supplementary materials


lh5612 scheme

Acta Cryst. (2013). E69, m333    [ doi:10.1107/S1600536813013317 ]

Bis(but-2-enoato-[kappa]O)triphenylbismuth(V)

P. V. Andreev, N. V. Somov, O. S. Kalistratova, A. V. Gushchin and E. V. Chuprunov

Abstract top

In the title molecule, [Bi(C6H5)3(C4H5O2)2], the BiV atom is in a distorted trigonal-bipyramidal environment with carboxylate O atoms in axial positions and phenyl C atoms in the equatorial plane. The Bi-O bond lengths are 2.283 (3) and 2.309 (2) Å, but as a result of additional long Bi...O interactions [2.787 (3) and 2.734 (3) Å], one of the C-Bi-C angles is 148.62 (13)°. In the crystal, weak C-H...O hydrogen bonds connect pairs of molecules into inversion dimers. These dimers are further connected by weak C-H...[pi] interactions into chains along [100] .

Comment top

Bis(but-2-enoate) triphenylbismuth C26H25O4Bi belongs to the family of triphenylbismuth diacylates. Compounds of triphenylbismuth and triphenylantimony diacylates contain two double bonds CC in the molecule, due to which they can be used for polymerization filling of polystyrene and polymethylmethacrylate. The title compound is a very promising monomer for developing metal-containing organic scintillators which have recently attracted much attention in high-energy physics. It was found that the participation of both acrylate groups in polymerization leads to cross-linking, considerably decreasing the thermooxidative destruction of the resulting polymer (Dodonov et al., 2004). Organic glasses based on triphenylantimony diacrylate and methylmethacrylate having increased fungal resistance are now available (Dodonov et al., 2004). The thermodynamic properties of triphenylantimony diacylates have been studied (Letyanina et al., 2012; Markin et al., 2011). The crystal structure and chemistry of a similar orgaonmetallic compound of antimony has been reported by Gushchin et al. (2013).

In the molecule of title compound the O—Bi—O angle is 172.64 (9)° and the Cphenyl—Bi—Cphenyl angles are 148.62 (13)°, 106.20 (13)°, 150.10 (13)°. Such a deviation for the latter from the ideal 120° is typical for triphenylantomony diacylates because of additional long Bi···O interactions. A similar geometries were observed in triphenylantomony diacylates (Gushchin et al., 2011; Gushchin et al., 2013; Andreev et al., 2013). The Bi–O2A and Bi–O2B distances are 2.787 (3) Å and 2.734 (3) Å, respectively and are significantly shorter than the sum of the van der Waals radii of these atoms (3.85 Å) (Batsanov, 2001). A similar interaction was observed in triphenylantimony dimetacrylate (Gushchin et al., 2011), bis[(E)-3-(4-methoxyphenyl)prop-2-enoato]triphenylantimony(V) (Andreev et al., 2013), triphenylantimony dicrotonate (Gushchin et al., 2013) and triphenylantimony-bis(cinnamate) (Belsky, 1996). In the crystal, weak C—H···O hydrogen bonds connect pairs of molecules into inversion dimers. These dimers are further connected by weak C—H···π interactions into chains along [100] (see Fig.2).

Related literature top

For the isotypic (C6H5)3Sb(C4H5O2)2 structure, see: Gushchin et al. (2013). For closely related structures, see: Andreev et al. (2013); Belsky (1996). For the chemistry of triphenyantimony diacylates, see: Gushchin et al. (2011), for their thermodynamic properties, see: Letyanina et al. (2012); Markin et al. (2011) and for their applications, see: Dodonov & Gushchin (2004). For van der Waals radii, see: Batsanov (2001).

Experimental top

The synthesis was carried out on the oxidation addition reaction of triphenylbismuth, crotonic acid and tert-butyl hydroperoxide. To a solution of 0.56 ml of 92.6% aqueous tert-butyl hydroperoxide and 0.86 g of crotonic acid in 20 ml of diethyl ether was added a solution of 2.2 g of triphenylbismuth. The mixture was kept for 24 h at room temperature. The yellow crystals formed were filtered off and dried to obtain 1.91 g (73%) of triphenylbismuth bis(but-2-enoate). The product was recrystallized twice from chloroform-hexane mixture (1:4), m.p. 426 K. A crystal for X-ray diffraction analysis was obtained from benzene solution.

Refinement top

H atoms were positioned geometrically (C—H=0.95–1.00 Å) and refined using a riding model with the Uiso(H)=1.2Ueq(C) (1.5Ueq(C) for methyl groups). In the refinment the anisotropic displacment parameters of atoms pairs C9/C10 and C16/C17 were restrained using the DELU instruction in SHELXL (Sheldrick, 2008).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis RED (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. H atoms are presented as small spheres of arbitrary radius.
[Figure 2] Fig. 2. Part of the crystal structure with weak C—H···O and C—H···π interactions shown as dashed lines connecting moleclues along [100].
Bis(but-2-enoato-κO)triphenylbismuth(V) top
Crystal data top
[Bi(C6H5)3(C4H5O2)2]Z = 2
Mr = 610.44F(000) = 592
Triclinic, P1Dx = 1.661 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 10.4710 (3) ÅCell parameters from 9953 reflections
b = 10.4957 (3) Åθ = 3.4–32.8°
c = 11.9774 (3) ŵ = 7.25 mm1
α = 84.941 (2)°T = 293 K
β = 83.633 (2)°Sphere, colourless
γ = 69.084 (3)°0.09 mm (radius)
V = 1220.32 (6) Å3
Data collection top
Agilent Xcalibur (Sapphire3, Gemini)
diffractometer
4946 independent reflections
Graphite monochromator4620 reflections with I > 2σ(I)
Detector resolution: 16.0302 pixels mm-1Rint = 0.024
ω scansθmax = 26.4°, θmin = 3.4°
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2011)
h = 1313
Tmin = 0.810, Tmax = 1k = 1313
17262 measured reflectionsl = 1414
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.020Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.050H-atom parameters constrained
S = 1.11 w = 1/[σ2(Fo2) + (0.0212P)2 + 0.9058P]
where P = (Fo2 + 2Fc2)/3
4946 reflections(Δ/σ)max = 0.001
280 parametersΔρmax = 0.65 e Å3
2 restraintsΔρmin = 0.84 e Å3
Crystal data top
[Bi(C6H5)3(C4H5O2)2]γ = 69.084 (3)°
Mr = 610.44V = 1220.32 (6) Å3
Triclinic, P1Z = 2
a = 10.4710 (3) ÅMo Kα radiation
b = 10.4957 (3) ŵ = 7.25 mm1
c = 11.9774 (3) ÅT = 293 K
α = 84.941 (2)°0.09 mm (radius)
β = 83.633 (2)°
Data collection top
Agilent Xcalibur (Sapphire3, Gemini)
diffractometer
4946 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2011)
4620 reflections with I > 2σ(I)
Tmin = 0.810, Tmax = 1Rint = 0.024
17262 measured reflectionsθmax = 26.4°
Refinement top
R[F2 > 2σ(F2)] = 0.020H-atom parameters constrained
wR(F2) = 0.050Δρmax = 0.65 e Å3
S = 1.11Δρmin = 0.84 e Å3
4946 reflectionsAbsolute structure: ?
280 parametersFlack parameter: ?
2 restraintsRogers parameter: ?
Special details top

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 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
xyzUiso*/Ueq
Bi0.714269 (12)0.636573 (11)0.737494 (10)0.03886 (5)
O1A0.4935 (3)0.6470 (3)0.7972 (2)0.0561 (7)
O1B0.9413 (3)0.5981 (3)0.6880 (2)0.0595 (7)
O2A0.4728 (3)0.8624 (3)0.7607 (2)0.0574 (7)
O2B0.8411 (3)0.8212 (3)0.6718 (2)0.0552 (6)
C10.6556 (3)0.6872 (3)0.5635 (3)0.0416 (7)
C20.6338 (4)0.8145 (4)0.5113 (3)0.0564 (9)
H20.64650.88330.54760.068*
C1A0.4227 (4)0.7768 (4)0.7950 (3)0.0479 (8)
C1B0.9455 (4)0.7179 (4)0.6631 (3)0.0485 (8)
C30.5922 (5)0.8372 (5)0.4026 (4)0.0679 (12)
H30.57770.9220.36520.082*
C2A0.2745 (4)0.8208 (5)0.8375 (3)0.0598 (10)
H2A0.22180.91280.82780.072*
C2B1.0828 (4)0.7244 (5)0.6218 (4)0.0641 (11)
H2B1.15850.6440.62470.077*
C40.5722 (4)0.7356 (5)0.3504 (3)0.0663 (12)
H40.54310.75250.27820.08*
C3A0.2156 (5)0.7417 (6)0.8858 (4)0.0697 (12)
H3A0.26830.64940.89260.084*
C3B1.1031 (4)0.8329 (5)0.5829 (3)0.0617 (11)
H3B1.02620.91240.58130.074*
C50.5947 (5)0.6103 (5)0.4032 (4)0.0650 (11)
H50.58150.54210.36640.078*
C4A0.0675 (5)0.7837 (6)0.9334 (4)0.0850 (16)
H4A10.06340.7531.01110.127*
H4A20.01920.74350.89220.127*
H4A30.02580.88140.9270.127*
C4B1.2384 (5)0.8463 (6)0.5391 (4)0.0845 (16)
H4B31.22410.93960.51430.127*
H4B21.27780.78860.4770.127*
H4B11.29950.81940.59790.127*
C60.6372 (4)0.5830 (4)0.5115 (3)0.0553 (9)
H60.65290.49750.54780.066*
C70.7323 (3)0.7074 (4)0.9006 (3)0.0424 (7)
C80.7989 (5)0.6056 (5)0.9773 (3)0.0664 (11)
H80.83240.51410.96020.08*
C90.8137 (6)0.6466 (7)1.0826 (4)0.0850 (16)
H90.85880.58151.13640.102*
C100.7615 (6)0.7831 (7)1.1063 (4)0.0817 (16)
H100.77060.80911.17640.098*
C110.6975 (5)0.8790 (6)1.0283 (5)0.0787 (14)
H110.66390.97051.04520.094*
C120.6811 (4)0.8437 (4)0.9245 (4)0.0620 (11)
H120.63650.91020.87140.074*
C130.7740 (5)0.4106 (4)0.7598 (3)0.0580 (11)
C140.8981 (6)0.3282 (4)0.7091 (4)0.0794 (15)
H140.95790.3670.66950.095*
C150.9322 (8)0.1884 (5)0.7176 (6)0.105 (2)
H151.01510.13180.6840.126*
C160.8411 (10)0.1335 (6)0.7771 (6)0.121 (3)
H160.86410.03910.78280.145*
C170.7176 (8)0.2141 (6)0.8281 (6)0.105 (2)
H170.65760.17510.86710.126*
C180.6848 (6)0.3539 (5)0.8202 (4)0.0782 (15)
H180.60270.41010.85530.094*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Bi0.04616 (8)0.02998 (7)0.04346 (8)0.01683 (5)0.00534 (5)0.00091 (5)
O1A0.0565 (16)0.0633 (17)0.0606 (16)0.0385 (14)0.0047 (12)0.0079 (13)
O1B0.0508 (15)0.0522 (16)0.0720 (18)0.0142 (12)0.0046 (13)0.0134 (14)
O2A0.0568 (16)0.0524 (16)0.0637 (17)0.0219 (13)0.0041 (13)0.0029 (13)
O2B0.0543 (16)0.0501 (15)0.0643 (17)0.0235 (13)0.0009 (12)0.0026 (12)
C10.0444 (18)0.0370 (17)0.0413 (18)0.0136 (14)0.0008 (14)0.0014 (14)
C20.064 (2)0.046 (2)0.060 (2)0.0233 (18)0.0027 (19)0.0064 (18)
C1A0.0438 (19)0.059 (2)0.0399 (18)0.0153 (17)0.0087 (15)0.0013 (16)
C1B0.0429 (19)0.056 (2)0.0445 (19)0.0155 (17)0.0027 (15)0.0108 (16)
C30.072 (3)0.067 (3)0.057 (3)0.021 (2)0.004 (2)0.024 (2)
C2A0.057 (2)0.067 (3)0.056 (2)0.021 (2)0.0122 (18)0.003 (2)
C2B0.045 (2)0.067 (3)0.078 (3)0.0170 (19)0.005 (2)0.012 (2)
C40.057 (2)0.096 (4)0.043 (2)0.025 (2)0.0034 (18)0.007 (2)
C3A0.064 (3)0.092 (3)0.062 (3)0.039 (3)0.013 (2)0.010 (2)
C3B0.057 (2)0.087 (3)0.049 (2)0.036 (2)0.0039 (18)0.000 (2)
C50.068 (3)0.078 (3)0.054 (2)0.029 (2)0.008 (2)0.011 (2)
C4A0.052 (3)0.129 (5)0.078 (3)0.042 (3)0.000 (2)0.008 (3)
C4B0.066 (3)0.133 (5)0.070 (3)0.059 (3)0.000 (2)0.005 (3)
C60.069 (3)0.048 (2)0.053 (2)0.0231 (19)0.0108 (19)0.0015 (17)
C70.0435 (18)0.0462 (19)0.0433 (18)0.0229 (15)0.0007 (14)0.0077 (15)
C80.094 (3)0.063 (3)0.051 (2)0.040 (2)0.007 (2)0.003 (2)
C90.116 (4)0.119 (4)0.043 (2)0.070 (4)0.014 (2)0.011 (3)
C100.097 (4)0.124 (4)0.050 (3)0.071 (4)0.021 (3)0.036 (3)
C110.068 (3)0.089 (4)0.086 (4)0.030 (3)0.005 (3)0.049 (3)
C120.056 (2)0.056 (2)0.078 (3)0.0197 (19)0.006 (2)0.025 (2)
C130.092 (3)0.0321 (18)0.056 (2)0.0221 (19)0.034 (2)0.0034 (16)
C140.111 (4)0.039 (2)0.081 (3)0.010 (2)0.031 (3)0.011 (2)
C150.156 (6)0.042 (3)0.106 (4)0.007 (3)0.048 (4)0.014 (3)
C160.206 (8)0.043 (3)0.126 (5)0.036 (4)0.104 (5)0.017 (3)
C170.172 (6)0.055 (3)0.114 (5)0.061 (4)0.079 (4)0.034 (3)
C180.117 (4)0.049 (2)0.085 (3)0.044 (3)0.043 (3)0.022 (2)
Geometric parameters (Å, º) top
Bi—C72.201 (3)C5—H50.93
Bi—C12.205 (3)C4A—H4A10.96
Bi—C132.226 (4)C4A—H4A20.96
Bi—O1B2.283 (3)C4A—H4A30.96
Bi—O1A2.309 (2)C4B—H4B30.96
Bi—O2A2.787 (3)C4B—H4B20.96
Bi—O2B2.734 (3)C4B—H4B10.96
O1A—C1A1.297 (5)C6—H60.93
O1B—C1B1.281 (5)C7—C121.380 (5)
O2A—C1A1.215 (4)C7—C81.382 (6)
O2B—C1B1.237 (4)C8—C91.409 (6)
C1—C21.376 (5)C8—H80.93
C1—C61.385 (5)C9—C101.381 (8)
C2—C31.392 (6)C9—H90.93
C2—H20.93C10—C111.352 (8)
C1A—C2A1.495 (5)C10—H100.93
C1B—C2B1.491 (5)C11—C121.373 (6)
C3—C41.369 (7)C11—H110.93
C3—H30.93C12—H120.93
C2A—C3A1.268 (6)C13—C141.386 (7)
C2A—H2A0.93C13—C181.386 (6)
C2B—C3B1.271 (6)C14—C151.377 (7)
C2B—H2B0.93C14—H140.93
C4—C51.360 (6)C15—C161.385 (10)
C4—H40.93C15—H150.93
C3A—C4A1.511 (6)C16—C171.377 (11)
C3A—H3A0.93C16—H160.93
C3B—C4B1.506 (6)C17—C181.380 (7)
C3B—H3B0.93C17—H170.93
C5—C61.391 (6)C18—H180.93
C7—Bi—C1148.62 (13)C3A—C4A—H4A1109.5
C7—Bi—C13106.20 (13)C3A—C4A—H4A2109.5
C1—Bi—C13105.10 (13)H4A1—C4A—H4A2109.5
C7—Bi—O1B90.15 (11)C3A—C4A—H4A3109.5
C1—Bi—O1B94.14 (11)H4A1—C4A—H4A3109.5
C13—Bi—O1B86.30 (14)H4A2—C4A—H4A3109.5
C7—Bi—O1A89.80 (11)C3B—C4B—H4B3109.5
C1—Bi—O1A89.73 (11)C3B—C4B—H4B2109.5
C13—Bi—O1A86.65 (14)H4B3—C4B—H4B2109.5
O1B—Bi—O1A172.64 (9)C3B—C4B—H4B1109.5
C7—Bi—O2B78.59 (10)H4B3—C4B—H4B1109.5
C1—Bi—O2B80.12 (11)H4B2—C4B—H4B1109.5
C13—Bi—O2B137.31 (14)C1—C6—C5117.9 (4)
O1B—Bi—O2B51.02 (9)C1—C6—H6121
O1A—Bi—O2B136.05 (9)C5—C6—H6121
C1A—O1A—Bi104.0 (2)C12—C7—C8122.4 (4)
C1B—O1B—Bi103.8 (2)C12—C7—Bi122.4 (3)
C1B—O2B—Bi83.6 (2)C8—C7—Bi115.1 (3)
C2—C1—C6122.2 (3)C7—C8—C9117.0 (5)
C2—C1—Bi122.7 (3)C7—C8—H8121.5
C6—C1—Bi115.1 (2)C9—C8—H8121.5
C1—C2—C3118.0 (4)C10—C9—C8120.4 (5)
C1—C2—H2121C10—C9—H9119.8
C3—C2—H2121C8—C9—H9119.8
O2A—C1A—O1A122.4 (3)C11—C10—C9120.4 (4)
O2A—C1A—C2A119.5 (4)C11—C10—H10119.8
O1A—C1A—C2A118.1 (3)C9—C10—H10119.8
O2B—C1B—O1B121.6 (3)C10—C11—C12121.2 (5)
O2B—C1B—C2B122.4 (4)C10—C11—H11119.4
O1B—C1B—C2B115.9 (3)C12—C11—H11119.4
C4—C3—C2120.5 (4)C11—C12—C7118.6 (5)
C4—C3—H3119.7C11—C12—H12120.7
C2—C3—H3119.7C7—C12—H12120.7
C3A—C2A—C1A124.7 (4)C14—C13—C18120.7 (4)
C3A—C2A—H2A117.6C14—C13—Bi119.4 (3)
C1A—C2A—H2A117.6C18—C13—Bi119.9 (3)
C3B—C2B—C1B124.2 (4)C15—C14—C13119.6 (6)
C3B—C2B—H2B117.9C15—C14—H14120.2
C1B—C2B—H2B117.9C13—C14—H14120.2
C5—C4—C3120.6 (4)C14—C15—C16119.0 (7)
C5—C4—H4119.7C14—C15—H15120.5
C3—C4—H4119.7C16—C15—H15120.5
C2A—C3A—C4A126.0 (5)C17—C16—C15122.1 (5)
C2A—C3A—H3A117C17—C16—H16118.9
C4A—C3A—H3A117C15—C16—H16118.9
C2B—C3B—C4B126.8 (5)C16—C17—C18118.6 (7)
C2B—C3B—H3B116.6C16—C17—H17120.7
C4B—C3B—H3B116.6C18—C17—H17120.7
C4—C5—C6120.7 (4)C17—C18—C13120.0 (6)
C4—C5—H5119.6C17—C18—H18120
C6—C5—H5119.6C13—C18—H18120
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C3—H3···O2Ai0.932.533.450 (6)171
C4B—H4B1···C1Aii0.962.743.683 (6)167
C4B—H4B1···C2Aii0.962.853.613 (7)137
Symmetry codes: (i) x+1, y+2, z+1; (ii) x+1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C3—H3···O2Ai0.932.533.450 (6)171
C4B—H4B1···C1Aii0.962.743.683 (6)167.0
C4B—H4B1···C2Aii0.962.853.613 (7)136.7
Symmetry codes: (i) x+1, y+2, z+1; (ii) x+1, y, z.
references
References top

Agilent (2011). CrysAlis PRO and CrysAlis RED. Agilent Technologies, Yarnton, England.

Andreev, P. V., Somov, N. V., Kalistratova, O. S., Gushchin, A. V. & Chuprunov, E. V. (2013). Acta Cryst. E69, m167.

Batsanov, S. S. (2001). Inorg. Mater. 37, 871–885.

Belsky, V. K. (1996). Private communication (refcode NAGXOI). CCDC, Cambridge, England.

Dodonov, V. A. & Gushchin, A. V. (2004). Vestn. NNovg. Univ. 82, 86–94.

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