A New Tri-nuclear Cu-carbonate Cluster Utilizing CO2 as C1-Building Block-Reactive Intermediates, Probable Mechanism, EPR and Magnetic Studies
Das, Biswanath; Bhadbhade, Mohan; Thapper, Anders; Ling, Chris D.; Colbran, Stephen Boyd; Dalton Transactions  (2019) –; doi:10.1039/C8DT04858D

data_7048786
_publ_section_title
;
 A New Tri-nuclear Cu-carbonate Cluster Utilizing CO2 as C1-Building
 Block-Reactive Intermediates, Probable Mechanism, EPR and Magnetic
 Studies
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/C8DT04858D
_journal_year                    2019
_chemical_formula_moiety         'C36.33 H48 Cu N4 O, 4(F2 P0.33)'
_chemical_formula_sum            'C36.33 H48 Cu F8 N4 O P1.33'
_chemical_formula_weight         813.62
_space_group_crystal_system      trigonal
_space_group_IT_number           146
_space_group_name_Hall           'R 3'
_space_group_name_H-M_alt        'R 3'
_symmetry_space_group_name_Hall  'R 3'
_symmetry_space_group_name_H-M   'R 3 :H'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc2145q3
_audit_creation_date             2018-10-22
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-01-24 deposited with the CCDC.
2019-01-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            9
_cell_length_a                   19.4230(19)
_cell_length_b                   19.4230(19)
_cell_length_c                   29.434(3)
_cell_measurement_reflns_used    2663
_cell_measurement_temperature    149.99
_cell_measurement_theta_max      18.041
_cell_measurement_theta_min      2.518
_cell_volume                     9616.4(17)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      149.99
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1113
_diffrn_reflns_av_unetI/netI     0.1420
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            23382
_diffrn_reflns_point_group_measured_fraction_full 0.921
_diffrn_reflns_point_group_measured_fraction_max 0.921
_diffrn_reflns_theta_full        24.998
_diffrn_reflns_theta_max         24.998
_diffrn_reflns_theta_min         2.789
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.627
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6255
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.1278 before and 0.0776 after correction. The Ratio of minimum to maximum transmission is 0.8389. The \l/2 correction factor is 0.00150.'
_exptl_crystal_colour            'bluish green'
_exptl_crystal_colour_modifier   bluish
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.264
_exptl_crystal_description       plate
_exptl_crystal_F_000             3807
_exptl_crystal_size_max          0.114
_exptl_crystal_size_mid          0.107
_exptl_crystal_size_min          0.036
_refine_diff_density_max         0.687
_refine_diff_density_min         -1.068
_refine_diff_density_rms         0.081
_refine_ls_abs_structure_details
;
 Flack x determined using 1164 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.033(18)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     488
_refine_ls_number_reflns         6937
_refine_ls_number_restraints     330
_refine_ls_restrained_S_all      1.090
_refine_ls_R_factor_all          0.1592
_refine_ls_R_factor_gt           0.0812
_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^)+(0.1356P)^2^+3.2895P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2111
_refine_ls_wR_factor_ref         0.2586
_reflns_Friedel_coverage         0.844
_reflns_Friedel_fraction_full    0.843
_reflns_Friedel_fraction_max     0.843
_reflns_number_gt                3786
_reflns_number_total             6937
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8dt04858d2.cif
_cod_data_source_block           bishwanath_27sept16_cu_0m_a
_cod_original_cell_volume        9616(2)
_cod_database_code               7048786
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.978
_shelx_estimated_absorpt_t_min   0.932
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C27-CAD
 2.52 with sigma of 0.02
 C1AA-C1
 1.54 with sigma of 0.02
 C3BA-C24
 2.52 with sigma of 0.02
 C24-C12
 2.52 with sigma of 0.02
 C12-C3BA
 2.52 with sigma of 0.02
 C8AA-C00J
 1.54 with sigma of 0.02
 P2-F4 = P2-F5
 1.64 with sigma of 0.02
 P2-F3AA
 1.64 with sigma of 0.02
 P2-F17 = P2-F4AA = P2-F13
 1.64 with sigma of 0.02
 F17-F4AA
 2.32 with sigma of 0.02
 F3AA-F4AA
 2.32 with sigma of 0.02
 F13-F3AA
 2.32 with sigma of 0.02
 C17-C6 = C9-C30
 2.52 with sigma of 0.02
 C1-C27 = C7AA-C2AA
 2.52 with sigma of 0.02
 C27-CAD = C2AA-C4
 2.52 with sigma of 0.02
 CAD-C1 = C4-C7AA
 2.52 with sigma of 0.02
 C1BA-C0CA = C4BA-C18 = C5AA-C16
 2.52 with sigma of 0.02
 P1-F0AA
 1.64 with sigma of 0.02
 P1-F2AA
 1.64 with sigma of 0.02
 P1-F12
 1.64 with sigma of 0.02
 C32-C5 = C3BA-C24
 2.52 with sigma of 0.02
 C32-C21 = C6BA-C24
 2.52 with sigma of 0.02
 C3BA-C2 = C5-C2 = C24-C2 = C2-C12 = C21-C2
 1.54 with sigma of 0.02
 C21-C5
 2.52 with sigma of 0.02
 C21-C5 = C6BA-C3BA
 2.52 with sigma of 0.02
 C19-C1BA = C0AA-C4BA = C4AA-C5AA
 2.52 with sigma of 0.02
 C0CA-C19 = C18-C0AA = C16-C4AA
 2.52 with sigma of 0.02
 C30-C28 = C13-C6
 2.52 with sigma of 0.02
 C9-C28 = C17-C13
 2.52 with sigma of 0.02
 F2AB-F8A
 2.32 with sigma of 0.02
 F6AA-P2
 1.64 with sigma of 0.02
 P2-F13 = P2-F8AA = P2-F5 = P2-F31 = P2-F17 = P2-F3AA = P2-F3BA = P2-F7AA = P2-
 F4
 1.64 with sigma of 0.02
 P2-F6AA
 1.64 with sigma of 0.02
 F4AA-F31
 2.32 with sigma of 0.02
 F31-F4
 2.32 with sigma of 0.02
 F13-F8AA
 2.32 with sigma of 0.02
 F4-F8AA
 2.32 with sigma of 0.02
 F7AA-F2
 2.32 with sigma of 0.02
 CAD-C1AA \\sim C27-C1AA
 with sigma of 0.02
 F4AA-F13 \\sim F4AA-F3AA \\sim F4AA-F17 \\sim F13-F3AA
 with sigma of 0.04
 P2-F4AA \\sim P2-F13 \\sim P2-F3AA \\sim P2-F17
 with sigma of 0.02
 C2AA-C1AA \\sim C27-C1AA \\sim C7AA-C1AA \\sim C1AA-C1 \\sim C4-C1AA \\sim
CAD-C1AA
 with sigma of 0.02
 P1-F2AA \\sim P1-F12
 with sigma of 0.02
 P1-F20 \\sim P1-F0AA \\sim P1-F2AA \\sim P1-F8 \\sim P1-F18
 with sigma of 0.02
 F0AA-F18 \\sim F8-F20
 with sigma of 0.02
 P1-F2AA \\sim P1-F2AB
 with sigma of 0.02
 P1-F0AA \\sim P1-F0AB
 with sigma of 0.02
 P1-F20 \\sim P1-F20A
 with sigma of 0.02
 P1-F8 \\sim P1-F8A
 with sigma of 0.02
 P1-F0AB \\sim P1-F20 \\sim P1-F20A \\sim P1-F8 \\sim P1-F8A \\sim P1-F2AA
\\sim P1-F2AB \\sim P1-F0AA
 with sigma of 0.02
 C21-C2 \\sim C6BA-C2 \\sim C5-C2 \\sim C3BA-C2 \\sim C24-C2 \\sim C32-C2
 with sigma of 0.02
 C5AA-C00J \\sim C0CA-C00J \\sim C18-C00J \\sim C16-C00J \\sim C19-C00J \\sim
C0AA-C00J \\sim C4AA-
 C00J \\sim C1BA-C00J \\sim C4BA-C00J
 with sigma of 0.02
 C26-C13 \\sim C9-C26 \\sim C26-C17 \\sim C30-C26 \\sim C6-C26 \\sim C28-C26
 with sigma of 0.02
 F2-F7AA \\sim F2-F3BA \\sim F2-F6AA \\sim F2-F5 \\sim F17-F7AA \\sim F17-F3BA
\\sim F17-F5 \\sim F7AA-
 F3BA \\sim F3BA-F6AA \\sim F6AA-F5
 with sigma of 0.04
 P2-F2 \\sim P2-F17 \\sim P2-F7AA \\sim P2-F3BA \\sim P2-F6AA \\sim P2-F5
 with sigma of 0.02
3. Rigid bond restraints
 F0AA, F2AA
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 F8, F2AA, F0AA, F20
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C21, CAD, C4, C1, C7AA, C27, C2AA
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(C6BA) = Uanis(C2)
Uanis(C4) = Uanis(C1AA)
Uanis(C2AA) = Uanis(C1AA)
Uanis(C7AA) = Uanis(C1AA)
Uanis(C2) = Uanis(C21)
Uanis(C16) = Uanis(C19) = Uanis(C0AA) = Uanis(C1BA) = Uanis(C4BA) = Uanis(C5AA)
= Uanis(C0CA) = Uanis(C18) = Uanis(C4AA) = Uanis(C00J)
Uanis(C32) = Uanis(C2)
Uanis(C6) = Uanis(C26)
Uiso(F17) = Uiso(F31)
Uanis(C2AA) = Uanis(C27)
Uanis(Cu1) = Uanis(O00E)
Uanis(C2) = Uanis(C5)
Uiso(F6AA) = Uiso(F2)
Uiso(F31) = Uiso(F4AA)
5. Rigid body (RIGU) restrains
 C3BA, C2
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C21, C2
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C9A, C2AA, CAD, C4, C1, C7AA, C27
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C9, C17, C30, C6, C28, C13, C26
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cu1, O00E
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O00E, C00V
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cu1, O00E, C00V
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C6, C30, C17, C9, C13, C28
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
6. Others
 Fixed Sof: P1(0.33333) F4(0.5) F5(0.5) CAD(0.5) HADA(0.5) HADB(0.5) HADC(0.5)
 C5(0.5) H5A(0.5) H5B(0.5) H5C(0.5) C24(0.5) H24A(0.5) H24B(0.5) H24C(0.5)
 C21(0.5) H21A(0.5) H21B(0.5) H21C(0.5) C3BA(0.5) H3BA(0.5) H3BB(0.5) H3BC(0.5)
 C27(0.5) H27A(0.5) H27B(0.5) H27C(0.5) C1(0.5) H1C(0.5) H1D(0.5) H1E(0.5)
 F12(0.33333) F3AA(0.5) F4AA(0.5) F13(0.5) F17(0.5) C28(0.5) H28A(0.5)
 H28B(0.5) H28C(0.5) C4(0.5) H4C(0.5) H4D(0.5) H4E(0.5) C2AA(0.5) H2AA(0.5)
 H2AB(0.5) H2AC(0.5) C32(0.5) H32A(0.5) H32B(0.5) H32C(0.5) C1BA(0.33333)
 H1BA(0.33333) H1BB(0.33333) H1BC(0.33333) C5AA(0.33333) H5AA(0.33333)
 H5AB(0.33333) H5AC(0.33333) C4BA(0.33333) H4BA(0.33333) H4BB(0.33333)
 H4BC(0.33333) C7AA(0.5) H7AA(0.5) H7AB(0.5) H7AC(0.5) F6AA(0.5) F7AA(0.5)
 C6BA(0.5) H6BA(0.5) H6BB(0.5) H6BC(0.5) C0CA(0.33333) H0CA(0.33333)
 H0CB(0.33333) H0CC(0.33333) F3BA(0.5) F8AA(0.5) F31(0.5) C17(0.5) H17A(0.5)
 H17B(0.5) H17C(0.5) C4AA(0.33333) H4AA(0.33333) H4AB(0.33333) H4AC(0.33333)
 C18(0.33333) H18A(0.33333) H18B(0.33333) H18C(0.33333) C30(0.5) H30A(0.5)
 H30B(0.5) H30C(0.5) C9(0.5) H9C(0.5) H9D(0.5) H9E(0.5) C6(0.5) H6A(0.5)
 H6B(0.5) H6C(0.5) C13(0.5) H13A(0.5) H13B(0.5) H13C(0.5) C0AA(0.33333)
 H0AA(0.33333) H0AB(0.33333) H0AC(0.33333) C16(0.33333) H16A(0.33333)
 H16B(0.33333) H16C(0.33333) C19(0.33333) H19A(0.33333) H19B(0.33333)
 H19C(0.33333) F2AA(0.16667) F0AA(0.16667) F20(0.16667) F8(0.16667)
 F18(0.33333) F20A(0.16666) F0AB(0.16666) F2AB(0.16666) F8A(0.16666) F2(0.5)
 Fixed Uiso: F2AA(0.1) F0AA(0.1) F20(0.1) F8(0.1) F20A(0.1) F0AB(0.1)
 F2AB(0.1) F8A(0.1)
7.a Riding coordinates:
 CAD(HADA,HADB,HADC), C5(H5A,H5B,H5C), C24(H24A,H24B,H24C), C21(H21A,H21B,
 H21C), C3BA(H3BA,H3BB,H3BC), C27(H27A,H27B,H27C), C1(H1C,H1D,H1E), C28(H28A,
 H28B,H28C), C4(H4C,H4D,H4E), C2AA(H2AA,H2AB,H2AC), C32(H32A,H32B,H32C),
 C1BA(H1BA,H1BB,H1BC), C5AA(H5AA,H5AB,H5AC), C4BA(H4BA,H4BB,H4BC), C7AA(H7AA,
 H7AB,H7AC), C6BA(H6BA,H6BB,H6BC), C0CA(H0CA,H0CB,H0CC), C17(H17A,H17B,H17C),
 C4AA(H4AA,H4AB,H4AC), C18(H18A,H18B,H18C), C30(H30A,H30B,H30C), C9(H9C,H9D,
 H9E), C6(H6A,H6B,H6C), C13(H13A,H13B,H13C), C0AA(H0AA,H0AB,H0AC), C16(H16A,
 H16B,H16C), C19(H19A,H19B,H19C)
7.b Free rotating group:
 P2(F4,F5)
7.c Aromatic/amide H refined with riding coordinates:
 C1A(H1A), C2A(H2A), C4A(H4A), C7A(H7A), C9A(H9A), C10A(H10A), C1B(H1B),
 C2B(H2B), C4B(H4B), C7B(H7B), C9B(H9B), C10B(H10B)
;
_shelx_res_checksum              33099
_olex2_submission_special_instructions 'No special instructions were received'