Reductive cyclotrimerization of CO and isonitriles with a highly reactive CaI synthon
Thum, Stefan; Mai, Jonathan; Schmidt, Marcel A.; Langer, Jens; Harder, Sjoerd; Chemical Science 16 (2025) 12058–12067; doi:10.1039/D5SC02829A

data_1574738
_publ_section_title
;
 Reductive cyclotrimerization of CO and isonitriles with a highly reactive
 CaI synthon
;
_journal_issue                   26
_journal_name_full               'Chemical Science'
_journal_page_first              12058
_journal_page_last               12067
_journal_paper_doi               10.1039/D5SC02829A
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C79 H123 Ca N5, 0.5[C6H14]'
_chemical_formula_sum            'C82 H130 Ca N5'
_chemical_formula_weight         1225.98
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-03-04
_audit_creation_method
;
Olex2 1.5
(compiled 2025.02.27 svn.r83f5de26 for OlexSys, GUI svn.r7172)
;
_audit_update_record
;
2025-03-04 deposited with the CCDC.	2025-05-27 downloaded from the CCDC.
;
_cell_angle_alpha                75.108(3)
_cell_angle_beta                 77.232(3)
_cell_angle_gamma                64.237(3)
_cell_formula_units_Z            2
_cell_length_a                   13.5980(4)
_cell_length_b                   14.8279(5)
_cell_length_c                   21.9613(7)
_cell_measurement_reflns_used    11422
_cell_measurement_temperature    100.0(5)
_cell_measurement_theta_max      72.2990
_cell_measurement_theta_min      3.3250
_cell_volume                     3823.4(2)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/2 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(5)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2903
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.965
_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    -64.00  31.00   1.00    5.00    --  -40.61  38.00 -90.00   95
  2  \w   -114.00 -16.00   1.00    5.00    --  -40.61 -38.00  90.00   98
  3  \w     57.00  97.00   1.00    5.00    --   40.61-125.00 -90.00   40
  4  \w    -31.00  69.00   1.00    5.00    --   40.61 -57.00 -30.00  100
  5  \w     79.00 109.00   1.00   20.00    --  104.57-111.00-120.00   30
  6  \w     32.00 108.00   1.00   20.00    --  104.57 -61.00   0.00   76
  7  \w     29.00 153.00   1.00   20.00    --  104.57 -15.00 -30.00  124
  8  \w    121.00 149.00   1.00   20.00    --  104.57  77.00 -60.00   28
  9  \w     38.00 133.00   1.00   20.00    --  104.57 -30.00 120.00   95
 10  \w     39.00 109.00   1.00   20.00    --  104.57-111.00 150.00   70
 11  \w     28.00  95.00   1.00   20.00    --  104.57-111.00 -60.00   67
 12  \w     35.00 122.00   1.00   20.00    --  104.57 -61.00 120.00   87
 13  \w     49.00 109.00   1.00   20.00    --  104.57-111.00   0.00   60
 14  \w     30.00 131.00   1.00   20.00    --  104.57 -30.00-120.00  101
;
_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      0.1020376000
_diffrn_orient_matrix_UB_12      -0.0028647000
_diffrn_orient_matrix_UB_13      -0.0482942000
_diffrn_orient_matrix_UB_21      0.0735754000
_diffrn_orient_matrix_UB_22      -0.0926701000
_diffrn_orient_matrix_UB_23      0.0440195000
_diffrn_orient_matrix_UB_31      -0.0159205000
_diffrn_orient_matrix_UB_32      -0.0719372000
_diffrn_orient_matrix_UB_33      -0.0329130000
_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  0.0349
_diffrn_reflns_av_unetI/netI     0.0508
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.965
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            25197
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.965
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.459
_diffrn_reflns_theta_min         3.367
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.026
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.841
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
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            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.065
_exptl_crystal_description       block
_exptl_crystal_F_000             1354
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.111
_exptl_crystal_size_min          0.082
_refine_diff_density_max         0.244
_refine_diff_density_min         -0.389
_refine_diff_density_rms         0.039
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     838
_refine_ls_number_reflns         14615
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.022
_refine_ls_R_factor_all          0.0509
_refine_ls_R_factor_gt           0.0406
_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^)+(0.0453P)^2^+0.2991P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0955
_refine_ls_wR_factor_ref         0.1024
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12196
_reflns_number_total             14615
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc02829a2.cif
_cod_data_source_block           hasj220207a
_cod_depositor_comments
'Adding full bibliography for 1574737--1574741.cif.'
_cod_original_cell_volume        3823.5(2)
_cod_database_code               1574738
_shelx_shelxl_version_number     2019/2
_chemical_oxdiff_formula         C82CaH130N5
_shelx_estimated_absorpt_t_max   0.921
_shelx_estimated_absorpt_t_min   0.861
_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. Others
 Sof(N5A)=Sof(C76A)=Sof(C77A)=Sof(H77d)=Sof(H77e)=Sof(H77f)=Sof(C78A)=
 Sof(H78d)=Sof(H78e)=Sof(H78f)=Sof(C79A)=Sof(H79d)=Sof(H79e)=Sof(H79f)=1-FVAR(1)
 Sof(N5)=Sof(C76)=Sof(C77)=Sof(H77a)=Sof(H77b)=Sof(H77c)=Sof(C78)=Sof(H78a)=
 Sof(H78b)=Sof(H78c)=Sof(C79)=Sof(H79a)=Sof(H79b)=Sof(H79c)=FVAR(1)
3.a Ternary CH refined with riding coordinates:
 C12(H12), C17(H17), C28(H28), C33(H33), C49(H49), C54(H54), C65(H65), C70(H70)
3.b Secondary CH2 refined with riding coordinates:
 C13(H13a,H13b), C15(H15a,H15b), C18(H18a,H18b), C20(H20a,H20b), C29(H29a,
 H29b), C31(H31a,H31b), C34(H34a,H34b), C36(H36a,H36b), C50(H50a,H50b),
 C52(H52a,H52b), C55(H55a,H55b), C57(H57a,H57b), C66(H66a,H66b), C68(H68a,H68b),
  C71(H71a,H71b), C73(H73a,H73b)
3.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C8(H8), C9(H9), C10(H10), C24(H24), C25(H25), C26(H26), C40(H40),
 C45(H45), C46(H46), C47(H47), C61(H61), C62(H62), C63(H63)
3.d Idealised Me refined as rotating group:
 C1(H1a,H1b,H1c), C5(H5a,H5b,H5c), C14(H14a,H14b,H14c), C16(H16a,H16b,H16c),
 C19(H19a,H19b,H19c), C21(H21a,H21b,H21c), C30(H30a,H30b,H30c), C32(H32a,H32b,
 H32c), C35(H35a,H35b,H35c), C37(H37a,H37b,H37c), C38(H38a,H38b,H38c), C42(H42a,
 H42b,H42c), C51(H51a,H51b,H51c), C53(H53a,H53b,H53c), C56(H56a,H56b,H56c),
 C58(H58a,H58b,H58c), C67(H67a,H67b,H67c), C69(H69a,H69b,H69c), C72(H72a,H72b,
 H72c), C74(H74a,H74b,H74c), C77(H77a,H77b,H77c), C78(H78a,H78b,H78c), C79(H79a,
 H79b,H79c), C77A(H77d,H77e,H77f), C78A(H78d,H78e,H78f), C79A(H79d,H79e,H79f)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              73673
_shelx_fab_checksum              37219
_olex2_date_sample_data_collection 2022-02-07
_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 2.726
_oxdiff_exptl_absorpt_empirical_full_min 0.671