Coordination chemistry of [2 + 2] Schiff-base macrocycles derived from the dianilines [(2-NH<sub>2</sub>C<sub>6</sub>H<sub>4</sub>)<sub>2</sub>X] (X = CH<sub>2</sub>CH<sub>2</sub>, O): structural studies and ROP capability towards cyclic esters.
Wang, Kuiyuan; Prior, Timothy J.; Hughes, David L.; Arbaoui, Abdessamad; Redshaw, Carl; Dalton transactions (Cambridge, England : 2003) 50 (2021) 8057–8069; doi:10.1039/d1dt00711d

data_7707359
_publ_section_title
;
 Coordination chemistry of [2 + 2] Schiff-base macrocycles derived from
 the dianilines
 [(2-NH<sub>2</sub>C<sub>6</sub>H<sub>4</sub>)<sub>2</sub>X] (X =
 CH<sub>2</sub>CH<sub>2</sub>, O): structural studies and ROP capability
 towards cyclic esters.
;
_journal_issue                   23
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              8057
_journal_page_last               8069
_journal_paper_doi               10.1039/d1dt00711d
_journal_volume                  50
_journal_year                    2021
_chemical_formula_moiety         'C52 H52 Br Cu N4 O2, Br2 Cu, 2(C2 H3 N)'
_chemical_formula_sum            'C56 H58 Br3 Cu2 N6 O2'
_chemical_formula_weight         1213.89
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-04-29
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-04-29 deposited with the CCDC.	2021-05-04 downloaded from the CCDC.
;
_cell_angle_alpha                71.443(2)
_cell_angle_beta                 82.738(2)
_cell_angle_gamma                76.600(2)
_cell_formula_units_Z            2
_cell_length_a                   10.0808(2)
_cell_length_b                   15.0015(4)
_cell_length_c                   18.6604(4)
_cell_measurement_reflns_used    28839
_cell_measurement_temperature    99.9(6)
_cell_measurement_theta_max      70.1660
_cell_measurement_theta_min      4.5320
_cell_volume                     2598.16(11)
_computing_cell_refinement       'CrysAlisPro 1.171.40.39a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.39a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.39a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.9(6)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 0.985
_diffrn_measured_fraction_theta_max 0.984
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -84.00  94.00   0.50    0.50    --    5.00  37.00  82.00  356
  2  \w   -179.00  -1.00   0.50    0.50    --  -90.00  37.00  82.00  356
  3  \w    -89.00  89.00   0.50    0.50    --    0.00   0.00-180.00  356
  4  \w    -89.00  89.00   0.50    0.50    --    0.00  37.00  82.00  356
  5  \w   -179.00  -1.00   0.50    0.50    --  -90.00  56.00 -63.82  356
  6  \w   -179.00  -1.00   0.50    0.50    --  -90.00  58.00-161.78  356
  7  \w   -179.00  -1.00   0.50    0.50    --  -90.00  59.00   0.28  356
  8  \w   -179.00  -1.00   0.50    0.50    --  -90.00  59.00   0.28  356
  9  \w   -137.00 -58.00   0.50    0.50    --  -90.00  58.00 124.85  158
 10  \w   -169.00-127.00   0.50    0.50    --  -90.00  59.00-124.59   84
 11  \w   -107.00 -66.00   0.50    0.50    --  -90.00  59.00-124.59   82
 12  \w   -179.00  -2.00   0.50    0.50    --  -90.00  59.00  49.40  354
 13  \w   -179.00  -1.00   0.50    0.50    --  -90.00  59.00 -38.54  356
 14  \w    -58.00 -31.00   0.50    0.50    --  -90.00  58.00-161.78   54
 15  \w   -126.00 -93.00   0.50    0.50    --  -90.00  10.00 -60.00   66
 16  \w    -55.00 -16.00   0.50    0.50    --  -90.00  10.00 -60.00   78
 17  \w   -178.00 -49.00   0.50    0.50    --  -90.00  59.00-154.16  258
 18  \w   -179.00-149.00   0.50    0.50    --  -90.00  58.00  92.60   60
 19  \w   -139.00 -92.00   0.50    0.50    --  -90.00  58.00  92.60   94
 20  \w    -29.00  -2.00   0.50    0.50    --  -90.00  58.00  92.60   54
 21  \w   -135.00-109.00   0.50    0.50    --  -90.00  58.00  22.68   52
 22  \w    -55.00 -29.00   0.50    0.50    --  -90.00  58.00  22.68   52
 23  \w   -178.00-145.00   0.50    0.50    --  -90.00  20.00-180.00   66
 24  \w    -57.00 -30.00   0.50    0.50    --  -90.00  20.00-180.00   54
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC11 (RCD3): quarter-chi single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0461751000
_diffrn_orient_matrix_UB_12      -0.0655358000
_diffrn_orient_matrix_UB_13      -0.0512878000
_diffrn_orient_matrix_UB_21      0.1502457000
_diffrn_orient_matrix_UB_22      0.0009378000
_diffrn_orient_matrix_UB_23      0.0070840000
_diffrn_orient_matrix_UB_31      0.0074102000
_diffrn_orient_matrix_UB_32      -0.0891436000
_diffrn_orient_matrix_UB_33      0.0702008000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0834
_diffrn_reflns_av_unetI/netI     0.0348
_diffrn_reflns_Laue_measured_fraction_full 0.985
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            44092
_diffrn_reflns_point_group_measured_fraction_full 0.985
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.250
_diffrn_reflns_theta_min         2.502
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.064
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.14868
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.39a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark red'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.552
_exptl_crystal_description       plate
_exptl_crystal_F_000             1230
_exptl_crystal_size_max          0.7
_exptl_crystal_size_mid          0.6
_exptl_crystal_size_min          0.15
_refine_diff_density_max         3.448
_refine_diff_density_min         -1.244
_refine_diff_density_rms         0.133
_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     622
_refine_ls_number_reflns         9332
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0676
_refine_ls_R_factor_gt           0.0666
_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^)+(0.1141P)^2^+7.3661P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1824
_refine_ls_wR_factor_ref         0.1835
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8998
_reflns_number_total             9332
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt00711d2.cif
_cod_data_source_block           FeROP5
_cod_depositor_comments
'Adding full bibliography for 7707347--7707359.cif.'
_cod_original_cell_volume        2598.13(11)
_cod_database_code               7707359
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C56 H58 N6 O2 Br3 Cu2'
_chemical_oxdiff_usercomment     'Cu tBu macro'
_cell_oxdiff_angle_alpha         71.443(2)
_cell_oxdiff_angle_beta          82.738(2)
_cell_oxdiff_angle_gamma         76.600(2)
_cell_oxdiff_length_a            10.0808(2)
_cell_oxdiff_length_b            15.0015(4)
_cell_oxdiff_length_c            18.6604(4)
_cell_oxdiff_measurement_reflns_used 28839
_cell_oxdiff_volume              2598.13(11)
_shelx_estimated_absorpt_t_max   0.579
_shelx_estimated_absorpt_t_min   0.162
_reflns_odcompleteness_completeness 98.43
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C39-C40 \\sim C39-C40A
 with sigma of 0.02
 C40-C41 \\sim C40A-C41A
 with sigma of 0.02
 C41-C42 \\sim C41A-C42A
 with sigma of 0.02
 C41-C43 \\sim C41A-C43
 with sigma of 0.04
 C42-C43 \\sim C42A-C43
 with sigma of 0.02
 C39-C41 \\sim C39-C41A
 with sigma of 0.04
 C40-C42 \\sim C40A-C42A
 with sigma of 0.04
3. Others
 Sof(C42A)=Sof(H42A)=Sof(C41A)=Sof(H41A)=Sof(C40A)=Sof(H40A)=1-FVAR(1)
 Sof(C40)=Sof(H40)=Sof(C41)=Sof(H41)=Sof(C42)=Sof(H42)=FVAR(1)
4.a Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B), C19(H19A,H19B), C44(H44A,H44B), C45(H45A,H45B)
4.b Me refined with riding coordinates:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C34(H34A,H34B,H34C),
 C35(H35A,H35B,H35C), C36(H36A,H36B,H36C)
4.c Aromatic/amide H refined with riding coordinates:
 N2(H2), N4(H4), C3(H3), C5(H5), C11(H11), C13(H13), C14(H14), C15(H15),
 C16(H16), C21(H21), C22(H22), C23(H23), C24(H24), C26(H26), C29(H29), C31(H31),
  C37(H37), C39(H39), C40(H40), C41(H41), C42(H42), C47(H47), C48(H48),
 C49(H49), C50(H50), C52(H52), C42A(H42A), C41A(H41A), C40A(H40A)
4.d Idealised Me refined as rotating group:
 C54(H54A,H54B,H54C), C56(H56A,H56B,H56C)
;
_shelx_res_checksum              62699
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.423
_oxdiff_exptl_absorpt_empirical_full_min 0.374