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Acta Cryst. (2007). E63, m2520-m2521    [ doi:10.1107/S1600536807043814 ]

A redetermination of chlorido[hydridotris(3-tert-butyl-5-methylpyrazolyl)borato]nickel(II)

A. D. Beitelman and G. M. Ferrence

Abstract top

In the title complex, [NiCl(C24H40BN6)], the Ni atom is coordinated by three N atoms, with the typical facial arrangement imposed by trispyrazolylborate ligands, and a chloride ligand in a distorted tetrahedral geometry. A structure of the title complex was previously reported in a lower symmetry space group [Santi, Romano, Sommazzi, Grande, Bianchini & Mantovani (2005). J. Mol. Catal. A: Chem. 229, 191-197].

Comment top

The chemistry of scorpionate supported transition-metal complexes has been the subject of intense research with in excess of 2000 papers published on polypyrazolylborate complexes spanning over seventy elements of the periodic table (Trofimenko, 2004; Trofimenko, 1999). The Cambridge Structural Database includes data for over 2800 crystal structures of trispyrazolylborate (Tp) metal complexes, many with bulky derivatives, including 54 incorporating the tris(3-tert-butyl-5-methylpyrazolyl)borate ligand, TptBu,Me (Allen, 2002). The coordination number of Tp coordinated metals is heavily controlled by the steric properties of the substituents attached to the 3-pyrazolyl carbon atoms. Sterically demanding Tp ligands have been found to be well suited for the isolation of low coordinate metal complexes; those with tert-butyl groups attached to the pyrazolyl 3-positions have been referred to as tetrahedral enforcers (Trofimenko et al. 1987). The title complex, (TptBu,Me)NiCl is consistent with this generalization.

The molecular structure of (I) is shown in Fig. 1. A l l bond distances and angles are indistinguishable from those previously reported. (Santi et al., 2005). The core geometry of (I) is indistinguishable, with few bond distances or angles differing more than within error, from those of the related complexes, including, (TptBu)NiCl (Belderrain et al., 2002), (TpiPr,iPr)NiCl (Shirasawa et al., 2001), (TpMes)NiCl (Kunrath et al., 2003), (TpPh,Me)NiCl (Uehara et al., 2002), and (TpMe,Me)NiCl (Desrochers et al., 2003). The Ni atom is coordinated by three N atoms, arranged with the typical facial arrangement imposed by trispyrazolylborato ligands, and a chloride ligand in a distorted tetrahedral geometry.

Arguably the most interesting feature of the structure is that the title compound preserves its highest possible, C3v, point group symmetry in the solid state by residing upon appropriate crystallographic symmetry elements. Specifically, the H—B—Ni—Cl axis lies along a crystallographic threefold axis, and the pyrazolyl ring planes reside on crystallographic mirror planes. About 600 of the over 2800 crystallographically characterized trispyrazolylborate complexes have atomic connectivity capable of idealized C3v point group symmetry. Of these, less than 65 have a Tp ligand with an H—B axis coincident with a crystallographic threefold axis, and only (TptBu)BeH (Han & Parkin, 1992), (TptBu,Me)CoNO (Thyagarajan et al., 2003), and (TptBu,Me)ZnOH (Alsfasser et al., 1991) additionally lie on the necessary crystallographic mirror planes to display true C3v symmetry in the solid state. Curiously, these three examples, like the title compound, contain Tp ligands with tert-butyl groups on the 3-pyrazolyl positions.

Related literature top

A previously reported structure of the title complex was refined in the R3 space group (Santi et al., 2005). Checking this structure's CCDC deposited. cif with PLATON's (Spek, 2003) ADDSYM suggests R3m to be a better choice of space group. This is consistent with the R3m assignment of our structure; however, without processing the prior structure's data, at room temperature a polymorph cannot be absolutely ruled out. For related literature, see: Allen (2002); Alsfasser et al. (1991); Belderrain et al. (2002); Desrochers et al. (2003); Han & Parkin (1992); Kunrath et al. (2003); Shirasawa et al. (2001); Thyagarajan et al. (2003); Trofimenko (1999, 2004); Trofimenko et al. (1987); & Uehara et al. (2002).

Experimental top

Synthesis of (TptBu,Me)NiCl was carried out according to the procedure previously reported for (TptBu)NiCl, substituting KTptBu,Me for KTptBu (Trofimenko et al. 1987). An X-ray quality crystal was selected from crystals grown by slow evaporation of a mixture (2:1 ratio) of methylene chloride and acetonitrile).

Refinement top

The H atom attached to the B atom was identified through difference Fourier synthesis and refined with an isotropic displacement parameter. All other H atoms were included in the refinement in the riding-model approximation, with respective isotropic aromatic and methyl displacement parameters fixed at 1.2Ueq and 1.5Ueq of the parent atom (C–H = 0.95 and 0.98 Å). Atom C16 was refined as an idealized disordered methyl group with H atoms included using the HFIX 123 instruction in SHELXL97.

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SMART (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and publCIF (Westrip, 2007).

Figures top
[Figure 1] Fig. 1. The molecular structure of compound (I), with the atomic numbering scheme [symmetry codes: (i) 1 − y, x-y, z; (ii) x, x-y, z; (iii) 1 − x + y, y, z; (iv) 1 − y, 1 − x, z; (v) x, x-y, z]. H atoms except H1 are omitted for clarity. Displacement ellipsoids are drawn at the 50% probability level. Unlabeled atoms are related to the respective atoms C13, C14, C15, C17, and C18 of the asymmetric unit by 1 − y, x-y, z.
chlorido[hydridotris(3-tert-butyl-5-methylpyrazolyl)borato]nickel(II) top
Crystal data top
[NiCl(C24H40BN6)]Z = 3
Mr = 517.59F000 = 828
Trigonal, R3mDx = 1.247 Mg m−3
Hall symbol: R 3 -2"Mo Kα radiation
λ = 0.71073 Å
a = 15.8900 (4) ÅCell parameters from 5297 reflections
b = 15.8900 (4) Åθ = 2.6–26.3º
c = 9.4584 (5) ŵ = 0.82 mm−1
α = 90ºT = 193 (2) K
β = 90ºPrism, violet
γ = 120º0.66 × 0.4 × 0.31 mm
V = 2068.22 (13) Å3
Data collection top
CCD area detector
diffractometer		964 reflections with I > > 2σ(I)
T = 193(2) KRint = 0.020
φ and ω scansθmax = 26.3º
Absorption correction: multi-scan
SADABS (Sheldrick, 1996)		θmin = 3.7º
Tmin = 0.682, Tmax = 0.785h = −19→19
4349 measured reflectionsk = −19→19
964 independent reflectionsl = −11→10
Refinement top
Refinement on F2H atoms treated by a mixture of
independent and constrained refinement
Least-squares matrix: full  w = 1/[σ2(Fo2) + (0.0143P)2 + 0.6826P]
where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.018(Δ/σ)max = <0.001
wR(F2) = 0.045Δρmax = 0.23 e Å−3
S = 1.08Δρmin = −0.14 e Å−3
964 reflectionsExtinction correction: none
69 parametersAbsolute structure: Flack (1983), 444 Friedel pairs
1 restraintFlack parameter: 0.033 (11)
Crystal data top
[NiCl(C24H40BN6)]γ = 120º
Mr = 517.59V = 2068.22 (13) Å3
Trigonal, R3mZ = 3
a = 15.8900 (4) ÅMo Kα
b = 15.8900 (4) ŵ = 0.82 mm−1
c = 9.4584 (5) ÅT = 193 (2) K
α = 90º0.66 × 0.4 × 0.31 mm
β = 90º
Data collection top
CCD area detector
diffractometer		964 independent reflections
Absorption correction: multi-scan
SADABS (Sheldrick, 1996)		964 reflections with I > > 2σ(I)
Tmin = 0.682, Tmax = 0.785Rint = 0.020
4349 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.018H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.045Δρmax = 0.23 e Å−3
S = 1.08Δρmin = −0.14 e Å−3
964 reflectionsAbsolute structure: Flack (1983), 444 Friedel pairs
69 parametersFlack parameter: 0.033 (11)
1 restraint
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Cl0.66670.33330.42261 (9)0.0350 (2)
Ni0.66670.33330.65602 (2)0.01925 (10)
N110.71951 (5)0.43902 (11)0.91467 (16)0.0216 (3)
N120.72792 (5)0.45584 (11)0.77144 (18)0.0220 (3)
B0.66670.33330.9718 (4)0.0219 (7)
C130.77645 (7)0.55289 (13)0.7537 (2)0.0266 (4)
C140.79873 (7)0.59746 (13)0.8855 (3)0.0329 (4)
H140.83270.66540.90350.039*
C150.76206 (7)0.52412 (14)0.9853 (2)0.0272 (4)
C160.76527 (8)0.53054 (16)1.1429 (2)0.0381 (5)
H16A0.73240.46491.18310.057*0.5
H16B0.73240.56551.17450.057*0.25
H16C0.83310.56541.17450.057*0.25
H16D0.79950.5991.17160.057*0.5
H16E0.79960.49841.18030.057*0.25
H16F0.69890.49851.18030.057*0.25
C170.80046 (7)0.60092 (14)0.6087 (2)0.0333 (4)
C180.85597 (9)0.71194 (17)0.6292 (3)0.0613 (8)
H18A0.87190.74390.53670.092*
H18B0.9160.73130.68190.092*0.5
H18C0.81530.73120.68220.092*0.5
C190.70656 (13)0.57256 (12)0.52716 (18)0.0420 (4)
H19A0.72270.6040.43420.063*
H19B0.66740.59370.58020.063*
H19C0.66960.50190.5150.063*
H10.66670.33331.090 (4)0.023 (9)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl0.0435 (3)0.0435 (3)0.0179 (4)0.02173 (16)00
Ni0.02115 (12)0.02115 (12)0.01547 (18)0.01057 (6)00
N110.0241 (5)0.0220 (7)0.0181 (8)0.0110 (3)−0.0006 (3)−0.0012 (6)
N120.0254 (5)0.0219 (7)0.0176 (7)0.0110 (3)0.0005 (3)0.0011 (6)
B0.0238 (10)0.0238 (10)0.0181 (18)0.0119 (5)00
C130.0279 (6)0.0237 (8)0.0268 (10)0.0118 (4)0.0010 (4)0.0020 (7)
C140.0403 (8)0.0192 (8)0.0321 (11)0.0096 (4)−0.0022 (4)−0.0043 (8)
C150.0297 (7)0.0252 (8)0.0251 (10)0.0126 (4)−0.0021 (4)−0.0041 (7)
C160.0498 (9)0.0322 (10)0.0263 (11)0.0161 (5)−0.0037 (4)−0.0073 (8)
C170.0434 (8)0.0236 (9)0.0263 (11)0.0118 (5)0.0024 (4)0.0047 (8)
C180.0949 (18)0.0235 (10)0.0418 (15)0.0117 (5)0.0036 (5)0.0072 (10)
C190.0557 (9)0.0446 (8)0.0340 (9)0.0314 (7)−0.0017 (8)0.0066 (7)
Geometric parameters (Å, °) top
Cl—Ni2.2077 (9)C16—H16B0.98
Ni—N122.0084 (15)C16—H16C0.98
N11—C151.348 (2)C16—H16D0.98
N11—N121.374 (2)C16—H16E0.98
N11—B1.552 (2)C16—H16F0.98
N12—C131.346 (2)C17—C191.534 (2)
B—H11.12 (4)C17—C181.540 (3)
C13—C141.389 (3)C18—H18A0.98
C13—C171.522 (3)C18—H18B0.98
C14—C151.382 (3)C18—H18C0.98
C14—H140.95C19—H19A0.98
C15—C161.493 (3)C19—H19B0.98
C16—H16A0.98C19—H19C0.98
N12i—Ni—N1293.26 (6)C15—C16—H16D109.5
N12—Ni—Cl122.93 (5)C15—C16—H16E109.5
C15—N11—N12110.02 (15)H16C—C16—H16E56.3
C15—N11—B129.89 (19)H16D—C16—H16E109.5
N12—N11—B120.08 (18)C15—C16—H16F109.5
C13—N12—N11106.84 (15)H16C—C16—H16F141.1
C13—N12—Ni139.93 (14)H16D—C16—H16F109.5
N11—N12—Ni113.23 (11)H16E—C16—H16F109.5
N11i—B—N11108.53 (15)C13—C17—C19110.04 (11)
N11—B—H1110.40 (14)C19—C17—C19ii111.36 (19)
N12—C13—C14109.06 (18)C13—C17—C18108.5 (2)
N12—C13—C17122.88 (18)C19—C17—C18108.41 (12)
C14—C13—C17128.06 (18)C17—C18—H18A109.5
C15—C14—C13106.89 (17)C17—C18—H18B109.5
C15—C14—H14126.6H18A—C18—H18B109.5
C13—C14—H14126.6C17—C18—H18C109.5
N11—C15—C14107.18 (17)H18A—C18—H18C109.5
N11—C15—C16123.11 (18)H18B—C18—H18C109.5
C14—C15—C16129.71 (19)C17—C19—H19A109.5
C15—C16—H16A109.5C17—C19—H19B109.5
C15—C16—H16B109.5H19A—C19—H19B109.5
H16A—C16—H16B109.5C17—C19—H19C109.5
C15—C16—H16C109.5H19A—C19—H19C109.5
H16A—C16—H16C109.5H19B—C19—H19C109.5
H16B—C16—H16C109.5
C15—N11—N12—C130Ni—N12—C13—C170.0000 (10)
B—N11—N12—C13180N12—C13—C14—C150
C15—N11—N12—Ni180C17—C13—C14—C15180
B—N11—N12—Ni0N12—N11—C15—C140
N12i—Ni—N12—C13133.27 (4)B—N11—C15—C14180
Cl—Ni—N12—C130N12—N11—C15—C16180
N12i—Ni—N12—N11−46.73 (4)B—N11—C15—C160.0000 (10)
Cl—Ni—N12—N11180C13—C14—C15—N110
C15—N11—B—N11i−121.12 (18)C13—C14—C15—C16180.0000 (10)
N12—N11—B—N11i58.88 (18)N12—C13—C17—C1961.54 (12)
N11—N12—C13—C140C14—C13—C17—C19−118.46 (12)
Ni—N12—C13—C14180N12—C13—C17—C18180.0000 (10)
N11—N12—C13—C17180C14—C13—C17—C180.0000 (10)
Symmetry codes: (i) −x+y+1, −x+1, z; (ii) −x+y+1, y, z.
Selected geometric parameters (Å, °) top
Cl—Ni2.2077 (9)N11—N121.374 (2)
Ni—N122.0084 (15)N11—B1.552 (2)
N12i—Ni—N1293.26 (6)N12—Ni—Cl122.93 (5)
Symmetry codes: (i) −x+y+1, −x+1, z.
Acknowledgements top

GMF gratefully acknowledges Research Corporation (grant No. CC6205) and the National Science Foundation (NSF; grant No. CHE-0348158) for support, and Dr Robert McDonald of the University of Alberta Structure Determination Laboratory for collecting the low-temperature CCD X-ray data and for useful discussions.

references
References top

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