Second-order nonlinear optical properties of copper-based hybrid organic-inorganic perovskites induced by chiral amines.
Li, Bin; Yu, Ying; Xin, Mingyang; Xu, Jialiang; Zhao, Tianzhe; Kang, Huimin; Xing, Guoxiang; Zhao, Peisheng; Zhang, Tianyong; Jiang, Shuang; Nanoscale 15 (2023) 1595–1601; doi:10.1039/d2nr05022f

data_1568073
_publ_section_title
;
 Second-order nonlinear optical properties of copper-based hybrid
 organic-inorganic perovskites induced by chiral amines.
;
_journal_issue                   4
_journal_name_full               Nanoscale
_journal_page_first              1595
_journal_page_last               1601
_journal_paper_doi               10.1039/d2nr05022f
_journal_volume                  15
_journal_year                    2023
_chemical_absolute_configuration ad
_chemical_formula_moiety
'Cl2 Cu0.5, Cl3 Cu, Cl5 Cu1.5, 2(Cl), 6(C8 H18 N)'
_chemical_formula_sum            'C48 H108 Cl12 Cu3 N6'
_chemical_formula_weight         1385.42
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'I 2y'
_space_group_name_H-M_alt        'I 1 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2022-01-06
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2022-09-09 deposited with the CCDC.	2022-12-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 107.039(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.4795(5)
_cell_length_b                   18.1694(4)
_cell_length_c                   19.6068(6)
_cell_measurement_reflns_used    30693
_cell_measurement_temperature    200.00(10)
_cell_measurement_theta_max      30.1150
_cell_measurement_theta_min      2.2300
_cell_volume                     6975.5(3)
_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 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      200.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.845
_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    -56.00   4.00   0.50    1.00    --    4.99 -19.00   0.00  120
  2  \w    -51.00   3.00   0.50    1.00    --    4.99 -19.00 120.00  108
  3  \w     -3.00  24.00   0.50    1.00    --    4.99  97.00  58.00   54
  4  \w    -49.00  -6.00   0.50    1.00    --    4.99 -19.00-120.00   86
  5  \w    -21.00  36.00   0.50    1.00    --    4.99 -99.00  90.00  114
  6  \w    -23.00  24.00   0.50    1.00    --   -6.79 -99.00 150.00   94
  7  \w    -23.00  26.00   0.50    1.00    --   -6.79 -99.00 -90.00   98
  8  \w    -21.00  35.00   0.50    1.00    --    4.99 -99.00-180.00  112
  9  \w    -15.00  13.00   0.50    1.00    --   -6.79 -97.00 -49.00   56
 10  \w    -28.00  37.00   0.50    1.00    --    4.99 -97.00 -49.00  130
 11  \w    -32.00  26.00   0.50    1.00    --   -6.79  97.00  58.00  116
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at offset/far, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0118898000
_diffrn_orient_matrix_UB_12      -0.0365613000
_diffrn_orient_matrix_UB_13      -0.0080727000
_diffrn_orient_matrix_UB_21      -0.0056058000
_diffrn_orient_matrix_UB_22      -0.0028753000
_diffrn_orient_matrix_UB_23      0.0339231000
_diffrn_orient_matrix_UB_31      -0.0337552000
_diffrn_orient_matrix_UB_32      0.0133585000
_diffrn_orient_matrix_UB_33      -0.0147346000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0402
_diffrn_reflns_av_unetI/netI     0.0409
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.845
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            65436
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.795
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.755
_diffrn_reflns_theta_min         2.080
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.400
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.56402
_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            'clear light brown'
_exptl_crystal_density_diffrn    1.319
_exptl_crystal_description       needle
_exptl_crystal_F_000             2916
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.532
_refine_diff_density_min         -0.446
_refine_diff_density_rms         0.067
_refine_ls_abs_structure_details
;
 Flack x determined using 5675 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.013(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.089
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     666
_refine_ls_number_reflns         17343
_refine_ls_number_restraints     795
_refine_ls_restrained_S_all      1.124
_refine_ls_R_factor_all          0.0550
_refine_ls_R_factor_gt           0.0398
_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^)+(0.0605P)^2^+1.3575P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1078
_refine_ls_wR_factor_ref         0.1144
_reflns_Friedel_coverage         0.829
_reflns_Friedel_fraction_full    0.996
_reflns_Friedel_fraction_max     0.742
_reflns_number_gt                13675
_reflns_number_total             17343
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2nr05022f2.cif
_cod_data_source_block           exp_110
_cod_depositor_comments
'Adding full bibliography for 1568070--1568073.cif.'
_cod_database_code               1568073
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         'C16 H34 N2 Cu Cl4'
_diffrn_oxdiff_digest_frames
;
01a1429a82b15e9e85286be9d1c40ae04b010881855
;
_diffrn_oxdiff_digest_hkl
;
01847c124da34ea5fc39a379d11d3c47281bd2
;
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Restrained distances
 C2-C1 = C2-C8 = C1-C4 = C4-C5 = C5-C6 = C6-C8
 1.54 with sigma of 0.02
 C2-C4 = C2-C6 = C1-C5 = C4-C6 = C5-C8
 2.54 with sigma of 0.04
 C2-C1 \\sim C1-C4 \\sim C4-C5 \\sim C5-C6 \\sim C6-C8 \\sim C8-C2
 with sigma of 0.02
 C2-C6 \\sim C4-C6 \\sim C1-C8 \\sim C1-C5 \\sim C5-C8 \\sim C2-C4
 with sigma of 0.04
 C9-C10 \\sim C10-C11 \\sim C11-C12 \\sim C12-C13 \\sim C13-C14 \\sim C14-C9
 with sigma of 0.02
 C9-C13 \\sim C11-C13 \\sim C10-C14 \\sim C10-C12 \\sim C12-C14 \\sim C9-C11
 with sigma of 0.04
 C11-C13 \\sim C11A-C13A
 with sigma of 0.04
 C9-C14 \\sim C9A-C14A
 with sigma of 0.02
 C00Y-C14 \\sim C00Y-C14A
 with sigma of 0.02
 C9-C10 \\sim C9A-C10A
 with sigma of 0.02
 C10-C12 \\sim C10A-C12A
 with sigma of 0.04
 C11-C12 \\sim C11A-C12A
 with sigma of 0.02
 C12-C13 \\sim C12A-C13A
 with sigma of 0.02
 C10-C11 \\sim C10A-C11A
 with sigma of 0.02
 C13-C14 \\sim C13A-C14A
 with sigma of 0.02
 C10-C14 \\sim C10A-C14A
 with sigma of 0.04
 C12-C14 \\sim C12A-C14A
 with sigma of 0.04
 C00Y-C9 \\sim C00Y-C9A
 with sigma of 0.04
 C00Y-C13 \\sim C00Y-C13A
 with sigma of 0.04
 C9-C11 \\sim C9A-C11A
 with sigma of 0.04
 C9-C13 \\sim C9A-C13A
 with sigma of 0.04
2. Uiso/Uaniso restraints and constraints
C2 \\sim C1 \\sim C4 \\sim C5 \\sim C6 \\sim C8: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
C9 \\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(C6) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C4) \\sim
Ueq, Uanis(C1) \\sim Ueq, Uanis(C5) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.01
Uanis(C11A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C13) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C11) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C01J) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
3. Rigid body (RIGU) restrains
 C2, C1, C4, C5, C6, C8
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C9, C10, C11, C12, C13, C14
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
4. Others
 Sof(H00D)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(C10A)=Sof(H10C)=Sof(H10D)=
 Sof(C11A)=Sof(H11C)=Sof(H11D)=Sof(C12A)=Sof(H12C)=Sof(H12D)=Sof(C13A)=
 Sof(H13C)=Sof(H13D)=Sof(C14A)=Sof(H14A)=1-FVAR(1)
 Sof(H00Y)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(C11)=
 Sof(H11A)=Sof(H11B)=Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(C13)=Sof(H13A)=Sof(H13B)=
 Sof(C14)=Sof(H14)=FVAR(1)
5.a Free rotating group:
 C9(C10,C11,C12,C13,C14), C9A(C10A,C11A,C12A,C13A,C14A)
5.b Ternary CH refined with riding coordinates:
 C00J(H00J), C00N(H00P), C00P(H00R), C00Q(H00Q), C00T(H00X), C00Y(H00Y),
 C00Y(H00D), C012(H012), C018(H018), C01A(H01), C01F(H5AA), C6(H6), C14(H14),
 C14A(H14A)
5.c Secondary CH2 refined with riding coordinates:
 C00R(H00H,H00I), C00S(H00V,H00W), C00U(H00Z,HD), C00V(H1AA,HE), C00W(H00K,
 H00L), C00X(H00,HF), C00Z(H2AA,HG), C011(H01D,H01E), C013(H01F,H01G),
 C014(H01Z,HH), C017(H01M,H01N), C019(H01U,H01V), C01B(H01O,H01P), C01C(H3AA,
 HI), C01E(H4AA,HJ), C01G(H01W,H01X), C01J(H01Q,H01R), C01K(H01S,H01T),
 C01Q(H01H,H01I), C7(H7A,H7B), C2(H2A,H2B), C1(H1A,H1B), C4(H4A,H4B), C5(H5A,
 H5B), C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B),
  C13(H13A,H13B), C9A(H9AA,H9AB), C10A(H10C,H10D), C11A(H11C,H11D), C12A(H12C,
 H12D), C13A(H13C,H13D)
5.d Idealised Me refined as rotating group:
 N00H(H00E,H00F,H00G), N00I(H00M,H00N,H00O), N00K(H00S,H00T,H00U), N00L(H00A,
 H00B,H00C), N00M(H0AA,H,HA), N00O(H7AA,HB,HC), C010(H01A,H01B,H01C), C015(H01J,
 H01K,H01L), C01I(H6AA,HK,HL), C01L(H8AA,HM,HN), C01M(H01Y,HO,HP), C3(H3A,H3B,
 H3C)
;
_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 1.468
_oxdiff_exptl_absorpt_empirical_full_min 0.655