Ni(II) and Pd(II) complexes of a new redox-active pentadentate azo-appended 2-aminophenol ligand: Pd(II)-assisted intraligand cyclization forms a phenoxazinyl ring.
Bhowmik, Saumitra; Sengupta, Arunava; Mukherjee, Rabindranath; Dalton transactions (Cambridge, England : 2003) 53 (2024) 14046–14064; doi:10.1039/d4dt01513d

data_7716743
_publ_section_title
;
 Ni(II) and Pd(II) complexes of a new redox-active pentadentate
 azo-appended 2-aminophenol ligand: Pd(II)-assisted intraligand
 cyclization forms a phenoxazinyl ring.
;
_journal_issue                   33
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              14046
_journal_page_last               14064
_journal_paper_doi               10.1039/d4dt01513d
_journal_volume                  53
_journal_year                    2024
_chemical_formula_moiety
'2(F6 Sb), 2(C40 H48 N4 Ni O2), C H2 Cl2, 3[CH2Cl2]'
_chemical_formula_sum            'C84 H104 Cl8 F12 N8 Ni2 O4 Sb2'
_chemical_formula_weight         2162.27
_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
_audit_creation_date             2024-05-23
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-05-23 deposited with the CCDC.	2024-07-24 downloaded from the CCDC.
;
_cell_angle_alpha                81.734(4)
_cell_angle_beta                 83.363(4)
_cell_angle_gamma                85.055(4)
_cell_formula_units_Z            2
_cell_length_a                   9.5233(14)
_cell_length_b                   18.212(3)
_cell_length_c                   27.463(4)
_cell_measurement_reflns_used    17291
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28.319
_cell_measurement_theta_min      2.158
_cell_volume                     4670.3(12)
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0546
_diffrn_reflns_av_unetI/netI     0.0547
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            56507
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.027
_diffrn_reflns_theta_max         25.027
_diffrn_reflns_theta_min         2.508
_exptl_absorpt_coefficient_mu    1.274
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            'clear brownish red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   brownish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.538
_exptl_crystal_description       block
_exptl_crystal_F_000             2196
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.02
_exptl_transmission_factor_max   0.977
_exptl_transmission_factor_min   0.920
_refine_diff_density_max         0.780
_refine_diff_density_min         -0.770
_refine_diff_density_rms         0.083
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1141
_refine_ls_number_reflns         16486
_refine_ls_number_restraints     73
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0513
_refine_ls_R_factor_gt           0.0385
_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^)+(0.0350P)^2^+5.9080P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0903
_refine_ls_wR_factor_ref         0.0983
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13430
_reflns_number_total             16486
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt01513d2.cif
_cod_data_source_block           3
_cod_depositor_comments
'Adding full bibliography for 7716740--7716743.cif.'
_cod_original_cell_volume        4670.2(12)
_cod_database_code               7716743
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.975
_shelx_estimated_absorpt_t_min   0.905
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 C69-C02C \\sim C69-C70
 with sigma of 0.02
 C37-C03F \\sim C37-C39
 with sigma of 0.02
 C30-C34 \\sim C30-C8A
 with sigma of 0.02
 C34-C30 \\sim C7A-C30 \\sim C31-C30 \\sim C8A-C30 \\sim C33-C30 \\sim C13-C8
\\sim C6A-C30
 with sigma of 0.04
 C02C-C72 \\sim C70-C32
 with sigma of 0.02
 C02C-C71 \\sim C70-C0
 with sigma of 0.02
 C69-C72 \\sim C69-C32
 with sigma of 0.04
 C71-C72 \\sim C0-C32
 with sigma of 0.04
 C02C-C73 \\sim C70-C03C
 with sigma of 0.02
 C72-C73 \\sim C32-C03C
 with sigma of 0.04
 C69-C71 \\sim C69-C0
 with sigma of 0.04
 C69-C73 \\sim C69-C03C
 with sigma of 0.04
 C71-C73 \\sim C0-C03C
 with sigma of 0.04
 C37-C038 \\sim C37-C38
 with sigma of 0.02
 C37-C03G \\sim C37-C03H
 with sigma of 0.02
 C30-C33 \\sim C30-C7A
 with sigma of 0.02
 C30-C31 \\sim C30-C6A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C39 \\sim C37: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
Uanis(C39) \\sim Ueq: with sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(C8A) \\sim Ueq: with sigma of 0.004 and sigma for terminal atoms of 0.008
Uanis(C32) \\sim Ueq: with sigma of 0.004 and sigma for terminal atoms of 0.008
Uanis(C02C) \\sim Ueq: with sigma of 0.004 and sigma for terminal atoms of 0.008
Uanis(C6A) \\sim Ueq: with sigma of 0.004 and sigma for terminal atoms of 0.008
4. Rigid body (RIGU) restrains
 C39
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C8A
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C30
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C6A, C33, C7A, C31
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: O6(0.55) H6(0.55) O3(0.55) H3(0.55) C02C(0.55) O2(0.45) H2(0.45)
 O5(0.45) H5(0.45) C71(0.55) H71A(0.55) H71B(0.55) H71C(0.55) C038(0.55)
 H03A(0.55) H03B(0.55) H03C(0.55) C72(0.55) H72A(0.55) H72B(0.55) H72C(0.55)
 C73(0.55) H73A(0.55) H73B(0.55) H73C(0.55) C03F(0.55) H03D(0.55) H03E(0.55)
 H03F(0.55) C03G(0.55) H03G(0.55) H03H(0.55) H03I(0.55) C70(0.45) C0(0.45)
 H0A(0.45) H0B(0.45) H0C(0.45) C32(0.45) H32A(0.45) H32B(0.45) H32C(0.45)
 C03C(0.45) H03M(0.45) H03N(0.45) H03O(0.45) C38(0.45) H38A(0.45) H38B(0.45)
 H38C(0.45) C39(0.45) H39A(0.45) H39B(0.45) H39C(0.45) C03H(0.45) H03J(0.45)
 H03K(0.45) H03L(0.45) C33(0.65) H33A(0.65) H33B(0.65) H33C(0.65) C31(0.65)
 H31A(0.65) H31B(0.65) H31C(0.65) C34(0.65) H34A(0.65) H34B(0.65) H34C(0.65)
 C7A(0.35) H7AA(0.35) H7AB(0.35) H7AC(0.35) C6A(0.35) H6AA(0.35) H6AB(0.35)
 H6AC(0.35) C8A(0.35) H8AA(0.35) H8AB(0.35) H8AC(0.35)
6.a Secondary CH2 refined with riding coordinates:
 C02R(H02D,H02E)
6.b Aromatic/amide H refined with riding coordinates:
 C53(H53), C7(H7), C63(H63), C62(H62), C64(H64), C16(H16), C25(H25), C22(H22),
 C65(H65), C24(H24), C19(H19), C13(H13), C17(H17), C56(H56), C18(H18), C47(H47),
  C57(H57), C23(H23), C74(H74), C58(H58), C59(H59), C35(H35)
6.c Tetrahedral OH refined with riding coordinates:
 O6(H6), O3(H3), O2(H2), O5(H5)
6.d Idealised Me refined as rotating group:
 C021(H02A,H02B,H02C), C10(H10A,H10B,H10C), C5(H5A,H5B,H5C), C12(H12A,H12B,
 H12C), C6(H6A,H6B,H6C), C46(H46A,H46B,H46C), C11(H11A,H11B,H11C), C50(H50A,
 H50B,H50C), C52(H52A,H52B,H52C), C4(H4A,H4B,H4C), C45(H45A,H45B,H45C),
 C44(H44A,H44B,H44C), C79(H79A,H79B,H79C), C78(H78A,H78B,H78C), C77(H77A,H77B,
 H77C), C71(H71A,H71B,H71C), C038(H03A,H03B,H03C), C72(H72A,H72B,H72C),
 C73(H73A,H73B,H73C), C03F(H03D,H03E,H03F), C03G(H03G,H03H,H03I), C0(H0A,H0B,
 H0C), C32(H32A,H32B,H32C), C03C(H03M,H03N,H03O), C38(H38A,H38B,H38C), C39(H39A,
 H39B,H39C), C03H(H03J,H03K,H03L), C33(H33A,H33B,H33C), C31(H31A,H31B,H31C),
 C34(H34A,H34B,H34C), C7A(H7AA,H7AB,H7AC), C6A(H6AA,H6AB,H6AC), C8A(H8AA,H8AB,
 H8AC)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 228 electrons were 
found in a volume of 760\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
3[CH2Cl2] per formula unit 
which account for 252 electrons 
per unit cell.
;
_shelx_res_checksum              50793
_shelx_hkl_checksum              88879
_shelx_fab_checksum              13600
_olex2_submission_special_instructions 'No special instructions were received'