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_7117079
_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         '1.5(C14 H30 N2), Cu3.01 I6'
_chemical_formula_sum            'C21 H45 Cu3.01 I6 N3'
_chemical_formula_weight         1292.40
_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
_atom_sites_solution_primary     iterative
_audit_creation_date             2014-11-24
_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                   8.6312(5)
_cell_length_b                   13.6767(8)
_cell_length_c                   31.2048(19)
_cell_measurement_reflns_used    2683
_cell_measurement_temperature    373.2(4)
_cell_measurement_theta_max      25.1480
_cell_measurement_theta_min      3.2420
_cell_volume                     3683.6(4)
_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)'
_computing_structure_solution
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      373.2(4)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0710
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.972
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
  1 omega  -32.00    5.00   1.0000   10.7750
omega____ theta____ kappa____ phi______ frames
    -       19.3738  -57.0000   90.0000 37

  2 omega   13.00   40.00   1.0000   10.7750
omega____ theta____ kappa____ phi______ frames
    -      -19.8425   77.0000  -30.0000 27

  3 omega  -47.00  -22.00   1.0000   10.7750
omega____ theta____ kappa____ phi______ frames
    -      -19.8425   77.0000  -30.0000 25

  4 omega  -83.00    7.00   1.0000   10.7750
omega____ theta____ kappa____ phi______ frames
    -      -19.8425  -77.0000 -150.0000 90
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0028920000
_diffrn_orient_matrix_UB_12      -0.0462622000
_diffrn_orient_matrix_UB_13      0.0102490000
_diffrn_orient_matrix_UB_21      -0.0023320000
_diffrn_orient_matrix_UB_22      -0.0233134000
_diffrn_orient_matrix_UB_23      -0.0202869000
_diffrn_orient_matrix_UB_31      0.0821066000
_diffrn_orient_matrix_UB_32      -0.0022961000
_diffrn_orient_matrix_UB_33      -0.0002238000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.710
_diffrn_reflns_av_R_equivalents  0.0586
_diffrn_reflns_av_unetI/netI     0.0862
_diffrn_reflns_Laue_measured_fraction_full 0.972
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            11568
_diffrn_reflns_point_group_measured_fraction_full 0.938
_diffrn_reflns_point_group_measured_fraction_max 0.963
_diffrn_reflns_theta_full        25.214
_diffrn_reflns_theta_max         24.997
_diffrn_reflns_theta_min         2.863
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    6.766
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.17511
_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    2.330
_exptl_crystal_description       column
_exptl_crystal_F_000             2389
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.745
_refine_diff_density_min         -0.701
_refine_diff_density_rms         0.152
_refine_ls_abs_structure_details
;
 Flack x determined using 1094 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.48(7)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     336
_refine_ls_number_reflns         6273
_refine_ls_number_restraints     9
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.1027
_refine_ls_R_factor_gt           0.0633
_refine_ls_shift/su_max          0.041
_refine_ls_shift/su_mean         0.004
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.0440P)^2^+3.3870P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1200
_refine_ls_wR_factor_ref         0.1444
_reflns_Friedel_coverage         0.700
_reflns_Friedel_fraction_full    0.892
_reflns_Friedel_fraction_max     0.918
_reflns_number_gt                3988
_reflns_number_total             6273
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5cc01154j2.cif
_cod_data_source_block           373k
_cod_database_code               7117079
_shelxl_version_number           2013-2
_chemical_oxdiff_formula         'Cu I C N H'
_chemical_oxdiff_usercomment     'Cu I C N H'
_shelx_estimated_absorpt_t_max   0.728
_shelx_estimated_absorpt_t_min   0.133
_reflns_odcompleteness_completeness 99.75
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     28.22
_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
 C12, C13
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.02
 C13, C14
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.02
 N2, C6
 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) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.01
Uanis(N3) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.01
Uanis(C20) = Uanis(C19)
Uanis(N3) = Uanis(N4)
4. Others
 Fixed Sof: 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) C22(0.5) H22a(0.5) H22b(0.5) C23(0.5) H23a(0.5) H23b(0.5)
 C24(0.5) H24a(0.5) H24b(0.5) N3(0.5) N4(0.5)
5.a Secondary CH2 refined with riding coordinates:
 C8(H8a,H8b), C4(H4a,H4b), C11(H11a,H11b), C3(H3a,H3b), C2(H2a,H2b), C10(H10a,
 H10b), C13(H13a,H13b), C9(H9a,H9b), C12(H12a,H12b), C7(H7a,H7b), C5(H5a,H5b),
 C6(H6a,H6b), C16(H16a,H16b), C17(H17a,H17b), C18(H18a,H18b), C19(H19a,H19b),
 C20(H20a,H20b), C21(H21a,H21b), C22(H22a,H22b), C23(H23a,H23b), C24(H24a,H24b)
5.b Idealised Me refined as rotating group:
 C1(H1a,H1b,H1c), C14(H14a,H14b,H14c), C15(H15a,H15b,H15c)
;