Unusually air-stable copper(i) complexes showing high selectivity for carbon monoxide.
Saeednia, Borna; Sragow, Aria M.; Lin, Yannan; Sheehan, Colton J.; Metlay, Amy S.; Gau, Michael R.; Dye, Samantha A.; O'Konski, Sarah P; Mallouk, Thomas E.; Dmochowski, Ivan J.; Chemical science 16 (2025) 5058–5063; doi:10.1039/d5sc00237k

data_1573940
_publ_section_title
;
 Unusually air-stable copper(i) complexes showing high selectivity for
 carbon monoxide.
;
_journal_issue                   12
_journal_name_full               'Chemical science'
_journal_page_first              5058
_journal_page_last               5063
_journal_paper_doi               10.1039/d5sc00237k
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety
'C51 H54 Cu N4 O6, F6 P, 0.55(C4 H10 O), 0.4(C2 H3 N)'
_chemical_formula_sum            'C54 H60.7 Cu F6 N4.4 O6.55 P'
_chemical_formula_weight         1084.68
_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             2024-05-29
_audit_creation_method
;
Olex2 1.5
(compiled 2021.10.07 svn.r9718050b for OlexSys, GUI svn.r6410)
;
_audit_update_record
;
2024-05-29 deposited with the CCDC.	2025-02-10 downloaded from the CCDC.
;
_cell_angle_alpha                70.349(2)
_cell_angle_beta                 82.732(2)
_cell_angle_gamma                88.868(2)
_cell_formula_units_Z            2
_cell_length_a                   11.8395(6)
_cell_length_b                   14.4553(7)
_cell_length_c                   15.7362(8)
_cell_measurement_reflns_used    9047
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      27.47
_cell_measurement_theta_min      2.28
_cell_volume                     2515.2(2)
_computing_cell_refinement       'Bruker SAINT v8.34A'
_computing_data_collection       'Bruker APEX2 v2018.1-0'
_computing_data_reduction        'Bruker SAINT v8.34A'
_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    'ShelXS-1997 (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.00
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'CCD area detector'
_diffrn_measurement_device_type  'Bruker APEXII'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0304
_diffrn_reflns_av_unetI/netI     0.0223
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            84884
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.551
_diffrn_reflns_theta_min         1.385
_diffrn_source                   'sealed tube'
_exptl_absorpt_coefficient_mu    0.545
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.7024
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS v2014/5'
_exptl_crystal_colour            colorless
_exptl_crystal_colour_primary    colorless
_exptl_crystal_density_diffrn    1.432
_exptl_crystal_description       prism
_exptl_crystal_F_000             1132
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.08
_refine_diff_density_max         1.078
_refine_diff_density_min         -0.923
_refine_diff_density_rms         0.062
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     979
_refine_ls_number_reflns         11588
_refine_ls_number_restraints     898
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0665
_refine_ls_R_factor_gt           0.0508
_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^)+(0.0718P)^2^+2.3525P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1329
_refine_ls_wR_factor_ref         0.1429
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9133
_reflns_number_total             11588
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc00237k2.cif
_cod_data_source_block           9737_CuL1_PF6
_cod_depositor_comments
'Adding full bibliography for 1573940--1573942.cif.'
_cod_original_formula_sum        'C54 H60.70 Cu F6 N4.40 O6.55 P'
_cod_database_code               1573940
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.958
_shelx_estimated_absorpt_t_min   0.899
_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, All N(H) groups,
  All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Cu1 \\sim Cu1' \\sim N1 \\sim N1' \\sim N3 \\sim N3' \\sim N4 \\sim N4' \\sim
C39 \\sim C40 \\sim C40' \\sim C41 \\sim C41' \\sim C42 \\sim C42' \\sim C43
\\sim C43' \\sim C44 \\sim C44' \\sim C45 \\sim C45' \\sim C46 \\sim C46' \\sim
C47 \\sim C47' \\sim C48 \\sim C48' \\sim C49 \\sim C49' \\sim C50 \\sim C50'
\\sim C51 \\sim C51': within 2A with sigma of 0.005 and sigma for terminal
atoms of 0.01 within 2A
N5' \\sim C52' \\sim C53': within 2A with sigma of 0.005 and sigma for terminal
atoms of 0.01 within 2A
O7 \\sim C52 \\sim C53 \\sim C54 \\sim C55 \\sim O7' \\sim C54' \\sim C55'
\\sim C56' \\sim C57' \\sim O8 \\sim C56 \\sim C57 \\sim C58 \\sim C60: within
2A with sigma of 0.002 and sigma for terminal atoms of 0.004 within 2A
O5 \\sim C38 \\sim C38': within 2A with sigma of 0.005 and sigma for terminal
atoms of 0.01 within 2A
P1 \\sim F1 \\sim F2 \\sim F3 \\sim F4 \\sim F5 \\sim F6 \\sim P1' \\sim F1'
\\sim F2' \\sim F3' \\sim F4' \\sim F5' \\sim F6': within 2A with sigma of
0.005 and sigma for terminal atoms of 0.01 within 2A
Uanis(C53) \\sim Ueq, Uanis(C52) \\sim Ueq, Uanis(O7) \\sim Ueq, Uanis(C54)
\\sim Ueq, Uanis(C55) \\sim Ueq, Uanis(C57) \\sim Ueq, Uanis(O8) \\sim Ueq,
Uanis(C58) \\sim Ueq, Uanis(C56) \\sim Ueq, Uanis(C60) \\sim Ueq, Uanis(C54')
\\sim Ueq, Uanis(O7') \\sim Ueq, Uanis(C55') \\sim Ueq, Uanis(C56') \\sim Ueq,
Uanis(C57') \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
3. Same fragment restrains
{Cu1, N1, N3, N4, C46, C47, C48, C49, C50, C51} sigma for 1-2: 0.02, 1-3: 0.04
as in
{Cu1', N1', N3', N4', C46', C47', C48', C49', C50', C51'}
4. Others
 Fixed Sof: Cu1(0.6) N1(0.6) H1(0.6) N3(0.6) H3(0.6) N4(0.6) C46(0.6)
 H46A(0.6) H46B(0.6) C47(0.6) H47A(0.6) H47B(0.6) C48(0.6) H48A(0.6) H48B(0.6)
 C49(0.6) H49A(0.6) H49B(0.6) C50(0.6) H50A(0.6) H50B(0.6) C51(0.6) H51A(0.6)
 H51B(0.6) Cu1'(0.4) N1'(0.4) H1'(0.4) N3'(0.4) H3'(0.4) N4'(0.4) C46'(0.4)
 H46C(0.4) H46D(0.4) C47'(0.4) H47C(0.4) H47D(0.4) C48'(0.4) H48C(0.4)
 H48D(0.4) C49'(0.4) H49C(0.4) H49D(0.4) C50'(0.4) H50C(0.4) H50D(0.4)
 C51'(0.4) H51C(0.4) H51D(0.4) H2A(0.6) H2B(0.4) H15A(0.6) H15B(0.6) H15C(0.4)
 H15D(0.4) C38(0.6) H38A(0.6) H38B(0.6) H38C(0.6) C38'(0.4) H38D(0.4) H38E(0.4)
 H38F(0.4) C40(0.6) H40(0.6) C40'(0.4) H40'(0.4) C41(0.6) H41(0.6) C41'(0.4)
 H41'(0.4) C42(0.6) C42'(0.4) C43(0.6) H43(0.6) C43'(0.4) H43'(0.4) C44(0.6)
 H44(0.6) C44'(0.4) H44'(0.4) C45(0.6) H45A(0.6) H45B(0.6) C45'(0.4) H45C(0.4)
 H45D(0.4) P1(0.6) F1(0.6) F2(0.6) F3(0.6) F4(0.6) F5(0.6) F6(0.6) P1'(0.4)
 F1'(0.4) F2'(0.4) F3'(0.4) F4'(0.4) F5'(0.4) F6'(0.4) C53(0.1) H53A(0.1)
 H53B(0.1) O7(0.1) C52(0.1) H52A(0.1) H52B(0.1) H52C(0.1) C54(0.1) H54A(0.1)
 H54B(0.1) C55(0.1) H55A(0.1) H55B(0.1) H55C(0.1) O7'(0.2) C54'(0.2) H54C(0.2)
 H54D(0.2) H54E(0.2) C55'(0.2) H55D(0.2) H55E(0.2) C56'(0.2) H56A(0.2)
 H56B(0.2) C57'(0.2) H57A(0.2) H57B(0.2) H57C(0.2) O8(0.25) C56(0.25)
 H56C(0.25) H56D(0.25) H56E(0.25) C57(0.25) H57D(0.25) H57E(0.25) C58(0.25)
 H58A(0.25) H58B(0.25) C60(0.25) H60A(0.25) H60B(0.25) H60C(0.25) N5'(0.4)
 C52'(0.4) C53'(0.4) H53C(0.4) H53D(0.4) H53E(0.4)
5.a Free rotating group:
 C53(O7,C52,C54,C55), O7'(C54',C55',C56',C57'), O8(C56,C57,C58,C60), N5'(C52',
 C53')
5.b Ternary CH refined with riding coordinates:
 N1(H1), N3(H3), N1'(H1'), N3'(H3'), N2(H2A), N2(H2B)
5.c Secondary CH2 refined with riding coordinates:
 C46(H46A,H46B), C47(H47A,H47B), C48(H48A,H48B), C49(H49A,H49B), C50(H50A,
 H50B), C51(H51A,H51B), C46'(H46C,H46D), C47'(H47C,H47D), C48'(H48C,H48D),
 C49'(H49C,H49D), C50'(H50C,H50D), C51'(H51C,H51D), C1(H1A,H1B), C15(H15A,H15B),
  C15(H15C,H15D), C16(H16A,H16B), C30(H30A,H30B), C31(H31A,H31B), C45(H45A,
 H45B), C45'(H45C,H45D), C53(H53A,H53B), C54(H54A,H54B), C55'(H55D,H55E),
 C56'(H56A,H56B), C57(H57D,H57E), C58(H58A,H58B)
5.d Me refined with riding coordinates:
 C52(H52A,H52B,H52C), C55(H55A,H55B,H55C)
5.e Aromatic/amide H refined with riding coordinates:
 C4(H4), C7(H7), C9(H9), C11(H11), C13(H13), C14(H14), C19(H19), C22(H22),
 C25(H25), C26(H26), C28(H28), C29(H29), C34(H34), C37(H37), C40(H40),
 C40'(H40'), C41(H41), C41'(H41'), C43(H43), C43'(H43'), C44(H44), C44'(H44')
5.f Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C23(H23A,H23B,H23C), C38(H38A,H38B,H38C), C38'(H38D,H38E,
 H38F), C54'(H54C,H54D,H54E), C57'(H57A,H57B,H57C), C56(H56C,H56D,H56E),
 C60(H60A,H60B,H60C), C53'(H53C,H53D,H53E)
;
_shelx_res_checksum              94480
_olex2_submission_special_instructions 'No special instructions were received'