Tetra-kis(1,1,1-trifluoro-acetyl-acetonato-κO,O')zirconium(IV) toluene solvate.

In the title compound, [Zr(C(5)H(4)F(3)O(2))(4)]·C(7)H(8), the Zr atom is in a square-anti-prismatic coordination geometry that comprises four O,O'-bidentate trifluoro-acetyl-acetonate ligands. The O-Zr-O bite angles of the acetonate ligands range from 75.27 (5) to 75.41 (5)°. The Zr atom is located on a twofold rotation axis.

Related literature

For β-diketone complexes of zirconium, see: Allard (1976 ▶); Clegg (1987 ▶); Calderazzo et al. (1998 ▶); Davis & Einstein (1978 ▶); Elder (1969 ▶); Silverton & Hoard (1963 ▶). For the unsolvated title complex, see: Kurat’eva et al. (2007 ▶). For a comparison with the isomorphous hafnium complex, see: Viljoen et al. (2008 ▶).

Experimental

Crystal data

[Zr(C5H4F3O2)4]·C7H8

M = 887.82

Monoclinic,

a = 22.537 (5) Å

b = 8.054 (5) Å

c = 22.786 (5) Å

β = 118.383 (5)°

V = 3639 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.41 mm−1

T = 100 (2) K

0.33 × 0.22 × 0.20 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1998 ▶) T min = 0.876, T max = 0.922

14897 measured reflections

3975 independent reflections

3559 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.070

S = 1.05

3975 reflections

259 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.50 e Å−3

Δρmin = −0.45 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT-Plus (Bruker, 2004 ▶); data reduction: SAINT-Plus and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808014499/ng2456sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808014499/ng2456Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Zr(C5H4F3O2)4]·C7H8	F000 = 1792
Mr = 887.82	Dx = 1.621 Mg m−3
Monoclinic, C2/c	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 7203 reflections
a = 22.537 (5) Å	θ = 2.7–28.3º
b = 8.054 (5) Å	µ = 0.41 mm−1
c = 22.786 (5) Å	T = 100 (2) K
β = 118.383 (5)º	Cuboid, colourless
V = 3639 (3) Å3	0.33 × 0.22 × 0.20 mm
Z = 4

Bruker SMART CCD area-detector diffractometer	3975 independent reflections
Radiation source: fine-focus sealed tube	3559 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.029
T = 100(2) K	θmax = 27.0º
φ and ω scans	θmin = 2.1º
Absorption correction: multi-scan(SADABS; Bruker, 1998)	h = −28→25
Tmin = 0.876, Tmax = 0.922	k = −10→7
14897 measured reflections	l = −28→29

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.029	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.070	w = 1/[σ2(Fo2) + (0.0265P)2 + 6.0538P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max = 0.001
3975 reflections	Δρmax = 0.50 e Å−3
259 parameters	Δρmin = −0.45 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Zr	0.5000	0.16714 (3)	0.7500	0.01245 (7)
F13	0.26810 (6)	−0.05226 (14)	0.66176 (6)	0.0295 (3)
F11	0.31909 (6)	−0.06998 (14)	0.76862 (6)	0.0287 (3)
F03	0.51411 (7)	0.40573 (15)	0.95310 (6)	0.0340 (3)
F02	0.45468 (7)	0.22014 (15)	0.96764 (6)	0.0368 (3)
O11	0.39952 (6)	0.08075 (15)	0.72452 (6)	0.0158 (3)
O02	0.51936 (6)	−0.05446 (15)	0.81277 (6)	0.0166 (3)
O01	0.49399 (6)	0.25443 (15)	0.83681 (6)	0.0169 (3)
F12	0.24250 (6)	0.11472 (15)	0.71971 (7)	0.0366 (3)
O12	0.43558 (6)	0.38983 (15)	0.71261 (6)	0.0171 (3)
F01	0.40934 (7)	0.38633 (18)	0.88399 (6)	0.0431 (4)
C13	0.33615 (9)	0.3227 (2)	0.71690 (10)	0.0200 (4)
C02	0.48042 (9)	0.1790 (2)	0.87851 (9)	0.0174 (4)
C05	0.50748 (11)	−0.2801 (2)	0.87225 (10)	0.0244 (4)
H05A	0.5085	−0.3440	0.8372	0.037*
H05B	0.4693	−0.3129	0.8774	0.037*
H05C	0.5481	−0.2994	0.9132	0.037*
C12	0.34797 (9)	0.1566 (2)	0.72089 (8)	0.0160 (3)
C01	0.46413 (10)	0.2976 (2)	0.92118 (9)	0.0230 (4)
C11	0.29404 (9)	0.0373 (2)	0.71787 (10)	0.0214 (4)
C14	0.38103 (9)	0.4351 (2)	0.70992 (9)	0.0182 (4)
C03	0.47956 (10)	0.0124 (2)	0.88819 (9)	0.0200 (4)
C04	0.50208 (9)	−0.1001 (2)	0.85506 (9)	0.0174 (4)
C102	0.67683 (12)	0.0133 (3)	1.07100 (11)	0.0402 (6)
H102	0.6803	−0.0134	1.1122	0.048*
C15	0.36143 (10)	0.6138 (2)	0.69579 (11)	0.0257 (4)
H15A	0.4003	0.6786	0.7036	0.039*
H15B	0.3440	0.6517	0.7246	0.039*
H15C	0.3274	0.6260	0.6501	0.039*
C105	0.66546 (11)	0.0938 (4)	0.94967 (11)	0.0403 (6)
H105	0.6612	0.1195	0.9080	0.048*
C104	0.67351 (12)	−0.0692 (3)	0.96984 (12)	0.0428 (6)
H104	0.6748	−0.1519	0.9420	0.051*
C100	0.66358 (10)	0.2198 (3)	0.98939 (11)	0.0337 (5)
C101	0.66888 (11)	0.1768 (3)	1.05052 (11)	0.0352 (5)
H101	0.6671	0.2593	1.0782	0.042*
C103	0.67966 (12)	−0.1103 (3)	1.03094 (13)	0.0411 (6)
H103	0.6857	−0.2203	1.0450	0.049*
C106	0.65652 (13)	0.3975 (4)	0.96634 (16)	0.0586 (8)
H10A	0.6561	0.4691	0.9998	0.088*	0.50
H10B	0.6151	0.4103	0.9255	0.088*	0.50
H10C	0.6938	0.4262	0.9590	0.088*	0.50
H10D	0.6540	0.4013	0.9231	0.088*	0.50
H10E	0.6949	0.4601	0.9974	0.088*	0.50
H10F	0.6162	0.4442	0.9639	0.088*	0.50
H03	0.4677 (11)	−0.027 (3)	0.9208 (10)	0.024 (6)*
H13	0.2975 (12)	0.361 (3)	0.7144 (11)	0.028 (6)*

	U11	U22	U33	U12	U13	U23
Zr	0.01529 (12)	0.00880 (12)	0.01714 (12)	0.000	0.01087 (9)	0.000
F13	0.0252 (6)	0.0253 (6)	0.0364 (6)	−0.0084 (5)	0.0133 (5)	−0.0067 (5)
F11	0.0325 (6)	0.0214 (6)	0.0384 (7)	−0.0030 (5)	0.0221 (6)	0.0069 (5)
F03	0.0518 (8)	0.0227 (6)	0.0398 (7)	−0.0104 (6)	0.0318 (6)	−0.0121 (5)
F02	0.0681 (9)	0.0251 (6)	0.0407 (7)	−0.0054 (6)	0.0450 (7)	−0.0025 (5)
O11	0.0164 (6)	0.0125 (6)	0.0217 (6)	0.0012 (5)	0.0116 (5)	0.0004 (5)
O02	0.0188 (6)	0.0140 (6)	0.0206 (6)	0.0007 (5)	0.0123 (5)	0.0025 (5)
O01	0.0222 (6)	0.0131 (6)	0.0199 (6)	−0.0008 (5)	0.0136 (5)	0.0003 (5)
F12	0.0295 (7)	0.0204 (6)	0.0776 (10)	0.0012 (5)	0.0399 (7)	0.0000 (6)
O12	0.0193 (6)	0.0134 (6)	0.0231 (6)	0.0016 (5)	0.0136 (5)	0.0024 (5)
F01	0.0451 (8)	0.0518 (9)	0.0367 (7)	0.0246 (7)	0.0229 (6)	−0.0001 (6)
C13	0.0184 (9)	0.0161 (9)	0.0311 (10)	0.0030 (7)	0.0163 (8)	0.0012 (8)
C02	0.0192 (9)	0.0182 (9)	0.0173 (8)	−0.0009 (7)	0.0106 (7)	−0.0008 (7)
C05	0.0343 (11)	0.0156 (9)	0.0300 (10)	−0.0006 (8)	0.0208 (9)	0.0034 (8)
C12	0.0164 (8)	0.0158 (9)	0.0192 (8)	0.0001 (7)	0.0113 (7)	−0.0005 (7)
C01	0.0319 (11)	0.0205 (10)	0.0228 (9)	0.0012 (8)	0.0180 (8)	0.0014 (7)
C11	0.0203 (9)	0.0160 (9)	0.0342 (10)	0.0017 (7)	0.0180 (8)	0.0001 (8)
C14	0.0217 (9)	0.0146 (9)	0.0202 (9)	0.0034 (7)	0.0115 (7)	0.0012 (7)
C03	0.0260 (10)	0.0186 (9)	0.0212 (9)	−0.0010 (7)	0.0159 (8)	0.0023 (7)
C04	0.0163 (9)	0.0164 (9)	0.0194 (8)	−0.0018 (7)	0.0084 (7)	0.0020 (7)
C102	0.0378 (13)	0.0551 (16)	0.0294 (11)	−0.0099 (11)	0.0174 (10)	0.0037 (11)
C15	0.0268 (10)	0.0148 (9)	0.0406 (11)	0.0043 (8)	0.0202 (9)	0.0043 (8)
C105	0.0264 (11)	0.0699 (18)	0.0234 (10)	−0.0085 (11)	0.0108 (9)	−0.0024 (11)
C104	0.0286 (12)	0.0546 (17)	0.0453 (14)	−0.0078 (11)	0.0177 (11)	−0.0252 (12)
C100	0.0176 (10)	0.0387 (13)	0.0346 (11)	−0.0053 (9)	0.0040 (9)	0.0047 (10)
C101	0.0305 (12)	0.0414 (14)	0.0330 (11)	−0.0061 (10)	0.0145 (9)	−0.0128 (10)
C103	0.0284 (12)	0.0329 (13)	0.0552 (15)	−0.0059 (10)	0.0144 (11)	−0.0016 (11)
C106	0.0288 (13)	0.0518 (17)	0.0718 (19)	−0.0054 (12)	0.0048 (13)	0.0233 (15)

Zr—O01i	2.1633 (13)	C05—H05C	0.9600
Zr—O01	2.1633 (13)	C12—C11	1.525 (3)
Zr—O11	2.1679 (13)	C14—C15	1.496 (3)
Zr—O11i	2.1679 (13)	C03—C04	1.419 (3)
Zr—O02i	2.1973 (15)	C03—H03	0.95 (2)
Zr—O02	2.1973 (15)	C102—C103	1.372 (4)
Zr—O12i	2.2079 (15)	C102—C101	1.381 (4)
Zr—O12	2.2079 (15)	C102—H102	0.9300
F13—C11	1.336 (2)	C15—H15A	0.9600
F11—C11	1.335 (2)	C15—H15B	0.9600
F03—C01	1.333 (2)	C15—H15C	0.9600
F02—C01	1.330 (2)	C105—C104	1.374 (4)
O11—C12	1.280 (2)	C105—C100	1.374 (4)
O02—C04	1.254 (2)	C105—H105	0.9300
O01—C02	1.281 (2)	C104—C103	1.373 (4)
F12—C11	1.337 (2)	C104—H104	0.9300
O12—C14	1.256 (2)	C100—C101	1.384 (3)
F01—C01	1.326 (2)	C100—C106	1.506 (4)
C13—C12	1.359 (3)	C101—H101	0.9300
C13—C14	1.421 (3)	C103—H103	0.9300
C13—H13	0.90 (2)	C106—H10A	0.9600
C02—C03	1.362 (3)	C106—H10B	0.9600
C02—C01	1.527 (3)	C106—H10C	0.9600
C05—C04	1.492 (3)	C106—H10D	0.9600
C05—H05A	0.9600	C106—H10E	0.9600
C05—H05B	0.9600	C106—H10F	0.9600
O01i—Zr—O01	142.07 (7)	F13—C11—C12	111.10 (15)
O01i—Zr—O11	111.77 (5)	F12—C11—C12	112.97 (15)
O01—Zr—O11	80.66 (5)	O12—C14—C13	122.83 (16)
O01i—Zr—O11i	80.66 (5)	O12—C14—C15	118.18 (16)
O01—Zr—O11i	111.77 (5)	C13—C14—C15	118.94 (17)
O11—Zr—O11i	142.56 (7)	C02—C03—C04	120.48 (17)
O01i—Zr—O02i	75.41 (5)	C02—C03—H03	118.7 (13)
O01—Zr—O02i	141.24 (5)	C04—C03—H03	120.5 (13)
O11—Zr—O02i	72.91 (5)	O02—C04—C03	122.81 (17)
O11i—Zr—O02i	76.85 (5)	O02—C04—C05	118.06 (16)
O01i—Zr—O02	141.24 (5)	C03—C04—C05	119.11 (16)
O01—Zr—O02	75.41 (5)	C103—C102—C101	120.5 (2)
O11—Zr—O02	76.85 (5)	C103—C102—H102	119.8
O11i—Zr—O02	72.91 (5)	C101—C102—H102	119.8
O02i—Zr—O02	71.36 (7)	C14—C15—H15A	109.5
O01i—Zr—O12i	76.90 (5)	C14—C15—H15B	109.5
O01—Zr—O12i	72.46 (5)	H15A—C15—H15B	109.5
O11—Zr—O12i	140.87 (5)	C14—C15—H15C	109.5
O11i—Zr—O12i	75.27 (5)	H15A—C15—H15C	109.5
O02i—Zr—O12i	143.29 (5)	H15B—C15—H15C	109.5
O02—Zr—O12i	121.20 (5)	C104—C105—C100	121.7 (2)
O01i—Zr—O12	72.46 (5)	C104—C105—H105	119.1
O01—Zr—O12	76.90 (5)	C100—C105—H105	119.1
O11—Zr—O12	75.27 (5)	C103—C104—C105	120.2 (2)
O11i—Zr—O12	140.87 (5)	C103—C104—H104	119.9
O02i—Zr—O12	121.20 (5)	C105—C104—H104	119.9
O02—Zr—O12	143.29 (5)	C105—C100—C101	117.6 (2)
O12i—Zr—O12	71.35 (7)	C105—C100—C106	120.2 (2)
C12—O11—Zr	131.65 (12)	C101—C100—C106	122.2 (2)
C04—O02—Zr	134.45 (12)	C102—C101—C100	120.9 (2)
C02—O01—Zr	131.67 (12)	C102—C101—H101	119.5
C14—O12—Zr	134.72 (12)	C100—C101—H101	119.5
C12—C13—C14	120.47 (17)	C102—C103—C104	119.1 (2)
C12—C13—H13	119.8 (15)	C102—C103—H103	120.5
C14—C13—H13	119.4 (15)	C104—C103—H103	120.5
O01—C02—C03	127.88 (17)	C100—C106—H10A	109.5
O01—C02—C01	112.97 (16)	C100—C106—H10B	109.5
C03—C02—C01	119.15 (16)	H10A—C106—H10B	109.5
C04—C05—H05A	109.5	C100—C106—H10C	109.5
C04—C05—H05B	109.5	H10A—C106—H10C	109.5
H05A—C05—H05B	109.5	H10B—C106—H10C	109.5
C04—C05—H05C	109.5	C100—C106—H10D	109.5
H05A—C05—H05C	109.5	H10A—C106—H10D	141.1
H05B—C05—H05C	109.5	H10B—C106—H10D	56.3
O11—C12—C13	128.12 (17)	H10C—C106—H10D	56.3
O11—C12—C11	112.42 (15)	C100—C106—H10E	109.5
C13—C12—C11	119.40 (16)	H10A—C106—H10E	56.3
F01—C01—F02	107.98 (17)	H10B—C106—H10E	141.1
F01—C01—F03	106.60 (17)	H10C—C106—H10E	56.3
F02—C01—F03	106.60 (15)	H10D—C106—H10E	109.5
F01—C01—C02	111.26 (16)	C100—C106—H10F	109.5
F02—C01—C02	113.01 (16)	H10A—C106—H10F	56.3
F03—C01—C02	111.06 (16)	H10B—C106—H10F	56.3
F11—C11—F13	106.99 (15)	H10C—C106—H10F	141.1
F11—C11—F12	106.91 (15)	H10D—C106—H10F	109.5
F13—C11—F12	106.87 (15)	H10E—C106—H10F	109.5
F11—C11—C12	111.66 (15)
O01i—Zr—O11—C12	−89.06 (15)	C14—C13—C12—O11	6.1 (3)
O01—Zr—O11—C12	53.60 (14)	C14—C13—C12—C11	−170.90 (17)
O11i—Zr—O11—C12	167.40 (15)	O01—C02—C01—F01	62.8 (2)
O02i—Zr—O11—C12	−155.08 (15)	C03—C02—C01—F01	−117.6 (2)
O02—Zr—O11—C12	130.68 (15)	O01—C02—C01—F02	−175.56 (16)
O12i—Zr—O11—C12	6.91 (18)	C03—C02—C01—F02	4.1 (3)
O12—Zr—O11—C12	−25.20 (14)	O01—C02—C01—F03	−55.8 (2)
O01i—Zr—O02—C04	−163.83 (14)	C03—C02—C01—F03	123.82 (19)
O01—Zr—O02—C04	28.28 (16)	O11—C12—C11—F11	54.2 (2)
O11—Zr—O02—C04	−55.32 (16)	C13—C12—C11—F11	−128.38 (18)
O11i—Zr—O02—C04	147.03 (17)	O11—C12—C11—F13	−65.2 (2)
O02i—Zr—O02—C04	−131.45 (18)	C13—C12—C11—F13	112.26 (19)
O12i—Zr—O02—C04	86.84 (17)	O11—C12—C11—F12	174.73 (15)
O12—Zr—O02—C04	−13.9 (2)	C13—C12—C11—F12	−7.8 (3)
O01i—Zr—O01—C02	167.64 (16)	Zr—O12—C14—C13	−17.5 (3)
O11—Zr—O01—C02	54.03 (15)	Zr—O12—C14—C15	165.24 (13)
O11i—Zr—O01—C02	−89.17 (15)	C12—C13—C14—O12	−6.0 (3)
O02i—Zr—O01—C02	6.93 (19)	C12—C13—C14—C15	171.22 (18)
O02—Zr—O01—C02	−24.70 (15)	O01—C02—C03—C04	7.0 (3)
O12i—Zr—O01—C02	−154.76 (16)	C01—C02—C03—C04	−172.56 (17)
O12—Zr—O01—C02	130.96 (16)	Zr—O02—C04—C03	−20.3 (3)
O01i—Zr—O12—C14	145.52 (17)	Zr—O02—C04—C05	161.44 (13)
O01—Zr—O12—C14	−57.13 (16)	C02—C03—C04—O02	−4.8 (3)
O11—Zr—O12—C14	26.49 (16)	C02—C03—C04—C05	173.47 (18)
O11i—Zr—O12—C14	−165.63 (15)	C100—C105—C104—C103	0.3 (4)
O02i—Zr—O12—C14	85.53 (17)	C104—C105—C100—C101	−1.1 (3)
O02—Zr—O12—C14	−15.3 (2)	C104—C105—C100—C106	178.4 (2)
O12i—Zr—O12—C14	−132.77 (19)	C103—C102—C101—C100	0.0 (4)
Zr—O01—C02—C03	15.3 (3)	C105—C100—C101—C102	1.0 (3)
Zr—O01—C02—C01	−165.07 (12)	C106—C100—C101—C102	−178.5 (2)
Zr—O11—C12—C13	17.1 (3)	C101—C102—C103—C104	−0.9 (4)
Zr—O11—C12—C11	−165.74 (11)	C105—C104—C103—C102	0.8 (4)

Zr—O01	2.1633 (13)
Zr—O11	2.1679 (13)
Zr—O02	2.1973 (15)
Zr—O12	2.2079 (15)

O01i—Zr—O01	142.07 (7)
O01—Zr—O11	80.66 (5)
O11—Zr—O11i	142.56 (7)
O01—Zr—O02	75.41 (5)
O11—Zr—O02	76.85 (5)
O01—Zr—O12	76.90 (5)
O11—Zr—O12	75.27 (5)

Symmetry code: (i) .