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_1574737
_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         'C100 H157 Ca2 N7 O, C6 H14'
_chemical_formula_sum            'C106 H171 Ca2 N7 O'
_chemical_formula_weight         1639.65
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-02-28
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-03-04 deposited with the CCDC.	2025-05-27 downloaded from the CCDC.
;
_cell_angle_alpha                82.572(3)
_cell_angle_beta                 88.483(3)
_cell_angle_gamma                63.757(3)
_cell_formula_units_Z            1
_cell_length_a                   12.6865(4)
_cell_length_b                   13.1676(5)
_cell_length_c                   16.5859(6)
_cell_measurement_reflns_used    13850
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      72.4900
_cell_measurement_theta_min      3.7610
_cell_volume                     2462.78(16)
_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  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2903
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.996
_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   -115.00 -16.00   1.00    6.32    --  -40.61 -38.00 120.00   99
  2  \w    -65.00  34.00   1.00    6.32    --  -40.61  38.00 -60.00   99
  3  \w     30.00  99.00   1.00    6.32    --   40.61-130.00 -91.00   69
  4  \w    -32.00  69.00   1.00    6.32    --   40.61 -57.00   0.00  101
  5  \w     32.00 134.00   1.00   25.28    --  104.57 -61.00 150.00  102
  6  \w     28.00 109.00   1.00   25.28    --  104.57-111.00  30.00   81
  7  \w     22.00 106.00   1.00   25.28    --  104.57 -94.00  90.00   84
  8  \w     28.00 109.00   1.00   25.28    --  104.57-111.00-180.00   81
  9  \w     32.00 130.00   1.00   25.28    --  104.57 -45.00 -60.00   98
 10  \w    103.00 178.00   1.00   25.28    --  104.57  77.00  90.00   75
 11  \w    103.00 178.00   1.00   25.28    --  104.57  77.00  30.00   75
 12  \w    103.00 178.00   1.00   25.28    --  104.57  77.00-120.00   75
 13  \w     23.00 157.00   1.00   25.28    --  104.57 -15.00  60.00  134
 14  \w     28.00 109.00   1.00   25.28    --  104.57-111.00 -30.00   81
 15  \w   -113.00 -12.00   1.00    6.32    --  -40.61 -57.00  30.00  101
 16  \w   -113.00 -12.00   1.00    6.32    --  -40.61 -57.00-150.00  101
 17  \w   -113.00 -12.00   1.00    6.32    --  -40.61 -57.00 -60.00  101
 18  \w    -34.00  65.00   1.00    6.32    --   40.61 -38.00  90.00   99
 19  \w     52.00 178.00   1.00   25.28    --  104.57  15.00 -60.00  126
 20  \w     76.00 178.00   1.00   25.28    --  104.57  30.00-180.00  102
;
_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      0.0334876000
_diffrn_orient_matrix_UB_12      0.0852180000
_diffrn_orient_matrix_UB_13      -0.0535880000
_diffrn_orient_matrix_UB_21      0.0233065000
_diffrn_orient_matrix_UB_22      0.0424472000
_diffrn_orient_matrix_UB_23      0.0768176000
_diffrn_orient_matrix_UB_31      0.1291730000
_diffrn_orient_matrix_UB_32      -0.0908209000
_diffrn_orient_matrix_UB_33      0.0034245000
_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  0.0252
_diffrn_reflns_av_unetI/netI     0.0234
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            27358
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.497
_diffrn_reflns_theta_min         2.688
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.371
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.414
_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 yellowish orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.106
_exptl_crystal_description       block
_exptl_crystal_F_000             904
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.209
_exptl_crystal_size_min          0.088
_refine_diff_density_max         0.338
_refine_diff_density_min         -0.277
_refine_diff_density_rms         0.038
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     891
_refine_ls_number_reflns         9517
_refine_ls_number_restraints     1132
_refine_ls_restrained_S_all      0.991
_refine_ls_R_factor_all          0.0553
_refine_ls_R_factor_gt           0.0494
_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^)+(0.0773P)^2^+0.8357P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1363
_refine_ls_wR_factor_ref         0.1425
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8359
_reflns_number_total             9517
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc02829a2.cif
_cod_data_source_block           hasj210609a
_cod_depositor_comments
'Adding full bibliography for 1574737--1574741.cif.'
_cod_database_code               1574737
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C106H171Ca2N7O
_shelx_estimated_absorpt_t_max   0.889
_shelx_estimated_absorpt_t_min   0.610
_reflns_odcompleteness_completeness 99.74
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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, All C(H,H,H,H,H,H) groups
2. Restrained distances
 C57-C56 \\sim C55-C54 \\sim C56-C55 \\sim C54-C53 \\sim C58-C53 \\sim C58-C57
 with sigma of 0.02
 C12A-C7 \\sim C12-C7
 with sigma of 0.02
 C15A-C12A \\sim C15-C12 \\sim C12A-C13A \\sim C13-C12
 with sigma of 0.02
 C14-C13 \\sim C14A-C13A \\sim C15A-C16A \\sim C16-C15
 with sigma of 0.02
 C66A-C65A \\sim C65-C66
 with sigma of 0.02
 C60A-C61A \\sim C60-C61 \\sim C62-C61 \\sim C62A-C61A
 with sigma of 0.02
 O1A-C63A \\sim O1-C63 \\sim O1-C59 \\sim O1A-C59A
 with sigma of 0.02
 C60A-C59A \\sim C60-C59 \\sim C63-C62 \\sim C63A-C62A
 with sigma of 0.02
 C65-C64 \\sim C65A-C64A \\sim C64A-C64A_$2 \\sim C64-C64_$2
 with sigma of 0.02
 C19A-C18A \\sim C19-C18 \\sim C21-C20 \\sim C20A-C21A
 with sigma of 0.02
 C17-C11 \\sim C17A-C11
 with sigma of 0.02
 C18-C17 \\sim C18A-C17A \\sim C20-C17 \\sim C20A-C17A
 with sigma of 0.02
 Ca1-O1 \\sim Ca1-O1A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C64A \\sim C65A \\sim C66A \\sim C64 \\sim C65 \\sim C66: within 4A with sigma
of 0.02 and sigma for terminal atoms of 0.04 within 4A
O1 \\sim C59 \\sim C60 \\sim C61 \\sim C63 \\sim C47 \\sim C48 \\sim C49 \\sim
C50 \\sim C51 \\sim C52: within 4A with sigma of 0.02 and sigma for terminal
atoms of 0.04 within 4A
C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C12A \\sim C13A \\sim C14A
\\sim C15A \\sim C16A: within 4A with sigma of 0.02 and sigma for terminal
atoms of 0.04 within 4A
O1 \\sim C59 \\sim C60 \\sim C61 \\sim C62 \\sim C63 \\sim O1A \\sim C59A \\sim
C60A \\sim C61A \\sim C62A \\sim C63A: within 4A with sigma of 0.02 and sigma
for terminal atoms of 0.04 within 4A
C17 \\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim C17A \\sim C18A \\sim C19A
\\sim C20A \\sim C21A: within 4A with sigma of 0.02 and sigma for terminal
atoms of 0.04 within 4A
4. Rigid body (RIGU) restrains
 C64A, C65A, C66A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
5. Others
 Sof(C12A)=Sof(H12A)=Sof(C13A)=Sof(H13c)=Sof(H13d)=Sof(C14A)=Sof(H14d)=
 Sof(H14e)=Sof(H14f)=Sof(C15A)=Sof(H15c)=Sof(H15d)=Sof(C16A)=Sof(H16d)=
 Sof(H16e)=Sof(H16f)=1-FVAR(1)
 Sof(C12)=Sof(H12)=Sof(C13)=Sof(H13a)=Sof(H13b)=Sof(C14)=Sof(H14a)=Sof(H14b)=
 Sof(H14c)=Sof(C15)=Sof(H15a)=Sof(H15b)=Sof(C16)=Sof(H16a)=Sof(H16b)=Sof(H16c)=
 FVAR(1)
 Sof(C64)=Sof(H64c)=Sof(H64d)=Sof(C65)=Sof(H65c)=Sof(H65d)=Sof(C66)=Sof(H66d)=
 Sof(H66e)=Sof(H66f)=1-FVAR(2)
 Sof(C64A)=Sof(H64a)=Sof(H64b)=Sof(C65A)=Sof(H65a)=Sof(H65b)=Sof(C66A)=
 Sof(H66a)=Sof(H66b)=Sof(H66c)=FVAR(2)
 Sof(H33a)=Sof(H37d)=Sof(H37e)=Sof(H37f)=Sof(C34A)=Sof(H34c)=Sof(H34d)=
 Sof(C35A)=Sof(H35d)=Sof(H35e)=Sof(H35f)=Sof(C36A)=Sof(H36c)=Sof(H36d)=1-FVAR(3)
 Sof(H33)=Sof(H37a)=Sof(H37b)=Sof(H37c)=Sof(C34)=Sof(H34a)=Sof(H34b)=Sof(C35)=
 Sof(H35a)=Sof(H35b)=Sof(H35c)=Sof(C36)=Sof(H36a)=Sof(H36b)=FVAR(3)
 Sof(O1A)=Sof(C59A)=Sof(H59c)=Sof(H59d)=Sof(C60A)=Sof(H60c)=Sof(H60d)=
 Sof(C61A)=Sof(H61c)=Sof(H61d)=Sof(C62A)=Sof(H62c)=Sof(H62d)=Sof(C63A)=
 Sof(H63c)=Sof(H63d)=0.5*(1-FVAR(5))
 Sof(O1)=Sof(C59)=Sof(H59a)=Sof(H59b)=Sof(C60)=Sof(H60a)=Sof(H60b)=Sof(C61)=
 Sof(H61a)=Sof(H61b)=Sof(C62)=Sof(H62a)=Sof(H62b)=Sof(C63)=Sof(H63a)=Sof(H63b)=
 0.5*FVAR(5)
 Sof(C17A)=Sof(H17A)=Sof(C18A)=Sof(H18c)=Sof(H18d)=Sof(C19A)=Sof(H19d)=
 Sof(H19e)=Sof(H19f)=Sof(C20A)=Sof(H20c)=Sof(H20d)=Sof(C21A)=Sof(H21d)=
 Sof(H21e)=Sof(H21f)=1-FVAR(5)
 Sof(C17)=Sof(H17)=Sof(C18)=Sof(H18a)=Sof(H18b)=Sof(C19)=Sof(H19a)=Sof(H19b)=
 Sof(H19c)=Sof(C20)=Sof(H20a)=Sof(H20b)=Sof(C21)=Sof(H21a)=Sof(H21b)=Sof(H21c)=
 FVAR(5)
 Fixed Sof: Ca1(0.5) Ca2(0.5) N3(0.5) N4(0.5) N5(0.5) C38(0.5) C39(0.5)
 C40(0.5) C41(0.5) H41(0.5) C42(0.5) H42a(0.5) H42b(0.5) C43(0.5) H43a(0.5)
 H43b(0.5) C44(0.5) H44a(0.5) H44b(0.5) C45(0.5) H45a(0.5) H45b(0.5) C46(0.5)
 H46a(0.5) H46b(0.5) C47(0.5) H47(0.5) C48(0.5) H48a(0.5) H48b(0.5) C49(0.5)
 H49a(0.5) H49b(0.5) C50(0.5) H50a(0.5) H50b(0.5) C51(0.5) H51a(0.5) H51b(0.5)
 C52(0.5) H52a(0.5) H52b(0.5) C53(0.5) H53(0.5) C54(0.5) H54a(0.5) H54b(0.5)
 C55(0.5) H55a(0.5) H55b(0.5) C56(0.5) H56a(0.5) H56b(0.5) C57(0.5) H57a(0.5)
 H57b(0.5) C58(0.5) H58a(0.5) H58b(0.5)
6.a Ternary CH refined with riding coordinates:
 C28(H28), C33(H33), C33(H33a), C12(H12), C17(H17), C12A(H12A), C17A(H17A),
 C41(H41), C47(H47), C53(H53)
6.b Secondary CH2 refined with riding coordinates:
 C29(H29a,H29b), C31(H31a,H31b), C13(H13a,H13b), C15(H15a,H15b), C18(H18a,
 H18b), C20(H20a,H20b), C34(H34a,H34b), C36(H36a,H36b), C13A(H13c,H13d),
 C15A(H15c,H15d), C18A(H18c,H18d), C20A(H20c,H20d), C34A(H34c,H34d), C36A(H36c,
 H36d), C59(H59a,H59b), C60(H60a,H60b), C61(H61a,H61b), C62(H62a,H62b),
 C63(H63a,H63b), C59A(H59c,H59d), C60A(H60c,H60d), C61A(H61c,H61d), C62A(H62c,
 H62d), C63A(H63c,H63d), C42(H42a,H42b), C43(H43a,H43b), C44(H44a,H44b),
 C45(H45a,H45b), C46(H46a,H46b), C48(H48a,H48b), C49(H49a,H49b), C50(H50a,H50b),
  C51(H51a,H51b), C52(H52a,H52b), C54(H54a,H54b), C55(H55a,H55b), C56(H56a,
 H56b), C57(H57a,H57b), C58(H58a,H58b), C64A(H64a,H64b), C65A(H65a,H65b),
 C64(H64c,H64d), C65(H65c,H65d)
6.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C24(H24), C25(H25), C26(H26)
6.d Idealised Me refined as rotating group:
 C1(H1a,H1b,H1c), C5(H5a,H5b,H5c), C30(H30a,H30b,H30c), C32(H32a,H32b,H32c),
 C37(H37a,H37b,H37c), C37(H37d,H37e,H37f), C14(H14a,H14b,H14c), C16(H16a,H16b,
 H16c), C19(H19a,H19b,H19c), C21(H21a,H21b,H21c), C35(H35a,H35b,H35c),
 C14A(H14d,H14e,H14f), C16A(H16d,H16e,H16f), C19A(H19d,H19e,H19f), C21A(H21d,
 H21e,H21f), C35A(H35d,H35e,H35f), C66A(H66a,H66b,H66c), C66(H66d,H66e,H66f)
;
_shelx_res_checksum              16811
_olex2_date_sample_data_collection 2021-06-09
_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 1.460
_oxdiff_exptl_absorpt_empirical_full_min 0.760