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_7719804
_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_formula_moiety         'C12 H26 Cl4 N24 O2 Zn3'
_chemical_formula_sum            'C12 H26 Cl4 N24 O2 Zn3'
_chemical_formula_weight         876.498
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_Int_Tables_number      2
_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                72.4808(12)
_cell_angle_beta                 79.2600(11)
_cell_angle_gamma                89.9677(10)
_cell_formula_units_Z            2
_cell_length_a                   10.53581(13)
_cell_length_b                   10.58069(13)
_cell_length_c                   13.86760(19)
_cell_measurement_reflns_used    36442
_cell_measurement_temperature    150.02(17)
_cell_measurement_theta_max      79.8210
_cell_measurement_theta_min      3.3990
_cell_volume                     1445.83(3)
_computing_cell_refinement       'CrysAlisPro 1.171.43.142a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.142a 64-bit (release 17-10-2024))'
_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)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.02(17)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.9990
_diffrn_measured_fraction_theta_max 0.9963
_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    -57.00  -9.00   0.50    4.00    --  -49.91 118.00 116.00   96
  2  \w     31.00  75.00   0.50    4.00    --   49.91-118.00  30.00   88
  3  \w    -77.00 -52.00   0.50    8.00    --  -90.00 118.00 116.00   50
  4  \w   -132.00-105.00   0.50    8.00    --  -90.00-118.00  30.00   54
  5  \w    100.00 149.00   0.50    8.00    --  111.50 118.00 116.00   98
  6  \w     84.00 110.00   0.50    8.00    --  111.50-118.00  30.00   52
  7  \w   -117.00 -74.00   0.50    4.00    --  -49.91-125.00-150.00   86
  8  \w    -61.00 -18.00   0.50    4.00    --  -49.91  57.00 -30.00   86
  9  \w   -115.00 -86.00   0.50    4.00    --  -49.91-125.00   0.00   58
 10  \w    -19.00  21.00   0.50    4.00    --  -49.91  19.00  30.00   80
 11  \w    -42.00  22.00   0.50    4.00    --  -49.91  37.00 -90.00  128
 12  \w    -16.00   9.00   0.50    4.00    --  -49.91  57.00 -30.00   50
 13  \w     32.00  57.00   0.50    4.00    --   49.91 -57.00  90.00   50
 14  \w    -19.00  26.00   0.50    4.00    --   49.91 -57.00  90.00   90
 15  \w    -20.00  13.00   0.50    4.00    --   49.91 -19.00 120.00   66
 16  \w    -70.00 -31.00   0.50    8.00    --  -90.00  61.00-120.00   78
 17  \w    -50.00 -19.00   0.50    8.00    --  -90.00  45.00  30.00   62
 18  \w   -138.00-111.00   0.50    8.00    --  -90.00 -30.00  30.00   54
 19  \w   -139.00 -82.00   0.50    8.00    --  -90.00 -45.00  90.00  114
 20  \w     72.00 105.00   0.50    8.00    --  111.50 -94.00 120.00   66
 21  \w     41.00  67.00   0.50    8.00    --  111.50 -94.00 120.00   52
 22  \w     44.00  71.00   0.50    8.00    --  111.50 -61.00 -90.00   54
 23  \w     54.00 106.00   0.50    8.00    --  111.50 -94.00-120.00  104
 24  \w    113.00 159.00   0.50    8.00    --  111.50  15.00-180.00   92
 25  \w     42.00  68.00   0.50    8.00    --  111.50 -77.00  30.00   52
 26  \w     42.00  71.00   0.50    8.00    --  111.50 -61.00-180.00   58
 27  \w    115.00 162.00   0.50    8.00    --  111.50  15.00-120.00   94
 28  \w     80.00 106.00   0.50    8.00    --  111.50 -77.00-120.00   52
 29  \w     41.00 105.00   0.50    8.00    --  111.50 -77.00 -30.00  128
 30  \w     44.00 111.00   0.50    8.00    --  111.50-125.00   0.00  134
 31  \w    113.00 140.00   0.50    8.00    --  111.50  45.00  90.00   54
 32  \w     98.00 124.00   0.50    8.00    --  111.50  77.00 -90.00   52
 33  \w     43.00  70.00   0.50    8.00    --  111.50 -61.00  30.00   54
 34  \w     42.00  70.00   0.50    8.00    --  111.50 -94.00 150.00   56
 35  \w     76.00 102.00   0.50    8.00    --  111.50 -94.00 150.00   52
 36  \w     42.00  70.00   0.50    8.00    --  111.50 -61.00  90.00   56
 37  \w     41.00  71.00   0.50    8.00    --  111.50 -61.00-150.00   60
 38  \w     44.00  71.00   0.50    8.00    --  111.50 -61.00 150.00   54
 39  \w    108.00 159.00   0.50    8.00    --  111.50  15.00  90.00  102
 40  \w     44.00 103.00   0.50    8.00    --  111.50 -94.00  90.00  118
 41  \w    108.00 173.00   0.50    8.00    --  111.50  30.00  30.00  130
 42  \w     64.00 109.00   0.50    8.00    --  111.50-125.00 -60.00   90
 43  \w    115.00 178.00   0.50    8.00    --  111.50  45.00 120.00  126
 44  \w     44.00  72.00   0.50    8.00    --  111.50 -94.00  30.00   56
 45  \w     77.00 104.00   0.50    8.00    --  111.50 -94.00  30.00   54
 46  \w    105.00 156.00   0.50    8.00    --  111.50  45.00-180.00  102
 47  \w     63.00 103.00   0.50    8.00    --  111.50 -94.00 -60.00   80
 48  \w    153.00 178.00   0.50    8.00    --  111.50  45.00  90.00   50
 49  \w     73.00 106.00   0.50    8.00    --  111.50 -94.00-180.00   66
 50  \w     79.00 106.00   0.50    8.00    --  111.50 -94.00 -30.00   54
 51  \w     73.00 106.00   0.50    8.00    --  111.50 -94.00  60.00   66
 52  \w     42.00  73.00   0.50    8.00    --  111.50 -77.00 150.00   62
 53  \w    112.00 171.00   0.50    8.00    --  111.50  30.00 -90.00  118
 54  \w     44.00  70.00   0.50    8.00    --  111.50 -61.00-120.00   52
 55  \w    -77.00 -52.00   0.50    8.00    --  -90.00 118.00 116.00   50
 56  \w    -81.00 -46.00   0.50    4.00    --  -49.91 -19.00-150.00   70
 57  \w    -96.00 -44.00   0.50    4.00    --  -49.91 -37.00 -60.00  104
 58  \w    -89.00 -45.00   0.50    4.00    --  -49.91 -39.00  61.05   88
 59  \w    -64.00 -31.00   0.50    4.00    --  -49.91 -77.00-150.00   66
 60  \w    -58.00 -31.00   0.50    4.00    --  -49.91 -77.00   0.00   54
 61  \w    -59.00 -30.00   0.50    4.00    --  -49.91 -77.00 -90.00   58
 62  \w    -73.00 -47.00   0.50    4.00    --  -49.91 -37.00 150.00   52
 63  \w    -56.00 -30.00   0.50    4.00    --  -49.91 -77.00  60.00   52
 64  \w    -60.00 -31.00   0.50    4.00    --  -49.91 -77.00-180.00   58
 65  \w    -66.00 -30.00   0.50    4.00    --  -49.91 -77.00 -60.00   72
 66  \w    -55.00 -30.00   0.50    4.00    --  -49.91 -77.00  30.00   50
 67  \w    -93.00 -44.00   0.50    4.00    --  -49.91 -40.00-132.44   98
 68  \w    -57.00 -32.00   0.50    4.00    --  -49.91 -77.00-120.00   50
 69  \w    -84.00 -44.00   0.50    4.00    --  -49.91 -37.00   0.00   80
 70  \w    -69.00 -30.00   0.50    4.00    --  -49.91 -77.00 150.00   78
 71  \w    -57.00 -30.00   0.50    4.00    --  -49.91 -77.00 120.00   54
 72  \w    -90.00 -48.00   0.50    4.00    --  -49.91 -37.00 120.00   84
 73  \w    -58.00 -31.00   0.50    4.00    --  -49.91 -77.00  90.00   54
 74  \w    -96.00 -70.00   0.50    8.00    --  -90.00 -77.00 -30.00   52
 75  \w    -97.00 -71.00   0.50    8.00    --  -90.00 -76.00 -68.72   52
 76  \w    -97.00 -71.00   0.50    8.00    --  -90.00 -76.00-157.21   52
 77  \w   -102.00 -76.00   0.50    8.00    --  -90.00 -64.00 -60.27   52
 78  \w   -102.00 -75.00   0.50    8.00    --  -90.00 -65.00  62.79   54
 79  \w    -99.00 -73.00   0.50    8.00    --  -90.00 -70.00 -23.86   52
 80  \w    -97.00 -70.00   0.50    8.00    --  -90.00 -77.00 -90.00   54
 81  \w    -96.00 -70.00   0.50    8.00    --  -90.00 -77.00   0.00   52
 82  \w    -98.00 -72.00   0.50    8.00    --  -90.00 -74.00-141.96   52
 83  \w    -98.00 -72.00   0.50    8.00    --  -90.00 -74.00 -58.30   52
 84  \w   -156.00-129.00   0.50    8.00    --  -90.00 -74.00 -58.30   54
 85  \w    -98.00 -72.00   0.50    8.00    --  -90.00 -77.00  30.00   52
 86  \w    -98.00 -72.00   0.50    8.00    --  -90.00 -72.00   8.02   52
 87  \w    -97.00 -70.00   0.50    8.00    --  -90.00 -77.00 150.00   54
 88  \w    -96.00 -70.00   0.50    8.00    --  -90.00 -77.00  97.86   52
 89  \w    -96.00 -70.00   0.50    8.00    --  -90.00 -77.00  60.00   52
 90  \w    -97.00 -71.00   0.50    8.00    --  -90.00 -76.00-170.77   52
 91  \w   -100.00 -72.00   0.50    8.00    --  -90.00 -74.00-109.34   56
 92  \w    -98.00 -72.00   0.50    8.00    --  -90.00 -77.00 120.00   52
 93  \w   -150.00-124.00   0.50    8.00    --  -90.00 -74.00-109.34   52
 94  \w    -99.00 -72.00   0.50    8.00    --  -90.00 -72.00 159.80   54
 95  \w    -98.00 -72.00   0.50    8.00    --  -90.00 -74.00 133.22   52
 96  \w    -96.00 -70.00   0.50    8.00    --  -90.00 -77.00  90.00   52
 97  \w   -156.00-130.00   0.50    8.00    --  -90.00 -74.00 133.22   52
 98  \w    -98.00 -72.00   0.50    8.00    --  -90.00 -73.00 -79.22   52
 99  \w   -101.00 -75.00   0.50    8.00    --  -90.00 -66.00 112.97   52
100  \w   -101.00 -75.00   0.50    8.00    --  -90.00 -65.00  30.49   52
101  \w    -96.00 -70.00   0.50    8.00    --  -90.00 -77.00-180.00   52
102  \w   -149.00-123.00   0.50    8.00    --  -90.00 -77.00  90.00   52
103  \w    -96.00 -70.00   0.50    8.00    --  -90.00 -77.00-120.00   52
104  \w    139.00 175.00   0.50    8.00    --  111.50  61.00  90.00   72
105  \w    133.00 161.00   0.50    8.00    --  111.50  77.00 -30.00   56
106  \w    100.00 130.00   0.50    8.00    --  111.50  61.00  90.00   60
107  \w     92.00 128.00   0.50    8.00    --  111.50  77.00-180.00   72
108  \w     92.00 129.00   0.50    8.00    --  111.50  77.00   0.00   74
109  \w     98.00 126.00   0.50    8.00    --  111.50  77.00 -30.00   56
110  \w    149.00 178.00   0.50    8.00    --  111.50  61.00 -90.00   58
111  \w    139.00 165.00   0.50    8.00    --  111.50  77.00-180.00   52
112  \w     92.00 133.00   0.50    8.00    --  111.50  77.00  60.00   82
113  \w     93.00 128.00   0.50    8.00    --  111.50  77.00  90.00   70
114  \w    102.00 128.00   0.50    8.00    --  111.50  61.00 -90.00   52
115  \w    100.00 138.00   0.50    8.00    --  111.50  61.00-150.00   76
116  \w    137.00 165.00   0.50    8.00    --  111.50  77.00  30.00   56
117  \w    139.00 175.00   0.50    8.00    --  111.50  77.00 -60.00   72
118  \w     92.00 134.00   0.50    8.00    --  111.50  77.00 -60.00   84
119  \w     93.00 118.00   0.50    8.00    --  111.50  77.00  30.00   50
120  \w     99.00 137.00   0.50    8.00    --  111.50  61.00 -60.00   76
121  \w    151.00 177.00   0.50    8.00    --  111.50  61.00  60.00   52
122  \w    151.00 176.00   0.50    8.00    --  111.50  77.00 150.00   50
123  \w     92.00 118.00   0.50    8.00    --  111.50  77.00 150.00   52
124  \w    100.00 127.00   0.50    8.00    --  111.50  61.00  60.00   54
125  \w    104.00 134.00   0.50    8.00    --  111.50  45.00 -90.00   60
126  \w    145.00 175.00   0.50    8.00    --  111.50  61.00-120.00   60
127  \w    131.00 166.00   0.50    8.00    --  111.50  77.00-150.00   70
128  \w    111.00 143.00   0.50    8.00    --  111.50 125.00 -30.00   64
129  \w     98.00 125.00   0.50    8.00    --  111.50  61.00-120.00   54
130  \w     63.00 113.00   0.50    8.00    --  111.50   0.00  60.00  100
131  \w     99.00 125.00   0.50    8.00    --  111.50  61.00   0.00   52
132  \w     97.00 123.00   0.50    8.00    --  111.50  77.00 120.00   52
133  \w     92.00 122.00   0.50    8.00    --  111.50  77.00-150.00   60
;
_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      0.0764559000
_diffrn_orient_matrix_UB_12      0.1351806000
_diffrn_orient_matrix_UB_13      -0.0331683000
_diffrn_orient_matrix_UB_21      -0.0090931000
_diffrn_orient_matrix_UB_22      0.0188860000
_diffrn_orient_matrix_UB_23      -0.1130285000
_diffrn_orient_matrix_UB_31      -0.1276709000
_diffrn_orient_matrix_UB_32      0.0690211000
_diffrn_orient_matrix_UB_33      0.0152686000
_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  0.0310
_diffrn_reflns_av_unetI/netI     0.0124
_diffrn_reflns_Laue_measured_fraction_full 0.9990
_diffrn_reflns_Laue_measured_fraction_max 0.9963
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            46915
_diffrn_reflns_point_group_measured_fraction_full 0.9990
_diffrn_reflns_point_group_measured_fraction_max 0.9963
_diffrn_reflns_theta_full        67.6840
_diffrn_reflns_theta_max         74.50
_diffrn_reflns_theta_min         3.41
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.874
_exptl_absorpt_correction_T_max  0.842
_exptl_absorpt_correction_T_min  0.654
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.142a (Rigaku Oxford Diffraction, 2024)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
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    2.013
_exptl_crystal_description       plate
_exptl_crystal_F_000             875.947
_exptl_crystal_size_max          0.082
_exptl_crystal_size_mid          0.074
_exptl_crystal_size_min          0.047
_refine_diff_density_max         0.8424
_refine_diff_density_min         -0.3605
_refine_diff_density_rms         0.0512
_refine_ls_d_res_high            0.8000
_refine_ls_d_res_low             12.9699
_refine_ls_goodness_of_fit_ref   1.0933
_refine_ls_hydrogen_treatment    refall
_refine_ls_matrix_type           full
_refine_ls_number_constraints    0
_refine_ls_number_parameters     640
_refine_ls_number_reflns         5911
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.0927
_refine_ls_R_factor_all          0.0175
_refine_ls_R_factor_gt           0.0172
_refine_ls_shift/su_max          -0.0007
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0192P)^2^+0.7155P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0422
_refine_ls_wR_factor_ref         0.0425
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              13
_reflns_limit_h_min              -12
_reflns_limit_k_max              13
_reflns_limit_k_min              -12
_reflns_limit_l_max              17
_reflns_limit_l_min              0
_reflns_number_gt                5832
_reflns_number_total             5911
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d5dt02245b2.cif
_cod_data_source_block           MG_ZnClMel_v1_abs
_cod_database_code               7719804
_chemical_oxdiff_formula         'C24  H52  Cl8  N48  O4  Zn6  '
_diffrn_oxdiff_digest_hkl
;
431ca4d522db4e72cecf54cf5fe37ad57ba091
;
_olex2_refinement_description
;
1. Uiso/Uaniso restraints and constraints
Uanis(H2) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.01
;
_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:   High
   METHOD:         M062X
   BASIS SET:      x2c-TZVPP
   CHARGE:         0
   MULTIPLICITY:   1
   DATE:           2024-12-05_07-45-14
;
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 2.636
_oxdiff_exptl_absorpt_empirical_full_min 0.478