Studies of a Series of [Ni(PR2NPh2)2(CH3CN)]2+ Complexes as Electrocatalysts for H2 Production: Substituent Variation at the Phosphorus Atom of the P2N2 Ligand
Uriah J. Kilgore; Michael P. Stewart; Monte L. Helm; William G. Dougherty; W. Scott Kassel; Mary Rakowski DuBois; Daniel L. DuBois; R. Morris Bullock; Inorganic Chemistry 50 (2011) 10908–10918; doi:10.1021/ic201461a

data_4326676
_publ_section_title
;
 Studies of a Series of [Ni(PR2NPh2)2(CH3CN)]2+ Complexes as
 Electrocatalysts for H2 Production: Substituent Variation at the
 Phosphorus Atom of the P2N2 Ligand
;
_journal_name_full               'Inorganic Chemistry'
_journal_page_first              10908
_journal_page_last               10918
_journal_paper_doi               10.1021/ic201461a
_journal_volume                  50
_journal_year                    2011
_chemical_formula_sum            'C71 H83.5 B2 F8 N6.5 Ni O1.5 P4'
_chemical_formula_weight         1408.15
_chemical_name_systematic
; 
 ? 
;
_space_group_IT_number           2
_symmetry_cell_setting           triclinic
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                71.0220(10)
_cell_angle_beta                 77.0320(10)
_cell_angle_gamma                83.3250(10)
_cell_formula_units_Z            2
_cell_length_a                   13.7067(6)
_cell_length_b                   15.1081(6)
_cell_length_c                   18.4128(8)
_cell_measurement_reflns_used    9901
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      32.24
_cell_measurement_theta_min      2.52
_cell_volume                     3509.9(3)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0571
_diffrn_reflns_av_sigmaI/netI    0.1461
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            52417
_diffrn_reflns_theta_full        25.00
_diffrn_reflns_theta_max         33.22
_diffrn_reflns_theta_min         2.12
_exptl_absorpt_coefficient_mu    0.438
_exptl_absorpt_correction_T_max  0.9494
_exptl_absorpt_correction_T_min  0.9373
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    1.332
_exptl_crystal_density_meas      0
_exptl_crystal_description       block
_exptl_crystal_F_000             1474
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.12
_platon_squeeze_details
;
Squeeze resutls constistent with three sites of THF/acetonitrle solvent 
disorder.  The disorder has been seen in the diffrence map but all attempts to 
refine these sites have failed.  The empirical formula has been adjusted to 
include this solvent assuming a 50:50 ratio tetrahydrofuran/acetonitrile
which agrees with the squeeze results.

PLATON Reference : Spek, A.L. (2003). J. Appl. Cryst. 36, 7-13.
                     Spek, A.L. (2009). Acta Cryst. D65, 148-155.
;
_refine_diff_density_max         1.436
_refine_diff_density_min         -0.961
_refine_diff_density_rms         0.092
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     706
_refine_ls_number_reflns         26690
_refine_ls_number_restraints     56
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.1423
_refine_ls_R_factor_gt           0.0676
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0530P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1447
_refine_ls_wR_factor_ref         0.1594
_reflns_number_gt                12381
_reflns_number_total             26690
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ic201461a_si_002_1.cif
_cod_data_source_block           pnl061s
_cod_original_formula_sum        'C71 H83.50 B2 F8 N6.50 Ni O1.50 P4'
_cod_database_code               4326676