Tetraethyl­ammonium tri­chloro­(tri­phenyl­phosphine)­nickelate(II)

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 (equivalent to Pa, 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.

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


 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


 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


 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

---

S1. Comment

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).

S2. Experimental

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.

S3. Refinement

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

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

Fig. 1. The structure of the title anion, with 50% probability displacement ellipsoids.

Tetraethylammonium trichloro(triphenylphosphine)nickelate(II)

Crystal data

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) Å^3	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

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.177	Only H-atom displacement parameters refined
S = 0.96	w = 1/[σ^2(Fo^2) + (0.0626P)^2] where P = (Fo^2 + 2Fc^2)/3
1445 reflections	(Δ/σ)max = 0.002
110 parameters	Δρmax = 0.27 e Å^−3
0 restraints	Δρmin = −0.23 e Å^−3

Special details

Experimental. Melting point 248 <o>C. λ_max / 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 (Ų)

	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

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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—Cl1^i	114.61 (6)	H2A—C2—H2C	109.5
Cl1—Ni—P1	103.65 (8)	H2B—C2—H2C	109.5
C11—P1—C11^i	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—C11^i	170.3 (3)
Cl1—Ni—P1—C11^ii	50.3 (3)

Symmetry codes: (i) −y+3/2, z+1/2, −x+1; (ii) −z+1, −x+3/2, y−1/2.