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_1568070
_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         '2(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     dual
_audit_creation_date             2022-01-14
_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                 107.343(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.7149(13)
_cell_length_b                   18.0468(8)
_cell_length_c                   19.5556(13)
_cell_measurement_reflns_used    14274
_cell_measurement_temperature    199.99(10)
_cell_measurement_theta_max      72.7860
_cell_measurement_theta_min      2.7340
_cell_volume                     6978.3(8)
_computing_cell_refinement       'CrysAlisPro 1.171.41.122a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.122a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.122a (Rigaku OD, 2021)'
_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    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      199.99(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 0.999
_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 -22.00   0.50    0.05    --  -47.12 110.00-161.00   68
  2  \w      5.00  88.00   0.50    0.05    --   47.12-110.00 103.00  166
  3  \w    -92.00 -65.00   0.50    0.17    -- -100.00 110.00-161.00   54
  4  \w   -171.00 -94.00   0.50    0.17    -- -100.00-110.00 103.00  154
  5  \w    -56.00 -31.00   0.50    0.17    -- -100.00 110.00-161.00   50
  6  \w    115.00 141.00   0.50    0.17    --  107.75 110.00-161.00   52
  7  \w    -21.00   5.00   0.50    0.05    --   12.00 100.00 132.53   52
  8  \w    -18.00   7.00   0.50    0.05    --   16.00 100.00 172.79   50
  9  \w    -13.00  12.00   0.50    0.05    --   20.00  97.00 -85.68   50
 10  \w      1.00  32.00   0.50    0.05    --   32.00  92.00  15.71   62
 11  \w     10.00  35.00   0.50    0.05    --   40.00  90.00 162.16   50
 12  \w    -44.00 -18.00   0.50    0.05    --  -44.00 -86.00-138.27   52
 13  \w     20.00  46.00   0.50    0.05    --   44.00  83.00  19.08   52
 14  \w   -120.00 -68.00   0.50    0.05    --  -47.12 -37.00  60.00  104
 15  \w    -63.00 -32.00   0.50    0.05    --  -47.12 -37.00  60.00   62
 16  \w     24.00  50.00   0.50    0.05    --   47.12  77.00  90.00   52
 17  \w    -25.00  63.00   0.50    0.05    --   47.12 -57.00 120.00  176
 18  \w     58.00 124.00   0.50    0.05    --   52.00  82.00 159.71  132
 19  \w     28.00  77.00   0.50    0.05    --   52.00  81.00 -55.89   98
 20  \w     28.00  87.00   0.50    0.05    --   52.00  81.00  90.70  118
 21  \w     25.00  51.00   0.50    0.05    --   52.00  84.00 -84.12   52
 22  \w     26.00  54.00   0.50    0.05    --   52.00  82.00 159.71   56
 23  \w     30.00  57.00   0.50    0.05    --   56.00  83.00   9.09   54
 24  \w     31.00  59.00   0.50    0.05    --   56.00  81.00-174.21   56
 25  \w    104.00 129.00   0.50    0.05    --   56.00  81.00-174.21   50
 26  \w     31.00  57.00   0.50    0.05    --   56.00  80.00-134.03   52
 27  \w     35.00  61.00   0.50    0.05    --   60.00  82.00  89.01   52
 28  \w     37.00  77.00   0.50    0.05    --   60.00  75.00-107.62   80
 29  \w     37.00  63.00   0.50    0.05    --   60.00  77.00 -75.22   52
 30  \w     93.00 120.00   0.50    0.05    --   60.00  75.00-107.62   54
 31  \w     38.00  64.00   0.50    0.05    --   60.00  73.00 -26.16   52
 32  \w    -87.00 -38.00   0.50    0.05    --  -64.00 -81.00 160.40   98
 33  \w    112.00 137.00   0.50    0.05    --   64.00  79.00   0.54   50
 34  \w     39.00  66.00   0.50    0.05    --   64.00  79.00   0.54   54
 35  \w    -67.00 -41.00   0.50    0.05    --  -68.00 -83.00  50.45   52
 36  \w     44.00  69.00   0.50    0.05    --   68.00  78.00 113.48   50
 37  \w    -74.00 -48.00   0.50    0.05    --  -72.00 -76.00-125.63   52
 38  \w   -137.00-111.00   0.50    0.05    --  -72.00 -83.00  88.97   52
 39  \w   -138.00-112.00   0.50    0.05    --  -72.00 -84.00 146.15   52
 40  \w    -73.00 -45.00   0.50    0.05    --  -72.00 -84.00 146.15   56
 41  \w    -82.00 -51.00   0.50    0.05    --  -72.00 -69.00-116.32   62
 42  \w    -71.00 -46.00   0.50    0.05    --  -72.00 -83.00  88.97   50
 43  \w    101.00 127.00   0.50    0.05    --   72.00  77.00-161.62   52
 44  \w     48.00  82.00   0.50    0.05    --   72.00  77.00-161.62   68
 45  \w    -80.00 -52.00   0.50    0.17    --  -76.00 -84.00 -32.54   56
 46  \w    -80.00 -49.00   0.50    0.17    --  -76.00 -83.00  40.92   62
 47  \w    -81.00 -51.00   0.50    0.17    --  -76.00 -79.00   6.06   60
 48  \w    -80.00 -50.00   0.50    0.17    --  -76.00 -81.00 -66.91   60
 49  \w    -81.00 -54.00   0.50    0.17    --  -76.00 -82.00  66.45   54
 50  \w    -76.00 -50.00   0.50    0.17    --  -76.00 -82.00 129.89   52
 51  \w    -91.00 -62.00   0.50    0.17    --  -84.00 -75.00 -81.73   58
 52  \w    -87.00 -58.00   0.50    0.17    --  -84.00 -84.00-114.69   58
 53  \w    -86.00 -60.00   0.50    0.17    --  -84.00 -76.00  93.97   52
 54  \w   -157.00-127.00   0.50    0.17    --  -84.00 -76.00  93.97   60
 55  \w    -91.00 -65.00   0.50    0.17    --  -84.00 -66.00-171.36   52
 56  \w   -107.00 -60.00   0.50    0.17    --  -84.00 -76.00 -97.53   94
 57  \w    -88.00 -63.00   0.50    0.17    --  -84.00 -74.00-146.64   50
 58  \w    -93.00 -57.00   0.50    0.17    --  -84.00 -84.00  45.80   72
 59  \w    -92.00 -66.00   0.50    0.17    --  -88.00 -73.00  55.60   52
 60  \w    -96.00 -70.00   0.50    0.17    --  -88.00 -67.00  71.28   52
 61  \w   -101.00 -66.00   0.50    0.17    --  -88.00 -72.00 133.09   70
 62  \w   -156.00-106.00   0.50    0.17    --  -88.00 -72.00 133.09  100
 63  \w   -102.00 -65.00   0.50    0.17    --  -88.00 -77.00-176.18   74
 64  \w   -142.00-117.00   0.50    0.17    --  -88.00 -67.00  71.28   50
 65  \w    -92.00 -66.00   0.50    0.17    --  -88.00 -74.00   1.09   52
 66  \w   -159.00-120.00   0.50    0.17    --  -88.00 -74.00   1.09   78
 67  \w   -112.00 -67.00   0.50    0.17    --  -88.00 -73.00-108.95   90
 68  \w   -145.00-119.00   0.50    0.17    --  -88.00 -73.00-108.95   52
 69  \w    -91.00 -66.00   0.50    0.17    --  -88.00 -73.00-169.35   50
 70  \w   -161.00-117.00   0.50    0.17    --  -88.00 -73.00-169.35   88
 71  \w   -165.00-122.00   0.50    0.17    --  -92.00 -66.00  65.09   86
 72  \w    -97.00 -72.00   0.50    0.17    --  -92.00 -68.00 -17.82   50
 73  \w   -106.00 -74.00   0.50    0.17    --  -92.00 -66.00  65.09   64
 74  \w   -167.00 -72.00   0.50    0.17    --  -96.00 -78.00  22.55  190
 75  \w    -98.00 -73.00   0.50    0.17    --  -96.00 -75.00 165.47   50
 76  \w   -101.00 -73.00   0.50    0.17    --  -96.00 -77.00 130.80   56
 77  \w   -142.00-116.00   0.50    0.17    --  -96.00 -77.00 130.80   52
 78  \w   -168.00-102.00   0.50    0.17    --  -96.00 -75.00 165.47  132
 79  \w   -169.00 -71.00   0.50    0.17    --  -96.00 -79.00 -28.89  196
 80  \w    -88.00 -52.00   0.50    0.17    -- -100.00  61.00  30.00   72
 81  \w   -173.00 -75.00   0.50    0.17    -- -100.00 -79.00 -74.25  196
 82  \w   -100.00 -75.00   0.50    0.17    -- -100.00 -80.00  64.43   50
 83  \w   -171.00-139.00   0.50    0.17    -- -100.00 -80.00  64.43   64
 84  \w   -139.00 -78.00   0.50    0.17    -- -100.00 -72.00 -18.38  122
 85  \w   -138.00 -81.00   0.50    0.17    -- -100.00 -66.00  23.49  114
 86  \w   -131.00 -81.00   0.50    0.17    -- -100.00 -64.00  85.80  100
 87  \w   -172.00 -77.00   0.50    0.17    -- -100.00 -79.00-142.34  190
 88  \w   -104.00 -79.00   0.50    0.17    -- -100.00 -71.00 -53.32   50
 89  \w   -169.00-124.00   0.50    0.17    -- -100.00 -71.00 -53.32   90
 90  \w   -110.00 -80.00   0.50    0.17    -- -100.00 -68.00 153.28   60
 91  \w   -173.00-119.00   0.50    0.17    -- -100.00 -68.00 153.28  108
 92  \w   -169.00 -76.00   0.50    0.17    -- -100.00 -79.00-121.79  186
 93  \w     42.00 108.00   0.50    0.17    --  107.75 -94.00 -30.00  132
 94  \w     67.00 109.00   0.50    0.17    --  107.75 -94.00 150.00   84
 95  \w     92.00 118.00   0.50    0.17    --  107.75 -61.00-180.00   52
 96  \w     36.00  79.00   0.50    0.17    --  107.75 -61.00-180.00   86
 97  \w     38.00  64.00   0.50    0.17    --  107.75 -94.00 150.00   52
 98  \w     57.00  94.00   0.50    0.17    --  107.75 -94.00 120.00   74
 99  \w     76.00 101.00   0.50    0.17    --  107.75 -94.00-180.00   50
100  \w     36.00  68.00   0.50    0.17    --  107.75 -94.00-180.00   64
101  \w     53.00 107.00   0.50    0.17    --  107.75 -94.00  30.00  108
102  \w     38.00 109.00   0.50    0.17    --  107.75 -94.00 -90.00  142
103  \w     48.00 112.00   0.50    0.17    --  107.75-110.00 103.00  128
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0666056000
_diffrn_orient_matrix_UB_12      0.0443203000
_diffrn_orient_matrix_UB_13      0.0191397000
_diffrn_orient_matrix_UB_21      -0.0369440000
_diffrn_orient_matrix_UB_22      0.0680969000
_diffrn_orient_matrix_UB_23      0.0177357000
_diffrn_orient_matrix_UB_31      0.0164982000
_diffrn_orient_matrix_UB_32      -0.0262135000
_diffrn_orient_matrix_UB_33      0.0782413000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0915
_diffrn_reflns_av_unetI/netI     0.0391
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            86146
_diffrn_reflns_point_group_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.079
_diffrn_reflns_theta_max         67.079
_diffrn_reflns_theta_min         2.728
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.544
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.779
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.122a (Rigaku Oxford Diffraction, 2021)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'light brown'
_exptl_crystal_density_diffrn    1.319
_exptl_crystal_description       block
_exptl_crystal_F_000             2916
_exptl_crystal_size_max          0.094
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.072
_refine_diff_density_max         0.574
_refine_diff_density_min         -0.769
_refine_diff_density_rms         0.088
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.07(3)
_refine_ls_extinction_coef       0.00035(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.097
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     637
_refine_ls_number_reflns         12326
_refine_ls_number_restraints     575
_refine_ls_restrained_S_all      1.105
_refine_ls_R_factor_all          0.0743
_refine_ls_R_factor_gt           0.0640
_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^)+(0.1115P)^2^+8.4340P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1851
_refine_ls_wR_factor_ref         0.1940
_reflns_Friedel_coverage         0.912
_reflns_Friedel_fraction_full    0.978
_reflns_Friedel_fraction_max     0.978
_reflns_number_gt                10439
_reflns_number_total             12326
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2nr05022f2.cif
_cod_data_source_block           053663_yypv_200k_a2
_cod_depositor_comments
'Adding full bibliography for 1568070--1568073.cif.'
_cod_database_code               1568070
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Cu Cl N C10'
_shelx_estimated_absorpt_t_max   0.691
_shelx_estimated_absorpt_t_min   0.624
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.93(3)
 0.07(3)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H5C,H5D,H5E} of N5, {H3C,H3D,H3E} of N3, {H6A,H6B,H6C} of
  N6, {H4A,H4B,H4C} of N4, {H1A,H1B,H1C} of N1, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, {H2D,H2E,H2F} of N2
3. Restrained distances
 C5-C41 = C5-C43
 1.49 with sigma of 0.02
 C41-C21
 1.58 with sigma of 0.02
 C41-C45
 1.53 with sigma of 0.02
 C43-C23
 1.54 with sigma of 0.02
 C45-C47
 1.56 with sigma of 0.02
 C21-C11 = C21-N5
 1.48 with sigma of 0.02
 C23-C47
 1.6 with sigma of 0.02
 C19-C37
 1.5 with sigma of 0.02
 C5-C45 = C5-C23
 2.49 with sigma of 0.04
 C41-N5
 2.48 with sigma of 0.04
 C5-C21 = C45-C23
 2.53 with sigma of 0.04
 C41-C11 = C41-C47
 2.54 with sigma of 0.04
 C43-C47
 2.59 with sigma of 0.04
4. Rigid bond restraints
 C21, C41, C5, C43, C23, C47, C45
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C17, C9, C39, C19, C37
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
5. Uiso/Uaniso restraints and constraints
C21 \\sim C41 \\sim C5 \\sim C43 \\sim C23 \\sim C47 \\sim C45: within 2A with
sigma of 0.005 and sigma for terminal atoms of 0.01 within 2A
C17 \\sim C9 \\sim C39 \\sim C19 \\sim C37: within 2A with sigma of 0.005 and
sigma for terminal atoms of 0.01 within 2A
Uanis(C32) \\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C26)
\\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C8) \\sim Ueq: with sigma of 0.1 and
sigma for terminal atoms of 0.2
6. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
7.a Ternary CH refined with riding coordinates:
 C1(H1), C4(H4), C6(H6), C10(H10), C24(H24), C32(H32), C36(H36), C46(H46),
 C33(H33), C17(H17), C41(H41), C21(H21)
7.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C12(H12A,H12B), C14(H14A,H14B), C16(H16A,H16B), C18(H18A,H18B),
 C20(H20A,H20B), C22(H22A,H22B), C26(H26A,H26B), C28(H28A,H28B), C30(H30A,H30B),
  C34(H34A,H34B), C40(H40A,H40B), C42(H42A,H42B), C44(H44A,H44B), C48(H48A,
 H48B), C3(H3A,H3B), C25(H25A,H25B), C13(H13A,H13B), C7(H7A,H7B), C31(H31A,
 H31B), C35(H35A,H35B), C9(H9A,H9B), C37(H37A,H37B), C19(H19A,H19B), C39(H39A,
 H39B), C5(H5A,H5B), C43(H43A,H43B), C45(H45A,H45B), C23(H23A,H23B), C47(H47A,
 H47B)
7.c Idealised Me refined as rotating group:
 N1(H1A,H1B,H1C), N4(H4A,H4B,H4C), N6(H6A,H6B,H6C), N3(H3C,H3D,H3E), C38(H38A,
 H38B,H38C), C27(H27A,H27B,H27C), C29(H29A,H29B,H29C), C15(H15A,H15B,H15C),
 N2(H2D,H2E,H2F), C2(H2A,H2B,H2C), C11(H11A,H11B,H11C), N5(H5C,H5D,H5E)
;
_shelx_res_checksum              35559
_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 4.629
_oxdiff_exptl_absorpt_empirical_full_min 0.247