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_7251890
_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
_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
_atom_sites_solution_secondary   difmap
_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                   15.1563(2)
_cell_length_b                   16.4024(2)
_cell_length_c                   27.3019(3)
_cell_measurement_reflns_used    46104
_cell_measurement_temperature    200.00(10)
_cell_measurement_theta_max      55.2750
_cell_measurement_theta_min      2.7190
_cell_volume                     6787.24(14)
_computing_cell_refinement       'CrysAlisPro 1.171.43.131a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.131a (Rigaku OD, 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 2025/1 (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     23.00 107.00   0.50    0.09    --   62.14-125.00 150.00  168
  2  \w     45.00  71.00   0.50    0.09    --   62.14 -77.00 120.00   52
  3  \w     23.00 109.00   0.50    0.09    --   62.14-125.00 -30.00  172
  4  \w     -4.00  92.00   0.50    0.09    --   62.14 -99.00 -30.00  192
  5  \w     -6.00  64.00   0.50    0.09    --   62.14 -77.00-150.00  140
  6  \w     44.00  78.00   0.50    0.09    --   62.14 -77.00-180.00   68
  7  \w     -4.00  25.00   0.50    0.09    --   62.14 -38.00-150.00   58
  8  \w     -6.00  20.00   0.50    0.09    --   62.14 -19.00-150.00   52
  9  \w     -8.00  41.00   0.50    0.09    --   62.14 -38.00-120.00   98
 10  \w    -13.00  20.00   0.50    0.09    --   62.14 -19.00 -60.00   66
 11  \w    -11.00  62.00   0.50    0.09    --   62.14 -57.00   0.00  146
 12  \w    -11.00  22.00   0.50    0.09    --   62.14 -77.00 120.00   66
 13  \w    -33.00  -6.00   0.50    0.09    --  -64.64  38.00-180.00   54
 14  \w    -62.00   7.00   0.50    0.09    --  -64.64  57.00-180.00  138
 15  \w    -95.00 -43.00   0.50    0.09    --  -64.64 125.00  30.00  104
 16  \w    -15.00  72.00   0.50    0.05    --   -1.25  57.00 -60.00  174
 17  \w     30.00  71.00   0.50    0.05    --   -1.25  57.00  30.00   82
 18  \w    -32.00   9.00   0.50    0.05    --   -1.25 -38.00 150.00   82
 19  \w    -60.00 -34.00   0.50    0.05    --   -1.25 -38.00 150.00   52
 20  \w   -137.00 -54.00   0.50    0.09    --  -64.64 -57.00  30.00  166
 21  \w   -130.00-105.00   0.50    0.09    --  -64.64 -99.00 -30.00   50
 22  \w   -120.00 -68.00   0.50    0.09    --  -64.64 -77.00   0.00  104
;
_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      -0.0185552000
_diffrn_orient_matrix_UB_12      -0.0266543000
_diffrn_orient_matrix_UB_13      0.0452188000
_diffrn_orient_matrix_UB_21      0.0120655000
_diffrn_orient_matrix_UB_22      -0.0770115000
_diffrn_orient_matrix_UB_23      -0.0148473000
_diffrn_orient_matrix_UB_31      0.0855209000
_diffrn_orient_matrix_UB_32      0.0050899000
_diffrn_orient_matrix_UB_33      0.0119021000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Ga K\a'
_diffrn_radiation_wavelength     1.3405
_diffrn_reflns_av_R_equivalents  0.0520
_diffrn_reflns_av_unetI/netI     0.0330
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            75276
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        53.543
_diffrn_reflns_theta_max         55.350
_diffrn_reflns_theta_min         2.732
_diffrn_source                   'micro-focus metaljet'
_exptl_absorpt_coefficient_mu    8.710
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.21945
_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            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.528
_exptl_crystal_description       block
_exptl_crystal_F_000             3136
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.262
_refine_diff_density_min         -1.231
_refine_diff_density_rms         0.129
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.049(18)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     973
_refine_ls_number_reflns         12935
_refine_ls_number_restraints     934
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0606
_refine_ls_R_factor_gt           0.0544
_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^)+(0.1000P)^2^+15.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1563
_refine_ls_wR_factor_ref         0.1613
_reflns_Friedel_coverage         0.812
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.976
_reflns_number_gt                11573
_reflns_number_total             12935
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6ce00120c2.cif
_cod_data_source_block           L-Sn4-Boc
_cod_depositor_comments
'Adding full bibliography for 7251889--7251892.cif.'
_cod_database_code               7251890
_shelx_shelxl_version_number     2025/1
_chemical_oxdiff_formula         'C H N O Sn Cl'
_shelx_estimated_absorpt_t_max   0.476
_shelx_estimated_absorpt_t_min   0.397
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.95062
 0.04938
2. Shared sites
{C43, C43A}
3. Restrained distances
 C40-C39 = C41-C40 = C42-C41 = C44-C43 = C45-C44 = C46-C45 = C48-C47 = C49-C48
 = C50-C49 = C52-C51 = C53-C52 = C54-C53
 1.54 with sigma of 0.01
 C25-C24 = C28-C25 = C26-C25 = C27-C25
 1.54 with sigma of 0.01
 C24-C23
 1.51 with sigma of 0.01
 C39-C41 = C42-C40 = C43-C45 = C46-C44 = C47-C49 = C48-C50 = C51-C53 = C54-C52
 2.515 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
C24 \\sim C25 \\sim C26 \\sim C27 \\sim C28 \\sim C25A \\sim C26A \\sim C27A
\\sim C28A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
C1 \\sim O3 \\sim N1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7
\\sim C8 \\sim C9 \\sim O3A \\sim N1A \\sim C2A \\sim C3A \\sim C4A \\sim C5A
\\sim C6A \\sim C7A \\sim C8A \\sim C9A: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
Sn4 \\sim C51 \\sim C52 \\sim C53 \\sim C54 \\sim C51A \\sim C52A \\sim C53A
\\sim C54A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
C47 \\sim C48 \\sim C49 \\sim C50 \\sim C48A \\sim C49A \\sim C50A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Sn2 \\sim C43 \\sim C44 \\sim C45 \\sim C46 \\sim C43A \\sim C44A \\sim C45A
\\sim C46A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
Sn1 \\sim C39 \\sim C40 \\sim C41 \\sim C42 \\sim C39A \\sim C40A \\sim C41A
\\sim C42A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
O4 \\sim O5 \\sim N2 \\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim
C15 \\sim C16 \\sim C17 \\sim C18 \\sim C19 \\sim O6 \\sim O7: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(C51) \\sim Ueq, Uanis(C52) \\sim Ueq, Uanis(C53) \\sim Ueq, Uanis(C54)
\\sim Ueq, Uanis(C51A) \\sim Ueq, Uanis(C52A) \\sim Ueq, Uanis(C53A) \\sim Ueq,
Uanis(C54A) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C43) = Uanis(C43A)
5. Same fragment restrains
{Sn1, C39A, C40A, C41A, C42A} sigma for 1-2: 0.01, 1-3: 0.01
as in
{Sn1, C39, C40, C41, C42}
{C47, C48A, C49A, C50A} sigma for 1-2: 0.01, 1-3: 0.01
as in
{C47, C48, C49, C50}
{O3A, N1A, C2A, C3A, C4A, C5A, C6A, C7A, C8A, C9A} sigma for 1-2: 0.01, 1-3:
0.01
as in
{O3, N1, C2, C3, C4, C5, C6, C7, C8, C9}
{Sn2, C43A, C44A, C45A, C46A} sigma for 1-2: 0.01, 1-3: 0.01
as in
{Sn2, C43, C44, C45, C46}
{Sn4, C51A, C52A, C53A, C54A} sigma for 1-2: 0.01, 1-3: 0.01
as in
{Sn4, C51, C52, C53, C54}
{C24, C25A, C26A, C27A, C28A} sigma for 1-2: 0.01, 1-3: 0.01
as in
{C24, C25, C26, C27, C28}
6. Others
 Sof(O3A)=Sof(N1A)=Sof(H1A)=Sof(C2A)=Sof(H2A)=Sof(C3A)=Sof(H3AA)=Sof(H3AB)=
 Sof(H3AC)=Sof(C4A)=Sof(C5A)=Sof(H5AA)=Sof(H5AB)=Sof(C6A)=Sof(C7A)=Sof(H7AA)=
 Sof(H7AB)=Sof(H7AC)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(H8AC)=Sof(C9A)=Sof(H9AA)=
 Sof(H9AB)=Sof(H9AC)=1-FVAR(1)
 Sof(O3)=Sof(N1)=Sof(H1)=Sof(C2)=Sof(H2)=Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(H3C)=
 Sof(C4)=Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(C6)=Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(H7C)=
 Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=FVAR(1)
 Sof(C39A)=Sof(H39C)=Sof(H39D)=Sof(C40A)=Sof(H40C)=Sof(H40D)=Sof(C41A)=
 Sof(H41C)=Sof(H41D)=Sof(C42A)=Sof(H42D)=Sof(H42E)=Sof(H42F)=1-FVAR(2)
 Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(C41)=Sof(H41A)=
 Sof(H41B)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(H42C)=FVAR(2)
 Sof(C43A)=Sof(H43C)=Sof(H43D)=Sof(C44A)=Sof(H44C)=Sof(H44D)=Sof(C45A)=
 Sof(H45C)=Sof(H45D)=Sof(C46A)=Sof(H46D)=Sof(H46E)=Sof(H46F)=1-FVAR(3)
 Sof(C43)=Sof(H43A)=Sof(H43B)=Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(C45)=Sof(H45A)=
 Sof(H45B)=Sof(C46)=Sof(H46A)=Sof(H46B)=Sof(H46C)=FVAR(3)
 Sof(H47C)=Sof(H47D)=Sof(C48A)=Sof(H48C)=Sof(H48D)=Sof(C49A)=Sof(H49C)=
 Sof(H49D)=Sof(C50A)=Sof(H50D)=Sof(H50E)=Sof(H50F)=1-FVAR(4)
 Sof(H47A)=Sof(H47B)=Sof(C48)=Sof(H48A)=Sof(H48B)=Sof(C49)=Sof(H49A)=Sof(H49B)=
 Sof(C50)=Sof(H50A)=Sof(H50B)=Sof(H50C)=FVAR(4)
 Sof(C51A)=Sof(H51C)=Sof(H51D)=Sof(C52A)=Sof(H52C)=Sof(H52D)=Sof(C53A)=
 Sof(H53C)=Sof(H53D)=Sof(C54A)=Sof(H54D)=Sof(H54E)=Sof(H54F)=1-FVAR(5)
 Sof(C51)=Sof(H51A)=Sof(H51B)=Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(C53)=Sof(H53A)=
 Sof(H53B)=Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(H54C)=FVAR(5)
 Sof(H24C)=Sof(H24D)=Sof(C25A)=Sof(C26A)=Sof(H26D)=Sof(H26E)=Sof(H26F)=
 Sof(C27A)=Sof(H27D)=Sof(H27E)=Sof(H27F)=Sof(C28A)=Sof(H28D)=Sof(H28E)=
 Sof(H28F)=1-FVAR(6)
 Sof(H24A)=Sof(H24B)=Sof(C25)=Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(H26C)=Sof(C27)=
 Sof(H27A)=Sof(H27B)=Sof(H27C)=Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)=FVAR(6)
7.a Riding coordinates:
 C42(H42A,H42B,H42C), C46(H46A,H46B,H46C), C28(H28A,H28B,H28C), C7(H7A,H7B,
 H7C), C9(H9A,H9B,H9C), C9A(H9AA,H9AB,H9AC), C27A(H27D,H27E,H27F), C28A(H28D,
 H28E,H28F), C42A(H42D,H42E,H42F), C46A(H46D,H46E,H46F), C50A(H50D,H50E,H50F),
 C54A(H54D,H54E,H54F)
7.b Ternary CH refined with riding coordinates:
 C18(H18), C21(H21), C37(H37), C2(H2), C2A(H2A)
7.c Secondary CH2 refined with riding coordinates:
 C39(H39A,H39B), C40(H40A,H40B), C41(H41A,H41B), C43(H43A,H43B), C44(H44A,
 H44B), C45(H45A,H45B), C51(H51A,H51B), C52(H52A,H52B), C53(H53A,H53B),
 C17(H17A,H17B), C19(H19A,H19B), C24(H24A,H24B), C24(H24C,H24D), C36(H36A,H36B),
  C38(H38A,H38B), C47(H47A,H47B), C47(H47C,H47D), C48(H48A,H48B), C49(H49A,
 H49B), C5(H5A,H5B), C5A(H5AA,H5AB), C39A(H39C,H39D), C40A(H40C,H40D),
 C41A(H41C,H41D), C43A(H43C,H43D), C44A(H44C,H44D), C45A(H45C,H45D), C48A(H48C,
 H48D), C49A(H49C,H49D), C51A(H51C,H51D), C52A(H52C,H52D), C53A(H53C,H53D)
7.d Aromatic/amide H refined with riding coordinates:
 N3(H3), C13(H13), C14(H14), C15(H15), C16(H16), C32(H32), C33(H33), C34(H34),
 C35(H35), N1(H1), N1A(H1A)
7.e Idealised Me refined as rotating group:
 C54(H54A,H54B,H54C), C22(H22A,H22B,H22C), C26(H26A,H26B,H26C), C27(H27A,H27B,
 H27C), C50(H50A,H50B,H50C), C3(H3A,H3B,H3C), C8(H8A,H8B,H8C), C3A(H3AA,H3AB,
 H3AC), C7A(H7AA,H7AB,H7AC), C8A(H8AA,H8AB,H8AC), C26A(H26D,H26E,H26F)
;
_shelx_res_checksum              9496
_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 2.671
_oxdiff_exptl_absorpt_empirical_full_min 0.522