Characterization of a Reactive Rh<sub>2</sub> Nitrenoid by Crystalline Matrix Isolation.
Das, Anuvab; Chen, Yu-Sheng; Reibenspies, Joseph H.; Powers, David C.; Journal of the American Chemical Society 141 (2019) 16232–16236; doi:10.1021/jacs.9b09064

data_4127695
_publ_section_title
;
 Characterization of a Reactive Rh<sub>2</sub> Nitrenoid by Crystalline
 Matrix Isolation.
;
_journal_issue                   41
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              16232
_journal_page_last               16236
_journal_paper_doi               10.1021/jacs.9b09064
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety         'C52 H70 N4.6 O8 Rh2, 0.7(N2), 2(C H2 Cl2)'
_chemical_formula_sum            'C54 H74 Cl4 N6 O8 Rh2'
_chemical_formula_weight         1282.81
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2019-08-01
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 107.025(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.0301(19)
_cell_length_b                   14.251(2)
_cell_length_c                   18.763(3)
_cell_measurement_reflns_used    8835
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      11.15
_cell_measurement_theta_min      2.22
_cell_volume                     2820.1(8)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_collection       'APEX3 (Bruker-AXS, 2015)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Bruker PHOTON 2 area detector'
_diffrn_detector_area_resol_mean 7.41
_diffrn_detector_type            'Charge-integrating Pixel Array Detector'
_diffrn_measured_fraction_theta_full 0.971
_diffrn_measured_fraction_theta_max 0.971
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 goniometer'
_diffrn_measurement_method       'omega and phi scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     0.33062
_diffrn_reflns_av_R_equivalents  0.1380
_diffrn_reflns_av_unetI/netI     0.0636
_diffrn_reflns_Laue_measured_fraction_full 0.971
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            59231
_diffrn_reflns_point_group_measured_fraction_full 0.971
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        11.388
_diffrn_reflns_theta_max         11.388
_diffrn_reflns_theta_min         0.899
_diffrn_source                   synchrotron
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.442
_exptl_absorpt_correction_T_max  0.7435
_exptl_absorpt_correction_T_min  0.3801
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.2010 before and 0.0836 after correction.
The Ratio of minimum to maximum transmission is 0.5112.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            blue-green
_exptl_crystal_density_diffrn    1.511
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1324
_exptl_crystal_size_max          0.45
_exptl_crystal_size_mid          0.38
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.672
_refine_diff_density_min         -0.549
_refine_diff_density_rms         0.091
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     484
_refine_ls_number_reflns         4877
_refine_ls_number_restraints     353
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0676
_refine_ls_R_factor_gt           0.0481
_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^)+(0.0509P)^2^+6.0849P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1230
_refine_ls_wR_factor_ref         0.1350
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3677
_reflns_number_total             4877
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b09064_si_002.cif
_cod_data_source_block           3b_37p5keV
_cod_original_cell_volume        2820.2(8)
_cod_database_code               4127695
_shelx_shelxl_version_number     2014/7
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N1N-N2N
 1.09 with sigma of 0.01
 C2_1-N1A \\sim C3_1-N1A \\sim C4_1-N1A
 with sigma of 0.02
 N1B-C2_2 \\sim N1B-C3_2 \\sim N1B-C4_2
 with sigma of 0.02
3. Restrained atomic chiral volume
 N1A, N1B
 fixed at 0 with sigma of 0.1
4. Rigid bond restraints
 C1_1, C2_1, C3_1, C4_1, C5_1, C6_1, C7_1, C8_1, C9_1, C10_1
 C1_2, C2_2, C3_2, C4_2, C5_2, C6_2, C7_2, C8_2, C9_2, C10_2
 with sigma for 1-2 distances of 0.003 and sigma for 1-3 distances of 0.003
 Cl1_3, Cl2_3, C1_3
 Cl1_4, Cl2_4, C1_4
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 N1A, N2A, N3A, N1B, N1N, N2N
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
5. Uiso/Uaniso restraints and constraints
C1_1 \\sim C2_1 \\sim C3_1 \\sim C4_1 \\sim C5_1 \\sim C6_1 \\sim C7_1 \\sim
C8_1 \\sim C9_1 \\sim C10_1 \\sim C1_2 \\sim C2_2 \\sim C3_2 \\sim C4_2 \\sim
C5_2 \\sim C6_2 \\sim C7_2 \\sim C8_2 \\sim C9_2 \\sim C10_2: within 2A with
sigma of 0.003 and sigma for terminal atoms of 0.006
Cl1_3 \\sim Cl2_3 \\sim C1_3 \\sim Cl1_4 \\sim Cl2_4 \\sim C1_4: within 2A with
sigma of 0.005 and sigma for terminal atoms of 0.01
N1A \\sim N2A \\sim N3A \\sim N1B \\sim N1N \\sim N2N: within 2A with sigma of
0.005 and sigma for terminal atoms of 0.01
Uanis(N1B) \\sim Ueq, Uanis(N1N) \\sim Ueq, Uanis(N2N) \\sim Ueq: with sigma of
0.005 and sigma for terminal atoms of 0.01
6. Same fragment restrains
{C1_2, C2_2, C3_2, C4_2, C5_2, C6_2, C7_2, C8_2, C9_2, C10_2}
as
{C1_1, C2_1, C3_1, C4_1, C5_1, C6_1, C7_1, C8_1, C9_1, C10_1} sigma for 1-2:
0.003 1-3: 0.04
{Cl1_4, Cl2_4, C1_4}
as
{Cl1_3, Cl2_3, C1_3} sigma for 1-2: 0.005 1-3: 0.04
7. Others
 Sof(N1B)=Sof(N1N)=Sof(N2N)=Sof(C1)=Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(C3)=Sof(H3A)=
 Sof(H3B)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(C5)=Sof(H5)=Sof(C6)=Sof(H6A)=Sof(H6B)=
 Sof(C7)=Sof(H7)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(C9)=Sof(H9)=Sof(C10)=Sof(H10A)=
 Sof(H10B)=1-FVAR(1)
 Sof(N1A)=Sof(N2A)=Sof(N3A)=Sof(C1)=Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(C3)=Sof(H3A)=
 Sof(H3B)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(C5)=Sof(H5)=Sof(C6)=Sof(H6A)=Sof(H6B)=
 Sof(C7)=Sof(H7)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(C9)=Sof(H9)=Sof(C10)=Sof(H10A)=
 Sof(H10B)=FVAR(1)
 Sof(Cl1)=Sof(Cl2)=Sof(C1)=Sof(H1A)=Sof(H1B)=1-FVAR(2)
 Sof(Cl1)=Sof(Cl2)=Sof(C1)=Sof(H1A)=Sof(H1B)=FVAR(2)
8.a Ternary CH refined with riding coordinates:
 C5(H5), C7(H7), C9(H9), C5(H5), C7(H7), C9(H9)
8.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C10(H10A,H10B), C1(H1A,H1B), C1(H1A,H1B), C2(H2A,H2B), C3(H3A,
 H3B), C4(H4A,H4B), C6(H6A,H6B), C8(H8A,H8B), C10(H10A,H10B), C2(H2A,H2B),
 C3(H3A,H3B), C4(H4A,H4B), C6(H6A,H6B), C8(H8A,H8B), C10(H10A,H10B)
8.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C7(H7), C8(H8), C9(H9)
8.d Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,
 H16C)
;
_shelx_res_checksum              19032
_shelx_hkl_checksum              58895
_olex2_submission_special_instructions 'No special instructions were received'