A chloride-doped Cu<sub>18</sub> nanocluster: synthesis, bonding and nonlinear optical properties.
Gong, Xuekun; Zheng, Chan; Zuo, Dongjie; Li, Simin; Fang, Wei-Hui; Shen, Hui; Dalton transactions (Cambridge, England : 2003) 54 (2025) 9368–9375; doi:10.1039/d5dt00851d

data_7718659
_publ_section_title
;
 A chloride-doped Cu<sub>18</sub> nanocluster: synthesis, bonding and
 nonlinear optical properties.
;
_journal_issue                   23
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              9368
_journal_page_last               9375
_journal_paper_doi               10.1039/d5dt00851d
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety         'C200 H204 Cl Cu18 P4 S16, 2(C H2 Cl2)'
_chemical_formula_sum            'C202 H208 Cl5 Cu18 P4 S16'
_chemical_formula_weight         4593.48
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-04-09
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2025-04-09 deposited with the CCDC.	2025-05-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.0930(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   27.4052(3)
_cell_length_b                   27.2127(4)
_cell_length_c                   27.7815(4)
_cell_measurement_reflns_used    29690
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      76.2410
_cell_measurement_theta_min      2.7560
_cell_volume                     20704.8(5)
_computing_cell_refinement       'CrysAlisPro 1.171.43.137a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.137a 64-bit (release 10-09-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.137a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.953
_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   -102.00 -30.00   0.50    0.20    -- -103.00  77.00 150.00  144
  2  \w    -63.00 -30.00   0.50    0.20    -- -103.00  57.00  90.00   66
  3  \w    -63.00 -30.00   0.50    0.20    -- -103.00  57.00  60.00   66
  4  \w    -63.00 -30.00   0.50    0.20    -- -103.00  57.00   0.00   66
  5  \w    -63.00 -30.00   0.50    0.20    -- -103.00  57.00-120.00   66
  6  \w    -23.00  28.00   0.50    0.10    --  -47.62  19.00 -90.00  102
  7  \w    -23.00  28.00   0.50    0.10    --  -47.62  19.00 150.00  102
  8  \w    -23.00  28.00   0.50    0.10    --  -47.62  19.00 -60.00  102
  9  \w    -23.00  28.00   0.50    0.10    --  -47.62  19.00-120.00  102
 10  \w     39.00  93.00   0.50    0.20    --  108.06-125.00-120.00  108
 11  \w     39.00 102.00   0.50    0.20    --  108.06 -99.00 -60.00  126
 12  \w     38.00 106.00   0.50    0.20    --  108.06-100.00  40.00  136
 13  \w    -16.00  81.00   0.50    0.10    --   47.62-100.00  40.00  194
 14  \w     37.00  69.00   0.50    0.20    --  108.06 -57.00 -90.00   64
 15  \w     36.00  61.00   0.50    0.20    --  108.06 -57.00-150.00   50
 16  \w     43.00  69.00   0.50    0.20    --  108.06 -57.00-180.00   52
 17  \w     40.00  67.00   0.50    0.20    --  108.06 -57.00-120.00   54
 18  \w     43.00  68.00   0.50    0.20    --  108.06 -57.00  30.00   50
 19  \w     37.00  63.00   0.50    0.20    --  108.06 -57.00  60.00   52
 20  \w    131.00 178.00   0.50    0.20    --  108.06  77.00  90.00   94
 21  \w    -80.00  22.00   0.50    0.10    --  -47.62 100.00 145.00  204
 22  \w    -80.00  22.00   0.50    0.10    --  -47.62 100.00 145.00  204
 23  \w   -106.00 -32.00   0.50    0.20    -- -103.00 100.00 145.00  148
 24  \w     91.00 129.00   0.50    0.20    --  108.06  77.00  90.00   76
 25  \w    111.00 136.00   0.50    0.20    --  108.06 100.00 145.00   50
 26  \w   -174.00 -90.00   0.50    0.20    -- -103.00 -19.00 -60.00  168
 27  \w   -174.00 -90.00   0.50    0.20    -- -103.00 -19.00 -60.00  168
 28  \w   -174.00 -85.00   0.50    0.20    -- -103.00-100.00  40.00  178
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0499623000
_diffrn_orient_matrix_UB_12      0.0031105000
_diffrn_orient_matrix_UB_13      0.0235611000
_diffrn_orient_matrix_UB_21      0.0053888000
_diffrn_orient_matrix_UB_22      -0.0537133000
_diffrn_orient_matrix_UB_23      0.0168988000
_diffrn_orient_matrix_UB_31      0.0253087000
_diffrn_orient_matrix_UB_32      0.0176444000
_diffrn_orient_matrix_UB_33      0.0472808000
_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  0.0692
_diffrn_reflns_av_unetI/netI     0.0508
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.953
_diffrn_reflns_limit_h_max       34
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       34
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            99385
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.953
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.735
_diffrn_reflns_theta_min         2.289
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.694
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.42093
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.137a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.474
_exptl_crystal_description       block
_exptl_crystal_F_000             9372
_refine_diff_density_max         1.692
_refine_diff_density_min         -1.279
_refine_diff_density_rms         0.169
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.300
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1268
_refine_ls_number_reflns         21076
_refine_ls_number_restraints     703
_refine_ls_restrained_S_all      1.308
_refine_ls_R_factor_all          0.1468
_refine_ls_R_factor_gt           0.1101
_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^)+(0.2400P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3417
_refine_ls_wR_factor_ref         0.3924
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13828
_reflns_number_total             21076
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt00851d2.cif
_cod_data_source_block           exp_445_auto
_cod_depositor_comments          'Adding full bibliography for 7718659.cif.'
_cod_database_code               7718659
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 99.68
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Others
 Fixed Sof: Cu8(0.5) Cu57(0.5) Cl53(0.5) Cu54(0.5) Cu12(0.5) S9(0.5) H69A(0.5)
 H69B(0.5) H69C(0.5) H69D(0.5) C118(0.5) H11C(0.5) H11D(0.5) C117(0.5)
 H11E(0.5) H11F(0.5) Cu1(0.5) C1(0.5) H1A(0.5) H1B(0.5) C2(0.5) H2A(0.5)
 H2B(0.5) S8(0.5) Cu5(0.5) Cu9(0.5) Cu10(0.5)
 Fixed U12: Cl53(0)
 Fixed U23: Cl53(0)
 Fixed Uiso: H10A(0.061) H10B(0.061) H93A(0.066) H93B(0.066) H35(0.108)
 H40(0.121) H39(0.108) H38(0.103) H37(0.092) H100(0.071) H99(0.086) H98(0.116)
 H97(0.129) H96(0.104) H94A(0.065) H94B(0.065) H46(0.08) H45(0.103) H44(0.096)
 H43(0.102) H42(0.084) H10C(0.07) H10D(0.07) H10E(0.07) H10F(0.07) H84(0.071)
 H83(0.076) H82(0.092) H81(0.099) H80(0.082) H52(0.065) H51(0.08) H50(0.1)
 H49(0.112) H48(0.095) H107(0.079) H4(0.082) H106(0.078) H105(0.08) H104(0.073)
 H77A(0.066) H77B(0.066) H112(0.1) H113(0.121) H114(0.121) H115(0.124)
 H116(0.104) H78A(0.074) H78B(0.074) H16(0.083) H17(0.085) H18(0.075)
 H19(0.082) H14(0.087) H85A(0.077) H85B(0.077) H92(0.116) H91(0.129) H90(0.125)
 H89(0.15) H88(0.124) H69A(0.105) H69B(0.105) H69C(0.105) H69D(0.105)
 H86A(0.104) H86B(0.104) H11A(0.084) H11B(0.084) H25(0.059) H24(0.075)
 H23(0.078) H22(0.081) H21(0.066) H10G(0.089) H10H(0.089) H124(0.107)
 H123(0.093) H122(0.121) H121(0.1) H120(0.087) H76(0.142) H75(0.16) H74(0.175)
 H73(0.165) H72(0.149) H70A(0.124) H70B(0.124) H11C(0.069) H11D(0.069)
 H11E(0.053) H11F(0.053) H63A(0.146) H63B(0.146) H68(0.16) H67(0.141)
 H66(0.134) H65(0.151) H64(0.16) H61A(0.16) H61B(0.16) H28(0.103) H6(0.127)
 H5(0.136) H3(0.12) H27(0.098) H7(0.103) H8(0.07) H9(0.069) H11(0.091)
 H12(0.099) H1A(0.074) H1B(0.074) H2A(0.087) H2B(0.087) H13A(0.155) H13B(0.155)
 H30(0.076) H29(0.087) H58(0.059) H34(0.065) H57(0.057) H54(0.068) H55(0.056)
 H32(0.078) H33(0.087) H31(0.093)
 Fixed X: Cl53(0.5) H10A(0.597379) H10B(0.623529) H93A(0.532501)
 H93B(0.578942) H35(0.343031) H40(0.36956) H39(0.449904) H38(0.500109)
 H37(0.476519) H100(0.636005) H99(0.678839) H98(0.641101) H97(0.559386)
 H96(0.513124) H94A(0.505998) H94B(0.552976) H46(0.394954) H45(0.409196)
 H44(0.420668) H43(0.418888) H42(0.402668) H10C(0.521187) H10D(0.550287)
 H10E(0.544081) H10F(0.523522) H84(0.300426) H83(0.281244) H82(0.326724)
 H81(0.391961) H80(0.411184) H52(0.330477) H51(0.247184) H50(0.190232)
 H49(0.214853) H48(0.298195) H107(0.559301) H4(0.572636) H106(0.584385)
 H105(0.582798) H104(0.569463) H77A(0.394632) H77B(0.43756) H112(0.795028)
 H113(0.798043) H114(0.743704) H115(0.672802) H116(0.664319) H78A(0.34061)
 H78B(0.383563) H16(0.726009) H17(0.805626) H18(0.824961) H19(0.761677)
 H14(0.681581) H85A(0.63903) H85B(0.66353) H92(0.712911) H91(0.771075)
 H90(0.824195) H89(0.819444) H88(0.763154) H69A(0.302865) H69B(0.322655)
 H69C(0.301568) H69D(0.331763) H86A(0.690151) H86B(0.715849) H11A(0.758428)
 H11B(0.70914) H25(0.682243) H24(0.660061) H23(0.581719) H22(0.525865)
 H21(0.547795) H10G(0.663278) H10H(0.711868) H124(0.522442) H123(0.484597)
 H122(0.407533) H121(0.368314) H120(0.406158) H76(0.253788) H75(0.170224)
 H74(0.109054) H73(0.131864) H72(0.21545) H70A(0.310529) H70B(0.293)
 H11C(0.493573) H11D(0.536297) H11E(0.449749) H11F(0.48761) H63A(0.594486)
 H63B(0.575112) H68(0.654724) H67(0.725716) H66(0.780718) H65(0.764728)
 H64(0.693737) H61A(0.651523) H61B(0.631858) H28(0.633144) H6(0.63703)
 H5(0.639237) H3(0.637558) H27(0.633672) H7(0.617555) H8(0.617417) H9(0.623856)
 H11(0.630572) H12(0.624133) H1A(0.539098) H1B(0.493793) H2A(0.486838)
 H2B(0.441164) H13A(0.822775) H13B(0.786981) H30(0.529215) H29(0.543456)
 H58(0.557524) H34(0.566881) H57(0.578624) H54(0.581009) H55(0.571651)
 H32(0.590989) H33(0.687647) H31(0.668293)
 Fixed Y: H10A(0.366034) H10B(0.38951) H93A(0.026895) H93B(0.049583)
 H35(0.031168) H40(0.043876) H39(0.068667) H38(0.085568) H37(0.066227) H100(-
 0.014114) H99(-0.083904) H98(-0.158334) H97(-0.164592) H96(-0.093302) H94A(-
 0.008389) H94B(0.013678) H46(-0.017345) H45(-0.098789) H44(-0.157739) H43(-
 0.135162) H42(-0.054218) H10C(0.397764) H10D(0.424769) H10E(0.417183)
 H10F(0.400163) H84(0.264151) H83(0.307716) H82(0.299238) H81(0.24408)
 H80(0.198285) H52(0.120926) H51(0.140603) H50(0.077473) H49(-0.002272) H48(-
 0.02082) H107(0.509856) H4(0.580398) H106(0.573621) H105(0.496303)
 H104(0.425761) H77A(0.256884) H77B(0.228741) H112(0.325959) H113(0.370645)
 H114(0.425844) H115(0.43356) H116(0.386603) H78A(0.192472) H78B(0.164573)
 H16(0.410273) H17(0.397155) H18(0.357142) H19(0.329459) H14(0.34477)
 H85A(0.053602) H85B(0.10424) H92(-0.028941) H91(-0.068946) H90(-0.020091)
 H89(0.060624) H88(0.099805) H69A(0.190576) H69B(0.159047) H69C(0.184816)
 H69D(0.161754) H86A(0.050816) H86B(0.100127) H11A(0.313023) H11B(0.341073)
 H25(0.468143) H24(0.551211) H23(0.576892) H22(0.523704) H21(0.438396)
 H10G(0.283357) H10H(0.256285) H124(0.421048) H123(0.469595) H122(0.447807)
 H121(0.377472) H120(0.328924) H76(0.138502) H75(0.116957) H74(0.177374)
 H73(0.257098) H72(0.280243) H70A(0.227464) H70B(0.260501) H11C(0.29583)
 H11D(0.335725) H11E(0.323816) H11F(0.367904) H63A(0.116185) H63B(0.098701)
 H68(0.054784) H67(0.00711) H66(0.018074) H65(0.076713) H64(0.124388)
 H61A(0.168976) H61B(0.151672) H28(0.302077) H6(0.289411) H5(0.356734)
 H3(0.436723) H27(0.44939) H7(0.415754) H8(0.487751) H9(0.483199) H11(0.334653)
 H12(0.339203) H1A(0.325622) H1B(0.288432) H2A(0.387141) H2B(0.349645)
 H13A(0.204393) H13B(0.214463) H30(0.546355) H29(0.463218) H58(0.497902)
 H34(0.576469) H57(0.585849) H54(0.51666) H55(0.438091) H32(0.593646)
 H33(0.488782) H31(0.567171)
 Fixed Z: Cl53(0.75) H10A(0.830804) H10B(0.785513) H93A(0.628099)
 H93B(0.656838) H35(0.507129) H40(0.431827) H39(0.420095) H38(0.485138)
 H37(0.563383) H100(0.679216) H99(0.661099) H98(0.654249) H97(0.672365)
 H96(0.690894) H94A(0.700447) H94B(0.72863) H46(0.692223) H45(0.71375)
 H44(0.653232) H43(0.573247) H42(0.550919) H10C(0.799183) H10D(0.757814)
 H10E(0.756893) H10F(0.80724) H84(0.523061) H83(0.453506) H82(0.386152)
 H81(0.386817) H80(0.454593) H52(0.616345) H51(0.617709) H50(0.605003)
 H49(0.593619) H48(0.587889) H107(0.772458) H4(0.819277) H106(0.902864)
 H105(0.939633) H104(0.892815) H77A(0.581084) H77B(0.554931) H112(0.917221)
 H113(0.988314) H114(1.003492) H115(0.95541) H116(0.884712) H78A(0.560375)
 H78B(0.533982) H16(0.608046) H17(0.63183) H18(0.704815) H19(0.751231)
 H14(0.727815) H85A(0.727835) H85B(0.713252) H92(0.753718) H91(0.70609)
 H90(0.663216) H89(0.667034) H88(0.711931) H69A(0.798184) H69B(0.84351)
 H69C(0.799815) H69D(0.845698) H86A(0.796091) H86B(0.778722) H11A(0.838911)
 H11B(0.823121) H25(0.690953) H24(0.703523) H23(0.668646) H22(0.643074)
 H21(0.630946) H10G(0.862894) H10H(0.882279) H124(0.521156) H123(0.46113)
 H122(0.428899) H121(0.456693) H120(0.516718) H76(0.876501) H75(0.882274)
 H74(0.872211) H73(0.878573) H72(0.866562) H70A(0.895614) H70B(0.850717)
 H11C(0.534708) H11D(0.545985) H11E(0.601284) H11F(0.610538) H63A(0.595206)
 H63B(0.542992) H68(0.606541) H67(0.605098) H66(0.543525) H65(0.483394)
 H64(0.484836) H61A(0.559605) H61B(0.506886) H28(0.586941) H6(0.50386)
 H5(0.451585) H3(0.482391) H27(0.565472) H7(0.449219) H8(0.495268) H9(0.57937)
 H11(0.571377) H12(0.487274) H1A(0.5659) H1B(0.560864) H2A(0.599303)
 H2B(0.594284) H13A(0.718438) H13B(0.761614) H30(0.679524) H29(0.651777)
 H58(0.747878) H34(0.781179) H57(0.864524) H54(0.914568) H55(0.881268)
 H32(0.693086) H33(0.688073) H31(0.715926)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_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 3.005
_oxdiff_exptl_absorpt_empirical_full_min 0.489