Supplementary Material (ESI) for Dalton Transactions This journal is (c) The Royal Society of Chemistry 2003 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 loop_ _publ_author_name G.Leigh P.B.Hitchcock 'Ting Huei Lee' _publ_contact_author_name 'Prof G Leigh' _publ_contact_author_address ; Physics and Environmental Science University of Sussex School of Chemistry Falmer Brighton BN1 9QJ UNITED KINGDOM ; _publ_contact_author_email G.J.LEIGH@SUSSEX.AC.UK _publ_section_title ; The Synthesis and Properties of a New PNP Proligand ; data_gjl-4 _database_code_CSD 201299 _audit_creation_date 2001-04-03T14:26:23-00:00 _audit_creation_method 'WinGX routine CIF_UPDATE' _audit_conform_dict_name cif_core.dic _audit_conform_dict_version 2.1 _audit_conform_dict_location ftp://ftp.iucr.org/cifdics/cif_core.dic #----------------------------------------------------------------------------# # CHEMICAL INFORMATION # #----------------------------------------------------------------------------# _chemical_name_systematic ; ? ; _chemical_name_common (NiBr4(P(NHEt2)2)2)(NiBr4) _chemical_formula_moiety '(C32 H62 Br4 N4 Ni1 P2)(Ni1 Br4)' _chemical_formula_sum 'C32 H62 Br8 N4 Ni2 P2' _chemical_formula_weight 1321.5 _chemical_compound_source 'synthesis as described' #----------------------------------------------------------------------------# # UNIT CELL INFORMATION # #----------------------------------------------------------------------------# _symmetry_cell_setting triclinic _symmetry_space_group_name_H-M P-1 _symmetry_space_group_name_Hall '-P 1' _symmetry_Int_Tables_number 2 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 12.1242(14) _cell_length_b 13.7869(17) _cell_length_c 15.5447(17) _cell_angle_alpha 69.712(6) _cell_angle_beta 82.206(6) _cell_angle_gamma 86.362(6) _cell_volume 2414.3(5) _cell_formula_units_Z 2 _cell_measurement_temperature 173(2) _cell_measurement_reflns_used 34269 _cell_measurement_theta_min 3.705 _cell_measurement_theta_max 25.028 _cell_measurement_wavelength 0.71073 #----------------------------------------------------------------------------# # CRYSTAL INFORMATION # #----------------------------------------------------------------------------# _exptl_crystal_description prism _exptl_crystal_colour green _exptl_crystal_size_max 0.3 _exptl_crystal_size_mid 0.3 _exptl_crystal_size_min 0.2 _exptl_crystal_density_diffrn 1.818 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1296 _exptl_special_details ; ? ; #----------------------------------------------------------------------------# # ABSORPTION CORRECTION # #----------------------------------------------------------------------------# _exptl_absorpt_coefficient_mu 7.492 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; [c.f. r.h. blessing, acta cryst. (1995), a51, 33-38] ; _exptl_absorpt_correction_T_min 0.135 _exptl_absorpt_correction_T_max 0.190 #----------------------------------------------------------------------------# # DATA COLLECTION # #----------------------------------------------------------------------------# _diffrn_ambient_temperature 173(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_monochromator graphite _diffrn_radiation_probe x-ray _diffrn_measurement_device KappaCCD _diffrn_measurement_method CCD _diffrn_reflns_number 16131 _diffrn_reflns_av_R_equivalents 0.0948 _diffrn_reflns_av_unetI/netI 0.1223 _diffrn_reflns_limit_h_min -14 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -16 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 18 _diffrn_reflns_theta_min 3.72 _diffrn_reflns_theta_max 25.1 _diffrn_reflns_theta_full 25.1 _diffrn_measured_fraction_theta_full 0.978 _diffrn_measured_fraction_theta_max 0.978 _reflns_number_total 8425 _reflns_number_gt 5473 _reflns_threshold_expression >2sigma(I) #----------------------------------------------------------------------------# # COMPUTER PROGRAMS USED # #----------------------------------------------------------------------------# _computing_cell_refinement 'HKL Scalepack (Otwinowski & Minor 1997)' _computing_data_reduction 'HKL Denzo and Scalepack (Otwinowski & Minor 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Ortep-3 for Windows (Farrugia, 1997)' _computing_publication_material 'WinGX publication routines (Farrugia, 1999)' #----------------------------------------------------------------------------# # REFINEMENT INFORMATION # #----------------------------------------------------------------------------# _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.1090P)^2^+4.6430P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment riding _refine_ls_extinction_method none _refine_ls_number_reflns 8425 _refine_ls_number_parameters 433 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1346 _refine_ls_R_factor_gt 0.083 _refine_ls_wR_factor_ref 0.2188 _refine_ls_wR_factor_gt 0.1884 _refine_ls_goodness_of_fit_ref 1.049 _refine_ls_restrained_S_all 1.049 _refine_ls_shift/su_max 0 _refine_ls_shift/su_mean 0 _refine_diff_density_max 1.371 _refine_diff_density_min -2.27 _refine_diff_density_rms 0.242 #----------------------------------------------------------------------------# # ATOMIC TYPES, COORDINATES AND THERMAL PARAMETERS # #----------------------------------------------------------------------------# loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0 0 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Ni Ni 0.3393 1.1124 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Ni1 Ni 0.76902(12) 0.49664(11) 0.28719(10) 0.0286(4) Uani 1 1 d . . . Ni2 Ni 0.47508(13) -0.07371(13) 0.79020(12) 0.0380(4) Uani 1 1 d . . . Br1 Br 0.89612(10) 0.55436(9) 0.13490(8) 0.0343(3) Uani 1 1 d . . . Br2 Br 0.62443(10) 0.44513(10) 0.43508(9) 0.0398(3) Uani 1 1 d . . . Br3 Br 0.91792(10) 0.47228(10) 0.39519(9) 0.0355(3) Uani 1 1 d . . . Br4 Br 0.60078(10) 0.50913(10) 0.19766(9) 0.0384(3) Uani 1 1 d . . . Br5 Br 0.37134(12) 0.01990(10) 0.66332(10) 0.0449(4) Uani 1 1 d . . . Br6 Br 0.55223(11) -0.22697(11) 0.76274(13) 0.0555(4) Uani 1 1 d . . . Br7 Br 0.62865(11) 0.02365(11) 0.79640(9) 0.0442(4) Uani 1 1 d . . . Br8 Br 0.33796(11) -0.07736(11) 0.91713(10) 0.0459(4) Uani 1 1 d . . . P1 P 0.7983(2) 0.3168(2) 0.2832(2) 0.0268(7) Uani 1 1 d . . . P2 P 0.7564(2) 0.6815(2) 0.2786(2) 0.0298(7) Uani 1 1 d . . . N1 N 0.7753(8) 0.3702(7) 0.0923(6) 0.031(2) Uani 1 1 d . . . H1A H 0.7763 0.4344 0.0995 0.037 Uiso 1 1 calc R . . N2 N 0.7134(8) 0.2131(7) 0.4701(6) 0.030(2) Uani 1 1 d . . . H2A H 0.6857 0.2765 0.473 0.036 Uiso 1 1 calc R . . N3 N 0.6348(8) 0.7553(8) 0.1225(7) 0.035(2) Uani 1 1 d . . . H3A H 0.6337 0.6859 0.1282 0.042 Uiso 1 1 calc R . . N4 N 0.7572(8) 0.6381(8) 0.4723(7) 0.034(2) Uani 1 1 d . . . H4A H 0.7803 0.5753 0.4655 0.041 Uiso 1 1 calc R . . C1 C 0.9353(9) 0.2528(9) 0.2822(8) 0.031(3) Uani 1 1 d . . . C2 C 0.9491(10) 0.1482(10) 0.2919(9) 0.037(3) Uani 1 1 d . . . H2 H 0.885 0.1078 0.3015 0.044 Uiso 1 1 calc R . . C3 C 1.0531(12) 0.1021(11) 0.2879(10) 0.050(4) Uani 1 1 d . . . H3 H 1.0607 0.0304 0.297 0.06 Uiso 1 1 calc R . . C4 C 1.1469(11) 0.1630(11) 0.2702(10) 0.042(3) Uani 1 1 d . . . H4 H 1.2191 0.1323 0.2671 0.05 Uiso 1 1 calc R . . C5 C 1.1360(9) 0.2671(10) 0.2573(8) 0.036(3) Uani 1 1 d . . . H5 H 1.2005 0.3082 0.2429 0.043 Uiso 1 1 calc R . . C6 C 1.0317(10) 0.3119(10) 0.2653(8) 0.035(3) Uani 1 1 d . . . H6 H 1.0248 0.3829 0.2593 0.042 Uiso 1 1 calc R . . C7 C 0.7397(9) 0.2934(9) 0.1880(7) 0.026(2) Uani 1 1 d . . . H7A H 0.7624 0.223 0.1884 0.031 Uiso 1 1 calc R . . H7B H 0.6574 0.2954 0.2001 0.031 Uiso 1 1 calc R . . C8 C 0.8913(11) 0.3505(11) 0.0541(9) 0.046(3) Uani 1 1 d . . . H8A H 0.9424 0.3471 0.0996 0.055 Uiso 1 1 calc R . . H8B H 0.9136 0.4095 -0.0027 0.055 Uiso 1 1 calc R . . C9 C 0.9046(12) 0.2501(11) 0.0310(11) 0.055(4) Uani 1 1 d . . . H9A H 0.982 0.2423 0.006 0.083 Uiso 1 1 calc R . . H9B H 0.8553 0.2532 -0.0149 0.083 Uiso 1 1 calc R . . H9C H 0.8851 0.1909 0.0872 0.083 Uiso 1 1 calc R . . C10 C 0.6882(11) 0.3786(10) 0.0310(8) 0.038(3) Uani 1 1 d . . . H10A H 0.615 0.3923 0.0618 0.045 Uiso 1 1 calc R . . H10B H 0.6841 0.3119 0.0208 0.045 Uiso 1 1 calc R . . C11 C 0.7126(16) 0.4648(12) -0.0624(10) 0.068(5) Uani 1 1 d . . . H11A H 0.6538 0.4677 -0.1007 0.103 Uiso 1 1 calc R . . H11B H 0.7845 0.4509 -0.0935 0.103 Uiso 1 1 calc R . . H11C H 0.715 0.5312 -0.0527 0.103 Uiso 1 1 calc R . . C12 C 0.7083(9) 0.2179(9) 0.3734(8) 0.030(3) Uani 1 1 d . . . H12A H 0.6302 0.2322 0.3599 0.036 Uiso 1 1 calc R . . H12B H 0.7299 0.1492 0.369 0.036 Uiso 1 1 calc R . . C13 C 0.6329(11) 0.1327(9) 0.5351(9) 0.040(3) Uani 1 1 d . . . H13A H 0.6174 0.1457 0.5944 0.049 Uiso 1 1 calc R . . H13B H 0.5618 0.1414 0.5083 0.049 Uiso 1 1 calc R . . C14 C 0.6724(12) 0.0246(11) 0.5543(9) 0.050(4) Uani 1 1 d . . . H14A H 0.6157 -0.0222 0.5965 0.075 Uiso 1 1 calc R . . H14B H 0.7415 0.0143 0.5828 0.075 Uiso 1 1 calc R . . H14C H 0.6862 0.0101 0.4964 0.075 Uiso 1 1 calc R . . C15 C 0.8277(10) 0.2012(12) 0.4995(8) 0.041(3) Uani 1 1 d . . . H15A H 0.8597 0.133 0.5006 0.049 Uiso 1 1 calc R . . H15B H 0.8762 0.2553 0.454 0.049 Uiso 1 1 calc R . . C16 C 0.8251(12) 0.2097(12) 0.5920(9) 0.055(4) Uani 1 1 d . . . H16A H 0.9007 0.201 0.6095 0.082 Uiso 1 1 calc R . . H16B H 0.7776 0.1558 0.6373 0.082 Uiso 1 1 calc R . . H16C H 0.7952 0.2779 0.5906 0.082 Uiso 1 1 calc R . . C17 C 0.8803(9) 0.7650(9) 0.2385(8) 0.031(3) Uani 1 1 d . . . C18 C 0.9854(11) 0.7217(11) 0.2305(9) 0.039(3) Uani 1 1 d . . . H18 H 0.9942 0.6488 0.2468 0.047 Uiso 1 1 calc R . . C19 C 1.0783(11) 0.7841(12) 0.1988(10) 0.050(4) Uani 1 1 d . . . H19 H 1.1502 0.7528 0.1961 0.06 Uiso 1 1 calc R . . C20 C 1.0686(12) 0.8893(11) 0.1713(10) 0.050(4) Uani 1 1 d . . . H20 H 1.1327 0.9313 0.1493 0.06 Uiso 1 1 calc R . . C21 C 0.9617(13) 0.9338(12) 0.1765(11) 0.058(4) Uani 1 1 d . . . H21 H 0.9539 1.007 0.1552 0.069 Uiso 1 1 calc R . . C22 C 0.8661(12) 0.8737(10) 0.2119(10) 0.048(4) Uani 1 1 d . . . H22 H 0.7945 0.9047 0.2178 0.057 Uiso 1 1 calc R . . C23 C 0.6428(10) 0.7596(9) 0.2165(8) 0.033(3) Uani 1 1 d . . . H23A H 0.5711 0.7366 0.2553 0.04 Uiso 1 1 calc R . . H23B H 0.6521 0.8327 0.2101 0.04 Uiso 1 1 calc R . . C24 C 0.7347(11) 0.8031(11) 0.0539(9) 0.043(3) Uani 1 1 d . . . H24A H 0.8037 0.7802 0.0835 0.052 Uiso 1 1 calc R . . H24B H 0.7289 0.8794 0.0354 0.052 Uiso 1 1 calc R . . C25 C 0.7411(14) 0.7719(13) -0.0312(9) 0.060(4) Uani 1 1 d . . . H25A H 0.8059 0.8038 -0.0746 0.091 Uiso 1 1 calc R . . H25B H 0.6732 0.7953 -0.0609 0.091 Uiso 1 1 calc R . . H25C H 0.7483 0.6965 -0.0131 0.091 Uiso 1 1 calc R . . C26 C 0.5279(10) 0.8057(11) 0.0861(9) 0.043(3) Uani 1 1 d . . . H26A H 0.522 0.8769 0.0879 0.051 Uiso 1 1 calc R . . H26B H 0.5308 0.8104 0.0208 0.051 Uiso 1 1 calc R . . C27 C 0.4254(9) 0.7469(11) 0.1408(11) 0.047(4) Uani 1 1 d . . . H27A H 0.3587 0.7835 0.1153 0.07 Uiso 1 1 calc R . . H27B H 0.4219 0.7419 0.2056 0.07 Uiso 1 1 calc R . . H27C H 0.429 0.6773 0.1369 0.07 Uiso 1 1 calc R . . C28 C 0.6975(9) 0.6957(10) 0.3905(9) 0.034(3) Uani 1 1 d . . . H28A H 0.696 0.7701 0.3827 0.041 Uiso 1 1 calc R . . H28B H 0.6194 0.6725 0.4046 0.041 Uiso 1 1 calc R . . C29 C 0.8602(10) 0.6900(10) 0.4755(9) 0.038(3) Uani 1 1 d . . . H29A H 0.9101 0.6991 0.4174 0.045 Uiso 1 1 calc R . . H29B H 0.8991 0.6434 0.5269 0.045 Uiso 1 1 calc R . . C30 C 0.8428(12) 0.7942(12) 0.4882(11) 0.054(4) Uani 1 1 d . . . H30A H 0.915 0.8215 0.4896 0.081 Uiso 1 1 calc R . . H30B H 0.7954 0.7863 0.5464 0.081 Uiso 1 1 calc R . . H30C H 0.8068 0.8422 0.4366 0.081 Uiso 1 1 calc R . . C31 C 0.6768(11) 0.6120(11) 0.5612(9) 0.045(3) Uani 1 1 d . . . H31A H 0.6562 0.6761 0.575 0.054 Uiso 1 1 calc R . . H31B H 0.6081 0.5835 0.5522 0.054 Uiso 1 1 calc R . . C32 C 0.7263(13) 0.5352(14) 0.6415(9) 0.070(5) Uani 1 1 d . . . H32A H 0.6724 0.5212 0.6973 0.104 Uiso 1 1 calc R . . H32B H 0.794 0.5634 0.651 0.104 Uiso 1 1 calc R . . H32C H 0.7447 0.4708 0.6289 0.104 Uiso 1 1 calc R . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Ni1 0.0289(8) 0.0274(8) 0.0270(8) -0.0058(7) -0.0016(6) -0.0055(6) Ni2 0.0360(9) 0.0336(9) 0.0404(10) -0.0051(8) -0.0083(7) -0.0057(7) Br1 0.0385(7) 0.0327(7) 0.0289(7) -0.0075(6) 0.0035(5) -0.0128(5) Br2 0.0353(7) 0.0370(7) 0.0444(8) -0.0139(6) 0.0075(6) -0.0071(5) Br3 0.0349(7) 0.0379(7) 0.0341(7) -0.0111(6) -0.0087(5) -0.0002(5) Br4 0.0338(7) 0.0320(7) 0.0488(8) -0.0105(6) -0.0105(6) -0.0046(5) Br5 0.0553(9) 0.0357(7) 0.0429(8) -0.0081(6) -0.0189(7) 0.0007(6) Br6 0.0329(7) 0.0368(8) 0.0925(12) -0.0160(8) -0.0060(7) -0.0072(6) Br7 0.0448(8) 0.0468(8) 0.0413(8) -0.0153(7) 0.0009(6) -0.0157(6) Br8 0.0477(8) 0.0397(8) 0.0408(8) -0.0015(6) -0.0019(6) -0.0099(6) P1 0.0256(15) 0.0273(16) 0.0228(15) -0.0029(13) 0.0021(12) -0.0089(12) P2 0.0299(16) 0.0299(17) 0.0295(17) -0.0086(14) -0.0063(13) -0.0037(13) N1 0.037(6) 0.027(5) 0.025(5) -0.008(5) 0.007(4) -0.011(4) N2 0.040(6) 0.025(5) 0.024(5) -0.008(5) 0.001(4) -0.007(4) N3 0.044(6) 0.024(5) 0.030(6) 0.000(5) -0.005(5) -0.006(5) N4 0.030(5) 0.042(6) 0.033(6) -0.016(5) -0.004(4) 0.002(5) C1 0.029(6) 0.037(7) 0.026(6) -0.012(6) 0.002(5) -0.001(5) C2 0.033(7) 0.037(7) 0.041(8) -0.016(6) 0.006(6) -0.010(6) C3 0.059(9) 0.029(7) 0.054(9) -0.001(7) -0.012(7) -0.003(7) C4 0.037(7) 0.043(8) 0.050(8) -0.024(7) -0.009(6) 0.015(6) C5 0.023(6) 0.045(8) 0.037(7) -0.007(6) -0.007(5) 0.000(5) C6 0.046(8) 0.034(7) 0.025(6) -0.010(6) 0.003(6) -0.013(6) C7 0.033(6) 0.022(6) 0.017(6) 0.002(5) -0.003(5) -0.006(5) C8 0.047(8) 0.056(9) 0.031(7) -0.013(7) 0.013(6) -0.020(7) C9 0.058(9) 0.044(9) 0.061(10) -0.022(8) 0.016(8) -0.008(7) C10 0.055(8) 0.029(7) 0.022(6) 0.001(6) -0.005(6) -0.009(6) C11 0.119(15) 0.046(9) 0.031(8) 0.009(7) -0.027(9) -0.021(9) C12 0.030(6) 0.034(7) 0.024(6) -0.010(6) 0.008(5) -0.012(5) C13 0.048(8) 0.032(7) 0.030(7) 0.000(6) 0.021(6) -0.023(6) C14 0.069(10) 0.046(9) 0.027(7) -0.002(7) 0.010(7) -0.031(7) C15 0.038(7) 0.060(9) 0.022(7) -0.008(6) -0.007(6) -0.006(6) C16 0.062(10) 0.060(10) 0.032(8) 0.000(7) -0.005(7) -0.020(8) C17 0.020(6) 0.037(7) 0.035(7) -0.012(6) -0.004(5) -0.006(5) C18 0.050(8) 0.041(8) 0.031(7) -0.015(6) -0.006(6) -0.012(6) C19 0.039(8) 0.068(11) 0.049(9) -0.027(8) 0.005(7) -0.018(7) C20 0.060(10) 0.034(8) 0.051(9) -0.006(7) -0.004(7) -0.026(7) C21 0.073(11) 0.038(8) 0.060(10) -0.007(8) -0.020(9) -0.018(8) C22 0.052(9) 0.028(7) 0.058(9) -0.006(7) -0.012(7) -0.014(6) C23 0.042(7) 0.033(7) 0.032(7) -0.014(6) -0.015(6) -0.009(5) C24 0.040(8) 0.045(8) 0.043(8) -0.012(7) -0.011(6) 0.011(6) C25 0.089(12) 0.058(10) 0.024(7) -0.003(7) -0.002(8) 0.000(9) C26 0.046(8) 0.043(8) 0.039(8) -0.008(7) -0.024(6) 0.002(6) C27 0.017(6) 0.054(9) 0.073(10) -0.024(8) -0.017(6) 0.010(6) C28 0.031(7) 0.032(7) 0.045(8) -0.017(6) -0.015(6) 0.003(5) C29 0.036(7) 0.049(8) 0.029(7) -0.014(6) -0.003(6) -0.004(6) C30 0.060(9) 0.055(10) 0.052(9) -0.017(8) -0.029(8) 0.004(7) C31 0.043(8) 0.053(9) 0.032(7) -0.006(7) 0.007(6) -0.014(7) C32 0.072(11) 0.100(14) 0.019(7) 0.009(8) -0.010(7) -0.032(10) #----------------------------------------------------------------------------# # MOLECULAR GEOMETRY # #----------------------------------------------------------------------------# _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Ni1 P2 2.501(3) . ? Ni1 P1 2.503(3) . ? Ni1 Br1 2.5440(19) . ? Ni1 Br3 2.5581(18) . ? Ni1 Br4 2.5859(18) . ? Ni1 Br2 2.6068(19) . ? Ni2 Br8 2.390(2) . ? Ni2 Br7 2.3945(19) . ? Ni2 Br6 2.406(2) . ? Ni2 Br5 2.416(2) . ? P1 C1 1.832(12) . ? P1 C7 1.857(10) . ? P1 C12 1.861(11) . ? P2 C23 1.855(12) . ? P2 C17 1.855(11) . ? P2 C28 1.859(12) . ? N1 C10 1.490(15) . ? N1 C8 1.497(15) . ? N1 C7 1.520(14) . ? N2 C12 1.491(14) . ? N2 C15 1.498(15) . ? N2 C13 1.516(14) . ? N3 C23 1.498(14) . ? N3 C26 1.516(15) . ? N3 C24 1.517(16) . ? N4 C29 1.494(15) . ? N4 C28 1.499(15) . ? N4 C31 1.524(16) . ? C1 C2 1.399(17) . ? C1 C6 1.409(16) . ? C2 C3 1.379(18) . ? C3 C4 1.397(19) . ? C4 C5 1.379(17) . ? C5 C6 1.382(16) . ? C8 C9 1.540(18) . ? C10 C11 1.529(18) . ? C13 C14 1.475(18) . ? C15 C16 1.479(17) . ? C17 C18 1.381(17) . ? C17 C22 1.415(17) . ? C18 C19 1.390(18) . ? C19 C20 1.36(2) . ? C20 C21 1.40(2) . ? C21 C22 1.402(19) . ? C24 C25 1.518(18) . ? C26 C27 1.512(18) . ? C29 C30 1.513(18) . ? C31 C32 1.50(2) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag P2 Ni1 P1 174.15(12) . . ? P2 Ni1 Br1 87.82(9) . . ? P1 Ni1 Br1 86.52(8) . . ? P2 Ni1 Br3 86.70(8) . . ? P1 Ni1 Br3 92.62(9) . . ? Br1 Ni1 Br3 97.87(6) . . ? P2 Ni1 Br4 95.01(9) . . ? P1 Ni1 Br4 86.43(8) . . ? Br1 Ni1 Br4 89.64(6) . . ? Br3 Ni1 Br4 172.36(8) . . ? P2 Ni1 Br2 90.68(9) . . ? P1 Ni1 Br2 95.08(9) . . ? Br1 Ni1 Br2 174.99(8) . . ? Br3 Ni1 Br2 86.81(6) . . ? Br4 Ni1 Br2 85.73(6) . . ? Br8 Ni2 Br7 107.57(8) . . ? Br8 Ni2 Br6 123.37(9) . . ? Br7 Ni2 Br6 106.86(8) . . ? Br8 Ni2 Br5 99.69(8) . . ? Br7 Ni2 Br5 111.74(8) . . ? Br6 Ni2 Br5 107.42(8) . . ? C1 P1 C7 102.6(5) . . ? C1 P1 C12 103.9(6) . . ? C7 P1 C12 92.5(5) . . ? C1 P1 Ni1 123.3(4) . . ? C7 P1 Ni1 114.9(4) . . ? C12 P1 Ni1 114.8(4) . . ? C23 P2 C17 105.6(6) . . ? C23 P2 C28 93.3(5) . . ? C17 P2 C28 105.1(5) . . ? C23 P2 Ni1 115.5(4) . . ? C17 P2 Ni1 121.2(4) . . ? C28 P2 Ni1 112.3(4) . . ? C10 N1 C8 115.2(9) . . ? C10 N1 C7 109.7(8) . . ? C8 N1 C7 113.1(10) . . ? C12 N2 C15 115.7(9) . . ? C12 N2 C13 109.1(8) . . ? C15 N2 C13 113.3(10) . . ? C23 N3 C26 111.6(9) . . ? C23 N3 C24 112.1(9) . . ? C26 N3 C24 110.4(9) . . ? C29 N4 C28 113.5(10) . . ? C29 N4 C31 113.6(9) . . ? C28 N4 C31 110.5(9) . . ? C2 C1 C6 118.0(11) . . ? C2 C1 P1 122.6(9) . . ? C6 C1 P1 119.2(9) . . ? C3 C2 C1 121.8(11) . . ? C2 C3 C4 118.7(12) . . ? C5 C4 C3 120.7(12) . . ? C4 C5 C6 120.3(11) . . ? C5 C6 C1 120.3(12) . . ? N1 C7 P1 114.6(7) . . ? N1 C8 C9 113.8(10) . . ? N1 C10 C11 111.9(11) . . ? N2 C12 P1 115.0(7) . . ? C14 C13 N2 114.7(10) . . ? C16 C15 N2 111.5(11) . . ? C18 C17 C22 120.2(11) . . ? C18 C17 P2 120.1(9) . . ? C22 C17 P2 119.5(9) . . ? C17 C18 C19 120.4(13) . . ? C20 C19 C18 121.5(14) . . ? C19 C20 C21 118.3(13) . . ? C22 C21 C20 122.2(14) . . ? C21 C22 C17 117.4(13) . . ? N3 C23 P2 116.4(8) . . ? N3 C24 C25 110.9(11) . . ? C27 C26 N3 112.8(11) . . ? N4 C28 P2 116.4(8) . . ? N4 C29 C30 115.8(10) . . ? C32 C31 N4 112.1(11) . . ? #===END data_feb3801 _database_code_CSD 201300 _audit_creation_date 2001-02-28T15:05:17-00:00 _audit_creation_method 'WinGX routine CIF_UPDATE' _audit_conform_dict_name cif_core.dic _audit_conform_dict_version 2.1 _audit_conform_dict_location ftp://ftp.iucr.org/cifdics/cif_core.dic #----------------------------------------------------------------------------# # CHEMICAL INFORMATION # #----------------------------------------------------------------------------# _chemical_name_systematic ; ? ; _chemical_name_common [PhP(O)(NHEt2)2]/[PHP(NHEt2)2] _chemical_formula_moiety 'C16 H31 Br2 N2 O P' _chemical_formula_structural 'C16 H31 Br2 N2 O P' _chemical_formula_sum 'C16 H31 Br2 N2 O P' _chemical_formula_weight 458.22 _chemical_compound_source 'synthesis as described' #----------------------------------------------------------------------------# # UNIT CELL INFORMATION # #----------------------------------------------------------------------------# _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M Cc _symmetry_Int_Tables_number 9 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' 'x, -y, z+1/2' 'x+1/2, y+1/2, z' 'x+1/2, -y+1/2, z+1/2' _cell_length_a 17.9448(16) _cell_length_b 12.8400(11) _cell_length_c 10.8881(9) _cell_angle_alpha 90 _cell_angle_beta 125.675(4) _cell_angle_gamma 90 _cell_volume 2037.9(3) _cell_formula_units_Z 4 _cell_measurement_temperature 173(2) _cell_measurement_reflns_used 6167 _cell_measurement_theta_min 3.705 _cell_measurement_theta_max 25.028 _cell_measurement_wavelength 0.71073 #----------------------------------------------------------------------------# # CRYSTAL INFORMATION # #----------------------------------------------------------------------------# _exptl_crystal_description prism _exptl_crystal_colour colourless _exptl_crystal_size_max 0.2 _exptl_crystal_size_mid 0.2 _exptl_crystal_size_min 0.1 _exptl_crystal_density_diffrn 1.493 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 936 _exptl_special_details ; ? ; #----------------------------------------------------------------------------# # ABSORPTION CORRECTION # #----------------------------------------------------------------------------# _exptl_absorpt_coefficient_mu 4.06 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; [c.f. r.h. blessing, acta cryst. (1995), a51, 33-38] ; _exptl_absorpt_correction_T_min 0.490 _exptl_absorpt_correction_T_max 0.544 #----------------------------------------------------------------------------# # DATA COLLECTION # #----------------------------------------------------------------------------# _diffrn_ambient_temperature 173(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_monochromator graphite _diffrn_radiation_probe x-ray _diffrn_measurement_device KappaCCD _diffrn_measurement_method CCD _diffrn_reflns_number 5211 _diffrn_reflns_av_R_equivalents 0.0501 _diffrn_reflns_av_unetI/netI 0.072 _diffrn_reflns_limit_h_min -21 _diffrn_reflns_limit_h_max 19 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -12 _diffrn_reflns_limit_l_max 12 _diffrn_reflns_theta_min 3.74 _diffrn_reflns_theta_max 24.97 _diffrn_reflns_theta_full 24.97 _diffrn_measured_fraction_theta_full 0.993 _diffrn_measured_fraction_theta_max 0.993 _reflns_number_total 2991 _reflns_number_gt 2638 _reflns_threshold_expression >2sigma(I) #----------------------------------------------------------------------------# # COMPUTER PROGRAMS USED # #----------------------------------------------------------------------------# _computing_cell_refinement 'HKL Scalepack (Otwinowski & Minor 1997)' _computing_data_reduction 'HKL Denzo and Scalepack (Otwinowski & Minor 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Ortep-3 for Windows (Farrugia, 1997)' _computing_publication_material 'WinGX publication routines (Farrugia, 1999)' #----------------------------------------------------------------------------# # REFINEMENT INFORMATION # #----------------------------------------------------------------------------# _refine_special_details ; The crystal contains 69% of the phosphine-oxide and 31% of the phosphine. Refinement of F^2^ against ALL reflections. The formula is given for the phosphine-oxide. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0000P)^2^+7.1433P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment 'H on N refined: others riding' _refine_ls_extinction_method none _refine_ls_number_reflns 2991 _refine_ls_number_parameters 208 _refine_ls_number_restraints 2 _refine_ls_R_factor_all 0.0535 _refine_ls_R_factor_gt 0.0433 _refine_ls_wR_factor_ref 0.0948 _refine_ls_wR_factor_gt 0.0896 _refine_ls_goodness_of_fit_ref 1.054 _refine_ls_restrained_S_all 1.054 _refine_ls_shift/su_max 0.002 _refine_ls_shift/su_mean 0 _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack -0.006(15) _refine_diff_density_max 0.315 _refine_diff_density_min -0.618 _refine_diff_density_rms 0.084 #----------------------------------------------------------------------------# # ATOMIC TYPES, COORDINATES AND THERMAL PARAMETERS # #----------------------------------------------------------------------------# loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0 0 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.006 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Br1 Br 1.19641(5) 0.78754(6) 0.74113(6) 0.0398(2) Uani 1 1 d . . . Br2 Br 0.93440(6) 0.67354(6) 0.90459(8) 0.0511(3) Uani 1 1 d . . . P P 0.96865(14) 0.91434(15) 0.6502(2) 0.0319(5) Uani 1 1 d . . . N1 N 0.9781(5) 0.7308(4) 0.5147(7) 0.0280(14) Uani 1 1 d . . . H1A H 1.038(6) 0.749(6) 0.578(9) 0.05(2) Uiso 1 1 d . . . N2 N 1.1375(4) 0.9008(5) 0.9362(7) 0.0350(15) Uani 1 1 d . . . H2A H 1.146(4) 0.878(5) 0.874(7) 0.014(17) Uiso 1 1 d . . . C1 C 0.8642(5) 0.9692(5) 0.6099(8) 0.0312(17) Uani 1 1 d . . . C2 C 0.8307(6) 1.0600(6) 0.5265(8) 0.049(2) Uani 1 1 d . . . H2 H 0.8622 1.0922 0.4906 0.059 Uiso 1 1 calc R . . C3 C 0.7501(7) 1.1042(7) 0.4951(10) 0.058(3) Uani 1 1 d . . . H3 H 0.7276 1.1675 0.4398 0.069 Uiso 1 1 calc R . . C4 C 0.7034(7) 1.0567(7) 0.5438(10) 0.057(2) Uani 1 1 d . . . H4 H 0.6485 1.0868 0.5217 0.068 Uiso 1 1 calc R . . C5 C 0.7356(7) 0.9660(7) 0.6240(10) 0.061(3) Uani 1 1 d . . . H5 H 0.7019 0.9322 0.6548 0.073 Uiso 1 1 calc R . . C6 C 0.8171(6) 0.9231(6) 0.6608(9) 0.052(2) Uani 1 1 d . . . H6 H 0.8408 0.8619 0.721 0.063 Uiso 1 1 calc R . . C7 C 0.9308(5) 0.7801(6) 0.5774(8) 0.0329(17) Uani 1 1 d . . . H7B H 0.9411 0.7358 0.6604 0.039 Uiso 1 1 calc R . . H7A H 0.864 0.7812 0.497 0.039 Uiso 1 1 calc R . . C8 C 0.9420(5) 0.7755(6) 0.3608(7) 0.0327(17) Uani 1 1 d . . . H8B H 0.9394 0.8524 0.3653 0.039 Uiso 1 1 calc R . . H8A H 0.8787 0.75 0.2864 0.039 Uiso 1 1 calc R . . C9 C 1.0011(6) 0.7464(7) 0.3070(9) 0.047(2) Uani 1 1 d . . . H9C H 1.0633 0.7737 0.3783 0.071 Uiso 1 1 calc R . . H9B H 0.9744 0.7764 0.2067 0.071 Uiso 1 1 calc R . . H9A H 1.0035 0.6704 0.3015 0.071 Uiso 1 1 calc R . . C10 C 0.9668(5) 0.6131(5) 0.5080(8) 0.0382(19) Uani 1 1 d . . . H10B H 0.9014 0.5961 0.4594 0.046 Uiso 1 1 calc R . . H10A H 0.9846 0.5834 0.4446 0.046 Uiso 1 1 calc R . . C11 C 1.0244(7) 0.5629(6) 0.6635(9) 0.054(2) Uani 1 1 d . . . H11C H 1.0895 0.5768 0.7103 0.08 Uiso 1 1 calc R . . H11B H 1.0137 0.4876 0.6536 0.08 Uiso 1 1 calc R . . H11A H 1.0072 0.5921 0.7268 0.08 Uiso 1 1 calc R . . C12 C 1.0362(5) 0.8988(6) 0.8551(7) 0.0342(17) Uani 1 1 d . . . H12B H 1.0189 0.9549 0.8964 0.041 Uiso 1 1 calc R . . H12A H 1.0192 0.8317 0.8774 0.041 Uiso 1 1 calc R . . C13 C 1.1858(7) 0.8254(7) 1.0650(9) 0.054(2) Uani 1 1 d . . . H13B H 1.1619 0.7544 1.0263 0.065 Uiso 1 1 calc R . . H13A H 1.2521 0.8254 1.1088 0.065 Uiso 1 1 calc R . . C14 C 1.1738(8) 0.8506(9) 1.1855(11) 0.072(3) Uani 1 1 d . . . H14C H 1.1992 0.9198 1.2265 0.108 Uiso 1 1 calc R . . H14B H 1.206 0.7987 1.2664 0.108 Uiso 1 1 calc R . . H14A H 1.1084 0.8498 1.1431 0.108 Uiso 1 1 calc R . . C15 C 1.1729(5) 1.0099(6) 0.9761(9) 0.045(2) Uani 1 1 d . . . H15B H 1.1606 1.0382 1.0473 0.054 Uiso 1 1 calc R . . H15A H 1.1384 1.053 0.8833 0.054 Uiso 1 1 calc R . . C16 C 1.2737(6) 1.0201(8) 1.0462(10) 0.064(3) Uani 1 1 d . . . H16C H 1.3086 0.979 1.1395 0.097 Uiso 1 1 calc R . . H16B H 1.2917 1.0934 1.0695 0.097 Uiso 1 1 calc R . . H16A H 1.2863 0.9944 0.9753 0.097 Uiso 1 1 calc R . . O O 1.0107(5) 0.9707(5) 0.5928(8) 0.039(3) Uani 0.684(17) 1 d P . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Br1 0.0323(4) 0.0514(5) 0.0327(4) -0.0048(4) 0.0174(4) 0.0006(4) Br2 0.0659(6) 0.0478(5) 0.0371(5) 0.0048(4) 0.0286(5) -0.0076(5) P 0.0369(12) 0.0296(10) 0.0274(10) -0.0013(8) 0.0177(10) 0.0028(9) N1 0.028(4) 0.026(3) 0.020(3) -0.003(2) 0.009(3) 0.001(3) N2 0.041(4) 0.037(4) 0.026(3) -0.002(3) 0.019(3) 0.010(3) C1 0.045(5) 0.019(3) 0.034(4) -0.002(3) 0.025(4) 0.005(3) C2 0.066(6) 0.049(5) 0.035(5) 0.011(4) 0.030(5) 0.014(5) C3 0.070(7) 0.045(5) 0.048(5) 0.019(4) 0.028(5) 0.033(5) C4 0.057(6) 0.066(6) 0.051(5) 0.010(5) 0.034(5) 0.024(5) C5 0.062(6) 0.062(6) 0.075(7) 0.006(5) 0.049(6) 0.014(5) C6 0.059(6) 0.046(5) 0.060(6) 0.007(4) 0.039(5) 0.017(4) C7 0.031(4) 0.042(4) 0.028(4) -0.005(3) 0.018(4) -0.007(4) C8 0.036(5) 0.038(4) 0.023(4) -0.003(3) 0.017(4) -0.002(4) C9 0.057(6) 0.055(5) 0.040(5) 0.000(4) 0.034(5) 0.001(4) C10 0.045(5) 0.025(4) 0.048(5) -0.008(3) 0.029(5) -0.001(4) C11 0.081(7) 0.027(4) 0.058(6) 0.007(4) 0.043(6) 0.004(4) C12 0.035(5) 0.036(4) 0.030(4) -0.008(3) 0.018(4) 0.002(3) C13 0.066(6) 0.056(6) 0.036(5) 0.013(4) 0.027(5) 0.013(5) C14 0.066(8) 0.104(9) 0.037(6) 0.014(5) 0.025(6) 0.010(6) C15 0.044(6) 0.035(4) 0.049(5) -0.008(4) 0.024(5) -0.004(4) C16 0.048(6) 0.074(7) 0.053(6) -0.001(5) 0.019(5) -0.013(5) O 0.042(5) 0.045(5) 0.033(5) 0.002(3) 0.024(4) -0.001(4) #----------------------------------------------------------------------------# # MOLECULAR GEOMETRY # #----------------------------------------------------------------------------# _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag P O 1.426(7) . ? P C1 1.800(7) . ? P C12 1.825(7) . ? P C7 1.853(7) . ? N1 C7 1.504(9) . ? N1 C8 1.514(8) . ? N1 C10 1.521(9) . ? N2 C12 1.489(9) . ? N2 C15 1.493(10) . ? N2 C13 1.496(10) . ? C1 C2 1.382(10) . ? C1 C6 1.384(11) . ? C2 C3 1.398(12) . ? C3 C4 1.369(13) . ? C4 C5 1.365(12) . ? C5 C6 1.387(12) . ? C8 C9 1.527(10) . ? C10 C11 1.519(10) . ? C13 C14 1.483(13) . ? C15 C16 1.504(12) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O P C1 115.8(4) . . ? O P C12 116.6(4) . . ? C1 P C12 101.3(3) . . ? O P C7 116.1(4) . . ? C1 P C7 101.0(3) . . ? C12 P C7 103.7(3) . . ? C7 N1 C8 110.6(5) . . ? C7 N1 C10 110.2(6) . . ? C8 N1 C10 111.4(5) . . ? C12 N2 C15 110.7(6) . . ? C12 N2 C13 112.5(6) . . ? C15 N2 C13 114.8(6) . . ? C2 C1 C6 119.4(8) . . ? C2 C1 P 118.9(6) . . ? C6 C1 P 121.8(6) . . ? C1 C2 C3 119.7(8) . . ? C4 C3 C2 120.2(8) . . ? C5 C4 C3 120.1(9) . . ? C4 C5 C6 120.4(9) . . ? C1 C6 C5 120.1(8) . . ? N1 C7 P 115.1(5) . . ? N1 C8 C9 112.8(6) . . ? C11 C10 N1 112.5(6) . . ? N2 C12 P 115.7(5) . . ? C14 C13 N2 112.6(7) . . ? N2 C15 C16 114.2(7) . . ? #===END data_feb1801 _database_code_CSD 201301 _audit_creation_date 2001-02-13T09:57:06-00:00 _audit_creation_method 'WinGX routine CIF_UPDATE' _audit_conform_dict_name cif_core.dic _audit_conform_dict_version 2.1 _audit_conform_dict_location ftp://ftp.iucr.org/cifdics/cif_core.dic #----------------------------------------------------------------------------# # CHEMICAL INFORMATION # #----------------------------------------------------------------------------# _chemical_name_systematic ; ? ; _chemical_name_common [Ni3Br6(thf)5] _chemical_formula_sum 'C20 H40 Br6 Ni3 O5' _chemical_formula_weight 1016.11 #----------------------------------------------------------------------------# # UNIT CELL INFORMATION # #----------------------------------------------------------------------------# _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M P2(1)/m loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z' '-x, -y, -z' 'x, -y-1/2, z' _cell_length_a 7.5876(11) _cell_length_b 21.728(3) _cell_length_c 9.1261(12) _cell_angle_alpha 90 _cell_angle_beta 92.690(5) _cell_angle_gamma 90 _cell_volume 1502.9(3) _cell_formula_units_Z 2 _cell_measurement_temperature 173(2) _cell_measurement_reflns_used 55160 _cell_measurement_theta_min 3.705 _cell_measurement_theta_max 21.967 #----------------------------------------------------------------------------# # CRYSTAL INFORMATION # #----------------------------------------------------------------------------# _exptl_crystal_size_max 0.2 _exptl_crystal_size_mid 0.1 _exptl_crystal_size_min 0.01 _exptl_crystal_density_diffrn 2.245 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 988 _exptl_special_details ; ? ; #----------------------------------------------------------------------------# # ABSORPTION CORRECTION # #----------------------------------------------------------------------------# _exptl_absorpt_coefficient_mu 9.865 _exptl_absorpt_factor_mur 0.926 _exptl_absorpt_correction_type refdelf _exptl_absorpt_process_details ; Sheldrick, G.M. (anon) SHELX97 Release 97-2 (1998) I/sigma threshold for reflections = 5.000 Delta(U)/lambda**2 = 0.000 Highest even order spherical harmonic = 6 Highest odd order spherical harmonic = 3 ; _exptl_absorpt_correction_T_min 0.243 _exptl_absorpt_correction_T_max 0.908 #----------------------------------------------------------------------------# # DATA COLLECTION # #----------------------------------------------------------------------------# _diffrn_ambient_temperature 173(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_monochromator graphite _diffrn_measurement_device KappaCCD _diffrn_measurement_method CCD _diffrn_reflns_number 4980 _diffrn_reflns_av_R_equivalents 0.0805 _diffrn_reflns_av_unetI/netI 0.0708 _diffrn_reflns_limit_h_min -7 _diffrn_reflns_limit_h_max 7 _diffrn_reflns_limit_k_min -22 _diffrn_reflns_limit_k_max 22 _diffrn_reflns_limit_l_min -9 _diffrn_reflns_limit_l_max 9 _diffrn_reflns_theta_min 3.75 _diffrn_reflns_theta_max 21.93 _diffrn_reflns_theta_full 21.93 _diffrn_measured_fraction_theta_full 0.963 _diffrn_measured_fraction_theta_max 0.963 _reflns_number_total 1809 _reflns_number_gt 1357 _reflns_threshold_expression >2sigma(I) #----------------------------------------------------------------------------# # COMPUTER PROGRAMS USED # #----------------------------------------------------------------------------# _computing_cell_refinement 'HKL Scalepack (Otwinowski & Minor 1997)' _computing_data_reduction 'HKL Denzo and Scalepack (Otwinowski & Minor 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' #----------------------------------------------------------------------------# # REFINEMENT INFORMATION # #----------------------------------------------------------------------------# _refine_special_details ; The compound crystallises as extremely thin plates stuck together in bundles. The fragment used was of irregular outline. I felt that , in these circumstances, an absorption correction of the refdelf type was reasonable. However, obviously, the displacement ellipsoids should be treated with caution. Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0819P)^2^+20.5544P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment riding _refine_ls_extinction_method none _refine_ls_number_reflns 1809 _refine_ls_number_parameters 163 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0926 _refine_ls_R_factor_gt 0.0698 _refine_ls_wR_factor_ref 0.1893 _refine_ls_wR_factor_gt 0.1768 _refine_ls_goodness_of_fit_ref 1.137 _refine_ls_restrained_S_all 1.137 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0 _refine_diff_density_max 1.68 _refine_diff_density_min -0.855 _refine_diff_density_rms 0.215 #----------------------------------------------------------------------------# # ATOMIC TYPES, COORDINATES AND THERMAL PARAMETERS # #----------------------------------------------------------------------------# loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0 0 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Ni Ni 0.3393 1.1124 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.006 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Ni1 Ni 0.0141(3) 0.41664(8) 0.9638(2) 0.0268(6) Uani 1 1 d . . . Ni2 Ni 0.0538(4) 0.25 0.8981(3) 0.0307(8) Uani 1 2 d S . . Br1 Br -0.1870(2) 0.50396(7) 0.88072(16) 0.0307(5) Uani 1 1 d . . . Br2 Br -0.1556(2) 0.33302(7) 0.81060(17) 0.0323(5) Uani 1 1 d . . . Br3 Br 0.2144(2) 0.32932(7) 1.04762(18) 0.0366(6) Uani 1 1 d . . . O1 O 0.1758(13) 0.4323(5) 0.7859(10) 0.033(3) Uani 1 1 d . . . O2 O -0.1495(13) 0.3983(5) 1.1414(10) 0.034(3) Uani 1 1 d . . . O3 O 0.205(2) 0.25 0.7233(16) 0.047(4) Uani 1 2 d S . . C1 C 0.108(3) 0.4378(10) 0.6364(17) 0.052(5) Uani 1 1 d . . . H1A H 0.0315 0.4744 0.625 0.062 Uiso 1 1 calc R . . H1B H 0.0388 0.4009 0.6073 0.062 Uiso 1 1 calc R . . C2 C 0.263(3) 0.4439(10) 0.5444(19) 0.058(6) Uani 1 1 d . . . H2A H 0.2548 0.4822 0.4858 0.069 Uiso 1 1 calc R . . H2B H 0.2696 0.4085 0.4765 0.069 Uiso 1 1 calc R . . C3 C 0.423(2) 0.4455(10) 0.6463(17) 0.054(5) Uani 1 1 d . . . H3A H 0.5064 0.4128 0.6201 0.065 Uiso 1 1 calc R . . H3B H 0.4831 0.4858 0.639 0.065 Uiso 1 1 calc R . . C4 C 0.367(3) 0.4362(10) 0.7948(19) 0.056(5) Uani 1 1 d . . . H4A H 0.4182 0.3977 0.8363 0.068 Uiso 1 1 calc R . . H4B H 0.4057 0.471 0.8584 0.068 Uiso 1 1 calc R . . C5 C -0.338(2) 0.3848(10) 1.1316(18) 0.055(5) Uani 1 1 d . . . H5A H -0.362 0.3514 1.0596 0.066 Uiso 1 1 calc R . . H5B H -0.4041 0.4217 1.0971 0.066 Uiso 1 1 calc R . . C6 C -0.399(3) 0.3659(12) 1.276(2) 0.075(7) Uani 1 1 d . . . H6A H -0.4626 0.3262 1.2693 0.09 Uiso 1 1 calc R . . H6B H -0.4773 0.3974 1.3164 0.09 Uiso 1 1 calc R . . C7 C -0.227(3) 0.3599(17) 1.370(3) 0.130(14) Uani 1 1 d . . . H7A H -0.232 0.3856 1.4594 0.156 Uiso 1 1 calc R . . H7B H -0.2076 0.3166 1.4004 0.156 Uiso 1 1 calc R . . C8 C -0.087(3) 0.3801(10) 1.2830(18) 0.056(6) Uani 1 1 d . . . H8A H -0.0254 0.4152 1.3322 0.067 Uiso 1 1 calc R . . H8B H -0.0002 0.3464 1.2744 0.067 Uiso 1 1 calc R . . C9 C 0.140(4) 0.25 0.575(2) 0.053(7) Uani 1 2 d S . . H9A H 0.067 0.287 0.555 0.063 Uiso 0.5 1 calc PR . . H9B H 0.067 0.213 0.555 0.063 Uiso 0.5 1 calc PR . . C10 C 0.294(4) 0.25 0.483(3) 0.058(8) Uani 1 2 d S . . H10A H 0.2912 0.287 0.4193 0.07 Uiso 0.5 1 calc PR . . H10B H 0.2912 0.213 0.4193 0.07 Uiso 0.5 1 calc PR . . C11 C 0.456(3) 0.25 0.581(2) 0.051(7) Uani 1 2 d S . . H11A H 0.5279 0.213 0.5619 0.061 Uiso 0.5 1 calc PR . . H11B H 0.5279 0.287 0.5619 0.061 Uiso 0.5 1 calc PR . . C12 C 0.402(3) 0.25 0.733(3) 0.050(7) Uani 1 2 d S . . H12A H 0.4478 0.287 0.7858 0.06 Uiso 0.5 1 calc PR . . H12B H 0.4478 0.213 0.7858 0.06 Uiso 0.5 1 calc PR . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Ni1 0.0298(12) 0.0239(12) 0.0269(11) 0.0021(8) 0.0029(9) -0.0018(8) Ni2 0.0322(19) 0.0249(16) 0.0347(17) 0 -0.0016(14) 0 Br1 0.0339(10) 0.0278(9) 0.0304(9) 0.0008(6) 0.0003(7) -0.0018(7) Br2 0.0343(10) 0.0267(10) 0.0357(10) -0.0007(6) -0.0010(8) -0.0009(7) Br3 0.0384(11) 0.0292(9) 0.0414(11) -0.0001(7) -0.0049(8) -0.0005(7) O1 0.018(6) 0.055(7) 0.028(6) 0.008(5) 0.008(5) -0.008(5) O2 0.022(6) 0.056(7) 0.024(6) 0.009(5) 0.008(5) -0.004(5) O3 0.052(12) 0.060(12) 0.029(9) 0 0.002(8) 0 C1 0.042(12) 0.080(14) 0.034(10) -0.002(9) 0.000(9) 0.010(10) C2 0.062(14) 0.078(15) 0.034(10) 0.018(9) 0.022(10) -0.012(11) C3 0.040(12) 0.096(16) 0.028(9) 0.003(10) 0.010(8) 0.002(11) C4 0.045(13) 0.081(15) 0.043(11) 0.004(10) -0.006(10) -0.003(11) C5 0.047(13) 0.086(16) 0.034(10) 0.012(10) 0.010(9) -0.008(11) C6 0.087(18) 0.087(17) 0.053(13) -0.004(12) 0.023(13) 0.000(14) C7 0.053(17) 0.24(4) 0.088(19) 0.09(2) -0.040(16) -0.07(2) C8 0.047(13) 0.093(16) 0.028(10) 0.014(10) 0.001(9) -0.008(11) C9 0.041(17) 0.08(2) 0.033(15) 0 0.005(13) 0 C10 0.10(3) 0.051(17) 0.025(13) 0 0.012(16) 0 C11 0.052(19) 0.08(2) 0.027(13) 0 0.017(13) 0 C12 0.018(14) 0.08(2) 0.050(16) 0 -0.018(12) 0 #----------------------------------------------------------------------------# # MOLECULAR GEOMETRY # #----------------------------------------------------------------------------# _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Ni1 O1 2.108(10) . ? Ni1 O2 2.125(10) . ? Ni1 Br3 2.527(2) . ? Ni1 Br1 2.529(2) . ? Ni1 Br1 2.557(2) 3_567 ? Ni1 Br2 2.597(2) . ? Ni2 O3 2.009(17) . ? Ni2 Br3 2.482(2) . ? Ni2 Br3 2.482(2) 4_565 ? Ni2 Br2 2.509(2) 4_565 ? Ni2 Br2 2.509(2) . ? Br1 Ni1 2.557(2) 3_567 ? O1 C1 1.439(18) . ? O1 C4 1.45(2) . ? O2 C8 1.413(18) . ? O2 C5 1.46(2) . ? O3 C9 1.42(3) . ? O3 C12 1.50(3) . ? C1 C2 1.48(3) . ? C2 C3 1.49(2) . ? C3 C4 1.45(2) . ? C5 C6 1.47(3) . ? C6 C7 1.54(3) . ? C7 C8 1.43(3) . ? C9 C10 1.47(4) . ? C10 C11 1.49(4) . ? C11 C12 1.47(3) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O1 Ni1 O2 178.4(4) . . ? O1 Ni1 Br3 89.5(3) . . ? O2 Ni1 Br3 89.6(3) . . ? O1 Ni1 Br1 90.8(3) . . ? O2 Ni1 Br1 90.2(3) . . ? Br3 Ni1 Br1 179.78(11) . . ? O1 Ni1 Br1 91.0(3) . 3_567 ? O2 Ni1 Br1 90.3(3) . 3_567 ? Br3 Ni1 Br1 93.02(8) . 3_567 ? Br1 Ni1 Br1 86.96(7) . 3_567 ? O1 Ni1 Br2 89.4(3) . . ? O2 Ni1 Br2 89.2(3) . . ? Br3 Ni1 Br2 85.05(7) . . ? Br1 Ni1 Br2 94.97(8) . . ? Br1 Ni1 Br2 178.03(9) 3_567 . ? O3 Ni2 Br3 98.8(3) . . ? O3 Ni2 Br3 98.8(3) . 4_565 ? Br3 Ni2 Br3 87.95(11) . 4_565 ? O3 Ni2 Br2 97.1(3) . 4_565 ? Br3 Ni2 Br2 164.00(14) . 4_565 ? Br3 Ni2 Br2 87.88(5) 4_565 4_565 ? O3 Ni2 Br2 97.1(3) . . ? Br3 Ni2 Br2 87.88(5) . . ? Br3 Ni2 Br2 164.00(14) 4_565 . ? Br2 Ni2 Br2 91.91(11) 4_565 . ? Ni1 Br1 Ni1 93.04(7) . 3_567 ? Ni2 Br2 Ni1 92.35(8) . . ? Ni2 Br3 Ni1 94.70(8) . . ? C1 O1 C4 111.0(12) . . ? C1 O1 Ni1 123.3(10) . . ? C4 O1 Ni1 125.6(9) . . ? C8 O2 C5 106.7(12) . . ? C8 O2 Ni1 124.5(10) . . ? C5 O2 Ni1 126.7(9) . . ? C9 O3 C12 111.1(19) . . ? C9 O3 Ni2 124.8(15) . . ? C12 O3 Ni2 124.0(13) . . ? O1 C1 C2 106.8(14) . . ? C1 C2 C3 106.9(14) . . ? C4 C3 C2 108.3(15) . . ? O1 C4 C3 106.9(13) . . ? O2 C5 C6 110.4(15) . . ? C5 C6 C7 103.3(19) . . ? C8 C7 C6 107.4(18) . . ? O2 C8 C7 111.6(16) . . ? O3 C9 C10 107(2) . . ? C9 C10 C11 108.1(19) . . ? C12 C11 C10 108(2) . . ? C11 C12 O3 105.2(18) . . ? #===END