A Series of Iron Nitrosyl Complexes {Fe-NO}<sup>6-9</sup> and a Fleeting {Fe-NO}<sup>10</sup> Intermediate en Route to a Metalacyclic Iron Nitrosoalkane.
Keilwerth, Martin; Hohenberger, Johannes; Heinemann, Frank W.; Sutter, Jörg; Scheurer, Andreas; Fang, Huayi; Bill, Eckhard; Neese, Frank; Ye, Shengfa; Meyer, Karsten; Journal of the American Chemical Society 141 (2019) 17217–17235; doi:10.1021/jacs.9b08053

data_4133702
_publ_section_title
;
 A Series of Iron Nitrosyl Complexes {Fe-NO}<sup>6-9</sup> and a Fleeting
 {Fe-NO}<sup>10</sup> Intermediate en Route to a Metalacyclic Iron
 Nitrosoalkane.
;
_journal_issue                   43
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              17217
_journal_page_last               17235
_journal_paper_doi               10.1021/jacs.9b08053
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety
'C44 H54 Fe N9 O, 2.4(B F4), B0.6 F2.41, 2(C2 H3 N)'
_chemical_formula_sum            'C48 H60 B3 F12 Fe N11 O'
_chemical_formula_weight         1123.35
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2017-10-10
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 105.1700(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   23.4382(16)
_cell_length_b                   12.0678(8)
_cell_length_c                   19.8297(13)
_cell_measurement_reflns_used    9038
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      26.79
_cell_measurement_theta_min      2.30
_cell_volume                     5413.3(6)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'SHELXTL 6.12 (Bruker AXS, 2002)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2016/6 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXTL 6.12 (Bruker AXS, 2002)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 83.33
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker Kappa APEX II'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'Quazar focussing montel optics'
_diffrn_radiation_source         'ImuS high brilliance micro-focus tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0561
_diffrn_reflns_av_unetI/netI     0.0353
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            86129
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.103
_diffrn_reflns_theta_min         2.071
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.367
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6112
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0999 before and 0.0506 after correction.
The Ratio of minimum to maximum transmission is 0.8197.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            brown
_exptl_crystal_density_diffrn    1.378
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             2328
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.921
_refine_diff_density_min         -0.614
_refine_diff_density_rms         0.079
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     905
_refine_ls_number_reflns         11935
_refine_ls_number_restraints     513
_refine_ls_restrained_S_all      1.096
_refine_ls_R_factor_all          0.0792
_refine_ls_R_factor_gt           0.0574
_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^)+(0.0783P)^2^+6.8656P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1467
_refine_ls_wR_factor_ref         0.1599
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9150
_reflns_number_total             11935
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b08053_si_002.cif
_cod_data_source_block           mk1702
_cod_database_code               4133702
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.975
_shelx_estimated_absorpt_t_min   0.911
_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. Uiso/Uaniso restraints and constraints
B1 \\sim F11 \\sim F12 \\sim F13 \\sim F14: within 2A with sigma of 0.005 and
sigma for terminal atoms of 0.01
B1A \\sim F11A \\sim F12A \\sim F13A \\sim F14A: within 2A with sigma of 0.005
and sigma for terminal atoms of 0.01
B2 \\sim F21 \\sim F22 \\sim F23 \\sim F24: within 2A with sigma of 0.005 and
sigma for terminal atoms of 0.01
B2A \\sim F21A \\sim F22A \\sim F23A \\sim F24A: within 2A with sigma of 0.005
and sigma for terminal atoms of 0.01
F21B \\sim F23B \\sim F24B: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01
N210 \\sim C211 \\sim C212 \\sim N220 \\sim C221 \\sim C222 \\sim N230 \\sim
C231 \\sim C232 \\sim N240 \\sim C241 \\sim C242: within 2A with sigma of 0.005
and sigma for terminal atoms of 0.01
Uanis(B1) \\sim Ueq, Uanis(F11) \\sim Ueq, Uanis(F12) \\sim Ueq, Uanis(F13)
\\sim Ueq, Uanis(F14) \\sim Ueq: with sigma of 0.005 and sigma for terminal
atoms of 0.01
Uanis(B1A) \\sim Ueq, Uanis(F11A) \\sim Ueq, Uanis(F12A) \\sim Ueq, Uanis(F13A)
\\sim Ueq, Uanis(F14A) \\sim Ueq: with sigma of 0.005 and sigma for terminal
atoms of 0.01
Uanis(B2) \\sim Ueq, Uanis(F21) \\sim Ueq, Uanis(F22) \\sim Ueq, Uanis(F23)
\\sim Ueq, Uanis(F24) \\sim Ueq: with sigma of 0.005 and sigma for terminal
atoms of 0.01
Uanis(B2A) \\sim Ueq, Uanis(F21A) \\sim Ueq, Uanis(F22A) \\sim Ueq, Uanis(F23A)
\\sim Ueq, Uanis(F24A) \\sim Ueq: with sigma of 0.005 and sigma for terminal
atoms of 0.01
Uanis(F21B) \\sim Ueq, Uanis(F23B) \\sim Ueq, Uanis(F24B) \\sim Ueq: with sigma
of 0.005 and sigma for terminal atoms of 0.01
3. Same fragment restrains
{B3, F31, F32, F33, F34} sigma for 1-2: 0.02, 1-3: 0.04
as
{B1, F11, F12, F13, F14}
{B3, F31, F32, F33, F34} sigma for 1-2: 0.02, 1-3: 0.04
as
{B1A, F11A, F12A, F13A, F14A}
{B3, F31, F32, F33, F34} sigma for 1-2: 0.02, 1-3: 0.04
as
{B2, F21, F22, F23, F24}
{B3, F31, F32, F33, F34} sigma for 1-2: 0.02, 1-3: 0.04
as
{B2A, F21A, F22A, F23A, F24A}
{F31, F32, F33, F34} sigma for 1-2: 0.02, 1-3: 0.04
as
{F21B, F23B, F24B, B3}
{N100, C101, C102} sigma for 1-2: 0.02, 1-3: 0.04
as
{N210, C211, C212}
{N100, C101, C102} sigma for 1-2: 0.02, 1-3: 0.04
as
{N220, C221, C222}
{N100, C101, C102} sigma for 1-2: 0.02, 1-3: 0.04
as
{N230, C231, C232}
{N100, C101, C102} sigma for 1-2: 0.02, 1-3: 0.04
as
{N240, C241, C242}
4. Others
 0.6*[Sof(F21)+Sof(F23)+Sof(F24)]+0.6*[Sof(F21B)+Sof(F23B)+Sof(F24B)]=0.6 with
 esd of 0.001
 1*[Sof(N210)+Sof(C211)+Sof(C212)+Sof(H21A)+Sof(H21B)+Sof(H21C)]+1*[Sof(N220)+
 Sof(C221)+Sof(C222)+Sof(H22D)+Sof(H22E)+Sof(H22F)]+1*[Sof(N230)+Sof(C231)+
 Sof(C232)+Sof(H23D)+Sof(H23E)+Sof(H23F)]+1*[Sof(N240)+Sof(C241)+Sof(C242)+
 Sof(H24D)+Sof(H24E)+Sof(H24F)]=1 with esd of 0.001
 Sof(F21)=Sof(F23)=Sof(F24)=0.6*FVAR(2)
 Sof(B1A)=Sof(F11A)=Sof(F12A)=Sof(F13A)=Sof(F14A)=1-FVAR(2)
 Sof(B1)=Sof(F11)=Sof(F12)=Sof(F13)=Sof(F14)=FVAR(2)
 Sof(N210)=Sof(C211)=Sof(C212)=Sof(H21A)=Sof(H21B)=Sof(H21C)=FVAR(3)
 Sof(N220)=Sof(C221)=Sof(C222)=Sof(H22D)=Sof(H22E)=Sof(H22F)=FVAR(4)
 Sof(N230)=Sof(C231)=Sof(C232)=Sof(H23D)=Sof(H23E)=Sof(H23F)=FVAR(5)
 Sof(F21B)=Sof(F23B)=Sof(F24B)=0.6*FVAR(7)
 Sof(N240)=Sof(C241)=Sof(C242)=Sof(H24D)=Sof(H24E)=Sof(H24F)=FVAR(7)
 Fixed Sof: B2(0.6) F22(0.6) B2A(0.4) F21A(0.4) F22A(0.4) F23A(0.4) F24A(0.4)
5.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C6(H6A,H6B), C7(H7A,H7B), C11(H11A,H11B), C12(H12A,
 H12B)
5.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C9(H9), C10(H10), C14(H14), C15(H15), C18(H18), C20(H20),
 C27(H27), C29(H29), C36(H36), C38(H38)
5.c Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C31(H31A,H31B,
 H31C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C40(H40A,H40B,H40C), C41(H41A,
 H41B,H41C), C42(H42A,H42B,H42C), C44(H44A,H44B,H44C), C102(H10A,H10B,H10C),
 C212(H21A,H21B,H21C), C222(H22D,H22E,H22F), C232(H23D,H23E,H23F), C242(H24D,
 H24E,H24F)
;
_shelx_res_checksum              59047
_shelx_hkl_checksum              37764
_olex2_submission_special_instructions 'No special instructions were received'