.15 (8)N16—C16—C15108.9 (2)
C2—Fe1—C695.44 (8)N17—C17—C18107.4 (2)
C3—Fe1—C498.63 (8)N18—C18—C17108.1 (2)
C3—Fe1—C584.80 (8)N19—C19—C20108.1 (2)
C3—Fe1—C6173.40 (8)N20—C20—C19109.5 (2)
C4—Fe1—C584.17 (8)N21—C21—C22107.8 (2)
C4—Fe1—C687.59 (8)N22—C22—C21109.1 (2)
C5—Fe1—C693.68 (8)N23—C23—C24108.1 (2)
C7—Fe2—C887.82 (8)N24—C24—C23108.6 (2)
C7—Fe2—C985.41 (8)HN13a—N13—HN13b109.5
C7—Fe2—C10177.85 (9)C13—N13—HN13a110.2
C7—Fe2—C1194.54 (8)C13—N13—HN13b110.2
C7—Fe2—C1287.22 (8)HN14a—N14—HN14b109.5
C8—Fe2—C988.52 (8)C14—N14—HN14b110.1
C8—Fe2—C1091.26 (8)C14—N14—HN14a110.0
C8—Fe2—C11174.87 (8)HN15a—N15—HN15b109.5
C8—Fe2—C1293.18 (8)C15—N15—HN15a109.8
C9—Fe2—C1092.63 (8)C15—N15—HN15b109.8
C9—Fe2—C1187.12 (8)HN16a—N16—HN16b109.5
C9—Fe2—C12172.38 (8)C16—N16—HN16b109.6
C10—Fe2—C1186.22 (8)C16—N16—HN16a109.6
C10—Fe2—C1294.76 (8)HN17a—N17—HN17b109.4
C11—Fe2—C1291.49 (8)C17—N17—HN17a110.3
Fe1—C1—N1iv178.3 (2)C17—N17—HN17b110.2
Fe1—C2—N2170.5 (2)HN18a—N18—HN18b109.5
Fe1—C3—N3175.3 (2)C18—N18—HN18a110.0
Fe1—C4—N4173.1 (2)C18—N18—HN18b110.0
Fe1—C5—N5170.5 (2)HN19a—N19—HN19b109.5
Fe1—C6—N6176.9 (2)C19—N19—HN19b109.9
Fe2—C7—N7176.9 (2)C19—N19—HN19a109.9
Fe2—C8—N8174.7 (2)HN20a—N20—HN20b109.5
Fe2—C9—N9171.6 (2)C20—N20—HN20a109.5
Fe2—C10—N10177.6 (2)C20—N20—HN20b109.5
Fe2—C11—N11176.1 (2)HN21a—N21—HN21b109.5
Fe2—C12—N12171.6 (2)C21—N21—HN21b110.1
N2—Ni1—N1193.36 (7)C21—N21—HN21a110.1
N2—Ni1—N13176.77 (6)HN22a—N22—HN22b109.5
N2—Ni1—N1494.78 (6)C22—N22—HN22a110.1
N2—Ni1—N1589.00 (6)C22—N22—HN22b110.1
N2—Ni1—N1690.05 (6)HN23a—N23—HN23b109.5
N11—Ni1—N1384.68 (6)C23—N23—HN23a110.3
N11—Ni1—N1493.80 (6)C23—N23—HN23b110.3
N11—Ni1—N15173.42 (8)HN24a—N24—HN24b109.5
N11—Ni1—N1691.89 (6)C24—N24—HN24a109.7
N13—Ni1—N1482.80 (6)C24—N24—HN24b109.7
N13—Ni1—N1593.23 (6)H13a—C13—H13b109.4
N13—Ni1—N1692.58 (6)N13—C13—H13a109.9
N14—Ni1—N1592.11 (6)C14—C13—H13a109.9
N14—Ni1—N16172.30 (7)N13—C13—H13b109.9
N15—Ni1—N1681.96 (6)C14—C13—H13b109.9
N1—Ni2—N1291.31 (7)H14a—C14—H14b109.5
N1—Ni2—N1785.22 (6)N14—C14—H14b109.8
N1—Ni2—N1894.18 (6)C13—C14—H14b109.8
N1—Ni2—N19173.75 (7)N14—C14—H14a109.8
N1—Ni2—N2091.75 (6)C13—C14—H14a109.8
N12—Ni2—N17175.95 (6)H15a—C15—H15b109.5
N12—Ni2—N1895.64 (6)N15—C15—H15a109.9
N12—Ni2—N1989.57 (6)C16—C15—H15a109.9
N12—Ni2—N2090.17 (6)N15—C15—H15b110.0
N17—Ni2—N1882.57 (6)C16—C15—H15b110.0
N17—Ni2—N1994.10 (6)H16a—C16—H16b109.5
N17—Ni2—N2092.02 (6)N16—C16—H16b109.6
N18—Ni2—N1991.89 (6)C15—C16—H16b109.6
N18—Ni2—N20171.60 (6)N16—C16—H16a109.6
N19—Ni2—N2082.06 (6)C15—C16—H16a109.6
N5—Ni3—N5i180.00H17a—C17—H17b109.4
N5—Ni3—N2192.50 (7)N17—C17—H17a110.0
N5—Ni3—N21i87.50 (7)C18—C17—H17a110.0
N5i—Ni3—N2187.50 (7)N17—C17—H17b110.0
N5i—Ni3—N21i92.50 (7)C18—C17—H17b110.0
N5i—Ni3—N2290.47 (6)H18a—C18—H18b109.5
N5i—Ni3—N22i89.53 (6)N18—C18—H18a109.8
N5—Ni3—N2289.53 (6)C17—C18—H18a109.8
N5—Ni3—N22i90.47 (6)N18—C18—H18b109.8
N21—Ni3—N21i180.00C17—C18—H18b109.8
N21—Ni3—N2283.33 (6)H19a—C19—H19b109.5
N21—Ni3—N22i96.67 (6)N19—C19—H19a109.8
N21i—Ni3—N2296.67 (6)C20—C19—H19a109.8
N21i—Ni3—N22i83.33 (6)N19—C19—H19b109.8
N22—Ni3—N22i180.00C20—C19—H19b109.8
N9—Ni4—N9ii180.00H20a—C20—H20b109.5
N9—Ni4—N2390.92 (7)N20—C20—H20a109.5
N9—Ni4—N23ii89.08 (7)C19—C20—H20a109.5
N9—Ni4—N2491.65 (6)N20—C20—H20b109.4
N9—Ni4—N24ii88.35 (6)C19—C20—H20b109.4
N9ii—Ni4—N2389.08 (7)H21a—C21—H21b109.4
N9ii—Ni4—N23ii90.92 (7)N21—C21—H21b109.9
N9ii—Ni4—N2488.35 (6)C22—C21—H21b109.9
N9ii—Ni4—N24ii91.65 (6)N21—C21—H21a109.9
N23—Ni4—N23ii180.00C22—C21—H21a109.9
N23—Ni4—N2482.77 (7)H22a—C22—H22b109.5
N23—Ni4—N24ii97.23 (7)N22—C22—H22b109.6
N23ii—Ni4—N2497.23 (7)C21—C22—H22b109.6
N23ii—Ni4—N24ii82.77 (7)N22—C22—H22a109.6
N24—Ni4—N24ii180.00C21—C22—H22a109.6
Ni1—N2—C2152.0 (2)H23a—C23—H23b109.5
Ni1—N11—C11168.1 (2)N23—C23—H23a109.8
Ni2—N1—C1iii168.6 (2)C24—C23—H23a109.8
Ni2—N12—C12149.7 (2)N23—C23—H23b109.8
Ni3—N5—C5155.0 (2)C24—C23—H23b109.8
Ni4—N9—C9154.4 (2)H24a—C24—H24b109.5
Ni1—N13—C13106.5 (1)N24—C24—H24a109.7
Ni1—N14—C14107.2 (1)C23—C24—H24a109.7
Ni1—N15—C15108.2 (1)N24—C24—H24b109.7
Ni1—N16—C16109.1 (1)C23—C24—H24b109.7
Ni2—N17—C17106.4 (1)H1a—O1—H1b86.4
Ni2—N18—C18107.3 (1)H2a—O2—H2b91.1
Ni2—N19—C19107.8 (1)H3a—O3—H3b101.6
Ni2—N20—C20109.4 (1)
Symmetry codes: (i) −x+1, −y+2, −z; (ii) −x+1, −y+1, −z; (iii) x, y−1, z; (iv) x, y+1, z.
(II) insert name here top
Crystal data top
[{Ni(C2H8N2)2}3{Co(CN)6}2]·3H2O]Z = 2
Mr = 1020.90F(000) = 1056
Triclinic, P1Dx = 1.618 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 9.6303 (8) ÅCell parameters from 7727 reflections
b = 14.787 (1) Åθ = 1.6–29.6°
c = 16.951 (1) ŵ = 2.16 mm−1
α = 107.500 (2)°T = 120 K
β = 101.464 (2)°Needle, violet
γ = 106.652 (2)°0.52 × 0.18 × 0.18 mm
V = 2095.6 (3) Å3
Data collection top
Siemens SMART CCD
diffractometer		9897 independent reflections
Radiation source: x-ray tube6342 reflections with I > 3σ(I)
Graphite monochromatorRint = 0.020
ω rotation scans with narrow framesθmax = 28.0°, θmin = 1.6°
Absorption correction: multi-scan
(SADABS: Sheldrick, 1996)		h = −13→13
Tmin = 0.382, Tmax = 0.678k = −20→14
17341 measured reflectionsl = −22→22
Refinement top
Refinement on F0 constraints
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.0281/{[σcs(F2) + 1.03F2]1/2-|F|}2
wR(F2) = 0.040(Δ/σ)max = 0.001
S = 1.39Δρmax = 1.16 (8) e Å−3
6342 reflectionsΔρmin = −0.63 (8) e Å−3
509 parametersExtinction correction: B-C type 1 Lorentzian isotropic Becker & Coppens (1974)
0 restraintsExtinction coefficient: 18 (5)
Crystal data top
[{Ni(C2H8N2)2}3{Co(CN)6}2]·3H2O]γ = 106.652 (2)°
Mr = 1020.90V = 2095.6 (3) Å3
Triclinic, P1Z = 2
a = 9.6303 (8) ÅMo Kα radiation
b = 14.787 (1) ŵ = 2.16 mm−1
c = 16.951 (1) ÅT = 120 K
α = 107.500 (2)°0.52 × 0.18 × 0.18 mm
β = 101.464 (2)°
Data collection top
Siemens SMART CCD
diffractometer		9897 independent reflections
Absorption correction: multi-scan
(SADABS: Sheldrick, 1996)		6342 reflections with I > 3σ(I)
Tmin = 0.382, Tmax = 0.678Rint = 0.020
17341 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0280 restraints
wR(F2) = 0.040H-atom parameters constrained
S = 1.39Δρmax = 1.16 (8) e Å−3
6342 reflectionsΔρmin = −0.63 (8) e Å−3
509 parameters
Special details top

Refinement. Sfls: F calc weight full matrix

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ni10.23661 (4)0.68020 (3)0.37062 (2)0.0101 (2)
Ni20.23772 (4)0.18375 (3)0.37629 (2)0.0098 (2)
Ni30.500001.000000.000000.0120 (3)
Ni40.500000.500000.000000.0121 (3)
Co10.51336 (4)0.94488 (3)0.27487 (2)0.0094 (3)
Co20.51113 (4)0.43813 (3)0.27140 (2)0.0098 (3)
N20.3972 (3)0.8174 (2)0.3770 (1)0.014 (2)
N30.2038 (3)0.8121 (2)0.1378 (2)0.021 (2)
N40.7003 (3)0.8170 (2)0.2172 (2)0.023 (2)
N50.5739 (3)1.0134 (2)0.1291 (1)0.016 (2)
N60.8070 (3)1.1017 (2)0.4140 (1)0.016 (2)
N70.2252 (3)0.2810 (2)0.1263 (2)0.031 (2)
N80.6812 (3)0.3024 (2)0.2000 (2)0.023 (2)
N90.5551 (3)0.5211 (2)0.1315 (1)0.017 (2)
N100.8059 (3)0.5968 (2)0.4088 (1)0.018 (2)
N110.3683 (3)0.5940 (2)0.3356 (1)0.015 (2)
N10.3706 (3)0.1000 (2)0.3400 (1)0.014 (2)
N120.3999 (3)0.3183 (2)0.3800 (1)0.013 (2)
N130.0860 (3)0.5438 (2)0.3694 (1)0.014 (2)
N140.3201 (3)0.7107 (2)0.5052 (1)0.014 (2)
N150.0843 (3)0.7564 (2)0.3908 (1)0.013 (2)
N160.1242 (3)0.6456 (2)0.2390 (1)0.015 (2)
N170.0876 (3)0.0462 (2)0.3748 (1)0.014 (2)
N180.3229 (3)0.2136 (2)0.5111 (1)0.014 (2)
N190.0886 (3)0.2615 (2)0.3988 (1)0.013 (2)
N200.1203 (3)0.1485 (2)0.2449 (1)0.015 (2)
N210.6074 (3)0.8976 (2)−0.0424 (1)0.019 (2)
N220.7115 (3)1.1106 (2)0.0199 (1)0.016 (2)
N230.2868 (3)0.5102 (2)0.0001 (2)0.020 (2)
N240.5690 (3)0.6582 (2)0.0305 (1)0.018 (2)
C10.4226 (3)1.0407 (2)0.3150 (2)0.012 (2)
C20.4496 (3)0.8725 (2)0.3454 (2)0.013 (2)
C30.3234 (3)0.8587 (2)0.1889 (2)0.015 (2)
C40.6228 (3)0.8598 (2)0.2386 (2)0.016 (2)
C50.5599 (3)0.9962 (2)0.1895 (2)0.012 (2)
C60.6965 (3)1.0407 (2)0.3621 (2)0.012 (2)
C70.3299 (3)0.3419 (2)0.1826 (2)0.019 (2)
C80.6169 (3)0.3514 (2)0.2297 (2)0.016 (2)
C90.5473 (3)0.4955 (2)0.1886 (2)0.013 (2)
C100.6947 (3)0.5354 (2)0.3577 (2)0.013 (2)
C110.4167 (3)0.5326 (2)0.3108 (2)0.012 (2)
C120.4511 (3)0.3688 (2)0.3443 (2)0.013 (2)
C130.1542 (3)0.5325 (2)0.4505 (2)0.015 (2)
C140.2082 (3)0.6352 (2)0.5249 (2)0.015 (2)
C150.0273 (3)0.7725 (2)0.3104 (2)0.018 (2)
C16−0.0113 (3)0.6747 (2)0.2337 (2)0.019 (2)
C170.1585 (3)0.0345 (2)0.4549 (2)0.017 (2)
C180.2117 (3)0.1370 (2)0.5302 (2)0.016 (2)
C190.0352 (3)0.2810 (2)0.3196 (2)0.018 (2)
C20−0.0080 (3)0.1846 (2)0.2407 (2)0.020 (2)
C210.7436 (3)0.9548 (2)−0.0602 (2)0.020 (2)
C220.8217 (3)1.0580 (2)0.0132 (2)0.022 (2)
C230.3189 (4)0.6190 (2)0.0511 (2)0.024 (2)
C240.4310 (4)0.6845 (2)0.0208 (2)0.023 (2)
O10.9410 (3)0.4240 (2)0.1595 (2)0.060 (2)
O20.0341 (3)0.3357 (2)0.0196 (1)0.039 (2)
O3−0.0363 (3)−0.0853 (2)0.1640 (2)0.050 (2)
H1a0.95260.38100.10780.050*
H1b0.86060.37700.16740.050*
H2a−0.03570.2873−0.03510.050*
H2b0.08690.29800.03970.050*
H3a−0.1231−0.12020.17690.050*
H3b0.0048−0.13610.14730.050*
HN13a0.07520.48740.32000.017*
HN13b−0.01110.54800.36780.017*
HN14a0.33040.77790.53870.017*
HN14b0.41650.70410.51810.017*
HN15a0.13590.82040.43830.016*
HN15b0.00140.71600.40290.016*
HN16a0.09310.57460.20670.018*
HN16b0.19140.68280.21570.018*
HN17a0.0759−0.01000.32490.017*
HN17b−0.00920.05020.37430.017*
HN18a0.33240.28050.54500.017*
HN18b0.41960.20750.52370.017*
HN19a0.14070.32420.44750.015*
HN19b0.00410.22060.40960.015*
HN20a0.08210.07670.21380.017*
HN20b0.18830.18120.21950.017*
HN21a0.54000.8415−0.09400.022*
HN21b0.63720.87330.00150.022*
HN22a0.74451.16320.07590.019*
HN22b0.70291.1391−0.02330.019*
HN23a0.23760.46790.02660.024*
HN23b0.22390.4902−0.05780.024*
HN24a0.62080.6760−0.00800.022*
HN24b0.63500.69420.08880.022*
H13a0.23820.51210.44570.018*
H13b0.08010.48280.46050.018*
H14a0.12400.65520.53020.018*
H14b0.25510.63080.57780.018*
H15a0.10370.82680.30660.021*
H15b−0.06130.78860.31090.021*
H16a−0.09370.62190.23510.023*
H16b−0.03950.68490.18100.023*
H17a0.24310.01520.44940.020*
H17b0.0860−0.01610.46500.020*
H18a0.12710.15630.53570.019*
H18b0.25910.13220.58280.019*
H19a0.11450.33470.31690.021*
H19b−0.05110.29970.32100.021*
H20a−0.09520.13340.23980.024*
H20b−0.03030.19830.18930.024*
H21a0.71340.9628−0.11370.024*
H21b0.81120.9189−0.06320.024*
H22a0.85571.04980.06630.026*
H22b0.90661.09750.00190.026*
H23a0.36150.63420.11130.029*
H23b0.22710.63190.04190.029*
H24a0.38620.6719−0.03850.028*
H24b0.45800.75460.05520.028*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0101 (2)0.0100 (2)0.0119 (2)0.0045 (2)0.0048 (2)0.0050 (1)
Ni20.0099 (2)0.0101 (2)0.0114 (2)0.0047 (2)0.0048 (1)0.0049 (1)
Ni30.0153 (3)0.0122 (3)0.0097 (2)0.0047 (2)0.0056 (2)0.0051 (2)
Ni40.0167 (3)0.0115 (3)0.0100 (2)0.0060 (2)0.0063 (2)0.0049 (2)
Co10.0101 (2)0.0101 (2)0.0093 (2)0.0045 (2)0.0040 (2)0.0043 (2)
Co20.0113 (2)0.0099 (2)0.0093 (2)0.0044 (2)0.0038 (2)0.0041 (2)
N20.013 (1)0.015 (1)0.015 (1)0.005 (1)0.004 (1)0.007 (1)
N30.021 (2)0.022 (1)0.018 (1)0.005 (1)0.003 (1)0.008 (1)
N40.025 (2)0.025 (1)0.020 (1)0.015 (1)0.004 (1)0.004 (1)
N50.017 (1)0.018 (1)0.014 (1)0.007 (1)0.006 (1)0.007 (1)
N60.013 (1)0.017 (1)0.017 (1)0.006 (1)0.006 (1)0.005 (1)
N70.033 (2)0.024 (2)0.026 (2)0.001 (1)−0.006 (1)0.013 (1)
N80.028 (2)0.022 (1)0.025 (1)0.015 (1)0.012 (1)0.009 (1)
N90.021 (1)0.017 (1)0.016 (1)0.008 (1)0.007 (1)0.007 (1)
N100.017 (1)0.020 (1)0.015 (1)0.006 (1)0.007 (1)0.004 (1)
N110.013 (1)0.016 (1)0.020 (1)0.008 (1)0.008 (1)0.009 (1)
N10.013 (1)0.016 (1)0.017 (1)0.007 (1)0.007 (1)0.008 (1)
N120.013 (1)0.012 (1)0.016 (1)0.004 (1)0.005 (1)0.006 (1)
N130.014 (1)0.012 (1)0.018 (1)0.006 (1)0.006 (1)0.005 (1)
N140.011 (1)0.015 (1)0.018 (1)0.004 (1)0.006 (1)0.008 (1)
N150.014 (1)0.013 (1)0.013 (1)0.005 (1)0.003 (1)0.004 (1)
N160.017 (1)0.013 (1)0.015 (1)0.006 (1)0.007 (1)0.005 (1)
N170.014 (1)0.014 (1)0.016 (1)0.006 (1)0.006 (1)0.005 (1)
N180.015 (1)0.015 (1)0.015 (1)0.006 (1)0.006 (1)0.008 (1)
N190.014 (1)0.012 (1)0.012 (1)0.006 (1)0.004 (1)0.003 (1)
N200.017 (1)0.013 (1)0.013 (1)0.006 (1)0.005 (1)0.003 (1)
N210.022 (1)0.015 (1)0.017 (1)0.007 (1)0.007 (1)0.004 (1)
N220.016 (1)0.017 (1)0.013 (1)0.005 (1)0.004 (1)0.007 (1)
N230.020 (1)0.019 (1)0.021 (1)0.007 (1)0.007 (1)0.006 (1)
N240.022 (1)0.018 (1)0.016 (1)0.008 (1)0.007 (1)0.006 (1)
C10.011 (2)0.013 (1)0.012 (1)0.002 (1)0.005 (1)0.006 (1)
C20.011 (2)0.013 (1)0.013 (1)0.005 (1)0.001 (1)0.003 (1)
C30.020 (2)0.012 (1)0.014 (1)0.006 (1)0.008 (1)0.006 (1)
C40.015 (2)0.015 (1)0.014 (1)0.004 (1)0.001 (1)0.005 (1)
C50.008 (1)0.012 (1)0.015 (1)0.004 (1)0.003 (1)0.003 (1)
C60.013 (2)0.015 (1)0.014 (1)0.009 (1)0.008 (1)0.008 (1)
C70.022 (2)0.018 (2)0.017 (1)0.006 (1)0.004 (1)0.010 (1)
C80.021 (2)0.014 (1)0.015 (1)0.006 (1)0.006 (1)0.008 (1)
C90.015 (2)0.011 (1)0.014 (1)0.005 (1)0.006 (1)0.004 (1)
C100.018 (2)0.015 (1)0.013 (1)0.009 (1)0.010 (1)0.007 (1)
C110.010 (2)0.015 (1)0.010 (1)0.002 (1)0.003 (1)0.006 (1)
C120.011 (2)0.014 (1)0.012 (1)0.005 (1)0.002 (1)0.003 (1)
C130.016 (2)0.013 (1)0.021 (1)0.006 (1)0.009 (1)0.009 (1)
C140.015 (2)0.019 (2)0.017 (1)0.007 (1)0.008 (1)0.011 (1)
C150.018 (2)0.023 (2)0.020 (1)0.013 (1)0.007 (1)0.012 (1)
C160.016 (2)0.023 (2)0.016 (1)0.007 (1)0.002 (1)0.008 (1)
C170.017 (2)0.017 (2)0.022 (2)0.009 (1)0.011 (1)0.011 (1)
C180.015 (2)0.019 (2)0.017 (1)0.006 (1)0.009 (1)0.009 (1)
C190.020 (2)0.019 (2)0.018 (1)0.012 (1)0.005 (1)0.008 (1)
C200.018 (2)0.023 (2)0.016 (1)0.009 (1)0.000 (1)0.003 (1)
C210.019 (2)0.025 (2)0.020 (1)0.012 (1)0.009 (1)0.008 (1)
C220.018 (2)0.025 (2)0.024 (2)0.009 (1)0.007 (1)0.010 (1)
C230.027 (2)0.024 (2)0.024 (2)0.016 (1)0.008 (1)0.007 (1)
C240.031 (2)0.020 (2)0.020 (2)0.014 (1)0.006 (1)0.008 (1)
O10.058 (2)0.031 (1)0.053 (2)−0.015 (1)0.036 (2)−0.015 (1)
O20.033 (2)0.040 (2)0.035 (1)0.012 (1)0.000 (1)0.012 (1)
O30.061 (2)0.020 (1)0.065 (2)0.008 (1)0.039 (2)0.007 (1)
Geometric parameters (Å, º) top
Co1—C11.898 (3)C13—C141.518 (4)
Co1—C21.907 (3)C15—C161.514 (4)
Co1—C31.893 (3)C17—C181.523 (4)
Co1—C41.904 (3)C19—C201.512 (4)
Co1—C51.897 (3)C21—C221.507 (4)
Co1—C61.891 (3)C23—C241.512 (4)
Co2—C71.893 (3)N13—HN13a0.950
Co2—C81.917 (3)N13—HN13b0.950
Co2—C91.884 (3)N14—HN14a0.950
Co2—C101.893 (3)N14—HN14b0.950
Co2—C111.906 (3)N15—HN15a0.950
Co2—C121.903 (3)N15—HN15b0.950
Ni1—N22.127 (2)N16—HN16a0.950
Ni1—N112.088 (2)N16—HN16b0.950
Ni1—N132.111 (2)N17—HN17a0.950
Ni1—N142.120 (2)N17—HN17b0.950
Ni1—N152.110 (2)N18—HN18a0.950
Ni1—N162.110 (2)N18—HN18b0.950
Ni2—N12.077 (2)N19—HN19a0.950
Ni2—N122.123 (2)N19—HN19b0.950
Ni2—N172.121 (2)N20—HN20a0.950
Ni2—N192.105 (2)N20—HN20b0.950
Ni2—N202.116 (2)N21—HN21a0.950
Ni2—N182.128 (2)N21—HN21b0.950
Ni3—N52.091 (2)N22—HN22a0.950
Ni3—N5i2.091 (2)N22—HN22b0.950
Ni3—N212.102 (2)N23—HN23a0.950
Ni3—N21i2.102 (3)N23—HN23b0.950
Ni3—N222.103 (2)N24—HN24b0.950
Ni3—N22i2.103 (2)N24—HN24a0.950
Ni4—N92.090 (2)C13—H13a0.950
Ni4—N9ii2.090 (2)C13—H13b0.950
Ni4—N232.102 (3)C14—H14a0.950
Ni4—N23ii2.102 (3)C14—H14b0.950
Ni4—N242.104 (2)C15—H15a0.950
Ni4—N24ii2.104 (2)C15—H15b0.950
N1—C1iii1.145 (3)C16—H16a0.950
N2—C21.157 (3)C16—H16b0.950
N3—C31.158 (4)C17—H17a0.950
N4—C41.152 (4)C17—H17b0.950
N5—C51.150 (3)C18—H18a0.950
N6—C61.149 (3)C18—H18b0.950
N7—C71.148 (4)C19—H19a0.950
N8—C81.150 (4)C19—H19b0.950
N9—C91.148 (3)C20—H20a0.950
N10—C101.150 (3)C20—H20b0.950
N11—C111.143 (4)C21—H21a0.950
N12—C121.159 (3)C21—H21b0.950
N13—C131.481 (4)C22—H22a0.950
N14—C141.484 (3)C22—H22b0.950
N15—C151.479 (3)C23—H23a0.950
N16—C161.481 (4)C23—H23b0.950
N17—C171.477 (4)C24—H24b0.950
N18—C181.483 (3)C24—H24a0.950
N19—C191.482 (3)O1—H1b0.942
N20—C201.476 (4)O1—H1a0.963
N21—C211.484 (4)O2—H2b0.945
N22—C221.486 (4)O2—H2a0.950
N23—C231.484 (4)O3—H3b0.943
N24—C241.480 (4)O3—H3a0.952
C1—Co1—C292.9 (1)Ni3—N21—C21106.9 (2)
C1—Co1—C388.4 (1)Ni3—N22—C22107.1 (2)
C1—Co1—C4174.4 (1)Ni4—N23—C23105.9 (2)
C1—Co1—C592.3 (1)Ni4—N24—C24108.2 (2)
C1—Co1—C686.7 (1)N13—C13—C14107.9 (2)
C2—Co1—C386.7 (1)N14—C14—C13107.9 (2)
C2—Co1—C490.1 (1)N15—C15—C16107.9 (2)
C2—Co1—C5170.7 (1)N16—C16—C15109.0 (2)
C2—Co1—C695.0 (1)N17—C17—C18107.8 (2)
C3—Co1—C496.5 (1)N18—C18—C17107.9 (2)
C3—Co1—C585.8 (1)N19—C19—C20108.6 (2)
C3—Co1—C6174.8 (1)N20—C20—C19109.4 (2)
C4—Co1—C585.4 (1)N21—C21—C22108.0 (2)
C4—Co1—C688.4 (1)N22—C22—C21109.0 (2)
C5—Co1—C693.0 (1)N23—C23—C24108.4 (2)
C7—Co2—C889.0 (1)N24—C24—C23108.7 (2)
C7—Co2—C985.7 (1)HN13a—N13—HN13b109.5
C7—Co2—C10178.2 (1)C13—N13—HN13a110.2
C7—Co2—C1193.2 (1)C13—N13—HN13b110.2
C7—Co2—C1287.2 (1)HN14a—N14—HN14b109.5
C8—Co2—C988.2 (1)C14—N14—HN14a110.0
C8—Co2—C1090.4 (1)C14—N14—HN14b110.0
C8—Co2—C11175.4 (1)HN15a—N15—HN15b109.5
C8—Co2—C1292.1 (1)C15—N15—HN15a109.8
C9—Co2—C1092.6 (1)C15—N15—HN15b109.8
C9—Co2—C1187.9 (1)HN16a—N16—HN16b109.5
C9—Co2—C12172.9 (1)C16—N16—HN16a109.6
C10—Co2—C1187.3 (1)C16—N16—HN16b109.6
C10—Co2—C1294.5 (1)HN17a—N17—HN17b109.5
C11—Co2—C1292.0 (1)C17—N17—HN17a110.3
Co1—C1—N1iv178.7 (3)C17—N17—HN17b110.3
Co1—C2—N2170.1 (2)HN18a—N18—HN18b109.5
Co1—C3—N3174.9 (3)C18—N18—HN18a110.0
Co1—C4—N4173.1 (3)C18—N18—HN18b110.0
Co1—C5—N5170.0 (2)HN19a—N19—HN19b109.5
Co1—C6—N6177.3 (3)C19—N19—HN19a110.0
Co2—C7—N7176.0 (3)C19—N19—HN19b110.0
Co2—C8—N8174.9 (3)HN20a—N20—HN20b109.5
Co2—C9—N9172.2 (3)C20—N20—HN20a109.4
Co2—C10—N10177.7 (3)C20—N20—HN20b109.4
Co2—C11—N11175.8 (3)HN21a—N21—HN21b109.5
Co2—C12—N12171.8 (2)C21—N21—HN21a110.1
N2—Ni1—N1193.90 (9)C21—N21—HN21b110.1
N2—Ni1—N13177.05 (9)HN22a—N22—HN22b109.5
N2—Ni1—N1494.92 (9)C22—N22—HN22a110.1
N2—Ni1—N1588.86 (9)C22—N22—HN22b110.1
N2—Ni1—N1690.09 (9)HN23a—N23—HN23b109.5
N11—Ni1—N1384.64 (9)C23—N23—HN23a110.4
N11—Ni1—N1493.95 (9)C23—N23—HN23b110.4
N11—Ni1—N15173.04 (8)HN24a—N24—HN24b109.5
N11—Ni1—N1691.54 (9)C24—N24—HN24b109.8
N13—Ni1—N1482.64 (9)C24—N24—HN24a109.8
N13—Ni1—N1592.88 (9)H13a—C13—H13b109.5
N13—Ni1—N1692.49 (9)N13—C13—H13a109.9
N14—Ni1—N1592.18 (9)C14—C13—H13a109.9
N14—Ni1—N16172.29 (9)N13—C13—H13b109.9
N15—Ni1—N1682.06 (9)C14—C13—H13b109.9
N1—Ni2—N1291.49 (9)H14a—C14—H14b109.5
N1—Ni2—N1785.27 (9)N14—C14—H14a109.9
N1—Ni2—N1894.20 (9)C13—C14—H14a109.9
N1—Ni2—N19173.79 (8)N14—C14—H14b109.9
N1—Ni2—N2091.81 (9)C13—C14—H14b109.9
N12—Ni2—N17176.27 (9)H15a—C15—H15b109.5
N12—Ni2—N1895.80 (9)N15—C15—H15a109.9
N12—Ni2—N1989.72 (9)C16—C15—H15a109.9
N12—Ni2—N2090.21 (9)N15—C15—H15b109.9
N17—Ni2—N1882.62 (9)C16—C15—H15b109.9
N17—Ni2—N1993.70 (9)H16a—C16—H16b109.5
N17—Ni2—N2091.74 (9)N16—C16—H16a109.6
N18—Ni2—N1991.75 (9)C15—C16—H16a109.6
N18—Ni2—N20171.38 (9)N16—C16—H16b109.6
N19—Ni2—N2082.08 (8)C15—C16—H16b109.6
N5—Ni3—N5i180.00H17a—C17—H17b109.5
N5—Ni3—N2192.57 (9)N17—C17—H17a109.9
N5—Ni3—N21i87.43 (9)C18—C17—H17a109.9
N5i—Ni3—N2187.43 (9)N17—C17—H17b109.9
N5i—Ni3—N21i92.57 (9)C18—C17—H17b109.9
N5—Ni3—N2289.56 (9)H18a—C18—H18b109.5
N5—Ni3—N22i90.44 (9)N18—C18—H18a109.9
N5i—Ni3—N2290.44 (9)C17—C18—H18a109.9
N5i—Ni3—N22i89.56 (9)N18—C18—H18b109.9
N21—Ni3—N21i180.00C17—C18—H18b109.9
N21—Ni3—N2283.29 (9)H19a—C19—H19b109.5
N21—Ni3—N22i96.71 (9)N19—C19—H19a109.7
N21i—Ni3—N2296.71 (9)C20—C19—H19a109.7
N21i—Ni3—N22i83.29 (9)N19—C19—H19b109.7
N22—Ni3—N22i180.00C20—C19—H19b109.7
N9—Ni4—N9ii180.00H20a—C20—H20b109.5
N9—Ni4—N2390.94 (9)N20—C20—H20a109.5
N9—Ni4—N23ii89.06 (9)C19—C20—H20a109.5
N9—Ni4—N2491.90 (9)N20—C20—H20b109.5
N9—Ni4—N24ii88.10 (9)C19—C20—H20b109.5
N9ii—Ni4—N2389.06 (9)H21a—C21—H21b109.5
N9ii—Ni4—N23ii90.94 (9)N21—C21—H21a109.8
N9ii—Ni4—N2488.10 (9)C22—C21—H21a109.8
N9ii—Ni4—N24ii91.90 (9)N21—C21—H21b109.8
N23—Ni4—N23ii180.00C22—C21—H21b109.8
N23—Ni4—N2483.18 (9)H22a—C22—H22b109.5
N23—Ni4—N24ii96.82 (9)N22—C22—H22a109.6
N23ii—Ni4—N2496.82 (9)C21—C22—H22a109.6
N23ii—Ni4—N24ii83.18 (9)N22—C22—H22b109.6
N24—Ni4—N24ii180.00C21—C22—H22b109.6
Ni1—N2—C2152.1 (2)H23a—C23—H23b109.5
Ni3—N5—C5154.6 (2)N23—C23—H23a109.8
Ni4—N9—C9154.1 (2)C24—C23—H23a109.7
Ni1—N11—C11168.0 (2)N23—C23—H23b109.7
Ni2—N1—C1iii169.1 (2)C24—C23—H23b109.7
Ni2—N12—C12149.9 (2)H24a—C24—H24b109.5
Ni1—N13—C13106.7 (2)N24—C24—H24b109.7
Ni1—N14—C14107.5 (2)C23—C24—H24b109.7
Ni1—N15—C15108.0 (2)N24—C24—H24a109.7
Ni1—N16—C16108.9 (2)C23—C24—H24a109.7
Ni2—N17—C17106.3 (2)H1a—O1—H1b101.2
Ni2—N18—C18107.2 (2)H2a—O2—H2b103.2
Ni2—N19—C19107.4 (2)H3a—O3—H3b101.9
Ni2—N20—C20109.6 (2)
Symmetry codes: (i) −x+1, −y+2, −z; (ii) −x+1, −y+1, −z; (iii) x, y−1, z; (iv) x, y+1, z.

Experimental details

(I)(II)
Crystal data
Chemical formula[{Ni(C2H8N2)2}3{Fe(CN)6}2]·3H2O][{Ni(C2H8N2)2}3{Co(CN)6}2]·3H2O]
Mr1014.721020.90
Crystal system, space groupTriclinic, P1Triclinic, P1
Temperature (K)120120
a, b, c (Å)9.6424 (9), 14.861 (2), 17.021 (2)9.6303 (8), 14.787 (1), 16.951 (1)
α, β, γ (°)107.604 (3), 101.474 (2), 106.528 (2)107.500 (2), 101.464 (2), 106.652 (2)
V (Å3)2117.6 (4)2095.6 (3)
Z22
Radiation typeMo KαMo Kα
µ (mm−1)2.042.16
Crystal size (mm)0.40 × 0.20 × 0.200.52 × 0.18 × 0.18
Data collection
DiffractometerSiemens SMART CCD
diffractometer		Siemens SMART CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)		Multi-scan
(SADABS: Sheldrick, 1996)
Tmin, Tmax0.505, 0.6500.382, 0.678
No. of measured, independent and
observed [I > 3σ(I)] reflections		19479, 10994, 7683 17341, 9897, 6342
Rint0.0170.020
(sin θ/λ)max (Å−1)0.6820.661
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.024, 0.033, 1.14 0.028, 0.040, 1.39
No. of reflections74566342
No. of parameters509509
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.52 (7), −0.37 (7)1.16 (8), −0.63 (8)

Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), SAINT, SIR97 (Cascarano et al., 1996) and KRYSTAL (Hazell, 1995)', SIR97 (Cascarano et al., 1996) and KRYSTAL (Hazell, 1995), modified ORFLS (1962) and KRYSTAL, modified ORFLS(1962) and KRYSTAL, ORTEPIII (Burnett & Johnson, 1996) and KRYSTAL, KRYSTAL.

Selected bond lengths (Å) for (I) top
Fe1—C11.941 (2)Ni1—N142.120 (2)
Fe1—C21.946 (2)Ni1—N152.107 (2)
Fe1—C31.939 (2)Ni1—N162.110 (2)
Fe1—C41.947 (2)Ni2—N12.071 (2)
Fe1—C51.934 (2)Ni2—N122.119 (2)
Fe1—C61.933 (2)Ni2—N172.117 (2)
Fe2—C71.937 (2)Ni2—N182.122 (2)
Fe2—C81.960 (2)Ni2—N192.100 (2)
Fe2—C91.929 (2)Ni2—N202.115 (2)
Fe2—C101.930 (2)Ni3—N52.079 (2)
Fe2—C111.947 (2)Ni3—N212.103 (2)
Fe2—C121.945 (2)Ni3—N222.104 (2)
Ni1—N22.117 (2)Ni4—N92.081 (2)
Ni1—N112.086 (2)Ni4—N232.105 (2)
Ni1—N132.113 (2)Ni4—N242.107 (2)
Selected bond lengths (Å) for (II) top
Co1—C11.898 (3)Ni1—N142.120 (2)
Co1—C21.907 (3)Ni1—N152.110 (2)
Co1—C31.893 (3)Ni1—N162.110 (2)
Co1—C41.904 (3)Ni2—N12.077 (2)
Co1—C51.897 (3)Ni2—N122.123 (2)
Co1—C61.891 (3)Ni2—N172.121 (2)
Co2—C71.893 (3)Ni2—N192.105 (2)
Co2—C81.917 (3)Ni2—N202.116 (2)
Co2—C91.884 (3)Ni2—N182.128 (2)
Co2—C101.893 (3)Ni3—N52.091 (2)
Co2—C111.906 (3)Ni3—N212.102 (2)
Co2—C121.903 (3)Ni3—N222.103 (2)
Ni1—N22.127 (2)Ni4—N92.090 (2)
Ni1—N112.088 (2)Ni4—N232.102 (3)
Ni1—N132.111 (2)Ni4—N242.104 (2)
 

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