Bottleable (Amino)(Carboxy) Radicals Derived from Cyclic (Alkyl)(Amino) Carbenes
Janell K. Mahoney; David Martin; Curtis E. Moore; Arnold L. Rheingold; Guy Bertrand; Journal of the American Chemical Society 135 (2013) 18766–18769; doi:10.1021/ja4104765

data_4121336
_publ_contact_author_address
;
UCSD-CNRS Joint Research Laboratory (UMI 3555) 
Department of Chemistry and Biochemistry, 
University of California, 
San Diego, La Jolla, CA 92093-0343, USA
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_publ_contact_author_email       gbertrand@ucsd.edu
_publ_contact_author_name        'Guy Bertrand'
_publ_contact_author_phone       '(+1)-858 534 5412'
_publ_section_title
;
 Bottleable (Amino)(Carboxy) Radicals Derived from Cyclic (Alkyl)(Amino)
 Carbenes
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              18766
_journal_page_last               18769
_journal_paper_doi               10.1021/ja4104765
_journal_volume                  135
_journal_year                    2013
_chemical_formula_moiety         'C75 H108 N3 O3, 5(C H2 Cl2)'
_chemical_formula_sum            'C80 H118 Cl10 N3 O3'
_chemical_formula_weight         1524.27
_chemical_name_systematic
;
 ?
;
_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     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-09-17
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2013.09.17 svn.r2790 for OlexSys, GUI svn.r4601)
;
_cell_angle_alpha                90
_cell_angle_beta                 90.466(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.6366(5)
_cell_length_b                   29.7863(13)
_cell_length_c                   23.7121(10)
_cell_measurement_reflns_used    9939
_cell_measurement_temperature    100
_cell_measurement_theta_max      23.580
_cell_measurement_theta_min      2.20
_cell_volume                     8218.6(6)
_computing_cell_refinement       'SAINT v8.32B (Bruker, 2013)'
_computing_data_collection       'APEX2 v2013.6-2 (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.32B (Bruker, 2013)'
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELX, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
SHELXT, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      100
_diffrn_detector                 'Bruker APEX-II CCD'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD Area Detector'
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_device       'Kappa Four-Circle Diffractometer'
_diffrn_measurement_device_type  'Bruker X8 APEX II'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0732
_diffrn_reflns_av_unetI/netI     0.0758
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       35
_diffrn_reflns_limit_k_min       -35
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            65716
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.431
_diffrn_reflns_theta_min         1.849
_diffrn_source                   'sealed tube'
_diffrn_source_type              fine-focus
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.386
_exptl_absorpt_correction_T_max  0.2590
_exptl_absorpt_correction_T_min  0.2155
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0698 before and 0.0516 after correction.
The Ratio of minimum to maximum transmission is 0.8320.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            Yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.232
_exptl_crystal_description       Block
_exptl_crystal_F_000             3252
_exptl_crystal_size_max          0.351
_exptl_crystal_size_mid          0.217
_exptl_crystal_size_min          0.143
_refine_diff_density_max         1.025
_refine_diff_density_min         -1.177
_refine_diff_density_rms         0.074
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     935
_refine_ls_number_reflns         15044
_refine_ls_number_restraints     27
_refine_ls_restrained_S_all      1.027
_refine_ls_R_factor_all          0.1290
_refine_ls_R_factor_gt           0.0716
_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^)+(0.0971P)^2^+10.8495P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1785
_refine_ls_wR_factor_ref         0.2135
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8947
_reflns_number_total             15044
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja4104765_si_006.cif
_cod_data_source_block           3c
_cod_depositor_comments
;
The following automatic conversions were performed:

'_exptl_crystal_colour_primary' value 'Yellow' changed to 'yellow'
according to the built-in table from CIF Core dictionary named
'cif_core.dic' version 2.4.1 from 2010-06-29.

Automatic conversion script
Id: cif_fix_values 2281 2013-09-26 08:29:07Z andrius 
;
_cod_database_code               4121336
_shelxl_version_number           2013-3
_shelx_estimated_absorpt_t_max   0.947
_shelx_estimated_absorpt_t_min   0.876
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Cl4B-C2SB = Cl3B-C2SB
 1.75 with sigma of 0.02
 Cl3B-Cl4B
 2.9 with sigma of 0.02
 Cl5S-C3S = Cl5B-C3S
 1.75 with sigma of 0.02
 Cl5B-Cl6B
 2.9 with sigma of 0.02
 Cl9B-C5SB = Cl1C-C5SB
 1.75 with sigma of 0.02
 Cl1C-Cl9B
 2.9 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(Cl8S) = Uanis(Cl8B)
Uanis(Cl6B) = Uanis(Cl6S)
Uanis(Cl5B) = Uanis(Cl5S)
Uanis(C2S) = Uanis(C2SB)
Uanis(Cl4B) = Uanis(Cl4S)
Uanis(C5S) = Uanis(C5SB)
Uanis(Cl9B) = Uanis(C5SB) = Uanis(Cl1C)
Uanis(Cl9S) = Uanis(Cl9B)
Uanis(Cl10) = Uanis(Cl1B) = Uanis(Cl1C)
4. Rigid body (RIGU) restrains
 C3S, Cl6S, Cl6B, Cl5S, Cl5B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. others
 Sof(Cl7B)=Sof(Cl8B)=Sof(C4SB)=Sof(H4SC)=Sof(H4SD)=1-FVAR(1)
 Sof(Cl7S)=Sof(Cl8S)=Sof(C4S)=Sof(H4SA)=Sof(H4SB)=FVAR(1)
 Sof(Cl5S)=Sof(Cl6S)=Sof(H3SA)=Sof(H3SB)=1-FVAR(2)
 Sof(Cl5B)=Sof(Cl6B)=Sof(H3SC)=Sof(H3SD)=FVAR(2)
 Sof(Cl3B)=Sof(Cl4B)=1-FVAR(3)
 Sof(Cl3S)=Sof(Cl4S)=FVAR(3)
 Sof(C2SB)=Sof(H2SC)=Sof(H2SD)=1-FVAR(4)
 Sof(C2S)=Sof(H2SA)=Sof(H2SB)=FVAR(4)
 Fixed Sof: Cl9S(0.9) Cl10(0.7) Cl1B(0.2) Cl1C(0.1) Cl9B(0.1) C5S(0.9)
 H5SA(0.7) H5SB(0.7) H5SC(0.2) H5SD(0.2) C5SB(0.1) H5SE(0.1) H5SF(0.1)
6.a Ternary CH refined with riding coordinates:
 C20(H20), C20A(H20A), C20B(H20B), C23(H23), C23A(H23A), C23B(H23B)
6.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C6A(H6AA,H6AB), C6B(H6BA,H6BB), C10(H10A,H10B), C10A(H10C,H10D),
 C10B(H10E,H10F), C12(H12A,H12B), C12A(H12C,H12D), C12B(H12E,H12F), C3S(H3SC,
 H3SD), C3S(H3SA,H3SB), C5S(H5SA,H5SB), C5S(H5SC,H5SD), C5SB(H5SE,H5SF),
 C4S(H4SA,H4SB), C4SB(H4SC,H4SD), C2S(H2SA,H2SB), C2SB(H2SC,H2SD), C1S(H1SA,
 H1SB)
6.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C4A(H4A), C4B(H4B), C16(H16), C16A(H16A), C16B(H16B), C17(H17),
 C17A(H17A), C17B(H17B), C18(H18), C18A(H18A), C18B(H18B)
6.d Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C8A(H8AA,H8AB,H8AC), C8B(H8BA,H8BB,H8BC), C9(H9A,H9B,H9C),
 C9A(H9AA,H9AB,H9AC), C9B(H9BA,H9BB,H9BC), C11(H11A,H11B,H11C), C11A(H11D,H11E,
 H11F), C11B(H11G,H11H,H11I), C13(H13A,H13B,H13C), C13A(H13D,H13E,H13F),
 C13B(H13G,H13H,H13I), C21(H21A,H21B,H21C), C21A(H21D,H21E,H21F), C21B(H21G,
 H21H,H21I), C22(H22A,H22B,H22C), C22A(H22D,H22E,H22F), C22B(H22G,H22H,H22I),
 C24(H24A,H24B,H24C), C24A(H24D,H24E,H24F), C24B(H24G,H24H,H24I), C25(H25A,H25B,
 H25C), C25A(H25D,H25E,H25F), C25B(H25G,H25H,H25I)
;
_shelx_res_checksum              40569