Tris(tert-butyl isocyanide-κC)carbonylnickel(0)

Imhof, W.; Görls, H.; Halbauer, K.

doi:10.1107/S1600536808020138

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page m1000

doi:10.1107/S1600536808020138

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Tris(tert-butyl isocyanide-κC)carbonylnickel(0)

Wolfgang Imhof,^a ^* Helmar Görls ^a and Kathi Halbauer ^a

^aInstitut für Anorganische und Analytische Chemie, Friedrich-Schiller-Universität Jena, August-Bebel-Strasse 2, 07743 Jena, Germany
^*Correspondence e-mail: wolfgang.imhof@uni-jena.de

(Received 28 May 2008; accepted 1 July 2008; online 5 July 2008)

The title compound, [Ni(C₅H₉N)₃(CO)], was prepared from Ni(CO)₄ and a tenfold excess of tert-butyl isocyanide. It crystallizes with two symmetry-independent molecules per asymmetric unit. The central Ni atom of each independent molecule has a nearly perfect tetrahedral coordination environment, comprising one carbon monoxide and three isocyanide ligands. The title compound is the first structurally characterized Ni⁰ compound with a mixed CO/RNC coordination.

Related literature

For related literature, see: Braga et al. (1993 ); Farrugia & Evans (2005 ); Hahn et al. (2004 ); Ladell et al. (1952 ); Bigorgne (1963a ,b ); Dönnecke & Imhof (2003 ); Desiraju & Steiner (1999 ); Halbauer et al. (2006 , 2007 ); Imhof & Halbauer (2006 ); Imhof, Halbauer, Dönnecke & Görls (2006 ); Ostuka et al. (1969 , 1971 ).

Experimental

Crystal data

[Ni(C₅H₉N)₃(CO)]
M_r = 336.11
Monoclinic, P 2₁ /n
a = 17.1621 (7) Å
b = 14.5687 (5) Å
c = 17.1627 (7) Å
β = 113.179 (3)°
V = 3944.8 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.99 mm⁻¹
T = 183 (2) K
0.06 × 0.05 × 0.05 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: none
26227 measured reflections
9006 independent reflections
5006 reflections with I > 2σ(I)
R_int = 0.083

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.136
S = 1.01
9006 reflections
397 parameters
H-atom parameters constrained
Δρ_max = 0.59 e Å⁻³
Δρ_min = −0.58 e Å⁻³

Data collection: COLLECT (Nonius, 1998 ); cell refinement: DENZO (Otwinowski & Minor, 1997 ); data reduction: DENZO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Siemens, 1990 ); software used to prepare material for publication: SHELXL97 and XP.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808020138/fj2122sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808020138/fj2122Isup2.hkl

checkCIF report

Comment top

Some of us recently published the synthesis of cyano complexes from the reaction of metal carbonyls with an excess of tert-butylisocyanide or iso-octylisocyanide, respectively (M = Ru: Dönnecke & Imhof (2003), Imhof & Halbauer (2006); M = Fe: Halbauer et al. (2006); M = Mn: Halbauer et al. (2007)). Mononuclear metal carbonyls like Fe(CO)₅ or Mo(CO)₆ under the same conditions do not react to give M(II) cyano complexes but yield substitution products of the corresponding carbonyl precursors (M = Fe: Halbauer et al. (2006); M = Mo: Imhof et al. (2006)). Due to the enhanced reactivity of Ni(CO)₄ we nevertheless attempted the synthesis of complexes of the type [Ni(CN)₂(^tBuNC)₄] from the reaction of Ni(CO)₄ with an excess of the corresponding isocyanide leading to the formation of the title compound.

The molecular structure of one of the symmetry independent molecules of the title compound is depicted in Fig. 1. As it is expected the central nickel atom is almost perfectly tetrahedrally coordinated by three isocyanide and one carbon monoxide ligand. The metal carbon bond lengths of the isocyanide carbons atom are about 11 pm in average longer compared to the Ni—CO bond reflecting the higher π-acceptor properties of the latter. Both CO and isocyanide ligands are nearly not bent out of linearity. The bond lengths of the two molecules in the asymmetric unit are identical within experimental errors. In contrast to this observation the bond angles show slight deviations which may be caused by the bulkiness of the tert-butyl groups connected with packing effects. As it is expected the shortest intermolecular distances are of the C—H···O type. But whereas O1B is engaged in the three shortest interactions observed (C6A—H6AC···O1B 2.721 (8) Å; C11A—H11B···O1B 2.817 (8) Å; C16A—H16A···O1B 2.876 (8)), O1A shows only one contact below 3 Å (C16B—H16E···O1A 2.949 (9) Å). All of these contacts are well in the range discussed by Desiraju & Steiner as C—H···O hydrogen bonds (Desiraju & Steiner (1999).

With ^tBuNC as the ligand only [Ni(CO)₂(^tBuNC)₂] (Ostuka et al. (1971)) and [Ni(^tBuNC)₄] (Ostuka et al. (1969)) were reported but not structurally characterized. The same is true for the compounds [Ni(CO)_4-n(RNC)_n] (R = Me, Et, ⁿBu, Ph; n = 1, 2, 3, 4; Bigorgne (1963a,b)). The only complexes to be structurally characterized were the homoleptic [Ni(RNC)₄] (R = Ph, 2,6-Me—Ph, 2-NO₂—Ph; Hahn et al. (2004)) and Ni(CO)₄ itself (Farrugia & Evans (2005); Braga et al. (1993); Ladell et al. (1952)). So the title compound is the first [Ni(CO)_4-n(RNC)_n] compound to be structurally characterized.

Related literature top

For related literature, see: Braga et al. (1993); Farrugia & Evans (2005); Hahn et al. (2004); Ladell et al. (1952); Bigorgne (1963a, 1963b); Dönnecke & Imhof (2003); Desiraju & Steiner (1999); Halbauer et al. (2006, 2007); Imhof & Halbauer (2006); Imhof, Halbauer, Dönnecke & Görls (2006); Ostuka et al. (1969, 1971).

Experimental top

0.3 ml of a 2 M solution of Ni(CO)₄ (0.059 mmol) in toluene and 0.7 ml tert. butylisocyanide (5.86 mmol) together with another 3 ml of anhydrous toluene are transferred into a stainless steel autoclave and are heated to 130°C for 18 h. After cooling down the autoclave the resulting solution is transferrd to a Schlenk tube, all volatile material is evaporated and the resulting red oily residue is dissolved in anhydrous light petroleum (b.p. 40–60°C). After three days at -20°C the title compound crystallizes as colorless crystals. Yield: 12 mg (59%). IR (KBr pellets) [cm^-1]: 2984m, 2936m, 2873w, 2140m, 2090 s, 2057 s, 2001m, 1920vs, 1914vs, 1453m, 1393m, 1369m, 1229m, 1208m. MS (DEI) [m/z(%)]: 336 (1) [MH⁺], 307 (13) [M⁺ - CO], 252 (65) [M⁺ - ^tBuNC], 224 (51) [Ni(^tBuNC)₂]⁺, 195 (10) [Ni(CO)(^tBuNC)H]⁺, 168 (100) [Ni(^tBuNC)(CN)H]⁺, 141 (16) [Ni(^tBuNC)]⁺, 112 (99) [Ni(CO)(CN)]^{+. 1}H-NMR (400 MHz, CDCl₃, 298 K) [p.p.m.]: 1.41(s). ¹³C-NMR (400 MHz, CDCl₃, 298 K) [p.p.m.]: 30.54 (CH₃), 55.83 (C), 151.89 (NC), 197.87 (CO).

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Siemens, 1990); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and XP (Siemens, 1990).

Figures top

Fig. 1. Molecular structure of one of the symmetry independent molecules of the title compound showing the labelling scheme. Displacement ellipsoids are drawn at the 40% probability level.

Tris(tert-butyl isocyanide-κC)carbonylnickel(0) top

Crystal data top

[Ni(C₅H₉N)₃(CO)]	F(000) = 1440
M_r = 336.11	D_x = 1.132 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 26227 reflections
a = 17.1621 (7) Å	θ = 2.6–27.5°
b = 14.5687 (5) Å	µ = 0.99 mm⁻¹
c = 17.1627 (7) Å	T = 183 K
β = 113.179 (3)°	Prism, colourless
V = 3944.8 (3) Å³	0.06 × 0.05 × 0.05 mm
Z = 8

Data collection top

Nonius KappaCCD diffractometer	5006 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.083
Graphite monochromator	θ_max = 27.5°, θ_min = 2.6°
ϕ and ω scans	h = −18→22
26227 measured reflections	k = −17→18
9006 independent reflections	l = −19→22

Refinement top

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) = 0.136	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0556P)² + 0.2606P] where P = (F_o² + 2F_c²)/3
9006 reflections	(Δ/σ)_max = 0.001
397 parameters	Δρ_max = 0.59 e Å⁻³
0 restraints	Δρ_min = −0.58 e Å⁻³

Crystal data top

[Ni(C₅H₉N)₃(CO)]	V = 3944.8 (3) Å³
M_r = 336.11	Z = 8
Monoclinic, P2₁/n	Mo Kα radiation
a = 17.1621 (7) Å	µ = 0.99 mm⁻¹
b = 14.5687 (5) Å	T = 183 K
c = 17.1627 (7) Å	0.06 × 0.05 × 0.05 mm
β = 113.179 (3)°

Data collection top

Nonius KappaCCD diffractometer	5006 reflections with I > 2σ(I)
26227 measured reflections	R_int = 0.083
9006 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.136	H-atom parameters constrained
S = 1.01	Δρ_max = 0.59 e Å⁻³
9006 reflections	Δρ_min = −0.58 e Å⁻³
397 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Ni1A	0.05645 (3)	0.23726 (3)	0.89365 (3)	0.03256 (13)
O1A	0.1424 (2)	0.3476 (2)	1.0444 (2)	0.0930 (11)
N1A	0.15666 (18)	0.27062 (19)	0.78571 (19)	0.0442 (7)
N2A	−0.13150 (19)	0.27889 (19)	0.8137 (2)	0.0474 (8)
N3A	0.06472 (17)	0.03062 (18)	0.91591 (19)	0.0406 (7)
C1A	0.1073 (3)	0.3018 (3)	0.9861 (3)	0.0495 (10)
C2A	0.1142 (2)	0.2584 (2)	0.8233 (2)	0.0368 (8)
C3A	0.2158 (2)	0.2906 (3)	0.7461 (2)	0.0495 (10)
C4A	0.2853 (2)	0.3508 (3)	0.8056 (3)	0.0604 (11)
H4AA	0.3132	0.3194	0.8600	0.091*
H4AB	0.2608	0.4087	0.8145	0.091*
H4AC	0.3269	0.3636	0.7810	0.091*
C5A	0.2521 (3)	0.2004 (3)	0.7310 (3)	0.0850 (16)
H5AA	0.2791	0.1676	0.7848	0.128*
H5AB	0.2943	0.2128	0.7070	0.128*
H5AC	0.2064	0.1627	0.6913	0.128*
C6A	0.1655 (3)	0.3404 (4)	0.6631 (3)	0.0858 (16)
H6AA	0.1387	0.3950	0.6749	0.129*
H6AB	0.1218	0.2993	0.6252	0.129*
H6AC	0.2038	0.3587	0.6360	0.129*
C7A	−0.0591 (2)	0.2639 (2)	0.8422 (2)	0.0389 (8)
C8A	−0.2222 (2)	0.2960 (3)	0.7798 (3)	0.0517 (10)
C9A	−0.2462 (3)	0.3409 (4)	0.6944 (3)	0.0969 (18)
H9AA	−0.2201	0.4018	0.7016	0.145*
H9AB	−0.3080	0.3470	0.6672	0.145*
H9AC	−0.2262	0.3030	0.6588	0.145*
C10A	−0.2666 (3)	0.2032 (3)	0.7710 (3)	0.0737 (13)
H10A	−0.2509	0.1635	0.7333	0.111*
H10B	−0.3281	0.2124	0.7470	0.111*
H10C	−0.2491	0.1743	0.8268	0.111*
C11A	−0.2407 (3)	0.3558 (3)	0.8424 (3)	0.0732 (13)
H11A	−0.2107	0.4144	0.8487	0.110*
H11B	−0.2215	0.3247	0.8974	0.110*
H11C	−0.3018	0.3672	0.8217	0.110*
C12A	0.0622 (2)	0.1099 (2)	0.9093 (2)	0.0377 (8)
C13A	0.0707 (2)	−0.0698 (2)	0.9185 (2)	0.0369 (8)
C14A	−0.0192 (2)	−0.1076 (2)	0.8829 (3)	0.0506 (10)
H14A	−0.0489	−0.0863	0.8245	0.076*
H14B	−0.0492	−0.0861	0.9176	0.076*
H14C	−0.0173	−0.1749	0.8838	0.076*
C15A	0.1184 (2)	−0.0983 (2)	0.8643 (2)	0.0495 (10)
H15A	0.0867	−0.0786	0.8057	0.074*
H15B	0.1248	−0.1652	0.8661	0.074*
H15C	0.1746	−0.0695	0.8862	0.074*
C16A	0.1176 (2)	−0.0972 (2)	1.0110 (2)	0.0458 (9)
H16A	0.1735	−0.0679	1.0337	0.069*
H16B	0.1245	−0.1641	1.0150	0.069*
H16C	0.0850	−0.0774	1.0437	0.069*
Ni1B	−0.03653 (3)	0.74217 (3)	0.61221 (3)	0.03316 (13)
O1B	−0.21523 (19)	0.7099 (2)	0.5102 (2)	0.0873 (11)
N1B	0.06832 (18)	0.66226 (18)	0.52198 (19)	0.0408 (7)
N2B	−0.03902 (19)	0.9488 (2)	0.62247 (19)	0.0462 (8)
N3B	0.0221 (2)	0.64140 (19)	0.7800 (2)	0.0467 (8)
C1B	−0.1440 (3)	0.7201 (3)	0.5515 (3)	0.0493 (10)
C2B	0.0296 (2)	0.6961 (2)	0.5572 (2)	0.0355 (8)
C3B	0.1153 (2)	0.6134 (2)	0.4808 (3)	0.0440 (9)
C4B	0.1229 (6)	0.5173 (4)	0.5100 (7)	0.245 (6)
H4BA	0.0662	0.4912	0.4951	0.368*
H4BB	0.1540	0.5152	0.5716	0.368*
H4BC	0.1535	0.4816	0.4826	0.368*
C5B	0.0701 (4)	0.6220 (6)	0.3882 (4)	0.175 (4)
H5BA	0.0166	0.5880	0.3697	0.262*
H5BB	0.1053	0.5970	0.3601	0.262*
H5BC	0.0582	0.6869	0.3731	0.262*
C6B	0.2014 (3)	0.6551 (4)	0.5071 (4)	0.101 (2)
H6BA	0.1960	0.7188	0.4874	0.152*
H6BB	0.2346	0.6201	0.4822	0.152*
H6BC	0.2300	0.6537	0.5690	0.152*
C7B	−0.0316 (2)	0.8695 (2)	0.6218 (2)	0.0361 (8)
C8B	−0.0605 (3)	1.0458 (2)	0.6121 (3)	0.0574 (11)
C9B	0.0215 (5)	1.0972 (4)	0.6294 (5)	0.160 (4)
H9BA	0.0617	1.0844	0.6874	0.241*
H9BB	0.0100	1.1633	0.6229	0.241*
H9BC	0.0457	1.0772	0.5892	0.241*
C10B	−0.1210 (6)	1.0587 (4)	0.5234 (3)	0.190 (5)
H10D	−0.1738	1.0260	0.5143	0.286*
H10E	−0.0964	1.0345	0.4849	0.286*
H10F	−0.1330	1.1243	0.5123	0.286*
C11B	−0.0955 (3)	1.0733 (3)	0.6757 (3)	0.0795 (15)
H11D	−0.1445	1.0347	0.6689	0.119*
H11E	−0.1131	1.1378	0.6669	0.119*
H11F	−0.0518	1.0655	0.7329	0.119*
C12B	0.0011 (2)	0.6833 (2)	0.7177 (3)	0.0423 (9)
C13B	0.0452 (2)	0.5740 (2)	0.8480 (2)	0.0468 (10)
C14B	0.1115 (3)	0.5123 (3)	0.8381 (4)	0.0912 (18)
H14D	0.0882	0.4831	0.7821	0.137*
H14E	0.1281	0.4650	0.8822	0.137*
H14F	0.1613	0.5490	0.8435	0.137*
C15B	0.0784 (4)	0.6238 (3)	0.9314 (3)	0.0905 (18)
H15D	0.1295	0.6581	0.9373	0.136*
H15E	0.0921	0.5793	0.9778	0.136*
H15F	0.0351	0.6665	0.9335	0.136*
C16B	−0.0329 (3)	0.5185 (3)	0.8384 (3)	0.0729 (13)
H16D	−0.0524	0.4844	0.7849	0.109*
H16E	−0.0779	0.5600	0.8383	0.109*
H16F	−0.0189	0.4753	0.8858	0.109*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1A	0.0291 (2)	0.0315 (2)	0.0424 (3)	0.00252 (17)	0.0198 (2)	0.00508 (19)
O1A	0.107 (3)	0.100 (3)	0.059 (2)	−0.005 (2)	0.017 (2)	−0.029 (2)
N1A	0.0384 (17)	0.0591 (18)	0.0423 (19)	0.0001 (14)	0.0235 (16)	0.0023 (14)
N2A	0.0310 (18)	0.0544 (19)	0.059 (2)	0.0067 (14)	0.0195 (16)	0.0065 (15)
N3A	0.0365 (17)	0.0355 (17)	0.055 (2)	0.0067 (12)	0.0233 (15)	0.0101 (13)
C1A	0.054 (3)	0.052 (2)	0.049 (3)	0.0049 (18)	0.027 (2)	0.001 (2)
C2A	0.0321 (18)	0.0364 (18)	0.042 (2)	0.0037 (14)	0.0146 (16)	0.0029 (15)
C3A	0.037 (2)	0.084 (3)	0.036 (2)	0.0044 (19)	0.0229 (19)	0.004 (2)
C4A	0.044 (3)	0.087 (3)	0.056 (3)	−0.008 (2)	0.025 (2)	0.004 (2)
C5A	0.073 (3)	0.107 (4)	0.101 (4)	0.001 (3)	0.062 (3)	−0.023 (3)
C6A	0.046 (3)	0.167 (5)	0.049 (3)	0.006 (3)	0.024 (2)	0.028 (3)
C7A	0.038 (2)	0.0364 (18)	0.048 (2)	0.0006 (15)	0.0237 (19)	0.0067 (16)
C8A	0.029 (2)	0.080 (3)	0.047 (3)	0.0111 (18)	0.0161 (19)	0.016 (2)
C9A	0.054 (3)	0.165 (5)	0.074 (4)	0.024 (3)	0.027 (3)	0.052 (4)
C10A	0.046 (3)	0.108 (4)	0.062 (3)	−0.013 (2)	0.016 (2)	0.001 (3)
C11A	0.055 (3)	0.090 (3)	0.087 (4)	0.013 (2)	0.041 (3)	−0.005 (3)
C12A	0.0289 (19)	0.040 (2)	0.050 (3)	0.0031 (14)	0.0220 (18)	0.0062 (16)
C13A	0.038 (2)	0.0294 (17)	0.048 (2)	0.0064 (14)	0.0219 (18)	0.0076 (15)
C14A	0.041 (2)	0.043 (2)	0.068 (3)	−0.0038 (16)	0.023 (2)	−0.0006 (18)
C15A	0.046 (2)	0.059 (2)	0.048 (3)	0.0130 (18)	0.023 (2)	0.0020 (18)
C16A	0.053 (2)	0.042 (2)	0.046 (3)	0.0088 (16)	0.024 (2)	0.0057 (17)
Ni1B	0.0321 (2)	0.0330 (2)	0.0378 (3)	−0.00067 (17)	0.0174 (2)	−0.00341 (19)
O1B	0.0411 (19)	0.140 (3)	0.085 (3)	−0.0278 (18)	0.0283 (18)	−0.053 (2)
N1B	0.0389 (17)	0.0412 (16)	0.049 (2)	0.0042 (13)	0.0247 (16)	−0.0002 (14)
N2B	0.052 (2)	0.0366 (17)	0.044 (2)	0.0012 (13)	0.0119 (16)	−0.0018 (13)
N3B	0.059 (2)	0.0396 (17)	0.047 (2)	0.0062 (14)	0.0271 (18)	0.0058 (15)
C1B	0.043 (2)	0.060 (2)	0.053 (3)	−0.0105 (18)	0.027 (2)	−0.0198 (19)
C2B	0.0324 (19)	0.0351 (18)	0.038 (2)	−0.0013 (14)	0.0129 (17)	0.0000 (15)
C3B	0.041 (2)	0.043 (2)	0.058 (3)	0.0052 (15)	0.030 (2)	−0.0093 (18)
C4B	0.374 (13)	0.045 (3)	0.525 (18)	0.053 (5)	0.401 (14)	0.044 (6)
C5B	0.056 (4)	0.388 (13)	0.071 (5)	0.054 (5)	0.014 (3)	−0.090 (6)
C6B	0.045 (3)	0.172 (5)	0.094 (4)	−0.019 (3)	0.037 (3)	−0.065 (4)
C7B	0.034 (2)	0.043 (2)	0.032 (2)	0.0000 (15)	0.0128 (17)	−0.0001 (15)
C8B	0.096 (3)	0.0279 (19)	0.053 (3)	0.0079 (19)	0.034 (3)	0.0045 (17)
C9B	0.202 (8)	0.051 (3)	0.311 (12)	−0.035 (4)	0.189 (8)	−0.033 (5)
C10B	0.348 (12)	0.101 (4)	0.046 (4)	0.130 (6)	−0.005 (5)	0.005 (3)
C11B	0.123 (4)	0.054 (3)	0.077 (4)	0.022 (3)	0.056 (3)	0.008 (2)
C12B	0.049 (2)	0.0350 (19)	0.052 (3)	−0.0004 (15)	0.029 (2)	−0.0063 (18)
C13B	0.066 (3)	0.0312 (19)	0.048 (3)	0.0040 (17)	0.028 (2)	0.0081 (17)
C14B	0.104 (4)	0.064 (3)	0.132 (5)	0.031 (3)	0.074 (4)	0.039 (3)
C15B	0.147 (5)	0.059 (3)	0.044 (3)	−0.022 (3)	0.015 (3)	0.004 (2)
C16B	0.090 (4)	0.056 (3)	0.076 (4)	−0.013 (2)	0.037 (3)	0.007 (2)

Geometric parameters (Å, º) top

Ni1A—C1A	1.753 (4)	Ni1B—C1B	1.755 (4)
Ni1A—C2A	1.864 (3)	Ni1B—C7B	1.861 (3)
Ni1A—C7A	1.867 (4)	Ni1B—C2B	1.864 (3)
Ni1A—C12A	1.872 (3)	Ni1B—C12B	1.874 (4)
O1A—C1A	1.155 (5)	O1B—C1B	1.156 (4)
N1A—C2A	1.162 (4)	N1B—C2B	1.169 (4)
N1A—C3A	1.457 (4)	N1B—C3B	1.451 (4)
N2A—C7A	1.162 (4)	N2B—C7B	1.163 (4)
N2A—C8A	1.453 (4)	N2B—C8B	1.454 (4)
N3A—C12A	1.159 (4)	N3B—C12B	1.158 (4)
N3A—C13A	1.466 (4)	N3B—C13B	1.457 (5)
C3A—C4A	1.509 (5)	C3B—C5B	1.475 (7)
C3A—C5A	1.519 (6)	C3B—C4B	1.475 (6)
C3A—C6A	1.526 (5)	C3B—C6B	1.493 (5)
C4A—H4AA	0.9800	C4B—H4BA	0.9800
C4A—H4AB	0.9800	C4B—H4BB	0.9800
C4A—H4AC	0.9800	C4B—H4BC	0.9800
C5A—H5AA	0.9800	C5B—H5BA	0.9800
C5A—H5AB	0.9800	C5B—H5BB	0.9800
C5A—H5AC	0.9800	C5B—H5BC	0.9800
C6A—H6AA	0.9800	C6B—H6BA	0.9800
C6A—H6AB	0.9800	C6B—H6BB	0.9800
C6A—H6AC	0.9800	C6B—H6BC	0.9800
C8A—C9A	1.507 (6)	C8B—C10B	1.479 (7)
C8A—C11A	1.511 (5)	C8B—C11B	1.492 (5)
C8A—C10A	1.529 (6)	C8B—C9B	1.515 (7)
C9A—H9AA	0.9800	C9B—H9BA	0.9800
C9A—H9AB	0.9800	C9B—H9BB	0.9800
C9A—H9AC	0.9800	C9B—H9BC	0.9800
C10A—H10A	0.9800	C10B—H10D	0.9800
C10A—H10B	0.9800	C10B—H10E	0.9800
C10A—H10C	0.9800	C10B—H10F	0.9800
C11A—H11A	0.9800	C11B—H11D	0.9800
C11A—H11B	0.9800	C11B—H11E	0.9800
C11A—H11C	0.9800	C11B—H11F	0.9800
C13A—C15A	1.519 (4)	C13B—C15B	1.503 (6)
C13A—C16A	1.523 (5)	C13B—C16B	1.517 (5)
C13A—C14A	1.522 (5)	C13B—C14B	1.512 (5)
C14A—H14A	0.9800	C14B—H14D	0.9800
C14A—H14B	0.9800	C14B—H14E	0.9800
C14A—H14C	0.9800	C14B—H14F	0.9800
C15A—H15A	0.9800	C15B—H15D	0.9800
C15A—H15B	0.9800	C15B—H15E	0.9800
C15A—H15C	0.9800	C15B—H15F	0.9800
C16A—H16A	0.9800	C16B—H16D	0.9800
C16A—H16B	0.9800	C16B—H16E	0.9800
C16A—H16C	0.9800	C16B—H16F	0.9800

C1A—Ni1A—C2A	107.16 (16)	C1B—Ni1B—C7B	103.66 (16)
C1A—Ni1A—C7A	111.99 (16)	C1B—Ni1B—C2B	109.91 (15)
C2A—Ni1A—C7A	113.31 (15)	C7B—Ni1B—C2B	112.86 (14)
C1A—Ni1A—C12A	114.96 (17)	C1B—Ni1B—C12B	111.80 (17)
C2A—Ni1A—C12A	104.26 (13)	C7B—Ni1B—C12B	112.61 (14)
C7A—Ni1A—C12A	105.07 (14)	C2B—Ni1B—C12B	106.11 (14)
C2A—N1A—C3A	174.3 (4)	C2B—N1B—C3B	175.5 (3)
C7A—N2A—C8A	178.4 (4)	C7B—N2B—C8B	171.2 (4)
C12A—N3A—C13A	175.1 (3)	C12B—N3B—C13B	169.3 (4)
O1A—C1A—Ni1A	176.1 (4)	O1B—C1B—Ni1B	176.7 (4)
N1A—C2A—Ni1A	174.0 (3)	N1B—C2B—Ni1B	175.9 (3)
N1A—C3A—C4A	108.1 (3)	N1B—C3B—C5B	109.0 (3)
N1A—C3A—C5A	108.4 (3)	N1B—C3B—C4B	107.0 (3)
C4A—C3A—C5A	110.5 (3)	C5B—C3B—C4B	112.7 (6)
N1A—C3A—C6A	106.7 (3)	N1B—C3B—C6B	109.0 (3)
C4A—C3A—C6A	111.2 (4)	C5B—C3B—C6B	109.3 (4)
C5A—C3A—C6A	111.8 (4)	C4B—C3B—C6B	109.8 (5)
C3A—C4A—H4AA	109.5	C3B—C4B—H4BA	109.5
C3A—C4A—H4AB	109.5	C3B—C4B—H4BB	109.5
H4AA—C4A—H4AB	109.5	H4BA—C4B—H4BB	109.5
C3A—C4A—H4AC	109.5	C3B—C4B—H4BC	109.5
H4AA—C4A—H4AC	109.5	H4BA—C4B—H4BC	109.5
H4AB—C4A—H4AC	109.5	H4BB—C4B—H4BC	109.5
C3A—C5A—H5AA	109.5	C3B—C5B—H5BA	109.5
C3A—C5A—H5AB	109.5	C3B—C5B—H5BB	109.5
H5AA—C5A—H5AB	109.5	H5BA—C5B—H5BB	109.5
C3A—C5A—H5AC	109.5	C3B—C5B—H5BC	109.5
H5AA—C5A—H5AC	109.5	H5BA—C5B—H5BC	109.5
H5AB—C5A—H5AC	109.5	H5BB—C5B—H5BC	109.5
C3A—C6A—H6AA	109.5	C3B—C6B—H6BA	109.5
C3A—C6A—H6AB	109.5	C3B—C6B—H6BB	109.5
H6AA—C6A—H6AB	109.5	H6BA—C6B—H6BB	109.5
C3A—C6A—H6AC	109.5	C3B—C6B—H6BC	109.5
H6AA—C6A—H6AC	109.5	H6BA—C6B—H6BC	109.5
H6AB—C6A—H6AC	109.5	H6BB—C6B—H6BC	109.5
N2A—C7A—Ni1A	176.7 (3)	N2B—C7B—Ni1B	171.8 (3)
N2A—C8A—C9A	107.6 (3)	N2B—C8B—C10B	106.9 (3)
N2A—C8A—C11A	107.8 (3)	N2B—C8B—C11B	109.1 (3)
C9A—C8A—C11A	112.8 (4)	C10B—C8B—C11B	113.3 (5)
N2A—C8A—C10A	107.5 (3)	N2B—C8B—C9B	106.6 (4)
C9A—C8A—C10A	110.6 (4)	C10B—C8B—C9B	111.2 (5)
C11A—C8A—C10A	110.2 (3)	C11B—C8B—C9B	109.5 (4)
C8A—C9A—H9AA	109.5	C8B—C9B—H9BA	109.5
C8A—C9A—H9AB	109.5	C8B—C9B—H9BB	109.5
H9AA—C9A—H9AB	109.5	H9BA—C9B—H9BB	109.5
C8A—C9A—H9AC	109.5	C8B—C9B—H9BC	109.5
H9AA—C9A—H9AC	109.5	H9BA—C9B—H9BC	109.5
H9AB—C9A—H9AC	109.5	H9BB—C9B—H9BC	109.5
C8A—C10A—H10A	109.5	C8B—C10B—H10D	109.5
C8A—C10A—H10B	109.5	C8B—C10B—H10E	109.5
H10A—C10A—H10B	109.5	H10D—C10B—H10E	109.5
C8A—C10A—H10C	109.5	C8B—C10B—H10F	109.5
H10A—C10A—H10C	109.5	H10D—C10B—H10F	109.5
H10B—C10A—H10C	109.5	H10E—C10B—H10F	109.5
C8A—C11A—H11A	109.5	C8B—C11B—H11D	109.5
C8A—C11A—H11B	109.5	C8B—C11B—H11E	109.5
H11A—C11A—H11B	109.5	H11D—C11B—H11E	109.5
C8A—C11A—H11C	109.5	C8B—C11B—H11F	109.5
H11A—C11A—H11C	109.5	H11D—C11B—H11F	109.5
H11B—C11A—H11C	109.5	H11E—C11B—H11F	109.5
N3A—C12A—Ni1A	177.5 (3)	N3B—C12B—Ni1B	175.4 (3)
N3A—C13A—C15A	107.6 (3)	N3B—C13B—C15B	108.6 (3)
N3A—C13A—C16A	107.2 (3)	N3B—C13B—C16B	108.8 (3)
C15A—C13A—C16A	112.0 (3)	C15B—C13B—C16B	110.4 (4)
N3A—C13A—C14A	107.5 (3)	N3B—C13B—C14B	106.8 (3)
C15A—C13A—C14A	111.2 (3)	C15B—C13B—C14B	112.0 (4)
C16A—C13A—C14A	111.1 (3)	C16B—C13B—C14B	110.1 (3)
C13A—C14A—H14A	109.5	C13B—C14B—H14D	109.5
C13A—C14A—H14B	109.5	C13B—C14B—H14E	109.5
H14A—C14A—H14B	109.5	H14D—C14B—H14E	109.5
C13A—C14A—H14C	109.5	C13B—C14B—H14F	109.5
H14A—C14A—H14C	109.5	H14D—C14B—H14F	109.5
H14B—C14A—H14C	109.5	H14E—C14B—H14F	109.5
C13A—C15A—H15A	109.5	C13B—C15B—H15D	109.5
C13A—C15A—H15B	109.5	C13B—C15B—H15E	109.5
H15A—C15A—H15B	109.5	H15D—C15B—H15E	109.5
C13A—C15A—H15C	109.5	C13B—C15B—H15F	109.5
H15A—C15A—H15C	109.5	H15D—C15B—H15F	109.5
H15B—C15A—H15C	109.5	H15E—C15B—H15F	109.5
C13A—C16A—H16A	109.5	C13B—C16B—H16D	109.5
C13A—C16A—H16B	109.5	C13B—C16B—H16E	109.5
H16A—C16A—H16B	109.5	H16D—C16B—H16E	109.5
C13A—C16A—H16C	109.5	C13B—C16B—H16F	109.5
H16A—C16A—H16C	109.5	H16D—C16B—H16F	109.5
H16B—C16A—H16C	109.5	H16E—C16B—H16F	109.5

Experimental details

Crystal data
Chemical formula	[Ni(C₅H₉N)₃(CO)]
M_r	336.11
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	183
a, b, c (Å)	17.1621 (7), 14.5687 (5), 17.1627 (7)
β (°)	113.179 (3)
V (Å³)	3944.8 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.99
Crystal size (mm)	0.06 × 0.05 × 0.05

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	26227, 9006, 5006
R_int	0.083
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.136, 1.01
No. of reflections	9006
No. of parameters	397
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.59, −0.58

Computer programs: COLLECT (Nonius, 1998), DENZO (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and XP (Siemens, 1990).

Acknowledgements

The authors gratefully acknowledge financial support by the Deutsche Forschungsgemeinschaft. KH thanks the Free State of Thuringia for a PhD grant.

References

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