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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 71| Part 5| May 2015| Pages o339-o340
https://doi.org/10.1107/S205698901500763X

Crystal structure of bis­­(3,3-di­methyl-2-oxobut­yl)di­phenyl­phospho­nium bromide chloro­form monosolvate

Alyssa A. Kulesza,a Richard J. Staplesb and Shannon M. Birosa*

aDepartment of Chemistry, Grand Valley State University, 1 Campus Dr., Allendale, MI 49401, USA, and bCenter for Crystallographic Research, Department of Chemistry, Michigan State University, 578 S. Shaw Lane, East Lansing, MI 48824, USA
*Correspondence e-mail: biross@gvsu.edu

Edited by S. Parkin, University of Kentucky, USA (Received 8 April 2015; accepted 17 April 2015; online 25 April 2015)

In the title salt solvate, C24H32O2P+·Br−·CHCl3, the P atom has a distorted tetra­hedral geometry, and the planes of the phenyl rings form a dihedral angle of 71.86 (14)° with one another. The bromide anion is disordered and was modelled over three positions (occupancy ratio 0.50:0.35:0.15). The crystal also contains one disordered chloro­form solvent mol­ecule that was modeled over three positions (occupancy ratio 0.50:0.35:0.15). Weak inter­molecular inter­actions (C—H⋯Br and C—H⋯O) exist between the complex cation and the bromide anion fragments. The resulting supramolecular structure is an oval-shaped arrangement of phosphonium salt molecules that surround the disordered bromide anion.

CCDC reference: 1060276

Similar articles

1. Related literature

The title compound was synthesized using an Arbuzov reaction, as described by Schuster et al. (2009[Schuster, E. M., Nisnevich, G., Botoshansky, M. & Gandelman, M. (2009). Organometallics, 28, 5025-5031.]). The Cambridge Structural Database (CSD, Version 5.36, November 2014; Groom & Allen, 2014[Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662-671.]) contains four structures of acyclic tetra­valent phospho­nium salts where the P atom is bonded to two phenyl rings and two β-carbonyl groups. In each structure, the phospho­nium salt is coordinated to a silver(I) (Vicente et al., 1989[Vicente, J., Chicote, M. T., Saura-Llamas, I. & Jones, P. G. (1989). Organometallics, 8, 767-770.]) or palladium(II) (Vicente et al., 1990[Vicente, J., Chicote, M.-T., Saura-Llamas, I., Lopez-Munoz, M.-J. & Jones, P. G. (1990). J. Chem. Soc. Dalton Trans. pp. 3683-3689.]) metal center via the carbon α to the P atom.

[Scheme 1]

2. Experimental

2.1. Crystal data

  • C24H32O2P+·Br−·CHCl3

  • Mr = 582.74

  • Monoclinic, C 2/c

  • a = 23.6380 (18) Å

  • b = 13.6273 (10) Å

  • c = 18.1817 (13) Å

  • β = 108.702 (1)°

  • V = 5547.5 (7) Å3

  • Z = 8

  • Mo Kα radiation

  • μ = 1.85 mm−1

  • T = 173 K

  • 0.34 × 0.15 × 0.09 mm

2.2. Data collection

  • Bruker SMART APEX CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2013[Bruker (2013). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.667, Tmax = 0.745

  • 25767 measured reflections

  • 5090 independent reflections

  • 3862 reflections with I > 2σ(I)

  • Rint = 0.040

2.3. Refinement

  • R[F2 > 2σ(F2)] = 0.064

  • wR(F2) = 0.206

  • S = 1.04

  • 5090 reflections

  • 373 parameters

  • 66 restraints

  • H-atom parameters constrained

  • Δρmax = 1.30 e Å−3

  • Δρmin = −1.10 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
C2—H2A⋯Br1Bi 0.99 2.85 3.840 (9) 174
C2—H2A⋯Br1Ci 0.99 2.75 3.712 (6) 164
C2—H2A⋯Br1Ai 0.99 2.95 3.941 (7) 177
C2—H2B⋯Br1B 0.99 2.95 3.767 (9) 141
C2—H2B⋯Br1C 0.99 2.97 3.717 (6) 133
C2—H2B⋯Br1A 0.99 2.97 3.831 (7) 145
C3—H3B⋯Br1B 0.99 2.78 3.740 (9) 163
C3—H3B⋯Br1C 0.99 2.70 3.644 (6) 159
C3—H3B⋯Br1A 0.99 2.86 3.816 (7) 164
C16—H16⋯O1ii 0.95 2.43 3.287 (5) 150
C1A—H1A⋯Br1A 1.00 2.59 3.527 (9) 156
Symmetry codes: (i) [-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]; (ii) [-x+{\script{3\over 2}}, -y+{\script{1\over 2}}, -z+1].

Data collection: APEX2 (Bruker, 2013[Bruker (2013). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2013[Bruker (2013). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]); molecular graphics: CrystalMaker (Palmer, 2007[Palmer, D. (2007). CrystalMaker. CrystalMaker Software, Bicester, Oxfordshire, England.]); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009[Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339-341.]; Bourhis et al., 2015[Bourhis, L. J., Dolomanov, O. V., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2015). Acta Cryst. A71, 59-75.]).

Supporting information

CCDC reference: 1060276

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S205698901500763X/pk2549sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698901500763X/pk2549Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S205698901500763X/pk2549Isup3.cml

checkCIF report


Structural commentary top

The molecular structure of I is shown in Figure 1, along with the atom numbering scheme. Compound I crystallized in the monoclinic space group C2/c, and the asymmetric unit contains the entire molecule along with one disordered bromide anion and one disordered molecule of chloro­form. Atom P1 has a distorted tetra­hedral geometry with C—P—C bond angles ranging from 106.37 (18) to 113.10 (18)°.

Supra­molecular features top

Weak inter­molecular C—H···Br and C—H···O inter­actions can be found throughout the crystal lattice (Table 1). CH···O hydrogen bonds (2.43 Å) exist between the carbonyl oxygen O1 and an aromatic hydrogen H16 (Figure 2). The bromide ion is engaged in a variety of weak inter­actions with nearby hydrogen atoms, with inter­atomic H···Br distances ranging from 2.70 to 2.97 Å. In the fragment that has the highest occupancy ratio (50%), a weak CH···Br inter­action is also present between the chloro­form molecule and bromide ion. Based on the amount of disorder present in this structure, it is clear these inter­molecular inter­actions are quite weak in nature.

Synthesis and crystallization top

The title compound was prepared via an Arbuzov reaction between bromo­pinacolone and an excess of iso-propoxydi­phenyl phosphane following the procedure of Schuster et al. (2009). 1H NMR (CDCl3, 300 MHz), δ 7.95-7.27 (m, 10H), 5.47 (d, JHP =6 Hz, 4H), 3.6 (d, J=2 Hz, 2H), 1.1 (s, 18 H). Crystals of I suitable for analysis by X-Ray diffraction were grown from vapor diffusion of ethyl acetate into a solution of CHCl3 containing Tb(NO3)3.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. The positions of all hydrogen atoms were calculated geometrically and refined to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C) for methine, methyl­ene and aryl groups, and Uiso(H) = 1.5Ueq(C) for methyl groups.

The disordered bromide ion was modelled over three positions with a 50:35:15 occupancy ratio. An EADP instruction was included in the refinement to constrain the thermal ellipoids of these fragments to the same size and shape. The disordered chloro­form molecule was also modelled in three parts with a 50:35:15 occupancy ratio. To restrain the CHCl3 geometry to accepted values, each C—Cl bond length was restrained with a DFIX instruction to 1.78 Å, and the Cl—Cl inter­atomic bond distances were restrained with a DANG instruction to 2.87 Å. Finally, each chlofororm fragment was treated with SIMU and DELU instructions to ensure uniform thermal ellipsoids.

Related literature top

The title compound was synthesized following using an Arbuzov reaction, as described by Schuster et al. (2009). The Cambridge Structural Database (CSD, Version 5.36, November 2014; Groom & Allen, 2014) contains four structures of acyclic tetravalent phosphonium salts where the P atom is bonded to two phenyl rings and two β-carbonyl groups. In each structure, the phosphonium salt is coordinated to a silver(I) (Vicente et al., 1989) or palladium(II) (Vicente et al., 1990) metal center via the carbon α to the P atom.

Structure description top

The molecular structure of I is shown in Figure 1, along with the atom numbering scheme. Compound I crystallized in the monoclinic space group C2/c, and the asymmetric unit contains the entire molecule along with one disordered bromide anion and one disordered molecule of chloro­form. Atom P1 has a distorted tetra­hedral geometry with C—P—C bond angles ranging from 106.37 (18) to 113.10 (18)°.

Weak inter­molecular C—H···Br and C—H···O inter­actions can be found throughout the crystal lattice (Table 1). CH···O hydrogen bonds (2.43 Å) exist between the carbonyl oxygen O1 and an aromatic hydrogen H16 (Figure 2). The bromide ion is engaged in a variety of weak inter­actions with nearby hydrogen atoms, with inter­atomic H···Br distances ranging from 2.70 to 2.97 Å. In the fragment that has the highest occupancy ratio (50%), a weak CH···Br inter­action is also present between the chloro­form molecule and bromide ion. Based on the amount of disorder present in this structure, it is clear these inter­molecular inter­actions are quite weak in nature.

The title compound was synthesized following using an Arbuzov reaction, as described by Schuster et al. (2009). The Cambridge Structural Database (CSD, Version 5.36, November 2014; Groom & Allen, 2014) contains four structures of acyclic tetravalent phosphonium salts where the P atom is bonded to two phenyl rings and two β-carbonyl groups. In each structure, the phosphonium salt is coordinated to a silver(I) (Vicente et al., 1989) or palladium(II) (Vicente et al., 1990) metal center via the carbon α to the P atom.

Synthesis and crystallization top

The title compound was prepared via an Arbuzov reaction between bromo­pinacolone and an excess of iso-propoxydi­phenyl phosphane following the procedure of Schuster et al. (2009). 1H NMR (CDCl3, 300 MHz), δ 7.95-7.27 (m, 10H), 5.47 (d, JHP =6 Hz, 4H), 3.6 (d, J=2 Hz, 2H), 1.1 (s, 18 H). Crystals of I suitable for analysis by X-Ray diffraction were grown from vapor diffusion of ethyl acetate into a solution of CHCl3 containing Tb(NO3)3.

Refinement details top

Crystal data, data collection and structure refinement details are summarized in Table 1. The positions of all hydrogen atoms were calculated geometrically and refined to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C) for methine, methyl­ene and aryl groups, and Uiso(H) = 1.5Ueq(C) for methyl groups.

The disordered bromide ion was modelled over three positions with a 50:35:15 occupancy ratio. An EADP instruction was included in the refinement to constrain the thermal ellipoids of these fragments to the same size and shape. The disordered chloro­form molecule was also modelled in three parts with a 50:35:15 occupancy ratio. To restrain the CHCl3 geometry to accepted values, each C—Cl bond length was restrained with a DFIX instruction to 1.78 Å, and the Cl—Cl inter­atomic bond distances were restrained with a DANG instruction to 2.87 Å. Finally, each chlofororm fragment was treated with SIMU and DELU instructions to ensure uniform thermal ellipsoids.

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: CrystalMaker (Palmer, 2007); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009; Bourhis et al., 2015).

Figures top
[Figure 1] Fig. 1. Structure of the asymmetric unit of I along with the atom numbering scheme. This drawing is done with 50% probability ellipsoids using standard CPK colors; only one position of the disordered bromide ion and chloroform molecule is shown, and all hydrogen atoms have been omitted for clarity.
[Figure 2] Fig. 2. Weak intermolecular interactions (denoted with dashed lines) found throughout the crystal lattice of the title compound (Table 1). Only the major position of the disordered fragments are shown. The aryl rings, tert-butyl groups, and all hydrogen atoms not involved in these interactions have been omitted for clarity. This drawing is done as a ball and stick with standard CPK colors. Symmetry codes: (i) 3/2 - x, -1/2 + y, 3/2 - z; (ii) 3/2 - x, 1/2 - y, 1 - z.
Bis(3,3-dimethyl-2-oxobutyl)diphenylphosphonium bromide chloroform monosolvate top
Crystal data top
C24H32O2P+·Br−·CHCl3F(000) = 2400
Mr = 582.74Dx = 1.395 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 23.6380 (18) ÅCell parameters from 9180 reflections
b = 13.6273 (10) Åθ = 2.3–25.3°
c = 18.1817 (13) ŵ = 1.85 mm−1
β = 108.702 (1)°T = 173 K
V = 5547.5 (7) Å3Plate, colourless
Z = 80.34 × 0.15 × 0.09 mm
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		5090 independent reflections
Radiation source: sealed tube3862 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.040
Detector resolution: 8 pixels mm-1θmax = 25.4°, θmin = 1.8°
ω and φ scansh = −28→28
Absorption correction: multi-scan
(SADABS; Bruker, 2013)		k = −15→16
Tmin = 0.667, Tmax = 0.745l = −19→21
25767 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.064H-atom parameters constrained
wR(F2) = 0.206 w = 1/[σ2(Fo2) + (0.1214P)2 + 22.4904P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.001
5090 reflectionsΔρmax = 1.30 e Å−3
373 parametersΔρmin = −1.10 e Å−3
66 restraints
Crystal data top
C24H32O2P+·Br−·CHCl3V = 5547.5 (7) Å3
Mr = 582.74Z = 8
Monoclinic, C2/cMo Kα radiation
a = 23.6380 (18) ŵ = 1.85 mm−1
b = 13.6273 (10) ÅT = 173 K
c = 18.1817 (13) Å0.34 × 0.15 × 0.09 mm
β = 108.702 (1)°
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		5090 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2013)		3862 reflections with I > 2σ(I)
Tmin = 0.667, Tmax = 0.745Rint = 0.040
25767 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.06466 restraints
wR(F2) = 0.206H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.1214P)2 + 22.4904P]
where P = (Fo2 + 2Fc2)/3
5090 reflectionsΔρmax = 1.30 e Å−3
373 parametersΔρmin = −1.10 e Å−3
Special details top

Experimental. SADABS-2012/1 (Bruker, 2013) was used for absorption correction. wR2(int) was 0.0613 before and 0.0433 after correction. The Ratio of minimum to maximum transmission is 0.8956. The λ/2 correction factor is 0.0015.

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)
P10.69139 (4)0.39763 (7)0.58769 (6)0.0214 (3)
O10.80869 (13)0.3191 (2)0.60430 (17)0.0309 (7)
O20.58476 (13)0.3136 (2)0.46946 (18)0.0305 (7)
C10.81047 (17)0.3556 (3)0.6659 (2)0.0243 (9)
C20.75533 (17)0.4046 (3)0.6746 (2)0.0254 (9)
H2A0.76440.47450.68830.030*
H2B0.74520.37310.71780.030*
C30.67433 (17)0.2690 (3)0.5678 (2)0.0233 (8)
H3A0.70250.24100.54320.028*
H3B0.68050.23420.61760.028*
C40.61055 (17)0.2511 (3)0.5150 (2)0.0237 (8)
C50.86786 (19)0.3561 (3)0.7359 (2)0.0306 (10)
C60.9052 (3)0.2661 (5)0.7318 (4)0.0618 (17)
H6A0.88270.20650.73420.093*
H6B0.94240.26700.77570.093*
H6C0.91450.26710.68300.093*
C70.9016 (3)0.4498 (5)0.7256 (4)0.0568 (15)
H7A0.87570.50710.72130.085*
H7B0.91290.44400.67840.085*
H7C0.93770.45770.77070.085*
C80.8561 (3)0.3630 (6)0.8130 (3)0.0650 (18)
H8A0.83540.42470.81520.098*
H8B0.89420.36130.85550.098*
H8C0.83130.30760.81810.098*
C90.63073 (18)0.4559 (3)0.6102 (2)0.0273 (9)
C100.6175 (2)0.4284 (5)0.6759 (3)0.0496 (14)
H100.64060.37930.70950.060*
C110.5699 (3)0.4733 (6)0.6925 (4)0.0682 (19)
H110.56070.45540.73790.082*
C120.5360 (2)0.5440 (4)0.6428 (4)0.0560 (16)
H120.50360.57450.65420.067*
C130.5489 (2)0.5695 (4)0.5781 (4)0.0557 (16)
H130.52540.61760.54400.067*
C140.5961 (2)0.5261 (4)0.5616 (3)0.0458 (13)
H140.60490.54470.51600.055*
C150.70589 (17)0.4604 (3)0.5093 (2)0.0240 (8)
C160.69455 (19)0.4162 (3)0.4366 (2)0.0291 (9)
H160.67940.35120.42810.035*
C170.7055 (2)0.4676 (4)0.3773 (3)0.0365 (11)
H170.69850.43740.32810.044*
C180.7268 (2)0.5631 (4)0.3890 (3)0.0402 (11)
H180.73300.59890.34740.048*
C190.7389 (2)0.6061 (4)0.4609 (3)0.0411 (12)
H190.75430.67100.46890.049*
C200.7288 (2)0.5556 (3)0.5220 (3)0.0353 (10)
H200.73740.58540.57160.042*
C210.58202 (18)0.1535 (3)0.5240 (3)0.0285 (9)
C220.6255 (2)0.0693 (4)0.5296 (3)0.0435 (12)
H22A0.64090.07230.48560.065*
H22B0.60490.00670.52850.065*
H22C0.65880.07470.57830.065*
C230.5652 (2)0.1610 (4)0.5987 (3)0.0456 (12)
H23A0.60160.16610.64350.068*
H23B0.54280.10240.60400.068*
H23C0.54040.21940.59620.068*
C240.5254 (2)0.1393 (4)0.4537 (3)0.0427 (12)
H24A0.49810.19430.45060.064*
H24B0.50580.07780.45960.064*
H24C0.53640.13670.40610.064*
Cl1A0.61055 (18)0.1585 (4)0.9366 (2)0.1062 (18)0.5
Cl2A0.53420 (17)0.1851 (3)0.77966 (18)0.0794 (11)0.5
Cl3A0.5717 (5)0.3487 (3)0.8797 (5)0.094 (3)0.5
C1A0.5960 (3)0.2348 (4)0.8538 (3)0.061 (3)0.5
H1A0.63190.24230.83650.074*0.5
Cl1B0.5809 (3)0.1342 (3)0.8669 (5)0.0963 (18)0.35
Cl2B0.6295 (4)0.2351 (6)1.0065 (4)0.061 (2)0.35
Cl3B0.5721 (5)0.3442 (4)0.8666 (6)0.096 (5)0.35
C1B0.6172 (5)0.2428 (4)0.9116 (10)0.078 (4)0.35
H1B0.65650.24790.90220.093*0.35
Cl1C0.6129 (8)0.2150 (13)0.9961 (6)0.060 (5)0.15
Cl2C0.5472 (5)0.3486 (8)0.8770 (10)0.045 (3)0.15
Cl3C0.6339 (3)0.2186 (5)0.8493 (5)0.0368 (17)0.15
C1C0.5777 (5)0.2284 (8)0.8944 (7)0.051 (5)0.15
H1C0.54600.17750.87400.061*0.15
Br1B0.7228 (3)0.1780 (6)0.7727 (5)0.0420 (5)0.35
Br1C0.7376 (2)0.1642 (3)0.7613 (3)0.0420 (5)0.15
Br1A0.7134 (2)0.1856 (4)0.7786 (3)0.0420 (5)0.5
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
P10.0198 (5)0.0230 (5)0.0183 (5)0.0017 (4)0.0015 (4)−0.0006 (4)
O10.0306 (16)0.0357 (17)0.0222 (16)0.0038 (13)0.0026 (12)−0.0079 (13)
O20.0246 (15)0.0291 (16)0.0307 (17)0.0039 (12)−0.0011 (13)0.0053 (13)
C10.023 (2)0.023 (2)0.024 (2)0.0004 (16)0.0030 (16)0.0006 (17)
C20.0222 (19)0.030 (2)0.0189 (19)−0.0005 (16)0.0000 (15)−0.0048 (16)
C30.0196 (19)0.0214 (19)0.024 (2)−0.0006 (15)0.0004 (16)−0.0012 (16)
C40.0218 (19)0.026 (2)0.022 (2)0.0043 (16)0.0049 (16)−0.0032 (17)
C50.026 (2)0.039 (2)0.021 (2)0.0037 (18)−0.0012 (17)−0.0057 (18)
C60.042 (3)0.072 (4)0.054 (4)0.024 (3)−0.009 (3)−0.006 (3)
C70.042 (3)0.064 (4)0.057 (4)−0.012 (3)0.006 (3)−0.011 (3)
C80.036 (3)0.120 (6)0.029 (3)0.009 (3)−0.004 (2)−0.007 (3)
C90.024 (2)0.025 (2)0.029 (2)−0.0022 (16)0.0042 (17)−0.0087 (17)
C100.037 (3)0.078 (4)0.034 (3)0.015 (3)0.013 (2)0.008 (3)
C110.049 (3)0.122 (6)0.042 (3)0.011 (4)0.025 (3)−0.014 (4)
C120.033 (3)0.059 (4)0.078 (4)0.004 (3)0.021 (3)−0.032 (3)
C130.038 (3)0.039 (3)0.092 (5)0.016 (2)0.025 (3)0.002 (3)
C140.043 (3)0.042 (3)0.059 (3)0.014 (2)0.025 (3)0.011 (2)
C150.0220 (19)0.027 (2)0.021 (2)0.0041 (16)0.0036 (16)0.0037 (16)
C160.030 (2)0.029 (2)0.027 (2)0.0009 (17)0.0077 (18)−0.0013 (18)
C170.040 (3)0.048 (3)0.022 (2)0.006 (2)0.0098 (19)0.004 (2)
C180.037 (3)0.045 (3)0.043 (3)0.005 (2)0.017 (2)0.016 (2)
C190.041 (3)0.030 (2)0.055 (3)−0.005 (2)0.018 (2)0.005 (2)
C200.037 (2)0.033 (2)0.035 (3)−0.0035 (19)0.010 (2)−0.006 (2)
C210.023 (2)0.029 (2)0.029 (2)−0.0031 (17)0.0013 (17)0.0030 (18)
C220.040 (3)0.030 (2)0.055 (3)0.000 (2)0.008 (2)0.004 (2)
C230.041 (3)0.058 (3)0.039 (3)−0.010 (2)0.014 (2)0.003 (2)
C240.034 (3)0.040 (3)0.043 (3)−0.012 (2)−0.004 (2)0.002 (2)
Cl1A0.066 (2)0.165 (5)0.081 (3)0.035 (3)0.014 (2)0.074 (3)
Cl2A0.096 (3)0.090 (3)0.0519 (19)0.032 (2)0.0233 (18)−0.0061 (17)
Cl3A0.105 (8)0.092 (6)0.077 (4)0.007 (5)0.017 (5)−0.015 (4)
C1A0.057 (8)0.071 (9)0.061 (8)0.013 (7)0.026 (7)0.022 (7)
Cl1B0.082 (4)0.084 (4)0.119 (5)−0.001 (3)0.028 (4)−0.001 (4)
Cl2B0.062 (4)0.056 (5)0.069 (3)0.008 (3)0.029 (3)0.020 (3)
Cl3B0.078 (8)0.092 (7)0.094 (7)−0.011 (6)−0.005 (5)0.041 (5)
C1B0.076 (9)0.075 (8)0.082 (7)−0.009 (7)0.025 (8)0.020 (8)
Cl1C0.063 (10)0.029 (6)0.099 (10)0.001 (7)0.039 (7)0.023 (6)
Cl2C0.052 (7)0.028 (4)0.047 (6)0.008 (4)0.006 (6)0.004 (4)
Cl3C0.033 (4)0.034 (4)0.049 (4)−0.002 (3)0.022 (3)−0.017 (3)
C1C0.048 (10)0.031 (9)0.081 (10)0.004 (9)0.033 (8)−0.001 (10)
Br1B0.0474 (16)0.0398 (10)0.0380 (10)0.0058 (9)0.0124 (8)0.0082 (7)
Br1C0.0474 (16)0.0398 (10)0.0380 (10)0.0058 (9)0.0124 (8)0.0082 (7)
Br1A0.0474 (16)0.0398 (10)0.0380 (10)0.0058 (9)0.0124 (8)0.0082 (7)
Geometric parameters (Å, º) top
P1—C21.805 (4)C15—C161.398 (6)
P1—C31.809 (4)C15—C201.397 (6)
P1—C91.798 (4)C16—H160.9500
P1—C151.786 (4)C16—C171.379 (6)
O1—C11.214 (5)C17—H170.9500
O2—C41.208 (5)C17—C181.387 (7)
C1—C21.517 (6)C18—H180.9500
C1—C51.534 (6)C18—C191.376 (7)
C2—H2A0.9900C19—H190.9500
C2—H2B0.9900C19—C201.391 (7)
C3—H3A0.9900C20—H200.9500
C3—H3B0.9900C21—C221.522 (6)
C3—C41.526 (5)C21—C231.536 (7)
C4—C211.523 (6)C21—C241.537 (6)
C5—C61.526 (7)C22—H22A0.9800
C5—C71.549 (8)C22—H22B0.9800
C5—C81.517 (7)C22—H22C0.9800
C6—H6A0.9800C23—H23A0.9800
C6—H6B0.9800C23—H23B0.9800
C6—H6C0.9800C23—H23C0.9800
C7—H7A0.9800C24—H24A0.9800
C7—H7B0.9800C24—H24B0.9800
C7—H7C0.9800C24—H24C0.9800
C8—H8A0.9800Cl1A—C1A1.770 (5)
C8—H8B0.9800Cl2A—Cl2Ai1.631 (7)
C8—H8C0.9800Cl2A—C1A1.774 (5)
C9—C101.379 (7)Cl3A—C1A1.772 (5)
C9—C141.380 (7)C1A—H1A1.0000
C10—H100.9500Cl1B—C1B1.772 (5)
C10—C111.397 (8)Cl2B—C1B1.66 (2)
C11—H110.9500Cl3B—C1B1.776 (5)
C11—C121.386 (10)C1B—H1B1.0000
C12—H120.9500Cl1C—C1C1.778 (5)
C12—C131.351 (9)Cl2C—C1C1.777 (5)
C13—H130.9500Cl3C—C1C1.776 (5)
C13—C141.378 (7)C1C—H1C1.0000
C14—H140.9500
C2—P1—C3107.24 (19)C13—C14—C9120.9 (5)
C9—P1—C2106.40 (19)C13—C14—H14119.6
C9—P1—C3109.30 (19)C16—C15—P1121.4 (3)
C15—P1—C2110.60 (19)C20—C15—P1118.4 (3)
C15—P1—C3113.08 (19)C20—C15—C16120.2 (4)
C15—P1—C9110.0 (2)C15—C16—H16120.2
O1—C1—C2120.0 (4)C17—C16—C15119.6 (4)
O1—C1—C5121.8 (4)C17—C16—H16120.2
C2—C1—C5118.2 (3)C16—C17—H17119.8
P1—C2—H2A109.0C16—C17—C18120.4 (4)
P1—C2—H2B109.0C18—C17—H17119.8
C1—C2—P1113.1 (3)C17—C18—H18120.0
C1—C2—H2A109.0C19—C18—C17120.0 (4)
C1—C2—H2B109.0C19—C18—H18120.0
H2A—C2—H2B107.8C18—C19—H19119.6
P1—C3—H3A108.9C18—C19—C20120.8 (4)
P1—C3—H3B108.9C20—C19—H19119.6
H3A—C3—H3B107.8C15—C20—H20120.5
C4—C3—P1113.1 (3)C19—C20—C15118.9 (4)
C4—C3—H3A108.9C19—C20—H20120.5
C4—C3—H3B108.9C4—C21—C23106.6 (4)
O2—C4—C3119.9 (4)C4—C21—C24108.5 (4)
O2—C4—C21123.1 (4)C22—C21—C4110.6 (3)
C21—C4—C3117.0 (3)C22—C21—C23110.6 (4)
C1—C5—C7104.9 (4)C22—C21—C24110.5 (4)
C6—C5—C1109.2 (4)C23—C21—C24109.9 (4)
C6—C5—C7109.2 (5)C21—C22—H22A109.5
C8—C5—C1113.1 (4)C21—C22—H22B109.5
C8—C5—C6112.0 (5)C21—C22—H22C109.5
C8—C5—C7108.3 (5)H22A—C22—H22B109.5
C5—C6—H6A109.5H22A—C22—H22C109.5
C5—C6—H6B109.5H22B—C22—H22C109.5
C5—C6—H6C109.5C21—C23—H23A109.5
H6A—C6—H6B109.5C21—C23—H23B109.5
H6A—C6—H6C109.5C21—C23—H23C109.5
H6B—C6—H6C109.5H23A—C23—H23B109.5
C5—C7—H7A109.5H23A—C23—H23C109.5
C5—C7—H7B109.5H23B—C23—H23C109.5
C5—C7—H7C109.5C21—C24—H24A109.5
H7A—C7—H7B109.5C21—C24—H24B109.5
H7A—C7—H7C109.5C21—C24—H24C109.5
H7B—C7—H7C109.5H24A—C24—H24B109.5
C5—C8—H8A109.5H24A—C24—H24C109.5
C5—C8—H8B109.5H24B—C24—H24C109.5
C5—C8—H8C109.5Cl2Ai—Cl2A—C1A154.5 (3)
H8A—C8—H8B109.5Cl1A—C1A—Cl2A108.1 (4)
H8A—C8—H8C109.5Cl1A—C1A—Cl3A106.2 (4)
H8B—C8—H8C109.5Cl1A—C1A—H1A112.0
C10—C9—P1119.7 (4)Cl2A—C1A—H1A112.0
C10—C9—C14119.4 (4)Cl3A—C1A—Cl2A106.2 (4)
C14—C9—P1120.8 (4)Cl3A—C1A—H1A112.0
C9—C10—H10120.4Cl1B—C1B—Cl3B107.9 (4)
C9—C10—C11119.3 (5)Cl1B—C1B—H1B108.7
C11—C10—H10120.4Cl2B—C1B—Cl1B108.7 (10)
C10—C11—H11120.0Cl2B—C1B—Cl3B114.0 (10)
C12—C11—C10120.1 (6)Cl2B—C1B—H1B108.7
C12—C11—H11120.0Cl3B—C1B—H1B108.7
C11—C12—H12120.0Cl1C—C1C—H1C111.1
C13—C12—C11120.1 (5)Cl2C—C1C—Cl1C107.9 (4)
C13—C12—H12120.0Cl2C—C1C—H1C111.1
C12—C13—H13119.9Cl3C—C1C—Cl1C107.6 (4)
C12—C13—C14120.3 (5)Cl3C—C1C—Cl2C107.9 (4)
C14—C13—H13119.9Cl3C—C1C—H1C111.1
C9—C14—H14119.6
P1—C3—C4—O226.8 (5)C3—C4—C21—C22−44.8 (5)
P1—C3—C4—C21−152.1 (3)C3—C4—C21—C2375.5 (4)
P1—C9—C10—C11−179.3 (5)C3—C4—C21—C24−166.2 (4)
P1—C9—C14—C13178.9 (4)C5—C1—C2—P1−179.7 (3)
P1—C15—C16—C17179.1 (3)C9—P1—C2—C1178.4 (3)
P1—C15—C20—C19−178.4 (3)C9—P1—C3—C444.9 (3)
O1—C1—C2—P11.7 (5)C9—P1—C15—C16−112.2 (3)
O1—C1—C5—C6−29.7 (6)C9—P1—C15—C2067.6 (4)
O1—C1—C5—C787.1 (5)C9—C10—C11—C120.7 (10)
O1—C1—C5—C8−155.1 (5)C10—C9—C14—C130.6 (8)
O2—C4—C21—C22136.3 (4)C10—C11—C12—C130.0 (10)
O2—C4—C21—C23−103.4 (5)C11—C12—C13—C14−0.5 (9)
O2—C4—C21—C2414.9 (6)C12—C13—C14—C90.2 (9)
C2—P1—C3—C4159.8 (3)C14—C9—C10—C11−1.1 (8)
C2—P1—C9—C10−51.0 (4)C15—P1—C2—C1−62.2 (3)
C2—P1—C9—C14130.8 (4)C15—P1—C3—C4−78.0 (3)
C2—P1—C15—C16130.6 (3)C15—P1—C9—C10−170.8 (4)
C2—P1—C15—C20−49.7 (4)C15—P1—C9—C1411.0 (4)
C2—C1—C5—C6151.7 (4)C15—C16—C17—C18−1.1 (7)
C2—C1—C5—C7−91.5 (5)C16—C15—C20—C191.3 (7)
C2—C1—C5—C826.3 (6)C16—C17—C18—C192.1 (7)
C3—P1—C2—C161.5 (3)C17—C18—C19—C20−1.4 (7)
C3—P1—C9—C1064.5 (4)C18—C19—C20—C15−0.3 (7)
C3—P1—C9—C14−113.7 (4)C20—C15—C16—C17−0.7 (6)
C3—P1—C15—C1610.3 (4)Cl2Ai—Cl2A—C1A—Cl1A113.6 (8)
C3—P1—C15—C20−169.9 (3)Cl2Ai—Cl2A—C1A—Cl3A0.0 (11)
Symmetry code: (i) −x+1, y, −z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2A···Br1Bii0.992.853.840 (9)174
C2—H2A···Br1Cii0.992.753.712 (6)164
C2—H2A···Br1Aii0.992.953.941 (7)177
C2—H2B···Br1B0.992.953.767 (9)141
C2—H2B···Br1C0.992.973.717 (6)133
C2—H2B···Br1A0.992.973.831 (7)145
C3—H3B···Br1B0.992.783.740 (9)163
C3—H3B···Br1C0.992.703.644 (6)159
C3—H3B···Br1A0.992.863.816 (7)164
C16—H16···O1iii0.952.433.287 (5)150
C1A—H1A···Br1A1.002.593.527 (9)156
Symmetry codes: (ii) −x+3/2, y+1/2, −z+3/2; (iii) −x+3/2, −y+1/2, −z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2A···Br1Bi0.992.853.840 (9)173.7
C2—H2A···Br1Ci0.992.753.712 (6)164.3
C2—H2A···Br1Ai0.992.953.941 (7)176.9
C2—H2B···Br1B0.992.953.767 (9)140.9
C2—H2B···Br1C0.992.973.717 (6)132.6
C2—H2B···Br1A0.992.973.831 (7)145.3
C3—H3B···Br1B0.992.783.740 (9)163.4
C3—H3B···Br1C0.992.703.644 (6)159.1
C3—H3B···Br1A0.992.863.816 (7)163.7
C16—H16···O1ii0.952.433.287 (5)149.5
C1A—H1A···Br1A1.002.593.527 (9)156.0
Symmetry codes: (i) −x+3/2, y+1/2, −z+3/2; (ii) −x+3/2, −y+1/2, −z+1.
 

Acknowledgements

The authors thank GVSU for financial support (Weldon Fund, CSCE, OURS) and the NSF for student support (REU-1062944). The CCD-based X-ray diffractometers at Michigan State University were upgraded and/or replaced by departmental funds.

References

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ISSN: 2056-9890
Volume 71| Part 5| May 2015| Pages o339-o340
https://doi.org/10.1107/S205698901500763X
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