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_1574739
_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         'C81 H125 Ca N5, 1[C6H14]'
_chemical_formula_sum            'C87 H139 Ca N5'
_chemical_formula_weight         1295.10
_chemical_properties_physical    Moisture-sensitive
_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                68.531(2)
_cell_angle_beta                 87.284(2)
_cell_angle_gamma                76.379(2)
_cell_formula_units_Z            2
_cell_length_a                   13.4820(3)
_cell_length_b                   16.3223(5)
_cell_length_c                   20.2700(5)
_cell_measurement_reflns_used    24862
_cell_measurement_temperature    100.0(4)
_cell_measurement_theta_max      72.3040
_cell_measurement_theta_min      3.3400
_cell_volume                     4030.60(19)
_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 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(4)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2903
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.973
_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    -69.00  33.00   1.00    2.00    --  -40.61  57.00-150.00  102
  2  \w   -115.00 -16.00   1.00    2.00    --  -40.61 -38.00 -90.00   99
  3  \w    -65.00  34.00   1.00    2.00    --  -40.61  38.00  90.00   99
  4  \w     27.00  97.00   1.00    2.00    --   40.61-125.00-120.00   70
  5  \w     32.00 130.00   1.00    6.00    --  104.57 -45.00  60.00   98
  6  \w    103.00 178.00   1.00    6.00    --  104.57  77.00-150.00   75
  7  \w     21.00 106.00   1.00    6.00    --  104.57 -89.00-123.00   85
  8  \w     28.00 109.00   1.00    6.00    --  104.57-111.00-180.00   81
  9  \w     32.00 130.00   1.00    6.00    --  104.57 -45.00 -90.00   98
 10  \w     28.00 109.00   1.00    6.00    --  104.57-111.00 -30.00   81
 11  \w    103.00 178.00   1.00    6.00    --  104.57  77.00   0.00   75
 12  \w     28.00 109.00   1.00    6.00    --  104.57-111.00  30.00   81
 13  \w     32.00 130.00   1.00    6.00    --  104.57 -45.00 150.00   98
 14  \w     22.00 106.00   1.00    6.00    --  104.57 -94.00  60.00   84
 15  \w     52.00 178.00   1.00    6.00    --  104.57  15.00 -30.00  126
 16  \w   -113.00 -12.00   1.00    2.00    --  -40.61 -57.00  90.00  101
 17  \w   -113.00 -12.00   1.00    2.00    --  -40.61 -57.00   0.00  101
 18  \w    -65.00  34.00   1.00    2.00    --  -40.61  38.00 -30.00   99
 19  \w   -113.00 -12.00   1.00    2.00    --  -40.61 -57.00-180.00  101
 20  \w     52.00 178.00   1.00    6.00    --  104.57  15.00 150.00  126
;
_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      0.1028263000
_diffrn_orient_matrix_UB_12      -0.0307925000
_diffrn_orient_matrix_UB_13      -0.0304542000
_diffrn_orient_matrix_UB_21      0.0566133000
_diffrn_orient_matrix_UB_22      -0.0097514000
_diffrn_orient_matrix_UB_23      0.0677023000
_diffrn_orient_matrix_UB_31      -0.0084345000
_diffrn_orient_matrix_UB_32      -0.0992089000
_diffrn_orient_matrix_UB_33      0.0342202000
_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  0.0238
_diffrn_reflns_av_unetI/netI     0.0224
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            44575
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.570
_diffrn_reflns_theta_min         2.993
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.996
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.335
_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 colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.067
_exptl_crystal_description       block
_exptl_crystal_F_000             1432
_exptl_crystal_size_max          0.49
_exptl_crystal_size_mid          0.337
_exptl_crystal_size_min          0.203
_refine_diff_density_max         0.533
_refine_diff_density_min         -0.346
_refine_diff_density_rms         0.044
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.069
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1132
_refine_ls_number_reflns         15568
_refine_ls_number_restraints     3373
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.0628
_refine_ls_R_factor_gt           0.0580
_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^)+(0.0916P)^2^+1.3758P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1628
_refine_ls_wR_factor_ref         0.1683
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13929
_reflns_number_total             15568
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc02829a2.cif
_cod_data_source_block           hasj210813a
_cod_depositor_comments
'Adding full bibliography for 1574737--1574741.cif.'
_cod_database_code               1574739
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         C87CaH139N5
_shelx_estimated_absorpt_t_max   0.823
_shelx_estimated_absorpt_t_min   0.641
_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
 C57A-C58A \\sim C57-C58 \\sim C56A-C55A \\sim C55-C56 \\sim C32-C31 \\sim
C32A-C31A \\sim C29A-C30A ~
 C30-C29 \\sim C21-C20 \\sim C20A-C21A \\sim C67-C66 \\sim C67A-C66A \\sim
C69-C68 \\sim C69A-C68A ~
 C74A-C73A \\sim C71A-C72A \\sim C72-C71 \\sim C74-C73
 with sigma of 0.02
 N5-C76A \\sim N5-C76
 with sigma of 0.02
 N4A-C41 \\sim N4-C41
 with sigma of 0.02
 C66A-C68A \\sim C68-C66 \\sim C73A-C71A \\sim C73-C71 \\sim C31A-C29A \\sim
C31-C29 \\sim C20A-C18 ~
 C57A-C55A \\sim C57-C55 \\sim C20-C18
 with sigma of 0.02
 C65A-C60A \\sim C65-C60 \\sim C70-C64 \\sim C64A-C70A \\sim C54-C48 \\sim
C54A-C48 \\sim C28A-C23 ~
 C28-C23
 with sigma of 0.02
 N4A-C59A \\sim N4-C59
 with sigma of 0.02
 C71-C70 \\sim C70-C73 \\sim C71A-C70A \\sim C70A-C73A \\sim C65A-C66A \\sim
C65A-C68A \\sim C68-C65 ~
 C66-C65 \\sim C29-C28 \\sim C28A-C29A \\sim C31-C28 \\sim C28A-C31A \\sim
C20A-C17 \\sim C20-C17 ~
 C54A-C57A \\sim C57-C54 \\sim C55-C54 \\sim C54A-C55A
 with sigma of 0.02
 C61-C62 \\sim C62A-C61A \\sim C63-C62 \\sim C62A-C63A
 with sigma of 0.02
 C60-C59 \\sim C59A-C60A \\sim C64-C59 \\sim C64A-C59A
 with sigma of 0.02
 C76-C81 \\sim C76A-C81A \\sim C76A-C77A \\sim C77-C76
 with sigma of 0.02
 C61-C60 \\sim C60A-C61A \\sim C63-C64 \\sim C64A-C63A
 with sigma of 0.02
 C80-C81 \\sim C80A-C81A \\sim C78-C77 \\sim C78A-C77A
 with sigma of 0.02
 C79-C80 \\sim C80A-C79A \\sim C79-C78 \\sim C78A-C79A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
N4A \\sim C59A \\sim C60A \\sim C61A \\sim C62A \\sim C63A \\sim C64A \\sim
C65A \\sim C66A \\sim C67A \\sim C68A \\sim C69A \\sim C70A \\sim C71A \\sim
C72A \\sim C73A \\sim C74A \\sim N4 \\sim C59 \\sim C60 \\sim C61 \\sim C62
\\sim C63 \\sim C64 \\sim C65 \\sim C66 \\sim C67 \\sim C68 \\sim C69 \\sim C70
\\sim C71 \\sim C72 \\sim C73 \\sim C74: within 4A with sigma of 0.02 and sigma
for terminal atoms of 0.04 within 4A
C76A \\sim C77A \\sim C78A \\sim C79A \\sim C80A \\sim C81A \\sim C76 \\sim C77
\\sim C78 \\sim C79 \\sim C80 \\sim C81: within 4A with sigma of 0.02 and sigma
for terminal atoms of 0.04 within 4A
C23 \\sim C28A \\sim C29A \\sim C30A \\sim C31A \\sim C32A \\sim C28 \\sim C29
\\sim C30 \\sim C31 \\sim C32: within 4A with sigma of 0.02 and sigma for
terminal atoms of 0.04 within 4A
C17 \\sim C20A \\sim C21A \\sim C20 \\sim C21: within 4A with sigma of 0.02 and
sigma for terminal atoms of 0.04 within 4A
C54A \\sim C55A \\sim C56A \\sim C57A \\sim C58A \\sim C54 \\sim C55 \\sim C56
\\sim C57 \\sim C58: within 4A with sigma of 0.02 and sigma for terminal atoms
of 0.04 within 4A
4. Rigid body (RIGU) restrains
 C17, C20A, C21A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(N4A)=Sof(C59A)=Sof(C60A)=Sof(C61A)=Sof(H61A)=Sof(C62A)=Sof(H62A)=
 Sof(C63A)=Sof(H63A)=Sof(C64A)=Sof(C65A)=Sof(H65A)=Sof(C66A)=Sof(H66A)=
 Sof(H66B)=Sof(C67A)=Sof(H67A)=Sof(H67B)=Sof(H67C)=Sof(C68A)=Sof(H68A)=
 Sof(H68B)=Sof(C69A)=Sof(H69A)=Sof(H69B)=Sof(H69C)=Sof(C70A)=Sof(H70A)=
 Sof(C71A)=Sof(H71A)=Sof(H71B)=Sof(C72A)=Sof(H72A)=Sof(H72B)=Sof(H72C)=
 Sof(C73A)=Sof(H73A)=Sof(H73B)=Sof(C74A)=Sof(H74A)=Sof(H74B)=Sof(H74C)=1-FVAR(1)
 Sof(N4)=Sof(C59)=Sof(C60)=Sof(C61)=Sof(H61)=Sof(C62)=Sof(H62)=Sof(C63)=
 Sof(H63)=Sof(C64)=Sof(C65)=Sof(H65)=Sof(C66)=Sof(H66C)=Sof(H66D)=Sof(C67)=
 Sof(H67D)=Sof(H67E)=Sof(H67F)=Sof(C68)=Sof(H68C)=Sof(H68D)=Sof(C69)=Sof(H69D)=
 Sof(H69E)=Sof(H69F)=Sof(C70)=Sof(H70)=Sof(C71)=Sof(H71C)=Sof(H71D)=Sof(C72)=
 Sof(H72D)=Sof(H72E)=Sof(H72F)=Sof(C73)=Sof(H73C)=Sof(H73D)=Sof(C74)=Sof(H74D)=
 Sof(H74E)=Sof(H74F)=FVAR(1)
 Sof(C76A)=Sof(H76A)=Sof(C77A)=Sof(H77A)=Sof(H77B)=Sof(C78A)=Sof(H78A)=
 Sof(H78B)=Sof(C79A)=Sof(H79A)=Sof(H79B)=Sof(C80A)=Sof(H80A)=Sof(H80B)=
 Sof(C81A)=Sof(H81A)=Sof(H81B)=1-FVAR(2)
 Sof(C76)=Sof(H76)=Sof(C77)=Sof(H77C)=Sof(H77D)=Sof(C78)=Sof(H78C)=Sof(H78D)=
 Sof(C79)=Sof(H79C)=Sof(H79D)=Sof(C80)=Sof(H80C)=Sof(H80D)=Sof(C81)=Sof(H81C)=
 Sof(H81D)=FVAR(2)
 Sof(C54A)=Sof(H54A)=Sof(C55A)=Sof(H55A)=Sof(H55B)=Sof(C56A)=Sof(H56A)=
 Sof(H56B)=Sof(H56C)=Sof(C57A)=Sof(H57A)=Sof(H57B)=Sof(C58A)=Sof(H58A)=
 Sof(H58B)=Sof(H58C)=1-FVAR(3)
 Sof(C54)=Sof(H54)=Sof(C55)=Sof(H55C)=Sof(H55D)=Sof(C56)=Sof(H56D)=Sof(H56E)=
 Sof(H56F)=Sof(C57)=Sof(H57C)=Sof(H57D)=Sof(C58)=Sof(H58D)=Sof(H58E)=Sof(H58F)=
 FVAR(3)
 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)=1-FVAR(4)
 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)=
 FVAR(4)
 Sof(H17A)=Sof(C20A)=Sof(H20A)=Sof(H20B)=Sof(C21A)=Sof(H21A)=Sof(H21B)=
 Sof(H21C)=1-FVAR(5)
 Sof(H17)=Sof(C20)=Sof(H20C)=Sof(H20D)=Sof(C21)=Sof(H21D)=Sof(H21E)=Sof(H21F)=
 FVAR(5)
6.a Ternary CH refined with riding coordinates:
 C12(H12), C17(H17), C17(H17A), C33(H33), C49(H49), C28A(H28A), C54A(H54A),
 C65A(H65A), C70A(H70A), C76A(H76A), C28(H28), C54(H54), C65(H65), C70(H70),
 C76(H76)
6.b Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C15(H15A,H15B), C18(H18A,H18B), C34(H34A,H34B), C36(H36A,
 H36B), C50(H50A,H50B), C52(H52A,H52B), C20A(H20A,H20B), C29A(H29A,H29B),
 C31A(H31A,H31B), C55A(H55A,H55B), C57A(H57A,H57B), C66A(H66A,H66B), C68A(H68A,
 H68B), C71A(H71A,H71B), C73A(H73A,H73B), C77A(H77A,H77B), C78A(H78A,H78B),
 C79A(H79A,H79B), C80A(H80A,H80B), C81A(H81A,H81B), C20(H20C,H20D), C29(H29C,
 H29D), C31(H31C,H31D), C55(H55C,H55D), C57(H57C,H57D), C66(H66C,H66D),
 C68(H68C,H68D), C71(H71C,H71D), C73(H73C,H73D), C77(H77C,H77D), C78(H78C,H78D),
  C79(H79C,H79D), C80(H80C,H80D), C81(H81C,H81D)
6.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), C61A(H61A), C62A(H62A), C63A(H63A), C61(H61),
 C62(H62), C63(H63)
6.d Idealised Me refined with riding coordinates:
 C67A(H67A,H67B,H67C)
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), C35(H35A,H35B,H35C), C37(H37A,H37B,H37C), C38(H38A,H38B,
 H38C), C42(H42A,H42B,H42C), C51(H51A,H51B,H51C), C53(H53A,H53B,H53C),
 C21A(H21A,H21B,H21C), C30A(H30A,H30B,H30C), C32A(H32A,H32B,H32C), C56A(H56A,
 H56B,H56C), C58A(H58A,H58B,H58C), C69A(H69A,H69B,H69C), C72A(H72A,H72B,H72C),
 C74A(H74A,H74B,H74C), C21(H21D,H21E,H21F), C30(H30D,H30E,H30F), C32(H32D,H32E,
 H32F), C56(H56D,H56E,H56F), C58(H58D,H58E,H58F), C67(H67D,H67E,H67F), C69(H69D,
 H69E,H69F), C72(H72D,H72E,H72F), C74(H74D,H74E,H74F)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              63783
_shelx_fab_checksum              13697
_olex2_date_sample_data_collection 2021-08-13
_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 1.592
_oxdiff_exptl_absorpt_empirical_full_min 0.818