Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801016348/cf6111sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801016348/cf6111Isup2.hkl |
CCDC reference: 175973
To a solution of [NEt4][Fe({SCH2CH2}3N)(CO)] (0.59 g, 1.44 mmol) in MeCN (25 ml) was added a solution of [NiCl2(PPh3)2] (1.17 g, 1.79 mmol) in MeCN (100 ml). The dark-red solution that immediately formed was stirred for 90 min under an atmosphere of CO. Upon standing overnight, dark crystals of [Ni{Fe({SCH2CH2}3N)(CO)}2] (0.25 g, 56%) formed. These were collected by filtration, washed repeatedly with diethyl ether and dried in vacuo. Over a period of 3 d, the retained filtrate, under a dinitrogen atmosphere, slowly changed to a dark-blue colour whilst giving a crystalline precipitate of PPh3. The solution was evaporated to ~15 ml under vacuum and then filtered to remove PPh3. Diethyl ether (5 ml) was added to the blue filtrate, leading to the formation of large royal blue crystals of [NEt4][NiCl3(PPh3)] and white crystals of [NEt4]Cl. These were collected by filtration, washed with diethyl ether and dried in vacuo. A crystal of [NEt4][NiCl3(PPh3)] was selected for the X-ray study.
Data were collected and the structure determined in a space group setting involving exchange of h and k indices, and of x and y coordinates relative to the standard setting of Pa3; we have denoted this as Pb3. Data above θ=24° were weak, as a consequence of the disorder, and were not used. H atoms were subject to riding-model constraints; isotropic displacement parameters were freely refined for those of the anion.
Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1992); cell refinement: CAD-4 EXPRESS; data reduction: CAD-4 (Hursthouse, 1976); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL93 (Sheldrick, 1993); molecular graphics: ORTEPII (Johnson, 1971); software used to prepare material for publication: SHELXL93.
C8H20N+·C18H15Cl3NiP− | Melting point: 521 K |
Mr = 557.58 | Mo Kα radiation, λ = 0.71069 Å |
Cubic, Pb3 | Cell parameters from 25 reflections |
Hall symbol: -p 2bc 2ac 3 | θ = 10–11° |
a = 17.6676 (7) Å | µ = 1.07 mm−1 |
V = 5514.8 (4) Å3 | T = 293 K |
Z = 8 | Octahedra, translucent intense blue |
F(000) = 2336 | 0.36 × 0.29 × 0.24 mm |
Dx = 1.343 Mg m−3 |
Enraf-Nonius CAD-4 diffractometer | 497 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.022 |
Graphite monochromator | θmax = 24.0°, θmin = 1.5° |
ω scans | h = −4→13 |
Absorption correction: ψ scan (EMPABS; Sheldrick et al., 1977) | k = −4→14 |
Tmin = 0.728, Tmax = 0.774 | l = −1→20 |
1750 measured reflections | 3 standard reflections every 400 reflections |
1445 independent reflections | intensity decay: none |
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)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.177 | Only H-atom displacement parameters refined |
S = 0.96 | w = 1/[σ2(Fo2) + (0.0626P)2] where P = (Fo2 + 2Fc2)/3 |
1445 reflections | (Δ/σ)max = 0.002 |
110 parameters | Δρmax = 0.27 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
C8H20N+·C18H15Cl3NiP− | Z = 8 |
Mr = 557.58 | Mo Kα radiation |
Cubic, Pb3 | µ = 1.07 mm−1 |
a = 17.6676 (7) Å | T = 293 K |
V = 5514.8 (4) Å3 | 0.36 × 0.29 × 0.24 mm |
Enraf-Nonius CAD-4 diffractometer | 497 reflections with I > 2σ(I) |
Absorption correction: ψ scan (EMPABS; Sheldrick et al., 1977) | Rint = 0.022 |
Tmin = 0.728, Tmax = 0.774 | θmax = 24.0° |
1750 measured reflections | 3 standard reflections every 400 reflections |
1445 independent reflections | intensity decay: none |
R[F2 > 2σ(F2)] = 0.055 | 0 restraints |
wR(F2) = 0.177 | Only H-atom displacement parameters refined |
S = 0.96 | Δρmax = 0.27 e Å−3 |
1445 reflections | Δρmin = −0.23 e Å−3 |
110 parameters |
Experimental. Melting point 248 <o>C. λmax / nm (CH3CN) 326 (ε / dm3 mol-1 cm-1 1423), 617 (149). |
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 on F2 for ALL reflections except for 0 with very negative F2 or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating _R_factor_obs 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 | Occ. (<1) | |
Ni | 0.80870 (5) | 0.69130 (5) | 0.19130 (5) | 0.0722 (6) | |
Cl1 | 0.7878 (2) | 0.79346 (13) | 0.1199 (2) | 0.1112 (10) | |
P1 | 0.88460 (11) | 0.61540 (11) | 0.11540 (11) | 0.0560 (9) | |
C11 | 0.8359 (4) | 0.5758 (4) | 0.0345 (4) | 0.058 (2) | |
C12 | 0.8477 (4) | 0.5025 (5) | 0.0093 (4) | 0.068 (2) | |
H12 | 0.8806 | 0.4712 | 0.0359 | 0.06 (2)* | |
C13 | 0.8115 (5) | 0.4749 (6) | −0.0544 (5) | 0.085 (3) | |
H13 | 0.8196 | 0.4254 | −0.0705 | 0.10 (3)* | |
C14 | 0.7635 (6) | 0.5217 (6) | −0.0935 (6) | 0.099 (3) | |
H14 | 0.7383 | 0.5034 | −0.1360 | 0.10 (3)* | |
C15 | 0.7520 (6) | 0.5947 (7) | −0.0713 (6) | 0.107 (3) | |
H15 | 0.7208 | 0.6267 | −0.0990 | 0.09 (3)* | |
C16 | 0.7874 (5) | 0.6198 (5) | −0.0069 (5) | 0.085 (3) | |
H16 | 0.7781 | 0.6690 | 0.0093 | 0.05 (2)* | |
N1 | 0.6154 (4) | 0.3846 (4) | 0.1154 (4) | 0.071 (3) | |
C1 | 0.650 (2) | 0.464 (3) | 0.099 (3) | 0.155 (14)* | 0.33333 |
H1A | 0.6860 | 0.4755 | 0.1387 | 0.185* | 0.33333 |
H1B | 0.6784 | 0.4607 | 0.0518 | 0.185* | 0.33333 |
C2 | 0.601 (2) | 0.524 (2) | 0.093 (2) | 0.146 (15)* | 0.33333 |
H2A | 0.6285 | 0.5699 | 0.0826 | 0.219* | 0.33333 |
H2B | 0.5732 | 0.5300 | 0.1394 | 0.219* | 0.33333 |
H2C | 0.5655 | 0.5152 | 0.0523 | 0.219* | 0.33333 |
C3 | 0.660 (2) | 0.3057 (18) | 0.1048 (17) | 0.111 (10)* | 0.33333 |
H3A | 0.6611 | 0.2927 | 0.0515 | 0.133* | 0.33333 |
H3B | 0.7120 | 0.3122 | 0.1215 | 0.133* | 0.33333 |
C4 | 0.627 (2) | 0.247 (2) | 0.145 (2) | 0.128 (13)* | 0.33333 |
H4A | 0.6560 | 0.2010 | 0.1370 | 0.191* | 0.33333 |
H4B | 0.5763 | 0.2391 | 0.1281 | 0.191* | 0.33333 |
H4C | 0.6272 | 0.2586 | 0.1981 | 0.191* | 0.33333 |
C5 | 0.5406 (17) | 0.3678 (16) | 0.0718 (16) | 0.089 (8)* | 0.33333 |
H5A | 0.5200 | 0.3199 | 0.0892 | 0.107* | 0.33333 |
H5B | 0.5039 | 0.4070 | 0.0831 | 0.107* | 0.33333 |
C6 | 0.5523 (16) | 0.3640 (18) | −0.0126 (18) | 0.099 (10)* | 0.33333 |
H6A | 0.5176 | 0.3282 | −0.0342 | 0.149* | 0.33333 |
H6B | 0.6032 | 0.3485 | −0.0232 | 0.149* | 0.33333 |
H6C | 0.5435 | 0.4131 | −0.0343 | 0.149* | 0.33333 |
C7 | 0.609 (2) | 0.403 (3) | 0.194 (2) | 0.153 (14)* | 0.33333 |
H7A | 0.5773 | 0.3642 | 0.2162 | 0.184* | 0.33333 |
H7B | 0.5799 | 0.4496 | 0.1963 | 0.184* | 0.33333 |
C8 | 0.6715 (17) | 0.4139 (19) | 0.248 (2) | 0.108 (11)* | 0.33333 |
H8A | 0.6511 | 0.4259 | 0.2974 | 0.162* | 0.33333 |
H8B | 0.7033 | 0.4546 | 0.2316 | 0.162* | 0.33333 |
H8C | 0.7007 | 0.3682 | 0.2517 | 0.162* | 0.33333 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni | 0.0722 (6) | 0.0722 (6) | 0.0722 (6) | 0.0077 (6) | 0.0077 (6) | −0.0077 (6) |
Cl1 | 0.127 (2) | 0.078 (2) | 0.129 (2) | 0.0215 (15) | −0.025 (2) | −0.0001 (15) |
P1 | 0.0560 (9) | 0.0560 (9) | 0.0560 (9) | 0.0012 (10) | 0.0012 (10) | −0.0012 (10) |
C11 | 0.060 (5) | 0.053 (5) | 0.061 (5) | 0.006 (4) | 0.003 (4) | 0.003 (4) |
C12 | 0.080 (6) | 0.066 (5) | 0.058 (5) | −0.004 (5) | −0.004 (5) | 0.004 (5) |
C13 | 0.088 (7) | 0.096 (8) | 0.070 (6) | −0.017 (6) | −0.012 (6) | −0.014 (6) |
C14 | 0.106 (8) | 0.118 (9) | 0.072 (7) | −0.024 (7) | −0.024 (6) | −0.017 (7) |
C15 | 0.115 (8) | 0.123 (9) | 0.082 (7) | 0.021 (8) | −0.045 (6) | 0.004 (7) |
C16 | 0.111 (8) | 0.066 (6) | 0.076 (6) | 0.010 (5) | −0.009 (6) | −0.006 (5) |
N1 | 0.071 (3) | 0.071 (3) | 0.071 (3) | −0.002 (4) | 0.002 (4) | −0.002 (4) |
Ni—Cl1 | 2.233 (2) | C2—H2A | 0.96 |
Ni—P1 | 2.322 (4) | C2—H2B | 0.96 |
P1—C11 | 1.809 (7) | C2—H2C | 0.96 |
C11—C16 | 1.369 (10) | C3—C4 | 1.39 (4) |
C11—C12 | 1.385 (9) | C3—H3A | 0.97 |
C12—C13 | 1.384 (10) | C3—H3B | 0.97 |
C12—H12 | 0.93 | C4—H4A | 0.96 |
C13—C14 | 1.372 (11) | C4—H4B | 0.96 |
C13—H13 | 0.93 | C4—H4C | 0.96 |
C14—C15 | 1.364 (11) | C5—C6 | 1.51 (4) |
C14—H14 | 0.93 | C5—H5A | 0.97 |
C15—C16 | 1.371 (11) | C5—H5B | 0.97 |
C15—H15 | 0.93 | C6—H6A | 0.96 |
C16—H16 | 0.93 | C6—H6B | 0.96 |
N1—C7 | 1.44 (4) | C6—H6C | 0.96 |
N1—C5 | 1.56 (3) | C7—C8 | 1.47 (5) |
N1—C1 | 1.56 (4) | C7—H7A | 0.97 |
N1—C3 | 1.61 (3) | C7—H7B | 0.97 |
C1—C2 | 1.38 (5) | C8—H8A | 0.96 |
C1—H1A | 0.97 | C8—H8B | 0.96 |
C1—H1B | 0.97 | C8—H8C | 0.96 |
Cl1—Ni—Cl1i | 114.61 (6) | H2A—C2—H2C | 109.5 |
Cl1—Ni—P1 | 103.65 (8) | H2B—C2—H2C | 109.5 |
C11—P1—C11i | 104.7 (3) | C4—C3—N1 | 113 (3) |
C11—P1—Ni | 113.9 (2) | C4—C3—H3A | 109.0 |
C16—C11—C12 | 116.9 (7) | N1—C3—H3A | 109.0 |
C16—C11—P1 | 120.1 (6) | C4—C3—H3B | 109.0 |
C12—C11—P1 | 122.9 (6) | N1—C3—H3B | 109.0 |
C13—C12—C11 | 121.5 (8) | H3A—C3—H3B | 107.8 |
C13—C12—H12 | 119.3 | C3—C4—H4A | 109.5 |
C11—C12—H12 | 119.3 | C3—C4—H4B | 109.5 |
C14—C13—C12 | 118.9 (9) | H4A—C4—H4B | 109.5 |
C14—C13—H13 | 120.6 | C3—C4—H4C | 109.5 |
C12—C13—H13 | 120.6 | H4A—C4—H4C | 109.5 |
C15—C14—C13 | 121.1 (10) | H4B—C4—H4C | 109.5 |
C15—C14—H14 | 119.4 | C6—C5—N1 | 112 (2) |
C13—C14—H14 | 119.4 | C6—C5—H5A | 109.1 |
C14—C15—C16 | 118.5 (9) | N1—C5—H5A | 109.1 |
C14—C15—H15 | 120.7 | C6—C5—H5B | 109.1 |
C16—C15—H15 | 120.7 | N1—C5—H5B | 109.1 |
C11—C16—C15 | 123.0 (9) | H5A—C5—H5B | 107.9 |
C11—C16—H16 | 118.5 | C5—C6—H6A | 109.5 |
C15—C16—H16 | 118.5 | C5—C6—H6B | 109.5 |
C7—N1—C5 | 117 (2) | H6A—C6—H6B | 109.5 |
C7—N1—C1 | 90 (3) | C5—C6—H6C | 109.5 |
C5—N1—C1 | 114.4 (18) | H6A—C6—H6C | 109.5 |
C7—N1—C3 | 110 (2) | H6B—C6—H6C | 109.5 |
C5—N1—C3 | 101.1 (16) | N1—C7—C8 | 127 (3) |
C1—N1—C3 | 124 (2) | N1—C7—H7A | 105.5 |
C2—C1—N1 | 117 (3) | C8—C7—H7A | 105.5 |
C2—C1—H1A | 108.0 | N1—C7—H7B | 105.5 |
N1—C1—H1A | 108.0 | C8—C7—H7B | 105.5 |
C2—C1—H1B | 108.0 | H7A—C7—H7B | 106.1 |
N1—C1—H1B | 108.0 | C7—C8—H8A | 109.5 |
H1A—C1—H1B | 107.2 | C7—C8—H8B | 109.5 |
C1—C2—H2A | 109.5 | H8A—C8—H8B | 109.5 |
C1—C2—H2B | 109.5 | C7—C8—H8C | 109.5 |
H2A—C2—H2B | 109.5 | H8A—C8—H8C | 109.5 |
C1—C2—H2C | 109.5 | H8B—C8—H8C | 109.5 |
Cl1—Ni—P1—C11 | −69.7 (3) | Cl1—Ni—P1—C11i | 170.3 (3) |
Cl1—Ni—P1—C11ii | 50.3 (3) |
Symmetry codes: (i) −y+3/2, z+1/2, −x+1; (ii) −z+1, −x+3/2, y−1/2. |
Experimental details
Crystal data | |
Chemical formula | C8H20N+·C18H15Cl3NiP− |
Mr | 557.58 |
Crystal system, space group | Cubic, Pb3 |
Temperature (K) | 293 |
a (Å) | 17.6676 (7) |
V (Å3) | 5514.8 (4) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 1.07 |
Crystal size (mm) | 0.36 × 0.29 × 0.24 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (EMPABS; Sheldrick et al., 1977) |
Tmin, Tmax | 0.728, 0.774 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1750, 1445, 497 |
Rint | 0.022 |
θmax (°) | 24.0 |
(sin θ/λ)max (Å−1) | 0.572 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.177, 0.96 |
No. of reflections | 1445 |
No. of parameters | 110 |
H-atom treatment | Only H-atom displacement parameters refined |
Δρmax, Δρmin (e Å−3) | 0.27, −0.23 |
Computer programs: CAD-4 EXPRESS (Enraf-Nonius, 1992), CAD-4 EXPRESS, CAD-4 (Hursthouse, 1976), SHELXS86 (Sheldrick, 1990), SHELXL93 (Sheldrick, 1993), ORTEPII (Johnson, 1971), SHELXL93.
Ni—Cl1 | 2.233 (2) | P1—C11 | 1.809 (7) |
Ni—P1 | 2.322 (4) | ||
Cl1—Ni—Cl1i | 114.61 (6) | C11—P1—C11i | 104.7 (3) |
Cl1—Ni—P1 | 103.65 (8) | C11—P1—Ni | 113.9 (2) |
Cl1—Ni—P1—C11 | −69.7 (3) | Cl1—Ni—P1—C11i | 170.3 (3) |
Cl1—Ni—P1—C11ii | 50.3 (3) |
Symmetry codes: (i) −y+3/2, z+1/2, −x+1; (ii) −z+1, −x+3/2, y−1/2. |
The title compound, (I), was isolated as a secondary product in an alternative preparation of [Ni{Fe[{SCH2CH2}3N](CO)}2)] (Smith et al., 2001) from [NEt4][Fe({SCH2CH2}3N)(CO)] and [NiCl2(PPh3)2] under a carbon monoxide atmosphere. Related compounds containing the same anion have been previously prepared (Yamamoto, 1954; Smith, 1982; Brenndörfer et al., 1985) and the crystal structure of [PH(C6H11)3] [NiCl3(PPh3)] has been reported (Brenndörfer et al., 1985).
The X-ray analysis of (I) shows that both ions lie on the threefold rotation axis along the body-diagonal vectors of the unit cell. The anion (Fig. 1) lies with the Ni—P bond coincidental with the axis; the cation N atom lies on the rotation axis and the cation is disordered with each carbon having 1/3 occupancy (i.e there are three discrete orientations possible for each cation). The Ni atom is tetrahedrally coordinated to the three symmetry-related Cl atoms and the P atom, with Cl—Ni—Cl and Cl—Ni—P angles of 114.61 (6) and 103.65 (8)°, respectively, and Ni—P and Ni—Cl bond lengths of 2.322 (4) and 2.233 (2) Å, respectively. Torsion angles Cl1—Ni—P1—C11 about the Ni—P1 axis are -69.7 (3), 50.3 (3) and 170.3 (3)° for the three symmetry-related C atoms, showing a staggered conformation about the Ni—P bond. The cation shows an apparently distorted tetrahedral arrangement about the N atom, with poorly determined C—N—C angles ranging from 90 (3) to 124 (2)° and N—C bond lengths ranging from 1.44 (4) to 1.61 (3) Å. Normal van der Waals contacts bind the ions in a three-dimensional network.
The structure of the related monoclinic crystals of [PH(C6H11)3][NiCl3(PPh3)] (Brenndörfer et al., 1985) has the space group P21/n, but shows the anion to be essentially identical to that of compound (I).