Reactions of Rh(PNP) pincer complexes with terminal alkynes: homocoupling through a ring or not at all.
Hood, Thomas M.; Chaplin, Adrian B.; Dalton transactions (Cambridge, England : 2003) 49 (2020) 16649–16652; doi:10.1039/d0dt03550e

data_7705855
_publ_section_title
;
 Reactions of Rh(PNP) pincer complexes with terminal alkynes: homocoupling
 through a ring or not at all.
;
_journal_issue                   46
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              16649
_journal_page_last               16652
_journal_paper_doi               10.1039/d0dt03550e
_journal_volume                  49
_journal_year                    2020
_chemical_formula_moiety         'C39 H69 N O2 P2 Rh, C32 H12 B F24'
_chemical_formula_sum            'C71 H81 B F24 N O2 P2 Rh'
_chemical_formula_weight         1612.02
_chemical_melting_point          ?
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2020-07-22
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3510 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-08-27 deposited with the CCDC.	2020-11-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   26.22570(10)
_cell_length_b                   18.19050(10)
_cell_length_c                   15.82860(10)
_cell_measurement_reflns_used    67311
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      73.5250
_cell_measurement_theta_min      3.3200
_cell_volume                     7551.17(7)
_computing_cell_refinement       'CrysAlisPro 1.171.40.61a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.61a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.61a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3046
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w     17.00 116.00   1.00    2.50    --   41.82  37.00-150.00   99
  2  \w    -21.00  74.00   1.00    2.50    --   41.82 -77.00-150.00   95
  3  \w      6.00  83.00   1.00    2.50    --   41.82 -99.00 -90.00   77
  4  \w     97.00 178.00   1.00   10.00    --  107.00 125.00 150.00   81
  5  \w     78.00 178.00   1.00   10.00    --  107.00  61.00 120.00  100
  6  \w    104.00 178.00   1.00   10.00    --  107.00  99.00 136.00   74
  7  \w     97.00 178.00   1.00   10.00    --  107.00 125.00   0.00   81
  8  \w     34.00 112.00   1.00   10.00    --  107.00-125.00  90.00   78
  9  \w    103.00 178.00   1.00   10.00    --  107.00  77.00  60.00   75
 10  \w    103.00 178.00   1.00   10.00    --  107.00  77.00   0.00   75
 11  \w     24.00 107.00   1.00   10.00    --  107.00 -94.00  90.00   83
 12  \w    -66.00  33.00   1.00    2.50    --  -41.82  37.00 120.00   99
 13  \w     14.00 115.00   1.00    2.50    --   41.82  57.00  60.00  101
 14  \w     17.00 116.00   1.00    2.50    --   41.82  37.00 -30.00   99
 15  \w     78.00 178.00   1.00   10.00    --  107.00  61.00 -30.00  100
 16  \w     81.00 178.00   1.00   10.00    --  107.00  45.00-120.00   97
 17  \w     78.00 178.00   1.00   10.00    --  107.00  61.00-180.00  100
 18  \w     24.00 107.00   1.00   10.00    --  107.00 -94.00 150.00   83
 19  \w     78.00 178.00   1.00   10.00    --  107.00  61.00  60.00  100
 20  \w     81.00 178.00   1.00   10.00    --  107.00  45.00 -60.00   97
 21  \w   -114.00 -14.00   1.00    2.50    --  -41.82 -57.00  90.00  100
 22  \w   -114.00 -14.00   1.00    2.50    --  -41.82 -57.00-150.00  100
 23  \w     14.00 115.00   1.00    2.50    --   41.82  57.00   0.00  101
 24  \w     78.00 114.00   1.00   10.00    --  107.00  61.00   0.00   36
 25  \w     34.00 112.00   1.00   10.00    --  107.00-125.00   0.00   78
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'Rigaku Oxford Diffraction: SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0062373000
_diffrn_orient_matrix_UB_12      -0.0815460000
_diffrn_orient_matrix_UB_13      -0.0241178000
_diffrn_orient_matrix_UB_21      0.0552608000
_diffrn_orient_matrix_UB_22      0.0014147000
_diffrn_orient_matrix_UB_23      0.0328804000
_diffrn_orient_matrix_UB_31      -0.0189185000
_diffrn_orient_matrix_UB_32      -0.0228057000
_diffrn_orient_matrix_UB_33      0.0883801000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0353
_diffrn_reflns_av_unetI/netI     0.0208
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            96134
_diffrn_reflns_point_group_measured_fraction_full 0.956
_diffrn_reflns_point_group_measured_fraction_max 0.956
_diffrn_reflns_theta_full        70.067
_diffrn_reflns_theta_max         70.067
_diffrn_reflns_theta_min         6.328
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.140
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.353
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.61a (Rigaku Oxford Diffraction, 2019)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.418
_exptl_crystal_density_meas      ?
_exptl_crystal_description       block
_exptl_crystal_F_000             3304
_exptl_crystal_recrystallization_method
'Crystals grown from Et2O-SiMe4 at 293 K'
_exptl_crystal_size_max          0.29
_exptl_crystal_size_mid          0.226
_exptl_crystal_size_min          0.123
_refine_diff_density_max         1.008
_refine_diff_density_min         -0.365
_refine_diff_density_rms         0.054
_refine_ls_abs_structure_details
;
 Flack x determined using 5988 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.012(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     970
_refine_ls_number_reflns         13711
_refine_ls_number_restraints     541
_refine_ls_restrained_S_all      1.119
_refine_ls_R_factor_all          0.0340
_refine_ls_R_factor_gt           0.0323
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0564P)^2^+4.6160P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0864
_refine_ls_wR_factor_ref         0.0881
_reflns_Friedel_coverage         0.845
_reflns_Friedel_fraction_full    0.911
_reflns_Friedel_fraction_max     0.911
_reflns_number_gt                13478
_reflns_number_total             13711
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0dt03550e2.cif
_cod_data_source_block           0565abc19s
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_chemical_melting_point' value 'not measured' was changed
to '?' -- the value is undefined or not given.

data item '_exptl_crystal_density_meas' value 'not measured' was
changed to '?' -- the value is perceived as not measured.

Automatic conversion script
Id: cif_fix_values 7556 2019-12-06 15:28:31Z antanas 
;
_cod_database_code               7705855
_shelx_shelxl_version_number     2014/7
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C207-F1 \\sim C207-F2 \\sim C207-F3 \\sim C207-F1A \\sim C207-F2A \\sim
C207-F3A
 with sigma of 0.01
 F1-F2 \\sim F2-F3 \\sim F3-F1 \\sim F1A-F2A \\sim F2A-F3A \\sim F3A-F1A
 with sigma of 0.01
 C203-F1 \\sim C203-F2 \\sim C203-F3 \\sim C203-F1A \\sim C203-F2A \\sim
C203-F3A
 with sigma of 0.01
 C216-F10 \\sim C216-F11 \\sim C216-F12 \\sim C216-F10A \\sim C216-F11A \\sim
C216-F12A
 with sigma of 0.01
 F10-F11 \\sim F11-F12 \\sim F12-F10 \\sim F10A-F11A \\sim F11A-F12A \\sim
F12A-F10A
 with sigma of 0.01
 C213-F10 \\sim C213-F11 \\sim C213-F12 \\sim C213-F10A \\sim C213-F11A \\sim
C213-F12A
 with sigma of 0.01
 C223-F13 \\sim C223-F14 \\sim C223-F15 \\sim C223-F13A \\sim C223-F14A \\sim
C223-F15A
 with sigma of 0.01
 F13-F14 \\sim F14-F15 \\sim F15-F13 \\sim F13A-F14A \\sim F14A-F15A \\sim
F15A-F13A
 with sigma of 0.01
 C219-F13 \\sim C219-F14 \\sim C219-F15 \\sim C219-F13A \\sim C219-F14A \\sim
C219-F15A
 with sigma of 0.01
 C215-F7 \\sim C215-F8 \\sim C215-F9 \\sim C215-F7A \\sim C215-F8A \\sim
C215-F9A
 with sigma of 0.01
 F7-F8 \\sim F8-F9 \\sim F9-F7 \\sim F7A-F8A \\sim F8A-F9A \\sim F9A-F7A
 with sigma of 0.01
 C211-F7 \\sim C211-F8 \\sim C211-F9 \\sim C211-F7A \\sim C211-F8A \\sim
C211-F9A
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
F1 \\sim F1A \\sim F2 \\sim F2A \\sim F3 \\sim F3A \\sim F4 \\sim F5 \\sim F6
\\sim F7 \\sim F7A \\sim F8 \\sim F8A \\sim F9 \\sim F9A \\sim F10 \\sim F10A
\\sim F11 \\sim F11A \\sim F12 \\sim F12A \\sim F13 \\sim F13A \\sim F14 \\sim
F14A \\sim F15 \\sim F15A \\sim F16 \\sim F17 \\sim F18 \\sim F19 \\sim F20
\\sim F21 \\sim F22 \\sim F23 \\sim F24: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02
Uanis(F1) \\sim Ueq, Uanis(F1A) \\sim Ueq, Uanis(F2) \\sim Ueq, Uanis(F2A)
\\sim Ueq, Uanis(F3) \\sim Ueq, Uanis(F3A) \\sim Ueq, Uanis(F4) \\sim Ueq,
Uanis(F5) \\sim Ueq, Uanis(F6) \\sim Ueq, Uanis(F7) \\sim Ueq, Uanis(F7A) \\sim
Ueq, Uanis(F8) \\sim Ueq, Uanis(F8A) \\sim Ueq, Uanis(F9) \\sim Ueq, Uanis(F9A)
\\sim Ueq, Uanis(F10) \\sim Ueq, Uanis(F10A) \\sim Ueq, Uanis(F11) \\sim Ueq,
Uanis(F11A) \\sim Ueq, Uanis(F12) \\sim Ueq, Uanis(F12A) \\sim Ueq, Uanis(F13)
\\sim Ueq, Uanis(F13A) \\sim Ueq, Uanis(F14) \\sim Ueq, Uanis(F14A) \\sim Ueq,
Uanis(F15) \\sim Ueq, Uanis(F15A) \\sim Ueq, Uanis(F16) \\sim Ueq, Uanis(F17)
\\sim Ueq, Uanis(F18) \\sim Ueq, Uanis(F19) \\sim Ueq, Uanis(F20) \\sim Ueq,
Uanis(F21) \\sim Ueq, Uanis(F22) \\sim Ueq, Uanis(F23) \\sim Ueq, Uanis(F24)
\\sim Ueq: with sigma of 0.007 and sigma for terminal atoms of 0.014
Uanis(F12) = Uanis(F12A)
Uanis(F10A) = Uanis(F10)
Uanis(F11A) = Uanis(F11)
Uanis(F7A) = Uanis(F7)
Uanis(F9) = Uanis(F8A)
Uanis(F9A) = Uanis(F8)
Uanis(F13) = Uanis(F13A)
Uanis(F15A) = Uanis(F15)
Uanis(F14A) = Uanis(F14)
Uanis(F3A) = Uanis(F3)
Uanis(F2) = Uanis(F2A)
Uanis(F1A) = Uanis(F1)
4. Others
 Sof(F1A)=Sof(F2A)=Sof(F3A)=1-FVAR(1)
 Sof(F1)=Sof(F2)=Sof(F3)=FVAR(1)
 Sof(F13A)=Sof(F14A)=Sof(F15A)=1-FVAR(2)
 Sof(F13)=Sof(F14)=Sof(F15)=FVAR(2)
 Sof(F7A)=Sof(F8A)=Sof(F9A)=1-FVAR(3)
 Sof(F7)=Sof(F8)=Sof(F9)=FVAR(3)
 Fixed Sof: F10(0.5) F10A(0.5) F11(0.5) F11A(0.5) F12(0.5) F12A(0.5)
5.a Secondary CH2 refined with riding coordinates:
 C117(H11V,H11W), C118(H11X,H11Y), C119(H11Z,H), C120(H12D,H12E), C121(H12F,
 H12G), C122(H12H,H12I), C123(H12J,H12K), C124(H12L,H12M), C125(H12N,H12O),
 C126(H12P,H12Q), C127(H12R,H12S), C128(H12T,H12U), C129(H12V,H12W), C130(H13D,
 H13E)
5.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C103(H103), C104(H104), C105(H105), C202(H202), C204(H204),
 C206(H206), C210(H210), C212(H212), C214(H214), C218(H218), C220(H220),
 C222(H222), C226(H226), C228(H228), C230(H230)
5.c Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C11(H11A,H11B,H11C),
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C110(H11D,H11E,H11F), C111(H11G,H11H,
 H11I), C112(H11J,H11K,H11L), C114(H11M,H11N,H11O), C115(H11P,H11Q,H11R),
 C116(H11S,H11T,H11U)
;
_shelx_res_checksum              71651
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.890
_oxdiff_exptl_absorpt_empirical_full_min 0.753