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_7117077
_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_absolute_configuration ad
_chemical_formula_moiety         'C7 H13 N, C14 H30 N2, Cu3 I6'
_chemical_formula_sum            'C21 H45 Cu3 I6 N3'
_chemical_formula_weight         1291.62
_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     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2015-01-17
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:54:37, GUI svn.r4466)
;
_audit_update_record
;
2015-01-29 deposited with the CCDC.
2015-03-30 downloaded from the CCDC.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   8.6000(5)
_cell_length_b                   31.212(2)
_cell_length_c                   13.5728(8)
_cell_measurement_reflns_used    2901
_cell_measurement_temperature    253.2(2)
_cell_measurement_theta_max      27.0500
_cell_measurement_theta_min      3.4190
_cell_volume                     3643.3(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
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      253.2(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0710
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.9978
_diffrn_measured_fraction_theta_max 0.7801
_diffrn_measurement_details
;
  1 omega   20.00   87.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -       19.3738   57.0000 -150.0000 67

  2 omega   -5.00   30.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -       19.3738   77.0000 -180.0000 35

  3 omega  -41.00   22.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -       19.3738  -38.0000 -120.0000 63
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0029153000
_diffrn_orient_matrix_UB_12      -0.0102593000
_diffrn_orient_matrix_UB_13      0.0466087000
_diffrn_orient_matrix_UB_21      0.0023384000
_diffrn_orient_matrix_UB_22      0.0202721000
_diffrn_orient_matrix_UB_23      0.0235812000
_diffrn_orient_matrix_UB_31      -0.0823658000
_diffrn_orient_matrix_UB_32      0.0002183000
_diffrn_orient_matrix_UB_33      0.0023116000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0288
_diffrn_reflns_av_unetI/netI     0.0476
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -37
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            10968
_diffrn_reflns_theta_full        25.00
_diffrn_reflns_theta_max         25.00
_diffrn_reflns_theta_min         2.80
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    6.834
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.29488
_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_density_diffrn    2.355
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             2388
_exptl_crystal_size_max          0.48
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.629
_refine_diff_density_min         -0.922
_refine_diff_density_rms         0.155
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.52(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.073
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     341
_refine_ls_number_reflns         6101
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.073
_refine_ls_R_factor_all          0.0597
_refine_ls_R_factor_gt           0.0450
_refine_ls_shift/su_max          0.076
_refine_ls_shift/su_mean         0.004
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0310P)^2^+8.2982P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0864
_refine_ls_wR_factor_ref         0.0934
_reflns_number_gt                5032
_reflns_number_total             6101
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c5cc01154j2.cif
_cod_data_source_block           250k
_cod_original_cell_volume        3643.2(4)
_cod_database_code               7117077
_chemical_oxdiff_formula         'Cu I C N H'
_chemical_oxdiff_usercomment     'Cu I C N H'
_reflns_odcompleteness_completeness 99.78
_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. Uiso/Uaniso restraints and constraints
Uanis(N4) = Uanis(N3)
3. Others
 Sof(Cu1')=1-FVAR(1)
 Sof(Cu1)=FVAR(1)
 Fixed Sof: 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) 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)
4.a Secondary CH2 refined with riding coordinates:
 C22(H22A,H22B), C23(H23A,H23B), C24(H24A,H24B), C2(H2A,H2B), C3(H3A,H3B),
 C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B), C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B),
 C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B), C13(H13A,H13B), C16(H16A,H16B),
  C17(H17A,H17B), C19(H19A,H19B), C20(H20A,H20B), C21(H21A,H21B)
4.b Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C)
;