Synthesis and characterization of <sup>15</sup>N-labeled tetranuclear Ir complexes <i>via</i> Li<sub>2</sub>C<sup>15</sup>N<sub>2</sub>.
Yan, Xuechao; Ji, Shu-Xiao; Zhang, Shengyuan; Wang, Qianru; Guo, Jianping; Chen, Ping; Xi, Zhenfeng; Wei, Junnian; Dalton transactions (Cambridge, England : 2003) 54 (2025) 6246–6251; doi:10.1039/d5dt00644a

data_7718377
_publ_section_title
;
 Synthesis and characterization of <sup>15</sup>N-labeled tetranuclear Ir
 complexes <i>via</i> Li<sub>2</sub>C<sup>15</sup>N<sub>2</sub>.
;
_journal_issue                   15
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              6246
_journal_page_last               6251
_journal_paper_doi               10.1039/d5dt00644a
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety         '2(C45 H63 Ir4 N8), 2(C F3 O3 S), 1.5(C7 H8)'
_chemical_formula_sum            'C102.5 H138 F6 Ir8 N16 O6 S2'
_chemical_formula_weight         3406.00
_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   geom
_audit_creation_date             2024-12-21
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2024-12-21 deposited with the CCDC.	2025-03-18 downloaded from the CCDC.
;
_cell_angle_alpha                68.321(3)
_cell_angle_beta                 85.575(2)
_cell_angle_gamma                75.402(3)
_cell_formula_units_Z            2
_cell_length_a                   13.2902(4)
_cell_length_b                   20.7356(6)
_cell_length_c                   22.0373(6)
_cell_measurement_reflns_used    34932
_cell_measurement_temperature    179.99(10)
_cell_measurement_theta_max      30.1740
_cell_measurement_theta_min      2.1540
_cell_volume                     5460.4(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.33c (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.33c (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.33c (Rigaku OD, 2017)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      179.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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    -43.00 -17.00   0.50    3.18    --   -5.70 -38.00  60.00   52
  2  \w    -89.00 -64.00   0.50    3.18    --   -5.70 -38.00  60.00   50
  3  \w     32.00  91.00   0.50    3.18    --    6.00  38.00  30.00  118
  4  \w    -28.00  68.00   0.50    3.18    --    6.00  77.00 -90.00  192
  5  \w     38.00  87.00   0.50    3.18    --    6.00  38.00-180.00   98
  6  \w     -1.00  25.00   0.50    3.18    --    6.00  38.00   0.00   52
  7  \w      3.00  29.00   0.50    3.18    --    6.00  38.00 -30.00   52
  8  \w     29.00  55.00   0.50    3.18    --    6.00  38.00   0.00   52
  9  \w     63.00  93.00   0.50    3.18    --    6.00  38.00 -30.00   60
 10  \w    -82.00  -5.00   0.50    3.18    --    6.00 -77.00 -30.00  154
 11  \w    -26.00  88.00   0.50    3.18    --    6.00  77.00  60.00  228
 12  \w    -12.00  25.00   0.50    3.18    --    6.00  38.00 -60.00   74
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0451485000
_diffrn_orient_matrix_UB_12      -0.0240110000
_diffrn_orient_matrix_UB_13      -0.0052975000
_diffrn_orient_matrix_UB_21      0.0315928000
_diffrn_orient_matrix_UB_22      0.0200054000
_diffrn_orient_matrix_UB_23      0.0060260000
_diffrn_orient_matrix_UB_31      0.0024533000
_diffrn_orient_matrix_UB_32      -0.0214947000
_diffrn_orient_matrix_UB_33      0.0336999000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0514
_diffrn_reflns_av_unetI/netI     0.0452
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            103623
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.482
_diffrn_reflns_theta_min         2.128
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    9.814
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.28260
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.33c (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    2.072
_exptl_crystal_description       plate
_exptl_crystal_F_000             3230
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         2.701
_refine_diff_density_min         -2.319
_refine_diff_density_rms         0.205
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1402
_refine_ls_number_reflns         24978
_refine_ls_number_restraints     1185
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.0507
_refine_ls_R_factor_gt           0.0339
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0424P)^2^+11.5055P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0781
_refine_ls_wR_factor_ref         0.0837
_reflns_Friedel_coverage         0.000
_reflns_number_gt                19886
_reflns_number_total             24978
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt00644a2.cif
_cod_data_source_block           exp_14843
_cod_depositor_comments
'Adding full bibliography for 7718376--7718378.cif.'
_cod_original_formula_sum        'C102.50 H138 F6 Ir8 N16 O6 S2'
_cod_database_code               7718377
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N O Ir Cl S F'
_shelx_estimated_absorpt_t_max   0.440
_shelx_estimated_absorpt_t_min   0.244
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C92-F5 = C92-F6 = C92-F4
 1.33 with sigma of 0.02
 C92-S6
 1.82 with sigma of 0.02
 S6-O7 = S6-O8 = S6-O9
 1.44 with sigma of 0.02
 C100-S2
 1.82 with sigma of 0.02
 S2-O6 = S2-O4 = S2-O5
 1.44 with sigma of 0.02
 C100-F7 = C100-F8 = C100-F9
 1.33 with sigma of 0.02
 C107-C101
 1.51 with sigma of 0.02
 C92-O7
 2.58 with sigma of 0.04
 C100-O4
 2.56 with sigma of 0.04
 C92-O9
 2.57 with sigma of 0.04
 C92-O8
 2.56 with sigma of 0.04
 C100-O6
 2.58 with sigma of 0.04
 C100-O5
 2.57 with sigma of 0.04
 S2-O6 \\sim S2-O4 \\sim S2-O5
 with sigma of 0.02
 C100-O6 \\sim C100-O4 \\sim C100-O5
 with sigma of 0.04
 C92-F5 \\sim C92-F6 \\sim C92-F4
 with sigma of 0.02
 F5-F6 \\sim F6-F4 \\sim F4-F5
 with sigma of 0.04
 O6-O4 \\sim O4-O5 \\sim O6-O5
 with sigma of 0.04
 S6-F5 \\sim S6-F6 \\sim S6-F4
 with sigma of 0.04
 S6-O7 \\sim S6-O8 \\sim S6-O9
 with sigma of 0.02
 O7-O8 \\sim O8-O9 \\sim O7-O9
 with sigma of 0.04
 C92-O7 \\sim C92-O8 \\sim C92-O9
 with sigma of 0.04
 C100-F7 \\sim C100-F8 \\sim C100-F9
 with sigma of 0.02
 F7-F8 \\sim F8-F9 \\sim F9-F7
 with sigma of 0.04
 S2-F7 \\sim S2-F8 \\sim S2-F9
 with sigma of 0.04
 C102-C107 \\sim C107-C106
 with sigma of 0.01
3. Restrained planarity
 C107, C101, C102, C106
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
S1 \\sim F1 \\sim F2 \\sim F3 \\sim O1 \\sim O2 \\sim O3 \\sim C91: within 3A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 3A
S2 \\sim F7 \\sim F8 \\sim F9 \\sim O4 \\sim O5 \\sim O6 \\sim C100: within 2A
with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
S6 \\sim F4 \\sim F5 \\sim F6 \\sim O7 \\sim O8 \\sim O9 \\sim C92: within 2A
with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
S2 \\sim S6 \\sim F4 \\sim F5 \\sim F6 \\sim F7 \\sim F8 \\sim F9 \\sim O4
\\sim O5 \\sim O6 \\sim O7 \\sim O8 \\sim O9 \\sim C92 \\sim C100: within 3A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 3A
C101 \\sim C106 \\sim C105 \\sim C104 \\sim C103 \\sim C102 \\sim C107: within
3A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 3A
S1 \\sim S2 \\sim S6: within 3A with sigma of 0.01 and sigma for terminal atoms
of 0.02 within 3A
Uanis(C99) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C50) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C107) \\sim Ueq, Uanis(C101) \\sim Ueq, Uanis(C102) \\sim Ueq,
Uanis(C103) \\sim Ueq, Uanis(C104) \\sim Ueq, Uanis(C105) \\sim Ueq,
Uanis(C106) \\sim Ueq, Uanis(O1) \\sim Ueq, Uanis(O2) \\sim Ueq, Uanis(S1)
\\sim Ueq, Uanis(O3) \\sim Ueq, Uanis(F2) \\sim Ueq, Uanis(C91) \\sim Ueq,
Uanis(F1) \\sim Ueq, Uanis(F3) \\sim Ueq, Uanis(C99) \\sim Ueq, Uanis(C93)
\\sim Ueq, Uanis(C98) \\sim Ueq, Uanis(C97) \\sim Ueq, Uanis(C96) \\sim Ueq,
Uanis(C95) \\sim Ueq, Uanis(C94) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 S2, F7, F8, F9, O4, O5, O6, C100
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S6, F4, F5, F6, O7, O8, O9, C92
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(S2)=Sof(F7)=Sof(F8)=Sof(F9)=Sof(O4)=Sof(O5)=Sof(O6)=Sof(C100)=1-FVAR(1)
 Sof(S6)=Sof(F4)=Sof(F5)=Sof(F6)=Sof(O7)=Sof(O8)=Sof(O9)=Sof(C92)=FVAR(1)
 Fixed Sof: C101(0.5) C106(0.5) H106(0.5) C105(0.5) H105(0.5) C104(0.5)
 H104(0.5) C103(0.5) H103(0.5) C102(0.5) H102(0.5) C107(0.5) H10A(0.5)
 H10B(0.5) H10C(0.5)
7.a Aromatic/amide H refined with riding coordinates:
 C94(H94), C95(H95), C96(H96), C97(H97), C98(H98), C106(H106), C105(H105),
 C104(H104), C103(H103), C102(H102)
7.b Fitted hexagon refined as free rotating group:
 C101(C106,C105,C104,C103,C102)
7.c Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C13(H13A,H13B,
 H13C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C21(H21A,H21B,H21C), C22(H22A,
 H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C),
 C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C34(H34A,H34B,
 H34C), C35(H35A,H35B,H35C), C41(H41A,H41B,H41C), C42(H42A,H42B,H42C), C43(H43A,
 H43B,H43C), C44(H44A,H44B,H44C), C45(H45A,H45B,H45C), C50(H50A,H50B,H50C),
 C56(H56A,H56B,H56C), C57(H57A,H57B,H57C), C58(H58A,H58B,H58C), C59(H59A,H59B,
 H59C), C60(H60A,H60B,H60C), C66(H66A,H66B,H66C), C67(H67A,H67B,H67C), C68(H68A,
 H68B,H68C), C69(H69A,H69B,H69C), C70(H70A,H70B,H70C), C76(H76A,H76B,H76C),
 C77(H77A,H77B,H77C), C78(H78A,H78B,H78C), C79(H79A,H79B,H79C), C80(H80A,H80B,
 H80C), C86(H86A,H86B,H86C), C87(H87A,H87B,H87C), C88(H88A,H88B,H88C), C89(H89A,
 H89B,H89C), C90(H90A,H90B,H90C), C99(H99A,H99B,H99C), C107(H10A,H10B,H10C)
;
_shelx_res_checksum              57054
_shelx_hkl_checksum              20761
_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 2.729
_oxdiff_exptl_absorpt_empirical_full_min 0.692