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_7251891
_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 syn
_chemical_formula_moiety         'C58 H77.969 Cl2 N4 O16 Sn4'
_chemical_formula_sum            'C58 H77.97 Cl2 N4 O16 Sn4'
_chemical_formula_weight         1632.86
_chemical_name_systematic        Sn4-Cbz
_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                   15.0434(2)
_cell_length_b                   15.2331(3)
_cell_length_c                   29.7454(7)
_cell_measurement_reflns_used    29204
_cell_measurement_temperature    99.99(14)
_cell_measurement_theta_max      54.7840
_cell_measurement_theta_min      2.8200
_cell_volume                     6816.4(2)
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.99(14)
_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 0.992
_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    -97.00 -47.00   0.50    0.19    --  -70.72  77.00 -30.00  100
  2  \w    -95.00   5.00   0.50    0.19    --  -70.72  77.00  30.00  200
  3  \w    -65.00   5.00   0.50    0.19    --  -70.72  57.00  30.00  140
  4  \w    -15.00  10.00   0.50    0.19    --  -70.72  19.00 -30.00   50
  5  \w    -26.00  80.00   0.50    0.05    --   -1.17  19.00-150.00  212
  6  \w    -11.00  69.00   0.50    0.05    --   -1.17  57.00 -90.00  160
  7  \w    -97.00 -41.00   0.50    0.19    --  -70.72 125.00  30.00  112
  8  \w   -107.00 -39.00   0.50    0.19    --  -70.72 -38.00-150.00  136
  9  \w   -152.00-125.00   0.50    0.19    --  -70.72 -38.00-150.00   54
 10  \w   -145.00 -54.00   0.50    0.19    --  -70.72 -57.00-180.00  182
 11  \w     -2.00  25.00   0.50    0.05    --   -1.17 -99.00-180.00   54
 12  \w     87.00 118.00   0.50    0.19    --   68.38 125.00-150.00   62
 13  \w     20.00 112.00   0.50    0.19    --   68.38-125.00 150.00  184
 14  \w     12.00 105.00   0.50    0.19    --   68.38 -99.00 150.00  186
 15  \w     -6.00  23.00   0.50    0.05    --   -1.17 -99.00 120.00   58
 16  \w     14.00  65.00   0.50    0.19    --   68.38 -57.00 150.00  102
 17  \w     34.00 142.00   0.50    0.19    --   68.38  77.00 -60.00  216
 18  \w     -7.00  62.00   0.50    0.19    --   68.38 -57.00-150.00  138
 19  \w    -10.00  37.00   0.50    0.19    --   68.38 -38.00 -90.00   94
 20  \w   -132.00 -82.00   0.50    0.19    --  -70.72-125.00 -60.00  100
;
_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      0.0861137000
_diffrn_orient_matrix_UB_12      0.0116077000
_diffrn_orient_matrix_UB_13      -0.0097838000
_diffrn_orient_matrix_UB_21      0.0175999000
_diffrn_orient_matrix_UB_22      0.0126382000
_diffrn_orient_matrix_UB_23      0.0436584000
_diffrn_orient_matrix_UB_31      0.0141573000
_diffrn_orient_matrix_UB_32      -0.0862105000
_diffrn_orient_matrix_UB_33      0.0050564000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.3405
_diffrn_reflns_av_R_equivalents  0.0633
_diffrn_reflns_av_unetI/netI     0.0371
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            67027
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        53.543
_diffrn_reflns_theta_max         54.964
_diffrn_reflns_theta_min         2.583
_diffrn_source                   'micro-focus metaljet'
_exptl_absorpt_coefficient_mu    8.759
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.20631
_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    1.591
_exptl_crystal_description       block
_exptl_crystal_F_000             3264
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.2
_refine_diff_density_max         2.161
_refine_diff_density_min         -1.455
_refine_diff_density_rms         0.140
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.14(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.019
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     835
_refine_ls_number_reflns         12843
_refine_ls_number_restraints     712
_refine_ls_restrained_S_all      1.011
_refine_ls_R_factor_all          0.1069
_refine_ls_R_factor_gt           0.0865
_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^)+(0.0945P)^2^+54.8856P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2197
_refine_ls_wR_factor_ref         0.2353
_reflns_Friedel_coverage         0.809
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.979
_reflns_number_gt                9951
_reflns_number_total             12843
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6ce00120c2.cif
_cod_data_source_block           D-Sn4-Cbz
_cod_depositor_comments
'Adding full bibliography for 7251889--7251892.cif.'
_cod_database_code               7251891
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'c h n o Cl Sn'
_diffrn_oxdiff_ac3_digest_hkl    41c8613027336e53a470b10f042745e41212bb
_diffrn_oxdiff_digest_hkl
;
01e4460a94e892571391bb52710aa85534d4ea
;
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.86397
 0.13603
2. Restrained distances
 C49-C50 = C49-C48
 1.54 with sigma of 0.01
 C67-C66 = C59-C60
 1.54 with sigma of 0.02
 C59-C61
 2.4 with sigma of 0.02
 C22-C23 = C21-C22 = C21-C20
 1.54 with sigma of 0.02
 C65-C59
 2.4 with sigma of 0.02
 C54-C53 = C52-C53
 1.54 with sigma of 0.02
 C61-C59
 2.4 with sigma of 0.02
 C23-C21
 2.5 with sigma of 0.02
 O16-C60
 2.4 with sigma of 0.02
 C54-C52
 2.5 with sigma of 0.02
 C60-O16
 2.4 with sigma of 0.02
 C52-C48
 1.54 with sigma of 0.01
 C37_$1-C62
 2.6 with sigma of 0.01
 C59-C60
 1.54 with sigma of 0.02
 O17-C67
 2.4 with sigma of 0.02
 C67-O17
 2.4 with sigma of 0.02
 C18-C19 = C17-C18 = C17-C16
 1.54 with sigma of 0.02
 O17-C66 = O16-C59
 1.48 with sigma of 0.02
 C59-C58
 2.4 with sigma of 0.02
 C17-C19
 2.5 with sigma of 0.02
 C3-C2 = C56-C57
 1.54 with sigma of 0.01
 C51-C49
 2.5 with sigma of 0.02
 C35-C34 = C36-C35
 1.54 with sigma of 0.01
 C13-C12 = C14-C13 = C15-C14
 1.54 with sigma of 0.01
 Sn1-C48 = Sn2-C34 = Sn3-C12
 2.1 with sigma of 0.02
 C53-C48
 2.5 with sigma of 0.02
 C66-C58
 2.4 with sigma of 0.02
 O16-N3
 2.4 with sigma of 0.02
 C46-C45
 1.54 with sigma of 0.02
 C37-C36 = C36-C35 = C35-C34
 1.54 with sigma of 0.02
 C37-C35
 2.52 with sigma of 0.02
 C36-C34
 2.52 with sigma of 0.02
 O2-C4
 1.2 with sigma of 0.02
 Sn4-C20
 2.1 with sigma of 0.02
 C20-C22
 2.5 with sigma of 0.02
 Sn4-C16
 2.1 with sigma of 0.02
 C18-C16
 2.5 with sigma of 0.02
 C55-C56
 1.54 with sigma of 0.01
 C26-C25 = C25-C24
 1.54 with sigma of 0.01
 C47-C46
 1.54 with sigma of 0.01
 C28-C27
 1.54 with sigma of 0.01
 C22-C21
 1.54 with sigma of 0.01
 C2-C1
 1.54 with sigma of 0.01
 C6-C5
 1.54 with sigma of 0.01
 C51-C50
 1.54 with sigma of 0.01
 C44-C40
 1.54 with sigma of 0.01
 C67-C66
 1.54 with sigma of 0.02
 C37-C36
 1.54 with sigma of 0.02
 C50-C48
 2.52 with sigma of 0.01
 C34-C36
 2.52 with sigma of 0.01
 C12-C14
 2.52 with sigma of 0.01
 C13-C15
 2.52 with sigma of 0.01
 C53-Cl1_$2
 2.6 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
C49 \\sim C52 \\sim C50 \\sim C53 \\sim C54 \\sim C51: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(C59) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C49) \\sim Ueq, Uanis(C5) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C50) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Sof(H48C)=Sof(H48D)=Sof(C54)=Sof(H54B)=Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(C52)=
 Sof(H52A)=Sof(H52B)=1-FVAR(1)
 Sof(H48A)=Sof(H48B)=Sof(C49)=Sof(H49A)=Sof(H49B)=Sof(C50)=Sof(H50A)=Sof(H50B)=
 Sof(C51)=Sof(H51A)=Sof(H51B)=Sof(H51C)=FVAR(1)
 Sof(C66)=Sof(H66A)=Sof(H66B)=Sof(O17)=Sof(C68)=Sof(H68)=Sof(C67)=Sof(C72)=
 Sof(H72)=Sof(C71)=Sof(H71)=Sof(C70)=Sof(H70)=Sof(C69)=Sof(H69)=1-FVAR(2)
 Sof(O16)=Sof(C59)=Sof(H59A)=Sof(H59B)=Sof(C65)=Sof(H65)=Sof(C60)=Sof(C61)=
 Sof(H15)=Sof(C62)=Sof(H62)=Sof(C63)=Sof(H63)=Sof(C64)=Sof(H64)=FVAR(2)
 Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(H19C)=Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(C17)=
 Sof(H17A)=Sof(H17B)=Sof(C16)=Sof(H16A)=Sof(H16B)=1-FVAR(3)
 Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(C22)=Sof(H22A)=
 Sof(H22B)=Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=FVAR(3)
 Fixed Sof: H54A(0.2537)
 Fixed X: C23(0.783463)
 Fixed Y: C59(0.366112) C54(0.447621)
 Fixed Z: C52(0.840368)
5.a Riding coordinates:
 C57(H57A,H57B,H57C), C51(H51A,H51B,H51C), C54(H54A,H54B), C23(H23A,H23B,H23C),
  C19(H19A,H19B,H19C)
5.b Ternary CH refined with riding coordinates:
 C25(H25), C46(H46), C2(H2), C56(H56)
5.c Secondary CH2 refined with riding coordinates:
 C45(H45A,H45B), C34(H34A,H34B), C24(H24A,H24B), C12(H12A,H12B), C35(H35A,
 H35B), C48(H48A,H48B), C48(H48C,H48D), C36(H36A,H36B), C5(H5A,H5B), C47(H47A,
 H47B), C26(H26A,H26B), C59(H59A,H59B), C13(H13A,H13B), C14(H14A,H14B),
 C49(H49A,H49B), C50(H50A,H50B), C53(H53A,H53B), C52(H52A,H52B), C66(H66A,H66B),
  C20(H20A,H20B), C21(H21A,H21B), C22(H22A,H22B), C18(H18A,H18B), C17(H17A,
 H17B), C16(H16A,H16B)
5.d Aromatic/amide H refined with riding coordinates:
 C44(H44), N3(H3), N4(H4), C41(H41), C42(H42), C43(H43), C29(H29), C30(H30),
 C31(H31), C27(H27), C7(H7), C11(H11), C10(H10), C9(H9), C8(H8), C65(H65),
 C61(H15), C62(H62), C63(H63), C64(H64), C68(H68), C72(H72), C71(H71), C70(H70),
  C69(H69)
5.e Fitted hexagon refined as free rotating group:
 C41(C42,C43,C38,C39,C40), C33(C28,C29,C30,C31,C32), C7(C6,C11,C10,C9,C8),
 C65(C60,C61,C62,C63,C64), C68(C67,C72,C71,C70,C69)
5.f Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C15(H15A,H15B,H15C), C37(H37A,H37B,H37C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              87628
_shelx_fab_checksum              30774
_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 2.890
_oxdiff_exptl_absorpt_empirical_full_min 0.556