Photochemically Switching Diamidocarbene Spin States Leads to Reversible Büchner Ring Expansions.
Perera, Tharushi A.; Reinheimer, Eric W.; Hudnall, Todd W.; Journal of the American Chemical Society  (2017) –; doi:10.1021/jacs.7b09264

data_4126558
_publ_section_title
;
 Photochemically Switching Diamidocarbene Spin States Leads to Reversible
 B\"uchner Ring Expansions.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.7b09264
_journal_year                    2017
_chemical_formula_moiety         'C29.36 H32.47 Cl0.89 N2 O2, 0.104(C4 H2 Cl)'
_chemical_formula_sum            'C29.78 H32.68 Cl N2 O2'
_chemical_formula_weight         486.00
_chemical_name_common            DAC-chlorobenene
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2017-08-14
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.03.02 svn.r3394 for Rigaku Oxford Diffraction, GUI svn.r5318)
;
_cell_angle_alpha                90
_cell_angle_beta                 95.838(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.6938(3)
_cell_length_b                   20.1350(5)
_cell_length_c                   14.4072(3)
_cell_measurement_reflns_used    8286
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      76.2740
_cell_measurement_theta_min      4.3330
_cell_volume                     2508.90(12)
_computing_cell_refinement       'CrysAlisPro 1.171.39.30d (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.30d (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.30d (Rigaku OD, 2017)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'HyPix-6000HE HPC'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_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    -22.00  30.00   0.50   16.95    --   49.17 -57.00  30.00  104
  2  \w     32.00  96.00   0.50   67.87    --  105.75 -19.00  60.00  128
  3  \w    110.00 135.00   0.50   67.87    --  105.75  37.00  60.00   50
  4  \w    153.00 178.00   0.50   67.87    --  105.75  37.00  60.00   50
  5  \w     60.00  86.00   0.50   67.87    --  105.75 -37.00 -60.00   52
  6  \w     47.00  73.00   0.50   67.87    --  105.75 -57.00-150.00   52
  7  \w     37.00 153.00   0.50   67.87    --  105.75   0.00-120.00  232
  8  \w     35.00  85.00   0.50   67.87    --  105.75 -57.00 -90.00  100
  9  \w     39.00 113.00   0.50   67.87    --  105.75 -57.00 -60.00  148
 10  \w     32.00 112.00   0.50   67.87    --  105.75 -19.00 120.00  160
 11  \w    -55.00  20.00   0.50   16.95    --  -49.17  19.00-180.00  150
 12  \w    -88.00 -15.00   0.50   67.87    --  -84.25  37.00   0.00  146
 13  \w   -118.00 -86.00   0.50   16.95    --  -49.17-125.00  90.00   64
 14  \w   -114.00 -80.00   0.50   16.95    --  -49.17-125.00-120.00   68
 15  \w   -107.00 -94.50   0.50   16.95    --  -49.17-125.00 -30.00   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0062181000
_diffrn_orient_matrix_UB_12      -0.0560820000
_diffrn_orient_matrix_UB_13      -0.0729442000
_diffrn_orient_matrix_UB_21      -0.1316624000
_diffrn_orient_matrix_UB_22      0.0364521000
_diffrn_orient_matrix_UB_23      -0.0589999000
_diffrn_orient_matrix_UB_31      0.1199001000
_diffrn_orient_matrix_UB_32      0.0371476000
_diffrn_orient_matrix_UB_33      -0.0523809000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0359
_diffrn_reflns_av_unetI/netI     0.0355
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            13442
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        66.579
_diffrn_reflns_theta_max         66.579
_diffrn_reflns_theta_min         5.567
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_diffrn_standards_decay_%        0
_diffrn_standards_interval_count 0
_diffrn_standards_interval_time  0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.575
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.72872
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.30d (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            pale-yellow
_exptl_crystal_density_diffrn    1.286
_exptl_crystal_description       plate
_exptl_crystal_F_000             1033.3
_exptl_crystal_size_max          0.156
_exptl_crystal_size_mid          0.095
_exptl_crystal_size_min          0.055
_refine_diff_density_max         0.332
_refine_diff_density_min         -0.289
_refine_diff_density_rms         0.050
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.116
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     352
_refine_ls_number_reflns         4407
_refine_ls_number_restraints     16
_refine_ls_restrained_S_all      1.116
_refine_ls_R_factor_all          0.0676
_refine_ls_R_factor_gt           0.0626
_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^)+(0.0437P)^2^+2.8255P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1520
_refine_ls_wR_factor_ref         0.1565
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4060
_reflns_number_total             4407
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b09264_si_002.cif
_cod_data_source_block           2d
_cod_database_code               4126558
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C35 H35 N35 O35 Cl35 Br1 '
_diffrn_oxdiff_ac3_digest_frames
;
01330b725b9561fc4cebbf1d9bc0c9a289000251e00
;
_diffrn_oxdiff_ac3_digest_hkl
;
01578e5a4ae45704b25bb85f33038d4808d804
;
_reflns_odcompleteness_completeness 99.50
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All H(H) groups, All C(H,H,H) groups
2. Restrained distances
 C4-C3 \\sim C5-C4 \\sim C6-C5
 with sigma of 0.001
3. Restrained planarity
 C6, C5, C4, C3, Cl2
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uanis(C6B) = Uanis(C6A)
Uanis(C1A) = Uanis(C1B)
Uanis(C5B) = Uanis(C5A)
Uanis(C2A) = Uanis(C2B)
Uanis(C4B) = Uanis(C4A)
Uanis(C3A) = Uanis(C3B)
Uanis(C1B) = Uanis(C6A)
Uanis(C1B) = Uanis(C5A)
Uanis(C5A) = Uanis(C2B)
Uanis(C3B) = Uanis(C4A)
Uiso(C4) = Uiso(C6)
5. Same fragment restrains
{C1A, C2A, C3A, C4A, C5A, C6A} sigma for 1-2: 0.02, 1-3: 0.04
as
{C1B, C2B, C3B, C4B, C5B, C6B}
6. Others
 1*[Sof(Cl1A)+Sof(C1A)+Sof(H1A)+Sof(C2A)+Sof(H2A)+Sof(C3A)+Sof(C4A)+Sof(H4A)+
 Sof(C5A)+Sof(H5A)+Sof(C6A)+Sof(H6A)]+1*[Sof(Cl1B)+Sof(C1B)+Sof(H1B)+Sof(C2B)+
 Sof(H2B)+Sof(C3B)+Sof(C4B)+Sof(H4B)+Sof(C5B)+Sof(H5B)+Sof(C6B)+Sof(H6B)]+1*
 [Sof(Cl2)+Sof(C3)+Sof(C4)+Sof(H4)+Sof(C5)+Sof(H5)+Sof(C6)]=1 with esd of 0.001
 Sof(Cl1A)=Sof(C1A)=Sof(H1A)=Sof(C2A)=Sof(H2A)=Sof(C3A)=Sof(C4A)=Sof(H4A)=
 Sof(C5A)=Sof(H5A)=Sof(C6A)=Sof(H6A)=FVAR(1)
 Sof(Cl1B)=Sof(C1B)=Sof(H1B)=Sof(C2B)=Sof(H2B)=Sof(C3B)=Sof(C4B)=Sof(H4B)=
 Sof(C5B)=Sof(H5B)=Sof(C6B)=Sof(H6B)=FVAR(2)
 Sof(Cl2)=Sof(C3)=Sof(C4)=Sof(H4)=Sof(C5)=Sof(H5)=Sof(C6)=FVAR(3)
 Fixed Uiso: Cl2(0.04) C3(0.04) C4(0.04) C5(0.04) C6(0.04)
7.a Aromatic/amide H refined with riding coordinates:
 C15(H15), C17(H17), C24(H24), C26(H26), C4(H4), C5(H5), C1A(H1A), C2A(H2A),
 C4A(H4A), C5A(H5A), C6A(H6A), C1B(H1B), C2B(H2B), C4B(H4B), C5B(H5B), C6B(H6B)
7.b Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C28(H28A,H28B,
 H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C33(H33A,H33B,H33C), C34(H34A,
 H34B,H34C)
;
_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 1.897
_oxdiff_exptl_absorpt_empirical_full_min 0.724