An Iron-Based Dehydration Catalyst for Selective Formation of Styrene
Nachtigall, Olaf; VanderWeide, Andrew I.; Brennessel, William W.; Jones, William D.; ACS Catalysis  (2021) 10885–10891; doi:10.1021/acscatal.1c03037

data_4518962
_publ_section_title
;
 An Iron-Based Dehydration Catalyst for Selective Formation of Styrene
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              10885
_journal_page_last               10891
_journal_paper_doi               10.1021/acscatal.1c03037
_journal_year                    2021
_chemical_formula_moiety         'C34 H30 F6 Fe2 N6 O13 S2, 2(C F3 O3 S)'
_chemical_formula_sum            'C36 H30 F12 Fe2 N6 O19 S4'
_chemical_formula_weight         1318.60
_chemical_name_common            jonon96
_chemical_name_systematic        {[(FOX)Fe(OTf)]2(u-O)}[OTf]2
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2021-05-15
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2020.11.27 svn.r5f609507 for Rigaku Oxford Diffraction, GUI svn.r6214)
;
_cell_angle_alpha                97.802(4)
_cell_angle_beta                 97.381(3)
_cell_angle_gamma                106.208(5)
_cell_formula_units_Z            2
_cell_length_a                   13.3866(5)
_cell_length_b                   13.6776(9)
_cell_length_c                   14.4554(5)
_cell_measurement_reflns_used    9515
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      74.1440
_cell_measurement_theta_min      3.1360
_cell_volume                     2479.2(2)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015b)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2015a)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.965
_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    -26.00   1.00   0.50    6.14    --  -49.62  75.00-133.00   54
  2  \w    -30.00  22.00   0.50    6.14    --  -49.62  38.00-150.00  104
  3  \w    -61.00 -30.00   0.50   24.57    --  -84.25  75.00-133.00   62
  4  \w    -42.00 -17.00   0.50   24.57    --  -84.25  45.00  30.00   50
  5  \w    -93.00 -31.00   0.50    6.14    --  -49.62 -75.00  98.00  124
  6  \w     31.00 115.00   0.50    6.14    --   49.62  75.00-133.00  168
  7  \w    150.00 177.00   0.50   24.57    --  105.75  75.00-133.00   54
  8  \w    109.00 175.00   0.50   24.57    --  105.75 125.00-150.00  132
  9  \w     97.00 135.00   0.50   24.57    --  105.75  75.00-133.00   76
 10  \w    102.00 161.00   0.50   24.57    --  105.75  15.00 -60.00  118
 11  \w     99.00 175.00   0.50   24.57    --  105.75  45.00  60.00  152
 12  \w    125.00 170.00   0.50   24.57    --  105.75 125.00 150.00   90
 13  \w     99.00 178.00   0.50   24.57    --  105.75  30.00 150.00  158
 14  \w    108.00 177.00   0.50   24.57    --  105.75  30.00 120.00  138
 15  \w     71.00 102.00   0.50   24.57    --  105.75 -75.00  98.00   62
 16  \w     85.00 112.00   0.50   24.57    --  105.75-125.00  30.00   54
 17  \w     86.00 116.00   0.50   24.57    --  105.75-125.00  60.00   60
 18  \w     74.00 131.00   0.50   24.57    --  105.75-144.00  -6.23  114
 19  \w     61.00  87.00   0.50   24.57    --  105.75 -94.00-150.00   52
 20  \w     44.00  78.00   0.50   24.57    --  105.75 -61.00 -90.00   68
 21  \w     34.00 100.00   0.50   24.57    --  105.75 -94.00 -90.00  132
 22  \w     35.00  82.00   0.50   24.57    --  105.75 -61.00 -60.00   94
 23  \w     98.00 158.00   0.50   24.57    --  105.75  15.00-120.00  120
 24  \w     99.00 161.00   0.50   24.57    --  105.75  15.00-150.00  124
 25  \w     51.00 109.00   0.50   24.57    --  105.75 -94.00  60.00  116
 26  \w     53.00  79.00   0.50   24.57    --  105.75 -61.00 150.00   52
 27  \w     46.00  72.00   0.50   24.57    --  105.75 -61.00 120.00   52
 28  \w     46.00 108.00   0.50   24.57    --  105.75 -94.00 120.00  124
 29  \w     39.00  67.00   0.50   24.57    --  105.75-125.00  60.00   56
 30  \w     31.00  94.00   0.50    6.14    --   49.62-125.00  90.00  126
 31  \w     34.00  62.00   0.50   24.57    --  105.75 -61.00 -30.00   56
 32  \w     37.00  87.00   0.50   24.57    --  105.75 -94.00 -60.00  100
 33  \w     38.00  87.00   0.50   24.57    --  105.75 -77.00-150.00   98
 34  \w     48.00 108.00   0.50   24.57    --  105.75 -94.00-180.00  120
 35  \w    -22.00   3.00   0.50    6.14    --   49.62 -19.00   0.00   50
 36  \w    -22.00   3.00   0.50    6.14    --   49.62 -19.00 -30.00   50
 37  \w      3.00  66.00   0.50    6.14    --   49.62 -75.00  98.00  126
 38  \w    -21.00   4.00   0.50    6.14    --   49.62 -19.00  90.00   50
 39  \w    -21.00   4.00   0.50    6.14    --   49.62 -19.00 120.00   50
 40  \w   -101.00 -73.00   0.50    6.14    --  -49.62-125.00  60.00   56
 41  \w   -114.00 -89.00   0.50    6.14    --  -49.62-125.00 120.00   50
 42  \w   -110.00 -85.00   0.50   24.57    --  -84.25 -75.00  98.00   50
;
_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      -0.0712269000
_diffrn_orient_matrix_UB_12      -0.0787063000
_diffrn_orient_matrix_UB_13      -0.0860354000
_diffrn_orient_matrix_UB_21      -0.0963871000
_diffrn_orient_matrix_UB_22      0.0312513000
_diffrn_orient_matrix_UB_23      0.0256843000
_diffrn_orient_matrix_UB_31      0.0212951000
_diffrn_orient_matrix_UB_32      0.0840017000
_diffrn_orient_matrix_UB_33      -0.0622456000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0374
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.965
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            18888
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.965
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         78.878
_diffrn_reflns_theta_min         3.134
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.416
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70803
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.766
_exptl_crystal_description       block
_exptl_crystal_F_000             1328
_exptl_crystal_size_max          0.105
_exptl_crystal_size_mid          0.059
_exptl_crystal_size_min          0.044
_refine_diff_density_max         1.181
_refine_diff_density_min         -1.133
_refine_diff_density_rms         0.170
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.287
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     969
_refine_ls_number_reflns         18888
_refine_ls_number_restraints     764
_refine_ls_restrained_S_all      1.281
_refine_ls_R_factor_all          0.1483
_refine_ls_R_factor_gt           0.1074
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2853
_refine_ls_wR_factor_ref         0.3316
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12885
_reflns_number_total             18888
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c03037_si_002.cif
_cod_data_source_block           D
_cod_database_code               4518962
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.736
_shelx_estimated_absorpt_t_min   0.510
_reflns_odcompleteness_completeness 98.94
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.6067(19)
 0.3933(19)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All O(H) groups
3. Restrained distances
 Fe1-O8 \\sim Fe1-O8A
 with sigma of 0.01
 O8-S1 \\sim O8A-S1A
 with sigma of 0.01
 S1-O9 \\sim S1-O10 \\sim S1A-O9A \\sim S1A-O10A
 with sigma of 0.01
 O8-O9 \\sim O8-O10 \\sim O8A-O9A \\sim O8A-O10A
 with sigma of 0.02
 O9-O10 \\sim O9A-O10A
 with sigma of 0.02
 S1-C33 \\sim S1A-C33A
 with sigma of 0.01
 C33-F1 \\sim C33-F2 \\sim C33-F3 \\sim C33A-F1A \\sim C33A-F2A \\sim C33A-F3A
 with sigma of 0.01
 F1-F2 \\sim F2-F3 \\sim F3-F1 \\sim F1A-F2A \\sim F2A-F3A \\sim F3A-F1A
 with sigma of 0.02
 Fe2-O11 \\sim Fe2-O11A
 with sigma of 0.01
 O11-S2 \\sim O11A-S2A
 with sigma of 0.01
 S2-O12 \\sim S2-O13 \\sim S2A-O12A \\sim S2A-O13A
 with sigma of 0.01
 O11-O12 \\sim O11-O13 \\sim O11A-O12A \\sim O11A-O13A
 with sigma of 0.02
 O12-O13 \\sim O12A-O13A
 with sigma of 0.02
 S2-C34 \\sim S2A-C34A
 with sigma of 0.01
 C34-F4 \\sim C34-F5 \\sim C34-F6 \\sim C34A-F4A \\sim C34A-F5A \\sim C34A-F6A
 with sigma of 0.01
 F4-F5 \\sim F5-F6 \\sim F6-F4 \\sim F4A-F5A \\sim F5A-F6A \\sim F6A-F4A
 with sigma of 0.02
 S3-C35 \\sim S3-C35A
 with sigma of 0.01
 C35-F7 \\sim C35-F8 \\sim C35-F9 \\sim C35A-F7A \\sim C35A-F8A \\sim C35A-F9A
 with sigma of 0.01
 F7-F8 \\sim F8-F9 \\sim F9-F7 \\sim F7A-F8A \\sim F8A-F9A \\sim F9A-F7A
 with sigma of 0.02
 S4-O17 \\sim S4-O18 \\sim S4-O19 \\sim S4A-O17A \\sim S4A-O18A \\sim S4A-O19A
 with sigma of 0.01
 O17-O18 \\sim O18-O19 \\sim O19-O17 \\sim O17A-O18A \\sim O18A-O19A \\sim
O19A-O17A
 with sigma of 0.02
 S4-C36 \\sim S4A-C36A
 with sigma of 0.01
 C36-F10 \\sim C36-F11 \\sim C36-F12 \\sim C36A-F10A \\sim C36A-F11A \\sim
C36A-F12A
 with sigma of 0.01
 F10-F11 \\sim F11-F12 \\sim F12-F10 \\sim F10A-F11A \\sim F11A-F12A \\sim
F12A-F10A
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 1.2A with sigma of 0.02 and sigma
for terminal atoms of 0.04 within 1.2A
O11 \\sim O11A: within 2A with sigma of 0.002 and sigma for terminal atoms of
0.004 within 2A
Uanis(O8) \\sim Ueq, Uanis(O8A) \\sim Ueq, Uanis(O9) \\sim Ueq, Uanis(O9A)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 S1, F1, F2, F3, O8, O9, O10, C33
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S1A, F1A, F2A, F3A, O8A, O9A, O10A, C33A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S2, F4, F5, F6, O11, O12, O13, C34
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S2A, F4A, F5A, F6A, O11A, O12A, O13A, C34A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S3, F7, F8, F9, C35
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S3, F7A, F8A, F9A, C35A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S4, F10, F11, F12, O17, O18, O19, C36
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S4A, F10A, F11A, F12A, O17A, O18A, O19A, C36A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(S2A)=Sof(F4A)=Sof(F5A)=Sof(F6A)=Sof(O11A)=Sof(O12A)=Sof(O13A)=Sof(C34A)=1-
 FVAR(1)
 Sof(S2)=Sof(F4)=Sof(F5)=Sof(F6)=Sof(O11)=Sof(O12)=Sof(O13)=Sof(C34)=FVAR(1)
 Sof(F7A)=Sof(F8A)=Sof(F9A)=Sof(C35A)=1-FVAR(2)
 Sof(F7)=Sof(F8)=Sof(F9)=Sof(C35)=FVAR(2)
 Sof(S4A)=Sof(F10A)=Sof(F11A)=Sof(F12A)=Sof(O17A)=Sof(O18A)=Sof(O19A)=
 Sof(C36A)=1-FVAR(3)
 Sof(S4)=Sof(F10)=Sof(F11)=Sof(F12)=Sof(O17)=Sof(O18)=Sof(O19)=Sof(C36)=FVAR(3)
 Sof(S1A)=Sof(F1A)=Sof(F2A)=Sof(F3A)=Sof(O8A)=Sof(O9A)=Sof(O10A)=Sof(C33A)=1-
 FVAR(4)
 Sof(S1)=Sof(F1)=Sof(F2)=Sof(F3)=Sof(O8)=Sof(O9)=Sof(O10)=Sof(C33)=FVAR(4)
7.a Riding coordinates:
 O1(H1), O4(H4)
7.b Ternary CH refined with riding coordinates:
 C4(H4A), C6(H6), C20(H20), C22(H22)
7.c Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C3(H3A,H3B), C5(H5A,H5B), C17(H17A,H17B), C19(H19A,H19B)
7.d Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C11(H11), C13(H13), C14(H14), C15(H15), C16(H16),
 C26(H26), C27(H27), C29(H29), C30(H30), C31(H31), C32(H32)
;
_shelx_res_checksum              50021
_olex2_submission_original_sample_id jonon96
_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 3.773
_oxdiff_exptl_absorpt_empirical_full_min 0.294