Synthesis and Catalytic Reactivity of a Dicopper(II) μ-η(2):η(2)-Peroxo Species Supported by 1,4,7-Tri-tert-butyl-1,4,7-triazacyclononane.
Karahalis, Gregory J.; Thangavel, Arumugam; Chica, Bryant; Bacsa, John; Dyer, R. Brian; Scarborough, Christopher C.; Inorganic chemistry 55 (2016) 1102–1107; doi:10.1021/acs.inorgchem.5b02205

data_4344698
_publ_section_title
;
 Synthesis and Catalytic Reactivity of a Dicopper(II)
 \m-\h(2):\h(2)-Peroxo Species Supported by
 1,4,7-Tri-tert-butyl-1,4,7-triazacyclononane.
;
_journal_issue                   3
_journal_name_full               'Inorganic chemistry'
_journal_page_first              1102
_journal_page_last               1107
_journal_paper_doi               10.1021/acs.inorgchem.5b02205
_journal_volume                  55
_journal_year                    2016
_chemical_formula_moiety         'C19 H39 Cu F3 N3 O3 S'
_chemical_formula_sum            'C19 H39 Cu F3 N3 O3 S'
_chemical_formula_weight         510.13
_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'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2014-08-29
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2014.07.22 svn.r2960 for OlexSys, GUI svn.r4862)
;
_cell_angle_alpha                90
_cell_angle_beta                 90.080(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.1634(11)
_cell_length_b                   10.6776(11)
_cell_length_c                   20.125(2)
_cell_measurement_reflns_used    3175
_cell_measurement_temperature    110(2)
_cell_measurement_theta_max      22.887
_cell_measurement_theta_min      2.642
_cell_volume                     2398.9(4)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'APEX2 v2014.1-1 (Bruker, 2014)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      110(2)
_diffrn_detector_area_resol_mean 512
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker D8 diffractometer with APEX2 detector'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0508
_diffrn_reflns_av_unetI/netI     0.0515
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            18054
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.482
_diffrn_reflns_theta_min         1.908
_diffrn_source                   'fine-focus sealed tube'
_diffrn_source_current           30
_diffrn_source_voltage           45
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.047
_exptl_absorpt_correction_T_max  0.7333
_exptl_absorpt_correction_T_min  0.4447
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/2 (Bruker,2014) was used for absorption correction.
wR2(int) was 0.1244 before and 0.0529 after correction.
The Ratio of minimum to maximum transmission is 0.6064.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.416
_exptl_crystal_description       plate
_exptl_crystal_F_000             1080
_exptl_crystal_recrystallization_method
'The material was recrystallised from benzene by chemical reaction'
_exptl_crystal_size_max          0.389
_exptl_crystal_size_mid          0.34
_exptl_crystal_size_min          0.146
_refine_diff_density_max         0.914
_refine_diff_density_min         -0.648
_refine_diff_density_rms         0.109
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     296
_refine_ls_number_reflns         5347
_refine_ls_number_restraints     576
_refine_ls_restrained_S_all      1.083
_refine_ls_R_factor_all          0.0893
_refine_ls_R_factor_gt           0.0627
_refine_ls_shift/su_max          0.007
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0655P)^2^+7.9128P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1489
_refine_ls_wR_factor_ref         0.1684
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3943
_reflns_number_total             5347
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic5b02205_si_001.cif
_cod_data_source_block           gjk-cuotftacn_monoclin_twin
_cod_original_cell_volume        2398.9(7)
_cod_database_code               4344698
_shelxl_version_number           2013-4
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C4A-C3A
 1.52 with sigma of 0.01
 Cu1-O1A \\sim Cu1-O1
 with sigma of 0.005
 C4A-C3A \\sim C6B-C5A \\sim C2A-C1B
 with sigma of 0.002
 C5A-C4A \\sim C3A-C2A \\sim C6B-C1B
 with sigma of 0.005
 N3A-C15 \\sim N3B-C15 \\sim N1A-C7 \\sim N1B-C7 \\sim N2A-C11 \\sim N2B-C11
 with sigma of 0.005
 C6A-C5A \\sim C6B-C5B \\sim C4A-C3A \\sim C4B-C3B \\sim C2A-C1A \\sim C2B-C1B
 with sigma of 0.002
 N2B-C3B \\sim N2A-C3A
 with sigma of 0.005
 N2B-C2B \\sim N2A-C3A
 with sigma of 0.005
 N3A-C5A \\sim N3B-C5B
 with sigma of 0.005
 N3A-C5A \\sim N3B-C5B \\sim N3B-C4B \\sim N3A-C4A
 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
Uanis(C4A) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(N1A) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(N1A) \\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.006
Uanis(N2B) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C19) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(S2) = Uanis(S1A)
Uanis(C19A) = Uanis(C19)
Uanis(O1A) = Uanis(O1)
Uanis(O2A) = Uanis(O2)
Uanis(O3) = Uanis(O3A)
Uanis(F2A) = Uanis(F8)
Uanis(F3A) = Uanis(F7)
Uanis(F9) = Uanis(F1A)
Uanis(N1B) = Uanis(N1A)
Uanis(C6A) = Uanis(C6B)
Uanis(C5B) = Uanis(C5A)
Uanis(N3A) = Uanis(N3B)
Uanis(C4B) = Uanis(C4A)
Uanis(C3B) = Uanis(C3A)
Uanis(N2B) = Uanis(N2A)
Uanis(C2B) = Uanis(C2A)
Uanis(C1A) = Uanis(C1B)
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
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
5. Others
 Fixed Sof: N1A(0.5) C1A(0.5) H1AA(0.5) H1AB(0.5) C2A(0.5) H2AA(0.5) H2AB(0.5)
 N2A(0.5) C3A(0.5) H3AA(0.5) H3AB(0.5) C4A(0.5) H4AA(0.5) H4AB(0.5) N3A(0.5)
 C5A(0.5) H5AA(0.5) H5AB(0.5) C6A(0.5) H6AA(0.5) H6AB(0.5) N1B(0.5) C1B(0.5)
 H1BA(0.5) H1BB(0.5) C2B(0.5) H2BA(0.5) H2BB(0.5) N2B(0.5) C3B(0.5) H3BA(0.5)
 H3BB(0.5) C4B(0.5) H4BA(0.5) H4BB(0.5) N3B(0.5) C5B(0.5) H5BA(0.5) H5BB(0.5)
 C6B(0.5) H6BA(0.5) H6BB(0.5) S1A(0.5) O3A(0.5) O1A(0.5) O2A(0.5) C19A(0.5)
 F1A(0.5) F2A(0.5) F3A(0.5) S2(0.5) O2(0.5) O1(0.5) O3(0.5) C19(0.5) F7(0.5)
 F8(0.5) F9(0.5)
6.a Free rotating group:
 S1A(O3A,O1A,O2A,C19A,F1A,F2A,F3A), S2(O2,O1,O3,C19,F7,F8,F9)
6.b Secondary CH2 refined with riding coordinates:
 C1A(H1AA,H1AB), C2A(H2AA,H2AB), C3A(H3AA,H3AB), C4A(H4AA,H4AB), C5A(H5AA,
 H5AB), C6A(H6AA,H6AB), C1B(H1BA,H1BB), C2B(H2BA,H2BB), C3B(H3BA,H3BB),
 C4B(H4BA,H4BB), C5B(H5BA,H5BB), C6B(H6BA,H6BB)
6.c Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C12(H12A,H12B,H12C),
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C16(H16A,H16B,H16C), C17(H17A,H17B,
 H17C), C18(H18A,H18B,H18C)
;
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a loop with paratone oil'
_olex2_submission_original_sample_id GJK-CuOTFtacn
_olex2_submission_special_instructions 'No special instructions were received'