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_1574740
_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         'C83 H123 Ca N5'
_chemical_formula_sum            'C83 H123 Ca N5'
_chemical_formula_weight         1230.94
_chemical_properties_physical    Moisture-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 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                90
_cell_angle_beta                 108.952(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.1763(3)
_cell_length_b                   17.4722(2)
_cell_length_c                   26.1660(3)
_cell_measurement_reflns_used    12251
_cell_measurement_temperature    100.0(6)
_cell_measurement_theta_max      72.1430
_cell_measurement_theta_min      3.0580
_cell_volume                     7426.9(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 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(6)
_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 0.966
_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  34.00   1.00    2.60    --  -40.61  38.00 150.00   98
  2  \w    -73.00  25.00   1.00    2.60    --  -40.61  77.00-150.00   98
  3  \w     42.00  96.00   1.00   10.60    --  104.57 -94.00 -60.00   54
  4  \w    104.00 172.00   1.00   10.60    --  104.57 111.00-180.00   68
  5  \w     49.00 109.00   1.00   10.60    --  104.57-111.00  30.00   60
  6  \w     28.00 109.00   1.00   10.60    --  104.57-111.00 -90.00   81
  7  \w     28.00 133.00   1.00   10.60    --  104.57 -30.00  90.00  105
  8  \w    103.00 175.00   1.00   10.60    --  104.57  77.00 150.00   72
;
_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      0.0307112000
_diffrn_orient_matrix_UB_12      -0.0775593000
_diffrn_orient_matrix_UB_13      0.0270688000
_diffrn_orient_matrix_UB_21      0.0592904000
_diffrn_orient_matrix_UB_22      0.0419840000
_diffrn_orient_matrix_UB_23      0.0490664000
_diffrn_orient_matrix_UB_31      -0.0673048000
_diffrn_orient_matrix_UB_32      0.0015162000
_diffrn_orient_matrix_UB_33      0.0270900000
_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  0.0305
_diffrn_reflns_av_unetI/netI     0.0416
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.966
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            28338
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.966
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.424
_diffrn_reflns_theta_min         3.096
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.061
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.547
_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    1.101
_exptl_crystal_description       block
_exptl_crystal_F_000             2704
_exptl_crystal_size_max          0.318
_exptl_crystal_size_mid          0.228
_exptl_crystal_size_min          0.196
_refine_diff_density_max         0.495
_refine_diff_density_min         -0.422
_refine_diff_density_rms         0.041
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1019
_refine_ls_number_reflns         14219
_refine_ls_number_restraints     2001
_refine_ls_restrained_S_all      0.971
_refine_ls_R_factor_all          0.0515
_refine_ls_R_factor_gt           0.0427
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0538P)^2^+1.7497P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1048
_refine_ls_wR_factor_ref         0.1119
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12065
_reflns_number_total             14219
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc02829a2.cif
_cod_data_source_block           hasj211027a
_cod_depositor_comments
'Adding full bibliography for 1574737--1574741.cif.'
_cod_database_code               1574740
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C83H123CaN5
_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 C(H,H,H) groups
2. Restrained distances
 C73-C71 \\sim C71-C73A
 with sigma of 0.01
 N2-C22A \\sim N2-C22
 with sigma of 0.02
 C28-C23 \\sim C23A-C28A \\sim C27A-C33A \\sim C33-C27 \\sim C64-C70A \\sim
C64-C70 \\sim C54-C48 ~
 C54A-C48
 with sigma of 0.02
 C71-C70A \\sim C71-C70 \\sim C73A-C70A \\sim C73-C70 \\sim C57-C54 \\sim
C57-C54A \\sim C55-C54 ~
 C55A-C54A \\sim C31-C28 \\sim C28A-C31A \\sim C29-C28 \\sim C28A-C29A \\sim
C36-C33 \\sim C36A-C33A ~
 C33A-C34A \\sim C34-C33
 with sigma of 0.02
 C73A-C74A \\sim C74-C73 \\sim C56-C55 \\sim C55A-C56A \\sim C37-C36 \\sim
C37A-C36A \\sim C35A-C34A ~
 C35-C34 \\sim C30A-C29A \\sim C30-C29 \\sim C31A-C32A \\sim C32-C31
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C57 \\sim C54A \\sim C55A \\sim C54 \\sim C55: within 3A with sigma of 0.02 and
sigma for terminal atoms of 0.04 within 3A
C64 \\sim C71 \\sim C70A \\sim C73A \\sim C70 \\sim C73: within 4A with sigma
of 0.02 and sigma for terminal atoms of 0.04 within 4A
C22A \\sim C23A \\sim C24A \\sim C25A \\sim C26A \\sim C27A \\sim C28A \\sim
C29A \\sim C30A \\sim C31A \\sim C32A \\sim C33A \\sim C34A \\sim C35A \\sim
C36A \\sim C22 \\sim C23 \\sim C24 \\sim C25 \\sim C26 \\sim C27 \\sim C28
\\sim C29 \\sim C30 \\sim C31 \\sim C32 \\sim C33 \\sim C34 \\sim C35 \\sim C36
\\sim C37: within 4A with sigma of 0.02 and sigma for terminal atoms of 0.04
within 4A
Uanis(C32A) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
4. Rigid body (RIGU) restrains
 C48, C57, C54A, C55A
 with sigma for 1-2 distances of 0.003 and sigma for 1-3 distances of 0.003
 C64, C71, C70A, C73A
 with sigma for 1-2 distances of 0.003 and sigma for 1-3 distances of 0.003
 C22A, C26A, C27A, C33A, C34A, C36A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C23A, C28A, C29A, C31A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
5. Others
 Sof(C54A)=Sof(H54A)=Sof(C55A)=Sof(H55a)=Sof(H55b)=Sof(C56A)=Sof(H56a)=
 Sof(H56b)=Sof(H56c)=1-FVAR(1)
 Sof(C54)=Sof(H54)=Sof(C55)=Sof(H55c)=Sof(H55d)=Sof(C56)=Sof(H56d)=Sof(H56e)=
 Sof(H56f)=FVAR(1)
 Sof(H57c)=Sof(H57d)=Sof(H71c)=Sof(H71d)=Sof(C70A)=Sof(H70A)=Sof(C73A)=
 Sof(H73a)=Sof(H73b)=Sof(C74A)=Sof(H74a)=Sof(H74b)=Sof(H74c)=1-FVAR(2)
 Sof(H57a)=Sof(H57b)=Sof(H71a)=Sof(H71b)=Sof(C70)=Sof(H70)=Sof(C73)=Sof(H73c)=
 Sof(H73d)=Sof(C74)=Sof(H74d)=Sof(H74e)=Sof(H74f)=FVAR(2)
 Sof(C22A)=Sof(C27A)=Sof(C26A)=Sof(H26A)=Sof(C25A)=Sof(H25A)=Sof(C24A)=
 Sof(H24A)=Sof(C23A)=Sof(C28A)=Sof(H28A)=Sof(C29A)=Sof(H29a)=Sof(H29b)=
 Sof(C30A)=Sof(H30a)=Sof(H30b)=Sof(H30c)=Sof(C31A)=Sof(H31a)=Sof(H31b)=
 Sof(C32A)=Sof(H32a)=Sof(H32b)=Sof(H32c)=Sof(C33A)=Sof(H33A)=Sof(C34A)=
 Sof(H34a)=Sof(H34b)=Sof(C35A)=Sof(H35a)=Sof(H35b)=Sof(H35c)=Sof(C36A)=
 Sof(H36a)=Sof(H36b)=Sof(C37A)=Sof(H37a)=Sof(H37b)=Sof(H37c)=1-FVAR(3)
 Sof(C22)=Sof(C23)=Sof(C24)=Sof(H24)=Sof(C25)=Sof(H25)=Sof(C26)=Sof(H26)=
 Sof(C27)=Sof(C28)=Sof(H28)=Sof(C29)=Sof(H29c)=Sof(H29d)=Sof(C30)=Sof(H30d)=
 Sof(H30e)=Sof(H30f)=Sof(C31)=Sof(H31c)=Sof(H31d)=Sof(C32)=Sof(H32d)=Sof(H32e)=
 Sof(H32f)=Sof(C33)=Sof(H33)=Sof(C34)=Sof(H34c)=Sof(H34d)=Sof(C35)=Sof(H35d)=
 Sof(H35e)=Sof(H35f)=Sof(C36)=Sof(H36c)=Sof(H36d)=Sof(C37)=Sof(H37d)=Sof(H37e)=
 Sof(H37f)=FVAR(3)
6.a Ternary CH refined with riding coordinates:
 C12(H12), C17(H17), C49(H49), C65(H65), C28A(H28A), C33A(H33A), C54A(H54A),
 C70A(H70A), C28(H28), C33(H33), C54(H54), C70(H70)
6.b Secondary CH2 refined with riding coordinates:
 C13(H13a,H13b), C15(H15a,H15b), C18(H18a,H18b), C20(H20a,H20b), C50(H50a,
 H50b), C52(H52a,H52b), C57(H57a,H57b), C57(H57c,H57d), C66(H66a,H66b),
 C68(H68a,H68b), C71(H71a,H71b), C71(H71c,H71d), C29A(H29a,H29b), C31A(H31a,
 H31b), C34A(H34a,H34b), C36A(H36a,H36b), C55A(H55a,H55b), C73A(H73a,H73b),
 C29(H29c,H29d), C31(H31c,H31d), C34(H34c,H34d), C36(H36c,H36d), C55(H55c,H55d),
  C73(H73c,H73d)
6.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C8(H8), C9(H9), C10(H10), C40(H40), C45(H45), C46(H46), C47(H47),
 C61(H61), C62(H62), C63(H63), C78(H78), C79(H79), C80(H80), C26A(H26A),
 C25A(H25A), C24A(H24A), C24(H24), C25(H25), C26(H26)
6.d Fitted hexagon refined as free rotating group:
 C22A(C27A,C26A,C25A,C24A,C23A)
6.e 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), C38(H38a,H38b,H38c), C42(H42a,H42b,
 H42c), C51(H51a,H51b,H51c), C53(H53a,H53b,H53c), C58(H58a,H58b,H58c), C67(H67a,
 H67b,H67c), C69(H69a,H69b,H69c), C72(H72a,H72b,H72c), C82(H82a,H82b,H82c),
 C83(H83a,H83b,H83c), C30A(H30a,H30b,H30c), C32A(H32a,H32b,H32c), C35A(H35a,
 H35b,H35c), C37A(H37a,H37b,H37c), C56A(H56a,H56b,H56c), C74A(H74a,H74b,H74c),
 C30(H30d,H30e,H30f), C32(H32d,H32e,H32f), C35(H35d,H35e,H35f), C37(H37d,H37e,
 H37f), C56(H56d,H56e,H56f), C74(H74d,H74e,H74f)
;
_shelx_res_checksum              69926
_olex2_date_sample_data_collection 2021-10-27
_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 4.295
_oxdiff_exptl_absorpt_empirical_full_min 0.733