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The ions of the title compound, (C8H20N)[NiCl3(C18H15P)], both lie on the threefold rotation axes along the body diagonal vectors of a cubic unit cell in the space group Pb\overline 3 (equivalent to Pa\overline 3, No. 205, with h and k indices interchanged). The Ni atom within the anion is tetrahedrally coordinated to three symmetry-related Cl atoms and the P atom. The cation is disordered.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801016348/cf6111sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801016348/cf6111Isup2.hkl
Contains datablock I

CCDC reference: 175973

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.013 Å
  • Disorder in solvent or counterion
  • R factor = 0.055
  • wR factor = 0.177
  • Data-to-parameter ratio = 13.1

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Red Alert Alert Level A:
SYMMG_01 From the CIF: _symmetry_space_group_number 205 From the CIF: _symmetry_space_group_name_H-M P b -3 Int. Tables space group number for P b -3 is 0 Alert A Unrecognised _symmetry_space_group_name_H-M SYMMG_02 From the CIF: _symmetry_equiv_pos_as_xyz x, y, z x+1/2, -y, -z+1/2 -x, -y+1/2, z+1/2 -x+1/2, y+1/2, -z z, x, y z+1/2, -x, -y+1/2 -z, -x+1/2, y+1/2 -z+1/2, x+1/2, -y y, z, x y+1/2, -z, -x+1/2 -y, -z+1/2, x+1/2 -y+1/2, z+1/2, -x -x, -y, -z -x-1/2, y, z-1/2 x, y-1/2, -z-1/2 x-1/2, -y-1/2, z -z, -x, -y -z-1/2, x, y-1/2 z, x-1/2, -y-1/2 z-1/2, -x-1/2, y -y, -z, -x -y-1/2, z, x-1/2 y, z-1/2, -x-1/2 y-1/2, -z-1/2, x These symops generate the Hall space group symbol -p_2bc_2ac_3 which is equivalent to the H-M space group symbol Alert A Supplied _symmetry_space_group_name_H-M not recognised
Amber Alert Alert Level B:
THETM_01 Alert B The value of sine(theta_max)/wavelength is less than 0.575 Calculated sin(theta_max)/wavelength = 0.5723
Yellow Alert Alert Level C:
PLAT_302 Alert C Anion/Solvent Disorder ....................... 32.00 Perc. PLAT_721 Alert C Bond Calc 0.97108, Rep 0.96000, Dev. 0.01 Ang. C4 -H4A 1.555 1.555 General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 24.00 From the CIF: _reflns_number_total 1445 From the CIF: _diffrn_reflns_limit_ max hkl 13. 14. 20. From the CIF: _diffrn_reflns_limit_ min hkl -4. -4. -1. TEST1: Expected hkl limits for theta max Calculated maximum hkl 20. 20. 20. Calculated minimum hkl -20. -20. -20. ALERT: Expected hkl max differ from CIF values
2 Alert Level A = Potentially serious problem
1 Alert Level B = Potential problem
2 Alert Level C = Please check

Comment top

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).

Experimental top

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.

Refinement top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The structure of the title anion, with 50% probability displacement ellipsoids.
Tetraethylammonium trichloro(triphenylphosphine)nickelate(II) top
Crystal data top
C8H20N+·C18H15Cl3NiPMelting point: 521 K
Mr = 557.58Mo Kα radiation, λ = 0.71069 Å
Cubic, Pb3Cell parameters from 25 reflections
Hall symbol: -p 2bc 2ac 3θ = 10–11°
a = 17.6676 (7) ŵ = 1.07 mm1
V = 5514.8 (4) Å3T = 293 K
Z = 8Octahedra, translucent intense blue
F(000) = 23360.36 × 0.29 × 0.24 mm
Dx = 1.343 Mg m3
Data collection top
Enraf-Nonius CAD-4
diffractometer
497 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.022
Graphite monochromatorθmax = 24.0°, θmin = 1.5°
ω scansh = 413
Absorption correction: ψ scan
(EMPABS; Sheldrick et al., 1977)
k = 414
Tmin = 0.728, Tmax = 0.774l = 120
1750 measured reflections3 standard reflections every 400 reflections
1445 independent reflections intensity decay: none
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.055Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.177Only 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 parametersΔρmax = 0.27 e Å3
0 restraintsΔρmin = 0.23 e Å3
Crystal data top
C8H20N+·C18H15Cl3NiPZ = 8
Mr = 557.58Mo Kα radiation
Cubic, Pb3µ = 1.07 mm1
a = 17.6676 (7) ÅT = 293 K
V = 5514.8 (4) Å30.36 × 0.29 × 0.24 mm
Data collection top
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 = 0.774θmax = 24.0°
1750 measured reflections3 standard reflections every 400 reflections
1445 independent reflections intensity decay: none
Refinement top
R[F2 > 2σ(F2)] = 0.0550 restraints
wR(F2) = 0.177Only H-atom displacement parameters refined
S = 0.96Δρmax = 0.27 e Å3
1445 reflectionsΔρmin = 0.23 e Å3
110 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ni0.80870 (5)0.69130 (5)0.19130 (5)0.0722 (6)
Cl10.7878 (2)0.79346 (13)0.1199 (2)0.1112 (10)
P10.88460 (11)0.61540 (11)0.11540 (11)0.0560 (9)
C110.8359 (4)0.5758 (4)0.0345 (4)0.058 (2)
C120.8477 (4)0.5025 (5)0.0093 (4)0.068 (2)
H120.88060.47120.03590.06 (2)*
C130.8115 (5)0.4749 (6)0.0544 (5)0.085 (3)
H130.81960.42540.07050.10 (3)*
C140.7635 (6)0.5217 (6)0.0935 (6)0.099 (3)
H140.73830.50340.13600.10 (3)*
C150.7520 (6)0.5947 (7)0.0713 (6)0.107 (3)
H150.72080.62670.09900.09 (3)*
C160.7874 (5)0.6198 (5)0.0069 (5)0.085 (3)
H160.77810.66900.00930.05 (2)*
N10.6154 (4)0.3846 (4)0.1154 (4)0.071 (3)
C10.650 (2)0.464 (3)0.099 (3)0.155 (14)*0.33333
H1A0.68600.47550.13870.185*0.33333
H1B0.67840.46070.05180.185*0.33333
C20.601 (2)0.524 (2)0.093 (2)0.146 (15)*0.33333
H2A0.62850.56990.08260.219*0.33333
H2B0.57320.53000.13940.219*0.33333
H2C0.56550.51520.05230.219*0.33333
C30.660 (2)0.3057 (18)0.1048 (17)0.111 (10)*0.33333
H3A0.66110.29270.05150.133*0.33333
H3B0.71200.31220.12150.133*0.33333
C40.627 (2)0.247 (2)0.145 (2)0.128 (13)*0.33333
H4A0.65600.20100.13700.191*0.33333
H4B0.57630.23910.12810.191*0.33333
H4C0.62720.25860.19810.191*0.33333
C50.5406 (17)0.3678 (16)0.0718 (16)0.089 (8)*0.33333
H5A0.52000.31990.08920.107*0.33333
H5B0.50390.40700.08310.107*0.33333
C60.5523 (16)0.3640 (18)0.0126 (18)0.099 (10)*0.33333
H6A0.51760.32820.03420.149*0.33333
H6B0.60320.34850.02320.149*0.33333
H6C0.54350.41310.03430.149*0.33333
C70.609 (2)0.403 (3)0.194 (2)0.153 (14)*0.33333
H7A0.57730.36420.21620.184*0.33333
H7B0.57990.44960.19630.184*0.33333
C80.6715 (17)0.4139 (19)0.248 (2)0.108 (11)*0.33333
H8A0.65110.42590.29740.162*0.33333
H8B0.70330.45460.23160.162*0.33333
H8C0.70070.36820.25170.162*0.33333
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni0.0722 (6)0.0722 (6)0.0722 (6)0.0077 (6)0.0077 (6)0.0077 (6)
Cl10.127 (2)0.078 (2)0.129 (2)0.0215 (15)0.025 (2)0.0001 (15)
P10.0560 (9)0.0560 (9)0.0560 (9)0.0012 (10)0.0012 (10)0.0012 (10)
C110.060 (5)0.053 (5)0.061 (5)0.006 (4)0.003 (4)0.003 (4)
C120.080 (6)0.066 (5)0.058 (5)0.004 (5)0.004 (5)0.004 (5)
C130.088 (7)0.096 (8)0.070 (6)0.017 (6)0.012 (6)0.014 (6)
C140.106 (8)0.118 (9)0.072 (7)0.024 (7)0.024 (6)0.017 (7)
C150.115 (8)0.123 (9)0.082 (7)0.021 (8)0.045 (6)0.004 (7)
C160.111 (8)0.066 (6)0.076 (6)0.010 (5)0.009 (6)0.006 (5)
N10.071 (3)0.071 (3)0.071 (3)0.002 (4)0.002 (4)0.002 (4)
Geometric parameters (Å, º) top
Ni—Cl12.233 (2)C2—H2A0.96
Ni—P12.322 (4)C2—H2B0.96
P1—C111.809 (7)C2—H2C0.96
C11—C161.369 (10)C3—C41.39 (4)
C11—C121.385 (9)C3—H3A0.97
C12—C131.384 (10)C3—H3B0.97
C12—H120.93C4—H4A0.96
C13—C141.372 (11)C4—H4B0.96
C13—H130.93C4—H4C0.96
C14—C151.364 (11)C5—C61.51 (4)
C14—H140.93C5—H5A0.97
C15—C161.371 (11)C5—H5B0.97
C15—H150.93C6—H6A0.96
C16—H160.93C6—H6B0.96
N1—C71.44 (4)C6—H6C0.96
N1—C51.56 (3)C7—C81.47 (5)
N1—C11.56 (4)C7—H7A0.97
N1—C31.61 (3)C7—H7B0.97
C1—C21.38 (5)C8—H8A0.96
C1—H1A0.97C8—H8B0.96
C1—H1B0.97C8—H8C0.96
Cl1—Ni—Cl1i114.61 (6)H2A—C2—H2C109.5
Cl1—Ni—P1103.65 (8)H2B—C2—H2C109.5
C11—P1—C11i104.7 (3)C4—C3—N1113 (3)
C11—P1—Ni113.9 (2)C4—C3—H3A109.0
C16—C11—C12116.9 (7)N1—C3—H3A109.0
C16—C11—P1120.1 (6)C4—C3—H3B109.0
C12—C11—P1122.9 (6)N1—C3—H3B109.0
C13—C12—C11121.5 (8)H3A—C3—H3B107.8
C13—C12—H12119.3C3—C4—H4A109.5
C11—C12—H12119.3C3—C4—H4B109.5
C14—C13—C12118.9 (9)H4A—C4—H4B109.5
C14—C13—H13120.6C3—C4—H4C109.5
C12—C13—H13120.6H4A—C4—H4C109.5
C15—C14—C13121.1 (10)H4B—C4—H4C109.5
C15—C14—H14119.4C6—C5—N1112 (2)
C13—C14—H14119.4C6—C5—H5A109.1
C14—C15—C16118.5 (9)N1—C5—H5A109.1
C14—C15—H15120.7C6—C5—H5B109.1
C16—C15—H15120.7N1—C5—H5B109.1
C11—C16—C15123.0 (9)H5A—C5—H5B107.9
C11—C16—H16118.5C5—C6—H6A109.5
C15—C16—H16118.5C5—C6—H6B109.5
C7—N1—C5117 (2)H6A—C6—H6B109.5
C7—N1—C190 (3)C5—C6—H6C109.5
C5—N1—C1114.4 (18)H6A—C6—H6C109.5
C7—N1—C3110 (2)H6B—C6—H6C109.5
C5—N1—C3101.1 (16)N1—C7—C8127 (3)
C1—N1—C3124 (2)N1—C7—H7A105.5
C2—C1—N1117 (3)C8—C7—H7A105.5
C2—C1—H1A108.0N1—C7—H7B105.5
N1—C1—H1A108.0C8—C7—H7B105.5
C2—C1—H1B108.0H7A—C7—H7B106.1
N1—C1—H1B108.0C7—C8—H8A109.5
H1A—C1—H1B107.2C7—C8—H8B109.5
C1—C2—H2A109.5H8A—C8—H8B109.5
C1—C2—H2B109.5C7—C8—H8C109.5
H2A—C2—H2B109.5H8A—C8—H8C109.5
C1—C2—H2C109.5H8B—C8—H8C109.5
Cl1—Ni—P1—C1169.7 (3)Cl1—Ni—P1—C11i170.3 (3)
Cl1—Ni—P1—C11ii50.3 (3)
Symmetry codes: (i) y+3/2, z+1/2, x+1; (ii) z+1, x+3/2, y1/2.

Experimental details

Crystal data
Chemical formulaC8H20N+·C18H15Cl3NiP
Mr557.58
Crystal system, space groupCubic, Pb3
Temperature (K)293
a (Å)17.6676 (7)
V3)5514.8 (4)
Z8
Radiation typeMo Kα
µ (mm1)1.07
Crystal size (mm)0.36 × 0.29 × 0.24
Data collection
DiffractometerEnraf-Nonius CAD-4
diffractometer
Absorption correctionψ scan
(EMPABS; Sheldrick et al., 1977)
Tmin, Tmax0.728, 0.774
No. of measured, independent and
observed [I > 2σ(I)] reflections
1750, 1445, 497
Rint0.022
θmax (°)24.0
(sin θ/λ)max1)0.572
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.055, 0.177, 0.96
No. of reflections1445
No. of parameters110
H-atom treatmentOnly H-atom displacement parameters refined
Δρmax, Δρmin (e Å3)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.

Selected geometric parameters (Å, º) top
Ni—Cl12.233 (2)P1—C111.809 (7)
Ni—P12.322 (4)
Cl1—Ni—Cl1i114.61 (6)C11—P1—C11i104.7 (3)
Cl1—Ni—P1103.65 (8)C11—P1—Ni113.9 (2)
Cl1—Ni—P1—C1169.7 (3)Cl1—Ni—P1—C11i170.3 (3)
Cl1—Ni—P1—C11ii50.3 (3)
Symmetry codes: (i) y+3/2, z+1/2, x+1; (ii) z+1, x+3/2, y1/2.
 

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