BCN Encapsulated Nano-nickel Synergistically Promotes Ambient Electrochemical Dinitrogen Reduction.
Zhao, Xue; Yang, Ziqiong; Kuklin, Artem V.; Baryshnikov, Glib V.; Agren, Hans; Liu, Wenjing; Zhang, Haibo; Zhou, Xiaohai; ACS applied materials & interfaces  (2020) –; doi:10.1021/acsami.0c06649

data_4517835
_publ_section_title
;
 BCN Encapsulated Nano-nickel Synergistically Promotes Ambient
 Electrochemical Dinitrogen Reduction.
;
_journal_name_full               'ACS applied materials &amp; interfaces'
_journal_paper_doi               10.1021/acsami.0c06649
_journal_year                    2020
_chemical_formula_moiety         'B12 H12, C16 H24 N8 Ni, 2(C4 H6 N2), H2 O'
_chemical_formula_sum            'C24 H50 B12 N12 Ni O'
_chemical_formula_weight         711.19
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2019-04-25
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.0312(2)
_cell_length_b                   17.5337(2)
_cell_length_c                   17.5386(2)
_cell_measurement_reflns_used    9388
_cell_measurement_temperature    150.01(10)
_cell_measurement_theta_max      73.5100
_cell_measurement_theta_min      3.5500
_cell_volume                     3699.79(9)
_computing_cell_refinement       'CrysAlisPro 1.171.38.30e (Agilent, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.30e (Agilent, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.30e (Agilent, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.6525
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w    -61.00  33.00   1.00    1.00    --  -39.95  57.00 120.00   94
  2  \w   -109.00 -13.00   1.00    1.00    --  -39.95 -57.00 -30.00   96
  3  \w    -64.00  34.00   1.00    1.00    --  -39.95  38.00 -90.00   98
  4  \w     44.00  96.00   1.00    1.00    --   39.95-125.00 -60.00   52
  5  \w    101.00 177.00   1.00    2.82    --  105.48  30.00-180.00   76
  6  \w     53.00 118.00   1.00    2.82    --  105.48-125.00-150.00   65
  7  \w     32.00 118.00   1.00    2.82    --  105.48-125.00  60.00   86
  8  \w    144.00 177.00   1.00    2.82    --  105.48  61.00 -30.00   33
  9  \w     74.00 161.00   1.00    2.82    --  105.48  77.00  30.00   87
 10  \w     79.00 174.00   1.00    2.82    --  105.48  77.00 -90.00   95
 11  \w     79.00 127.00   1.00    2.82    --  105.48  61.00 -30.00   48
 12  \w     94.00 178.00   1.00    2.82    --  105.48 125.00-150.00   84
 13  \w     30.00 132.00   1.00    2.82    --  105.48 -77.00-150.00  102
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0485961000
_diffrn_orient_matrix_UB_12      -0.0727953000
_diffrn_orient_matrix_UB_13      -0.0109058000
_diffrn_orient_matrix_UB_21      0.0708549000
_diffrn_orient_matrix_UB_22      -0.0490430000
_diffrn_orient_matrix_UB_23      0.0250511000
_diffrn_orient_matrix_UB_31      -0.0184108000
_diffrn_orient_matrix_UB_32      0.0034674000
_diffrn_orient_matrix_UB_33      0.1250831000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0378
_diffrn_reflns_av_unetI/netI     0.0318
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            21263
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        65.889
_diffrn_reflns_theta_max         65.889
_diffrn_reflns_theta_min         3.564
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.063
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.88310
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.30e (Agilent, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.277
_exptl_crystal_description       block
_exptl_crystal_F_000             1496
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.16
_refine_diff_density_max         1.979
_refine_diff_density_min         -0.346
_refine_diff_density_rms         0.131
_refine_ls_abs_structure_details
;
 Flack x determined using 2667 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.003(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.078
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     523
_refine_ls_number_reflns         6436
_refine_ls_number_restraints     545
_refine_ls_restrained_S_all      1.095
_refine_ls_R_factor_all          0.0737
_refine_ls_R_factor_gt           0.0726
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1566P)^2^+0.2552P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1847
_refine_ls_wR_factor_ref         0.1873
_reflns_Friedel_coverage         0.785
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                6312
_reflns_number_total             6436
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            am0c06649_si_002.cif
_cod_data_source_block           ni
_cod_database_code               4517835
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_usercomment     P20
_shelx_estimated_absorpt_t_max   0.848
_shelx_estimated_absorpt_t_min   0.832
_reflns_odcompleteness_completeness 99.88
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.487(3)
 0.513(3)
2. Fixed Uiso
 At 1.2 times of:
  All B(H) groups, All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
3. Restrained distances
 C11-C12
 1.5 with sigma of 0.02
 C27-C28
 1.5 with sigma of 0.02
 C28-C27
 1.6 with sigma of 0.02
 C7-N3
 1.4 with sigma of 0.02
 H14A-H1WB_$1
 2.2 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
N8 \\sim C16 \\sim C13 \\sim C14 \\sim C15 \\sim C9 \\sim C10 \\sim N6 \\sim
C11 \\sim C12: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
C16 \\sim C15 \\sim C10 \\sim N6 \\sim C11: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08
N3 \\sim C7 \\sim N4 \\sim C5 \\sim C8 \\sim C6: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08
All non-hydrogen atoms restrained to be isotropic: with sigma of 0.01 and sigma
for terminal atoms of 0.02
Uanis(C24) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(Ni1A) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C12) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C23) \\sim Ueq: with sigma of
0.001 and sigma for terminal atoms of 0.002
Uanis(C11) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C19) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(N12) \\sim Ueq, Uanis(N9) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(N6) \\sim Ueq, Uanis(N7) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(N5) \\sim Ueq, Uanis(C16) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(C20) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(Ni1) = Uanis(Ni1A)
Uanis(N11) = Uanis(N10)
5. Others
 Sof(C19)=Sof(N12)=Sof(C17)=Sof(H17)=Sof(C18)=Sof(H18)=Sof(N11)=Sof(H11)=
 Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=1-FVAR(1)
 Sof(N9)=Sof(C22)=Sof(H22)=Sof(C21)=Sof(H21)=Sof(N10)=Sof(H10)=Sof(C23)=
 Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=FVAR(1)
 Sof(C9)=Sof(H9)=Sof(C10)=Sof(H10A)=Sof(N6)=Sof(H6A)=Sof(C11)=Sof(N5)=Sof(C12)=
 Sof(H12A)=Sof(H12B)=Sof(H12C)=1-FVAR(2)
 Sof(N8)=Sof(C16)=Sof(N7)=Sof(H7)=Sof(C13)=Sof(H13)=Sof(C14)=Sof(H14)=Sof(C15)=
 Sof(H15A)=Sof(H15B)=Sof(H15C)=FVAR(2)
 Sof(Ni1A)=1-FVAR(3)
 Sof(Ni1)=FVAR(3)
6.a Riding coordinates:
 N7(H7), N10(H10), O1W(H1WA,H1WB), N11(H11), N6(H6A)
6.b Aromatic/amide H refined with riding coordinates:
 C13(H13), C14(H14), N3(H3), C22(H22), C21(H21), N14(H14A), C25(H25), C26(H26),
  C1(H1), C2(H2), C5(H5), C30(H30), N16(H16), C6(H6), N2(H2A), C29(H29),
 C17(H17), C18(H18), C9(H9), C10(H10A)
6.c Fitted pentagon refined as free rotating group:
 N8(C16,N7,C13,C14), N9(C22,C21,N10,C23), N14(C25,C26,N13,C27), C19(N12,C17,
 C18,N11), C9(C10,N6,C11,N5)
6.d Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C24(H24A,H24B,H24C), C15(H15A,H15B,H15C), C28(H28A,H28B,
 H28C), C8(H8A,H8B,H8C), C32(H32A,H32B,H32C), C20(H20A,H20B,H20C), C12(H12A,
 H12B,H12C)
6.e Boron cage BH refined with riding coordinates:
 B4(H4), B7(H7A), B3(H3A), B1(H1A), B12(H12), B6(H6B), B10(H10B), B5(H5A),
 B9(H9A), B11(H11A), B2(H2B), B8(H8)
;
_shelx_res_checksum              71817
_shelx_hkl_checksum              43298
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.232
_oxdiff_exptl_absorpt_empirical_full_min 0.714