Ligand Modification on Organotin-Oxo Clusters for Enhanced Third-Order Nonlinear Optical Response
Liu, Yang-Hong; Li, Hao; Lou, Hui-Ru; Chen, Er-Xia; Yang, Jin-Xia; Lin, Qipu; CrystEngComm  (2026) –; doi:10.1039/D6CE00120C

data_7251889
_publ_section_title
;
 Ligand modification on organotin-oxo clusters for enhanced third-order
 nonlinear optical response
;
_journal_issue                   21
_journal_name_full               CrystEngComm
_journal_page_first              3298
_journal_page_last               3304
_journal_paper_doi               10.1039/D6CE00120C
_journal_volume                  28
_journal_year                    2026
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C54 H86 Cl2 N4 O14 Sn4'
_chemical_formula_sum            'C54 H86 Cl2 N4 O14 Sn4'
_chemical_formula_weight         1560.92
_chemical_name_systematic        Sn4-boc
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2026-01-14
_audit_creation_method
;
Olex2 1.5
(compiled 2025.03.04 svn.red2d20d0 for OlexSys, GUI svn.r7188)
;
_audit_update_record
;
2026-01-14 deposited with the CCDC.	2026-04-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.1734(2)
_cell_length_b                   16.3910(2)
_cell_length_c                   27.2785(4)
_cell_measurement_reflns_used    49677
_cell_measurement_temperature    200.00(10)
_cell_measurement_theta_max      55.2510
_cell_measurement_theta_min      2.7230
_cell_volume                     6784.36(16)
_computing_cell_refinement       'CrysAlisPro 1.171.43.131a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.131a 64-bit (release 19-07-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.131a (Rigaku OD, 2024)'
_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 2014/5 (Sheldrick, 2014)'
_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 1.000
_diffrn_measured_fraction_theta_max 0.989
_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   -106.00 -20.00   0.50    0.05    --  -64.64 125.00-150.00  172
  2  \w    -13.00  13.00   0.50    0.05    --   -1.25  57.00 -30.00   52
  3  \w     25.00  69.00   0.50    0.05    --   -1.25  57.00 -30.00   88
  4  \w     -7.00  47.00   0.50    0.05    --   -1.25  19.00 -60.00  108
  5  \w    -51.00 -22.00   0.50    0.05    --  -64.64 125.00  60.00   58
  6  \w    -98.00 -32.00   0.50    0.05    --  -64.64 125.00  30.00  132
  7  \w   -100.00 -62.00   0.50    0.05    --  -64.64 125.00  60.00   76
  8  \w    -38.00   1.00   0.50    0.05    --  -64.64  57.00  30.00   78
  9  \w    -66.00  -4.00   0.50    0.05    --  -64.64  57.00  60.00  124
 10  \w    -55.00  -9.00   0.50    0.05    --  -64.64  57.00   0.00   92
 11  \w    -38.00   9.00   0.50    0.05    --  -64.64  38.00 120.00   94
 12  \w    -35.00   2.00   0.50    0.05    --  -64.64  57.00 -30.00   74
 13  \w    -26.00  11.00   0.50    0.05    --  -64.64  19.00 -30.00   74
 14  \w    -30.00   8.00   0.50    0.05    --  -64.64  38.00 -90.00   76
 15  \w    -14.00  11.00   0.50    0.05    --  -64.64  19.00-120.00   50
 16  \w    -17.00  10.00   0.50    0.05    --  -64.64  19.00-150.00   54
 17  \w    -56.00 -12.00   0.50    0.05    --  -64.64  57.00-180.00   88
 18  \w    -66.00   0.00   0.50    0.05    --  -64.64  57.00-150.00  132
 19  \w    -22.00   6.00   0.50    0.05    --   -1.25 -19.00 120.00   56
 20  \w    -77.00 -33.00   0.50    0.05    --   -1.25 -19.00 120.00   88
 21  \w     21.00  47.00   0.50    0.05    --   62.14-125.00   0.00   52
 22  \w     81.00 107.00   0.50    0.05    --   62.14-125.00   0.00   52
 23  \w     21.00  95.00   0.50    0.05    --   62.14 -99.00 -60.00  148
 24  \w     46.00 134.00   0.50    0.05    --   62.14  57.00-120.00  176
 25  \w     49.00 113.00   0.50    0.05    --   62.14  38.00-180.00  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      -0.0416796000
_diffrn_orient_matrix_UB_12      0.0109266000
_diffrn_orient_matrix_UB_13      0.0427635000
_diffrn_orient_matrix_UB_21      0.0455821000
_diffrn_orient_matrix_UB_22      0.0688762000
_diffrn_orient_matrix_UB_23      0.0073697000
_diffrn_orient_matrix_UB_31      -0.0630900000
_diffrn_orient_matrix_UB_32      0.0425491000
_diffrn_orient_matrix_UB_33      -0.0229371000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.3405
_diffrn_reflns_av_R_equivalents  0.0546
_diffrn_reflns_av_unetI/netI     0.0322
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            77159
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        53.543
_diffrn_reflns_theta_max         55.406
_diffrn_reflns_theta_min         2.734
_diffrn_source                   'micro-focus metaljet'
_exptl_absorpt_coefficient_mu    8.713
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.30572
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.131a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'light yellow'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.528
_exptl_crystal_description       block
_exptl_crystal_F_000             3136
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.2
_refine_diff_density_max         1.125
_refine_diff_density_min         -1.129
_refine_diff_density_rms         0.118
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.042(17)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.081
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     915
_refine_ls_number_reflns         12977
_refine_ls_number_restraints     689
_refine_ls_restrained_S_all      1.080
_refine_ls_R_factor_all          0.0554
_refine_ls_R_factor_gt           0.0503
_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^)+(0.0675P)^2^+21.1798P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1365
_refine_ls_wR_factor_ref         0.1401
_reflns_Friedel_coverage         0.813
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.978
_reflns_number_gt                11835
_reflns_number_total             12977
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6ce00120c2.cif
_cod_data_source_block           D-Sn4-Boc
_cod_depositor_comments
'Adding full bibliography for 7251889--7251892.cif.'
_cod_database_code               7251889
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C N O H Sn Cl'
_shelx_estimated_absorpt_t_max   0.275
_shelx_estimated_absorpt_t_min   0.128
_diffrn_oxdiff_digest_hkl
;
01d399d6f9d3f204f1f2cf29a06febabf63652
;
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.95827
 0.04173
2. Restrained distances
 C46-C45
 1.54 with sigma of 0.01
 C26-C25 = C24-C25 = C27-C26 = C28-C27 = C23-C24 = C22-C23
 1.54 with sigma of 0.02
 O1-C39
 1.24 with sigma of 0.01
 O1-C39 = O2-C40
 1.23 with sigma of 0.02
 C40-C38 = C39-C38
 1.54 with sigma of 0.02
 N1-C39 = N1-C40
 1.47 with sigma of 0.02
 C24-C22
 2.5 with sigma of 0.02
 C18-C19 = C20-C19 = C20-C21
 1.54 with sigma of 0.01
 C38-C40 = C39-C38
 1.54 with sigma of 0.02
 C43-C41 = C42-C41
 1.54 with sigma of 0.02
 C18-C20
 2.5 with sigma of 0.01
 C35-C33
 2.5 with sigma of 0.02
 C37-C33
 2.5 with sigma of 0.02
 C46-C45 = C44-C45 = C50-C49 = C48-C49
 1.54 with sigma of 0.02
 C38-C31 = C38-C34 = C34-C33 = C34-C37
 1.54 with sigma of 0.02
 C6-C4 = C3-C4 = C8-C4 = C2-C7 = C2-C5 = C2-C1
 1.54 with sigma of 0.01
 C44-C46
 2.5 with sigma of 0.02
 C6-C3
 2.5 with sigma of 0.01
 C6-C8
 2.5 with sigma of 0.01
 C8-C3
 2.5 with sigma of 0.01
 C48-C50
 2.5 with sigma of 0.02
 C51-C52 = C53-C52 = C57-C56 = C56-C55
 1.54 with sigma of 0.02
 C7-C1
 2.5 with sigma of 0.01
 C5-C1
 2.5 with sigma of 0.01
 C51-C53
 2.5 with sigma of 0.02
 C47-C48 = C47-C46
 1.54 with sigma of 0.02
 Sn4-C47
 2.1 with sigma of 0.02
 C47-C49
 2.5 with sigma of 0.02
 C36-C31 = C32-C31 = C31-C30
 1.54 with sigma of 0.02
 C47-C45
 2.5 with sigma of 0.02
 C36-C32
 2.5 with sigma of 0.02
 C32-C30
 2.5 with sigma of 0.02
 C23-C32
 2.8 with sigma of 0.01
 C25-C23
 2.5 with sigma of 0.02
 C14-C15 = C16-C15 = C16-C17
 1.54 with sigma of 0.01
 C26-C25 = C55-C54 = C56-C55 = C57-C56
 1.54 with sigma of 0.01
 C57-C56
 1.54 with sigma of 0.01
 C52-C54
 2.5 with sigma of 0.02
 C14-C16
 2.5 with sigma of 0.01
 C55-C57
 2.5 with sigma of 0.02
 C56-C54
 2.5 with sigma of 0.02
 C25-C27
 2.5 with sigma of 0.02
 C26-C28
 2.5 with sigma of 0.02
 C35-C34
 1.54 with sigma of 0.01
 C19-C21
 2.5 with sigma of 0.01
 C15-C17
 2.5 with sigma of 0.01
 C5-C7
 2.5 with sigma of 0.01
 C36-C30
 2.5 with sigma of 0.02
 C37-C35
 2.5 with sigma of 0.02
 O2-N1
 2.4 with sigma of 0.02
 O1-N1
 2.4 with sigma of 0.02
 C38-O2
 2.4 with sigma of 0.02
 O1-C38
 2.4 with sigma of 0.02
 C10-C9
 1.54 with sigma of 0.02
 C9-C2 = C9-C4
 1.54 with sigma of 0.02
 C53-C54
 1.54 with sigma of 0.02
 C42-C41
 1.54 with sigma of 0.02
 C28-C27
 1.54 with sigma of 0.02
 C25-C24
 1.54 with sigma of 0.02
 C76-C75 = C77-C76
 1.54 with sigma of 0.02
 C67-C66 = C66-C65
 1.54 with sigma of 0.02
 C64-C60
 1.54 with sigma of 0.02
 C74-C72
 1.54 with sigma of 0.02
 O1_$1-N4_$2
 3.2 with sigma of 0.01
 C35-C33
 2.52 with sigma of 0.01
 C16-C14
 2.52 with sigma of 0.01
 C17-C15
 2.52 with sigma of 0.01
3. Rigid bond restraints
 C38, C39
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C27, C28
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C2, C9
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
4. Uiso/Uaniso restraints and constraints
C25 \\sim C26 \\sim C24 \\sim C23 \\sim C22 \\sim C28 \\sim C27: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C37 \\sim C32 \\sim C31 \\sim C34 \\sim C36 \\sim C35 \\sim C33 \\sim C30:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
O1 \\sim O2 \\sim C39 \\sim C40: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
C18 \\sim C14 \\sim C19 \\sim C15 \\sim C16 \\sim C20 \\sim C21 \\sim C17:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C42 \\sim N4 \\sim C43: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C44 \\sim C50 \\sim C49 \\sim C45 \\sim C48 \\sim C46 \\sim C47: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C5 \\sim C6 \\sim C4 \\sim C8 \\sim C7 \\sim C2 \\sim C3 \\sim C1: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C57 \\sim C51 \\sim C52 \\sim C56 \\sim C55 \\sim C53: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(C37) \\sim Ueq, Uanis(C34) \\sim Ueq, Uanis(C39) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C17) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C20)
\\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C18) \\sim Ueq,
Uanis(C14) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C44) \\sim Ueq, Uanis(C50) \\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(C49)
\\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(C46) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
5. Others
 Sof(H19C)=Sof(H19D)=Sof(C24)=Sof(H18A)=Sof(H18B)=Sof(C23)=Sof(H17A)=Sof(H17B)=
 Sof(C22)=Sof(H16A)=Sof(H16B)=Sof(H16C)=1-FVAR(1)
 Sof(H19A)=Sof(H19B)=Sof(C26)=Sof(H20A)=Sof(H20B)=Sof(C27)=Sof(H21A)=Sof(H21B)=
 Sof(C28)=Sof(H22A)=Sof(H22B)=Sof(H22C)=FVAR(1)
 Sof(C48)=Sof(H34A)=Sof(H34B)=Sof(C49)=Sof(H33A)=Sof(H33B)=Sof(C50)=Sof(H32A)=
 Sof(H32B)=Sof(H32C)=Sof(HNTC)=Sof(HNTD)=1-FVAR(2)
 Sof(C45)=Sof(H37A)=Sof(H37B)=Sof(C46)=Sof(H38A)=Sof(H38B)=Sof(C44)=Sof(H36A)=
 Sof(H36B)=Sof(H36C)=Sof(HNTA)=Sof(HNTB)=FVAR(2)
 Sof(C19)=Sof(H28A)=Sof(H28B)=Sof(C18)=Sof(H27A)=Sof(H27B)=Sof(H27C)=Sof(C20)=
 Sof(H29A)=Sof(H29B)=Sof(C21)=Sof(H30A)=Sof(H30B)=1-FVAR(3)
 Sof(C17)=Sof(H31A)=Sof(H31B)=Sof(C15)=Sof(H24A)=Sof(H24B)=Sof(C16)=Sof(H25A)=
 Sof(H25B)=Sof(C14)=Sof(H23A)=Sof(H23B)=Sof(H23C)=FVAR(3)
 Sof(H75C)=Sof(H75D)=Sof(C51)=Sof(H78A)=Sof(H78B)=Sof(H78C)=Sof(C52)=Sof(H77A)=
 Sof(H77B)=Sof(C53)=Sof(H29)=Sof(H76B)=1-FVAR(4)
 Sof(H75A)=Sof(H75B)=Sof(C55)=Sof(H74A)=Sof(H74B)=Sof(C56)=Sof(H73A)=Sof(H73B)=
 Sof(C57)=Sof(H72A)=Sof(H72B)=Sof(H72C)=FVAR(4)
 Sof(H48C)=Sof(H48D)=Sof(C5)=Sof(H45A)=Sof(H45B)=Sof(H45C)=Sof(C7)=Sof(H46A)=
 Sof(H46B)=Sof(H46C)=Sof(C2)=Sof(C1)=Sof(H42A)=Sof(H42B)=Sof(H42C)=1-FVAR(5)
 Sof(H48A)=Sof(H48B)=Sof(C4)=Sof(C8)=Sof(H47A)=Sof(H47B)=Sof(H47C)=Sof(C3)=
 Sof(H40A)=Sof(H40B)=Sof(H40C)=Sof(C6)=Sof(H44A)=Sof(H44B)=Sof(H44C)=FVAR(5)
 Sof(H8BC)=Sof(H8BD)=Sof(C36)=Sof(H4A)=Sof(H4B)=Sof(H4C)=Sof(C32)=Sof(H7A)=
 Sof(H7B)=Sof(H7C)=Sof(C31)=Sof(C30)=Sof(H6A)=Sof(H6B)=Sof(H6C)=1-FVAR(6)
 Sof(H8AA)=Sof(H8AB)=Sof(C33)=Sof(H1C)=Sof(H1D)=Sof(H1E)=Sof(C34)=Sof(C35)=
 Sof(H3A)=Sof(H3B)=Sof(H3C)=Sof(C37)=Sof(H11A)=Sof(H11B)=Sof(H11C)=FVAR(6)
 Sof(H1B)=Sof(C40)=Sof(O2)=1-FVAR(7)
 Sof(H1A)=Sof(O1)=Sof(C39)=FVAR(7)
 Sof(H13A)=Sof(C43)=Sof(H12A)=Sof(H12B)=Sof(H12C)=1-FVAR(8)
 Sof(H13)=Sof(C42)=Sof(H14A)=Sof(H14B)=Sof(H14C)=FVAR(8)
 Fixed X: C39(0.678885)
 Fixed Y: C39(0.356313) C22(0.687545)
 Fixed Z: C51(0.373096)
6.a Riding coordinates:
 C3(H40A,H40B,H40C), C6(H44A,H44B,H44C), C33(H1C,H1D,H1E), C22(H16A,H16B,H16C),
  C44(H36A,H36B,H36C), C50(H32A,H32B,H32C), C18(H27A,H27B,H27C), C43(H12A,H12B,
 H12C)
6.b Ternary CH refined with riding coordinates:
 C76(H61), C66(H70), C11(H51), C41(H13), C41(H13A)
6.c Secondary CH2 refined with riding coordinates:
 C54(H75A,H75B), C54(H75C,H75D), C77(H62A,H62B), C25(H19A,H19B), C25(H19C,
 H19D), C67(H71A,H71B), C75(H60A,H60B), C38(H8AA,H8AB), C38(H8BC,H8BD), C9(H48A,
 H48B), C9(H48C,H48D), C65(H69A,H69B), C55(H74A,H74B), C17(H31A,H31B), C15(H24A,
 H24B), C56(H73A,H73B), C16(H25A,H25B), C45(H37A,H37B), C26(H20A,H20B),
 C46(H38A,H38B), C27(H21A,H21B), C24(H18A,H18B), C23(H17A,H17B), C48(H34A,H34B),
  C49(H33A,H33B), C19(H28A,H28B), C20(H29A,H29B), C21(H30A,H30B), C52(H77A,
 H77B), C53(H29,H76B), C47(HNTA,HNTB), C47(HNTC,HNTD)
6.d Aromatic/amide H refined with riding coordinates:
 N4(H4), C74(H59), C64(H68), N1(H1A), N1(H1B), C69(H53), C71(H58), C70(H57),
 C59(H66), C58(H65), C61(H64)
6.e Fitted hexagon refined as free rotating group:
 C69(C68,C73,C72,C71,C70), C59(C58,C61,C62,C63,C60)
6.f Idealised Me refined as rotating group:
 C12(H50A,H50B,H50C), C8(H47A,H47B,H47C), C35(H3A,H3B,H3C), C37(H11A,H11B,
 H11C), C57(H72A,H72B,H72C), C28(H22A,H22B,H22C), C14(H23A,H23B,H23C), C51(H78A,
 H78B,H78C), C5(H45A,H45B,H45C), C7(H46A,H46B,H46C), C1(H42A,H42B,H42C),
 C36(H4A,H4B,H4C), C32(H7A,H7B,H7C), C30(H6A,H6B,H6C), C42(H14A,H14B,H14C)
;
_shelx_res_checksum              511
_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 2.683
_oxdiff_exptl_absorpt_empirical_full_min 0.642