Synthesis and reactivity of iridium complexes of a macrocyclic PNP pincer ligand.
Hood, Thomas M.; Chaplin, Adrian B.; Dalton transactions (Cambridge, England : 2003) 50 (2021) 2472–2482; doi:10.1039/d0dt04303f

data_7706527
_publ_section_title
;
 Synthesis and reactivity of iridium complexes of a macrocyclic PNP pincer
 ligand.
;
_journal_issue                   7
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              2472
_journal_page_last               2482
_journal_paper_doi               10.1039/d0dt04303f
_journal_volume                  50
_journal_year                    2021
_chemical_formula_moiety         'C36 H63 N P2 Rh, C32 H12 B F24'
_chemical_formula_sum            'C68 H75 B F24 N P2 Rh'
_chemical_formula_weight         1537.95
_chemical_melting_point          ?
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2020-10-29
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3510 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-12-18 deposited with the CCDC.	2021-01-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 108.2733(13)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   25.6746(3)
_cell_length_b                   14.06969(19)
_cell_length_c                   40.5239(5)
_cell_measurement_reflns_used    31066
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      73.3750
_cell_measurement_theta_min      3.2790
_cell_volume                     13900.4(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_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    -70.00  31.00   1.00    8.00    --  -41.82  57.00 120.00  101
  2  \w   -116.00 -17.00   1.00    8.00    --  -41.82 -37.00 -30.00   99
  3  \w    -87.00  -6.00   1.00    8.00    --  -41.82 125.00-180.00   81
  4  \w      8.00  34.00   1.00    8.00    --   41.82  83.00 -24.90   26
  5  \w     34.00 112.00   1.00   32.00    --  107.00-125.00 120.00   78
  6  \w     24.00 107.00   1.00   32.00    --  107.00 -94.00 -90.00   83
  7  \w     81.00 178.00   1.00   32.00    --  107.00  45.00-180.00   97
  8  \w     24.00 107.00   1.00   32.00    --  107.00 -94.00 -30.00   83
  9  \w    103.00 178.00   1.00   32.00    --  107.00  77.00  90.00   75
 10  \w     24.00 107.00   1.00   32.00    --  107.00 -94.00 120.00   83
 11  \w     34.00 112.00   1.00   32.00    --  107.00-125.00 -30.00   78
 12  \w     34.00 112.00   1.00   32.00    --  107.00-125.00  90.00   78
 13  \w     81.00 178.00   1.00   32.00    --  107.00  45.00 150.00   97
 14  \w     29.00 108.00   1.00   32.00    --  107.00-107.00 113.87   79
 15  \w    103.00 178.00   1.00   32.00    --  107.00  77.00   0.00   75
 16  \w     35.00 118.00   1.00   32.00    --  107.00-133.00  14.00   83
 17  \w     30.00 108.00   1.00   32.00    --  107.00-109.00 164.98   78
 18  \w     27.00 107.00   1.00   32.00    --  107.00-101.00  12.93   80
 19  \w   -114.00 -14.00   1.00    8.00    --  -41.82 -57.00  90.00  100
 20  \w      8.00  42.00   1.00    8.00    --   41.82  81.00-102.20   34
 21  \w      9.00  42.00   1.00    8.00    --   41.82  79.00 172.31   33
 22  \w      9.00  42.00   1.00    8.00    --   41.82  76.00 121.89   33
 23  \w     81.00 136.00   1.00   32.00    --  107.00  45.00 -60.00   55
;
_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      0.0058323000
_diffrn_orient_matrix_UB_12      -0.0723793000
_diffrn_orient_matrix_UB_13      -0.0271039000
_diffrn_orient_matrix_UB_21      -0.0068222000
_diffrn_orient_matrix_UB_22      -0.0821327000
_diffrn_orient_matrix_UB_23      0.0234933000
_diffrn_orient_matrix_UB_31      -0.0625544000
_diffrn_orient_matrix_UB_32      0.0021976000
_diffrn_orient_matrix_UB_33      -0.0177893000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0512
_diffrn_reflns_av_unetI/netI     0.0303
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       48
_diffrn_reflns_limit_l_min       -49
_diffrn_reflns_number            69644
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        70.071
_diffrn_reflns_theta_max         70.071
_diffrn_reflns_theta_min         6.546
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.360
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.24635
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.82a (Rigaku Oxford Diffraction, 2020)
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    1.470
_exptl_crystal_density_meas      ?
_exptl_crystal_description       plate
_exptl_crystal_F_000             6288
_exptl_crystal_recrystallization_method
'Crystals grown from Et2O-SiMe4 at 278 K'
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.927
_refine_diff_density_min         -1.095
_refine_diff_density_rms         0.070
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.006
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1047
_refine_ls_number_reflns         13181
_refine_ls_number_restraints     1146
_refine_ls_restrained_S_all      1.180
_refine_ls_R_factor_all          0.0506
_refine_ls_R_factor_gt           0.0459
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0602P)^2^+42.2544P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1152
_refine_ls_wR_factor_ref         0.1200
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11927
_reflns_number_total             13181
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0dt04303f2.cif
_cod_data_source_block           0609abc20s
_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 

 Adding full bibliography for 7706524--7706528.cif.
;
_cod_database_code               7706527
_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
 C408-F4 \\sim C408-F5 \\sim C408-F6 \\sim C408-F4A \\sim C408-F5A \\sim
C408-F6A
 with sigma of 0.01
 F4-F5 \\sim F5-F6 \\sim F6-F4 \\sim F4A-F5A \\sim F5A-F6A \\sim F6A-F4A
 with sigma of 0.01
 C405-F4 \\sim C405-F5 \\sim C405-F6 \\sim C405-F4A \\sim C405-F5A \\sim
C405-F6A
 with sigma of 0.01
 C415-F7 \\sim C415-F8 \\sim C415-F9 \\sim C415-F7A \\sim C415-F8A \\sim
C415-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
 C411-F7 \\sim C411-F8 \\sim C411-F9 \\sim C411-F7A \\sim C411-F8A \\sim
C411-F9A
 with sigma of 0.01
 C423-F13 \\sim C423-F14 \\sim C423-F15 \\sim C423-F13A \\sim C423-F14A \\sim
C423-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
 C419-F13 \\sim C419-F14 \\sim C419-F15 \\sim C419-F13A \\sim C419-F14A \\sim
C419-F15A
 with sigma of 0.01
 C424-F16 \\sim C424-F17 \\sim C424-F18 \\sim C424-F16A \\sim C424-F17A \\sim
C424-F18A
 with sigma of 0.01
 F16-F17 \\sim F17-F18 \\sim F18-F16 \\sim F16A-F17A \\sim F17A-F18A \\sim
F18A-F16A
 with sigma of 0.01
 C421-F16 \\sim C421-F17 \\sim C421-F18 \\sim C421-F16A \\sim C421-F17A \\sim
C421-F18A
 with sigma of 0.01
 C431-F19 \\sim C431-F20 \\sim C431-F21 \\sim C431-F19A \\sim C431-F20A \\sim
C431-F21A
 with sigma of 0.01
 F19-F20 \\sim F20-F21 \\sim F21-F19 \\sim F19A-F20A \\sim F20A-F21A \\sim
F21A-F19A
 with sigma of 0.01
 C427-F19 \\sim C427-F20 \\sim C427-F21 \\sim C427-F19A \\sim C427-F20A \\sim
C427-F21A
 with sigma of 0.01
 C432-F22 \\sim C432-F23 \\sim C432-F24 \\sim C432-F22A \\sim C432-F23A \\sim
C432-F24A
 with sigma of 0.01
 F22-F23 \\sim F23-F24 \\sim F24-F22 \\sim F22A-F23A \\sim F23A-F24A \\sim
F24A-F22A
 with sigma of 0.01
 C429-F22 \\sim C429-F23 \\sim C429-F24 \\sim C429-F22A \\sim C429-F23A \\sim
C429-F24A
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
F1 \\sim F2 \\sim F3 \\sim F4 \\sim F4A \\sim F5 \\sim F5A \\sim F6 \\sim F6A
\\sim F7 \\sim F7A \\sim F8 \\sim F8A \\sim F9 \\sim F9A \\sim F10 \\sim F11
\\sim F12 \\sim F13 \\sim F13A \\sim F14 \\sim F14A \\sim F15 \\sim F15A \\sim
F16 \\sim F16A \\sim F17 \\sim F17A \\sim F18 \\sim F18A \\sim F19 \\sim F19A
\\sim F20 \\sim F20A \\sim F21 \\sim F21A \\sim F22 \\sim F22A \\sim F23 \\sim
F23A \\sim F24 \\sim F24A \\sim C431 \\sim C432 \\sim C423 \\sim C415 \\sim
C408 \\sim C424 \\sim C214 \\sim C216 \\sim C215 \\sim C229 \\sim C228 \\sim
C227 \\sim C226 \\sim C225 \\sim C224 \\sim C223 \\sim C222 \\sim C221 \\sim
C220 \\sim C219 \\sim C218: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(F1) \\sim Ueq, Uanis(F2) \\sim Ueq, Uanis(F3) \\sim Ueq, Uanis(F4) \\sim
Ueq, Uanis(F4A) \\sim Ueq, Uanis(F5) \\sim Ueq, Uanis(F5A) \\sim Ueq, Uanis(F6)
\\sim Ueq, Uanis(F6A) \\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(F11) \\sim Ueq, Uanis(F12) \\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(F16A) \\sim Ueq, Uanis(F17) \\sim Ueq, Uanis(F17A) \\sim Ueq, Uanis(F18)
\\sim Ueq, Uanis(F18A) \\sim Ueq, Uanis(F19) \\sim Ueq, Uanis(F19A) \\sim Ueq,
Uanis(F20) \\sim Ueq, Uanis(F20A) \\sim Ueq, Uanis(F21) \\sim Ueq, Uanis(F21A)
\\sim Ueq, Uanis(F22) \\sim Ueq, Uanis(F22A) \\sim Ueq, Uanis(F23) \\sim Ueq,
Uanis(F23A) \\sim Ueq, Uanis(F24) \\sim Ueq, Uanis(F24A) \\sim Ueq, Uanis(C431)
\\sim Ueq, Uanis(C432) \\sim Ueq, Uanis(C423) \\sim Ueq, Uanis(C415) \\sim Ueq,
Uanis(C408) \\sim Ueq, Uanis(C424) \\sim Ueq, Uanis(C214) \\sim Ueq,
Uanis(C216) \\sim Ueq, Uanis(C215) \\sim Ueq, Uanis(C229) \\sim Ueq,
Uanis(C228) \\sim Ueq, Uanis(C227) \\sim Ueq, Uanis(C226) \\sim Ueq,
Uanis(C225) \\sim Ueq, Uanis(C224) \\sim Ueq, Uanis(C223) \\sim Ueq,
Uanis(C222) \\sim Ueq, Uanis(C221) \\sim Ueq, Uanis(C220) \\sim Ueq,
Uanis(C219) \\sim Ueq, Uanis(C218) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
4. Others
 Sof(F19A)=Sof(F20A)=Sof(F21A)=1-FVAR(1)
 Sof(F19)=Sof(F20)=Sof(F21)=FVAR(1)
 Sof(F22A)=Sof(F23A)=Sof(F24A)=1-FVAR(2)
 Sof(F22)=Sof(F23)=Sof(F24)=FVAR(2)
 Sof(F7A)=Sof(F8A)=Sof(F9A)=1-FVAR(3)
 Sof(F7)=Sof(F8)=Sof(F9)=FVAR(3)
 Sof(F13A)=Sof(F14A)=Sof(F15A)=1-FVAR(4)
 Sof(F13)=Sof(F14)=Sof(F15)=FVAR(4)
 Sof(F4A)=Sof(F5A)=Sof(F6A)=1-FVAR(5)
 Sof(F4)=Sof(F5)=Sof(F6)=FVAR(5)
 Fixed Sof: F16(0.5) F16A(0.5) F17(0.5) F17A(0.5) F18(0.5) F18A(0.5)
5.a Ternary CH refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C9(H9)
5.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C8(H8A,H8B), C10(H10A,H10B), C207(H20A,H20B), C208(H20C,H20D),
 C217(H21S,H21T), C218(H21U,H21V), C219(H21W,H21X), C220(H22A,H22B), C221(H22C,
 H22D), C222(H22E,H22F), C223(H22G,H22H), C224(H22I,H22J), C225(H22K,H22L),
 C226(H22M,H22N), C227(H22O,H22P), C228(H22Q,H22R), C229(H22S,H22T), C230(H23A,
 H23B)
5.c Aromatic/amide H refined with riding coordinates:
 C203(H203), C204(H204), C205(H205), C402(H402), C404(H404), C406(H406),
 C410(H410), C412(H412), C414(H414), C418(H418), C420(H420), C422(H422),
 C426(H426), C428(H428), C430(H430)
5.d Idealised Me refined as rotating group:
 C210(H21A,H21B,H21C), C211(H21D,H21E,H21F), C212(H21G,H21H,H21I), C214(H21J,
 H21K,H21L), C215(H21M,H21N,H21O), C216(H21P,H21Q,H21R)
;
_shelx_res_checksum              7360
_shelx_hkl_checksum              76955
_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 2.980
_oxdiff_exptl_absorpt_empirical_full_min 0.446