Synthesis and group 9 complexes of macrocyclic PCP and POCOP pincer ligands.
Leforestier, Baptiste; Gyton, Matthew R.; Chaplin, Adrian B.; Dalton transactions (Cambridge, England : 2003) 49 (2020) 2087–2101; doi:10.1039/c9dt04835a

data_7703488
_publ_section_title
;
 Synthesis and group 9 complexes of macrocyclic PCP and POCOP pincer
 ligands.
;
_journal_issue                   7
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              2087
_journal_page_last               2101
_journal_paper_doi               10.1039/c9dt04835a
_journal_volume                  49
_journal_year                    2020
_chemical_formula_moiety         'C28 H56 B2 O2 P2'
_chemical_formula_sum            'C28 H56 B2 O2 P2'
_chemical_formula_weight         508.28
_chemical_melting_point          ?
_space_group_crystal_system      orthorhombic
_space_group_IT_number           29
_space_group_name_Hall           'P 2c -2ac'
_space_group_name_H-M_alt        'P c a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2019-04-17
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3510 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-12-18 deposited with the CCDC.	2020-01-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   36.2517(2)
_cell_length_b                   6.78334(5)
_cell_length_c                   13.08712(7)
_cell_measurement_reflns_used    26521
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      73.5430
_cell_measurement_theta_min      4.1500
_cell_volume                     3218.22(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.45a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.45a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.45a (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   -115.00 -69.00   1.00    2.00    --  -40.77-132.00  27.00   46
  2  \w    -67.00  35.00   1.00    2.00    --  -40.77  37.00 -60.00  102
  3  \w      1.00  83.00   1.00    2.00    --   40.77 -99.00-150.00   82
  4  \w     23.00  98.00   1.00    2.00    --   40.77-125.00 -60.00   75
  5  \w     24.00 109.00   1.00    8.00    --  108.00 -94.00 -90.00   85
  6  \w     80.00 178.00   1.00    8.00    --  108.00  45.00 150.00   98
  7  \w     74.00 178.00   1.00    8.00    --  108.00  77.00 150.00  104
  8  \w    100.00 178.00   1.00    8.00    --  108.00 111.00 120.00   78
  9  \w     77.00 178.00   1.00    8.00    --  108.00  30.00 -90.00  101
 10  \w   -119.00  -7.00   1.00    2.00    --  -40.77 -77.00-120.00  112
 11  \w   -115.00 -11.00   1.00    2.00    --  -40.77 -57.00   0.00  104
 12  \w     29.00 142.00   1.00    8.00    --  108.00 -77.00  60.00  113
 13  \w     80.00 178.00   1.00    8.00    --  108.00  45.00  90.00   98
 14  \w     74.00 178.00   1.00    8.00    --  108.00  77.00 -60.00  104
 15  \w     77.00 178.00   1.00    8.00    --  108.00  30.00  30.00  101
 16  \w   -115.00 -11.00   1.00    2.00    --  -40.77 -57.00 120.00  104
 17  \w      1.00  83.00   1.00    2.00    --   40.77 -99.00  90.00   82
 18  \w     80.00 178.00   1.00    8.00    --  108.00  45.00-150.00   98
 19  \w     74.00 178.00   1.00    8.00    --  108.00  77.00  30.00  104
 20  \w     74.00 178.00   1.00    8.00    --  108.00  77.00  90.00  104
 21  \w     30.00 116.00   1.00    8.00    --  108.00-111.00-120.00   86
 22  \w   -119.00  -7.00   1.00    2.00    --  -40.77 -77.00 -30.00  112
 23  \w   -115.00 -65.00   1.00    2.00    --  -40.77-137.00-148.00   50
 24  \w     74.00 178.00   1.00    8.00    --  108.00  77.00 -90.00  104
 25  \w     74.00 149.00   1.00    8.00    --  108.00  77.00-120.00   75
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0194287000
_diffrn_orient_matrix_UB_12      0.0923189000
_diffrn_orient_matrix_UB_13      0.0931477000
_diffrn_orient_matrix_UB_21      0.0377867000
_diffrn_orient_matrix_UB_22      -0.0425862000
_diffrn_orient_matrix_UB_23      -0.0491249000
_diffrn_orient_matrix_UB_31      -0.0009034000
_diffrn_orient_matrix_UB_32      0.2030494000
_diffrn_orient_matrix_UB_33      -0.0526359000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0240
_diffrn_reflns_av_unetI/netI     0.0137
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       44
_diffrn_reflns_limit_h_min       -44
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            39875
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        70.049
_diffrn_reflns_theta_max         70.049
_diffrn_reflns_theta_min         6.526
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.368
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.548
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.45a (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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.049
_exptl_crystal_density_meas      ?
_exptl_crystal_description       block
_exptl_crystal_F_000             1120
_exptl_crystal_recrystallization_method 'Crystals grown from hexane at 293 K'
_exptl_crystal_size_max          0.264
_exptl_crystal_size_mid          0.234
_exptl_crystal_size_min          0.072
_refine_diff_density_max         0.562
_refine_diff_density_min         -0.354
_refine_diff_density_rms         0.071
_refine_ls_abs_structure_details
;
 Flack x determined using 2776 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.011(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     503
_refine_ls_number_reflns         6086
_refine_ls_number_restraints     1187
_refine_ls_restrained_S_all      1.185
_refine_ls_R_factor_all          0.0721
_refine_ls_R_factor_gt           0.0711
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1441P)^2^+2.6672P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2063
_refine_ls_wR_factor_ref         0.2077
_reflns_Friedel_coverage         0.908
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                6000
_reflns_number_total             6086
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9dt04835a3.cif
_cod_data_source_block           0253abc16s
_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 7703488--7703497.cif.
;
_cod_original_cell_volume        3218.23(4)
_cod_database_code               7703488
_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, All C(H,H,H,H) groups
 At 1.5 times of:
  All B(H,H,H) groups, All C(H,H,H) groups
2. Restrained distances
 P2-C117 \\sim P2-C217 \\sim P3-C130
 with sigma of 0.01
 C218-C217 \\sim C118-C117 \\sim C219-C218 \\sim C119-C118 \\sim C220-C219
\\sim C120-C119 \\sim C221-
 C220 \\sim C121-C120 \\sim C222-C221 \\sim C122-C121 \\sim C223-C222 \\sim
C224-C223 \\sim C123-C122 ~
 C225-C224 \\sim C226-C225 \\sim C124-C123 \\sim C227-C226 \\sim C125-C124
\\sim C126-C125 \\sim C228-
 C227 \\sim C127-C126 \\sim C128-C127 \\sim C229-C228 \\sim C129-C128 \\sim
C130-C129 \\sim C229-C130
 with sigma of 0.01
 P2-C209 \\sim P2-C109 \\sim P3-C113
 with sigma of 0.01
 C211-C209 \\sim C111-C109 \\sim C110-C109 \\sim C210-C209 \\sim C212-C209
\\sim C112-C109 \\sim C216-
 C113 \\sim C116-C113 \\sim C115-C113 \\sim C215-C113 \\sim C214-C113 \\sim
C114-C113
 with sigma of 0.01
 C110-C111 \\sim C111-C112 \\sim C112-C110 \\sim C210-C211 \\sim C211-C212
\\sim C212-C210 \\sim C114-
 C115 \\sim C115-C116 \\sim C116-C114 \\sim C214-C215 \\sim C215-C216 \\sim
C216-C214
 with sigma of 0.01
 C211-P2 \\sim C111-P2 \\sim C110-P2 \\sim C210-P2 \\sim C212-P2 \\sim C112-P2
\\sim C216-P3 \\sim C116-P3
 \\sim C115-P3 \\sim C215-P3 \\sim C214-P3 \\sim C114-P3
 with sigma of 0.01
 B3-H3C \\sim B3-H3B \\sim B3-H3A \\sim B2-H2C \\sim B2-H2A \\sim B2-H2B
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C109 \\sim C110 \\sim C111 \\sim C112 \\sim C114 \\sim C115 \\sim C116 \\sim
C117 \\sim C118 \\sim C119 \\sim C120 \\sim C121 \\sim C122 \\sim C123 \\sim
C124 \\sim C125 \\sim C126 \\sim C127 \\sim C128 \\sim C129 \\sim C130 \\sim
C209 \\sim C210 \\sim C211 \\sim C212 \\sim C214 \\sim C215 \\sim C216 \\sim
C217 \\sim C218 \\sim C219 \\sim C220 \\sim C221 \\sim C222 \\sim C223 \\sim
C224 \\sim C225 \\sim C226 \\sim C227 \\sim C228 \\sim C229: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C130) \\sim Ueq, Uanis(C117) \\sim Ueq, Uanis(C225) \\sim Ueq,
Uanis(C224) \\sim Ueq, Uanis(C129) \\sim Ueq, Uanis(C226) \\sim Ueq,
Uanis(C228) \\sim Ueq, Uanis(C128) \\sim Ueq, Uanis(C229) \\sim Ueq,
Uanis(C227) \\sim Ueq, Uanis(C127) \\sim Ueq, Uanis(C119) \\sim Ueq,
Uanis(C223) \\sim Ueq, Uanis(C222) \\sim Ueq, Uanis(C218) \\sim Ueq,
Uanis(C121) \\sim Ueq, Uanis(C120) \\sim Ueq, Uanis(C124) \\sim Ueq,
Uanis(C125) \\sim Ueq, Uanis(C126) \\sim Ueq, Uanis(C122) \\sim Ueq,
Uanis(C123) \\sim Ueq, Uanis(C219) \\sim Ueq, Uanis(C220) \\sim Ueq,
Uanis(C221) \\sim Ueq, Uanis(C118) \\sim Ueq, Uanis(C217) \\sim Ueq,
Uanis(C109) \\sim Ueq, Uanis(C111) \\sim Ueq, Uanis(C110) \\sim Ueq,
Uanis(C112) \\sim Ueq, Uanis(C209) \\sim Ueq, Uanis(C212) \\sim Ueq,
Uanis(C210) \\sim Ueq, Uanis(C211) \\sim Ueq, Uanis(C114) \\sim Ueq,
Uanis(C214) \\sim Ueq, Uanis(C215) \\sim Ueq, Uanis(C115) \\sim Ueq,
Uanis(C216) \\sim Ueq, Uanis(C116) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
4. Others
 Fixed Sof: C109(0.5) C110(0.5) H11A(0.5) H11B(0.5) H11C(0.5) C111(0.5)
 H11D(0.5) H11E(0.5) H11F(0.5) C112(0.5) H11G(0.5) H11H(0.5) H11I(0.5)
 C114(0.5) H11J(0.5) H11K(0.5) H11L(0.5) C115(0.5) H11M(0.5) H11N(0.5)
 H11O(0.5) C116(0.5) H11P(0.5) H11Q(0.5) H11R(0.5) C117(0.5) H11S(0.5)
 H11T(0.5) C118(0.5) H11U(0.5) H11V(0.5) C119(0.5) H11W(0.5) H11X(0.5)
 C120(0.5) H12A(0.5) H12B(0.5) C121(0.5) H12C(0.5) H12D(0.5) C122(0.5)
 H12E(0.5) H12F(0.5) C123(0.5) H12G(0.5) H12H(0.5) C124(0.5) H12I(0.5)
 H12J(0.5) C125(0.5) H12K(0.5) H12L(0.5) C126(0.5) H12M(0.5) H12N(0.5)
 C127(0.5) H12O(0.5) H12P(0.5) C128(0.5) H12Q(0.5) H12R(0.5) C129(0.5)
 H12S(0.5) H12T(0.5) H13A(0.5) H13B(0.5) H13C(0.5) H13D(0.5) C209(0.5)
 C210(0.5) H21A(0.5) H21B(0.5) H21C(0.5) C211(0.5) H21D(0.5) H21E(0.5)
 H21F(0.5) C212(0.5) H21G(0.5) H21H(0.5) H21I(0.5) C214(0.5) H21J(0.5)
 H21K(0.5) H21L(0.5) C215(0.5) H21M(0.5) H21N(0.5) H21O(0.5) C216(0.5)
 H21P(0.5) H21Q(0.5) H21R(0.5) C217(0.5) H21S(0.5) H21T(0.5) C218(0.5)
 H21U(0.5) H21V(0.5) C219(0.5) H21W(0.5) H21X(0.5) C220(0.5) H22A(0.5)
 H22B(0.5) C221(0.5) H22C(0.5) H22D(0.5) C222(0.5) H22E(0.5) H22F(0.5)
 C223(0.5) H22G(0.5) H22H(0.5) C224(0.5) H22I(0.5) H22J(0.5) C225(0.5)
 H22K(0.5) H22L(0.5) C226(0.5) H22M(0.5) H22N(0.5) C227(0.5) H22O(0.5)
 H22P(0.5) C228(0.5) H22Q(0.5) H22R(0.5) C229(0.5) H22S(0.5) H22T(0.5)
5.a Secondary CH2 refined with riding coordinates:
 C117(H11S,H11T), C118(H11U,H11V), C119(H11W,H11X), C120(H12A,H12B), C121(H12C,
 H12D), C122(H12E,H12F), C123(H12G,H12H), C124(H12I,H12J), C125(H12K,H12L),
 C126(H12M,H12N), C127(H12O,H12P), C128(H12Q,H12R), C129(H12S,H12T), C130(H13A,
 H13B), C130(H13C,H13D), 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)
5.b Aromatic/amide H refined with riding coordinates:
 C101(H101), C103(H103), C104(H104), C105(H105)
5.c Idealised Me refined as rotating group:
 C110(H11A,H11B,H11C), C111(H11D,H11E,H11F), C112(H11G,H11H,H11I), C114(H11J,
 H11K,H11L), C115(H11M,H11N,H11O), C116(H11P,H11Q,H11R), C210(H21A,H21B,H21C),
 C211(H21D,H21E,H21F), C212(H21G,H21H,H21I), C214(H21J,H21K,H21L), C215(H21M,
 H21N,H21O), C216(H21P,H21Q,H21R)
5.d Idealised Me refined as rotating group with stretchable bonds:
 B3(H3A,H3B,H3C), B2(H2A,H2B,H2C)
;
_shelx_res_checksum              72302
_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 1.713
_oxdiff_exptl_absorpt_empirical_full_min 0.722