Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807038226/ci2433sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807038226/ci2433Isup2.hkl |
CCDC reference: 660079
Key indicators
- Single-crystal X-ray study
- T = 90 K
- Mean (C-C) = 0.003 Å
- R factor = 0.026
- wR factor = 0.068
- Data-to-parameter ratio = 10.7
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.09 PLAT164_ALERT_4_C Nr. of Refined C-H H-Atoms in Heavy-At Struct... 2
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Ni1 (2) 2.24
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
A solution of Ni(hfac)2 was added to a solution of 2 equivalents of pyrazine-dioxide in acetonitrile at room temperature. Slow evaporation of the resulting solution over five days resulted in a large crop of green parallelepiped shaped crystals (yield 73%).
The dionato H atoms were placed in geometrically idealized positions (C—H = 0.95 Å) and constrained to ride on their parent atom, with Uiso(H) = 1.2Ueq(C). Acetonitrile methyl H atoms were freely refined due to their involvement in H-bonding. The highest residual density peak and the deepest hole are located 1.00 and 0.82 Å, respectively, from atom F1.
The title compound, (I), is centrosymmetric with a trans orientation of the ligands, and is shown in Fig. 1. Although the ligand disposition around Ni1 is not perfectly perpendicular (see Table 1), the mean plane through the C and O atoms of both hexafluoroacetylacetonate (hfac) ligands and the Ni1 atom is perpendicular to the plane through the acetonitrile-Ni plane. The CF3 groups of the hfac ligands are in a symmetry imposed eclipsed conformation.
trans-[Cp(PPh3)2RuCN]2Ni(hfac)2 is the only known structurally related species with a similar trans Ni(hfac)2(cyano)2 core (Chen et al., 2000). Although the substituents on the cyano group distort the geometry, the central hfac-Ni core is also perpendicular to the N—Ni—N vector as seen in (I). A related ruthenium analogue, cis-Ru(hfac)2(MeCN)2 (Baird et al., 1999) is a cis-isomer.
There is weak bifurcated intermolecular hydrogen bonding between the acetonitrile methyl group and the propanedionato oxygen (Fig. 2, Table 2), linking the molecules into a chain synthon parallel to the b-axis. The chains are further arranged into sheets parallel to the bc plane.
For related literature, see: Baird et al. (1999); Chen et al. (2000).
Data collection: SMART (Bruker, 2003); cell refinement: SAINT-Plus (Bruker, 2006); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Bruker, 2003); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: publCIF (Westrip, 2007).
[Ni(C5HF6O2)2(C2H3N)2] | F(000) = 1096 |
Mr = 554.93 | Dx = 1.806 Mg m−3 |
Orthorhombic, Cmca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2bc 2 | Cell parameters from 7181 reflections |
a = 20.4841 (6) Å | θ = 2.9–30.0° |
b = 7.1692 (2) Å | µ = 1.08 mm−1 |
c = 13.9008 (4) Å | T = 90 K |
V = 2041.4 (1) Å3 | Parallelepiped, light green |
Z = 4 | 0.21 × 0.20 × 0.10 mm |
Bruker SMART APEX CCD area-detector diffractometer | 956 independent reflections |
Radiation source: normal-focus sealed tube | 890 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
Detector resolution: 8.3 pixels mm-1 | θmax = 25.3°, θmin = 2.0° |
ω scans | h = −24→24 |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | k = −8→8 |
Tmin = 0.805, Tmax = 0.900 | l = −16→16 |
14542 measured reflections |
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) = 0.069 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0363P)2 + 3.0631P] where P = (Fo2 + 2Fc2)/3 |
956 reflections | (Δ/σ)max = 0.001 |
89 parameters | Δρmax = 0.50 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
[Ni(C5HF6O2)2(C2H3N)2] | V = 2041.4 (1) Å3 |
Mr = 554.93 | Z = 4 |
Orthorhombic, Cmca | Mo Kα radiation |
a = 20.4841 (6) Å | µ = 1.08 mm−1 |
b = 7.1692 (2) Å | T = 90 K |
c = 13.9008 (4) Å | 0.21 × 0.20 × 0.10 mm |
Bruker SMART APEX CCD area-detector diffractometer | 956 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | 890 reflections with I > 2σ(I) |
Tmin = 0.805, Tmax = 0.900 | Rint = 0.025 |
14542 measured reflections |
R[F2 > 2σ(F2)] = 0.026 | 0 restraints |
wR(F2) = 0.069 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | Δρmax = 0.50 e Å−3 |
956 reflections | Δρmin = −0.24 e Å−3 |
89 parameters |
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 | 0.5000 | 0.0000 | 0.5000 | 0.01765 (16) | |
C1 | 0.37064 (9) | 0.1065 (2) | 0.43182 (13) | 0.0243 (4) | |
C2 | 0.33788 (13) | 0.0000 | 0.5000 | 0.0294 (6) | |
H2 | 0.2915 | 0.0000 | 0.5000 | 0.035* | |
C3 | 0.33054 (10) | 0.2315 (3) | 0.36471 (15) | 0.0344 (5) | |
C4 | 0.5000 | 0.3617 (4) | 0.63509 (18) | 0.0225 (5) | |
C5 | 0.5000 | 0.5185 (4) | 0.7013 (2) | 0.0268 (6) | |
H5A | 0.5364 (12) | 0.514 (4) | 0.741 (2) | 0.061 (8)* | |
H5B | 0.5000 | 0.628 (6) | 0.665 (3) | 0.058 (12)* | |
F1 | 0.26677 (6) | 0.1999 (2) | 0.36833 (12) | 0.0604 (5) | |
F2 | 0.33928 (7) | 0.41007 (19) | 0.38887 (11) | 0.0531 (4) | |
F3 | 0.35020 (7) | 0.2156 (2) | 0.27393 (9) | 0.0495 (4) | |
N1 | 0.5000 | 0.2359 (3) | 0.58532 (15) | 0.0242 (5) | |
O1 | 0.43089 (6) | 0.12008 (17) | 0.41713 (9) | 0.0226 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0161 (3) | 0.0194 (3) | 0.0174 (2) | 0.000 | 0.000 | 0.00028 (17) |
C1 | 0.0214 (9) | 0.0249 (9) | 0.0266 (10) | 0.0009 (7) | −0.0029 (7) | −0.0029 (8) |
C2 | 0.0176 (13) | 0.0353 (15) | 0.0353 (15) | 0.000 | 0.000 | 0.0019 (12) |
C3 | 0.0235 (10) | 0.0442 (13) | 0.0354 (11) | 0.0042 (9) | −0.0041 (8) | 0.0075 (10) |
C4 | 0.0246 (13) | 0.0231 (13) | 0.0198 (12) | 0.000 | 0.000 | 0.0051 (11) |
C5 | 0.0385 (17) | 0.0209 (13) | 0.0209 (14) | 0.000 | 0.000 | −0.0011 (11) |
F1 | 0.0231 (7) | 0.0842 (11) | 0.0738 (10) | 0.0021 (7) | −0.0135 (7) | 0.0323 (9) |
F2 | 0.0610 (9) | 0.0372 (8) | 0.0610 (9) | 0.0183 (7) | −0.0115 (7) | 0.0081 (7) |
F3 | 0.0478 (8) | 0.0700 (9) | 0.0307 (7) | 0.0158 (7) | −0.0109 (6) | 0.0065 (6) |
N1 | 0.0275 (12) | 0.0235 (12) | 0.0215 (11) | 0.000 | 0.000 | 0.0008 (10) |
O1 | 0.0204 (6) | 0.0257 (7) | 0.0218 (6) | 0.0012 (5) | −0.0020 (5) | 0.0022 (5) |
Ni1—O1i | 2.0180 (12) | C2—C1i | 1.390 (2) |
Ni1—O1 | 2.0180 (12) | C2—H2 | 0.95 |
Ni1—O1ii | 2.0180 (12) | C3—F1 | 1.327 (2) |
Ni1—O1iii | 2.0180 (12) | C3—F3 | 1.329 (2) |
Ni1—N1 | 2.066 (2) | C3—F2 | 1.335 (3) |
Ni1—N1ii | 2.066 (2) | C4—N1 | 1.137 (3) |
C1—O1 | 1.255 (2) | C4—C5 | 1.453 (4) |
C1—C2 | 1.390 (2) | C5—H5A | 0.93 (3) |
C1—C3 | 1.532 (3) | C5—H5B | 0.93 (4) |
O1i—Ni1—O1 | 90.90 (7) | C2—C1—C3 | 118.54 (18) |
O1i—Ni1—O1ii | 89.10 (7) | C1—C2—C1i | 122.3 (3) |
O1—Ni1—O1ii | 180.0 | C1—C2—H2 | 118.9 |
O1i—Ni1—O1iii | 180.00 (5) | C1i—C2—H2 | 118.9 |
O1—Ni1—O1iii | 89.10 (7) | F1—C3—F3 | 108.63 (18) |
O1ii—Ni1—O1iii | 90.90 (7) | F1—C3—F2 | 106.62 (18) |
O1i—Ni1—N1 | 91.23 (6) | F3—C3—F2 | 106.28 (18) |
O1—Ni1—N1 | 88.77 (6) | F1—C3—C1 | 113.87 (18) |
O1ii—Ni1—N1 | 91.23 (6) | F3—C3—C1 | 111.43 (17) |
O1iii—Ni1—N1 | 88.77 (6) | F2—C3—C1 | 109.62 (17) |
O1i—Ni1—N1ii | 88.77 (6) | N1—C4—C5 | 178.2 (3) |
O1—Ni1—N1ii | 91.23 (6) | C4—C5—H5A | 110.5 (18) |
O1ii—Ni1—N1ii | 88.77 (6) | C4—C5—H5B | 108 (2) |
O1iii—Ni1—N1ii | 91.23 (6) | H5A—C5—H5B | 110 (2) |
N1—Ni1—N1ii | 180.0 | C4—N1—Ni1 | 177.6 (2) |
O1—C1—C2 | 128.94 (18) | C1—O1—Ni1 | 124.34 (12) |
O1—C1—C3 | 112.50 (16) |
Symmetry codes: (i) x, −y, −z+1; (ii) −x+1, −y, −z+1; (iii) −x+1, y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5B···O1iv | 0.93 (4) | 2.56 (4) | 3.381 (3) | 147 (1) |
C5—H5B···O1v | 0.93 (4) | 2.56 (4) | 3.381 (3) | 147 (1) |
Symmetry codes: (iv) −x+1, −y+1, −z+1; (v) x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Ni(C5HF6O2)2(C2H3N)2] |
Mr | 554.93 |
Crystal system, space group | Orthorhombic, Cmca |
Temperature (K) | 90 |
a, b, c (Å) | 20.4841 (6), 7.1692 (2), 13.9008 (4) |
V (Å3) | 2041.4 (1) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.08 |
Crystal size (mm) | 0.21 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2004) |
Tmin, Tmax | 0.805, 0.900 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14542, 956, 890 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.600 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.069, 1.08 |
No. of reflections | 956 |
No. of parameters | 89 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.50, −0.24 |
Computer programs: SMART (Bruker, 2003), SAINT-Plus (Bruker, 2006), SAINT-Plus, SHELXTL (Bruker, 2003), SHELXTL, publCIF (Westrip, 2007).
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5B···O1i | 0.93 (4) | 2.56 (4) | 3.381 (3) | 146.5 (6) |
C5—H5B···O1ii | 0.93 (4) | 2.56 (4) | 3.381 (3) | 146.5 (6) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+1, −z+1. |
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The title compound, (I), is centrosymmetric with a trans orientation of the ligands, and is shown in Fig. 1. Although the ligand disposition around Ni1 is not perfectly perpendicular (see Table 1), the mean plane through the C and O atoms of both hexafluoroacetylacetonate (hfac) ligands and the Ni1 atom is perpendicular to the plane through the acetonitrile-Ni plane. The CF3 groups of the hfac ligands are in a symmetry imposed eclipsed conformation.
trans-[Cp(PPh3)2RuCN]2Ni(hfac)2 is the only known structurally related species with a similar trans Ni(hfac)2(cyano)2 core (Chen et al., 2000). Although the substituents on the cyano group distort the geometry, the central hfac-Ni core is also perpendicular to the N—Ni—N vector as seen in (I). A related ruthenium analogue, cis-Ru(hfac)2(MeCN)2 (Baird et al., 1999) is a cis-isomer.
There is weak bifurcated intermolecular hydrogen bonding between the acetonitrile methyl group and the propanedionato oxygen (Fig. 2, Table 2), linking the molecules into a chain synthon parallel to the b-axis. The chains are further arranged into sheets parallel to the bc plane.