Copper porphyrin catalyzed esterification of C(sp3)‒H via a cross-dehydrogenative coupling reaction
Wang, Hua-Hua; Wen, Wei-Hong; Zou, Huai-Bo; Cheng, Fan; Ali, Atif; Shi, Lei; Liu, Hai-Yang; Chang, Chi-Kwong; New J. Chem. 41 (2017) 3508–; doi:10.1039/C6NJ03876J

data_7056142
_publ_section_title
;
 Copper porphyrin catalyzed esterification of C(sp3)--H via a
 cross-dehydrogenative coupling reaction
;
_journal_issue                   9
_journal_name_full               'New J. Chem.'
_journal_page_first              3508
_journal_paper_doi               10.1039/C6NJ03876J
_journal_volume                  41
_journal_year                    2017
_chemical_formula_moiety         'C32 H28 Cu N4 O8'
_chemical_formula_sum            'C32 H28 Cu N4 O8'
_chemical_formula_weight         660.12
_chemical_name_common            CuTECP
_chemical_name_systematic
'5,10,15,20-tetra-(ethoxylcarbonyl)porphyrin copper(II)'
_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   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_creation_date             2014-11-29
_audit_creation_method
;
Olex2 1.2
(compiled 2014.11.28 svn.r3106 for OlexSys, GUI svn.r4957)
;
_audit_update_record
;
2016-09-18 deposited with the CCDC.
2017-03-29 downloaded from the CCDC.
;
_cell_angle_alpha                85.110(7)
_cell_angle_beta                 88.215(6)
_cell_angle_gamma                83.692(6)
_cell_formula_units_Z            1
_cell_length_a                   6.4200(5)
_cell_length_b                   8.6707(7)
_cell_length_c                   12.9072(10)
_cell_measurement_reflns_used    3201
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      62.3540
_cell_measurement_theta_min      5.9330
_cell_volume                     711.37(10)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector_area_resol_mean 16.0855
_diffrn_measured_fraction_theta_full 0.987
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_details
;
  1 omega -106.00  -56.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -34.2729 -179.0000  -30.0000 50

  2 omega -111.00  -73.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -34.2729  179.0000   90.0000 38

  3 omega -110.00  -77.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -34.2729 -179.0000 -120.0000 33

  4 omega   36.00   63.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       34.2729  179.0000 -150.0000 27

  5 omega  -39.00   71.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       34.2729  -19.0000  150.0000 110

  6 omega   19.00   92.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       34.2729   57.0000  -30.0000 73

  7 omega   84.00  118.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       90.3500   30.0000  120.0000 34

  8 omega   26.00   68.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       90.3500  -30.0000 -180.0000 42

  9 omega   84.00  122.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       90.3500  -92.0000 -130.6309 38

 10 omega   96.00  134.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       90.3500  179.0000  -90.0000 38

 11 omega   24.00   73.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       90.3500 -111.0000 -120.0000 49

 12 omega  119.00  153.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       90.3500   61.0000  150.0000 34

 13 omega   23.00   68.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       90.3500  -94.0000  -30.0000 45

 14 omega   19.00   75.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       90.3500 -111.0000   60.0000 56

 15 omega   42.00   70.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       90.3500  179.0000  -90.0000 28

 16 omega   83.00  110.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       90.3500  -92.0000   58.5368 27

 17 omega   50.00  106.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       90.3500  -77.0000   60.0000 56

 18 omega   72.00  162.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       90.3500   30.0000 -150.0000 90

 19 omega   68.00  147.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       90.3500   77.0000  -90.0000 79

 20 omega   33.00   77.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       90.3500 -111.0000   30.0000 44

 21 omega  132.00  163.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       90.3500   30.0000  120.0000 31

 22 omega   56.00   94.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       90.3500  179.0000    0.0000 38

 23 omega   78.00  129.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       90.3500  -93.0000  154.7851 51

 24 omega   70.00  105.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       90.3500   61.0000  150.0000 35

 25 omega   86.00  111.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       90.3500  -92.0000  -55.8673 25

 26 omega   29.00   69.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       90.3500  -30.0000    0.0000 40

 27 omega   35.00   66.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       90.3500 -111.0000  150.0000 31

 28 omega   58.00   96.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       90.3500 -125.0000  112.0000 38

 29 omega   78.00  118.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       90.3500   45.0000    0.0000 40

 30 omega   34.00   61.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       90.3500  -92.0000  -55.8673 27

 31 omega    4.00  104.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       34.2729   77.0000   60.0000 100

 32 omega   32.00  111.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       34.2729 -179.0000   60.0000 79

 33 omega    4.00  104.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       34.2729   77.0000 -180.0000 100

 34 omega    4.00  104.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       34.2729   77.0000    0.0000 100

 35 omega   14.00  103.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       34.2729   57.0000  150.0000 89

 36 omega   14.00  103.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       34.2729   57.0000  -90.0000 89

 37 omega   69.00  158.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       90.3500   61.0000   30.0000 89

 38 omega   67.00  139.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       90.3500   45.0000   90.0000 72

 39 omega   18.00   69.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       90.3500  -30.0000  120.0000 51

 40 omega   69.00  158.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       90.3500   61.0000 -120.0000 89
;
_diffrn_measurement_device_type  'Xcalibur, Sapphire3, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0276972000
_diffrn_orient_matrix_UB_12      -0.0723538000
_diffrn_orient_matrix_UB_13      -0.1051656000
_diffrn_orient_matrix_UB_21      0.0053907000
_diffrn_orient_matrix_UB_22      -0.1639586000
_diffrn_orient_matrix_UB_23      0.0568325000
_diffrn_orient_matrix_UB_31      -0.2398279000
_diffrn_orient_matrix_UB_32      0.0074038000
_diffrn_orient_matrix_UB_33      -0.0082143000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0440
_diffrn_reflns_av_unetI/netI     0.0416
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            6928
_diffrn_reflns_theta_full        62.51
_diffrn_reflns_theta_max         62.51
_diffrn_reflns_theta_min         5.96
_diffrn_source                   'Enhance Ultra (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.615
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.46682
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            purple
_exptl_crystal_density_diffrn    1.541
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             341
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: DCM, Hexane'
_refine_diff_density_max         0.319
_refine_diff_density_min         -0.406
_refine_diff_density_rms         0.076
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     223
_refine_ls_number_reflns         2249
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0430
_refine_ls_R_factor_gt           0.0380
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0491P)^2^+0.5628P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0957
_refine_ls_wR_factor_ref         0.1016
_reflns_number_gt                2012
_reflns_number_total             2249
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c6nj03876j2.cif
_cod_data_source_block           CuTECP
_cod_original_cell_volume        711.37(9)
_cod_database_code               7056142
_chemical_oxdiff_formula         'C11 H10 N O'
_reflns_odcompleteness_completeness 88.16
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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.a Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C15(H15A,H15B)
2.b Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C13(H13A,H13B,H13C)
;
_olex2_submission_special_instructions 'No special instructions were received'