C(sp<sup>3</sup>)-H cyanation by a formal copper(iii) cyanide complex.
Bower, Jamey K.; Reese, Maxwell S.; Mazin, Ilia M.; Zarnitsa, Lina M.; Cypcar, Andrew D.; Moore, Curtis E.; Sokolov, Alexander Yu; Zhang, Shiyu; Chemical science 14 (2023) 1301–1307; doi:10.1039/d2sc06573h

data_1568277
_publ_section_title
;
 C(sp<sup>3</sup>)-H cyanation by a formal copper(iii) cyanide complex.
;
_journal_issue                   5
_journal_name_full               'Chemical science'
_journal_page_first              1301
_journal_page_last               1307
_journal_paper_doi               10.1039/d2sc06573h
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety
'C32 H37 Cu N4 O2, 3.153(C4 H8 O), 0.347(C5 H12)'
_chemical_formula_sum            'C46.35 H66.39 Cu N4 O5.15'
_chemical_formula_weight         825.57
_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
_atom_sites_solution_secondary   difmap
_audit_block_doi                 10.5517/ccdc.csd.cc2b9f9d
_audit_creation_date             2022-02-17
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2021.12.21 svn.raa29eb21 for OlexSys, GUI svn.r6440)
;
_audit_update_record
;
2022-02-22 deposited with the CCDC.	2023-01-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.8870(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.0154(3)
_cell_length_b                   15.4677(3)
_cell_length_c                   22.5915(5)
_cell_measurement_reflns_used    9048
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      68.276
_cell_measurement_theta_min      3.474
_cell_volume                     4505.06(17)
_computing_cell_refinement       'SAINT V8.40B (Bruker, 2021)'
_computing_data_collection       'APEX3 v2019.1-0 (Bruker, 2019)'
_computing_data_reduction        'SAINT V8.40B (Bruker, 2021)'
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_detector                 'Bruker Photon II area detector'
_diffrn_detector_area_resol_mean 10.5
_diffrn_detector_type            'CMOS area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'Kappa Four-Circle Diffractometer'
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'Double Bounce Multilayer Mirrors'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0359
_diffrn_reflns_av_unetI/netI     0.0145
_diffrn_reflns_Laue_measured_fraction_full 0.999
_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       -17
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            102731
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        68.000
_diffrn_reflns_theta_max         68.409
_diffrn_reflns_theta_min         3.473
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_type              'Incoatec I\mus'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.060
_exptl_absorpt_correction_T_max  0.1665
_exptl_absorpt_correction_T_min  0.0657
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1106 before and 0.0587 after correction.
The Ratio of minimum to maximum transmission is 0.3946.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'Dark Blue'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.217
_exptl_crystal_description       Plate
_exptl_crystal_F_000             1771
_exptl_crystal_size_max          0.271
_exptl_crystal_size_mid          0.254
_exptl_crystal_size_min          0.082
_refine_diff_density_max         0.478
_refine_diff_density_min         -0.341
_refine_diff_density_rms         0.058
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     626
_refine_ls_number_reflns         8262
_refine_ls_number_restraints     276
_refine_ls_restrained_S_all      1.087
_refine_ls_R_factor_all          0.0587
_refine_ls_R_factor_gt           0.0525
_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^)+(0.0761P)^2^+3.2881P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1399
_refine_ls_wR_factor_ref         0.1487
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7280
_reflns_number_total             8262
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc06573h2.cif
_cod_data_source_block           Zhang_JKB323
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_diffrn_radiation_probe' value 'X-ray' was changed to
'x-ray' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

data item '_exptl_crystal_colour_modifier' value 'Dark' was changed
to 'dark' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

data item '_exptl_crystal_colour_primary' value 'Blue' was changed to
'blue' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 7556 2019-12-06 15:28:31Z antanas 

 Adding full bibliography for 1568276--1568277.cif.
;
_cod_database_code               1568277
_shelx_shelxl_version_number     2019/1
_shelx_estimated_absorpt_t_max   0.918
_shelx_estimated_absorpt_t_min   0.762
_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. Shared sites
{O3S, O3SB}
3. Restrained distances
 C13S-C14S = C15S-C14S = C15S-C16S = C16S-C17S
 1.54 with sigma of 0.02
 O2S-C8SB = O2S-C8S = O2S-C5S = O2S-C5SB = C5SB-C6S = C5S-C6S = C7S-C6S = C7S-
 C8SB = C7S-C8S
 1.5 with sigma of 0.02
 C18S-O4S
 1.54 with sigma of 0.02
 C21S-C20S
 1.45 with sigma of 0.02
 C19S-C18S
 1.54 with sigma of 0.02
 C20S-C19S
 1.54 with sigma of 0.02
 O4S-C21S
 1.45 with sigma of 0.02
 C15S-C13S
 2.54 with sigma of 0.02
 C16S-C14S
 2.54 with sigma of 0.02
 C15S-C17S
 2.54 with sigma of 0.02
 C19S-C21S
 2.4 with sigma of 0.02
 C20S-C18S
 2.4 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
Uanis(C8SB) = Uanis(C8S)
Uanis(C5S) = Uanis(C5SB)
Uanis(C9S) = Uanis(C9SB)
Uanis(O3S) = Uanis(O3SB)
Uanis(C12B) = Uanis(C12S)
Uanis(C12C) = Uanis(C10S)
Uanis(C11C) = Uanis(C10S)
Uanis(O3SC) = Uanis(O3SB)
Uanis(C10C) = Uanis(C11S)
Uanis(C10S) = Uanis(C11B)
Uanis(C10B) = Uanis(C10S)
Uanis(C3S) = Uanis(C3SB)
Uanis(C2SB) = Uanis(C2S)
Uanis(C14S) = Uanis(C20S)
Uanis(C15S) = Uanis(C21S)
5. Rigid body (RIGU) restrains
 O3S, C9S, C10S, C11S, C12S, C9SB, C10B, C11B
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C13S, C14S, C15S, C16S
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 O3S, C9S, C10S, C11S, C12S, O3SB, C9SB, C10B, C11B, C12B, O3SC, C9SC, C10C,
 C11C, C12C
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 O1S, C1S, C4S, C2S, C3S, C2SB, C3SB
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 O4S, C18S, C19S, C20S, C21S, C13S, C14S, C15S, C16S, C17S
 with sigma for 1-2 distances of 0.0005 and sigma for 1-3 distances of 0.0005
6. Same fragment restrains
{O3S, C12S, C9S, C11S, C10S} sigma for 1-2: 0.02, 1-3: 0.02
{O3SB, C9SB, C12B, C10B, C11B} sigma for 1-2: 0.02, 1-3: 0.02
{O3SC, C9SC, C12C, C10C, C11C} sigma for 1-2: 0.02, 1-3: 0.02
as in
{O1S, C1S, C4S, C2S, C3S}
7. Others
 1*[Sof(O3S)+Sof(C12S)+Sof(H12A)+Sof(H12B)+Sof(C9S)+Sof(H9SA)+Sof(H9SB)+
 Sof(C11S)+Sof(H11A)+Sof(H11B)+Sof(C10S)+Sof(H10A)+Sof(H10B)]+1*[Sof(O3SB)+
 Sof(C9SB)+Sof(H9SC)+Sof(H9SD)+Sof(C12B)+Sof(H12C)+Sof(H12D)+Sof(C10B)+
 Sof(H10C)+Sof(H10D)+Sof(C11B)+Sof(H11C)+Sof(H11D)]+1*[Sof(O3SC)+Sof(C9SC)+
 Sof(H9SE)+Sof(H9SF)+Sof(C12C)+Sof(H12E)+Sof(H12F)+Sof(C10C)+Sof(H10E)+
 Sof(H10F)+Sof(C11C)+Sof(H11E)+Sof(H11F)]=1 with esd of 0
 Sof(H6SC)=Sof(H6SD)=Sof(H7SC)=Sof(H7SD)=Sof(C5SB)=Sof(H5SC)=Sof(H5SD)=
 Sof(C8SB)=Sof(H8SC)=Sof(H8SD)=1-FVAR(1)
 Sof(H6SA)=Sof(H6SB)=Sof(H7SA)=Sof(H7SB)=Sof(C5S)=Sof(H5SA)=Sof(H5SB)=Sof(C8S)=
 Sof(H8SA)=Sof(H8SB)=FVAR(1)
 Sof(O3S)=Sof(C12S)=Sof(H12A)=Sof(H12B)=Sof(C9S)=Sof(H9SA)=Sof(H9SB)=Sof(C11S)=
 Sof(H11A)=Sof(H11B)=Sof(C10S)=Sof(H10A)=Sof(H10B)=FVAR(2)
 Sof(O3SB)=Sof(C9SB)=Sof(H9SC)=Sof(H9SD)=Sof(C12B)=Sof(H12C)=Sof(H12D)=
 Sof(C10B)=Sof(H10C)=Sof(H10D)=Sof(C11B)=Sof(H11C)=Sof(H11D)=FVAR(3)
 Sof(O3SC)=Sof(C9SC)=Sof(H9SE)=Sof(H9SF)=Sof(C12C)=Sof(H12E)=Sof(H12F)=
 Sof(C10C)=Sof(H10E)=Sof(H10F)=Sof(C11C)=Sof(H11E)=Sof(H11F)=FVAR(4)
 Sof(H1SC)=Sof(H1SD)=Sof(H4SC)=Sof(H4SD)=Sof(C2SB)=Sof(H2SC)=Sof(H2SD)=
 Sof(C3SB)=Sof(H3SC)=Sof(H3SD)=1-FVAR(5)
 Sof(H1SA)=Sof(H1SB)=Sof(H4SA)=Sof(H4SB)=Sof(C2S)=Sof(H2SA)=Sof(H2SB)=Sof(C3S)=
 Sof(H3SA)=Sof(H3SB)=FVAR(5)
 Sof(O4S)=Sof(C18S)=Sof(H18A)=Sof(H18B)=Sof(C19S)=Sof(H19D)=Sof(H19E)=
 Sof(C20S)=Sof(H20D)=Sof(H20E)=Sof(C21S)=Sof(H21A)=Sof(H21B)=0.5*(1-FVAR(7))
 Sof(C13S)=Sof(H13A)=Sof(H13B)=Sof(H13C)=Sof(C14S)=Sof(H14A)=Sof(H14B)=
 Sof(C15S)=Sof(H15A)=Sof(H15B)=Sof(C16S)=Sof(H16D)=Sof(H16E)=Sof(C17S)=
 Sof(H17D)=Sof(H17E)=Sof(H17F)=0.5*FVAR(7)
8.a Ternary CH refined with riding coordinates:
 C15(H15), C18(H18), C27(H27), C30(H30)
8.b Secondary CH2 refined with riding coordinates:
 C1S(H1SA,H1SB), C1S(H1SC,H1SD), C4S(H4SA,H4SB), C4S(H4SC,H4SD), C2S(H2SA,
 H2SB), C3S(H3SA,H3SB), C2SB(H2SC,H2SD), C3SB(H3SC,H3SD), C6S(H6SA,H6SB),
 C6S(H6SC,H6SD), C7S(H7SA,H7SB), C7S(H7SC,H7SD), C5S(H5SA,H5SB), C8S(H8SA,H8SB),
  C5SB(H5SC,H5SD), C8SB(H8SC,H8SD), C12S(H12A,H12B), C9S(H9SA,H9SB), C11S(H11A,
 H11B), C10S(H10A,H10B), C9SB(H9SC,H9SD), C12B(H12C,H12D), C10B(H10C,H10D),
 C11B(H11C,H11D), C9SC(H9SE,H9SF), C12C(H12E,H12F), C10C(H10E,H10F), C11C(H11E,
 H11F), C18S(H18A,H18B), C19S(H19D,H19E), C20S(H20D,H20E), C21S(H21A,H21B),
 C14S(H14A,H14B), C15S(H15A,H15B), C16S(H16D,H16E)
8.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C11(H11), C12(H12), C13(H13), C23(H23), C24(H24),
 C25(H25)
8.d Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C19(H19A,H19B,H19C), C20(H20A,H20B,
 H20C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C31(H31A,H31B,H31C), C32(H32A,
 H32B,H32C), C13S(H13A,H13B,H13C), C17S(H17D,H17E,H17F)
;
_shelx_res_checksum              11880
_shelx_hkl_checksum              76785
_olex2_submission_special_instructions 'No special instructions were received'