An organic-ligand-free thermochromic luminescent cuprous iodide trinuclear cluster: evidence for cluster centered emission and configuration distortion with temperature
Shi-Li Li; Fu-Qiang Zhang; Xian-Ming Zhang; Chem.Commun. 51 (2015) 8062–; doi:10.1039/C5cc01154J

data_7117078
_publ_section_title
;
 An organic-ligand-free thermochromic luminescent cuprous iodide
 trinuclear cluster: evidence for cluster centered emission and
 configuration distortion with temperature
;
_journal_name_full               Chem.Commun.
_journal_page_first              8062
_journal_paper_doi               10.1039/C5cc01154J
_journal_volume                  51
_journal_year                    2015
_chemical_formula_moiety         '3(C7 H15 N), Cu2.99 I6'
_chemical_formula_sum            'C21 H45 Cu2.99 I6 N3'
_chemical_formula_weight         1291.26
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      orthorhombic
_space_group_IT_number           18
_space_group_name_Hall           'P 2bc 2'
_space_group_name_H-M_alt        'P 2 21 21'
_symmetry_space_group_name_Hall  'P 2bc 2'
_symmetry_space_group_name_H-M   'P 2 21 21'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2014-11-25
_audit_creation_method
;
Olex2 1.2
(compiled 2014.09.19 svn.r3010 for OlexSys, GUI svn.r4874)
;
_audit_update_record
;
2015-01-29 deposited with the CCDC.
2015-03-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.6034(3)
_cell_length_b                   13.5945(6)
_cell_length_c                   31.2560(14)
_cell_measurement_reflns_used    3065
_cell_measurement_temperature    298(2)
_cell_measurement_theta_max      25.2780
_cell_measurement_theta_min      3.4060
_cell_volume                     3655.7(3)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      298(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0710
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
  1 omega   -3.00   38.00   1.0000   10.6250
omega____ theta____ kappa____ phi______ frames
    -       15.5636   38.0000   30.0000 41

  2 omega   58.00   83.00   1.0000   10.6250
omega____ theta____ kappa____ phi______ frames
    -       15.5636   77.0000   90.0000 25

  3 omega  -10.00   31.00   1.0000   10.6250
omega____ theta____ kappa____ phi______ frames
    -       15.5636   77.0000   90.0000 41

  4 omega  -25.00   36.00   1.0000   10.6250
omega____ theta____ kappa____ phi______ frames
    -       15.5636  -99.0000 -120.0000 61
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0140578000
_diffrn_orient_matrix_UB_12      0.0285168000
_diffrn_orient_matrix_UB_13      0.0186181000
_diffrn_orient_matrix_UB_21      0.0000165000
_diffrn_orient_matrix_UB_22      0.0434459000
_diffrn_orient_matrix_UB_23      -0.0125904000
_diffrn_orient_matrix_UB_31      -0.0811476000
_diffrn_orient_matrix_UB_32      -0.0049555000
_diffrn_orient_matrix_UB_33      -0.0032099000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0405
_diffrn_reflns_av_unetI/netI     0.0582
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            12554
_diffrn_reflns_point_group_measured_fraction_full 0.883
_diffrn_reflns_point_group_measured_fraction_max 0.870
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.371
_diffrn_reflns_theta_min         2.703
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    6.808
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.31936
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    2.346
_exptl_crystal_description       column
_exptl_crystal_F_000             2387
_exptl_crystal_size_max          0.48
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.951
_refine_diff_density_min         -0.932
_refine_diff_density_rms         0.152
_refine_ls_abs_structure_details
;
 Flack x determined using 1535 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.43(4)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     342
_refine_ls_number_reflns         6502
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.0685
_refine_ls_R_factor_gt           0.0498
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.0438P)^2^+3.4509P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1003
_refine_ls_wR_factor_ref         0.1112
_reflns_Friedel_coverage         0.545
_reflns_Friedel_fraction_full    0.733
_reflns_Friedel_fraction_max     0.704
_reflns_number_gt                5116
_reflns_number_total             6502
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5cc01154j2.cif
_cod_data_source_block           298K
_cod_database_code               7117078
_shelxl_version_number           2013-2
_chemical_oxdiff_formula         'Cu I C H N'
_shelx_estimated_absorpt_t_max   0.772
_shelx_estimated_absorpt_t_min   0.139
_reflns_odcompleteness_completeness 99.67
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid bond restraints
 C13, C14
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(N3) = Uanis(N4)
4. Others
 Fixed Sof: C23(0.5) H23A(0.5) H23B(0.5) C24(0.5) H24A(0.5) H24B(0.5) C22(0.5)
 H22A(0.5) H22B(0.5) C19(0.5) H19A(0.5) H19B(0.5) C20(0.5) H20A(0.5) H20B(0.5)
 C21(0.5) H21A(0.5) H21B(0.5) N3(0.5) N4(0.5)
5.a Secondary CH2 refined with riding coordinates:
 C23(H23A,H23B), C24(H24A,H24B), C22(H22A,H22B), C2(H2A,H2B), C3(H3A,H3B),
 C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B), C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B),
 C16(H16A,H16B), C11(H11A,H11B), C12(H12A,H12B), C13(H13A,H13B), C18(H18A,H18B),
  C19(H19A,H19B), C10(H10A,H10B), C17(H17A,H17B), C20(H20A,H20B), C21(H21A,H21B)
5.b Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C1(H1A,H1B,H1C), C15(H15A,H15B,H15C)
;