In Crystallo Lattice Adaptivity Triggered by Solid-Gas Reactions of Cationic Group 7 Pincer Complexes
Goodall, Joe C.; Sajjad, Muhammad Arif; Thompson, Emily A.; Page, Samuel J.; Kerrigan, Adam M.; Jenkins, Huw T.; Lynam, Jason Martin; Macgregor, Stuart Alan; Weller, Andrew S.; Chemical Communications  (2023) –; doi:10.1039/D3CC03201A

data_7132002
_publ_section_title
;
 In Crystallo Lattice Adaptivity Triggered by Solid-Gas Reactions of
 Cationic Group 7 Pincer Complexes
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D3CC03201A
_journal_year                    2023
_chemical_formula_moiety
'C23 H39 Mn N O5 P2, C32 H12 B F24, 0.5(C6 H14)'
_chemical_formula_sum            'C58 H58 B F24 Mn N O5 P2'
_chemical_formula_weight         1432.74
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2023-06-15
_audit_creation_method
;
Olex2 1.5
(compiled 2021.08.20 svn.r13c46975 for OlexSys, GUI svn.r6396)
;
_audit_update_record
;
2023-06-22 deposited with the CCDC.	2023-08-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.6838(4)
_cell_length_b                   23.8631(6)
_cell_length_c                   13.4251(3)
_cell_measurement_reflns_used    17110
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      70.8700
_cell_measurement_theta_min      3.7040
_cell_volume                     6306.0(2)
_computing_cell_refinement       'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution
;
Superflip  (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1450
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.982
_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    -29.00  42.00   1.00    3.00    --    0.00  77.00  90.00   71
  2  \w    -19.00  28.00   1.00    3.00    --    0.00 -77.00 -90.00   47
  3  \w    -17.00  14.00   1.00    3.00    --    0.00 -77.00 -30.00   31
  4  \w    -12.00  32.00   1.00    3.00    --    0.00  77.00-180.00   44
  5  \w     10.00  40.00   1.00    3.00    --    0.00  77.00-120.00   30
  6  \w    -16.00  84.00   1.00   22.50    --   54.00 -77.00  30.00  100
  7  \w     89.00 123.00   1.00   22.50    --   54.00  57.00-120.00   34
  8  \w     37.00  70.00   1.00   22.50    --   54.00 -57.00-180.00   33
  9  \w     61.00 122.00   1.00   22.50    --   54.00  57.00-150.00   61
 10  \w     36.00 110.00   1.00   22.50    --   54.00-125.00-150.00   74
 11  \w      1.00  75.00   1.00   22.50    --   54.00 -57.00 -90.00   74
 12  \w    -18.00  97.00   1.00   22.50    --   54.00 -19.00  60.00  115
 13  \w    108.00 143.00   1.00   30.00    --  108.00 111.00 120.00   35
 14  \w     37.00 123.00   1.00   30.00    --  108.00 -37.00-180.00   86
 15  \w     59.00 109.00   1.00   30.00    --  108.00-111.00 150.00   50
 16  \w     43.00 130.00   1.00   30.00    --  108.00 -50.00  90.00   87
 17  \w    101.00 138.00   1.00   30.00    --  108.00 -77.00 -30.00   37
 18  \w     52.00  77.00   1.00   30.00    --  108.00 -77.00 150.00   25
 19  \w    111.00 168.00   1.00   30.00    --  108.00  77.00-150.00   57
 20  \w     55.00 132.00   1.00   30.00    --  108.00 -37.00 -60.00   77
 21  \w     41.00 109.00   1.00   30.00    --  108.00-111.00-120.00   68
 22  \w     51.00 109.00   1.00   30.00    --  108.00-111.00  60.00   58
 23  \w     47.00 109.00   1.00   30.00    --  108.00-111.00 -30.00   62
 24  \w     40.00  81.00   1.00   30.00    --  108.00 -77.00 -30.00   41
 25  \w     86.00 160.00   1.00   30.00    --  108.00  37.00-180.00   74
 26  \w    145.00 173.00   1.00   30.00    --  108.00  77.00  90.00   28
 27  \w    104.00 176.00   1.00   30.00    --  108.00  77.00-120.00   72
 28  \w     97.00 132.00   1.00   30.00    --  108.00 -77.00 150.00   35
 29  \w    145.00 170.00   1.00   30.00    --  108.00   0.00-150.00   25
 30  \w     42.00  98.00   1.00   30.00    --  108.00   0.00-150.00   56
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0631451000
_diffrn_orient_matrix_UB_12      -0.0651702000
_diffrn_orient_matrix_UB_13      0.0022938000
_diffrn_orient_matrix_UB_21      -0.0102002000
_diffrn_orient_matrix_UB_22      -0.0079335000
_diffrn_orient_matrix_UB_23      -0.0639882000
_diffrn_orient_matrix_UB_31      0.0952300000
_diffrn_orient_matrix_UB_32      0.0426142000
_diffrn_orient_matrix_UB_33      -0.0083812000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0675
_diffrn_reflns_av_unetI/netI     0.0618
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_number            44881
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.270
_diffrn_reflns_theta_min         3.705
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.254
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.58866
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.113a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear orangish yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   orangish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.509
_exptl_crystal_description       block
_exptl_crystal_F_000             2916
_exptl_crystal_recrystallization_method
'Tetrahydrofuran solution layered with hexane at room temperature'
_exptl_crystal_size_max          0.198
_exptl_crystal_size_mid          0.105
_exptl_crystal_size_min          0.074
_refine_diff_density_max         0.872
_refine_diff_density_min         -0.889
_refine_diff_density_rms         0.098
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.897
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     953
_refine_ls_number_reflns         12038
_refine_ls_number_restraints     121
_refine_ls_restrained_S_all      0.905
_refine_ls_R_factor_all          0.0903
_refine_ls_R_factor_gt           0.0766
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1942P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2065
_refine_ls_wR_factor_ref         0.2295
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9811
_reflns_number_total             12038
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc03201a2.cif
_cod_data_source_block           asw21133
_cod_database_code               7132002
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C56 H57 Mn1 N1 O5 P2 B1 F24'
_chemical_oxdiff_usercomment     'Joe Goodall - iPrPONOPMn(THF)(CO)2 BArF4'
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.60917
 0.39083
2. Restrained distances
 C101-C100 = C102-C101 = C102-C103 = C104-C103 = C105-C104
 1.52 with sigma of 0.01
 F19A-F20
 2 with sigma of 0.02
 F20-F21
 2 with sigma of 0.02
 C100-C102 = C101-C103 = C102-C104 = C103-C105
 2.48 with sigma of 0.02
 C31-F5 \\sim C31-F4 \\sim C31-F6
 with sigma of 0.02
 F5-C31 \\sim F4-C31 \\sim F6-C31
 with sigma of 0.02
 C28-C31A \\sim C28-C31
 with sigma of 0.02
 C54-F19 \\sim C54-F20 \\sim C54-F21
 with sigma of 0.02
 F19-F20 \\sim F19-F21 \\sim F20-F21
 with sigma of 0.04
 C39-F10A \\sim C39-F12A \\sim C39-F11A \\sim C39-F12 \\sim C39-F10 \\sim
C39-F11
 with sigma of 0.02
 C31A-F5A \\sim C31A-F4A \\sim C31A-F6
 with sigma of 0.02
 F10A-F12A \\sim F10A-F11A \\sim F12A-F11A \\sim F12-F10 \\sim F12-F11
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
F5 \\sim F4 \\sim F6: within 2A with sigma of 0.04 and sigma for terminal atoms
of 0.08 within 2A
C31A \\sim C31: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
F11A \\sim F12A \\sim F10A: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
F5A \\sim F4A: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
F20 \\sim F19A \\sim F19 \\sim F21A \\sim F21: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
F5 \\sim F4 \\sim F4A \\sim F5A: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
Uanis(F5) \\sim Ueq, Uanis(F4) \\sim Ueq: with sigma of 1 and sigma for
terminal atoms of 0.01
Uanis(C31) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.1
4. Others
 Sof(F10A)=Sof(F12A)=Sof(F11A)=1-FVAR(1)
 Sof(F10)=Sof(F12)=Sof(F11)=FVAR(1)
 Sof(F5A)=Sof(F4A)=Sof(C31A)=1-FVAR(2)
 Sof(F5)=Sof(C31)=Sof(F4)=FVAR(2)
 Sof(F7A)=Sof(F8A)=Sof(F9A)=1-FVAR(3)
 Sof(F7)=Sof(F8)=Sof(F9)=FVAR(3)
 Sof(H3BC)=Sof(H3BD)=Sof(H6BC)=Sof(H6BD)=Sof(C4A)=Sof(H4AA)=Sof(H4AB)=Sof(C5A)=
 Sof(H5AA)=Sof(H5AB)=1-FVAR(4)
 Sof(H3AA)=Sof(H3AB)=Sof(H6AA)=Sof(H6AB)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(C5)=
 Sof(H5A)=Sof(H5B)=FVAR(4)
 Sof(F19A)=Sof(F21A)=1-FVAR(5)
 Sof(F21)=Sof(F19)=FVAR(5)
 Fixed Sof: C102(0.5) H10A(0.5) H10B(0.5) C104(0.5) H10C(0.5) H10D(0.5)
 C101(0.5) H10E(0.5) H10F(0.5) C100(0.5) H10G(0.5) H10H(0.5) H10I(0.5)
 C105(0.5) H10J(0.5) H10K(0.5) H10L(0.5) C103(0.5) H10M(0.5) H10N(0.5)
 Fixed Uiso: C102(0.1) C104(0.1) C101(0.1) C100(0.1) C105(0.1) C103(0.1)
5.a Ternary CH refined with riding coordinates:
 C10(H10), C16(H16), C13(H13), C7(H7)
5.b Secondary CH2 refined with riding coordinates:
 C3(H3AA,H3AB), C3(H3BC,H3BD), C6(H6AA,H6AB), C6(H6BC,H6BD), C4(H4A,H4B),
 C5(H5A,H5B), C4A(H4AA,H4AB), C5A(H5AA,H5AB), C102(H10A,H10B), C104(H10C,H10D),
 C101(H10E,H10F), C103(H10M,H10N)
5.c Aromatic/amide H refined with riding coordinates:
 C41(H41), C53(H53), C37(H37), C27(H27), C45(H45), C25(H25), C33(H33),
 C43(H43), C29(H29), C49(H49), C21(H21), C20(H20), C35(H35), C51(H51), C22(H22)
5.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C11(H11A,H11B,H11C), C8(H8A,H8B,H8C), C17(H17A,H17B,
 H17C), C18(H18A,H18B,H18C), C9(H9A,H9B,H9C), C14(H14A,H14B,H14C), C12(H12A,
 H12B,H12C), C100(H10G,H10H,H10I), C105(H10J,H10K,H10L)
;
_shelx_res_checksum              61145
_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 1.624
_oxdiff_exptl_absorpt_empirical_full_min 0.690