Triphenyl­bis[4-(trifluoro­meth­yl)benzoato-κO]anti­mony(V)

Quan, L.; Yin, H.; Cui, L.; Yang, M.; Wang, D.

doi:10.1107/S1600536809017449

Triphenylbis[4-(trifluoromethyl)benzoato-κO]antimony(V)

L. Quan, H. Yin, L. Cui, M. Yang and D. Wang

The title complex, [Sb(C₆H₅)₃(C₈H₄F₃O₂)₂], is located on a twofold axis defined by the metal center and two C atoms of a coordinated phenyl group. The environment of the Sb atom approximates a trigonal-bipyramidal geometry, with the axial positions occupied by the O atoms of symmetry-related 4-(trifluoromethyl)benzoate ligands. In this ligand, the CF₃ group is disordered by rotation about the C—C bond and the F atoms are distributed over two sets of sites with occupancies of 0.62 (3) and 0.38 (3). In the crystal, molecules are assembled in a three-dimensional framework through weak C—H

O hydrogen bonds.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536809017449/bh2229sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536809017449/bh2229Isup2.hkl Contains datablock I

CCDC reference: 679197

checkCIF report

Key indicators

Single-crystal X-ray study
T = 298 K
Mean (C-C) = 0.019 Å
Disorder in main residue
R factor = 0.058
wR factor = 0.145
Data-to-parameter ratio = 11.7

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT242_ALERT_2_B Check Low       Ueq as Compared to Neighbors for         C8

Alert level C
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.18
PLAT213_ALERT_2_C Atom F1      has ADP max/min Ratio .............       3.50 prola
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.02 Ratio
PLAT220_ALERT_2_C Large Non-Solvent    F     Ueq(max)/Ueq(min) ...       2.71 Ratio
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C11
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C13
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C17
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C2
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C5
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C15
PLAT342_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...         19
PLAT034_ALERT_1_C No Flack Parameter Given. Z .GT. Si, NonCentro .          ?
PLAT234_ALERT_4_C Large Hirshfeld Difference C4     --  C5      ..       0.15 Ang.
PLAT234_ALERT_4_C Large Hirshfeld Difference C13    --  C14     ..       0.20 Ang.
PLAT731_ALERT_1_C Bond    Calc     1.37(2), Rep    1.370(9) ......       2.22 su-Ra
              C10  -C11     1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     1.38(3), Rep   1.380(10) ......       3.00 su-Ra
              C11  -C12     1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     1.38(3), Rep   1.380(10) ......       3.00 su-Ra
              C12  -C13     1.555   1.555

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           25.00
           From the CIF: _reflns_number_total               2719
           Count of symmetry unique reflns         1435
           Completeness (_total/calc)            189.48%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1284
           Fraction of Friedel pairs measured     0.895
           Are heavy atom types Z>Si present        yes
PLAT301_ALERT_3_G Note Main Residue  Disorder ....................      12.00 Perc.
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         55

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
  17 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
  11 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

Some triorganoantimony(V) complexes with acetylferroceneoxime as ligand showed in vitro antitumor activity (Yin et al., 2008). The related title compound may show similar activity. The title complex is also related to triphenyl-bis(4-methylbenzoato-κO)-antimony(V), previously characterized (Sharutin et al., 2003), although both complexes are not isostructural and crystallize in different space groups.

The crystal structure of the title complex consists of isolated molecules which have C2 molecular symmetry. The 2-fold axis is defined by atoms Sb1/C15/C18. The coordination geometry around the antimony center is best described as a distorted trigonal bipyramid. Two carboxylate groups occupy the axial sites with O1—Sb1—-O1ⁱ angle being 176.0 (3)° [symmetry code: (i) 2 - x, 1 - y, z]. In the equatorial plane, the sum of angles C9—Sb1—C9ⁱ, C9—Sb1—C15 and C15—Sb1—C9ⁱ is 360.0°. The Sb1—O1 bond length, 2.150 (5) Å, is significantly different from the corresponding distance in [4-(C₅H₅FeC₅H₄)C₆H₄COO]₂Sb(C₆H₄F-4)₃, 2.087 (6) Å (Yu et al., 2004), but much shorter than the sum of the van der Waals radii for Sb and O, 3.2 Å. The Sb—C distances fall in the expected range found in the literature (Yu et al., 2004).

Related literature top

For related Sb(V) structures, see: Sharutin et al. (2003); Yin et al. (2008); Yu et al. (2004).

Experimental top

4-Trifluoromethylbenzoic acid (0.152 g, 0.8 mmol) and sodium methoxide (0.8 mmol) were added to a stirring solution containing dichlorotriphenylantimony (0.172 g, 0.4 mmol) in toluene (25 ml). After refluxing for 8 h., a colorless solution was obtained and then filtered. The solvent was gradually removed by evaporation under vacuum until a white solid was obtained. The solid was recrystallized from petroleum ether/dichoromethane (1:1) to give colorless crystals of the title complex.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title complex, with atom labels and 50% probability displacement ellipsoids for non-H atoms.
	Fig. 2. A chain of molecules linked by C3—H3···O2#1 intermolecular hydrogen bonds (dashed lines) (symmetry code #1: 1 - y, x-y, z - 1/3).

Triphenylbis[4-(trifluoromethyl)benzoato-κO]antimony(V) top

Crystal data top

[Sb(C₆H₅)₃(C₈H₄F₃O₂)₂]	D_x = 1.554 Mg m⁻³
M_r = 731.27	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P6₂	Cell parameters from 3513 reflections
Hall symbol: P 62	θ = 2.2–23.0°
a = 12.9879 (10) Å	µ = 0.96 mm⁻¹
c = 16.042 (2) Å	T = 298 K
V = 2343.5 (4) Å³	Block, colorless
Z = 3	0.44 × 0.31 × 0.24 mm
F(000) = 1092

Data collection top

Bruker SMART diffractometer	2719 independent reflections
Radiation source: fine-focus sealed tube	1962 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.053
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→9
T_min = 0.679, T_max = 0.803	k = −15→12
9708 measured reflections	l = −19→18

Refinement top

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)] = 0.058	H-atom parameters constrained
wR(F²) = 0.145	w = 1/[σ²(F_o²) + (0.0684P)² + 2.131P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.026
2719 reflections	Δρ_max = 0.90 e Å⁻³
233 parameters	Δρ_min = −0.41 e Å⁻³
55 restraints	Absolute structure: Flack (1983), 1284 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.04 (7)

Crystal data top

[Sb(C₆H₅)₃(C₈H₄F₃O₂)₂]	Z = 3
M_r = 731.27	Mo Kα radiation
Hexagonal, P6₂	µ = 0.96 mm⁻¹
a = 12.9879 (10) Å	T = 298 K
c = 16.042 (2) Å	0.44 × 0.31 × 0.24 mm
V = 2343.5 (4) Å³

Data collection top

Bruker SMART diffractometer	2719 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1962 reflections with I > 2σ(I)
T_min = 0.679, T_max = 0.803	R_int = 0.053
9708 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	H-atom parameters constrained
wR(F²) = 0.145	Δρ_max = 0.90 e Å⁻³
S = 1.08	Δρ_min = −0.41 e Å⁻³
2719 reflections	Absolute structure: Flack (1983), 1284 Friedel pairs
233 parameters	Absolute structure parameter: 0.04 (7)
55 restraints

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Sb1	1.0000	0.5000	0.10910 (15)	0.0641 (3)
F1	0.2113 (17)	0.1590 (11)	0.182 (2)	0.26 (2)	0.62 (3)
F2	0.241 (2)	0.294 (3)	0.2756 (10)	0.25 (2)	0.62 (3)
F3	0.2382 (14)	0.3226 (13)	0.1459 (10)	0.127 (8)	0.62 (3)
F1'	0.242 (3)	0.3496 (19)	0.228 (3)	0.23 (3)	0.38 (3)
F2'	0.209 (3)	0.215 (3)	0.1356 (11)	0.24 (3)	0.38 (3)
F3'	0.2233 (18)	0.1848 (16)	0.2607 (10)	0.096 (9)	0.38 (3)
O1	0.8139 (5)	0.4442 (5)	0.1045 (4)	0.0653 (16)
O2	0.8310 (6)	0.4481 (7)	0.2417 (4)	0.092 (2)
C1	0.7700 (8)	0.4310 (9)	0.1798 (6)	0.070 (3)
C2	0.6436 (8)	0.3930 (8)	0.1835 (6)	0.065 (2)
C3	0.5766 (9)	0.3813 (9)	0.1133 (7)	0.074 (3)
H3	0.6129	0.4011	0.0612	0.089*
C4	0.4582 (10)	0.3412 (10)	0.1200 (9)	0.092 (3)
H4	0.4137	0.3321	0.0723	0.110*
C5	0.4034 (10)	0.3138 (10)	0.1967 (9)	0.088 (3)
C6	0.4660 (10)	0.3246 (12)	0.2652 (8)	0.102 (4)
H6	0.4287	0.3057	0.3170	0.122*
C7	0.5843 (9)	0.3631 (12)	0.2599 (7)	0.098 (4)
H7	0.6266	0.3697	0.3082	0.117*
C8	0.2710 (11)	0.2707 (11)	0.2030 (8)	0.136 (7)
C9	1.0390 (9)	0.6667 (9)	0.1536 (6)	0.077 (3)
C10	1.0489 (11)	0.6986 (11)	0.2367 (6)	0.108 (4)
H10	1.0400	0.6439	0.2776	0.130*
C11	1.0718 (14)	0.8097 (13)	0.2596 (12)	0.157 (9)
H11	1.0778	0.8304	0.3156	0.189*
C12	1.0856 (16)	0.8904 (16)	0.1985 (12)	0.159 (9)
H12	1.1002	0.9657	0.2134	0.191*
C13	1.0781 (13)	0.8602 (11)	0.1153 (12)	0.146 (6)
H13	1.0888	0.9154	0.0744	0.176*
C14	1.0547 (11)	0.7483 (10)	0.0928 (8)	0.102 (4)
H14	1.0496	0.7278	0.0368	0.122*
C15	1.0000	0.5000	−0.0220 (6)	0.053 (3)
C16	1.0867 (9)	0.4904 (10)	−0.0660 (7)	0.090 (3)
H16	1.1470	0.4863	−0.0377	0.108*
C17	1.0832 (12)	0.4871 (14)	−0.1517 (7)	0.120 (5)
H17	1.1387	0.4757	−0.1807	0.144*
C18	1.0000	0.5000	−0.1948 (9)	0.116 (7)
H18	1.0000	0.5000	−0.2528	0.139*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sb1	0.0578 (5)	0.0795 (7)	0.0433 (3)	0.0256 (5)	0.000	0.000
F1	0.076 (11)	0.068 (10)	0.60 (7)	0.003 (8)	−0.06 (3)	0.05 (2)
F2	0.15 (2)	0.44 (6)	0.22 (2)	0.19 (3)	0.083 (19)	0.13 (3)
F3	0.065 (9)	0.100 (11)	0.22 (2)	0.043 (8)	−0.020 (10)	−0.016 (11)
F1'	0.11 (3)	0.083 (18)	0.50 (9)	0.047 (16)	0.09 (5)	0.03 (4)
F2'	0.074 (17)	0.37 (7)	0.20 (4)	0.06 (3)	−0.015 (17)	0.15 (4)
F3'	0.053 (11)	0.092 (16)	0.109 (16)	0.011 (10)	0.013 (10)	−0.009 (11)
O1	0.053 (3)	0.088 (4)	0.048 (3)	0.030 (3)	0.003 (3)	−0.003 (3)
O2	0.051 (4)	0.144 (7)	0.054 (4)	0.029 (4)	−0.005 (3)	0.000 (4)
C1	0.053 (6)	0.086 (7)	0.057 (5)	0.024 (5)	−0.002 (4)	−0.005 (4)
C2	0.058 (6)	0.060 (6)	0.062 (5)	0.019 (5)	0.000 (4)	−0.004 (4)
C3	0.068 (6)	0.084 (7)	0.062 (5)	0.033 (5)	−0.003 (6)	0.003 (6)
C4	0.075 (7)	0.093 (8)	0.105 (9)	0.040 (6)	−0.027 (7)	0.010 (7)
C5	0.060 (7)	0.071 (7)	0.121 (10)	0.024 (6)	0.014 (7)	0.024 (7)
C6	0.068 (7)	0.141 (11)	0.077 (8)	0.037 (7)	0.017 (6)	0.020 (8)
C7	0.069 (7)	0.154 (12)	0.054 (6)	0.044 (7)	0.004 (5)	0.000 (6)
C8	0.068 (10)	0.116 (15)	0.21 (2)	0.032 (10)	0.009 (12)	0.062 (14)
C9	0.055 (6)	0.082 (7)	0.085 (7)	0.027 (6)	0.013 (5)	−0.002 (6)
C10	0.086 (8)	0.109 (10)	0.100 (9)	0.026 (7)	0.016 (7)	−0.040 (7)
C11	0.097 (11)	0.147 (16)	0.17 (2)	0.019 (11)	0.027 (12)	−0.087 (15)
C12	0.108 (13)	0.096 (13)	0.23 (3)	0.016 (11)	0.036 (15)	−0.056 (14)
C13	0.107 (11)	0.098 (11)	0.21 (2)	0.030 (9)	0.033 (14)	0.001 (13)
C14	0.097 (9)	0.074 (8)	0.118 (11)	0.031 (7)	0.015 (8)	−0.007 (8)
C15	0.048 (7)	0.067 (8)	0.032 (5)	0.019 (6)	0.000	0.000
C16	0.079 (7)	0.141 (9)	0.056 (6)	0.060 (7)	−0.012 (5)	−0.019 (7)
C17	0.115 (10)	0.216 (16)	0.061 (7)	0.106 (11)	−0.005 (6)	−0.034 (8)
C18	0.097 (13)	0.22 (2)	0.037 (7)	0.083 (14)	0.000	0.000

Geometric parameters (Å, º) top

Sb1—C9	2.087 (10)	C6—C7	1.359 (15)
Sb1—C9ⁱ	2.087 (10)	C6—H6	0.9300
Sb1—C15	2.103 (10)	C7—H7	0.9300
Sb1—O1	2.150 (5)	C9—C14	1.377 (9)
Sb1—O1ⁱ	2.150 (5)	C9—C10	1.383 (9)
F1—C8	1.302 (9)	C10—C11	1.370 (9)
F2—C8	1.310 (10)	C10—H10	0.9300
F3—C8	1.328 (9)	C11—C12	1.380 (10)
F1'—C8	1.317 (10)	C11—H11	0.9300
F2'—C8	1.323 (10)	C12—C13	1.380 (10)
F3'—C8	1.341 (10)	C12—H12	0.9300
O1—C1	1.311 (11)	C13—C14	1.376 (9)
O2—C1	1.219 (10)	C13—H13	0.9300
C1—C2	1.459 (13)	C14—H14	0.9300
C2—C3	1.386 (14)	C15—C16ⁱ	1.386 (12)
C2—C7	1.395 (13)	C15—C16	1.386 (12)
C3—C4	1.359 (14)	C16—C17	1.375 (16)
C3—H3	0.9300	C16—H16	0.9300
C4—C5	1.375 (18)	C17—C18	1.362 (16)
C4—H4	0.9300	C17—H17	0.9300
C5—C6	1.333 (17)	C18—C17ⁱ	1.362 (16)
C5—C8	1.522 (16)	C18—H18	0.9300

C9—Sb1—C9ⁱ	140.0 (5)	F2—C8—F2'	133 (2)
C9—Sb1—C15	110.0 (3)	F1'—C8—F2'	110.0 (16)
C9ⁱ—Sb1—C15	110.0 (3)	F3'—C8—F2'	102.1 (13)
C9—Sb1—O1	90.6 (3)	F1—C8—F2'	47.2 (14)
C9ⁱ—Sb1—O1	90.8 (3)	F3—C8—F2'	56.8 (15)
C15—Sb1—O1	88.02 (16)	F2—C8—C5	112.6 (15)
C9—Sb1—O1ⁱ	90.8 (3)	F1'—C8—C5	116.3 (18)
C9ⁱ—Sb1—O1ⁱ	90.6 (3)	F3'—C8—C5	108.6 (13)
C15—Sb1—O1ⁱ	88.02 (16)	F1—C8—C5	109.0 (13)
O1—Sb1—O1ⁱ	176.0 (3)	F3—C8—C5	111.0 (11)
C1—O1—Sb1	110.8 (6)	F2'—C8—C5	114.2 (18)
O2—C1—O1	121.7 (9)	C14—C9—C10	119.7 (11)
O2—C1—C2	123.2 (8)	C14—C9—Sb1	115.0 (7)
O1—C1—C2	115.1 (8)	C10—C9—Sb1	125.3 (9)
C3—C2—C7	117.0 (9)	C11—C10—C9	120.8 (13)
C3—C2—C1	122.8 (9)	C11—C10—H10	119.6
C7—C2—C1	120.1 (9)	C9—C10—H10	119.6
C4—C3—C2	120.4 (11)	C10—C11—C12	119.1 (17)
C4—C3—H3	119.8	C10—C11—H11	120.4
C2—C3—H3	119.8	C12—C11—H11	120.4
C3—C4—C5	120.7 (11)	C13—C12—C11	120.5 (18)
C3—C4—H4	119.7	C13—C12—H12	119.8
C5—C4—H4	119.7	C11—C12—H12	119.8
C6—C5—C4	120.1 (11)	C14—C13—C12	120.0 (16)
C6—C5—C8	120.1 (12)	C14—C13—H13	120.0
C4—C5—C8	119.8 (12)	C12—C13—H13	120.0
C5—C6—C7	120.2 (11)	C9—C14—C13	119.8 (13)
C5—C6—H6	119.9	C9—C14—H14	120.1
C7—C6—H6	119.9	C13—C14—H14	120.1
C6—C7—C2	121.6 (11)	C16ⁱ—C15—C16	118.8 (12)
C6—C7—H7	119.2	C16ⁱ—C15—Sb1	120.6 (6)
C2—C7—H7	119.2	C16—C15—Sb1	120.6 (6)
F2—C8—F1'	46.9 (16)	C17—C16—C15	119.7 (10)
F2—C8—F3'	60.8 (14)	C17—C16—H16	120.1
F1'—C8—F3'	104.1 (14)	C15—C16—H16	120.1
F2—C8—F1	114.2 (14)	C18—C17—C16	121.3 (11)
F1'—C8—F1	135 (2)	C18—C17—H17	119.3
F3'—C8—F1	58.8 (14)	C16—C17—H17	119.3
F2—C8—F3	106.8 (13)	C17—C18—C17ⁱ	118.9 (15)
F1'—C8—F3	61.8 (19)	C17—C18—H18	120.5
F3'—C8—F3	140.1 (15)	C17ⁱ—C18—H18	120.5
F1—C8—F3	102.8 (12)

Symmetry code: (i) −x+2, −y+1, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O2ⁱⁱ	0.93	2.55	3.304 (13)	138

Symmetry code: (ii) −y+1, x−y, z−1/3.

Experimental details

Crystal data
Chemical formula	[Sb(C₆H₅)₃(C₈H₄F₃O₂)₂]
M_r	731.27
Crystal system, space group	Hexagonal, P6₂
Temperature (K)	298
a, c (Å)	12.9879 (10), 16.042 (2)
V (Å³)	2343.5 (4)
Z	3
Radiation type	Mo Kα
µ (mm⁻¹)	0.96
Crystal size (mm)	0.44 × 0.31 × 0.24

Data collection
Diffractometer	Bruker SMART diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.679, 0.803
No. of measured, independent and observed [I > 2σ(I)] reflections	9708, 2719, 1962
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.145, 1.08
No. of reflections	2719
No. of parameters	233
No. of restraints	55
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.90, −0.41
Absolute structure	Flack (1983), 1284 Friedel pairs
Absolute structure parameter	0.04 (7)

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Sb1—C9	2.087 (10)	Sb1—O1	2.150 (5)
Sb1—C9ⁱ	2.087 (10)	Sb1—O1ⁱ	2.150 (5)
Sb1—C15	2.103 (10)

C9—Sb1—C9ⁱ	140.0 (5)	C9ⁱ—Sb1—C15	110.0 (3)
C9—Sb1—C15	110.0 (3)	O1—Sb1—O1ⁱ	176.0 (3)