A complex with nitrogen single, double, and triple bonds to the same chromium atom: synthesis, structure, and reactivity
Beaumier, Evan P.; Billow, Brennan S.; Singh, Amrendra K.; Biros, Shannon M.; Odom, Aaron L.; Chem. Sci. 7 (2016) 2532–; doi:10.1039/C5SC04608D

data_1542272
_publ_section_title
;
 A complex with nitrogen single, double, and triple bonds to the same
 chromium atom: synthesis, structure, and reactivity
;
_journal_issue                   4
_journal_name_full               'Chem. Sci.'
_journal_page_first              2532
_journal_paper_doi               10.1039/C5SC04608D
_journal_volume                  7
_journal_year                    2016
_chemical_formula_moiety
'2(C18 H33 Cr N4), 2(C18 H36 K N2 O6), C5 H12'
_chemical_formula_sum            'C77 H150 Cr2 K2 N12 O12'
_chemical_formula_weight         1618.28
_chemical_name_systematic
;
 ?
;
_chemical_properties_physical    'Air-sensitive, Moisture-sensitive'
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2015-09-29
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_audit_update_record
;
2015-09-30 deposited with the CCDC.
2016-01-05 downloaded from the CCDC.
;
_cell_angle_alpha                117.7400(10)
_cell_angle_beta                 103.5150(10)
_cell_angle_gamma                90.4210(10)
_cell_formula_units_Z            1
_cell_length_a                   13.5650(11)
_cell_length_b                   13.6133(11)
_cell_length_c                   14.3228(11)
_cell_measurement_reflns_used    9934
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      25.277
_cell_measurement_theta_min      2.171
_cell_volume                     2255.3(3)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_diffrn_ambient_temperature      173.15
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0513
_diffrn_reflns_av_unetI/netI     0.0444
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            38126
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.423
_diffrn_reflns_theta_min         1.667
_diffrn_source                   'sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.393
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.7027
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0959 before and 0.0534 after correction.
The Ratio of minimum to maximum transmission is 0.9430.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.192
_exptl_crystal_description       plate
_exptl_crystal_F_000             878
_exptl_crystal_size_max          0.356
_exptl_crystal_size_mid          0.176
_exptl_crystal_size_min          0.132
_refine_diff_density_max         0.855
_refine_diff_density_min         -0.707
_refine_diff_density_rms         0.063
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     499
_refine_ls_number_reflns         8312
_refine_ls_number_restraints     115
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.0771
_refine_ls_R_factor_gt           0.0507
_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^)+(0.0786P)^2^+1.0267P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1309
_refine_ls_wR_factor_ref         0.1512
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5988
_reflns_number_total             8312
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5sc04608d2.cif
_cod_data_source_block           CrN123
_cod_depositor_comments
'Adding full bibliography for 1542271--1542274.cif.'
_cod_database_code               1542272
_shelxl_version_number           2013-3
_shelx_estimated_absorpt_t_max   0.950
_shelx_estimated_absorpt_t_min   0.873
_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
 C1S-C2S = C2S-C3S = C3S-C4S = C4S-C5S
 1.5 with sigma of 0.001
 C1R-C2R = C2R-C3R = C3R-C4R = C4R-C5R
 1.5 with sigma of 0.001
 C9C-C1S
 -4 with sigma of 0.02
 H1SC-H17D_$1
 -2.05 with sigma of 0.002
 H1SA-H3CB_$2
 -2.05 with sigma of 0.002
 H3RA-H9CB_$3
 -2.05 with sigma of 0.002
 H4SB-H9CB_$3
 -2.05 with sigma of 0.002
 H1RC-H18D_$1
 -2.05 with sigma of 0.002
 C1S-C3S = C2S-C4S = C3S-C5S
 2.5 with sigma of 0.002
 C1R-C3R = C2R-C4R = C3R-C5R
 2.5 with sigma of 0.002
3. Rigid bond restraints
 C3S, C1S, C2S, C4S, C5S
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C3R, C1R, C2R, C4R, C5R
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C3R \\sim C1R \\sim C2R \\sim C4R \\sim C5R: within 1.7A with sigma of 0.02 and
sigma for terminal atoms of 0.04
C3S \\sim C5S: within 1.7A with sigma of 0.02 and sigma for terminal atoms of
0.04
Uanis(C1S) \\sim Ueq, Uanis(C2S) \\sim Ueq, Uanis(C3S) \\sim Ueq, Uanis(C4S)
\\sim Ueq, Uanis(C5S) \\sim Ueq: with sigma of 0.025 and sigma for terminal
atoms of 0.05
Uanis(C2R) \\sim Ueq, Uanis(C2R) \\sim Ueq, Uanis(C3R) \\sim Ueq, Uanis(C4R)
\\sim Ueq, Uanis(C5R) \\sim Ueq: with sigma of 0.025 and sigma for terminal
atoms of 0.05
Uanis(C1S) = Uanis(C1R) = Uanis(C2S) = Uanis(C2R) = Uanis(C3S) = Uanis(C3R) =
Uanis(C4S) = Uanis(C4R) = Uanis(C5S) = Uanis(C5R)
5. Same fragment restrains
{C3R, C1R, C2R, C4R, C5R} sigma for 1-2: 0.01, 1-3: 0.01
as
{C3S, C1S, C2S, C4S, C5S}
6. Others
 Fixed Sof: C3R(0.25) H3RA(0.25) H3RB(0.25) C1R(0.25) H1RA(0.25) H1RB(0.25)
 H1RC(0.25) C2R(0.25) H2RA(0.25) H2RB(0.25) C4R(0.25) H4RA(0.25) H4RB(0.25)
 C5R(0.25) H5RA(0.25) H5RB(0.25) H5RC(0.25) C3S(0.25) H3SA(0.25) H3SB(0.25)
 C1S(0.25) H1SA(0.25) H1SB(0.25) H1SC(0.25) C2S(0.25) H2SA(0.25) H2SB(0.25)
 C4S(0.25) H4SA(0.25) H4SB(0.25) C5S(0.25) H5SA(0.25) H5SB(0.25) H5SC(0.25)
7.a Ternary CH refined with riding coordinates:
 C7(H7), C10(H10), C13(H13), C16(H16)
7.b Secondary CH2 refined with riding coordinates:
 C1C(H1CA,H1CB), C2C(H2CA,H2CB), C3C(H3CA,H3CB), C4C(H4CA,H4CB), C5C(H5CA,
 H5CB), C6C(H6CA,H6CB), C7C(H7CA,H7CB), C8C(H8CA,H8CB), C9C(H9CA,H9CB),
 C10C(H10A,H10B), C11C(H11A,H11B), C12C(H12A,H12B), C13C(H13A,H13B), C14C(H14A,
 H14B), C15C(H15A,H15B), C16C(H16A,H16B), C17C(H17A,H17B), C18C(H18A,H18B),
 C3R(H3RA,H3RB), C2R(H2RA,H2RB), C4R(H4RA,H4RB), C3S(H3SA,H3SB), C2S(H2SA,H2SB),
  C4S(H4SA,H4SB)
7.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6)
7.d Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C11(H11C,H11D,H11E), C12(H12C,H12D,H12E),
 C14(H14C,H14D,H14E), C15(H15C,H15D,H15E), C17(H17C,H17D,H17E), C18(H18C,H18D,
 H18E), C1R(H1RA,H1RB,H1RC), C5R(H5RA,H5RB,H5RC), C1S(H1SA,H1SB,H1SC), C5S(H5SA,
 H5SB,H5SC)
;
_shelx_res_checksum              6078
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_submission_special_instructions 'No special instructions were received'