Reversible Homolytic Activation of Water via Metal-Ligand Cooperativity in a T-Shaped Ni(II) Complex
Chang, Mu-Chieh; Jesse, Kate A.; Filatov, Alexander S.; Anderson, John S.; Chemical Science  (2019) –; doi:10.1039/C8SC03719A

data_1550195
_publ_section_title
;
 Reversible Homolytic Activation of Water via Metal-Ligand Cooperativity
 in a T-Shaped Ni(II) Complex
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C8SC03719A
_journal_year                    2019
_chemical_formula_moiety         'C64 H54 N10 Ni2 O'
_chemical_formula_sum            'C64 H54 N10 Ni2 O'
_chemical_formula_weight         1096.59
_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   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2018-07-18
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2018-08-07 deposited with the CCDC.
2018-11-06 downloaded from the CCDC.
;
_cell_angle_alpha                76.493(3)
_cell_angle_beta                 81.913(3)
_cell_angle_gamma                81.444(3)
_cell_formula_units_Z            4
_cell_length_a                   12.0657(16)
_cell_length_b                   23.067(3)
_cell_length_c                   23.079(3)
_cell_measurement_reflns_used    9702
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      14.74
_cell_measurement_theta_min      2.24
_cell_volume                     6138.6(14)
_computing_cell_refinement       'APEX3 v.2015.9-0 (Bruker AXS Inc., 2015)'
_computing_data_collection       'APEX3 v.2015.9-0 (Bruker AXS Inc., 2015)'
_computing_data_reduction        'APEX3 v.2015.9-0 (Bruker AXS Inc., 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Pilatus1M(CdTe) pixel array detector'
_diffrn_detector_area_resol_mean 30
_diffrn_detector_type            'CMOS pixel array detector'
_diffrn_measured_fraction_theta_full 0.967
_diffrn_measured_fraction_theta_max 0.943
_diffrn_measurement_device_type  'three-circle diffractometer'
_diffrn_measurement_method       'phi rotation'
_diffrn_radiation_collimation    '0.2 mm sinlge-pinhole'
_diffrn_radiation_monochromator  'Si(111) & Si(311)'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     0.41328
_diffrn_reflns_av_R_equivalents  0.0749
_diffrn_reflns_av_unetI/netI     0.0497
_diffrn_reflns_Laue_measured_fraction_full 0.967
_diffrn_reflns_Laue_measured_fraction_max 0.943
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            135413
_diffrn_reflns_point_group_measured_fraction_full 0.967
_diffrn_reflns_point_group_measured_fraction_max 0.943
_diffrn_reflns_theta_full        14.357
_diffrn_reflns_theta_max         14.761
_diffrn_reflns_theta_min         0.998
_diffrn_source                   synchrotron
_diffrn_source_type
'Insertion Device, Station 15 ID-B, APS, Argonne Nat'l Lab'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.160
_exptl_absorpt_correction_T_max  0.7438
_exptl_absorpt_correction_T_min  0.5499
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. 
wR2(int) was 0.1065 before and 0.0634 after correction. 
The Ratio of minimum to maximum transmission is 0.7393. 
;
_exptl_crystal_colour            violet
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.187
_exptl_crystal_description       block
_exptl_crystal_F_000             2288
_exptl_crystal_size_max          0.02
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.132
_refine_diff_density_min         -1.005
_refine_diff_density_rms         0.083
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.094
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1576
_refine_ls_number_reflns         22723
_refine_ls_number_restraints     307
_refine_ls_restrained_S_all      1.087
_refine_ls_R_factor_all          0.0866
_refine_ls_R_factor_gt           0.0680
_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^)+(0.0453P)^2^+20.3719P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1575
_refine_ls_wR_factor_ref         0.1680
_reflns_Friedel_coverage         0.000
_reflns_number_gt                17677
_reflns_number_total             22723
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8sc03719a2.cif
_cod_data_source_block           mu2_h2o
_cod_database_code               1550195
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.997
_shelx_estimated_absorpt_t_min   0.997
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups, All O(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C54-C53 \\sim C53-C52 \\sim C57-C52 \\sim C57-C56 \\sim C56-C55 \\sim C55-C54
 with sigma of 0.02
 C57A-C52A \\sim C53A-C52A \\sim C54A-C53A \\sim C55A-C54A \\sim C56A-C55A
\\sim C57A-C56A
 with sigma of 0.02
 C52A-C51 \\sim C52-C51 \\sim C52B-C51
 with sigma of 0.005
 C58A-C55A \\sim C58-C55 \\sim C58B-C55B
 with sigma of 0.005
 C6X-C1X \\sim C2X-C1X \\sim C3X-C2X \\sim C4X-C3X \\sim C5X-C4X \\sim C6X-C5X
 with sigma of 0.005
 C117-C116 \\sim C118-C117 \\sim C119-C118 \\sim C120-C119 \\sim C121-C120
\\sim C121-C116
 with sigma of 0.02
 C7X-C4X \\sim C122-C119
 with sigma of 0.005
3. Restrained planarity
 C51, C52A, C53A, C54A, C55A, C56A, C57A, C58A
 with sigma of 0.1
 C51, C52B, C53B, C54B, C55B, C56B, C57B, C58B
 with sigma of 0.1
 C51, C52, C53, C54, C55, C56, C57, C58
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uanis(C52A) = Uanis(C52)
Uanis(C52B) = Uanis(C52)
Uanis(C1X) = Uanis(C116)
Uanis(C7X) = Uanis(C122)
5. Rigid body (RIGU) restrains
 C52, C53, C54, C55, C56, C57, C58, C52A, C53A, C54A, C55A, C56A, C57A, C58A,
 C52B, C53B, C54B, C55B, C56B, C57B, C58B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C116, C117, C118, C119, C120, C121, C122, H4CA, C7X, C4X, C5X, C6X, C2X, C3X,
 C1X
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C1X)=Sof(C2X)=Sof(H7CA)=Sof(C3X)=Sof(H8CA)=Sof(C4X)=Sof(C5X)=Sof(H9CA)=
 Sof(C6X)=Sof(H0DA)=Sof(C122)=Sof(H1DA)=Sof(H2DA)=Sof(H3DA)=1-FVAR(1)
 Sof(C116)=Sof(C117)=Sof(H0CA)=Sof(C118)=Sof(H1CA)=Sof(C119)=Sof(C120)=
 Sof(H2CA)=Sof(C121)=Sof(H3CA)=Sof(C7X)=Sof(H4CA)=Sof(H5CA)=Sof(H6CA)=FVAR(1)
 Fixed Sof: C52(0.36) C53(0.36) H53(0.36) C54(0.36) H54(0.36) C55(0.36)
 C56(0.36) H56(0.36) C57(0.36) H57(0.36) C58(0.36) H58A(0.36) H58B(0.36)
 H58C(0.36) C52A(0.32) C53A(0.32) H53A(0.32) C54A(0.32) H54A(0.32) C55A(0.32)
 C56A(0.32) H56A(0.32) C57A(0.32) H57A(0.32) C58A(0.32) H58D(0.32) H58E(0.32)
 H58F(0.32) C52B(0.32) C53B(0.32) H53B(0.32) C54B(0.32) H54B(0.32) C55B(0.32)
 C56B(0.32) H56B(0.32) C57B(0.32) H57B(0.32) C58B(0.32) H58G(0.32) H58H(0.32)
 H58I(0.32)
7.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C9(H9), C10(H10), C12(H12), C13(H13),
 C16(H16), C17(H17), C21(H21), C22(H22), C24(H24), C25(H25), C28(H28), C29(H29),
  C30(H30), C31(H31), C32(H32), C34(H34), C35(H35), C36(H36), C37(H37),
 C38(H38), C41(H41), C42(H42), C44(H44), C45(H45), C48(H48), C49(H49), C60(H60),
  C61(H61), C62(H62), C63(H63), C64(H64), C53(H53), C54(H54), C56(H56),
 C57(H57), C53A(H53A), C54A(H54A), C56A(H56A), C57A(H57A), C53B(H53B),
 C54B(H54B), C56B(H56B), C57B(H57B), C66(HB), C67(HC), C68(HD), C69(HE),
 C70(HF), C73(HG), C74(HH), C76(HI), C77(HJ), C80(HN), C81(HO), C85(HP),
 C86(HQ), C88(HR), C89(HS), C92(HW), C93(HX), C94(HY), C95(HZ), C96(H0AA),
 C98(H1AA), C99(H2AA), C100(H3AA), C101(H4AA), C102(H5AA), C105(H6AA),
 C106(H7AA), C108(H8AA), C109(H9AA), C112(H3BA), C113(H4BA), C124(H5BA),
 C125(H6BA), C126(H7BA), C127(H8BA), C128(H9BA), C117(H0CA), C118(H1CA),
 C120(H2CA), C121(H3CA), C2X(H7CA), C3X(H8CA), C5X(H9CA), C6X(H0DA)
7.b Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C26(H26A,H26B,H26C), C46(H46A,H46B,H46C), C58(H58A,H58B,
 H58C), C58A(H58D,H58E,H58F), C58B(H58G,H58H,H58I), C78(HK,HL,HM), C90(HT,HU,
 HV), C110(H0BA,H1BA,H2BA), C7X(H4CA,H5CA,H6CA), C122(H1DA,H2DA,H3DA)
;
_shelx_res_checksum              65317
_shelx_fab_checksum              43515
_olex2_submission_special_instructions 'No special instructions were received'