Crystal Structures of CuCl2·2H2O (Eriochalcite) and NiCl2∙6H2O (Nickelbischofite) at Low Temperature: Full Refinement of Hydrogen Atoms Using Non-Spherical Atomic Scattering Factors
Boeré, René T.; Crystals 13 (2023) 293–; doi:10.3390/cryst13020293

data_1568589
_publ_section_title
;
 Crystal Structures of CuCl2&#x00B7;2H2O (Eriochalcite) and
 NiCl2&#x2219;6H2O (Nickelbischofite) at Low Temperature: Full Refinement
 of Hydrogen Atoms Using Non-Spherical Atomic Scattering Factors
;
_journal_issue                   2
_journal_name_full               Crystals
_journal_page_first              293
_journal_paper_doi               10.3390/cryst13020293
_journal_volume                  13
_journal_year                    2023
_chemical_formula_moiety         'Cl2 H8 Ni O4, 2(H2 O)'
_chemical_formula_sum            'Cl2 H12 Ni O6'
_chemical_formula_weight         237.690
_chemical_name_systematic        'Nickel(II) chloride hexahydrate'
_space_group_crystal_system      monoclinic
_space_group_IT_number           12
_space_group_name_Hall           '-I 2y'
_space_group_name_H-M_alt        'I 1 2/m 1'
_symmetry_Int_Tables_number      12
_atom_sites_solution_primary     dual
_audit_creation_date             2023-01-25
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2022.11.02 svn.ra8b101fa for OlexSys, GUI svn.r6635)
;
_cell_angle_alpha                90
_cell_angle_beta                 96.723(6)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   6.5628(4)
_cell_length_b                   7.0330(4)
_cell_length_c                   8.7326(6)
_cell_measurement_reflns_used    2918
_cell_measurement_temperature    99.98(10)
_cell_measurement_theta_max      35.8220
_cell_measurement_theta_min      3.6390
_cell_volume                     400.29(4)
_computing_cell_refinement       'CrysAlisPro 1.171.42.63a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.63a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.63a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.5-alpha (Bourhis et al., 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.98(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 1.0000
_diffrn_measured_fraction_theta_max 0.8918
_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     13.00  82.00   0.50    3.00    --   16.23  38.00 -60.00  138
  2  \w    -42.00   4.00   0.50    3.00    --  -19.05 -77.00 -90.00   92
  3  \w    -42.00   4.00   0.50    3.00    --  -19.05 -77.00 -30.00   92
  4  \w    -42.00  21.00   0.50    3.00    --  -19.05  77.00 -30.00  126
  5  \w    -88.00  50.00   0.50    3.00    --  -19.05   0.00 150.00  276
  6  \w      5.00  79.00   0.50    3.00    --   16.23  57.00 120.00  148
  7  \w    -50.00 -25.00   0.50    3.00    --   16.23 -38.00 -60.00   50
  8  \w     39.00  85.00   0.50    3.00    --   16.23 178.00 -30.00   92
  9  \w    -42.00   4.00   0.50    3.00    --  -19.05 -77.00 120.00   92
 10  \w    -42.00  21.00   0.50    3.00    --  -19.05  77.00 150.00  126
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Dual, Cu at home/near, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0110789000
_diffrn_orient_matrix_UB_12      0.0386281000
_diffrn_orient_matrix_UB_13      0.0754555000
_diffrn_orient_matrix_UB_21      -0.0451826000
_diffrn_orient_matrix_UB_22      -0.0829517000
_diffrn_orient_matrix_UB_23      0.0276851000
_diffrn_orient_matrix_UB_31      0.0984402000
_diffrn_orient_matrix_UB_32      -0.0424715000
_diffrn_orient_matrix_UB_33      0.0147991000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0318
_diffrn_reflns_av_unetI/netI     0.0233
_diffrn_reflns_Laue_measured_fraction_full 1.0000
_diffrn_reflns_Laue_measured_fraction_max 0.8918
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            4133
_diffrn_reflns_point_group_measured_fraction_full 1.0000
_diffrn_reflns_point_group_measured_fraction_max 0.8918
_diffrn_reflns_theta_full        25.2417
_diffrn_reflns_theta_max         35.72
_diffrn_reflns_theta_min         3.68
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    3.062
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76171
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.63a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.972
_exptl_crystal_description       prism
_exptl_crystal_F_000             245.494
_exptl_crystal_preparation       'BDH reagents, as received'
_exptl_crystal_recrystallization_method 'Recrystallized from d.H2O'
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.4019
_refine_diff_density_min         -0.5009
_refine_diff_density_rms         0.0860
_refine_ls_d_res_high            0.6087
_refine_ls_d_res_low             5.5305
_refine_ls_goodness_of_fit_ref   0.9955
_refine_ls_hydrogen_treatment    refall
_refine_ls_matrix_type           full
_refine_ls_number_constraints    0
_refine_ls_number_parameters     56
_refine_ls_number_reflns         890
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.9955
_refine_ls_R_factor_all          0.0186
_refine_ls_R_factor_gt           0.0175
_refine_ls_shift/su_max          -0.0006
_refine_ls_shift/su_mean         0.0001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0225P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0396
_refine_ls_wR_factor_ref         0.0400
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              10
_reflns_limit_h_min              -10
_reflns_limit_k_max              11
_reflns_limit_k_min              0
_reflns_limit_l_max              14
_reflns_limit_l_min              0
_reflns_number_gt                838
_reflns_number_total             890
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            Cu-NiCl2Hydrates_Boere-Crystals.cif
_cod_data_source_block           3a-NiCl2hexahydrate-Mo
_cod_database_code               1568589
_chemical_oxdiff_formula         'H12 Cl2 Ni O6'
_chemical_oxdiff_usercomment
'BDH reagents, recrystallized from a saturated warm solution'
_olex2_refinement_description
;
1. Rigid body (RIGU) restrains
 H1a, H2a, H1b, H1a, H1b, H1a, H1b, H1a, H2b, H1b
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
;
_olex2_exptl_crystal_mounting_method '50um MiTeGen, Paratone(TM) oil'
_olex2_refine_details
;
Refinement using NoSpherA2, an implementation of
NOn-SPHERical Atom-form-factors in Olex2.
Please cite:
F. Kleemiss et al. Chem. Sci. DOI 10.1039/D0SC05526C - 2021
NoSpherA2 implementation of HAR makes use of
tailor-made aspherical atomic form factors calculated
on-the-fly from a Hirshfeld-partitioned electron density (ED) - not from
spherical-atom form factors.

The ED is calculated from a gaussian basis set single determinant SCF
wavefunction - either Hartree-Fock or DFT using selected funtionals
 - for a fragment of the crystal.
This fragment can be embedded in an electrostatic crystal field by employing cluster charges
or modelled using implicit solvation models, depending on the software used.
The following options were used:
   SOFTWARE:       ORCA 5.0
   PARTITIONING:   NoSpherA2
   INT ACCURACY:   Normal
   METHOD:         PBE
   BASIS SET:      def2-TZVPP
   CHARGE:         0
   MULTIPLICITY:   3
   DATE:           2023-01-25_16-39-31
;
_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 1.295
_oxdiff_exptl_absorpt_empirical_full_min 0.777