#------------------------------------------------------------------------------
#$Date: 2016-03-25 16:19:32 +0200 (Fri, 25 Mar 2016) $
#$Revision: 179963 $
#$URL: svn://www.crystallography.net/cod/cif/7/02/57/7025718.cif $
#------------------------------------------------------------------------------
#
# This file is available in the Crystallography Open Database (COD),
# http://www.crystallography.net/
#
# All data on this site have been placed in the public domain by the
# contributors.
#
data_7025718
loop_
_publ_author_name
'Bettucci, Lorenzo'
'Bianchini, Claudio'
'Oberhauser, Werner'
'Vogt, Matthias'
'Grützmacher, Hansjörg'
_publ_section_title
;
 Chemoselective methoxycarbonylation of terminal alkynes catalyzed by
 Pd(II)-TROPP complexes.
;
_journal_issue                   28
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              6509
_journal_page_last               6517
_journal_paper_doi               10.1039/c002976a
_journal_volume                  39
_journal_year                    2010
_chemical_formula_moiety         'C31 H28 O P Pd,(P F6), 0.5 (C6 H6)'
_chemical_formula_sum            'C34 H31 F6 O P2 Pd'
_chemical_formula_weight         737.93
_chemical_name_common            (Pd(CH2CH2COCH3)(trop))(PF6)
_chemical_name_systematic        '[Pd(CH2CH2COCH3)(trop)](PF6)'
_space_group_IT_number           14
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2010-04-19T18:43:42-00:00
_audit_creation_method           'WinGX routine CIF_UPDATE'
_cell_angle_alpha                90
_cell_angle_beta                 110.763(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.9962(5)
_cell_length_b                   8.9054(2)
_cell_length_c                   21.4435(5)
_cell_measurement_temperature    180.2(2)
_cell_volume                     3213.42(15)
_computing_molecular_graphics    'ORTEP-3 (Farrugia, 1997)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SIR-97 (J. Appl. Cryst. 1999, 32, 115)'
_diffrn_ambient_temperature      180.2(2)
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.895
_diffrn_measurement_device_type  'Xcalibur 3, Oxford diffraction'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71069
_diffrn_reflns_av_unetI/netI     0.0629
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            10409
_diffrn_reflns_theta_full        25
_diffrn_reflns_theta_max         32.48
_diffrn_reflns_theta_min         3.72
_exptl_absorpt_coefficient_mu    0.738
_exptl_absorpt_correction_T_max  0.849
_exptl_absorpt_correction_T_min  0.745
_exptl_absorpt_correction_type   empirical
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.525
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             1492
_exptl_crystal_size_max          0.40
_exptl_crystal_size_mid          0.30
_exptl_crystal_size_min          0.20
_refine_diff_density_max         1.576
_refine_diff_density_min         -0.846
_refine_diff_density_rms         0.111
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     383
_refine_ls_number_reflns         10409
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.04
_refine_ls_R_factor_all          0.089
_refine_ls_R_factor_gt           0.0509
_refine_ls_shift/su_max          0.015
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[σ²(Fo²)+(0.0939P)²+0.1666P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1371
_refine_ls_wR_factor_ref         0.1615
_reflns_number_gt                6560
_reflns_number_total             10409
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c002976a.txt
_cod_data_source_block           trop180k
_cod_original_cell_volume        3213.42(14)
_cod_original_sg_symbol_H-M      'P 21/c'
_cod_database_code               7025718
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y-1/2, z-1/2'
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
Pd1 Pd 0.247155(14) 0.43560(3) 0.802247(11) 0.02894(9) Uani 1 1 d .
P1 P 0.19970(5) 0.55814(9) 0.70732(4) 0.02668(16) Uani 1 1 d .
P2 P 0.19299(7) 0.81877(12) 0.47970(5) 0.0494(3) Uani 1 1 d .
O1 O 0.27803(15) 0.2985(3) 0.88898(11) 0.0382(5) Uani 1 1 d .
F1 F 0.2654(3) 0.7395(4) 0.4694(3) 0.1306(16) Uani 1 1 d .
F2 F 0.1360(2) 0.7373(5) 0.41617(13) 0.1045(12) Uani 1 1 d .
F3 F 0.1200(2) 0.8924(4) 0.49430(19) 0.0910(10) Uani 1 1 d .
F4 F 0.2519(2) 0.8905(4) 0.54791(17) 0.0935(10) Uani 1 1 d .
F5 F 0.2054(4) 0.9596(5) 0.4428(3) 0.156(2) Uani 1 1 d .
F6 F 0.1819(2) 0.6775(3) 0.52174(15) 0.0860(9) Uani 1 1 d .
C1 C 0.2845(2) 0.6557(4) 0.69370(16) 0.0316(6) Uani 1 1 d .
H1 H 0.2644 0.7016 0.6493 0.038 Uiso 1 1 calc R
C2 C 0.3512(2) 0.5510(4) 0.69597(17) 0.0357(7) Uani 1 1 d .
C3 C 0.3696(3) 0.5345(5) 0.6384(2) 0.0511(10) Uani 1 1 d .
H3 H 0.3424 0.5907 0.6006 0.061 Uiso 1 1 calc R
C4 C 0.4285(3) 0.4346(5) 0.6372(3) 0.0626(13) Uani 1 1 d .
H4 H 0.4424 0.4284 0.5994 0.075 Uiso 1 1 calc R
C5 C 0.4658(3) 0.3458(6) 0.6907(3) 0.0662(13) Uani 1 1 d .
H5 H 0.5026 0.2747 0.6884 0.079 Uiso 1 1 calc R
C6 C 0.4489(2) 0.3615(5) 0.7489(2) 0.0552(10) Uani 1 1 d .
H6 H 0.4759 0.3022 0.7857 0.066 Uiso 1 1 calc R
C7 C 0.3920(2) 0.4651(4) 0.75310(19) 0.0386(8) Uani 1 1 d .
C8 C 0.3793(2) 0.4775(4) 0.81656(18) 0.0393(8) Uani 1 1 d .
H8 H 0.3892 0.3912 0.8427 0.047 Uiso 1 1 calc R
C9 C 0.3547(2) 0.5999(4) 0.84214(16) 0.0371(7) Uani 1 1 d .
H9 H 0.3464 0.5857 0.8821 0.045 Uiso 1 1 calc R
C10 C 0.3400(2) 0.7502(4) 0.81389(16) 0.0351(7) Uani 1 1 d .
C11 C 0.3569(2) 0.8711(5) 0.8582(2) 0.0465(9) Uani 1 1 d .
H11 H 0.3729 0.8522 0.9037 0.056 Uiso 1 1 calc R
C12 C 0.3506(3) 1.0184(5) 0.8362(2) 0.0511(10) Uani 1 1 d .
H12 H 0.364 1.0973 0.8665 0.061 Uiso 1 1 calc R
C13 C 0.3242(3) 1.0461(4) 0.7690(3) 0.0554(11) Uani 1 1 d .
H13 H 0.3194 1.1447 0.7538 0.067 Uiso 1 1 calc R
C14 C 0.3046(2) 0.9292(4) 0.7235(2) 0.0431(8) Uani 1 1 d .
H14 H 0.2865 0.9503 0.678 0.052 Uiso 1 1 calc R
C15 C 0.31155(19) 0.7812(4) 0.74463(16) 0.0333(7) Uani 1 1 d .
C16 C 0.13370(18) 0.7111(3) 0.70490(15) 0.0294(6) Uani 1 1 d .
C17 C 0.1177(2) 0.7477(4) 0.76223(16) 0.0332(7) Uani 1 1 d .
H17 H 0.137 0.687 0.7998 0.04 Uiso 1 1 calc R
C18 C 0.0729(2) 0.8742(4) 0.76342(18) 0.0415(8) Uani 1 1 d .
H18 H 0.0631 0.8991 0.8019 0.05 Uiso 1 1 calc R
C19 C 0.0431(2) 0.9633(4) 0.7070(2) 0.0421(8) Uani 1 1 d .
H19 H 0.0127 1.0473 0.7077 0.051 Uiso 1 1 calc R
C20 C 0.0579(2) 0.9289(4) 0.6496(2) 0.0420(8) Uani 1 1 d .
H20 H 0.0378 0.9896 0.6121 0.05 Uiso 1 1 calc R
C21 C 0.1031(2) 0.8029(4) 0.64844(15) 0.0345(7) Uani 1 1 d .
H21 H 0.113 0.7794 0.6099 0.041 Uiso 1 1 calc R
C22 C 0.1519(2) 0.4378(3) 0.63664(15) 0.0317(7) Uani 1 1 d .
C23 C 0.0719(2) 0.4463(4) 0.60102(18) 0.0410(8) Uani 1 1 d .
H23 H 0.0418 0.5219 0.6105 0.049 Uiso 1 1 calc R
C24 C 0.0348(3) 0.3415(5) 0.55025(18) 0.0517(10) Uani 1 1 d .
H24 H -0.0194 0.3475 0.5263 0.062 Uiso 1 1 calc R
C25 C 0.0800(3) 0.2296(5) 0.53639(18) 0.0535(11) Uani 1 1 d .
H25 H 0.056 0.1604 0.5028 0.064 Uiso 1 1 calc R
C26 C 0.1593(3) 0.2203(5) 0.57180(19) 0.0506(10) Uani 1 1 d .
H26 H 0.1892 0.1453 0.5617 0.061 Uiso 1 1 calc R
C27 C 0.1964(2) 0.3221(4) 0.62311(17) 0.0394(8) Uani 1 1 d .
H27 H 0.2503 0.3128 0.648 0.047 Uiso 1 1 calc R
C28 C 0.1422(2) 0.3220(4) 0.77880(17) 0.0399(8) Uani 1 1 d .
H28A H 0.0976 0.3881 0.7572 0.048 Uiso 1 1 calc R
H28B H 0.1404 0.2387 0.7492 0.048 Uiso 1 1 calc R
C29 C 0.1398(2) 0.2653(5) 0.84540(19) 0.0461(9) Uani 1 1 d .
H29A H 0.114 0.34 0.8637 0.055 Uiso 1 1 calc R
H29B H 0.1083 0.1742 0.8378 0.055 Uiso 1 1 calc R
C30 C 0.2193(2) 0.2344(4) 0.89393(17) 0.0400(8) Uani 1 1 d .
C31 C 0.2310(3) 0.1264(5) 0.9501(2) 0.0675(14) Uani 1 1 d .
H31A H 0.2822 0.1427 0.9838 0.101 Uiso 1 1 calc R
H31B H 0.2279 0.0255 0.9336 0.101 Uiso 1 1 calc R
H31C H 0.1903 0.1418 0.9688 0.101 Uiso 1 1 calc R
C32 C 0.5333(7) 0.3643(14) 0.9697(6) 0.175(4) Uiso 1 1 d D
H32 H 0.5559 0.2892 0.9521 0.21 Uiso 1 1 calc R
C33 C 0.4702(6) 0.3545(11) 0.9942(5) 0.150(3) Uiso 1 1 d D
H33 H 0.4444 0.2631 0.9922 0.18 Uiso 1 1 calc R
C34 C 0.4464(6) 0.4757(10) 1.0205(4) 0.132(3) Uiso 1 1 d D
H34 H 0.4064 0.4508 1.0367 0.158 Uiso 1 1 calc R
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'
O O 0.0106 0.006 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
F F 0.0171 0.0103 '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'
Pd Pd -0.9988 1.0072 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
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
C28 Pd1 O1 82.14(13) . .
C28 Pd1 P1 89.77(10) . .
O1 Pd1 P1 171.85(7) . .
C28 Pd1 C8 158.20(15) . .
O1 Pd1 C8 92.23(11) . .
P1 Pd1 C8 94.95(9) . .
C28 Pd1 C9 167.27(14) . .
O1 Pd1 C9 96.53(11) . .
P1 Pd1 C9 91.58(9) . .
C8 Pd1 C9 34.08(13) . .
C16 P1 C22 108.22(15) . .
C16 P1 C1 102.23(15) . .
C22 P1 C1 108.49(15) . .
C16 P1 Pd1 116.05(10) . .
C22 P1 Pd1 113.31(10) . .
C1 P1 Pd1 107.76(11) . .
F5 P2 F2 95.7(3) . .
F5 P2 F1 90.9(3) . .
F2 P2 F1 89.4(2) . .
F5 P2 F3 92.6(3) . .
F2 P2 F3 91.7(2) . .
F1 P2 F3 176.2(3) . .
F5 P2 F6 176.9(3) . .
F2 P2 F6 87.25(19) . .
F1 P2 F6 90.1(2) . .
F3 P2 F6 86.4(2) . .
F5 P2 F4 88.6(3) . .
F2 P2 F4 175.6(2) . .
F1 P2 F4 89.7(2) . .
F3 P2 F4 88.93(19) . .
F6 P2 F4 88.5(2) . .
C30 O1 Pd1 111.9(2) . .
C2 C1 C15 112.6(3) . .
C2 C1 P1 113.1(2) . .
C15 C1 P1 107.5(2) . .
C2 C1 H1 107.8 . .
C15 C1 H1 107.8 . .
P1 C1 H1 107.8 . .
C3 C2 C7 119.9(3) . .
C3 C2 C1 118.2(3) . .
C7 C2 C1 121.8(3) . .
C4 C3 C2 120.3(4) . .
C4 C3 H3 119.8 . .
C2 C3 H3 119.8 . .
C5 C4 C3 120.6(4) . .
C5 C4 H4 119.7 . .
C3 C4 H4 119.7 . .
C4 C5 C6 119.9(4) . .
C4 C5 H5 120.1 . .
C6 C5 H5 120.1 . .
C5 C6 C7 121.3(4) . .
C5 C6 H6 119.4 . .
C7 C6 H6 119.4 . .
C6 C7 C2 117.9(4) . .
C6 C7 C8 117.9(3) . .
C2 C7 C8 124.3(3) . .
C9 C8 C7 128.0(3) . .
C9 C8 Pd1 73.6(2) . .
C7 C8 Pd1 110.9(2) . .
C9 C8 H8 116 . .
C7 C8 H8 116 . .
Pd1 C8 H8 85.2 . .
C8 C9 C10 127.3(3) . .
C8 C9 Pd1 72.3(2) . .
C10 C9 Pd1 114.8(2) . .
C8 C9 H9 116.4 . .
C10 C9 H9 116.4 . .
Pd1 C9 H9 82.5 . .
C11 C10 C15 118.3(3) . .
C11 C10 C9 117.5(3) . .
C15 C10 C9 124.1(3) . .
C12 C11 C10 121.8(4) . .
C12 C11 H11 119.1 . .
C10 C11 H11 119.1 . .
C13 C12 C11 119.0(4) . .
C13 C12 H12 120.5 . .
C11 C12 H12 120.5 . .
C12 C13 C14 120.9(4) . .
C12 C13 H13 119.6 . .
C14 C13 H13 119.6 . .
C13 C14 C15 120.9(4) . .
C13 C14 H14 119.6 . .
C15 C14 H14 119.6 . .
C14 C15 C10 119.1(3) . .
C14 C15 C1 119.8(3) . .
C10 C15 C1 121.0(3) . .
C17 C16 C21 118.9(3) . .
C17 C16 P1 119.5(2) . .
C21 C16 P1 121.4(2) . .
C18 C17 C16 120.4(3) . .
C18 C17 H17 119.8 . .
C16 C17 H17 119.8 . .
C19 C18 C17 119.7(3) . .
C19 C18 H18 120.2 . .
C17 C18 H18 120.2 . .
C20 C19 C18 120.8(3) . .
C20 C19 H19 119.6 . .
C18 C19 H19 119.6 . .
C19 C20 C21 119.6(3) . .
C19 C20 H20 120.2 . .
C21 C20 H20 120.2 . .
C20 C21 C16 120.5(3) . .
C20 C21 H21 119.7 . .
C16 C21 H21 119.7 . .
C23 C22 C27 119.4(3) . .
C23 C22 P1 121.8(3) . .
C27 C22 P1 118.3(3) . .
C22 C23 C24 120.6(4) . .
C22 C23 H23 119.7 . .
C24 C23 H23 119.7 . .
C25 C24 C23 119.4(4) . .
C25 C24 H24 120.3 . .
C23 C24 H24 120.3 . .
C26 C25 C24 120.2(4) . .
C26 C25 H25 119.9 . .
C24 C25 H25 119.9 . .
C25 C26 C27 120.9(4) . .
C25 C26 H26 119.5 . .
C27 C26 H26 119.5 . .
C22 C27 C26 119.5(4) . .
C22 C27 H27 120.3 . .
C26 C27 H27 120.3 . .
C29 C28 Pd1 105.3(2) . .
C29 C28 H28A 110.7 . .
Pd1 C28 H28A 110.7 . .
C29 C28 H28B 110.7 . .
Pd1 C28 H28B 110.7 . .
H28A C28 H28B 108.8 . .
C30 C29 C28 112.4(3) . .
C30 C29 H29A 109.1 . .
C28 C29 H29A 109.1 . .
C30 C29 H29B 109.1 . .
C28 C29 H29B 109.1 . .
H29A C29 H29B 107.8 . .
O1 C30 C29 120.0(3) . .
O1 C30 C31 119.0(4) . .
C29 C30 C31 121.0(4) . .
C30 C31 H31A 109.5 . .
C30 C31 H31B 109.5 . .
H31A C31 H31B 109.5 . .
C30 C31 H31C 109.5 . .
H31A C31 H31C 109.5 . .
H31B C31 H31C 109.5 . .
C33 C32 C34 101.5(10) . 3_667
C33 C32 H32 129.2 . .
C34 C32 H32 129.2 3_667 .
C34 C33 C32 121.3(11) . .
C34 C33 H33 119.4 . .
C32 C33 H33 119.3 . .
C33 C34 C32 137.1(9) . 3_667
C33 C34 H34 111.4 . .
C32 C34 H34 111.4 3_667 .
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
Pd1 C28 2.042(3) .
Pd1 O1 2.127(2) .
Pd1 P1 2.1981(8) .
Pd1 C8 2.318(4) .
Pd1 C9 2.333(3) .
P1 C16 1.796(3) .
P1 C22 1.806(3) .
P1 C1 1.867(3) .
P2 F5 1.541(3) .
P2 F2 1.563(3) .
P2 F1 1.566(4) .
P2 F3 1.595(3) .
P2 F6 1.601(3) .
P2 F4 1.604(3) .
O1 C30 1.239(4) .
C1 C2 1.506(5) .
C1 C15 1.517(5) .
C1 H1 0.98 .
C2 C3 1.396(5) .
C2 C7 1.410(5) .
C3 C4 1.390(6) .
C3 H3 0.93 .
C4 C5 1.359(7) .
C4 H4 0.93 .
C5 C6 1.393(6) .
C5 H5 0.93 .
C6 C7 1.406(5) .
C6 H6 0.93 .
C7 C8 1.462(5) .
C8 C9 1.363(5) .
C8 H8 0.93 .
C9 C10 1.454(5) .
C9 H9 0.93 .
C10 C11 1.397(5) .
C10 C15 1.416(5) .
C11 C12 1.385(6) .
C11 H11 0.93 .
C12 C13 1.370(7) .
C12 H12 0.93 .
C13 C14 1.385(6) .
C13 H13 0.93 .
C14 C15 1.385(5) .
C14 H14 0.93 .
C16 C17 1.397(4) .
C16 C21 1.402(4) .
C17 C18 1.390(5) .
C17 H17 0.93 .
C18 C19 1.387(5) .
C18 H18 0.93 .
C19 C20 1.382(5) .
C19 H19 0.93 .
C20 C21 1.391(5) .
C20 H20 0.93 .
C21 H21 0.93 .
C22 C23 1.373(5) .
C22 C27 1.397(5) .
C23 C24 1.410(5) .
C23 H23 0.93 .
C24 C25 1.383(6) .
C24 H24 0.93 .
C25 C26 1.361(6) .
C25 H25 0.93 .
C26 C27 1.399(5) .
C26 H26 0.93 .
C27 H27 0.93 .
C28 C29 1.530(5) .
C28 H28A 0.97 .
C28 H28B 0.97 .
C29 C30 1.466(6) .
C29 H29A 0.97 .
C29 H29B 0.97 .
C30 C31 1.497(5) .
C31 H31A 0.96 .
C31 H31B 0.96 .
C31 H31C 0.96 .
C32 C33 1.412(8) .
C32 C34 1.468(14) 3_667
C32 H32 0.93 .
C33 C34 1.356(8) .
C33 H33 0.93 .
C34 C32 1.468(14) 3_667
C34 H34 0.93 .
