(Acetyl­acetonato-κ2O,O′)dichlorido­bis(methano­lato-κO)niobium(V)

Herbst, L.; Visser, H.G.; Roodt, A.; Pretorius, C.

doi:10.1107/S1600536812042638

metal-organic compounds

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Volume 68| Part 11| November 2012| Page m1392

doi:10.1107/S1600536812042638

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(Acetylacetonato-κ²O,O′)dichloridobis(methanolato-κO)niobium(V)

Leandra Herbst,^a ^* Hendrik G. Visser,^a Andreas Roodt ^a and Carla Pretorius ^a

^aDepartment of Chemistry, University of the Free State, PO Box 339, Bloemfontein, 9300, South Africa
^*Correspondence e-mail: HerbstL@ufs.ac.za

(Received 10 October 2012; accepted 11 October 2012; online 20 October 2012)

In the title compound, [Nb(CH₃O)₂(C₅H₇O₂)Cl₂], a slightly distorted octahedral coordination geometry is observed around the Nb^V atom with Nb—O distances in the range of 1.8254 (16)–2.0892 (16) Å and Nb—Cl distances of 2.3997 (14) and 2.4023 (12) Å. The O—Nb—O angles vary between 81.36 (7) and 172.65 (7) °, while the trans Cl—Nb—Cl angle is 167.34 (2)°. There are no hydrogen bonds observed.

Related literature

For synthetic background, see: Herbst et al. (2010 ; 2011 ); Davies et al. (1999 ). For applications of acetylacetone-type ligands in industry, see: Steyn et al. (1992 , 1997 , 2008 ); Otto et al. (1998 ); Roodt & Steyn (2000 ); Brink et al. (2010 ); Viljoen et al. (2008 , 2009a ,b , 2010 ). For related niobium complexes, see: Sokolov et al. (1999 , 2005 ); Antinolo et al. (2000 ); Dahan et al. (1976 ).

Experimental

Crystal data

[Nb(CH₃O)₂(C₅H₇O₂)Cl₂]
M_r = 324.98
Monoclinic, P 2₁ /c
a = 7.7985 (2) Å
b = 11.6028 (3) Å
c = 14.6819 (2) Å
β = 111.279 (1)°
V = 1237.91 (5) Å³
Z = 4
Mo Kα radiation
μ = 1.39 mm⁻¹
T = 100 K
0.38 × 0.13 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.810, T_max = 0.895
25521 measured reflections
2995 independent reflections
2873 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.060
S = 1.04
2995 reflections
131 parameters
H-atom parameters constrained
Δρ_max = 1.90 e Å⁻³
Δρ_min = −1.14 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus; program(s) used to solve structure: SIR92 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2004 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812042638/bt6846sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812042638/bt6846Isup2.hkl

checkCIF report

Comment top

Acetylacetone and other β-diketones are strong chelating agents that find applications in homogenous catalysis and the separations industry (Steyn et al., 1992; 1997; Otto et al., 1998; Roodt & Steyn, 2000; Brink et al., 2010). This study forms part of ongoing research to investigate the interaction of transition metals used in the nuclear industry, specifically zirconium, hafnium, niobium and tantalum, with O,O'- and N,O-bidentate ligands. (Steyn et al., 2008; Viljoen et al., 2008; 2009a,b; 2010; Herbst et al., 2010; 2011).

The title complex crystallizes in the monoclinic space group P2₁/c with Z = 4. The assymetric unit consists of a niobium(V) atom surrounded by two methanolate groups, two chlorido ligands and an O,O'-bonded acetylacetonato ligand (Figure 1). The octahedral environment around the niobium metal centre is slightly disordered with Nb—O distances varying between 1.8254 (16) and 2.0892 (16) Å, while the Nb—Cl distances are 2.3997 (14) and 2.4023 (12) Å respectively. The O—Nb—O angles vary between and 81.36 (7) and 172.65 (7) °, while the trans Cl—Nb—Cl angle is 167.34 (2) °. All the bond distances and angles are similar to other relevant niobium(V) structures (Herbst et al., 2010; 2011; Sokolov et al., 1999; 2005; Antinolo et al., 2000 and Dahan et al., 1976).

Related literature top

For synthetic background, see: Herbst et al. (2010; 2011); Davies et al. (1999). For applications of acetylacetone-type ligands in industry, see: Steyn et al. (1992, 1997, 2008); Otto et al. (1998); Roodt & Steyn (2000); Brink et al. (2010); Viljoen et al. (2008, 2009a,b, 2010). For related niobium complexes, see: Sokolov et al. (1999, 2005); Antinolo et al. (2000); Dahan et al. (1976).

Experimental top

NbCl₅ (0.3134 g; 1.16 mmol) was carefully dissolved in absolute methanol (5 ml) (Care: exothermic reaction). Acetylacetone (0.119 ml; 1.16 mmol) was added to the solution. The colourless solution was stirred for 1 h at room temperature and the solution was left to stand at 252 K for 24 h after which pale-yellow crystals, suitable for X-ray diffraction were obtained.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus (Bruker, 2004); program(s) used to solve structure: SIR92 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2004); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. Molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability displacement level.

(Acetylacetonato-κ²O,O')dichloridobis(methanolato- κO)niobium(V) top

Crystal data top

[Nb(CH₃O)₂(C₅H₇O₂)Cl₂]	F(000) = 648
M_r = 324.98	D_x = 1.744 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ybc	Cell parameters from 9867 reflections
a = 7.7985 (2) Å	θ = 2.3–32.9°
b = 11.6028 (3) Å	µ = 1.39 mm⁻¹
c = 14.6819 (2) Å	T = 100 K
β = 111.279 (1)°	Cubiod, yellow
V = 1237.91 (5) Å³	0.38 × 0.13 × 0.08 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	2873 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ϕ and ω scans	θ_max = 28°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −10→9
T_min = 0.810, T_max = 0.895	k = −14→15
25521 measured reflections	l = −19→19
2995 independent reflections

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.060	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0177P)² + 2.6018P] where P = (F_o² + 2F_c²)/3
2995 reflections	(Δ/σ)_max = 0.001
131 parameters	Δρ_max = 1.90 e Å⁻³
0 restraints	Δρ_min = −1.14 e Å⁻³

Crystal data top

[Nb(CH₃O)₂(C₅H₇O₂)Cl₂]	V = 1237.91 (5) Å³
M_r = 324.98	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.7985 (2) Å	µ = 1.39 mm⁻¹
b = 11.6028 (3) Å	T = 100 K
c = 14.6819 (2) Å	0.38 × 0.13 × 0.08 mm
β = 111.279 (1)°

Data collection top

Bruker APEXII CCD diffractometer	2995 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	2873 reflections with I > 2σ(I)
T_min = 0.810, T_max = 0.895	R_int = 0.024
25521 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	0 restraints
wR(F²) = 0.060	H-atom parameters constrained
S = 1.04	Δρ_max = 1.90 e Å⁻³
2995 reflections	Δρ_min = −1.14 e Å⁻³
131 parameters

Special details top

Experimental. The intensity data was collected on a Bruker X8 ApexII 4 K Kappa CCD diffractometer using an exposure time of 60 s/frame. A total of 1033 frames were collected with a frame width of 0.5° covering up to θ = 28.32° with 99.8% completeness accomplished.

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
C1	0.5973 (4)	0.0556 (2)	0.41589 (19)	0.0291 (5)
H1A	0.5041	0.0091	0.3698	0.044*
H1B	0.5461	0.0949	0.4577	0.044*
H1C	0.697	0.0073	0.4547	0.044*
C2	0.6671 (3)	0.14217 (19)	0.36226 (16)	0.0209 (4)
C3	0.6842 (3)	0.25776 (19)	0.38971 (15)	0.0217 (4)
H3	0.6428	0.2801	0.439	0.026*
C4	0.7590 (3)	0.34165 (18)	0.34795 (15)	0.0189 (4)
C5	0.7749 (3)	0.4644 (2)	0.38144 (17)	0.0256 (5)
H5A	0.8962	0.4925	0.3915	0.038*
H5B	0.7531	0.4689	0.4416	0.038*
H5C	0.6856	0.5104	0.3326	0.038*
C6	1.0638 (4)	0.3334 (2)	0.1093 (2)	0.0351 (6)
H6A	1.0417	0.4104	0.1263	0.053*
H6B	1.0441	0.3302	0.0409	0.053*
H6C	1.1884	0.3119	0.1467	0.053*
C7	0.7155 (4)	−0.0737 (2)	0.12959 (19)	0.0315 (5)
H7A	0.6627	−0.0836	0.1788	0.047*
H7B	0.8087	−0.131	0.1379	0.047*
H7C	0.6213	−0.0817	0.0661	0.047*
O1	0.7114 (2)	0.10264 (14)	0.29243 (12)	0.0260 (3)
O2	0.8199 (2)	0.32042 (13)	0.27942 (12)	0.0236 (3)
O3	0.9420 (2)	0.25678 (14)	0.12973 (12)	0.0249 (3)
O4	0.7944 (2)	0.03654 (13)	0.13835 (12)	0.0235 (3)
Cl1	1.11377 (9)	0.13058 (6)	0.32569 (5)	0.03473 (14)
Cl2	0.51757 (8)	0.23365 (5)	0.10144 (4)	0.02774 (12)
Nb1	0.82643 (3)	0.178209 (17)	0.198700 (15)	0.02255 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0387 (13)	0.0244 (11)	0.0336 (12)	0.0020 (10)	0.0241 (11)	0.0074 (9)
C2	0.0234 (10)	0.0220 (10)	0.0208 (10)	0.0033 (8)	0.0122 (8)	0.0047 (8)
C3	0.0271 (11)	0.0233 (10)	0.0194 (10)	0.0032 (8)	0.0142 (9)	0.0006 (8)
C4	0.0204 (10)	0.0202 (10)	0.0166 (9)	0.0022 (8)	0.0074 (8)	−0.0015 (7)
C5	0.0325 (12)	0.0212 (10)	0.0277 (11)	−0.0021 (9)	0.0162 (10)	−0.0065 (9)
C6	0.0348 (13)	0.0404 (14)	0.0344 (13)	−0.0160 (11)	0.0177 (11)	−0.0021 (11)
C7	0.0391 (14)	0.0204 (11)	0.0358 (13)	−0.0076 (10)	0.0145 (11)	−0.0050 (10)
O1	0.0399 (9)	0.0187 (7)	0.0296 (8)	−0.0034 (7)	0.0247 (8)	−0.0019 (6)
O2	0.0349 (9)	0.0186 (7)	0.0246 (8)	−0.0050 (6)	0.0194 (7)	−0.0042 (6)
O3	0.0307 (8)	0.0245 (8)	0.0274 (8)	−0.0071 (7)	0.0199 (7)	−0.0046 (6)
O4	0.0291 (8)	0.0184 (7)	0.0279 (8)	−0.0037 (6)	0.0161 (7)	−0.0059 (6)
Cl1	0.0379 (3)	0.0295 (3)	0.0374 (3)	−0.0022 (2)	0.0144 (3)	−0.0032 (2)
Cl2	0.0297 (3)	0.0293 (3)	0.0283 (3)	−0.0040 (2)	0.0154 (2)	−0.0029 (2)
Nb1	0.03316 (12)	0.01790 (10)	0.02524 (11)	−0.00586 (8)	0.02096 (9)	−0.00534 (7)

Geometric parameters (Å, º) top

C1—C2	1.495 (3)	C6—H6A	0.96
C1—H1A	0.96	C6—H6B	0.96
C1—H1B	0.96	C6—H6C	0.96
C1—H1C	0.96	C7—O4	1.405 (3)
C2—O1	1.280 (3)	C7—H7A	0.96
C2—C3	1.393 (3)	C7—H7B	0.96
C3—C4	1.387 (3)	C7—H7C	0.96
C3—H3	0.93	O1—Nb1	2.0892 (16)
C4—O2	1.283 (3)	O2—Nb1	2.0429 (16)
C4—C5	1.497 (3)	O3—Nb1	1.8254 (16)
C5—H5A	0.96	O4—Nb1	1.8410 (17)
C5—H5B	0.96	Cl1—Nb1	2.4023 (12)
C5—H5C	0.96	Cl2—Nb1	2.3997 (14)
C6—O3	1.411 (3)

C2—C1—H1A	109.5	H6B—C6—H6C	109.5
C2—C1—H1B	109.5	O4—C7—H7A	109.5
H1A—C1—H1B	109.5	O4—C7—H7B	109.5
C2—C1—H1C	109.5	H7A—C7—H7B	109.5
H1A—C1—H1C	109.5	O4—C7—H7C	109.5
H1B—C1—H1C	109.5	H7A—C7—H7C	109.5
O1—C2—C3	123.49 (19)	H7B—C7—H7C	109.5
O1—C2—C1	115.9 (2)	C2—O1—Nb1	133.05 (15)
C3—C2—C1	120.6 (2)	C4—O2—Nb1	134.78 (14)
C4—C3—C2	124.00 (19)	C6—O3—Nb1	159.91 (16)
C4—C3—H3	118	C7—O4—Nb1	146.66 (15)
C2—C3—H3	118	O3—Nb1—O4	100.77 (7)
O2—C4—C3	123.2 (2)	O3—Nb1—O2	92.28 (7)
O2—C4—C5	115.49 (19)	O4—Nb1—O2	166.62 (7)
C3—C4—C5	121.35 (19)	O3—Nb1—O1	172.65 (7)
C4—C5—H5A	109.5	O4—Nb1—O1	85.79 (7)
C4—C5—H5B	109.5	O2—Nb1—O1	81.36 (7)
H5A—C5—H5B	109.5	O3—Nb1—Cl2	97.31 (7)
C4—C5—H5C	109.5	O4—Nb1—Cl2	91.23 (6)
H5A—C5—H5C	109.5	O2—Nb1—Cl2	84.13 (5)
H5B—C5—H5C	109.5	O1—Nb1—Cl2	85.76 (6)
O3—C6—H6A	109.5	O3—Nb1—Cl1	92.06 (7)
O3—C6—H6B	109.5	O4—Nb1—Cl1	95.37 (6)
H6A—C6—H6B	109.5	O2—Nb1—Cl1	87.03 (5)
O3—C6—H6C	109.5	O1—Nb1—Cl1	83.97 (7)
H6A—C6—H6C	109.5	Cl2—Nb1—Cl1	167.34 (2)

Experimental details

Crystal data
Chemical formula	[Nb(CH₃O)₂(C₅H₇O₂)Cl₂]
M_r	324.98
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	7.7985 (2), 11.6028 (3), 14.6819 (2)
β (°)	111.279 (1)
V (Å³)	1237.91 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.39
Crystal size (mm)	0.38 × 0.13 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.810, 0.895
No. of measured, independent and observed [I > 2σ(I)] reflections	25521, 2995, 2873
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.060, 1.04
No. of reflections	2995
No. of parameters	131
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.90, −1.14

Computer programs: APEX2 (Bruker, 2005), SAINT-Plus (Bruker, 2004), SIR92 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2004), WinGX (Farrugia, 1999).

Acknowledgements

Financial assistance from the Advanced Metals Initiative (AMI) of the Department of Science and Technology (DST) of South Africa, through the New Metals Development Network (NMDN) coordinated by the South African Nuclear Energy Corporation Limited (Necsa) and the University of the Free State is gratefully acknowledged.

References

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