Thermochromism and piezochromism of an atomically precise high-nuclearity silver sulfide nanocluster.
Sun, Qiao-Qiao; Li, Qian; Li, Hai-Yang; Zhang, Miao-Miao; Sun, Meng-En; Li, Si; Quan, Zewei; Zang, Shuang-Quan; Chemical communications (Cambridge, England) 57 (2021) 2372–2375; doi:10.1039/d0cc07085h

data_7127870
_publ_section_title
;
 Thermochromism and piezochromism of an atomically precise high-nuclearity
 silver sulfide nanocluster.
;
_journal_issue                   19
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              2372
_journal_page_last               2375
_journal_paper_doi               10.1039/d0cc07085h
_journal_volume                  57
_journal_year                    2021
_chemical_formula_moiety         'C378 H300 Ag50 F36 P12 S43'
_chemical_formula_sum            'C378 H300 Ag50 F36 P12 S43'
_chemical_formula_weight         12669.88
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-11-22
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-03-25 deposited with the CCDC.	2021-01-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.2910(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   30.1143(2)
_cell_length_b                   24.4007(2)
_cell_length_c                   33.4558(2)
_cell_measurement_reflns_used    51946
_cell_measurement_temperature    200.00(10)
_cell_measurement_theta_max      73.6860
_cell_measurement_theta_min      2.6780
_cell_volume                     24478.9(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.27b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.27b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.27b (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      200.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_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    -83.00 -56.00   0.25    0.25    --    0.00 -38.00-150.00  108
  2  \w    -12.00  41.00   0.25    0.25    --    0.00  82.00 120.00  212
  3  \w    -40.00  17.00   0.25    0.25    --    0.00 -38.00  30.00  228
  4  \w    -72.00 -47.00   0.25    0.25    --    0.00 -38.00  30.00  100
  5  \w    -89.00  12.00   0.25    0.25    --    0.00 -38.00 -60.00  404
  6  \w     67.00 115.00   0.25    2.00    --   95.20 -15.00 -30.00  192
  7  \w     11.00  48.00   0.25    2.00    --   95.20 -15.00 -30.00  148
  8  \w     65.00 104.00   0.25    2.00    --   95.20 -45.00 -30.00  156
  9  \w     68.00  99.00   0.25    2.00    --   95.20  77.00   0.00  124
 10  \w      6.00 115.00   0.25    2.00    --   95.20 -30.00 -30.00  436
 11  \w    128.00 178.00   0.25    2.00    --   95.20  77.00   0.00  200
 12  \w      7.00 127.00   0.25    2.00    --   95.20 -82.00 -60.00  480
 13  \w      7.00  54.00   0.25    2.00    --   95.20 -61.00-120.00  188
 14  \w     21.00  49.00   0.25    2.00    --   95.20 -45.00 -30.00  112
 15  \w     86.00 173.00   0.25    2.00    --   95.20  77.00 -60.00  348
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0183789000
_diffrn_orient_matrix_UB_12      0.0589480000
_diffrn_orient_matrix_UB_13      0.0014965000
_diffrn_orient_matrix_UB_21      0.0064071000
_diffrn_orient_matrix_UB_22      -0.0029751000
_diffrn_orient_matrix_UB_23      0.0461721000
_diffrn_orient_matrix_UB_31      0.0475443000
_diffrn_orient_matrix_UB_32      -0.0224058000
_diffrn_orient_matrix_UB_33      -0.0021968000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0470
_diffrn_reflns_av_unetI/netI     0.0432
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       35
_diffrn_reflns_limit_h_min       -35
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            143469
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        66.498
_diffrn_reflns_theta_max         66.498
_diffrn_reflns_theta_min         2.334
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    18.157
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.27499
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.27b (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.719
_exptl_crystal_description       needle
_exptl_crystal_F_000             12220
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.1
_refine_diff_density_max         4.021
_refine_diff_density_min         -2.389
_refine_diff_density_rms         0.171
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.068
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2569
_refine_ls_number_reflns         42989
_refine_ls_number_restraints     789
_refine_ls_restrained_S_all      1.084
_refine_ls_R_factor_all          0.0937
_refine_ls_R_factor_gt           0.0786
_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^)+(0.1342P)^2^+116.9603P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2248
_refine_ls_wR_factor_ref         0.2384
_reflns_Friedel_coverage         0.000
_reflns_number_gt                32999
_reflns_number_total             42989
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cc07085h2.cif
_cod_data_source_block           20190823d5_3_200_00-hy
_cod_depositor_comments
'Adding full bibliography for 7127868--7127870.cif.'
_cod_database_code               7127870
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.264
_shelx_estimated_absorpt_t_min   0.219
_reflns_odcompleteness_completeness 97.24
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     73.98
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 C107-C48 = C136-C107 = C137-C136 = C48-C41
 1.39 with sigma of 0.01
 C181-C180 = C181-C183
 1.39 with sigma of 0.01
 C180-C179 = C184-C179 = C184-C182 = C182-C183
 1.39 with sigma of 0.01
 C186-C134 = C187-C186 = C187-C185 = C185-C168 = C168-C84 = C134-C84
 1.39 with sigma of 0.01
 C192-C12 = C190-C12 = C192-C189 = C193-C190 = C158-C12 = C191-C158 = C188-
 C191 = C194-C188 = C193-C188 = C188-C189
 1.39 with sigma of 0.01
 C195-C12 = C194-C195
 1.39 with sigma of 0.01
3. Restrained planarity
 F17, C134, C168, C185, C186, C187
 with sigma of 0.1
 F18, C12, C158, C188, C190, C191, C193
 with sigma of 0.1
 F18, C12, C188, C189, C192, C194, C195
 with sigma of 0.1
4. Rigid bond restraints
 C163, C165
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
P6 \\sim C171 \\sim C172 \\sim C173 \\sim C174 \\sim C175 \\sim C176: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.01
P6 \\sim C160 \\sim C163 \\sim C164 \\sim C165: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.01
S5 \\sim F17 \\sim C84 \\sim C134 \\sim C168 \\sim C185 \\sim C186 \\sim C187:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.01
C71 \\sim C72 \\sim C198 \\sim C199: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.01
Uanis(Ag30) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(Ag33) \\sim Ueq, Uanis(F9) \\sim Ueq, Uanis(C63) \\sim Ueq, Uanis(F15)
\\sim Ueq, Uanis(C95) \\sim Ueq, Uanis(C108) \\sim Ueq, Uanis(F16) \\sim Ueq,
Uanis(C119) \\sim Ueq, Uanis(C126) \\sim Ueq, Uanis(C135) \\sim Ueq,
Uanis(C141) \\sim Ueq, Uanis(C143) \\sim Ueq, Uanis(C146) \\sim Ueq,
Uanis(C147) \\sim Ueq, Uanis(C153) \\sim Ueq, Uanis(C155) \\sim Ueq,
Uanis(C156) \\sim Ueq, Uanis(C157) \\sim Ueq, Uanis(C166) \\sim Ueq,
Uanis(C169) \\sim Ueq, Uanis(Ag34) \\sim Ueq, Uanis(Ag0A) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(Ag32) \\sim Ueq, Uanis(F9) \\sim Ueq, Uanis(F14) \\sim Ueq, Uanis(C127)
\\sim Ueq, Uanis(C148) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(Ag1A) \\sim Ueq, Uanis(Ag17) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(Ag1A) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C178) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C137) \\sim Ueq, Uanis(C131) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C175) \\sim Ueq, Uanis(C174) \\sim Ueq, Uanis(C173) \\sim Ueq,
Uanis(C176) \\sim Ueq, Uanis(C172) \\sim Ueq, Uanis(C171) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(F14) \\sim Ueq, Uanis(C139) \\sim Ueq, Uanis(C149) \\sim Ueq, Uanis(C103)
\\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(C87) \\sim Ueq, Uanis(C117) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C162) \\sim Ueq, Uanis(C163) \\sim Ueq, Uanis(C164) \\sim Ueq,
Uanis(C165) \\sim Ueq, Uanis(C160) \\sim Ueq, Uanis(C161) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C150) \\sim Ueq, Uanis(C154) \\sim Ueq, Uanis(C86) \\sim Ueq, Uanis(C159)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C183) \\sim Ueq, Uanis(C181) \\sim Ueq, Uanis(C182) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C179) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C184) \\sim Ueq, Uanis(C4) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C136) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C185) \\sim Ueq, Uanis(C187) \\sim Ueq, Uanis(C186) \\sim Ueq, Uanis(F17)
\\sim Ueq, Uanis(C168) \\sim Ueq, Uanis(C134) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C194) \\sim Ueq, Uanis(C191) \\sim Ueq, Uanis(C158) \\sim Ueq,
Uanis(C192) \\sim Ueq, Uanis(C189) \\sim Ueq, Uanis(C190) \\sim Ueq,
Uanis(C193) \\sim Ueq, Uanis(F18) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C75) \\sim Ueq, Uanis(C74) \\sim Ueq, Uanis(C70) \\sim Ueq, Uanis(C71)
\\sim Ueq, Uanis(C72) \\sim Ueq, Uanis(C73) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C70) \\sim Ueq, Uanis(C71) \\sim Ueq, Uanis(C72) \\sim Ueq, Uanis(C73)
\\sim Ueq, Uanis(C74) \\sim Ueq, Uanis(C75) \\sim Ueq, Uanis(C196) \\sim Ueq,
Uanis(C197) \\sim Ueq, Uanis(C198) \\sim Ueq, Uanis(C199) \\sim Ueq,
Uanis(C200) \\sim Ueq, Uanis(C201) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C47) \\sim Ueq, Uanis(C177) \\sim Ueq, Uanis(C202) \\sim Ueq, Uanis(C203)
\\sim Ueq, Uanis(C204) \\sim Ueq, Uanis(C205) \\sim Ueq, Uanis(C206) \\sim Ueq,
Uanis(C207) \\sim Ueq, Uanis(C208) \\sim Ueq, Uanis(C209) \\sim Ueq,
Uanis(C210) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F9) \\sim Ueq, Uanis(F14) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(F17) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C142) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Ag18) \\sim Ueq, Uanis(Ag34) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(Ag20) = Uanis(Ag32)
Uanis(Ag34) = Uanis(Ag18)
6. Others
 Sof(Ag26)=0.9*(1-FVAR(2))
 Sof(Ag25)=0.9*FVAR(2)
 Sof(Ag29)=1-FVAR(2)
 Sof(Ag24)=FVAR(2)
 Sof(Ag28)=1-FVAR(3)
 Sof(Ag16)=FVAR(3)
 Sof(Ag30)=1-FVAR(4)
 Sof(Ag22)=FVAR(4)
 Sof(Ag27)=1-FVAR(5)
 Sof(Ag19)=FVAR(5)
 Sof(Ag33)=1-FVAR(6)
 Sof(Ag23)=FVAR(6)
 Sof(Ag18)=1-FVAR(7)
 Sof(Ag32)=0.9*(1-FVAR(8))
 Sof(Ag20)=0.9*FVAR(8)
 Sof(Ag34)=FVAR(7)
 Sof(Ag1A)=1-FVAR(8)
 Sof(Ag17)=FVAR(8)
 Sof(C179)=Sof(H179)=Sof(C180)=Sof(H180)=Sof(C181)=Sof(H181)=Sof(C182)=
 Sof(H182)=Sof(C183)=Sof(H183)=Sof(C184)=1-FVAR(9)
 Sof(C4)=Sof(C86)=Sof(H86)=Sof(C150)=Sof(H150)=Sof(C154)=Sof(H154)=Sof(C159)=
 Sof(H159)=Sof(C167)=Sof(H167)=FVAR(9)
 Sof(C189)=Sof(H189)=Sof(C192)=Sof(H192)=Sof(C194)=Sof(H194)=Sof(C195)=
 Sof(H195)=1-FVAR(10)
 Sof(C158)=Sof(H158)=Sof(C190)=Sof(H190)=Sof(C191)=Sof(H191)=Sof(C193)=
 Sof(H193)=FVAR(10)
 Sof(C196)=Sof(H196)=Sof(C197)=Sof(C198)=Sof(H198)=Sof(C199)=Sof(H199)=
 Sof(C200)=Sof(H200)=Sof(C201)=Sof(H201)=1-FVAR(11)
 Sof(C70)=Sof(C71)=Sof(H71)=Sof(C72)=Sof(H72)=Sof(C73)=Sof(H73)=Sof(C74)=
 Sof(H74)=Sof(C75)=Sof(H75)=FVAR(11)
 Sof(C206)=Sof(H206)=Sof(C207)=Sof(H207)=Sof(C208)=Sof(H208)=Sof(C209)=
 Sof(H209)=Sof(C210)=Sof(H210)=1-FVAR(12)
 Sof(C177)=Sof(H177)=Sof(C202)=Sof(H202)=Sof(C203)=Sof(H203)=Sof(C204)=
 Sof(H204)=Sof(C205)=Sof(H205)=FVAR(12)
 Fixed Sof: Ag0A(0.1) Ag31(0.1) S22(0.5)
7.a Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C17(H17A,H17B), C43(H43A,H43B), C44(H44A,H44B), C59(H59A,H59B),
 C64(H64A,H64B), C76(H76A,H76B), C80(H80A,H80B), C122(H12A,H12B)
7.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C8(H8), C11(H11), C16(H16), C19(H19), C22(H22), C23(H23),
 C27(H27), C28(H28), C30(H30), C31(H31), C33(H33), C35(H35), C38(H38), C39(H39),
  C40(H40), C42(H42), C45(H45), C48(H48), C50(H50), C51(H51), C52(H52),
 C53(H53), C54(H54), C55(H55), C57(H57), C58(H58), C60(H60), C61(H61), C63(H63),
  C66(H66), C67(H67), C69(H69), C71(H71), C72(H72), C73(H73), C74(H74),
 C75(H75), C77(H77), C78(H78), C79(H79), C81(H81), C82(H82), C83(H83), C86(H86),
  C87(H87), C89(H89), C90(H90), C91(H91), C93(H93), C94(H94), C95(H95),
 C96(H96), C97(H97), C99(H99), C102(H102), C103(H103), C104(H104), C105(H105),
 C106(H106), C107(H107), C108(H108), C109(H109), C111(H111), C112(H112),
 C113(H113), C114(H114), C115(H115), C116(H116), C117(H117), C118(H118),
 C119(H119), C120(H120), C121(H121), C123(H123), C125(H125), C126(H126),
 C127(H127), C128(H128), C129(H129), C130(H130), C131(H131), C133(H133),
 C134(H134), C135(H135), C136(H136), C137(H137), C138(H138), C140(H140),
 C141(H141), C142(H142), C144(H144), C146(H146), C147(H147), C148(H148),
 C149(H149), C150(H150), C151(H151), C152(H152), C153(H153), C154(H154),
 C155(H155), C157(H157), C158(H158), C159(H159), C160(H160), C161(H161),
 C162(H162), C164(H164), C165(H165), C166(H166), C167(H167), C168(H168),
 C169(H169), C170(H170), C171(H171), C172(H172), C173(H173), C175(H175),
 C176(H176), C177(H177), C178(H178), C179(H179), C180(H180), C181(H181),
 C182(H182), C183(H183), C185(H185), C186(H186), C189(H189), C190(H190),
 C191(H191), C192(H192), C193(H193), C194(H194), C195(H195), C196(H196),
 C198(H198), C199(H199), C200(H200), C201(H201), C202(H202), C203(H203),
 C204(H204), C205(H205), C206(H206), C207(H207), C208(H208), C209(H209),
 C210(H210)
7.c Fitted hexagon refined as free rotating group:
 C26(C27,C28,C29,C30,C31), C70(C71,C72,C73,C74,C75), C160(C161,C162,C163,C164,
 C165), C171(C172,C173,C174,C175,C176), C196(C197,C198,C199,C200,C201)
;
_shelx_res_checksum              49171
_shelx_hkl_checksum              30234
_shelx_fab_checksum              40708
_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 2.296
_oxdiff_exptl_absorpt_empirical_full_min 0.632