Axial ligand-induced high electrocatalytic hydrogen evolution activity of molecular cobaloximes in homo- and heterogeneous medium.
Yadav, Jitendra Kumar; Singh, Baghendra; Mishra, Anjali; Pal, Sarvesh Kumar; Singh, Nanhai; Lama, Prem; Indra, Arindam; Kumar, Kamlesh; Dalton transactions (Cambridge, England : 2003) 53 (2024) 16747–16758; doi:10.1039/d4dt00650j

data_7717034
_publ_section_title
;
 Axial ligand-induced high electrocatalytic hydrogen evolution activity of
 molecular cobaloximes in homo- and heterogeneous medium.
;
_journal_issue                   40
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              16747
_journal_page_last               16758
_journal_paper_doi               10.1039/d4dt00650j
_journal_volume                  53
_journal_year                    2024
_chemical_formula_moiety         '2(C51 H43 Cl Co N7 O6), 6(C3 H7 N O), 2(H2 O)'
_chemical_formula_sum            'C120 H132 Cl2 Co2 N20 O20'
_chemical_formula_weight         2363.21
_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   mixed
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2023-04-08
_audit_creation_method
;
Olex2 1.2
(compiled 2013.12.10 svn.r2850 for OlexSys, GUI svn.r4736)
;
_audit_update_record
;
2023-05-16 deposited with the CCDC.	2024-09-12 downloaded from the CCDC.
;
_cell_angle_alpha                70.333(2)
_cell_angle_beta                 65.6550(10)
_cell_angle_gamma                64.1590(10)
_cell_formula_units_Z            2
_cell_length_a                   18.6907(8)
_cell_length_b                   19.1638(10)
_cell_length_c                   20.6132(9)
_cell_measurement_reflns_used    9930
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      26.06
_cell_measurement_theta_min      2.18
_cell_volume                     5942.3(5)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX3'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS-2013 (Sheldrick, 2008)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-III photon detector'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0359
_diffrn_reflns_av_unetI/netI     0.0357
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            78554
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        24.999
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         1.931
_exptl_absorpt_coefficient_mu    0.400
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            brown
_exptl_crystal_density_diffrn    1.321
_exptl_crystal_description       block
_exptl_crystal_F_000             2480
_exptl_crystal_size_max          0.31
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.22
_exptl_transmission_factor_max   0.7453
_exptl_transmission_factor_min   0.6584
_refine_diff_density_max         0.813
_refine_diff_density_min         -0.524
_refine_diff_density_rms         0.072
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1576
_refine_ls_number_reflns         20917
_refine_ls_number_restraints     4
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0770
_refine_ls_R_factor_gt           0.0564
_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^)+(0.0797P)^2^+8.6714P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1534
_refine_ls_wR_factor_ref         0.1701
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15092
_reflns_number_total             20917
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt00650j2.cif
_cod_data_source_block           JK_342_sq
_cod_depositor_comments
'Adding full bibliography for 7717032--7717034.cif.'
_cod_original_cell_volume        5942.4(5)
_cod_database_code               7717034
_shelx_estimated_absorpt_t_max   0.917
_shelx_estimated_absorpt_t_min   0.886
_olex2_refinement_description
;
1. Others
 Fixed Uiso: H1A(0.026) H2(0.035) H3(0.035) H4A(0.034) H5(0.027) H10(0.027)
 H11(0.038) H12(0.042) H13(0.04) H14(0.028) H15(0.03) H16(0.04) H17(0.043)
 H18(0.036) H19(0.026) H24(0.026) H25(0.031) H26(0.033) H27(0.033) H28(0.024)
 H29(0.024) H30(0.03) H32(0.027) H33(0.022) H52(0.032) H53(0.041) H54(0.045)
 H55(0.039) H56(0.028) H61(0.026) H62(0.033) H63(0.033) H64(0.033) H65(0.024)
 H66(0.026) H67(0.034) H68(0.035) H69(0.033) H70(0.026) H75(0.031) H76(0.042)
 H77(0.047) H78(0.044) H79(0.03) H80(0.023) H81(0.029) H83(0.026) H84(0.022)
 H85A(0.045) H85B(0.045) H88(0.052) H89(0.046) H90(0.042) H93(0.046) H94(0.048)
 H98A(0.059) H98B(0.059) H99A(0.078) H99B(0.078) H10A(0.082) H10B(0.082)
 H10C(0.075) H10D(0.075) H10E(0.06) H10F(0.06) H103(0.038) H10G(0.072)
 H10H(0.072) H10I(0.072) H10J(0.062) H10K(0.062) H10L(0.062) H106(0.044)
 H10M(0.074) H10N(0.074) H10O(0.074) H10P(0.067) H10Q(0.067) H10R(0.067)
 H109(0.045) H11A(0.099) H11B(0.099) H11C(0.099) H11D(0.07) H11E(0.07)
 H11F(0.07) H112(0.057) H11G(0.082) H11H(0.082) H11I(0.082) H11J(0.089)
 H11K(0.089) H11L(0.089) H115(0.103) H11M(0.12) H11N(0.12) H11O(0.12)
 H11P(0.105) H11Q(0.105) H11R(0.105) H118(0.089) H11S(0.117) H11T(0.117)
 H11U(0.117) H12A(0.119) H12B(0.119) H12C(0.119) H34A(0.025) H34B(0.025)
 H37A(0.034) H38A(0.036) H39A(0.028) H42A(0.032) H43A(0.034) H47A(0.045)
 H47B(0.045) H48A(0.059) H48B(0.059) H49A(0.061) H49B(0.061) H50A(0.063)
 H50B(0.063) H51A(0.049) H51B(0.049) H34C(0.035) H34D(0.035) H37B(0.021)
 H38B(0.05) H39B(0.033) H42B(0.043) H43B(0.028) C47B(0.06) H47C(0.072)
 H47D(0.072) C48B(0.06) H48C(0.072) H48D(0.072) C49B(0.06) H49C(0.072)
 H49D(0.072) C50B(0.06) H50C(0.072) H50D(0.072) C51B(0.06) H51C(0.072)
 H51D(0.072)
 Fixed X: H1A(0.569407) H2(0.663332) H3(0.777946) H4A(0.801198) H5(0.708703)
 H10(0.521338) H11(0.544977) H12(0.593534) H13(0.619945) H14(0.594558)
 H15(0.519906) H16(0.499015) H17(0.364604) H18(0.24915) H19(0.268127)
 H24(0.383943) H25(0.284534) H26(0.153858) H27(0.122905) H28(0.222985)
 H29(0.406814) H30(0.290858) H32(0.200614) H33(0.318146) H52(-0.021928) H53(-
 0.002318) H54(0.130615) H55(0.246831) H56(0.229329) H61(0.123842)
 H62(0.227985) H63(0.357486) H64(0.381856) H65(0.276932) H66(-0.071833) H67(-
 0.162849) H68(-0.273097) H69(-0.29404) H70(-0.205707) H75(-0.02054) H76(-
 0.040237) H77(-0.085454) H78(-0.110737) H79(-0.090194) H80(0.088575)
 H81(0.19883) H83(0.294194) H84(0.181311) H85A(0.312491) H85B(0.374352)
 H88(0.30221) H89(0.372463) H90(0.484282) H93(0.633103) H94(0.565917)
 H98A(0.487128) H98B(0.547838) H99A(0.547864) H99B(0.576956) H10A(0.694772)
 H10B(0.674576) H10C(0.779454) H10D(0.724216) H10E(0.682483) H10F(0.715548)
 H103(0.368377) H10G(0.338242) H10H(0.416618) H10I(0.42921) H10J(0.503001)
 H10K(0.534712) H10L(0.522178) H106(0.131957) H10M(0.151479) H10N(0.062856)
 H10O(0.067973) H10P(-0.001733) H10Q(-0.021643) H10R(-0.040761) H109(0.154681)
 H11A(0.136101) H11B(0.049256) H11C(0.058694) H11D(-0.047384) H11E(-0.052464)
 H11F(-0.076435) H112(0.342093) H11G(0.546606) H11H(0.575043) H11I(0.545692)
 H11J(0.363237) H11K(0.436505) H11L(0.453036) H115(0.304893) H11M(0.17809)
 H11N(0.256554) H11O(0.269433) H11P(0.235363) H11Q(0.265595) H11R(0.170878)
 H118(0.172647) H11S(0.222393) H11T(0.257049) H11U(0.31941) H12A(0.266295)
 H12B(0.342923) H12C(0.262506) H8O(0.09602) H34A(0.105072) H34B(0.155589)
 H37A(0.218005) H38A(0.181811) H39A(0.088866) H42A(-0.071261) H43A(-0.047794)
 H47A(0.076683) H47B(0.120855) H48A(0.05662) H48B(0.110934) H49A(-0.008349)
 H49B(-0.025757) H50A(-0.105899) H50B(-0.140939) H51A(-0.127292) H51B(-0.07153)
 H34C(0.135208) H34D(0.20731) H37B(0.190413) H38B(0.139136) H39B(0.020539)
 H42B(-0.109816) H43B(-0.04578) H47C(0.020242) H47D(-0.037888) H48C(-0.047597)
 H48D(-0.067158) H49C(-0.194145) H49D(-0.179671) H50C(-0.234267) H50D(-
 0.279428) H51C(-0.212814) H51D(-0.177677) H1O(0.53791) H9O(-0.034471)
 H2WA(0.332569) H1WA(0.16203) H2WB(0.30704) H1WB(0.18225)
 Fixed Y: H1A(0.916462) H2(0.932715) H3(0.825217) H4A(0.700603) H5(0.683703)
 H10(0.736517) H11(0.63857) H12(0.505982) H13(0.46951) H14(0.566461)
 H15(0.920272) H16(0.999896) H17(1.069261) H18(1.061155) H19(0.981189)
 H24(0.807277) H25(0.797706) H26(0.800426) H27(0.809884) H28(0.816221)
 H29(0.968263) H30(1.048254) H32(0.868427) H33(0.793395) H52(0.601058)
 H53(0.526475) H54(0.446667) H55(0.440437) H56(0.516861) H61(0.695456)
 H62(0.703898) H63(0.698272) H64(0.690536) H65(0.687295) H66(0.579362)
 H67(0.558684) H68(0.66511) H69(0.792769) H70(0.814201) H75(0.757795)
 H76(0.851673) H77(0.985448) H78(1.026502) H79(0.933936) H80(0.537266)
 H81(0.45998) H83(0.636356) H84(0.709375) H85A(0.456099) H85B(0.454107)
 H88(0.615144) H89(0.673957) H90(0.703031) H93(0.665246) H94(0.598475)
 H98A(0.806324) H98B(0.833031) H99A(0.887866) H99B(0.801255) H10A(0.837049)
 H10B(0.859071) H10C(0.733901) H10D(0.70257) H10E(0.744044) H10F(0.655361)
 H103(0.563108) H10G(0.395591) H10H(0.375491) H10I(0.341023) H10J(0.504137)
 H10K(0.411889) H10L(0.440304) H106(0.937428) H10M(1.112151) H10N(1.160775)
 H10O(1.134691) H10P(0.990181) H10Q(1.052305) H10R(1.082864) H109(0.65211)
 H11A(0.553508) H11B(0.588851) H11C(0.527145) H11D(0.696637) H11E(0.613629)
 H11F(0.686391) H112(0.833916) H11G(0.778173) H11H(0.805567) H11I(0.866655)
 H11J(0.929144) H11K(0.95788) H11L(0.898725) H115(0.555457) H11M(0.485186)
 H11N(0.404533) H11O(0.484474) H11P(0.451772) H11Q(0.376725) H11R(0.436365)
 H118(0.278016) H11S(0.153004) H11T(0.084366) H11U(0.121914) H12A(0.211274)
 H12B(0.145961) H12C(0.125359) H8O(0.809669) H34A(1.035089) H34B(1.068909)
 H37A(0.954832) H38A(0.888293) H39A(0.823203) H42A(0.790541) H43A(0.87297)
 H47A(0.650088) H47B(0.704632) H48A(0.693296) H48B(0.607183) H49A(0.586567)
 H49B(0.614466) H50A(0.742225) H50B(0.683526) H51A(0.784686) H51B(0.698612)
 H34C(1.06599) H34D(1.028183) H37B(0.899428) H38B(0.816809) H39B(0.788365)
 H42B(0.81519) H43B(0.888147) H47C(0.69051) H47D(0.660514) H48C(0.613007)
 H48D(0.698718) H49C(0.67941) H49D(0.645991) H50C(0.806773) H50D(0.766005)
 H51C(0.841747) H51D(0.751307) H1O(0.92215) H9O(0.58531) H2WA(0.70224)
 H1WA(0.7655) H2WB(0.739509) H1WB(0.77164)
 Fixed Z: H1A(-0.082507) H2(-0.198763) H3(-0.241334) H4A(-0.165722) H5(-
 0.04865) H10(-0.076756) H11(-0.134593) H12(-0.082488) H13(0.028034)
 H14(0.087057) H15(0.290323) H16(0.365292) H17(0.429943) H18(0.418972)
 H19(0.345829) H24(0.428367) H25(0.542485) H26(0.554727) H27(0.45257)
 H28(0.338118) H29(0.076725) H30(0.039226) H32(0.128525) H33(0.164458)
 H52(0.1962) H53(0.117114) H54(0.060718) H55(0.082258) H56(0.158813)
 H61(0.069179) H62(-0.043211) H63(-0.049154) H64(0.055634) H65(0.167017)
 H66(0.577672) H67(0.694645) H68(0.743768) H69(0.674425) H70(0.556595)
 H75(0.579397) H76(0.639725) H77(0.589968) H78(0.478825) H79(0.417232)
 H80(0.425914) H81(0.471936) H83(0.377805) H84(0.33491) H85A(0.50581)
 H85B(0.424501) H88(0.647484) H89(0.672203) H90(0.584439) H93(0.345689)
 H94(0.324571) H98A(0.494846) H98B(0.417102) H99A(0.505761) H99B(0.553373)
 H10A(0.487791) H10B(0.413466) H10C(0.418501) H10D(0.497284) H10E(0.366418)
 H10F(0.409357) H103(0.200933) H10G(0.316808) H10H(0.341913) H10I(0.2757)
 H10J(0.191425) H10K(0.191565) H10L(0.261385) H106(0.297656) H10M(0.185567)
 H10N(0.235325) H10O(0.167042) H10P(0.308562) H10Q(0.238098) H10R(0.30886)
 H109(0.643625) H11A(0.624419) H11B(0.607605) H11C(0.681178) H11D(0.756058)
 H11E(0.761178) H11F(0.697861) H112(0.85574) H11G(0.750956) H11H(0.798913)
 H11I(0.731799) H11J(0.876898) H11K(0.814515) H11L(0.887251) H115(0.763532)
 H11M(0.774164) H11N(0.773328) H11O(0.721125) H11P(0.932293) H11Q(0.897316)
 H11R(0.911118) H118(0.751258) H11S(0.741297) H11T(0.802627) H11U(0.734105)
 H12A(0.885622) H12B(0.841947) H12C(0.89987) H8O(0.272249) H34A(0.110644)
 H34B(0.030423) H37A(-0.169739) H38A(-0.222192) H39A(-0.151284) H42A(0.095283)
 H43A(0.140728) H47A(-0.014652) H47B(-0.083193) H48A(-0.155249) H48B(-0.122208)
 H49A(-0.032864) H49B(-0.109184) H50A(-0.088276) H50B(-0.017873) H51A(0.014008)
 H51B(0.045834) H34C(0.049673) H34D(-0.017681) H37B(-0.152199) H38B(-0.169894)
 H39B(-0.079152) H42B(0.166047) H43B(0.183669) H47C(-0.004018) H47D(0.074248)
 H48C(-0.010411) H48D(-0.060918) H49C(-0.004962) H49D(0.072415) H50C(0.003922)
 H50D(0.083302) H51C(0.088902) H51D(0.126011) H1O(0.08509) H9O(0.406219)
 H2WA(0.815941) H1WA(0.700589) H2WB(0.75805) H1WB(0.74816)
;
_shelx_res_checksum              12487
_shelx_hkl_checksum              64648
_shelx_fab_checksum              1441
_shelx_shelxl_version_number     2019/2