Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113009797/sk3482sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113009797/sk3482Isup2.hkl |
CCDC reference: 950359
Compound (I) was obtained as a secondary product of a synthesis carried out at room temperature, where Ni(acac)2 (acac is acetylacetonate), L-histidine, sodium tert-butoxide and sodium azide were mixed in a 3:2:3:3 molar ratio, using methanol as solvent. The reaction mixture was stirred for 30 min. The solid obtained was separated by filtration and the solution was allowed to stand at room temperature for slow evaporation. After three weeks, blue needle-shaped crystals of (I) were separated from the solution in a very low yield (around 15%). Compound (I) was characterized by FT–IR and solid UV–Vis spectroscopy. The FT–IR spectrum for (I) shows a very similar pattern of bands to the Ni(acac)2 precursor, with strong absorptions at 1592, 1514 and 1466 cm-1, attributable to stretching absorptions of C═C and C═O bonds characteristic for this type of compound. However, the band at 1522 cm-1 characteristic of the Ni(acac)2 precursor is absent from the [NaNi(acac)3]n chain in (I). This experimental evidence is explained by considering that the bands at 1514 and 1466 cm-1 are due to splitting of the band at 1522 cm-1 and are produced by the different interactions of the NiII and NaI cations with the acac ligand. The solid UV–Vis spectrum obtained for (I) is dominated by a strong absorption between 200 and 330 nm, corresponding to a π–π transition of the organic ligand. A very weak absorption in the zone of d–d transitions was also observed at 625 nm (16000 cm-1), which was attributed to a 3A2g ← 3T1g(F) transition associated with the NiII cation (Van Leeuwen, 1968).
The H-atom positions were calculated after each cycle of refinement using a riding model, with C—H = 0.95 or 0.98 Å [For which parent types?]. Uiso(H) values were set to 1.5Ueq(C) for methyl groups or 1.2Ueq(C) otherwise.
Data collection: APEX2 (Bruker, 2001); cell refinement: APEX2 (Bruker, 2001); data reduction: APEX2 (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: APEX2 (Bruker, 2001) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXTL-NT (Sheldrick, 2008).
[NaNi(C5H7O2)3] | Dx = 1.434 Mg m−3 |
Mr = 379.00 | Mo Kα radiation, λ = 0.71073 Å |
Trigonal, R3c | Cell parameters from 2266 reflections |
Hall symbol: -R 3 2"c | θ = 2.5–26.9° |
a = 16.133 (2) Å | µ = 1.15 mm−1 |
c = 11.684 (4) Å | T = 150 K |
V = 2633.6 (13) Å3 | Needle, light blue |
Z = 6 | 0.42 × 0.12 × 0.07 mm |
F(000) = 1188.0 |
Siemens SMART CCD area-detector diffractometer | 582 independent reflections |
Radiation source: fine-focus sealed tube | 506 reflections with I > 2σigma(I) |
Graphite monochromator | Rint = 0.035 |
ω scans | θmax = 26.0°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −19→19 |
Tmin = 0.534, Tmax = 0.890 | k = −19→19 |
5622 measured reflections | l = −14→14 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.026 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.070 | H-atom parameters constrained |
S = 1.14 | w = 1/[σ2(Fo2) + (0.0366P)2 + 2.4448P] where P = (Fo2 + 2Fc2)/3 |
582 reflections | (Δ/σ)max < 0.001 |
38 parameters | Δρmax = 0.36 e Å−3 |
0 restraints | Δρmin = −0.17 e Å−3 |
[NaNi(C5H7O2)3] | Z = 6 |
Mr = 379.00 | Mo Kα radiation |
Trigonal, R3c | µ = 1.15 mm−1 |
a = 16.133 (2) Å | T = 150 K |
c = 11.684 (4) Å | 0.42 × 0.12 × 0.07 mm |
V = 2633.6 (13) Å3 |
Siemens SMART CCD area-detector diffractometer | 582 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 506 reflections with I > 2σigma(I) |
Tmin = 0.534, Tmax = 0.890 | Rint = 0.035 |
5622 measured reflections |
R[F2 > 2σ(F2)] = 0.026 | 0 restraints |
wR(F2) = 0.070 | H-atom parameters constrained |
S = 1.14 | Δρmax = 0.36 e Å−3 |
582 reflections | Δρmin = −0.17 e Å−3 |
38 parameters |
Experimental. 0.3 ° between frames and 10 secs exposure (per frame) |
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. |
x | y | z | Uiso*/Ueq | ||
Ni1 | 0.0000 | 0.0000 | 0.2500 | 0.02055 (19) | |
Na1 | 0.0000 | 0.0000 | 0.5000 | 0.0266 (4) | |
O1 | 0.06355 (8) | 0.11485 (9) | 0.35654 (9) | 0.0244 (3) | |
C1 | 0.20596 (14) | 0.20596 (14) | 0.2500 | 0.0290 (5) | |
H1 | 0.2649 | 0.2649 | 0.2500 | 0.035* | |
C2 | 0.14657 (11) | 0.18715 (11) | 0.34524 (13) | 0.0253 (4) | |
C3 | 0.18062 (13) | 0.25706 (13) | 0.44329 (14) | 0.0352 (4) | |
H3A | 0.1411 | 0.2874 | 0.4482 | 0.053* | |
H3B | 0.2476 | 0.3062 | 0.4307 | 0.053* | |
H3C | 0.1754 | 0.2231 | 0.5149 | 0.053* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0238 (2) | 0.0238 (2) | 0.0141 (3) | 0.01190 (11) | 0.000 | 0.000 |
Na1 | 0.0330 (6) | 0.0330 (6) | 0.0138 (7) | 0.0165 (3) | 0.000 | 0.000 |
C1 | 0.0251 (9) | 0.0251 (9) | 0.0340 (13) | 0.0106 (10) | 0.0003 (5) | −0.0003 (5) |
O1 | 0.0283 (6) | 0.0253 (6) | 0.0178 (6) | 0.0121 (5) | 0.0006 (4) | −0.0010 (5) |
C2 | 0.0293 (9) | 0.0256 (8) | 0.0257 (8) | 0.0171 (7) | −0.0052 (7) | −0.0011 (6) |
C3 | 0.0364 (10) | 0.0336 (10) | 0.0340 (10) | 0.0161 (8) | −0.0044 (8) | −0.0089 (8) |
Ni1—O1 | 2.0332 (12) | Na1—O1 | 2.3226 (12) |
Ni1—O1i | 2.0332 (12) | Na1—O1viii | 2.3226 (12) |
Ni1—O1ii | 2.0332 (12) | Na1—Ni1viii | 2.9211 (10) |
Ni1—O1iii | 2.0332 (12) | O1—C2 | 1.269 (2) |
Ni1—O1iv | 2.0332 (12) | C2—C1 | 1.399 (2) |
Ni1—O1v | 2.0332 (12) | C2—C3 | 1.506 (2) |
Ni1—Na1 | 2.9211 (10) | C1—C2iv | 1.399 (2) |
Na1—O1v | 2.3226 (12) | C1—H1 | 0.9500 |
Na1—O1vi | 2.3226 (12) | C3—H3A | 0.9800 |
Na1—O1iii | 2.3226 (12) | C3—H3B | 0.9800 |
Na1—O1vii | 2.3226 (12) | C3—H3C | 0.9800 |
O1—Ni1—O1i | 174.43 (6) | O1iii—Na1—O1 | 73.66 (5) |
O1—Ni1—O1ii | 97.53 (6) | O1vii—Na1—O1 | 106.34 (5) |
O1i—Ni1—O1ii | 86.43 (5) | O1v—Na1—O1viii | 106.34 (5) |
O1—Ni1—O1iii | 86.43 (5) | O1vi—Na1—O1viii | 73.66 (5) |
O1i—Ni1—O1iii | 89.89 (6) | O1iii—Na1—O1viii | 106.34 (5) |
O1ii—Ni1—O1iii | 174.43 (6) | O1vii—Na1—O1viii | 73.66 (5) |
O1—Ni1—O1iv | 89.89 (6) | O1—Na1—O1viii | 180.00 (6) |
O1i—Ni1—O1iv | 86.43 (5) | C2—O1—Ni1 | 126.41 (10) |
O1ii—Ni1—O1iv | 86.43 (5) | C2—O1—Na1 | 130.58 (10) |
O1iii—Ni1—O1iv | 97.53 (6) | Ni1—O1—Na1 | 83.95 (5) |
O1—Ni1—O1v | 86.43 (5) | O1—C2—C1 | 125.16 (15) |
O1i—Ni1—O1v | 97.53 (6) | O1—C2—C3 | 115.57 (14) |
O1ii—Ni1—O1v | 89.89 (6) | C1—C2—C3 | 119.27 (16) |
O1iii—Ni1—O1v | 86.43 (5) | C2iv—C1—C2 | 126.4 (2) |
O1iv—Ni1—O1v | 174.43 (6) | C2iv—C1—H1 | 116.8 |
O1v—Na1—O1vi | 180.0 | C2—C1—H1 | 116.8 |
O1v—Na1—O1iii | 73.66 (5) | C2—C3—H3A | 109.5 |
O1vi—Na1—O1iii | 106.34 (5) | C2—C3—H3B | 109.5 |
O1v—Na1—O1vii | 106.34 (5) | H3A—C3—H3B | 109.5 |
O1vi—Na1—O1vii | 73.66 (5) | C2—C3—H3C | 109.5 |
O1iii—Na1—O1vii | 180.00 (4) | H3A—C3—H3C | 109.5 |
O1v—Na1—O1 | 73.66 (5) | H3B—C3—H3C | 109.5 |
O1vi—Na1—O1 | 106.34 (5) |
Symmetry codes: (i) x−y, −y, −z+1/2; (ii) −x, −x+y, −z+1/2; (iii) −x+y, −x, z; (iv) y, x, −z+1/2; (v) −y, x−y, z; (vi) y, −x+y, −z+1; (vii) x−y, x, −z+1; (viii) −x, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [NaNi(C5H7O2)3] |
Mr | 379.00 |
Crystal system, space group | Trigonal, R3c |
Temperature (K) | 150 |
a, c (Å) | 16.133 (2), 11.684 (4) |
V (Å3) | 2633.6 (13) |
Z | 6 |
Radiation type | Mo Kα |
µ (mm−1) | 1.15 |
Crystal size (mm) | 0.42 × 0.12 × 0.07 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2001) |
Tmin, Tmax | 0.534, 0.890 |
No. of measured, independent and observed [I > 2σigma(I)] reflections | 5622, 582, 506 |
Rint | 0.035 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.070, 1.14 |
No. of reflections | 582 |
No. of parameters | 38 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.36, −0.17 |
Computer programs: , SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), APEX2 (Bruker, 2001) and Mercury (Macrae et al., 2008), SHELXTL-NT (Sheldrick, 2008).
Ni1—O1 | 2.0332 (12) | Na1—O1 | 2.3226 (12) |
Ni1—Na1 | 2.9211 (10) | ||
O1—Ni1—O1i | 174.43 (6) | O1—Ni1—O1iii | 86.43 (5) |
O1—Ni1—O1ii | 97.53 (6) | O1—Ni1—O1iv | 89.89 (6) |
Symmetry codes: (i) x−y, −y, −z+1/2; (ii) −x, −x+y, −z+1/2; (iii) −x+y, −x, z; (iv) y, x, −z+1/2. |
The self-assembly of coordination polymers from various building blocks is of considerable interest, due to the intriguing diverse architectures that can be obtained, and their potential applications in catalysis and advanced materials (Chen et al. 2010; Stabnikov et al., 2010). In this respect, acetylacetonate (abbreviated as acac) is a bidentate and chelating ligand, and its complexes are widely used for the preparation of metal complexes and inorganic materials. This is mainly due to its lower basicity, which permits this ligand to be easily replaced by other ligands. This characteristic, in addition to the comparatively high volatility of acetylacetone, makes them perfect metal complex precursors (Zaworotko et al., 2009; Shahid et al., 2010; Kudrat-E-Zahan et al., 2010; Tenne et al., 2012; Sui et al., 2012). Furthermore, higher solubility in the most common organic solvents is observed when acac salts are replaced by hexafluoroacetylacetonate complexes (Horikoshi et al., 2003, 2005; Yu et al., 2007; Fursova et al., 2008).
Acac complexes have been described and structurally characterized for almost all transition metals and lanthanides [Cr (Morosin, 1965), Mn (Morosin & Brathovde, 1964), Mo (Raston & White, 1979), Rh (Morrow & Parker, 1973), Ru (Chao et al., 1973), Sc (Astbury, 1926; Anderson et al., 1973), Zr (Silverton & Hoard, 1963), Co (Hon & Pfluger, 1973), Fe (Iball & Morgan, 1967), Tc (Hashimoto et al., 1988), Os (Dallmann & Preetz, 1998), Ti (Yun et al., 1999), Ir (Davignon et al., 1970), V (Morosin & Montgomery, 1969) and Hf (Allard, 1976)]. All of them show an appropriate number of chelating and bidentate acac anions covalently bonded to the metal, but showing no covalency between the M(acac)n units. Despite their low basicity, the coordinated O atoms of M(acac)n could act as ligands and coordinate to other metal complexes having vacant sites. This has been observed in a variety of different systems (Yun et al., 1999; Lindoy et al., 1977; Rogachev et al., 2007; Castro et al., 1992). Within this class of compounds, there is a special group where the M(acac)n units are coordinated to naked cations, obtaining in this form heteropolymetallic complexes with different nuclearity and dimensionality (Shibata et al., 1984; Atencio et al., 2004; Greaney et al. 1975; Troyanov et al., 1999; Vreshch et al., 2010).
The title complex, catena-poly[tris(µ4-acetylacetonato)nickelate(II)sodium(I)], (I), consists of an anionic tris(acetylacetonato)nickelate(II) unit, [Ni(acac)3]-, with a highly regular octahedral coordination geometry (Fig. 1). Charge balance is provided by sodium cations. Each sodium cation is surrounded by two [Ni(acac)3]- units, each of which connected to the alkali metal by three O atoms, in a fac configuration (Table 1). This arrangement leads to the formation of linear [Na{Ni(acac)3}]n chains along the c axis (Fig. 2). This particular arrangement, forming chains along a spatial direction, was reported previously by Troyanov et al. (1999) for [K{Mn(hexafluoroacetylacetonate)3}]n. As mentioned above, the last interaction produces parallel [Na{Ni(acac)3}]n [chains? Text missing], where nickel and sodium cations appear in an alternate manner parallel to the c axis (Fig. 2), giving rise to a polymetallic one-dimensional structure based on NiII, NaI and acac units, where the Ni···Na and Ni···Ni distances are 2.9211 (10) and 5.842 (2) Å, respectively. Furthermore, no covalent interactions between the chains are observed. In the structure of (I), the bidentate coordination of three acac ligands to the NiII cation confers chirality on the [Ni(acac)3]- unit (Fig. 1). However, due to the L and D configurations of each NiII cation occurring alternately along the chain (Fig. 2), those properties cancel.
Compound (I) is isomorphous with the cobalt and sodium chain, [Na{Co(acac)3}], reported by Li et al. (2003). In that case, the authors also carried out the synthesis in a methanol medium but in the presence of sodium borohydride. A search of the Cambridge Structural Database (CSD, Version 5.33; Allen, 2002) shows 109 compounds containing transition metal cations and only acetylacetonante as ligand, but just two of them are derived from NiII. The first compound based on the [Ni(acac)3]- anion was reported by Watson & Lin (1966) with the formula Ag[Ni(acac)3].2AgNO3.H2O. According to those authors, this compound can be considered as a silver complex with the [Ni(acac)3]- anion forming an intricate three-dimensional polymeric structure. The unit cell is tetragonal in space group P41 [a = b = 15.053 (5) Å, c = 10.800 (7) Å]. The NiII cation is octahedrally surrounded by O atoms at an average distance of 2.04 (6) Å and an average O—Ni—O bond angle of 90 (3)°. The [Ni(acac)3]- anions are held together by one of the AgI cations in spiral chains parallel to the c cell axis. The second compound was reported by Atencio et al. (2004) with the formula K[Ni(acac)3].0.3H2O. In this case, the asymmetric unit is composed of a potassium cation, one complex [Ni(acac)3]- anion and a solvent water molecule with site occupancy 0.30. The unit cell is orthorhombic in space group Pna21. The metal complex contains three acac ligands coordinated through their O atoms and forming a distorted octahedral environment around the NiII centre. The O-atom disposition around the metal results in Ni—O bond lengths ranging between 2.049 (3) and 2.137 (3) Å, and O—Ni—O bond angles between 86.69 (12) and 93.75 (13)°, which are very close to those observed for Ag[Ni(acac)3].2AgNO3.H2O (Watson & Lin, 1966). Both compounds, similar to what has been described above for (I), are composed of one-dimensional chains formed by alternating cations and [M(acac)3]- anions.