Synthesis and SHG Properties of the Melamine-Based Material (C 3 N 6 H 7 )ZnX 3 (C 3 N 6 H 6 ) (X = Cl, Br)
Groß, Melena; Meyer, Hans-Juergen; Brand, Catharina D.; Schmidt, Patrick; Parker, Tim Maikel; Zhang, Dai; Romao, Carl P.; Dalton Transactions  (2025) –; doi:10.1039/D5DT02245B

data_7719807
_publ_section_title
;
 Synthesis and SHG Properties of the Melamine-Based Material (C 3 N 6 H 7
 )ZnX 3 (C 3 N 6 H 6 ) (X = Cl, Br)
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D5DT02245B
_journal_year                    2025
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C3 H6 Cl3 N6 Zn, C3 H7 N6'
_chemical_formula_sum            'C6 H13 Cl3 N12 Zn'
_chemical_formula_weight         425.004
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_Int_Tables_number      4
_atom_sites_solution_primary     dual
_audit_creation_date             2025-10-07
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2025-10-07 deposited with the CCDC.	2025-11-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.703(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.3366(2)
_cell_length_b                   6.6582(2)
_cell_length_c                   12.1344(3)
_cell_measurement_reflns_used    4944
_cell_measurement_temperature    150.00(11)
_cell_measurement_theta_max      79.5490
_cell_measurement_theta_min      3.6600
_cell_volume                     738.65(3)
_computing_cell_refinement       'CrysAlisPro 1.171.43.142a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.144a 64-bit (release 23-01-2025))'
_computing_data_reduction        'CrysAlisPro 1.171.43.142a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.5 (Bourhis et al., 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(11)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.9966
_diffrn_measured_fraction_theta_max 0.9961
_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    -82.00   3.00   0.50   10.00    --  -49.70 104.00-134.00  170
  2  \w     18.00  82.00   0.50   10.00    --   49.70-104.00 123.00  128
  3  \w    -81.00 -20.00   0.50   28.00    --  -90.00 104.00-134.00  122
  4  \w   -160.00 -84.00   0.50   28.00    --  -90.00-104.00 123.00  152
  5  \w     42.00 107.00   0.50   28.00    --  111.50-104.00 123.00  130
  6  \w    106.00 178.00   0.50   28.00    --  111.50 104.00-134.00  144
  7  \w   -118.00 -73.00   0.50   10.00    --  -49.70-125.00 -90.00   90
  8  \w   -118.00 -73.00   0.50   10.00    --  -49.70-125.00 -60.00   90
  9  \w   -120.00 -38.00   0.50   10.00    --  -49.70 -57.00  90.00  164
 10  \w   -118.00 -73.00   0.50   10.00    --  -49.70-125.00 -30.00   90
 11  \w   -120.00 -30.00   0.50   10.00    --  -49.70 -77.00  60.00  180
 12  \w   -120.00 -30.00   0.50   10.00    --  -49.70 -77.00  60.00  180
 13  \w    -51.00 -18.00   0.50   28.00    --  -90.00  45.00-150.00   66
 14  \w    -51.00 -18.00   0.50   28.00    --  -90.00  45.00 -30.00   66
 15  \w    -51.00 -18.00   0.50   28.00    --  -90.00  45.00-120.00   66
 16  \w   -138.00 -83.00   0.50   28.00    --  -90.00   0.00-180.00  110
 17  \w    -51.00 -18.00   0.50   28.00    --  -90.00  45.00  90.00   66
 18  \w     41.00 106.00   0.50   28.00    --  111.50 -94.00 150.00  130
 19  \w     43.00 111.00   0.50   28.00    --  111.50-125.00  90.00  136
 20  \w     43.00 111.00   0.50   28.00    --  111.50-125.00 -60.00  136
 21  \w     43.00 111.00   0.50   28.00    --  111.50-125.00  90.00  136
 22  \w     41.00  71.00   0.50   28.00    --  111.50 -61.00  90.00   60
 23  \w     41.00  71.00   0.50   28.00    --  111.50 -61.00 120.00   60
 24  \w     41.00 106.00   0.50   28.00    --  111.50 -94.00 -30.00  130
 25  \w    104.00 178.00   0.50   28.00    --  111.50  45.00 -30.00  148
 26  \w     41.00  71.00   0.50   28.00    --  111.50 -61.00 -30.00   60
 27  \w     41.00  71.00   0.50   28.00    --  111.50 -61.00   0.00   60
 28  \w     41.00  71.00   0.50   28.00    --  111.50 -61.00 -90.00   60
 29  \w    104.00 178.00   0.50   28.00    --  111.50  45.00 -60.00  148
 30  \w     92.00 178.00   0.50   28.00    --  111.50  77.00-150.00  172
 31  \w     43.00 111.00   0.50   28.00    --  111.50-125.00  60.00  136
 32  \w     43.00 111.00   0.50   28.00    --  111.50-125.00  60.00  136
 33  \w     43.00 111.00   0.50   28.00    --  111.50-125.00-120.00  136
 34  \w     41.00 106.00   0.50   28.00    --  111.50 -94.00 -30.00  130
 35  \w     98.00 178.00   0.50   28.00    --  111.50  61.00 -90.00  160
 36  \w     92.00 178.00   0.50   28.00    --  111.50  77.00   0.00  172
 37  \w     98.00 178.00   0.50   28.00    --  111.50  61.00 -90.00  160
 38  \w     63.00 118.00   0.50   28.00    --  111.50   0.00  90.00  110
 39  \w     41.00  71.00   0.50   28.00    --  111.50 -61.00  60.00   60
 40  \w     41.00 106.00   0.50   28.00    --  111.50 -94.00 -90.00  130
 41  \w     63.00 118.00   0.50   28.00    --  111.50   0.00 -30.00  110
 42  \w     43.00 111.00   0.50   28.00    --  111.50-125.00-150.00  136
 43  \w     43.00 111.00   0.50   28.00    --  111.50-125.00  30.00  136
 44  \w    104.00 178.00   0.50   28.00    --  111.50  45.00 -60.00  148
 45  \w     41.00  71.00   0.50   28.00    --  111.50 -61.00 -60.00   60
 46  \w     41.00 106.00   0.50   28.00    --  111.50 -94.00  60.00  130
 47  \w     41.00 106.00   0.50   28.00    --  111.50 -94.00-150.00  130
 48  \w     41.00 106.00   0.50   28.00    --  111.50 -94.00 -60.00  130
 49  \w     63.00 118.00   0.50   28.00    --  111.50   0.00  30.00  110
 50  \w     63.00 118.00   0.50   28.00    --  111.50   0.00-150.00  110
 51  \w   -120.00 -30.00   0.50   10.00    --  -49.70 -77.00-150.00  180
 52  \w   -120.00 -44.00   0.50   10.00    --  -49.70 -37.00 120.00  152
 53  \w   -120.00 -47.00   0.50   10.00    --  -49.70 -57.00 -30.00  146
 54  \w   -120.00 -30.00   0.50   10.00    --  -49.70 -77.00 -60.00  180
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0136888000
_diffrn_orient_matrix_UB_12      0.2219832000
_diffrn_orient_matrix_UB_13      0.0365108000
_diffrn_orient_matrix_UB_21      0.1679415000
_diffrn_orient_matrix_UB_22      -0.0191192000
_diffrn_orient_matrix_UB_23      0.0255852000
_diffrn_orient_matrix_UB_31      0.0029532000
_diffrn_orient_matrix_UB_32      0.0625159000
_diffrn_orient_matrix_UB_33      -0.1217446000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0378
_diffrn_reflns_av_unetI/netI     0.0273
_diffrn_reflns_Laue_measured_fraction_full 0.9966
_diffrn_reflns_Laue_measured_fraction_max 0.9961
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            15504
_diffrn_reflns_point_group_measured_fraction_full 0.9910
_diffrn_reflns_point_group_measured_fraction_max 0.9879
_diffrn_reflns_theta_full        67.6840
_diffrn_reflns_theta_max         70.06
_diffrn_reflns_theta_min         3.72
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.482
_exptl_absorpt_correction_T_max  0.942
_exptl_absorpt_correction_T_min  0.683
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.142a (Rigaku Oxford Diffraction, 2024)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.911
_exptl_crystal_description       plate
_exptl_crystal_F_000             428.212
_exptl_crystal_size_max          0.096
_exptl_crystal_size_mid          0.058
_exptl_crystal_size_min          0.008
_refine_diff_density_max         0.7981
_refine_diff_density_min         -0.3085
_refine_diff_density_rms         0.0859
_refine_ls_abs_structure_details
'Hooft, R.W.W., Straver, L.H., Spek, A.L. (2010). J. Appl. Cryst., 43, 665-668.'
_refine_ls_abs_structure_Flack   -0.009(8)
_refine_ls_d_res_high            0.8201
_refine_ls_d_res_low             11.8822
_refine_ls_goodness_of_fit_ref   1.0571
_refine_ls_hydrogen_treatment    refall
_refine_ls_matrix_type           full
_refine_ls_number_constraints    0
_refine_ls_number_parameters     251
_refine_ls_number_reflns         2767
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.0571
_refine_ls_R_factor_all          0.0274
_refine_ls_R_factor_gt           0.0253
_refine_ls_shift/su_max          0.0008
_refine_ls_shift/su_mean         0.0001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0417P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0584
_refine_ls_wR_factor_ref         0.0591
_reflns_Friedel_coverage         0.978
_reflns_limit_h_max              11
_reflns_limit_h_min              -11
_reflns_limit_k_max              8
_reflns_limit_k_min              -8
_reflns_limit_l_max              14
_reflns_limit_l_min              -14
_reflns_number_gt                2652
_reflns_number_total             2767
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d5dt02245b2.cif
_cod_data_source_block           CB126_v2_v4_abs4
_cod_original_sg_symbol_Hall     ' P 2yb'
_cod_database_code               7719807
_chemical_oxdiff_formula         'C6 H13 N12 Cl3 Zn1 '
_diffrn_oxdiff_digest_hkl
;
43713fb11fd3b818d0f98974f2f8161c0dd7ca
;
_olex2_refinement_description
;
;
_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 6.0
   PARTITIONING:   NoSpherA2
   INT ACCURACY:   High
   METHOD:         PBE0
   BASIS SET:      def2-TZVPD
   CHARGE:         0
   MULTIPLICITY:   1
   DATE:           2025-08-06_16-03-44
;
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in perfluoroether oil'
_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
- Detector area scaling
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 2.245
_oxdiff_exptl_absorpt_empirical_full_min 0.522