Chemical Control of Magnetic Ordering in Hybrid Fe–Cl Layered Double Perovskites
Xue, Jie; Wang, Ziyu; Comstock, Andrew; Wang, Zhiyu; Sung, Herman H. Y.; Williams, Ian D.; Sun, Dali; Liu, Junwei; Lu, Haipeng; Chemistry of Materials 34 (2022) 2813–2823; doi:10.1021/acs.chemmater.2c00163

data_4004074
_publ_section_title
;
 Chemical Control of Magnetic Ordering in Hybrid Fe--Cl Layered Double
 Perovskites
;
_journal_issue                   6
_journal_name_full               'Chemistry of Materials'
_journal_page_first              2813
_journal_page_last               2823
_journal_paper_doi               10.1021/acs.chemmater.2c00163
_journal_volume                  34
_journal_year                    2022
_chemical_formula_moiety         'Ag Cl8 Fe, 4(C8 H12 N)'
_chemical_formula_sum            'C32 H48 Ag Cl8 Fe N4'
_chemical_formula_weight         936.06
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2022-01-07
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2021.12.21 svn.raa29eb21 for OlexSys, GUI svn.r6440)
;
_cell_angle_alpha                90
_cell_angle_beta                 90.585(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   38.6306(11)
_cell_length_b                   7.3226(3)
_cell_length_c                   7.2843(2)
_cell_measurement_reflns_used    2019
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      76.4750
_cell_measurement_theta_min      4.5710
_cell_volume                     2060.45(12)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      173.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1788
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.989
_diffrn_measured_fraction_theta_max 0.957
_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     82.00 178.00   1.00   10.00    --  113.00  30.00   0.00   96
  2  \w    -70.00  32.00   1.00    3.00    --  -39.95  77.00  30.00  102
  3  \w    -34.00  70.00   1.00    3.00    --   39.95 -57.00 150.00  104
  4  \w     74.00 102.00   1.00   10.00    --  113.00-111.00 -30.00   28
  5  \w    104.00 171.00   1.00   10.00    --  113.00  77.00-150.00   67
  6  \w     35.00  61.00   1.00   10.00    --  113.00-111.00 -30.00   26
  7  \w     43.00 106.00   1.00   10.00    --  113.00 -94.00  60.00   63
  8  \w     36.00  97.00   1.00   10.00    --  113.00-111.00 -90.00   61
  9  \w     38.00 140.00   1.00   10.00    --  113.00 -45.00  60.00  102
;
_diffrn_measurement_device       'kappa diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0259685000
_diffrn_orient_matrix_UB_12      -0.1583446000
_diffrn_orient_matrix_UB_13      -0.0184993000
_diffrn_orient_matrix_UB_21      0.0301074000
_diffrn_orient_matrix_UB_22      0.1381168000
_diffrn_orient_matrix_UB_23      -0.0028800000
_diffrn_orient_matrix_UB_31      0.0031047000
_diffrn_orient_matrix_UB_32      -0.0118880000
_diffrn_orient_matrix_UB_33      0.2106002000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0446
_diffrn_reflns_av_unetI/netI     0.0659
_diffrn_reflns_Laue_measured_fraction_full 0.989
_diffrn_reflns_Laue_measured_fraction_max 0.957
_diffrn_reflns_limit_h_max       48
_diffrn_reflns_limit_h_min       -47
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_limit_l_min       -5
_diffrn_reflns_number            3872
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.958
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.940
_diffrn_reflns_theta_min         2.288
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_current           0.80
_diffrn_source_power             0.040
_diffrn_source_target            Cu
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    11.621
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.47335
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (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    1.509
_exptl_crystal_description       plate
_exptl_crystal_F_000             954
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.02
_refine_diff_density_max         3.456
_refine_diff_density_min         -1.715
_refine_diff_density_rms         0.153
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.39(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     354
_refine_ls_number_reflns         2994
_refine_ls_number_restraints     361
_refine_ls_restrained_S_all      1.017
_refine_ls_R_factor_all          0.0718
_refine_ls_R_factor_gt           0.0642
_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^)+(0.1029P)^2^+12.2129P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1678
_refine_ls_wR_factor_ref         0.1769
_reflns_Friedel_coverage         0.853
_reflns_Friedel_fraction_full    0.992
_reflns_Friedel_fraction_max     0.960
_reflns_number_gt                2657
_reflns_number_total             2994
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cm2c00163_si_004.cif
_cod_data_source_block           xuejie4cu_173k
_cod_original_cell_volume        2060.46(12)
_cod_database_code               4004074
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.801
_shelx_estimated_absorpt_t_min   0.205
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.61(6)
 0.39(6)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H,H,H,H,H,H) groups
3. Restrained distances
 C15-C16
 1.38 with sigma of 0.02
 C12-C13 = C11-C12
 1.52 with sigma of 0.02
 C3-C2 = C2-C1
 1.52 with sigma of 0.02
 C2A-C3A = C2A-C1A
 1.52 with sigma of 0.02
 C11A-C12A = C12A-C13A
 1.52 with sigma of 0.02
 C17A-C16A \\sim C17A-C18A \\sim C18A-C13A \\sim C14A-C13A \\sim C15A-C14A
\\sim C15A-C16A
 with sigma of 0.02
 C14-C13 \\sim C18-C13 \\sim C17-C18 \\sim C17-C16 \\sim C15-C16 \\sim C15-C14
 with sigma of 0.02
 C7-C8 \\sim C3-C8 \\sim C3-C4 \\sim C4-C5 \\sim C6-C5 \\sim C7-C6
 with sigma of 0.02
 C4A-C3A \\sim C4A-C5A \\sim C5A-C6A \\sim C6A-C7A \\sim C8A-C7A \\sim C3A-C8A
 with sigma of 0.02
4. Restrained planarity
 C13, C14, C15, C16, C17, C18
 with sigma of 0.02
 C3, C4, C5, C6, C7, C8
 with sigma of 0.02
 C3A, C4A, C5A, C6A, C7A, C8A
 with sigma of 0.02
 C13A, C14A, C15A, C16A, C17A, C18A
 with sigma of 0.02
5. Uiso/Uaniso restraints and constraints
Uanis(N1) \\sim Ueq, Uanis(N2) \\sim Ueq: with sigma of 0.002 and sigma for
terminal atoms of 0.005
Uanis(C18) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(Cl1) \\sim Ueq, Uanis(Cl3) \\sim Ueq: with sigma of 0.003 and sigma for
terminal atoms of 0.005
Uanis(C3A) \\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.005
Uanis(C17A) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.003
Uanis(C3) \\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.005
Uanis(C13A) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.003
Uanis(C7A) \\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.005
Uanis(C1A) \\sim Ueq, Uanis(C1) \\sim Ueq: with sigma of 0.003 and sigma for
terminal atoms of 0.005
Uanis(C11) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
6. Rigid body (RIGU) restrains
 N1, C1, C2, C3, C4, C5, C6, C7, C8
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 N2, C11A, C12A, C13A, C14A, C15A, C16A, C17A, C18A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C11, C12, C13, C14, C15, C16, C17, C18
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C1A, C3A, C4A, C5A, C6A, C7A, C8A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
7. Others
 Fixed Sof: H1AA(0.4) H1AB(0.4) H1AC(0.4) H1BD(0.6) H1BE(0.6) H1BF(0.6)
 C1(0.4) H1A(0.4) H1B(0.4) C1A(0.6) H1AD(0.6) H1AE(0.6) C2(0.4) H2A(0.4)
 H2B(0.4) C2A(0.6) H2AA(0.6) H2AB(0.6) C3(0.4) C3A(0.6) C4(0.4) H4(0.4)
 C4A(0.6) H4A(0.6) C5(0.4) H5(0.4) C5A(0.6) H5A(0.6) C6(0.4) H6(0.4) C6A(0.6)
 H6A(0.6) C7(0.4) H7(0.4) C7A(0.6) H7A(0.6) C8(0.4) H8(0.4) C8A(0.6) H8A(0.6)
 H2AC(0.4) H2AD(0.4) H2AE(0.4) H2BF(0.6) H2BG(0.6) H2BH(0.6) C11(0.4) H11A(0.4)
 H11B(0.4) C11A(0.6) H11C(0.6) H11D(0.6) C12(0.4) H12A(0.4) H12B(0.4) C12A(0.6)
 H12C(0.6) H12D(0.6) C13(0.4) C13A(0.6) C14(0.4) H14(0.4) C14A(0.6) H14A(0.6)
 C15(0.4) H15(0.4) C15A(0.6) H15A(0.6) C16(0.4) H16(0.4) C16A(0.6) H16A(0.6)
 C17(0.4) H17(0.4) C17A(0.6) H17A(0.6) C18(0.4) H18(0.4) C18A(0.6) H18A(0.6)
8.a Riding coordinates:
 N1(H1AA,H1AB,H1AC), N1(H1BD,H1BE,H1BF), N2(H2AC,H2AD,H2AE), N2(H2BF,H2BG,H2BH)
8.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C1A(H1AD,H1AE), C2(H2A,H2B), C2A(H2AA,H2AB), C11(H11A,H11B),
 C11A(H11C,H11D), C12(H12A,H12B), C12A(H12C,H12D)
8.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C4A(H4A), C5(H5), C5A(H5A), C6(H6), C6A(H6A), C7(H7), C7A(H7A),
 C8(H8), C8A(H8A), C14(H14), C14A(H14A), C15(H15), C15A(H15A), C16(H16),
 C16A(H16A), C17(H17), C17A(H17A), C18(H18), C18A(H18A)
;
_shelx_res_checksum              90650
_shelx_hkl_checksum              36749
_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 1.813
_oxdiff_exptl_absorpt_empirical_full_min 0.725