Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109003709/fa3180sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109003709/fa3180Isup2.hkl |
CCDC reference: 728195
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.
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)].
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—N≡C bonds are bent, the smallest angle being 133.94 (13)° for the Cd1—N8≡C8 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, C7≡N7, 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).
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).
[Cd3Co2(CN)12(C2H8N2)4] | F(000) = 1960 |
Mr = 1007.72 | Dx = 2.035 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 26539 reflections |
a = 21.7002 (11) Å | θ = 1.9–29.6° |
b = 7.7859 (5) Å | µ = 2.94 mm−1 |
c = 19.6450 (9) Å | T = 173 K |
β = 97.770 (4)° | Block, orange |
V = 3288.7 (3) Å3 | 0.42 × 0.33 × 0.21 mm |
Z = 4 |
Stoe IPDS-II diffractometer | 4410 independent reflections |
Radiation source: fine-focus sealed tube | 4101 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
ω and φ scans | θmax = 29.2°, θmin = 1.9° |
Absorption correction: multi-scan (MULscanABS in PLATON; Spek, 2003) | h = −29→29 |
Tmin = 0.440, Tmax = 0.540 | k = −10→10 |
19479 measured reflections | l = −26→25 |
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)] = 0.018 | H-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 reflections | Δρmax = 0.56 e Å−3 |
205 parameters | Δρmin = −0.60 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00080 (5) |
[Cd3Co2(CN)12(C2H8N2)4] | V = 3288.7 (3) Å3 |
Mr = 1007.72 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 21.7002 (11) Å | µ = 2.94 mm−1 |
b = 7.7859 (5) Å | T = 173 K |
c = 19.6450 (9) Å | 0.42 × 0.33 × 0.21 mm |
β = 97.770 (4)° |
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 = 0.540 | Rint = 0.023 |
19479 measured reflections |
R[F2 > 2σ(F2)] = 0.018 | 0 restraints |
wR(F2) = 0.044 | H-atom parameters constrained |
S = 1.11 | Δρmax = 0.56 e Å−3 |
4410 reflections | Δρmin = −0.60 e Å−3 |
205 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cd1 | 0.00000 | 0.69895 (2) | 0.25000 | 0.0139 (1) | |
Cd2 | 0.13702 (1) | 0.30343 (1) | 0.07415 (1) | 0.0137 (1) | |
Co1 | 0.10234 (1) | 0.79802 (2) | −0.11321 (1) | 0.0109 (1) | |
N1 | 0.16491 (7) | 0.1545 (2) | 0.18039 (8) | 0.0236 (4) | |
N2 | 0.24830 (7) | 0.2708 (2) | 0.08771 (8) | 0.0232 (4) | |
N3 | 0.13543 (6) | 0.55055 (17) | 0.14276 (7) | 0.0165 (3) | |
N4 | 0.00292 (6) | 0.64335 (18) | 0.13543 (7) | 0.0185 (3) | |
N5 | 0.13508 (7) | 0.48927 (19) | −0.01949 (7) | 0.0216 (4) | |
N6 | −0.07124 (7) | 0.91044 (19) | 0.21489 (8) | 0.0220 (4) | |
N7 | 0.23419 (7) | 0.8340 (2) | −0.14653 (9) | 0.0274 (4) | |
N8 | −0.07666 (7) | 0.46368 (19) | 0.22806 (7) | 0.0208 (4) | |
N9 | 0.12958 (7) | 0.06613 (18) | 0.00020 (8) | 0.0214 (4) | |
N10 | 0.03215 (7) | 0.24470 (19) | 0.08608 (8) | 0.0211 (4) | |
C1 | 0.22682 (9) | 0.0784 (2) | 0.18002 (10) | 0.0284 (5) | |
C2 | 0.27078 (9) | 0.2101 (2) | 0.15773 (10) | 0.0276 (5) | |
C3 | 0.11100 (8) | 0.7238 (2) | 0.12329 (9) | 0.0212 (4) | |
C4 | 0.04423 (8) | 0.7229 (2) | 0.09015 (9) | 0.0232 (5) | |
C5 | 0.12428 (7) | 0.6094 (2) | −0.05328 (8) | 0.0153 (4) | |
C6 | −0.08181 (7) | 1.02065 (19) | 0.17606 (8) | 0.0158 (4) | |
C7 | 0.18510 (7) | 0.81717 (19) | −0.13199 (8) | 0.0164 (4) | |
C8 | −0.08643 (7) | 0.36133 (19) | 0.18587 (8) | 0.0144 (4) | |
C9 | 0.11920 (7) | −0.03782 (19) | −0.04133 (8) | 0.0151 (4) | |
C10 | 0.01827 (7) | 0.77754 (19) | −0.09605 (8) | 0.0152 (4) | |
H1A | 0.16550 | 0.22970 | 0.21660 | 0.0280* | |
H1B | 0.13630 | 0.06980 | 0.18520 | 0.0280* | |
H1C | 0.22390 | −0.02070 | 0.14820 | 0.0340* | |
H1D | 0.24290 | 0.03640 | 0.22660 | 0.0340* | |
H2A | 0.26660 | 0.37440 | 0.08010 | 0.0280* | |
H2B | 0.25910 | 0.19310 | 0.05610 | 0.0280* | |
H2C | 0.27410 | 0.30840 | 0.19000 | 0.0330* | |
H2D | 0.31260 | 0.15880 | 0.15870 | 0.0330* | |
H3A | 0.17620 | 0.56800 | 0.16130 | 0.0200* | |
H3B | 0.11510 | 0.51770 | 0.17880 | 0.0200* | |
H3C | 0.13700 | 0.77600 | 0.09110 | 0.0250* | |
H3D | 0.11460 | 0.79670 | 0.16490 | 0.0250* | |
H4A | 0.00950 | 0.52690 | 0.13270 | 0.0220* | |
H4B | −0.03690 | 0.66250 | 0.11410 | 0.0220* | |
H4C | 0.03050 | 0.84230 | 0.07950 | 0.0280* | |
H4D | 0.04090 | 0.65840 | 0.04640 | 0.0280* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.0162 (1) | 0.0122 (1) | 0.0131 (1) | 0.0000 | 0.0014 (1) | 0.0000 |
Cd2 | 0.0144 (1) | 0.0134 (1) | 0.0133 (1) | −0.0005 (1) | 0.0014 (1) | −0.0002 (1) |
Co1 | 0.0114 (1) | 0.0097 (1) | 0.0117 (1) | −0.0004 (1) | 0.0015 (1) | −0.0006 (1) |
N1 | 0.0280 (7) | 0.0210 (7) | 0.0223 (7) | −0.0015 (6) | 0.0055 (6) | 0.0041 (5) |
N2 | 0.0193 (6) | 0.0260 (7) | 0.0243 (7) | −0.0011 (5) | 0.0035 (6) | 0.0009 (6) |
N3 | 0.0144 (6) | 0.0183 (6) | 0.0173 (6) | −0.0023 (5) | 0.0037 (5) | −0.0008 (5) |
N4 | 0.0171 (6) | 0.0208 (6) | 0.0175 (6) | 0.0002 (5) | 0.0025 (5) | −0.0021 (5) |
N5 | 0.0296 (7) | 0.0175 (6) | 0.0180 (6) | 0.0012 (5) | 0.0040 (5) | 0.0011 (5) |
N6 | 0.0230 (7) | 0.0194 (6) | 0.0236 (7) | 0.0049 (5) | 0.0031 (5) | 0.0042 (5) |
N7 | 0.0179 (7) | 0.0259 (7) | 0.0394 (9) | −0.0012 (6) | 0.0072 (6) | 0.0007 (7) |
N8 | 0.0229 (6) | 0.0212 (7) | 0.0187 (6) | −0.0041 (5) | 0.0048 (5) | −0.0041 (5) |
N9 | 0.0238 (7) | 0.0192 (6) | 0.0216 (7) | −0.0025 (5) | 0.0046 (5) | −0.0039 (5) |
N10 | 0.0181 (6) | 0.0211 (6) | 0.0244 (7) | −0.0026 (5) | 0.0042 (5) | −0.0046 (6) |
C1 | 0.0328 (9) | 0.0234 (8) | 0.0277 (9) | 0.0083 (7) | −0.0006 (7) | 0.0058 (7) |
C2 | 0.0214 (8) | 0.0309 (9) | 0.0281 (9) | 0.0028 (7) | −0.0057 (7) | −0.0004 (7) |
C3 | 0.0243 (8) | 0.0154 (7) | 0.0256 (8) | −0.0031 (6) | 0.0092 (6) | −0.0005 (6) |
C4 | 0.0260 (8) | 0.0251 (8) | 0.0199 (8) | 0.0059 (6) | 0.0079 (7) | 0.0055 (6) |
C5 | 0.0176 (6) | 0.0147 (6) | 0.0138 (7) | −0.0009 (5) | 0.0028 (5) | −0.0020 (5) |
C6 | 0.0138 (6) | 0.0150 (6) | 0.0187 (7) | 0.0011 (5) | 0.0025 (5) | −0.0012 (5) |
C7 | 0.0180 (7) | 0.0129 (6) | 0.0182 (7) | −0.0002 (5) | 0.0019 (6) | −0.0003 (5) |
C8 | 0.0134 (6) | 0.0144 (6) | 0.0158 (7) | −0.0010 (5) | 0.0030 (5) | 0.0012 (5) |
C9 | 0.0153 (6) | 0.0134 (6) | 0.0170 (7) | −0.0011 (5) | 0.0035 (5) | 0.0004 (5) |
C10 | 0.0170 (7) | 0.0134 (6) | 0.0154 (7) | −0.0001 (5) | 0.0025 (5) | −0.0021 (5) |
Cd1—N4 | 2.3013 (14) | N6—C6 | 1.150 (2) |
Cd1—N6 | 2.2997 (15) | N7—C7 | 1.147 (2) |
Cd1—N8 | 2.4728 (15) | N8—C8 | 1.149 (2) |
Cd1—N4i | 2.3013 (14) | N9—C9 | 1.150 (2) |
Cd1—N6i | 2.2997 (15) | N10—C10iii | 1.150 (2) |
Cd1—N8i | 2.4728 (15) | N1—H1B | 0.9200 |
Cd2—N1 | 2.3928 (16) | N1—H1A | 0.9200 |
Cd2—N2 | 2.4069 (15) | N2—H2A | 0.9200 |
Cd2—N3 | 2.3522 (13) | N2—H2B | 0.9200 |
Cd2—N5 | 2.3363 (14) | N3—H3B | 0.9200 |
Cd2—N9 | 2.3423 (15) | N3—H3A | 0.9200 |
Cd2—N10 | 2.3636 (15) | N4—H4A | 0.9200 |
Co1—C5 | 1.9021 (16) | N4—H4B | 0.9200 |
Co1—C7 | 1.8875 (16) | C1—C2 | 1.505 (3) |
Co1—C10 | 1.9063 (16) | C3—C4 | 1.506 (2) |
Co1—C9ii | 1.9032 (15) | C1—H1C | 0.9900 |
Co1—C8iii | 1.8875 (15) | C1—H1D | 0.9900 |
Co1—C6iv | 1.8887 (15) | C2—H2C | 0.9900 |
N1—C1 | 1.469 (2) | C2—H2D | 0.9900 |
N2—C2 | 1.474 (2) | C3—H3C | 0.9900 |
N3—C3 | 1.481 (2) | C3—H3D | 0.9900 |
N4—C4 | 1.481 (2) | C4—H4C | 0.9900 |
N5—C5 | 1.153 (2) | C4—H4D | 0.9900 |
N4—Cd1—N6 | 87.00 (5) | Cd2—N9—C9 | 170.36 (14) |
N4—Cd1—N8 | 78.29 (5) | Cd2—N10—C10iii | 175.27 (14) |
N4—Cd1—N4i | 158.32 (5) | H1A—N1—H1B | 108.00 |
N4—Cd1—N6i | 108.77 (5) | Cd2—N1—H1B | 110.00 |
N4—Cd1—N8i | 85.66 (5) | C1—N1—H1A | 110.00 |
N6—Cd1—N8 | 93.96 (5) | Cd2—N1—H1A | 110.00 |
N4i—Cd1—N6 | 108.77 (5) | C1—N1—H1B | 110.00 |
N6—Cd1—N6i | 88.55 (5) | Cd2—N2—H2B | 110.00 |
N6—Cd1—N8i | 172.66 (5) | C2—N2—H2A | 110.00 |
N4i—Cd1—N8 | 85.66 (5) | Cd2—N2—H2A | 110.00 |
N6i—Cd1—N8 | 172.66 (5) | H2A—N2—H2B | 108.00 |
N8—Cd1—N8i | 84.41 (5) | C2—N2—H2B | 110.00 |
N4i—Cd1—N6i | 87.00 (5) | H3A—N3—H3B | 106.00 |
N4i—Cd1—N8i | 78.29 (5) | C3—N3—H3B | 105.00 |
N6i—Cd1—N8i | 93.96 (5) | Cd2—N3—H3A | 105.00 |
N1—Cd2—N2 | 73.78 (5) | Cd2—N3—H3B | 105.00 |
N1—Cd2—N3 | 85.30 (5) | C3—N3—H3A | 105.00 |
N1—Cd2—N5 | 164.24 (5) | H4A—N4—H4B | 106.00 |
N1—Cd2—N9 | 98.44 (5) | Cd1—N4—H4B | 105.00 |
N1—Cd2—N10 | 87.32 (5) | C4—N4—H4A | 105.00 |
N2—Cd2—N3 | 96.61 (5) | Cd1—N4—H4A | 106.00 |
N2—Cd2—N5 | 93.64 (5) | C4—N4—H4B | 105.00 |
N2—Cd2—N9 | 88.25 (5) | N1—C1—C2 | 110.03 (14) |
N2—Cd2—N10 | 159.01 (5) | N2—C2—C1 | 110.31 (15) |
N3—Cd2—N5 | 86.82 (5) | N3—C3—C4 | 113.42 (13) |
N3—Cd2—N9 | 174.57 (5) | N4—C4—C3 | 111.55 (14) |
N3—Cd2—N10 | 90.72 (5) | Co1—C5—N5 | 175.92 (14) |
N5—Cd2—N9 | 90.45 (5) | Co1iv—C6—N6 | 177.77 (14) |
N5—Cd2—N10 | 106.43 (5) | Co1—C7—N7 | 176.24 (15) |
N9—Cd2—N10 | 85.55 (5) | Co1iii—C8—N8 | 177.11 (14) |
C5—Co1—C7 | 90.97 (7) | Co1v—C9—N9 | 177.35 (14) |
C5—Co1—C10 | 89.50 (7) | Co1—C10—N10iii | 176.13 (14) |
C5—Co1—C9ii | 93.00 (7) | N1—C1—H1C | 110.00 |
C5—Co1—C8iii | 88.02 (7) | N1—C1—H1D | 110.00 |
C5—Co1—C6iv | 177.34 (7) | C2—C1—H1C | 110.00 |
C7—Co1—C10 | 178.90 (7) | C2—C1—H1D | 110.00 |
C7—Co1—C9ii | 89.97 (7) | H1C—C1—H1D | 108.00 |
C7—Co1—C8iii | 89.18 (7) | N2—C2—H2C | 110.00 |
C6iv—Co1—C7 | 87.70 (7) | N2—C2—H2D | 110.00 |
C9ii—Co1—C10 | 91.00 (7) | C1—C2—H2C | 110.00 |
C8iii—Co1—C10 | 89.84 (7) | C1—C2—H2D | 110.00 |
C6iv—Co1—C10 | 91.80 (7) | H2C—C2—H2D | 108.00 |
C8iii—Co1—C9ii | 178.69 (7) | N3—C3—H3C | 109.00 |
C6iv—Co1—C9ii | 89.30 (7) | N3—C3—H3D | 109.00 |
C6iv—Co1—C8iii | 89.67 (7) | C4—C3—H3C | 109.00 |
Cd2—N1—C1 | 108.35 (11) | C4—C3—H3D | 109.00 |
Cd2—N2—C2 | 109.74 (11) | H3C—C3—H3D | 108.00 |
Cd2—N3—C3 | 129.03 (10) | N4—C4—H4C | 109.00 |
Cd1—N4—C4 | 127.42 (10) | N4—C4—H4D | 109.00 |
Cd2—N5—C5 | 159.51 (13) | C3—C4—H4C | 109.00 |
Cd1—N6—C6 | 143.00 (13) | C3—C4—H4D | 109.00 |
Cd1—N8—C8 | 133.94 (13) | H4C—C4—H4D | 108.00 |
N6—Cd1—N4—C4 | 89.22 (13) | N3—Cd2—N2—C2 | 72.40 (11) |
N8—Cd1—N4—C4 | −176.11 (13) | N5—Cd2—N2—C2 | 159.61 (11) |
N4i—Cd1—N4—C4 | −133.04 (14) | N9—Cd2—N2—C2 | −110.06 (11) |
N6i—Cd1—N4—C4 | 1.78 (14) | N10—Cd2—N2—C2 | −37.3 (2) |
N8i—Cd1—N4—C4 | −90.94 (13) | N1—Cd2—N3—C3 | −168.22 (13) |
N4—Cd1—N6—C6 | −43.4 (2) | N2—Cd2—N3—C3 | 118.75 (13) |
N8—Cd1—N6—C6 | −121.4 (2) | N5—Cd2—N3—C3 | 25.45 (13) |
N4i—Cd1—N6—C6 | 151.9 (2) | N10—Cd2—N3—C3 | −80.97 (13) |
N6i—Cd1—N6—C6 | 65.5 (2) | N2—Cd2—N5—C5 | −127.5 (4) |
N4—Cd1—N8—C8 | 18.52 (17) | N3—Cd2—N5—C5 | −31.1 (4) |
N6—Cd1—N8—C8 | 104.63 (17) | N9—Cd2—N5—C5 | 144.2 (4) |
N4i—Cd1—N8—C8 | −146.82 (18) | N10—Cd2—N5—C5 | 58.7 (4) |
N8i—Cd1—N8—C8 | −68.19 (17) | Cd2—N1—C1—C2 | 48.05 (16) |
N2—Cd2—N1—C1 | −19.62 (10) | Cd2—N2—C2—C1 | 39.73 (16) |
N3—Cd2—N1—C1 | −117.90 (11) | Cd2—N3—C3—C4 | 54.50 (19) |
N9—Cd2—N1—C1 | 66.06 (11) | Cd1—N4—C4—C3 | 47.95 (17) |
N10—Cd2—N1—C1 | 151.15 (11) | N1—C1—C2—N2 | −60.71 (19) |
N1—Cd2—N2—C2 | −10.74 (10) | N3—C3—C4—N4 | 57.59 (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, y−1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···N7vi | 0.92 | 2.62 | 3.291 (2) | 130 |
N3—H3A···N7vi | 0.92 | 2.14 | 2.960 (2) | 147 |
N3—H3B···N8i | 0.92 | 2.15 | 3.066 (2) | 172 |
N4—H4A···N10 | 0.92 | 2.46 | 3.338 (2) | 161 |
C1—H1C···N7vii | 0.99 | 2.61 | 3.407 (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] |
Mr | 1007.72 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 173 |
a, b, c (Å) | 21.7002 (11), 7.7859 (5), 19.6450 (9) |
β (°) | 97.770 (4) |
V (Å3) | 3288.7 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.94 |
Crystal size (mm) | 0.42 × 0.33 × 0.21 |
Data collection | |
Diffractometer | Stoe IPDS-II |
Absorption correction | Multi-scan (MULscanABS in PLATON; Spek, 2003) |
Tmin, Tmax | 0.440, 0.540 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19479, 4410, 4101 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.686 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.018, 0.044, 1.11 |
No. of reflections | 4410 |
No. of parameters | 205 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 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).
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3A···N7i | 0.92 | 2.14 | 2.960 (2) | 147 |
N3—H3B···N8ii | 0.92 | 2.15 | 3.066 (2) | 172 |
Symmetry codes: (i) −x+1/2, −y+3/2, −z; (ii) −x, y, −z+1/2. |
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—N≡C bonds are bent, the smallest angle being 133.94 (13)° for the Cd1—N8≡C8 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, C7≡N7, 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.