Campbell, J. A.

Cremer, Sheldon E.

Ekeland, R.

Larsen, R.

English

epublications@Marquette

Marquette Universitye-Publications@MarquetteChemistry Faculty Research and Publications Chemistry, Department of1-1-1986Structure of l,l-DiphenylphosphorinaniumBromide MonohydrateJ. A. CampbellMontana State University - BozemanR. LarsenMontana State UniversityR. EkelandMontana State UniversitySheldon E. CremerMarquette University, sheldon.cremer@marquette.eduPublished version. Acta Crystallographica Section C, C42 (1986): 251-252. DOI. © 1986International Union of Crystallography. Used with permission.V. KR,~MER AND I. REIS 251 Ap = 4.7, min. Ap = --4.9 e A -3 close to the heavy atoms (Pb, Bi). Scattering factors of neutral atoms (Cromer & Mann, 1968) were used and corrected for anomalous dispersion (Cromer & Liberman, 1970). The atomic coordinates are listed in Table 1, bond lengths in Table 2; the site-occupancy factors of In(l-3) > 1.0 indicate a partial substitution of In 3÷ by Bi 3÷. Fig. 1 displays a perspective view of the unit-cell contents in the [0101 direction. Related literature. The present paper is the second part of a series (part I: Kr~imer, 1983) on the study of lead indium bismuth chalcogenides. The authors thank Dr E. Keller for the intensity collection and the SCHAKAL plot, and Professor G. M. Sheldrick (G6ttingen) for kindly providing the SHELXS84 program system for testing purposes. Numerical computations were performed on the Sperry 1100/82 computer of the Rechenzentrum der Univer- sit,it Freiburg. References CROMER, D. T. & LIBERMAN, D. (1970). J. Chem. Phys. 53, 1891-1898. CROMER, D. T. & MANN, J. B. (1968). Acta Cryst. A24, 321-324. KELLER, E. (1984). SCHAKAL. Ein Fortran-Programm zur graphischen Darstellung yon Molekfflmodellen. Univ. of Freiburg. KRAMER, V. (1983). Acta Cryst. C39, 1328-1329. SHELDRICK, G. M. (1984). SHELXS84. Program for crystal structure solution. Private communication. STEWART, J. M., MACHIN, P. A., DICKINSON, C. W., AMMON, H. L., HECK, H. & FLACK, H. (1976). The XRA Y76 system. Tech. Rep. TR-446. Computer Science Center, Univ. of Maryland, College Park, Maryland. Acta Cryst. (1986). C42, 251-252 Structure of l,l-Diphenylphosphorinanium Bromide Monohydrate BY J. A. CAMPBELL,* R. LARSEN AND R. EKELAND Chemistry Department, Montana State University, Bozeman, Montana 59715, USA AND S. E. CREMER Chemistry Department, Marquette University, Milwaukee, Wisconsin 53233, USA (Received 20 June 1985; accepted 21 October 1985) Abstract. CITH20P+.Br-.H2 O, Mr=353"24, ortho- rhombic, P2~212 l, a = 8.542 (1), b= 12.202 (2), c =15.864(3) A, V= 1653.5A 3, Z=4,  D_=1.42 ,  D x = 1.42 g cm -3, Mo Ka, 2 = 0.71069 ~k, g = 27.2cm -t, F(000)= 728, T= 295 K, R =0.062, wR =0.067, 1270 observed reflections. The phos- phorus-carbon bond lengths are 1.794 (9), 1.806 (10), 1.796 (9) and 1.783 (10) A. The phos- phorus heterocyclic ring is in the chair form and the torsional angles indicate that it is highly symmetrical. The bond angles around the phosphorus atom are 103.7(5), 111.7(4), 110.5(4), 109-8(4), 111.0(4) and 109-9 (4) ° . Experimental. Title compound prepared by previously described methods (Gray, Cremer & Marsi, 1976). D m by flotation in ethanol and methyl iodide mixture. * Address all correspondence to this author. Present address: Dow Chemical Company, Analytical Laboratory, 574 Building, Midland, M1 48667, USA. 0108-2701/86/020251-02501.50 Colorless crystals suitable for X-ray analysis ob- tained by recrystallization from acetonitrile. Crystal size 0.2 x 0.25 x 0.43 mm, Nicolet R3m diffrac- tometer, graphite monochromator, accurate unit-cell parameters (Campana, 1981) from least-squares refine- ment of 25 reflections (0 range 10-20°); three standard reflections (057, 434, 623) measured every 100 reflec- tions, 4% variation. Range of hAl: O<h< 10, 0 _< k _< 14, 0 _< l < 18. Data taken as 0/20 scans, 1770 data measured (3 < 20 <_ 55 °) with 1270 observed I > 2o(/), corrections for Lorentz and polarization effects (decay correction ignored). Absorption correc- tions by numerical Gaussian integration method from crystal dimensions and indexed faces. Max. and min. transmission coefficients 0.63 and 0.59, respectively. Trial structure from Patterson map provided Br--ion position, refined by full-matrix least-squares procedures, w(IFol - - IF  c I) z minimized, w = 1/[tr2(F) + G(F) 21 and G=0.001;  non-hydrogen atoms anisotropic, H atoms located in AF map, idealized coordinates calculated, not refined, isotropic thermal parameters © 1986 International Union of Crystallography 252 1,1-DIPHENYLPHOSPHORINANIUM BROMIDE °MONOHYDRATE assigned as 0.049 A2; R -- 0.062, wR -- 0.067, scatter- ing factors for Br, P, O, C and H from International Tables for X-ray Crystallography (1962), S= 1.43. Anomalous-dispersion corrections for P and Br applied toward end of refinement (Cromer, 1965). In final cycle, largest shift in any parameter was 0.080. Final difference map showed no peaks larger than 0.60 e A -3 at 0 .97A from Br. Calculations carried out with SHELXTL package on Nicolet R3m crystallographic system (Sheldrick, 1980). C3 OBr Table 2. Bond lengths (A) and angles (o) P-C(1) 1.794 (9) P-C(5) 1.806 (10) P-C(6) 1.796 (9) P-C(12) 1.783 (10) C(1)-C(2) 1.544 (13) C(2)-C(13) 1.524 (14) C(3)-C(4) 1.516 (15) C(4)-C(5) 1.542 (15) C(6)-C(7) 1.376 (14) C(6)-C(1 I) 1.384 (13) C(7)-C(8) 1.373 (17) C(8)-C(9) 1.379 (17) C(9)-C(10) i.382 (17) C(10)-C(11) 1.372 (15) C(12)-C(13) 1.405 (14) C(12)-C(17) 1.363 (14) C(13)-C(14) 1.362 (15) C(14)-C(15) 1.367 (16) C(15)-C(16) 1.432 (16) C(16)-C(17) 1.407 (15) C(I)-P-C(5) 103.7 (5) C(1)-P-C(6) 111.7 (4) C(5)-P-C(6) 110.5 (4) C(1)-P-C(12) 109.8 (4) C(5)-P-C(12) I11.0 (4) C(6)-P-C(12) 109.9 (4) P-C(1)-C(2) 109.8 (6) C(1)--C(2)--C(3) 112.3 (9) C(2)-C(3)-C(4) 114.0 (9) C(3)-C(4)--C(5) 112. I (8) P-C(5)-C(4) 109.2 (7) P-C(6)-C(7) 120.0 (8) P-C(6)-C(I 1) 120-5 (7) C(7)-C(6)-C(1 I) 119.4 (9) C(6)-C(7)-C(8) 120.6 (11) C(7)-C(8)-C(9) 120.4 (11) C(8)-C(9)-C(10) 118.7 (11) C(9)-C(lO)-C(ll) 121.1 (10) C(6)-C(1 i)-C(IO) 119.6 (10) P-C(12)-C(13) 120.6 (7) P-C(12)-C(17) 120.8 (7) C(13)-C(12)-C(17) 118.6 (9) C(12)-C(13)-C(14) 121. I (10) C(13)-C(14)-C(15) 121.7 (10) C(14)-C(15)-C(16) 118.5 (10) C(15)-C(16)-C(17) 118-7 (10) C(12)-C(17)-C(16) 121.3 (10) Fig. 1. The structure and numbering scheme for l,l-diphenyl- phosphorinanium bromide monohydrate. Non-hydrogen atoms are represented as thermal ellipsoids scaled to enclose 50% probability. The hydrogen atoms are omitted for clarity. Table 1. Atomic coordinates (×104) and equivalent isotropic thermal parameters (A 2 x 103) x y z Ueq* Br -137 (1) 6591 (1) 4188 (1) 60 (1) P 4080 (3) 1099 (2) 2509 (2) 31 (1) O 2412 (10) 1554 (6) 9089 (5) 68 (3) C(1) 4419 (11) 1659 (8) 1479 (5) 34 (3) C(2) 5058 (13) 759 (7) 888 (6) 51 (3) C(3) 3952 (13) -216 (8) 819 (7) 49 (3) C(4) 3698 (14) -819 (8) 1644 (7) 55 (4) C(5) 2884 (12) -93 (8) 2308 (6) 43 (3) C(6) 3060 (11) 2048 (7) 3177 (6) 33 (3) C(7) 3308 (13) 2034 (10) 4034 (7) 54 (4) C(8) 2559 (16) 2770 (10) 4550 (7) 68 (5) C(9) 1566 (15) 3548 (8) 4215 (8) 66 (5) C(10) 1371 (14) 3586 (9) 3351 (7) 54 (4) C(I 1) 2058 (12) 2821 (8) 2835 (7) 43 (3) C(12) 5897 (1 I) 722 (7) 2980 (6) 33 (3) C(13) 5960 (12) -105 (9) 3594 (6) 42 (3) C(14) 7343 (14) -405 (9) 3954 (7) 50 (4) C(15) 8728 (13) 70 (10) 3723 (6) 49 (4) C(16) 8698 (13) 929 (10) 3108 (7) 56 (4) C(17) 7259(12) 1211 (9) 2736(6) 44(3) * Equivalent isotropic U defined as one third of the trace of the orthogonalized U u tensor. The structure and numbering scheme of the title compound are shown in Fig. 1. The atomic fractional coordinates with standard deviations and Ueq values (Hamilton, 1959) are given in Table 1.* Table 2 gives a list of the interatomic distances and angles with their standard deviations. Related literature. This structure is similar to two structures previously reported by Gallucci & Holmes (1980). * Lists of structure factors, anisotropic thermal parameters and H-atom parameters have been deposited with the British Library Lending Division as Supplementary Publication No. SUP 42544 ( ! I pp.). Copies may be obtained through The Executive Secretary, International Union of Crystallography, 5 Abbey Square, Chester CH I 2HU, England. References CAMPANA, C. F. (1981). Editor. Nicolet P3/R3 Data Collection Manual. Nicolet Analytical Instruments, Madison, Wisconsin. CROMER, D. T. (1965).Acta Cryst. 18, 17-23. GALLUCCl, J. C. & HOLMES, R. R. (1980). J. Am. Chem. Soc. 102, 4379-4386. GRAY, G., CREMER, S. E. & MARSi, K. L. (1976). J. Am. Chem. Soc. 98, 2109-21 !8. HAMILTON, W. C. (1959). Acta Cryst. 12, 609-610. International Tables for X-ray Crystallography (1962). Vol. Ill, 2nd ed. Birmingham: Kynoch Press. (Present distributor D. Reidel, Dordrecht.) SHELDRICK, G. M. (1980). Editor. Nicolet SHELXTL Structure Determination Manual. Nicolet Analytical Instruments, Madison, Wisconsin. 

Structure of l,l-Diphenylphosphorinanium Bromide Monohydrate

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Structure of l,l-Diphenylphosphorinanium Bromide Monohydrate

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