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The title coordination polymer, [Cd3Co2(CN)12(C2H8N2)4]n, has an infinite two-dimensional network structure. The asymmetric unit is composed of two crystallographically independent CdII atoms, one of which is located on a twofold rotation axis. There are two independent ethyl­ene­diamine (en) ligands, one of which bis-chelates to the Cd atom that sits in a general position, while the other bridges this Cd atom to that sitting on the twofold axis. The Cd atom located on the twofold rotation axis is linked to four equivalent CoIII atoms via cyanide bridges, while the Cd atom that sits in a general position is connected to three equivalent CoIII atoms via cyanide bridges. In this way, a series of trinuclear, tetra­nuclear and penta­nuclear macrocycles are linked to form a two-dimensional network structure lying parallel to the bc plane. In the crystal structure, these two-dimensional networks are linked via N—H...N hydrogen bonds involving an en NH2 H atom and a cyanide N atom, leading to the formation of a three-dimensional structure. This coordination polymer is only the second example involving a cyano­metallate where the en ligand is present in both chelating and bridging coordination modes.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109003709/fa3180sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270109003709/fa3180Isup2.hkl
Contains datablock I

CCDC reference: 728195

Comment top

Interest in the construction of multinuclear or polymeric complexes involving metal cyanides has been driven by application-oriented concepts, such as design and synthesis of molecular magnets, light-emitting devices and zeolite-like materials, and also by the advantages of using cyanometallates as building blocks (Cernák et al., 2002; Ohba & Okawa, 2000; Stasicka & Wasielewska, 1997; Verdaguer et al., 1999; Yanai et al., 2007). The dimensionality of the structures formed can be tuned to some extent by using blocking ligands, mainly of the amine type, coordinating several coordination sites on the central atom of the complex cation. Using this approach a large number of coordination polymers based on cyano complexes have been synthesized and structurally and magnetically characterized (Chen et al., 2005; Liu et al., 2006; Ostrovsky et al., 2007).

Transition metal complexes of the ligand ethylenediamine (en) subsequently complexed with metallocyanides have been used extensively to form coordination polymers. A search of such compounds in the Cambridge Structural Database (CSD; Version 5.29; last update November 2008; Allen, 2002) revealed over 170 structures with en in its chelated form, many being coordination polymers, but only nine entries where en is present in the briding coordination mode. There was only one example (CSD code HEGCEB; please also provide original reference) where en is present in both the chelating and the bridging modes: an infinite three-dimensional structure involving Cd2+/1,2-ethylenediamine/[Ni(CN)4]2- [catena-(hexakis(µ2-cyano)-(µ2ethylendiamino)- dicyano-bis(ethylenediamine)dicadmium(II)dinickel(II) tetraphenol clathrate; Yuge & Iwamoto, 1994]. We have investigated the system Cd2+/1,2-ethylenediamine/[Co(CN)6]3- and present here the crystal structure of the title compound, (I), a two-dimensional coordination polymer in which en is again present in both the chelating and bridging modes.

The asymmetric unit of complex (I) is illustrated in Fig. 1, and geometrical parameters are available in the archived CIF. The structure is an infinte two-dimensional network consisting of a series of trinuclear, tetranuclear and pentanuclear macrocyles linked to form a two-dimensional network lying parallel to the bc plane (Fig. 2). The various en ligands are both bridging and chelating. There are two crystallographically independent CdII atoms, Cd1 and Cd2. Atom Cd1 sits on a twofold rotation axis and exhibits a distorted octahedral [CdN6]2+ coordination, involving four N-bonded cyano groups and two N atoms of the bridging en ligands. Atom Cd2 also exhibits a distorted octahedral coordination geometry, involving one chelating en ligand, three N-bonded bridging cyano groups, and one N atom from a bridging en ligand that links it to atom Cd1.

The Cd—Namine bond distances are in the range 2.3013 (14)–2.4069 (15) Å, while the Cd—Ncyano bond distances vary from 2.2997 (15) to 2.4728 (15) Å, similar to the same distances in HEGCEB. The N—Cd—N angles range from 78.29 (5)–108.77 (5) and 158.32 (5)–172.66 (5)° about atom Cd1, and from 73.78 (5)–106.43 (5) and 159.01 (5)–174.57 (5)° about atom Cd2. Again these values are similar to those observed in HEGCEB. Some of the Cd—NC bonds are bent, the smallest angle being 133.94 (13)° for the Cd1—N8C8 bonds. Such deviations from linearity are frequent for this type of structure; For example, a value of only 128.64 (15)° has been observed in a cadmium(II) ethylenediamine hexacyanoferrate(III) complex (Mal'arová et al., 2003). The cobalt(II) atom of the [Co(CN)6]3- anion has a relatively regular octahedral coordination sphere. Five cyano groups exhibit bridging character, while the sixth, C7N7, is terminal, and this N atom is involved in hydrogen bonding (Table 1). It is worth noting that in the IR spectrum three absorption bands are present in the 2000–2200 cm-1 region. They can be assigned to the presence of terminal (2120 cm-1, weak) and bridging (2137 and 2158 cm-1, strong) cyano groups (Nakamoto, 1997).

In the crystal structure of (I) there are intra-polymer and inter-polymer N—H···N hydrogen bonds involving the N3 amino group and the cyano atoms N7 and N8 (Table 1). As can be seen in Fig. 3, the inter-polymer N3—H3A···N7(-x + 1/2, -y + 3/2, -z) hydrogen bonds link the two-dimensional networks to form a three-dimensional structure.

Related literature top

For related literature, see: Allen (2002); Chen et al. (2005); Liu et al. (2006); Mal'arová, Kuchár, Cernák & Massab (2003); Nakamoto (1997); Ohba & Okawa (2000); Ostrovsky et al. (2007); Stasicka & Wasielewska (1997); Verdaguer et al. (1999); Yanai et al. (2007); Yuge & Iwamoto (1994).

Experimental top

Complex (I) was obtained by adding an aqueous (30 ml) solution of CdCl2.2H2O (1 mmol, 0.219 g) to 1,2-ethylenediamine (en) (1 mmol, 0.07 ml) with stirring. K3[Co(CN)6]3.H2O (0.5 mmol, 0.165 g) was then added dropwise and the mixture was stirred for 30 min. To aid crystallization, NaClO4 (1 mmol, 0.12 g) was added with stirring and heating for a few minutes. The resulting solution was filtered and the filtrate placed undisturbed in the dark. After several days, a small quantity of orange crystals, suitable for X-ray analysis, were obtained.

Refinement top

H atoms were included in calculated positions and treated as riding atoms [N—H = 0.92 Å and C—H = 0.99 Å, with Uiso(H) = 1.2Ueq(N,C)].

Structure description top

Interest in the construction of multinuclear or polymeric complexes involving metal cyanides has been driven by application-oriented concepts, such as design and synthesis of molecular magnets, light-emitting devices and zeolite-like materials, and also by the advantages of using cyanometallates as building blocks (Cernák et al., 2002; Ohba & Okawa, 2000; Stasicka & Wasielewska, 1997; Verdaguer et al., 1999; Yanai et al., 2007). The dimensionality of the structures formed can be tuned to some extent by using blocking ligands, mainly of the amine type, coordinating several coordination sites on the central atom of the complex cation. Using this approach a large number of coordination polymers based on cyano complexes have been synthesized and structurally and magnetically characterized (Chen et al., 2005; Liu et al., 2006; Ostrovsky et al., 2007).

Transition metal complexes of the ligand ethylenediamine (en) subsequently complexed with metallocyanides have been used extensively to form coordination polymers. A search of such compounds in the Cambridge Structural Database (CSD; Version 5.29; last update November 2008; Allen, 2002) revealed over 170 structures with en in its chelated form, many being coordination polymers, but only nine entries where en is present in the briding coordination mode. There was only one example (CSD code HEGCEB; please also provide original reference) where en is present in both the chelating and the bridging modes: an infinite three-dimensional structure involving Cd2+/1,2-ethylenediamine/[Ni(CN)4]2- [catena-(hexakis(µ2-cyano)-(µ2ethylendiamino)- dicyano-bis(ethylenediamine)dicadmium(II)dinickel(II) tetraphenol clathrate; Yuge & Iwamoto, 1994]. We have investigated the system Cd2+/1,2-ethylenediamine/[Co(CN)6]3- and present here the crystal structure of the title compound, (I), a two-dimensional coordination polymer in which en is again present in both the chelating and bridging modes.

The asymmetric unit of complex (I) is illustrated in Fig. 1, and geometrical parameters are available in the archived CIF. The structure is an infinte two-dimensional network consisting of a series of trinuclear, tetranuclear and pentanuclear macrocyles linked to form a two-dimensional network lying parallel to the bc plane (Fig. 2). The various en ligands are both bridging and chelating. There are two crystallographically independent CdII atoms, Cd1 and Cd2. Atom Cd1 sits on a twofold rotation axis and exhibits a distorted octahedral [CdN6]2+ coordination, involving four N-bonded cyano groups and two N atoms of the bridging en ligands. Atom Cd2 also exhibits a distorted octahedral coordination geometry, involving one chelating en ligand, three N-bonded bridging cyano groups, and one N atom from a bridging en ligand that links it to atom Cd1.

The Cd—Namine bond distances are in the range 2.3013 (14)–2.4069 (15) Å, while the Cd—Ncyano bond distances vary from 2.2997 (15) to 2.4728 (15) Å, similar to the same distances in HEGCEB. The N—Cd—N angles range from 78.29 (5)–108.77 (5) and 158.32 (5)–172.66 (5)° about atom Cd1, and from 73.78 (5)–106.43 (5) and 159.01 (5)–174.57 (5)° about atom Cd2. Again these values are similar to those observed in HEGCEB. Some of the Cd—NC bonds are bent, the smallest angle being 133.94 (13)° for the Cd1—N8C8 bonds. Such deviations from linearity are frequent for this type of structure; For example, a value of only 128.64 (15)° has been observed in a cadmium(II) ethylenediamine hexacyanoferrate(III) complex (Mal'arová et al., 2003). The cobalt(II) atom of the [Co(CN)6]3- anion has a relatively regular octahedral coordination sphere. Five cyano groups exhibit bridging character, while the sixth, C7N7, is terminal, and this N atom is involved in hydrogen bonding (Table 1). It is worth noting that in the IR spectrum three absorption bands are present in the 2000–2200 cm-1 region. They can be assigned to the presence of terminal (2120 cm-1, weak) and bridging (2137 and 2158 cm-1, strong) cyano groups (Nakamoto, 1997).

In the crystal structure of (I) there are intra-polymer and inter-polymer N—H···N hydrogen bonds involving the N3 amino group and the cyano atoms N7 and N8 (Table 1). As can be seen in Fig. 3, the inter-polymer N3—H3A···N7(-x + 1/2, -y + 3/2, -z) hydrogen bonds link the two-dimensional networks to form a three-dimensional structure.

For related literature, see: Allen (2002); Chen et al. (2005); Liu et al. (2006); Mal'arová, Kuchár, Cernák & Massab (2003); Nakamoto (1997); Ohba & Okawa (2000); Ostrovsky et al. (2007); Stasicka & Wasielewska (1997); Verdaguer et al. (1999); Yanai et al. (2007); Yuge & Iwamoto (1994).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA (Stoe & Cie, 2005); data reduction: X-RED32 (Stoe & Cie, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of compound (I), showing the atom-numbering scheme and displacement ellipsoids drawn at the 50% probability level. [Symmetry operations: (i) -x, y, -z + 1/2; (ii) x, y + 1, z; (iii) -x, -y + 1, -z; (iv) -x, -y + 2, -z].] Not in accord with table
[Figure 2] Fig. 2. A view down the a axis of the crystal packing of compound (I), showing the various trinuclear, tetranuclear and pentanuclear macrocyles that are linked to form the two-dimensional network (H atoms have been omitted for clarity).
[Figure 3] Fig. 3. A view down the b axis of the crystal structure of compound (I), showing the N—H···N intra- and inter-polymer hydrogen bonds as dashed lines (see Table 1 for details; H atoms not involved in hydrogen bonding have been omitted for clarity).
Poly[deca-µ2-cyanido-dicyanidobis(µ2- ethylenediamine)bis(ethylenediamine)tricadmium(II)dicobalt(III)] top
Crystal data top
[Cd3Co2(CN)12(C2H8N2)4]F(000) = 1960
Mr = 1007.72Dx = 2.035 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 26539 reflections
a = 21.7002 (11) Åθ = 1.9–29.6°
b = 7.7859 (5) ŵ = 2.94 mm1
c = 19.6450 (9) ÅT = 173 K
β = 97.770 (4)°Block, orange
V = 3288.7 (3) Å30.42 × 0.33 × 0.21 mm
Z = 4
Data collection top
Stoe IPDS-II
diffractometer
4410 independent reflections
Radiation source: fine-focus sealed tube4101 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.023
ω and φ scansθmax = 29.2°, θmin = 1.9°
Absorption correction: multi-scan
(MULscanABS in PLATON; Spek, 2003)
h = 2929
Tmin = 0.440, Tmax = 0.540k = 1010
19479 measured reflectionsl = 2625
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.018H-atom parameters constrained
wR(F2) = 0.044 w = 1/[σ2(Fo2) + (0.0218P)2 + 3.6987P]
where P = (Fo2 + 2Fc2)/3
S = 1.11(Δ/σ)max = 0.001
4410 reflectionsΔρmax = 0.56 e Å3
205 parametersΔρmin = 0.60 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.00080 (5)
Crystal data top
[Cd3Co2(CN)12(C2H8N2)4]V = 3288.7 (3) Å3
Mr = 1007.72Z = 4
Monoclinic, C2/cMo Kα radiation
a = 21.7002 (11) ŵ = 2.94 mm1
b = 7.7859 (5) ÅT = 173 K
c = 19.6450 (9) Å0.42 × 0.33 × 0.21 mm
β = 97.770 (4)°
Data collection top
Stoe IPDS-II
diffractometer
4410 independent reflections
Absorption correction: multi-scan
(MULscanABS in PLATON; Spek, 2003)
4101 reflections with I > 2σ(I)
Tmin = 0.440, Tmax = 0.540Rint = 0.023
19479 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0180 restraints
wR(F2) = 0.044H-atom parameters constrained
S = 1.11Δρmax = 0.56 e Å3
4410 reflectionsΔρmin = 0.60 e Å3
205 parameters
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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) top
xyzUiso*/Ueq
Cd10.000000.69895 (2)0.250000.0139 (1)
Cd20.13702 (1)0.30343 (1)0.07415 (1)0.0137 (1)
Co10.10234 (1)0.79802 (2)0.11321 (1)0.0109 (1)
N10.16491 (7)0.1545 (2)0.18039 (8)0.0236 (4)
N20.24830 (7)0.2708 (2)0.08771 (8)0.0232 (4)
N30.13543 (6)0.55055 (17)0.14276 (7)0.0165 (3)
N40.00292 (6)0.64335 (18)0.13543 (7)0.0185 (3)
N50.13508 (7)0.48927 (19)0.01949 (7)0.0216 (4)
N60.07124 (7)0.91044 (19)0.21489 (8)0.0220 (4)
N70.23419 (7)0.8340 (2)0.14653 (9)0.0274 (4)
N80.07666 (7)0.46368 (19)0.22806 (7)0.0208 (4)
N90.12958 (7)0.06613 (18)0.00020 (8)0.0214 (4)
N100.03215 (7)0.24470 (19)0.08608 (8)0.0211 (4)
C10.22682 (9)0.0784 (2)0.18002 (10)0.0284 (5)
C20.27078 (9)0.2101 (2)0.15773 (10)0.0276 (5)
C30.11100 (8)0.7238 (2)0.12329 (9)0.0212 (4)
C40.04423 (8)0.7229 (2)0.09015 (9)0.0232 (5)
C50.12428 (7)0.6094 (2)0.05328 (8)0.0153 (4)
C60.08181 (7)1.02065 (19)0.17606 (8)0.0158 (4)
C70.18510 (7)0.81717 (19)0.13199 (8)0.0164 (4)
C80.08643 (7)0.36133 (19)0.18587 (8)0.0144 (4)
C90.11920 (7)0.03782 (19)0.04133 (8)0.0151 (4)
C100.01827 (7)0.77754 (19)0.09605 (8)0.0152 (4)
H1A0.165500.229700.216600.0280*
H1B0.136300.069800.185200.0280*
H1C0.223900.020700.148200.0340*
H1D0.242900.036400.226600.0340*
H2A0.266600.374400.080100.0280*
H2B0.259100.193100.056100.0280*
H2C0.274100.308400.190000.0330*
H2D0.312600.158800.158700.0330*
H3A0.176200.568000.161300.0200*
H3B0.115100.517700.178800.0200*
H3C0.137000.776000.091100.0250*
H3D0.114600.796700.164900.0250*
H4A0.009500.526900.132700.0220*
H4B0.036900.662500.114100.0220*
H4C0.030500.842300.079500.0280*
H4D0.040900.658400.046400.0280*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.0162 (1)0.0122 (1)0.0131 (1)0.00000.0014 (1)0.0000
Cd20.0144 (1)0.0134 (1)0.0133 (1)0.0005 (1)0.0014 (1)0.0002 (1)
Co10.0114 (1)0.0097 (1)0.0117 (1)0.0004 (1)0.0015 (1)0.0006 (1)
N10.0280 (7)0.0210 (7)0.0223 (7)0.0015 (6)0.0055 (6)0.0041 (5)
N20.0193 (6)0.0260 (7)0.0243 (7)0.0011 (5)0.0035 (6)0.0009 (6)
N30.0144 (6)0.0183 (6)0.0173 (6)0.0023 (5)0.0037 (5)0.0008 (5)
N40.0171 (6)0.0208 (6)0.0175 (6)0.0002 (5)0.0025 (5)0.0021 (5)
N50.0296 (7)0.0175 (6)0.0180 (6)0.0012 (5)0.0040 (5)0.0011 (5)
N60.0230 (7)0.0194 (6)0.0236 (7)0.0049 (5)0.0031 (5)0.0042 (5)
N70.0179 (7)0.0259 (7)0.0394 (9)0.0012 (6)0.0072 (6)0.0007 (7)
N80.0229 (6)0.0212 (7)0.0187 (6)0.0041 (5)0.0048 (5)0.0041 (5)
N90.0238 (7)0.0192 (6)0.0216 (7)0.0025 (5)0.0046 (5)0.0039 (5)
N100.0181 (6)0.0211 (6)0.0244 (7)0.0026 (5)0.0042 (5)0.0046 (6)
C10.0328 (9)0.0234 (8)0.0277 (9)0.0083 (7)0.0006 (7)0.0058 (7)
C20.0214 (8)0.0309 (9)0.0281 (9)0.0028 (7)0.0057 (7)0.0004 (7)
C30.0243 (8)0.0154 (7)0.0256 (8)0.0031 (6)0.0092 (6)0.0005 (6)
C40.0260 (8)0.0251 (8)0.0199 (8)0.0059 (6)0.0079 (7)0.0055 (6)
C50.0176 (6)0.0147 (6)0.0138 (7)0.0009 (5)0.0028 (5)0.0020 (5)
C60.0138 (6)0.0150 (6)0.0187 (7)0.0011 (5)0.0025 (5)0.0012 (5)
C70.0180 (7)0.0129 (6)0.0182 (7)0.0002 (5)0.0019 (6)0.0003 (5)
C80.0134 (6)0.0144 (6)0.0158 (7)0.0010 (5)0.0030 (5)0.0012 (5)
C90.0153 (6)0.0134 (6)0.0170 (7)0.0011 (5)0.0035 (5)0.0004 (5)
C100.0170 (7)0.0134 (6)0.0154 (7)0.0001 (5)0.0025 (5)0.0021 (5)
Geometric parameters (Å, º) top
Cd1—N42.3013 (14)N6—C61.150 (2)
Cd1—N62.2997 (15)N7—C71.147 (2)
Cd1—N82.4728 (15)N8—C81.149 (2)
Cd1—N4i2.3013 (14)N9—C91.150 (2)
Cd1—N6i2.2997 (15)N10—C10iii1.150 (2)
Cd1—N8i2.4728 (15)N1—H1B0.9200
Cd2—N12.3928 (16)N1—H1A0.9200
Cd2—N22.4069 (15)N2—H2A0.9200
Cd2—N32.3522 (13)N2—H2B0.9200
Cd2—N52.3363 (14)N3—H3B0.9200
Cd2—N92.3423 (15)N3—H3A0.9200
Cd2—N102.3636 (15)N4—H4A0.9200
Co1—C51.9021 (16)N4—H4B0.9200
Co1—C71.8875 (16)C1—C21.505 (3)
Co1—C101.9063 (16)C3—C41.506 (2)
Co1—C9ii1.9032 (15)C1—H1C0.9900
Co1—C8iii1.8875 (15)C1—H1D0.9900
Co1—C6iv1.8887 (15)C2—H2C0.9900
N1—C11.469 (2)C2—H2D0.9900
N2—C21.474 (2)C3—H3C0.9900
N3—C31.481 (2)C3—H3D0.9900
N4—C41.481 (2)C4—H4C0.9900
N5—C51.153 (2)C4—H4D0.9900
N4—Cd1—N687.00 (5)Cd2—N9—C9170.36 (14)
N4—Cd1—N878.29 (5)Cd2—N10—C10iii175.27 (14)
N4—Cd1—N4i158.32 (5)H1A—N1—H1B108.00
N4—Cd1—N6i108.77 (5)Cd2—N1—H1B110.00
N4—Cd1—N8i85.66 (5)C1—N1—H1A110.00
N6—Cd1—N893.96 (5)Cd2—N1—H1A110.00
N4i—Cd1—N6108.77 (5)C1—N1—H1B110.00
N6—Cd1—N6i88.55 (5)Cd2—N2—H2B110.00
N6—Cd1—N8i172.66 (5)C2—N2—H2A110.00
N4i—Cd1—N885.66 (5)Cd2—N2—H2A110.00
N6i—Cd1—N8172.66 (5)H2A—N2—H2B108.00
N8—Cd1—N8i84.41 (5)C2—N2—H2B110.00
N4i—Cd1—N6i87.00 (5)H3A—N3—H3B106.00
N4i—Cd1—N8i78.29 (5)C3—N3—H3B105.00
N6i—Cd1—N8i93.96 (5)Cd2—N3—H3A105.00
N1—Cd2—N273.78 (5)Cd2—N3—H3B105.00
N1—Cd2—N385.30 (5)C3—N3—H3A105.00
N1—Cd2—N5164.24 (5)H4A—N4—H4B106.00
N1—Cd2—N998.44 (5)Cd1—N4—H4B105.00
N1—Cd2—N1087.32 (5)C4—N4—H4A105.00
N2—Cd2—N396.61 (5)Cd1—N4—H4A106.00
N2—Cd2—N593.64 (5)C4—N4—H4B105.00
N2—Cd2—N988.25 (5)N1—C1—C2110.03 (14)
N2—Cd2—N10159.01 (5)N2—C2—C1110.31 (15)
N3—Cd2—N586.82 (5)N3—C3—C4113.42 (13)
N3—Cd2—N9174.57 (5)N4—C4—C3111.55 (14)
N3—Cd2—N1090.72 (5)Co1—C5—N5175.92 (14)
N5—Cd2—N990.45 (5)Co1iv—C6—N6177.77 (14)
N5—Cd2—N10106.43 (5)Co1—C7—N7176.24 (15)
N9—Cd2—N1085.55 (5)Co1iii—C8—N8177.11 (14)
C5—Co1—C790.97 (7)Co1v—C9—N9177.35 (14)
C5—Co1—C1089.50 (7)Co1—C10—N10iii176.13 (14)
C5—Co1—C9ii93.00 (7)N1—C1—H1C110.00
C5—Co1—C8iii88.02 (7)N1—C1—H1D110.00
C5—Co1—C6iv177.34 (7)C2—C1—H1C110.00
C7—Co1—C10178.90 (7)C2—C1—H1D110.00
C7—Co1—C9ii89.97 (7)H1C—C1—H1D108.00
C7—Co1—C8iii89.18 (7)N2—C2—H2C110.00
C6iv—Co1—C787.70 (7)N2—C2—H2D110.00
C9ii—Co1—C1091.00 (7)C1—C2—H2C110.00
C8iii—Co1—C1089.84 (7)C1—C2—H2D110.00
C6iv—Co1—C1091.80 (7)H2C—C2—H2D108.00
C8iii—Co1—C9ii178.69 (7)N3—C3—H3C109.00
C6iv—Co1—C9ii89.30 (7)N3—C3—H3D109.00
C6iv—Co1—C8iii89.67 (7)C4—C3—H3C109.00
Cd2—N1—C1108.35 (11)C4—C3—H3D109.00
Cd2—N2—C2109.74 (11)H3C—C3—H3D108.00
Cd2—N3—C3129.03 (10)N4—C4—H4C109.00
Cd1—N4—C4127.42 (10)N4—C4—H4D109.00
Cd2—N5—C5159.51 (13)C3—C4—H4C109.00
Cd1—N6—C6143.00 (13)C3—C4—H4D109.00
Cd1—N8—C8133.94 (13)H4C—C4—H4D108.00
N6—Cd1—N4—C489.22 (13)N3—Cd2—N2—C272.40 (11)
N8—Cd1—N4—C4176.11 (13)N5—Cd2—N2—C2159.61 (11)
N4i—Cd1—N4—C4133.04 (14)N9—Cd2—N2—C2110.06 (11)
N6i—Cd1—N4—C41.78 (14)N10—Cd2—N2—C237.3 (2)
N8i—Cd1—N4—C490.94 (13)N1—Cd2—N3—C3168.22 (13)
N4—Cd1—N6—C643.4 (2)N2—Cd2—N3—C3118.75 (13)
N8—Cd1—N6—C6121.4 (2)N5—Cd2—N3—C325.45 (13)
N4i—Cd1—N6—C6151.9 (2)N10—Cd2—N3—C380.97 (13)
N6i—Cd1—N6—C665.5 (2)N2—Cd2—N5—C5127.5 (4)
N4—Cd1—N8—C818.52 (17)N3—Cd2—N5—C531.1 (4)
N6—Cd1—N8—C8104.63 (17)N9—Cd2—N5—C5144.2 (4)
N4i—Cd1—N8—C8146.82 (18)N10—Cd2—N5—C558.7 (4)
N8i—Cd1—N8—C868.19 (17)Cd2—N1—C1—C248.05 (16)
N2—Cd2—N1—C119.62 (10)Cd2—N2—C2—C139.73 (16)
N3—Cd2—N1—C1117.90 (11)Cd2—N3—C3—C454.50 (19)
N9—Cd2—N1—C166.06 (11)Cd1—N4—C4—C347.95 (17)
N10—Cd2—N1—C1151.15 (11)N1—C1—C2—N260.71 (19)
N1—Cd2—N2—C210.74 (10)N3—C3—C4—N457.59 (18)
Symmetry codes: (i) x, y, z+1/2; (ii) x, y+1, z; (iii) x, y+1, z; (iv) x, y+2, z; (v) x, y1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···N7vi0.922.623.291 (2)130
N3—H3A···N7vi0.922.142.960 (2)147
N3—H3B···N8i0.922.153.066 (2)172
N4—H4A···N100.922.463.338 (2)161
C1—H1C···N7vii0.992.613.407 (2)138
Symmetry codes: (i) x, y, z+1/2; (vi) x+1/2, y+3/2, z; (vii) x+1/2, y+1/2, z.

Experimental details

Crystal data
Chemical formula[Cd3Co2(CN)12(C2H8N2)4]
Mr1007.72
Crystal system, space groupMonoclinic, C2/c
Temperature (K)173
a, b, c (Å)21.7002 (11), 7.7859 (5), 19.6450 (9)
β (°) 97.770 (4)
V3)3288.7 (3)
Z4
Radiation typeMo Kα
µ (mm1)2.94
Crystal size (mm)0.42 × 0.33 × 0.21
Data collection
DiffractometerStoe IPDS-II
Absorption correctionMulti-scan
(MULscanABS in PLATON; Spek, 2003)
Tmin, Tmax0.440, 0.540
No. of measured, independent and
observed [I > 2σ(I)] reflections
19479, 4410, 4101
Rint0.023
(sin θ/λ)max1)0.686
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.018, 0.044, 1.11
No. of reflections4410
No. of parameters205
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.56, 0.60

Computer programs: X-AREA (Stoe & Cie, 2005), X-RED32 (Stoe & Cie, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3A···N7i0.922.142.960 (2)147
N3—H3B···N8ii0.922.153.066 (2)172
Symmetry codes: (i) x+1/2, y+3/2, z; (ii) x, y, z+1/2.
 

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