Structural distortion by alkali metal cations modulates the redox and electronic properties of Ce<sup>3+</sup> imidophosphorane complexes.
Boggiano, Andrew C.; Studvick, Chad M.; Steiner, Alexander; Bacsa, John; Popov, Ivan A.; La Pierre, Henry S.; Chemical science 14 (2023) 11708–11717; doi:10.1039/d3sc04262f

data_1569948
_publ_section_title
;
 Structural distortion by alkali metal cations modulates the redox and
 electronic properties of Ce<sup>3+</sup> imidophosphorane complexes.
;
_journal_issue                   42
_journal_name_full               'Chemical science'
_journal_page_first              11708
_journal_page_last               11717
_journal_paper_doi               10.1039/d3sc04262f
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         '2(C56 H128 Ce Li N16 P4), C4 H10 O'
_chemical_formula_sum            'C116 H266 Ce2 Li2 N32 O P8'
_chemical_formula_weight         2667.47
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2023-03-08
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-03-13 deposited with the CCDC.	2023-09-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 115.73(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   28.658(6)
_cell_length_b                   22.627(5)
_cell_length_c                   25.312(5)
_cell_measurement_reflns_used    9839
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      25.35
_cell_measurement_theta_min      2.42
_cell_volume                     14786(7)
_computing_cell_refinement       'SAINT V8.40B (Bruker, 2016)'
_computing_data_collection       'APEX2  v2016.5-1 (Bruker, 2014)'
_computing_data_reduction        'SAINT V8.40B (Bruker, 2016)'
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2014 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 7.495
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker D8 VENTURE'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'multilayer mirror'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0772
_diffrn_reflns_av_unetI/netI     0.0415
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       34
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            249753
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.367
_diffrn_reflns_theta_min         1.844
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_current           1.4
_diffrn_source_voltage           50
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.748
_exptl_absorpt_correction_T_max  0.7453
_exptl_absorpt_correction_T_min  0.5826
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1161 before and 0.0964 after correction.
The Ratio of minimum to maximum transmission is 0.7817.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.198
_exptl_crystal_description       prism
_exptl_crystal_F_000             5744
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by as supplied'
_exptl_crystal_size_max          0.348
_exptl_crystal_size_mid          0.29
_exptl_crystal_size_min          0.224
_refine_diff_density_max         1.973
_refine_diff_density_min         -1.571
_refine_diff_density_rms         0.132
_refine_ls_extinction_coef       0.00051(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.146
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2160
_refine_ls_number_reflns         27060
_refine_ls_number_restraints     7411
_refine_ls_restrained_S_all      1.094
_refine_ls_R_factor_all          0.0931
_refine_ls_R_factor_gt           0.0858
_refine_ls_shift/su_max          0.008
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+165.3097P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1805
_refine_ls_wR_factor_ref         0.1847
_reflns_Friedel_coverage         0.000
_reflns_number_gt                24644
_reflns_number_total             27060
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc04262f2.cif
_cod_data_source_block           ag-jb
_cod_depositor_comments
'Adding full bibliography for 1569945--1569949.cif.'
_cod_original_cell_volume        14786(6)
_cod_database_code               1569948
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Shared sites
{N17, N17}
{N17, N17}
{N1, N1B}
3. Restrained distances
 C202-C201 = C204-C203
 1.528 with sigma of 0.002
 C24'-C23' = C24-C23
 1.525 with sigma of 0.002
 C2-C1
 1.525 with sigma of 0.002
 C12-C11 = C14-C13
 1.528 with sigma of 0.002
 C30D-C303
 1.528 with sigma of 0.002
 C94-C93 = C94'-C93 = C92-C91
 1.525 with sigma of 0.02
 C12_1-C11_1 = C127_7-C117_7 = C147_7-C137_7 = C127_8-C117_8 = C147_8-C137_8
 1.528 with sigma of 0.002
 C14_1-C13_1
 1.528 with sigma of 0.002
 C14_2-C13_2 = C12_2-C11_2 = C127_9-C117_9 = C147_9-C137_9
 1.525 with sigma of 0.03
 C27_3-C17_3 = C27_4-C17_4
 1.525 with sigma of 0.002
 P17_8-N47_8 \\sim P17_8-N57_8 \\sim P1_1-N3_1 \\sim P1_1-N2_1 \\sim P2-N22
\\sim P2-N21
 with sigma of 0.0002
 P2-N21 \\sim P2-N22
 with sigma of 0.002
 N20-N2 \\sim N30-N3 \\sim N67_9-N17_9 \\sim N4_2-N1_2
 with sigma of 0.0002
 N67_4-N47_4 \\sim N22-N20 \\sim N32-N30 \\sim N6-N4
 with sigma of 0.0002
 C27_7-C17_7 \\sim C27_8-C17_8 \\sim C54-C53 \\sim C2-C1 \\sim C27_4-C17_4
\\sim C34-C33 \\sim C2_1-
 C1_1 \\sim C24-C23
 with sigma of 0.002
 N30-N3 \\sim N67_4-N17_4
 with sigma of 0.0002
 N67_9-C117_9 \\sim N67_8-C117_8 \\sim N67_9-C137_9 \\sim N67_8-C137_8 \\sim
N50-C503 \\sim N50-
 C501 \\sim N30-C301 \\sim N30-C303 \\sim N67_3-C117_3 \\sim N67_4-C117_4
 with sigma of 0.002
 C322-C32 \\sim C323-C32 \\sim C321-C32 \\sim C67_9-C37_9 \\sim C47_9-C37_9
\\sim C67_3-C37_3 ~
 C47_3-C37_3 \\sim C57_3-C37_3
 with sigma of 0.002
 C522-C52 \\sim C521-C52 \\sim C523-C52 \\sim C512-C51 \\sim C511-C51 \\sim
C513-C51
 with sigma of 0.0002
 N67_7-N57_7 \\sim N67_8-N57_8 \\sim N6-N4
 with sigma of 0.0002
 N6-C11 \\sim N6-C13
 with sigma of 0.002
 C12-C11 \\sim C14-C13
 with sigma of 0.02
 C304-C303 \\sim C30D-C303
 with sigma of 0.002
 C30D-C303 \\sim C304-C303
 with sigma of 0.02
 O1-C93 \\sim O1-C91
 with sigma of 0.02
 P1_1-N1_1 \\sim P17_8-N17_8
 with sigma of 0.02
 N17_9-N1_2 \\sim N17_8-N1_1
 with sigma of 0.0002
 P17_8-N17_8 \\sim P1_1-N1_1
 with sigma of 0.0002
 N4_1-C13_1 \\sim N4_2-C13_2 \\sim N4_2-C11_2 \\sim N4_1-C11_1
 with sigma of 0.02
 P1_2-N1_2 \\sim P17_9-N17_9
 with sigma of 0.02
 P17_9-N17_9 \\sim P1_2-N1_2
 with sigma of 0.02
 C12_2-C11_2 \\sim C14_2-C13_2 \\sim C147_9-C137_9 \\sim C127_9-C117_9
 with sigma of 0.02
 P17_3-N57_3 \\sim P17_4-N57_4 \\sim P17_4-N47_4 \\sim P17_3-N47_3
 with sigma of 0.02
 C127_9-C117_9 \\sim C147_9-C137_9 \\sim C127_3-C117_3
 with sigma of 0.002
 P17_7-N17_7 \\sim P17_6-N17_6
 with sigma of 0.02
 C47_6-C37_6 \\sim C67_6-C37_6 \\sim C57_6-C37_6
 with sigma of 0.002
 P17_8-N17_8 \\sim P17_9-N17_9
 with sigma of 0.02
 P17_9-N47_9 \\sim P17_8-N47_8 \\sim P17_9-N57_9 \\sim P17_8-N57_8
 with sigma of 0.02
 P17_9-N67_9 \\sim P17_8-N67_8
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
Uanis(N21) \\sim Ueq, Uanis(N21') \\sim Ueq: with sigma of 0.002 and sigma for
terminal atoms of 0.004
Uanis(C211) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C1) \\sim Ueq, Uanis(C1B) \\sim Ueq, Uanis(N4B) \\sim Ueq, Uanis(N4)
\\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(N5B) \\sim Ueq, Uanis(N5) \\sim Ueq: with sigma of 0.002 and sigma for
terminal atoms of 0.004
Uanis(N6B) \\sim Ueq, Uanis(N6) \\sim Ueq: with sigma of 0.02 and sigma for
terminal atoms of 0.04
Uanis(C2) \\sim Ueq, Uanis(C2B) \\sim Ueq: with sigma of 0.002 and sigma for
terminal atoms of 0.004
Uanis(C8B) \\sim Ueq, Uanis(C8) \\sim Ueq: with sigma of 0.002 and sigma for
terminal atoms of 0.004
Uanis(C12) \\sim Ueq, Uanis(C12B) \\sim Ueq, Uanis(C9B) \\sim Ueq, Uanis(C9)
\\sim Ueq, Uanis(C11B) \\sim Ueq: with sigma of 0.002 and sigma for terminal
atoms of 0.004
Uanis(C10B) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(P17_4) \\sim Ueq, Uanis(P17_3) \\sim Ueq: with sigma of 0.02 and sigma
for terminal atoms of 0.04
Uanis(P17_3) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of
0.004
Uanis(N47_3) \\sim Ueq, Uanis(N47_4) \\sim Ueq: with sigma of 0.002 and sigma
for terminal atoms of 0.004
Uanis(N57_4) \\sim Ueq, Uanis(N57_3) \\sim Ueq: with sigma of 0.002 and sigma
for terminal atoms of 0.004
Uanis(C137_3) \\sim Ueq, Uanis(C137_4) \\sim Ueq, Uanis(N67_4) \\sim Ueq,
Uanis(N67_3) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of
0.004
Uanis(N67_3) \\sim Ueq, Uanis(N67_4) \\sim Ueq: with sigma of 0.02 and sigma
for terminal atoms of 0.04
Uanis(C17_3) \\sim Ueq, Uanis(C27_4) \\sim Ueq, Uanis(C27_3) \\sim Ueq: with
sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C17_4) \\sim Ueq, Uanis(C17_3) \\sim Ueq: with sigma of 0.002 and sigma
for terminal atoms of 0.004
Uanis(C27_3) \\sim Ueq, Uanis(C27_4) \\sim Ueq: with sigma of 0.002 and sigma
for terminal atoms of 0.004
Uanis(C37_4) \\sim Ueq, Uanis(C37_3) \\sim Ueq: with sigma of 0.002 and sigma
for terminal atoms of 0.004
Uanis(C127_3) \\sim Ueq, Uanis(C127_4) \\sim Ueq, Uanis(C117_4) \\sim Ueq,
Uanis(C117_3) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of
0.004
Uanis(C137_3) \\sim Ueq, Uanis(C137_4) \\sim Ueq: with sigma of 0.02 and sigma
for terminal atoms of 0.04
Uanis(P17_7) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of
0.004
Uanis(C147_7) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of
0.004
Uanis(N21) = Uanis(N22)
Uanis(C22') = Uanis(C22)
Uanis(C23') = Uanis(C23)
Uanis(C211) = Uanis(C21A)
Uanis(C21B) = Uanis(C212)
Uanis(C22A) = Uanis(C222)
Uanis(N1) = Uanis(N1B)
Uanis(P1B) = Uanis(P1)
Uanis(N4) = Uanis(N4B)
Uanis(N5) = Uanis(N5B)
Uanis(N6B) = Uanis(N6)
Uanis(C1) = Uanis(C1B)
Uanis(C2) = Uanis(C2B)
Uanis(C4) = Uanis(C4B)
Uanis(C5) = Uanis(C5B)
Uanis(C6) = Uanis(C6B)
Uanis(C8) = Uanis(C8B)
Uanis(C9) = Uanis(C9B)
Uanis(C10) = Uanis(C10B)
Uanis(C11) = Uanis(C11B)
Uanis(C12B) = Uanis(C12)
Uanis(C13B) = Uanis(C13)
Uanis(C14B) = Uanis(C14)
Uanis(C14) = Uanis(C14B)
Uanis(N17_8) = Uanis(N1_1)
Uanis(N1_2) = Uanis(N1_1)
Uanis(P1_2) = Uanis(P1_1)
Uanis(P1_1) = Uanis(P1_2)
Uanis(N2_1) = Uanis(N2_2)
Uanis(N3_1) = Uanis(N3_2)
Uanis(N4_2) = Uanis(N4_1)
Uanis(C5_1) = Uanis(C5_2)
Uanis(C6_2) = Uanis(C6_1)
Uanis(C7_1) = Uanis(C7_2)
Uanis(C11_2) = Uanis(C11_1)
Uanis(C13_1) = Uanis(C13_2)
Uanis(C14_1) = Uanis(C14_2)
Uanis(N17_9) = Uanis(N1_2)
Uanis(N17_3) = Uanis(N17_4)
Uanis(N47_4) = Uanis(N47_3)
Uanis(N57_3) = Uanis(N57_4)
Uanis(N67_4) = Uanis(N67_3)
Uanis(C17_3) = Uanis(C17_4)
Uanis(C107_4) = Uanis(C107_3)
Uanis(C147_3) = Uanis(C147_4)
Uanis(N17_6) = Uanis(N17_7)
Uanis(P17_6) = Uanis(P17_7)
Uanis(N57_6) = Uanis(N57_7)
Uanis(C27_6) = Uanis(C27_7)
Uanis(C47_7) = Uanis(C47_6)
Uanis(C77_6) = Uanis(C77_7)
Uanis(C87_6) = Uanis(C87_7)
Uanis(C97_7) = Uanis(C97_6)
Uanis(C117_6) = Uanis(C117_7)
Uanis(C127_6) = Uanis(C127_7)
Uanis(N17_8) = Uanis(N17_9)
Uanis(P17_8) = Uanis(P17_9)
Uanis(N47_9) = Uanis(N47_8)
Uanis(N47_8) = Uanis(N47_9)
Uanis(N57_8) = Uanis(N57_9)
Uanis(N67_9) = Uanis(N67_8)
Uanis(C47_9) = Uanis(C57_8)
Uanis(C67_8) = Uanis(C67_9)
Uanis(C97_8) = Uanis(C97_9)
Uanis(C117_8) = Uanis(C117_9)
Uanis(C127_8) = Uanis(C127_9)
Uanis(C147_9) = Uanis(C147_8)
5. Rigid body (RIGU) restrains
 P2, N20, C201, C202, C203, C204, N21, N22, C21, C23, C24, C211, C212, C213,
 N21', N22', C21', C21A, C21B, C21C, C23', C24', C22, C221, C222, C223, C22',
 C22A, C22B, C22C, N2
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
 P2, N2, N20, C201, C202, C203, C204, N21, N22, C21, C22, C23, C24, C211, C212,
  C213, C221, C222, C223
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
 P2, N2, N20, C201, C202, C203, C204, N21, N22, C21, C22, C23, C24, C211, C212,
  C213, C221, C222, C223, N21', N22', C21', C21A, C21B, C21C, C22', C22A, C22B,
 C22C, C23', C24'
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
 N1, P1, N4, N5, N6, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
 C93, C94
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0004
 C93, C94'
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0004
 N1_1, C9_2, C1_2, C12_1, P1_2, C8_1, C5_2, P1_1, C13_2, C6_1, N3_2, N2_1,
 C3_2, C10_1, C7_2, N3_1, C11_2, C14_1, N1_2, N4_1, N2_2, C7_1, N4_2, C1_1,
 C2_2, C9_1, C4_2, C2_1, C6_2, C11_1, C8_2, C3_1, C10_2, C13_1, C12_2, C4_1,
 C14_2, C5_1
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0004
 N1_1, P1_1, N2_1, N3_1, N4_1, C1_1, C7_1, C2_1, C3_1, C11_1, C13_1, C8_1,
 C9_1, C10_1, C4_1, C5_1, C6_1, C12_1, C14_1, N1_2, P1_2, N2_2, N3_2, N4_2,
 C1_2, C7_2, C2_2, C3_2, C11_2, C13_2, C8_2, C9_2, C10_2, C4_2, C5_2, C6_2,
 C12_2, C14_2
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0004
 P17_3, N47_3, N57_3, N67_3, C17_3, C27_3, C37_3, C47_3, C57_3, C67_3, C77_3,
 C87_3, C97_3, C107_3, C117_3, C127_3, C137_3, C147_3, P17_4, N47_4, N57_4,
 N67_4, C17_4, C27_4, C37_4, C47_4, C57_4, C67_4, C77_4, C87_4, C97_4, C107_4,
 C117_4, C127_4, C137_4, C147_4, N17_3, N17_4
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
 N17_4, C127_4, C87_4, P17_4, C67_4, N47_4, C107_4, N57_4, C147_4, N67_4,
 C77_4, C17_4, C97_4, C27_4, C117_4, C37_4, C137_4, C47_4, C57_4
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
 P17_4, N47_4, N57_4, N67_4, C17_4, C27_4, C37_4, C47_4, C57_4, C67_4, C77_4,
 C87_4, C97_4, C107_4, C117_4, C127_4, C137_4, C147_4, N17_4
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
 N17_6, C127_6, C87_6, P17_6, C67_6, N47_6, C107_6, N57_6, C147_6, N67_6,
 C77_6, C17_6, C97_6, C27_6, C117_6, C37_6, C137_6, C47_6, C57_6
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0004
 N17_7, C127_7, C87_7, P17_7, C67_7, N47_7, C107_7, N57_7, C147_7, N67_7,
 C77_7, C17_7, C97_7, C27_7, C117_7, C37_7, C137_7, C47_7, C57_7
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0004
 N17_7, H97C_7, C77_7, P17_7, C147_7, N47_7, H87C_7, N57_7, H10C_7, N67_7,
 H67B_7, C17_7, H87A_7, H17A_7, H97A_7, H17B_7, H10A_7, C27_7, C127_7, H27A_7,
 H67A_7, H27B_7, H67C_7, C37_7, C87_7, C47_7, H87B_7, H47A_7, C97_7, H47B_7,
 H97B_7, H47C_7, C107_7, C57_7, H10B_7, H57A_7, C117_7, H57B_7, C137_7, H57C_7,
 C67_7
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0004
 N17_8, C127_8, C87_8, P17_8, C67_8, N47_8, C107_8, N57_8, C147_8, N67_8,
 C77_8, C17_8, C97_8, C27_8, C117_8, C37_8, C137_8, C47_8, C57_8
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0004
 N17_9, C127_9, C87_9, P17_9, C67_9, N47_9, C107_9, N57_9, C147_9, N67_9,
 C77_9, C17_9, C97_9, C27_9, C117_9, C37_9, C137_9, C47_9, C57_9
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0004
6. Same fragment restrains
{P1, N4, N5, N6, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14}
sigma for 1-2: 0.02, 1-3: 0.02
as in
{P1B, N4B, N5B, N6B, C1B, C2B, C3B, C4B, C5B, C6B, C7B, C8B, C9B, C10B, C11B,
C12B, C13B, C14B}
{N1, P1, N4, N5, N6, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13,
C14} sigma for 1-2: 0.02, 1-3: 0.02
as in
{N1_1, P1_1, N2_1, N3_1, N4_1, C1_1, C2_1, C3_1, C4_1, C5_1, C6_1, C7_1, C8_1,
C9_1, C10_1, C11_1, C12_1, C13_1, C14_1}
{N1, P1, N4, N5, N6, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13,
C14} sigma for 1-2: 0.02, 1-3: 0.02
as in
{N17_9, P17_9, N47_9, N57_9, N67_9, C17_9, C27_9, C37_9, C47_9, C57_9, C67_9,
C77_9, C87_9, C97_9, C107_9, C117_9, C127_9, C137_9, C147_9}
{O1, C93, C94'} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O1, C91, C92}
{P1, N4, N5, N6, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14}
sigma for 1-2: 0.002, 1-3: 0.002
as in
{P17_4, N47_4, N57_4, N67_4, C17_4, C27_4, C37_4, C47_4, C57_4, C67_4, C77_4,
C87_4, C97_4, C107_4, C117_4, C127_4, C137_4, C147_4}
{N1, P1, N4, N5, N6, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13,
C14} sigma for 1-2: 0.02, 1-3: 0.02
as in
{N1_2, P1_2, N2_2, N3_2, N4_2, C1_2, C2_2, C3_2, C4_2, C5_2, C6_2, C7_2, C8_2,
C9_2, C10_2, C11_2, C12_2, C13_2, C14_2}
{P1, N4, N5, N6, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14}
sigma for 1-2: 0.02, 1-3: 0.02
as in
{P17_7, N47_7, N57_7, N67_7, C17_7, C27_7, C37_7, C47_7, C57_7, C67_7, C77_7,
C87_7, C97_7, C107_7, C117_7, C127_7, C137_7, C147_7}
{P1, N4, N5, N6, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14}
sigma for 1-2: 0.02, 1-3: 0.02
as in
{P17_8, N47_8, N57_8, N67_8, C17_8, C27_8, C37_8, C47_8, C57_8, C67_8, C77_8,
C87_8, C97_8, C107_8, C117_8, C127_8, C137_8, C147_8}
{P1, N4, N5, N6, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14}
sigma for 1-2: 0.02, 1-3: 0.02
as in
{P17_3, N47_3, N57_3, N67_3, C17_3, C27_3, C37_3, C47_3, C57_3, C67_3, C77_3,
C87_3, C97_3, C107_3, C117_3, C127_3, C137_3, C147_3}
{P1, N4, N5, N6, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14}
sigma for 1-2: 0.02, 1-3: 0.02
as in
{P17_6, N47_6, N57_6, N67_6, C17_6, C27_6, C37_6, C47_6, C57_6, C67_6, C77_6,
C87_6, C97_6, C107_6, C117_6, C127_6, C137_6, C147_6}
7. Others
 Sof(N1)=Sof(P1)=Sof(N2)=Sof(N3)=Sof(N4)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(C2)=
 Sof(H2A)=Sof(H2B)=Sof(C3)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=Sof(C5)=Sof(H5A)=
 Sof(H5B)=Sof(H5C)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=Sof(C7)=Sof(C8)=Sof(H8A)=
 Sof(H8B)=Sof(H8C)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=Sof(C10)=Sof(H10A)=
 Sof(H10B)=Sof(H10C)=Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(C12)=Sof(H12A)=Sof(H12B)=
 Sof(H12C)=Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=
 Sof(N17)=Sof(P17)=Sof(N47)=Sof(N57)=Sof(N67)=Sof(C17)=Sof(H17A)=Sof(H17B)=
 Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(C37)=Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(H47C)=
 Sof(C57)=Sof(H57A)=Sof(H57B)=Sof(H57C)=Sof(C67)=Sof(H67A)=Sof(H67B)=Sof(H67C)=
 Sof(C77)=Sof(C87)=Sof(H87A)=Sof(H87B)=Sof(H87C)=Sof(C97)=Sof(H97A)=Sof(H97B)=
 Sof(H97C)=Sof(C107)=Sof(H10A)=Sof(H10B)=Sof(H10C)=Sof(C117)=Sof(H11A)=
 Sof(H11B)=Sof(C127)=Sof(H12A)=Sof(H12B)=Sof(H12C)=Sof(C137)=Sof(H13A)=
 Sof(H13B)=Sof(C147)=Sof(H14A)=Sof(H14B)=Sof(H14C)=Sof(N17)=Sof(P17)=Sof(N47)=
 Sof(N57)=Sof(N67)=Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(C27)=Sof(H27A)=Sof(H27B)=
 Sof(C37)=Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(H47C)=Sof(C57)=Sof(H57A)=Sof(H57B)=
 Sof(H57C)=Sof(C67)=Sof(H67A)=Sof(H67B)=Sof(H67C)=Sof(C77)=Sof(C87)=Sof(H87A)=
 Sof(H87B)=Sof(H87C)=Sof(C97)=Sof(H97A)=Sof(H97B)=Sof(H97C)=Sof(C107)=Sof(H10A)=
 Sof(H10B)=Sof(H10C)=Sof(C117)=Sof(H11A)=Sof(H11B)=Sof(C127)=Sof(H12A)=
 Sof(H12B)=Sof(H12C)=Sof(C137)=Sof(H13A)=Sof(H13B)=Sof(C147)=Sof(H14A)=
 Sof(H14B)=Sof(H14C)=1-FVAR(1)
 Sof(N1)=Sof(P1)=Sof(N2)=Sof(N3)=Sof(N4)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(C2)=
 Sof(H2A)=Sof(H2B)=Sof(C3)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=Sof(C5)=Sof(H5A)=
 Sof(H5B)=Sof(H5C)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=Sof(C7)=Sof(C8)=Sof(H8A)=
 Sof(H8B)=Sof(H8C)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=Sof(C10)=Sof(H10A)=
 Sof(H10B)=Sof(H10C)=Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(C12)=Sof(H12A)=Sof(H12B)=
 Sof(H12C)=Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=
 Sof(N17)=Sof(P17)=Sof(N47)=Sof(N57)=Sof(N67)=Sof(C17)=Sof(H17A)=Sof(H17B)=
 Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(C37)=Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(H47C)=
 Sof(C57)=Sof(H57A)=Sof(H57B)=Sof(H57C)=Sof(C67)=Sof(H67A)=Sof(H67B)=Sof(H67C)=
 Sof(C77)=Sof(C87)=Sof(H87A)=Sof(H87B)=Sof(H87C)=Sof(C97)=Sof(H97A)=Sof(H97B)=
 Sof(H97C)=Sof(C107)=Sof(H10A)=Sof(H10B)=Sof(H10C)=Sof(C117)=Sof(H11A)=
 Sof(H11B)=Sof(C127)=Sof(H12A)=Sof(H12B)=Sof(H12C)=Sof(C137)=Sof(H13A)=
 Sof(H13B)=Sof(C147)=Sof(H14A)=Sof(H14B)=Sof(H14C)=Sof(N17)=Sof(P17)=Sof(N47)=
 Sof(N57)=Sof(N67)=Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(C27)=Sof(H27A)=Sof(H27B)=
 Sof(C37)=Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(H47C)=Sof(C57)=Sof(H57A)=Sof(H57B)=
 Sof(H57C)=Sof(C67)=Sof(H67A)=Sof(H67B)=Sof(H67C)=Sof(C77)=Sof(C87)=Sof(H87A)=
 Sof(H87B)=Sof(H87C)=Sof(C97)=Sof(H97A)=Sof(H97B)=Sof(H97C)=Sof(C107)=Sof(H10A)=
 Sof(H10B)=Sof(H10C)=Sof(C117)=Sof(H11A)=Sof(H11B)=Sof(C127)=Sof(H12A)=
 Sof(H12B)=Sof(H12C)=Sof(C137)=Sof(H13A)=Sof(H13B)=Sof(C147)=Sof(H14A)=
 Sof(H14B)=Sof(H14C)=FVAR(1)
 Fixed Sof: N21(0.5) N22(0.5) C21(0.5) C22(0.5) C23(0.5) H23A(0.5) H23B(0.5)
 C24(0.5) H24A(0.5) H24B(0.5) C211(0.5) H21A(0.5) H21B(0.5) H21C(0.5) C212(0.5)
 H21D(0.5) H21E(0.5) H21F(0.5) C213(0.5) H21G(0.5) H21H(0.5) H21I(0.5)
 C221(0.5) H22A(0.5) H22B(0.5) H22C(0.5) C222(0.5) H22D(0.5) H22E(0.5)
 H22F(0.5) C223(0.5) H22G(0.5) H22H(0.5) H22I(0.5) N21'(0.5) N22'(0.5)
 C21'(0.5) C21A(0.5) H21J(0.5) H21K(0.5) H21L(0.5) C21B(0.5) H21M(0.5)
 H21N(0.5) H21O(0.5) C21C(0.5) H21P(0.5) H21Q(0.5) H21R(0.5) C22'(0.5)
 C22A(0.5) H22J(0.5) H22K(0.5) H22L(0.5) C22B(0.5) H22M(0.5) H22N(0.5)
 H22O(0.5) C22C(0.5) H22P(0.5) H22Q(0.5) H22R(0.5) C23'(0.5) H23C(0.5)
 H23D(0.5) C24'(0.5) H24C(0.5) H24D(0.5) N1(0.5) P1(0.5) N4(0.5) N5(0.5)
 N6(0.5) C1(0.5) H1A(0.5) H1B(0.5) C2(0.5) H2A(0.5) H2B(0.5) C3(0.5) C4(0.5)
 H4A(0.5) H4B(0.5) H4C(0.5) C5(0.5) H5A(0.5) H5B(0.5) H5C(0.5) C6(0.5) H6A(0.5)
 H6B(0.5) H6C(0.5) C7(0.5) C8(0.5) H8A(0.5) H8B(0.5) H8C(0.5) C9(0.5) H9A(0.5)
 H9B(0.5) H9C(0.5) C10(0.5) H10A(0.5) H10B(0.5) H10C(0.5) C11(0.5) H11A(0.5)
 H11B(0.5) C12(0.5) H12A(0.5) H12B(0.5) H12C(0.5) C13(0.5) H13A(0.5) H13B(0.5)
 C14(0.5) H14A(0.5) H14B(0.5) H14C(0.5) N1B(0.5) P1B(0.5) N4B(0.5) N5B(0.5)
 N6B(0.5) C1B(0.5) H1BA(0.5) H1BB(0.5) C2B(0.5) H2BA(0.5) H2BB(0.5) C3B(0.5)
 C4B(0.5) H4BA(0.5) H4BB(0.5) H4BC(0.5) C5B(0.5) H5BA(0.5) H5BB(0.5) H5BC(0.5)
 C6B(0.5) H6BA(0.5) H6BB(0.5) H6BC(0.5) C7B(0.5) C8B(0.5) H8BA(0.5) H8BB(0.5)
 H8BC(0.5) C9B(0.5) H9BA(0.5) H9BB(0.5) H9BC(0.5) C10B(0.5) H10D(0.5) H10E(0.5)
 H10F(0.5) C11B(0.5) H11C(0.5) H11D(0.5) C12B(0.5) H12D(0.5) H12E(0.5)
 H12F(0.5) C13B(0.5) H13C(0.5) H13D(0.5) C14B(0.5) H14D(0.5) H14E(0.5)
 H14F(0.5) H30H(0.5) H30I(0.5) H30F(0.5) H30G(0.5) C304(0.5) H30J(0.5)
 H30K(0.5) H30L(0.5) C30D(0.5) H30M(0.5) H30N(0.5) H30O(0.5) H93C(0.5)
 H93D(0.5) H93A(0.5) H93B(0.5) C94'(0.5) H94A(0.5) H94B(0.5) H94C(0.5) C94(0.5)
 H94D(0.5) H94E(0.5) H94F(0.5) N17(0.5) P17(0.5) N47(0.5) N57(0.5) N67(0.5)
 C17(0.5) H17A(0.5) H17B(0.5) C27(0.5) H27A(0.5) H27B(0.5) C37(0.5) C47(0.5)
 H47A(0.5) H47B(0.5) H47C(0.5) C57(0.5) H57A(0.5) H57B(0.5) H57C(0.5) C67(0.5)
 H67A(0.5) H67B(0.5) H67C(0.5) C77(0.5) C87(0.5) H87A(0.5) H87B(0.5) H87C(0.5)
 C97(0.5) H97A(0.5) H97B(0.5) H97C(0.5) C107(0.5) H10A(0.5) H10B(0.5) H10C(0.5)
 C117(0.5) H11A(0.5) H11B(0.5) C127(0.5) H12A(0.5) H12B(0.5) H12C(0.5)
 C137(0.5) H13A(0.5) H13B(0.5) C147(0.5) H14A(0.5) H14B(0.5) H14C(0.5) N17(0.5)
 P17(0.5) N47(0.5) N57(0.5) N67(0.5) C17(0.5) H17A(0.5) H17B(0.5) C27(0.5)
 H27A(0.5) H27B(0.5) C37(0.5) C47(0.5) H47A(0.5) H47B(0.5) H47C(0.5) C57(0.5)
 H57A(0.5) H57B(0.5) H57C(0.5) C67(0.5) H67A(0.5) H67B(0.5) H67C(0.5) C77(0.5)
 C87(0.5) H87A(0.5) H87B(0.5) H87C(0.5) C97(0.5) H97A(0.5) H97B(0.5) H97C(0.5)
 C107(0.5) H10A(0.5) H10B(0.5) H10C(0.5) C117(0.5) H11A(0.5) H11B(0.5)
 C127(0.5) H12A(0.5) H12B(0.5) H12C(0.5) C137(0.5) H13A(0.5) H13B(0.5)
 C147(0.5) H14A(0.5) H14B(0.5) H14C(0.5)
8.a Secondary CH2 refined with riding coordinates:
 C201(H20A,H20B), C203(H20F,H20G), C23(H23A,H23B), C24(H24A,H24B), C23'(H23C,
 H23D), C24'(H24C,H24D), C301(H30A,H30B), C33(H33A,H33B), C34(H34A,H34B),
 C53(H53A,H53B), C54(H54A,H54B), C501(H50A,H50B), C503(H50F,H50G), C1(H1A,H1B),
 C2(H2A,H2B), C11(H11A,H11B), C13(H13A,H13B), C1B(H1BA,H1BB), C2B(H2BA,H2BB),
 C11B(H11C,H11D), C13B(H13C,H13D), C303(H30H,H30I), C303(H30F,H30G), C91(H91A,
 H91B), C93(H93C,H93D), C93(H93A,H93B), C1(H1A,H1B), C2(H2A,H2B), C11(H11A,
 H11B), C13(H13A,H13B), C1(H1A,H1B), C2(H2A,H2B), C11(H11A,H11B), C13(H13A,
 H13B), C17(H17A,H17B), C27(H27A,H27B), C117(H11A,H11B), C137(H13A,H13B),
 C17(H17A,H17B), C27(H27A,H27B), C117(H11A,H11B), C137(H13A,H13B), C17(H17A,
 H17B), C27(H27A,H27B), C117(H11A,H11B), C137(H13A,H13B), C17(H17A,H17B),
 C27(H27A,H27B), C117(H11A,H11B), C137(H13A,H13B), C17(H17A,H17B), C27(H27A,
 H27B), C117(H11A,H11B), C137(H13A,H13B), C17(H17A,H17B), C27(H27A,H27B),
 C117(H11A,H11B), C137(H13A,H13B)
8.b Idealised Me refined as rotating group:
 C202(H20C,H20D,H20E), C204(H20H,H20I,H20J), C211(H21A,H21B,H21C), C212(H21D,
 H21E,H21F), C213(H21G,H21H,H21I), C221(H22A,H22B,H22C), C222(H22D,H22E,H22F),
 C223(H22G,H22H,H22I), C21A(H21J,H21K,H21L), C21B(H21M,H21N,H21O), C21C(H21P,
 H21Q,H21R), C22A(H22J,H22K,H22L), C22B(H22M,H22N,H22O), C22C(H22P,H22Q,H22R),
 C302(H30C,H30D,H30E), C311(H31A,H31B,H31C), C312(H31D,H31E,H31F), C313(H31G,
 H31H,H31I), C321(H32A,H32B,H32C), C322(H32D,H32E,H32F), C323(H32G,H32H,H32I),
 C502(H50C,H50D,H50E), C504(H50H,H50I,H50J), C511(H51A,H51B,H51C), C512(H51D,
 H51E,H51F), C513(H51G,H51H,H51I), C521(H52A,H52B,H52C), C522(H52D,H52E,H52F),
 C523(H52G,H52H,H52I), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C),
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C12(H12A,H12B,H12C),
 C14(H14A,H14B,H14C), C4B(H4BA,H4BB,H4BC), C5B(H5BA,H5BB,H5BC), C6B(H6BA,H6BB,
 H6BC), C8B(H8BA,H8BB,H8BC), C9B(H9BA,H9BB,H9BC), C10B(H10D,H10E,H10F),
 C12B(H12D,H12E,H12F), C14B(H14D,H14E,H14F), C304(H30J,H30K,H30L), C30D(H30M,
 H30N,H30O), C92(H92A,H92B,H92C), C94'(H94A,H94B,H94C), C94(H94D,H94E,H94F),
 C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C8(H8A,H8B,H8C), C9(H9A,H9B,
 H9C), C10(H10A,H10B,H10C), C12(H12A,H12B,H12C), C14(H14A,H14B,H14C), C4(H4A,
 H4B,H4C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C),
 C10(H10A,H10B,H10C), C12(H12A,H12B,H12C), C14(H14A,H14B,H14C), C47(H47A,H47B,
 H47C), C57(H57A,H57B,H57C), C67(H67A,H67B,H67C), C87(H87A,H87B,H87C), C97(H97A,
 H97B,H97C), C107(H10A,H10B,H10C), C127(H12A,H12B,H12C), C147(H14A,H14B,H14C),
 C47(H47A,H47B,H47C), C57(H57A,H57B,H57C), C67(H67A,H67B,H67C), C87(H87A,H87B,
 H87C), C97(H97A,H97B,H97C), C107(H10A,H10B,H10C), C127(H12A,H12B,H12C),
 C147(H14A,H14B,H14C), C47(H47A,H47B,H47C), C57(H57A,H57B,H57C), C67(H67A,H67B,
 H67C), C87(H87A,H87B,H87C), C97(H97A,H97B,H97C), C107(H10A,H10B,H10C),
 C127(H12A,H12B,H12C), C147(H14A,H14B,H14C), C47(H47A,H47B,H47C), C57(H57A,H57B,
 H57C), C67(H67A,H67B,H67C), C87(H87A,H87B,H87C), C97(H97A,H97B,H97C),
 C107(H10A,H10B,H10C), C127(H12A,H12B,H12C), C147(H14A,H14B,H14C), C47(H47A,
 H47B,H47C), C57(H57A,H57B,H57C), C67(H67A,H67B,H67C), C87(H87A,H87B,H87C),
 C97(H97A,H97B,H97C), C107(H10A,H10B,H10C), C127(H12A,H12B,H12C), C147(H14A,
 H14B,H14C), C47(H47A,H47B,H47C), C57(H57A,H57B,H57C), C67(H67A,H67B,H67C),
 C87(H87A,H87B,H87C), C97(H97A,H97B,H97C), C107(H10A,H10B,H10C), C127(H12A,H12B,
 H12C), C147(H14A,H14B,H14C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              55013
_shelx_fab_checksum              32131
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a loop with paratone'
_olex2_submission_special_instructions 'No special instructions were received'