Photochemical CO<sub>2</sub> reduction in water using a co-immobilised nickel catalyst and a visible light sensitiser.
Neri, Gaia; Forster, Mark; Walsh, James J.; Robertson, C. M.; Whittles, T. J.; Farràs, Pau; Cowan, Alexander J.; Chemical communications (Cambridge, England) 52 (2016) 14200–14203; doi:10.1039/c6cc08590c

data_7125299
_publ_section_title
;
 Photochemical CO<sub>2</sub> reduction in water using a co-immobilised
 nickel catalyst and a visible light sensitiser.
;
_journal_issue                   99
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              14200
_journal_page_last               14203
_journal_paper_doi               10.1039/c6cc08590c
_journal_volume                  52
_journal_year                    2016
_chemical_formula_moiety         '0.5(C44 H100 N16 Ni4 O12 P4), 2(H2 O), 2(O)'
_chemical_formula_sum            'C22 H54 N8 Ni2 O10.01 P2'
_chemical_formula_weight         770.25
_chemical_name_common            NiCycP
_chemical_name_systematic
'[Ni([(1,4,8,11-tetraazacyclotetradecan-1-yl)methylene]phosphonic acid)]n'
_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
_audit_creation_date             2016-09-27
_audit_creation_method
;
Olex2 1.2
(compiled 2016.08.25 svn.r3337 for OlexSys, GUI svn.r5221)
;
_audit_update_record
;
2016-10-24 deposited with the CCDC.
2016-11-15 downloaded from the CCDC.
;
_cell_angle_alpha                90.0930(10)
_cell_angle_beta                 90.5310(11)
_cell_angle_gamma                90.0970(10)
_cell_formula_units_Z            4
_cell_length_a                   10.3977(3)
_cell_length_b                   14.1488(4)
_cell_length_c                   22.4532(7)
_cell_measurement_reflns_used    9979
_cell_measurement_temperature    100
_cell_measurement_theta_max      26.42
_cell_measurement_theta_min      2.32
_cell_volume                     3303.05(17)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0826
_diffrn_reflns_av_unetI/netI     0.0419
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            137618
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         26.372
_diffrn_reflns_theta_min         2.314
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.299
_exptl_absorpt_correction_T_max  0.9386
_exptl_absorpt_correction_T_min  0.7252
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1595 before and 0.1133 after correction.
The Ratio of minimum to maximum transmission is 0.7726.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            Purple
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.549
_exptl_crystal_description       block
_exptl_crystal_F_000             1632
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Water'
_exptl_crystal_size_max          0.198
_exptl_crystal_size_mid          0.092
_exptl_crystal_size_min          0.054
_refine_diff_density_max         1.030
_refine_diff_density_min         -0.643
_refine_diff_density_rms         0.124
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.116
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     805
_refine_ls_number_reflns         13486
_refine_ls_number_restraints     289
_refine_ls_restrained_S_all      1.106
_refine_ls_R_factor_all          0.0762
_refine_ls_R_factor_gt           0.0640
_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^)+(0.0001P)^2^+30.4206P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1399
_refine_ls_wR_factor_ref         0.1443
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11409
_reflns_number_total             13486
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6cc08590c2.cif
_cod_data_source_block           pbar1_a
_cod_database_code               7125299
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All O(H,H) groups
2. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3.a Free rotating group:
 O20(H20C,H20D), O15(H15C,H15D), O16(H16C,H16D), O18(H18C,H18D)
3.b Ternary CH refined with riding coordinates:
 N11(H11), N3(H3), N12(H12), N8(H8), N1(H1), N13(H13), N15(H15), N4(H4),
 N5(H5), N16(H16), N7(H7), N9(H9)
3.c Secondary CH2 refined with riding coordinates:
 C33(H33A,H33B), C4(H4A,H4B), C25(H25A,H25B), C30(H30A,H30B), C41(H41A,H41B),
 C14(H14A,H14B), C17(H17A,H17B), C27(H27A,H27B), C5(H5A,H5B), C32(H32A,H32B),
 C26(H26A,H26B), C16(H16A,H16B), C29(H29A,H29B), C9(H9A,H9B), C23(H23A,H23B),
 C24(H24A,H24B), C19(H19A,H19B), C2(H2A,H2B), C34(H34A,H34B), C13(H13A,H13B),
 C1(H1A,H1B), C7(H7A,H7B), C10(H10A,H10B), C22(H22A,H22B), C6(H6A,H6B),
 C21(H21A,H21B), C36(H36A,H36B), C43(H43A,H43B), C37(H37A,H37B), C12(H12A,H12B),
  C39(H39A,H39B), C40(H40A,H40B), C8(H8A,H8B), C18(H18A,H18B), C38(H38A,H38B),
 C15(H15A,H15B), C28(H28A,H28B), C3(H3A,H3B), C11(H11A,H11B), C35(H35A,H35B),
 C20(H20A,H20B), C42(H42A,H42B), C44(H44A,H44B), C31(H31A,H31B)
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'