Cubane-like tetranuclear Cu(ii) complexes bearing a Cu4O4 core: crystal structure, magnetic properties, DFT calculations and phenoxazinone synthase like activity.
Sagar, Shipra; Sengupta, Swaraj; Mota, Antonio J.; Chattopadhyay, Shyamal K.; Espinosa Ferao, Arturo; Riviere, Eric; Lewis, William; Naskar, Subhendu; Dalton transactions (Cambridge, England : 2003) 46 (2017) 1249–1259; doi:10.1039/c6dt03754b

data_7041515
_publ_section_title
;
 Cubane-like tetranuclear Cu(ii) complexes bearing a Cu4O4 core: crystal
 structure, magnetic properties, DFT calculations and phenoxazinone
 synthase like activity.
;
_journal_issue                   4
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              1249
_journal_page_last               1259
_journal_paper_doi               10.1039/c6dt03754b
_journal_volume                  46
_journal_year                    2017
_chemical_formula_moiety
'C40 H28 Br4 Cu4 N8 O8 S4, 2(C2 H6 O S), 2(O)'
_chemical_formula_sum            'C44 H44 Br4 Cu4 N8 O12 S6'
_chemical_formula_weight         1643.03
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_creation_date             2015-01-15
_audit_creation_method
;
Olex2 1.2
(compiled 2014.11.28 svn.r3106 for OlexSys, GUI svn.r4959)
;
_audit_update_record
;
2016-09-27 deposited with the CCDC.
2016-12-07 downloaded from the CCDC.
;
_cell_angle_alpha                81.325(9)
_cell_angle_beta                 70.620(9)
_cell_angle_gamma                71.468(9)
_cell_formula_units_Z            2
_cell_length_a                   14.5404(14)
_cell_length_b                   15.0453(15)
_cell_length_c                   15.6677(16)
_cell_measurement_reflns_used    7686
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      73.6040
_cell_measurement_theta_min      4.1080
_cell_volume                     3061.7(6)
_computing_cell_refinement
'CrysAlisPro, Agilent Technologies, Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET) (compiled Aug 13 2014,18:06:01)'
_computing_data_collection
'CrysAlisPro, Agilent Technologies, Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET) (compiled Aug 13 2014,18:06:01)'
_computing_data_reduction
'CrysAlisPro, Agilent Technologies, Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET) (compiled Aug 13 2014,18:06:01)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120(2)
_diffrn_crystal_treatment        'flash frozen in gaseous N2'
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 10.3613
_diffrn_detector_type            'Agilent Diffraction Atlas detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
  1 omega  -91.00  -64.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000 -164.0000 -101.0000 27

  2 omega -108.00  -16.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000  -57.0000 -180.0000 92

  3 omega  -90.00  -54.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000  125.0000   30.0000 36

  4 omega -109.00  -13.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000  -57.0000   60.0000 96

  5 omega  -64.00   32.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000   57.0000  -30.0000 96

  6 omega   87.00  114.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -       43.1277  164.0000  -76.0000 27

  7 omega   37.00   70.00   1.0000  240.0000
omega____ theta____ kappa____ phi______ frames
    -      107.3822  -30.0000  -30.0000 33

  8 omega   42.00   98.00   1.0000  240.0000
omega____ theta____ kappa____ phi______ frames
    -      107.3822  -95.0000 -180.0000 56

  9 omega   89.00  171.00   1.0000  240.0000
omega____ theta____ kappa____ phi______ frames
    -      107.3822   45.0000    0.0000 82

 10 omega   39.00   72.00   1.0000  240.0000
omega____ theta____ kappa____ phi______ frames
    -      107.3822  -30.0000   60.0000 33

 11 omega   36.00   87.00   1.0000  240.0000
omega____ theta____ kappa____ phi______ frames
    -      107.3822  -30.0000    0.0000 51

 12 omega   61.00  119.00   1.0000  240.0000
omega____ theta____ kappa____ phi______ frames
    -      107.3822 -125.0000   90.0000 58

 13 omega   41.00   91.00   1.0000  240.0000
omega____ theta____ kappa____ phi______ frames
    -      107.3822  -30.0000   90.0000 50

 14 omega   64.00   91.00   1.0000  240.0000
omega____ theta____ kappa____ phi______ frames
    -      107.3822  -95.0000  120.0000 27

 15 omega   44.00   92.00   1.0000  240.0000
omega____ theta____ kappa____ phi______ frames
    -      107.3822  -45.0000  150.0000 48

 16 omega   27.00  151.00   1.0000  240.0000
omega____ theta____ kappa____ phi______ frames
    -      107.3822  -15.0000 -180.0000 124

 17 omega   56.00   87.00   1.0000  240.0000
omega____ theta____ kappa____ phi______ frames
    -      107.3822  -30.0000 -120.0000 31

 18 omega   36.00   89.00   1.0000  240.0000
omega____ theta____ kappa____ phi______ frames
    -      107.3822  -45.0000   60.0000 53

 19 omega   47.00  121.00   1.0000  240.0000
omega____ theta____ kappa____ phi______ frames
    -      107.3822 -125.0000  -60.0000 74

 20 omega   39.00  132.00   1.0000  240.0000
omega____ theta____ kappa____ phi______ frames
    -      107.3822  -77.0000  -90.0000 93

 21 omega   50.00  105.00   1.0000  240.0000
omega____ theta____ kappa____ phi______ frames
    -      107.3822  -95.0000   90.0000 55

 22 omega -109.00  -12.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000  -57.0000  -60.0000 97

 23 omega   12.00  117.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -       43.1277   77.0000   30.0000 105

 24 omega   12.00  117.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -       43.1277   77.0000  120.0000 105

 25 omega   23.00   98.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -       43.1277 -125.0000   60.0000 75

 26 omega    1.00   83.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -       43.1277  -99.0000 -180.0000 82

 27 omega   16.00  113.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -       43.1277   57.0000  -90.0000 97

 28 omega   21.00  168.00   1.0000  240.0000
omega____ theta____ kappa____ phi______ frames
    -      107.3822    0.0000  -60.0000 147
;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'MiTeGen micromount'
_diffrn_orient_matrix_UB_11      -0.0428575000
_diffrn_orient_matrix_UB_12      0.1076500000
_diffrn_orient_matrix_UB_13      0.0020253000
_diffrn_orient_matrix_UB_21      0.0180375000
_diffrn_orient_matrix_UB_22      0.0064053000
_diffrn_orient_matrix_UB_23      -0.1030574000
_diffrn_orient_matrix_UB_31      -0.1076382000
_diffrn_orient_matrix_UB_32      -0.0079647000
_diffrn_orient_matrix_UB_33      0.0163575000
_diffrn_radiation_collimation    'focusing mirrors'
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1181
_diffrn_reflns_av_unetI/netI     0.1041
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            32366
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        66.601
_diffrn_reflns_theta_max         66.601
_diffrn_reflns_theta_min         3.364
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_target            Cu
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_exptl_absorpt_coefficient_mu    7.049
_exptl_absorpt_correction_T_max  0.836
_exptl_absorpt_correction_T_min  0.472
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
'CrysAlisPro, Agilent Technologies, Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET) (compiled Aug 13 2014,18:06:01) 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 light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.782
_exptl_crystal_description       needle
_exptl_crystal_F_000             1624
_exptl_crystal_size_max          0.209
_exptl_crystal_size_mid          0.0662
_exptl_crystal_size_min          0.0264
_refine_diff_density_max         2.629
_refine_diff_density_min         -1.089
_refine_diff_density_rms         0.225
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.221
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     723
_refine_ls_number_reflns         10828
_refine_ls_number_restraints     1351
_refine_ls_restrained_S_all      1.178
_refine_ls_R_factor_all          0.1781
_refine_ls_R_factor_gt           0.1273
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3317
_refine_ls_wR_factor_ref         0.3879
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6385
_reflns_number_total             10828
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6dt03754b2.cif
_cod_data_source_block           skwllh_sq
_cod_depositor_comments
'Adding full bibliography for 7041513--7041515.cif.'
_cod_database_code               7041515
_nottingham_internal_coll_name   SKWLLH
_nottingham_internal_coll_number 14030
_nottingham_internal_coll_client SN/WL
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method 'omega scans'
_nottingham_internal_coll_frame_time '60.0000, 240.0000'
_nottingham_internal_coll_frame_width 1.0000
_nottingham_internal_coll_user   pczwl
_nottingham_internal_coll_date   02/10/2014
_nottingham_internal_coll_location NOTTS
_nottingham_internal_process_date 15/01/2015
_nottingham_internal_process_user pczwl
_nottingham_internal_solution_date 3/10/2014
_nottingham_internal_solution_user pczwl
_nottingham_internal_refinement_date 15/1/2015
_nottingham_internal_refinement_user pczwl
_nottingham_internal_validation_date 15/1/2015
_nottingham_internal_validation_user pczwl
_nottingham_internal_archive_date 15/1/2015
_platon_squeeze_void_probe_radius 1.20
_chemical_oxdiff_formula         'C44 H44 Br4 Cu4 N8 O12 S6'
_chemical_oxdiff_usercomment
'SKWLLH #14030 SN-314 IN FOMBLIN FILM ON A MICROMOUNT FOR SN/WL'
_reflns_odcompleteness_completeness 99.95
_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 N(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
 S85-O86 \\sim S85A-O86
 with sigma of 0.02
 S85A-C88 \\sim S85-C88 \\sim S85-C87 \\sim S85A-C87
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(S85A)=Sof(H87D)=Sof(H87E)=Sof(H87F)=Sof(H88D)=Sof(H88E)=Sof(H88F)=1-FVAR(1)
 Sof(S85)=Sof(H87A)=Sof(H87B)=Sof(H87C)=Sof(H88A)=Sof(H88B)=Sof(H88C)=FVAR(1)
 Sof(C84A)=Sof(H84D)=Sof(H84E)=Sof(H84F)=1-FVAR(2)
 Sof(C84)=Sof(H84A)=Sof(H84B)=Sof(H84C)=FVAR(2)
6.a Riding coordinates:
 C84A(H84D,H84E,H84F)
6.b Ternary CH refined with riding coordinates:
 C7(H7), C27(H27), C47(H47), C67(H67)
6.c Me refined with riding coordinates:
 C83(H83A,H83B,H83C), C84(H84A,H84B,H84C), C87(H87A,H87B,H87C), C87(H87D,H87E,
 H87F), C88(H88A,H88B,H88C), C88(H88D,H88E,H88F)
6.d Aromatic/amide H refined with riding coordinates:
 N6(H6), N26(H26), N46(H46), N66(H66), C12(H12), C4(H4), C5(H5), C11(H11),
 C14(H14), C24(H24), C25(H25), C31(H31), C32(H32), C34(H34), C44(H44), C45(H45),
  C51(H51), C52(H52), C54(H54), C64(H64), C65(H65), C71(H71), C72(H72), C74(H74)
;
_shelx_res_checksum              22977
_shelx_fab_checksum              77926
_shelx_shelxl_version_number     2014/7
_nottingham_internal_coll_instrument 'SN, XDA 017/09'
_olex2_exptl_crystal_mounting_method 'in fomblin film on a micromount'
_olex2_submission_special_instructions 'No special instructions were received'