Chiral tetranuclear and dinuclear copper(ii) complexes for TEMPO-mediated aerobic oxidation of alcohols: are four metal centres better than two?
Zhang, Guoqi; Proni, Gloria; Zhao, Sherry; Constable, Edwin C.; Housecroft, Catherine E.; Neuburger, Markus; Zampese, Jennifer A.; Dalton transactions (Cambridge, England : 2003) 43 (2014) 12313–12320; doi:10.1039/c4dt01224k

data_7031491
_publ_section_title
;
 Chiral tetranuclear and dinuclear copper(ii) complexes for TEMPO-mediated
 aerobic oxidation of alcohols: are four metal centres better than two?
;
_journal_issue                   32
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              12313
_journal_page_last               12320
_journal_paper_doi               10.1039/c4dt01224k
_journal_volume                  43
_journal_year                    2014
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C58 H66 Cu2 N2 O4, 0.7(C H2 Cl2)'
_chemical_formula_sum            'C58.7 H67.4 Cl1.4 Cu2 N2 O4'
_chemical_formula_weight         1041.72
_space_group_IT_number           18
_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_Hall  'P 2 2ab'
_symmetry_space_group_name_H-M   'P 21 21 2'
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     direct
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.3910(14)
_cell_length_b                   22.5070(17)
_cell_length_c                   13.8020(10)
_cell_measurement_reflns_used    9953
_cell_measurement_temperature    123
_cell_measurement_theta_max      28
_cell_measurement_theta_min      3
_cell_volume                     5713.0(7)
_computing_cell_refinement       'Apex2 (Bruker AXS, 2006)'
_computing_data_collection       'Apex2 (Bruker AXS, 2006)'
_computing_data_reduction        'Apex2 (Bruker AXS, 2006)'
_computing_molecular_graphics    'CAMERON (Watkin et al., 1996)'
_computing_publication_material  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_refinement  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_solution    'SIR92 (Altomare et al., 1994)'
_diffrn_ambient_temperature      123
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.984
_diffrn_measurement_device       Area
_diffrn_measurement_device_type  'Bruker Kappa Apex2'
_diffrn_measurement_method       '\f & \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.041
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            13209
_diffrn_reflns_theta_full        26.477
_diffrn_reflns_theta_max         27.871
_diffrn_reflns_theta_min         1.731
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.854
_exptl_absorpt_correction_T_max  0.94
_exptl_absorpt_correction_T_min  0.94
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS (Siemens, 1996)'
_exptl_crystal_colour            notknown
_exptl_crystal_density_diffrn    1.211
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             2189.600
_exptl_crystal_size_max          0.220
_exptl_crystal_size_mid          0.170
_exptl_crystal_size_min          0.070
_refine_diff_density_max         1.11
_refine_diff_density_min         -0.69
_refine_ls_abs_structure_details 'Flack (1983), 0 Friedel-pairs'
_refine_ls_abs_structure_Flack   0.010(8)
_refine_ls_extinction_method     None
_refine_ls_goodness_of_fit_ref   1.0844
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     651
_refine_ls_number_reflns         10612
_refine_ls_number_restraints     995
_refine_ls_R_factor_all          0.0483
_refine_ls_R_factor_gt           0.0403
_refine_ls_shift/su_max          0.0412057
_refine_ls_shift/su_mean         0.0002476
_refine_ls_structure_factor_coef F
_refine_ls_weighting_details
;
 Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) 
 [weight] = 1.0/[A~0~*T~0~(x)+A~1~*T~1~(x) ... +A~n-1~]*T~n-1~(x)] 
 where A~i~ are the Chebychev coefficients listed below and x= Fcalc/Fmax 
 Method = Robust Weighting (Prince, 1982) 
 W = [weight] * [1-(deltaF/6*sigmaF)^2^]^2^ 
 A~i~ are: 
 13.0 9.28 10.4 5.75 
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_all         0.0465
_refine_ls_wR_factor_gt          0.0436
_refine_ls_wR_factor_ref         0.0425
_reflns_limit_h_max              24
_reflns_limit_h_min              -24
_reflns_limit_k_max              29
_reflns_limit_k_min              0
_reflns_limit_l_max              17
_reflns_limit_l_min              0
_reflns_number_gt                11344
_reflns_number_total             13209
_reflns_threshold_expression     I>2.0\s(I)
_oxford_diffrn_Wilson_B_factor   1.70
_oxford_diffrn_Wilson_scale      209.02
_oxford_refine_ls_r_factor_ref   0.0387
_oxford_refine_ls_scale          2.217(2)
_oxford_reflns_number_all        13164
_oxford_reflns_threshold_expression_ref I>3.0\s(I)
_cod_data_source_file            c4dt01224k1.cif
_cod_data_source_block           1
_cod_depositor_comments
'Adding full bibliography for 7031490--7031491.cif.'
_cod_original_sg_symbol_H-M      'P 21 21 2 '
_cod_original_formula_sum        'C58.70 H67.40 Cl1.40 Cu2 N2 O4'
_cod_database_code               7031491
_iucr_refine_instruction_details_constraints
;
BLOCK SCALE X'S, U'S 
CONT ENANTIO 
EQUIVALENCE PART(1001, OCC) 
CONTINUE    PART(1002, OCC) 
WEIGHT -1   PART(1002, OCC) 
RIDE C   (   3,X'S) H   (  31,X'S) 
RIDE C   (   5,X'S) H   (  51,X'S) 
RIDE C   (   7,X'S) H   (  71,X'S) 
RIDE C   (   8,X'S) H   (  81,X'S) 
RIDE C   (   9,X'S) H   (  91,X'S) 
RIDE C   (  11,X'S) H   ( 111,X'S) H   ( 112,X'S) H   ( 113,X'S) 
RIDE C   (  12,X'S) H   ( 121,X'S) H   ( 122,X'S) H   ( 123,X'S) 
RIDE C   (  13,X'S) H   ( 131,X'S) H   ( 132,X'S) H   ( 133,X'S) 
RIDE C   (  15,X'S) H   ( 151,X'S) H   ( 152,X'S) H   ( 153,X'S) 
RIDE C   (  16,X'S) H   ( 161,X'S) H   ( 162,X'S) H   ( 163,X'S) 
RIDE C   (  17,X'S) H   ( 171,X'S) H   ( 172,X'S) H   ( 173,X'S) 
RIDE C   (  19,X'S) H   ( 191,X'S) 
RIDE C   (  20,X'S) H   ( 201,X'S) 
RIDE C   (  21,X'S) H   ( 211,X'S) 
RIDE C   (  22,X'S) H   ( 221,X'S) 
RIDE C   (  23,X'S) H   ( 231,X'S) 
RIDE C   (  25,X'S) H   ( 251,X'S) 
RIDE C   (  26,X'S) H   ( 261,X'S) 
RIDE C   (  27,X'S) H   ( 271,X'S) 
RIDE C   (  28,X'S) H   ( 281,X'S) 
RIDE C   (  29,X'S) H   ( 291,X'S) 
RIDE C   (  32,X'S) H   ( 321,X'S) 
RIDE C   (  34,X'S) H   ( 341,X'S) 
RIDE C   (  36,X'S) H   ( 361,X'S) 
RIDE C   (  37,X'S) H   ( 371,X'S) 
RIDE C   (  38,X'S) H   ( 381,X'S) 
RIDE C   (  40,X'S) H   ( 401,X'S) H   ( 402,X'S) H   ( 403,X'S) 
RIDE C   (  41,X'S) H   ( 411,X'S) H   ( 412,X'S) H   ( 413,X'S) 
RIDE C   (  42,X'S) H   ( 421,X'S) H   ( 422,X'S) H   ( 423,X'S) 
RIDE C   (  44,X'S) H   ( 441,X'S) H   ( 442,X'S) H   ( 443,X'S) 
RIDE C   (  45,X'S) H   ( 451,X'S) H   ( 452,X'S) H   ( 453,X'S) 
RIDE C   (  46,X'S) H   ( 461,X'S) H   ( 462,X'S) H   ( 463,X'S) 
RIDE C   (  48,X'S) H   ( 481,X'S) 
RIDE C   (  49,X'S) H   ( 491,X'S) 
RIDE C   (  50,X'S) H   ( 501,X'S) 
RIDE C   (  51,X'S) H   ( 511,X'S) 
RIDE C   (  52,X'S) H   ( 521,X'S) 
RIDE C   (  54,X'S) H   ( 541,X'S) 
RIDE C   (  55,X'S) H   ( 551,X'S) 
RIDE C   (  56,X'S) H   ( 561,X'S) 
RIDE C   (  57,X'S) H   ( 571,X'S) 
RIDE C   (  58,X'S) H   ( 581,X'S) 
RIDE C   (  59,X'S) H   ( 591,X'S) H   ( 592,X'S) 
RIDE C   ( 159,X'S) H   (1591,X'S) H   (1592,X'S) 
END                                                                             
;
_iucr_refine_instruction_details_restraints
;
NO 
REM   HREST   START (DO NOT REMOVE THIS LINE) 
REM   HREST   END (DO NOT REMOVE THIS LINE) 
REM   SHIFTLIMIT   START (DO NOT REMOVE THIS LINE) 
LIMIT      0.01000000 U[ISO] 
LIMIT      0.01000000 X 
LIMIT      0.01000000 Y 
LIMIT      0.01000000 Z 
LIMIT      0.01000000 U[11] 
LIMIT      0.01000000 U[22] 
LIMIT      0.01000000 U[33] 
LIMIT      0.01000000 U[12] 
LIMIT      0.01000000 U[13] 
LIMIT      0.01000000 U[23] 
LIMIT      0.01000000 OCC 
REM   SHIFTLIMIT   END (DO NOT REMOVE THIS LINE) 
REM   ASSEMBLY1   START (DO NOT REMOVE THIS LINE) 
REM   INTERNAL BONDS 
DISTANCES  0.0 , 0.01  = MEAN 
CONTINUE C(59) TO CL(1) C(159) TO CL(101) 
CONTINUE C(59) TO CL(2) C(159) TO CL(102) 
REM   ANGLES RESTRAINTS 
ANGLES  0.0 , 0.10  = MEAN 
CONTINUE CL(2) TO C(59) TO CL(1) CL(102) TO C(159) TO CL(101) 
REM   VIBRATIONAL RESTRAINTS 
VIBRATIONS 0.0, 0.0100  = 
CONTINUE C(59) TO CL(1) C(159) TO CL(101) 
CONTINUE C(59) TO CL(2) C(159) TO CL(102) 
VIBRATIONS 0.0, 0.00100  = 
CONTINUE C(59) TO C(159) 
CONTINUE CL(1) TO CL(101) 
CONTINUE CL(2) TO CL(102) 
REM   SIMILARITY RESTRAINTS 
U(IJ)'S 0.0, 0.0200  = 
CONTINUE C(59) TO CL(1) C(159) TO CL(101) 
CONTINUE C(59) TO CL(2) C(159) TO CL(102) 
U(IJ)'S 0.0, 0.00200  = 
CONTINUE C(59) TO C(159) 
CONTINUE CL(1) TO CL(101) 
CONTINUE CL(2) TO CL(102) 
REM   ASSEMBLY1   END (DO NOT REMOVE THIS LINE) 
END                                                                             
;