# Supplementary Information (SI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2024

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_shelx
_database_code_depnum_ccdc_archive 'CCDC 2311348'
loop_
_audit_author_name
_audit_author_address
'MUNIYANDI SANKARALINGAM'
;National Institute of Technology Calicut
India
;
_audit_update_record             
;
2024-07-16 deposited with the CCDC.	2024-07-19 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2018/3
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C15 H18 Br Cu N3 O3'
_chemical_formula_weight         431.77

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cu Cu -1.9646 0.5888 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Br Br -0.6763 1.2805 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 21/n'
_space_group_name_Hall           '-P 2yn'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x-1/2, -y-1/2, z-1/2'

_cell_length_a                   7.9149(8)
_cell_length_b                   18.466(2)
_cell_length_c                   11.1514(11)
_cell_angle_alpha                90
_cell_angle_beta                 94.607(7)
_cell_angle_gamma                90
_cell_volume                     1624.6(3)
_cell_formula_units_Z            4
_cell_measurement_temperature    300(2)
_cell_measurement_reflns_used    2275
_cell_measurement_theta_min      4.64
_cell_measurement_theta_max      60.05

_exptl_crystal_description       block
_exptl_crystal_colour            green
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.765
_exptl_crystal_F_000             868
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.042
_exptl_crystal_size_mid          0.030
_exptl_crystal_size_min          0.025
_exptl_absorpt_coefficient_mu    4.939
_shelx_estimated_absorpt_T_min   0.819
_shelx_estimated_absorpt_T_max   0.886
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.5665
_exptl_absorpt_correction_T_max  0.7525
_exptl_absorpt_process_details   'SADABS-2016/2 - Bruker AXS'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      300(2)
_diffrn_radiation_wavelength     1.54178
_diffrn_radiation_type           CuK\a
_diffrn_source                   'micro focus sealed tube'
_diffrn_measurement_device_type  'Bruker D8 Venture Diffractometer'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            9012
_diffrn_reflns_av_unetI/netI     0.1498
_diffrn_reflns_av_R_equivalents  0.1366
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_theta_min         4.643
_diffrn_reflns_theta_max         64.737
_diffrn_reflns_theta_full        64.737
_diffrn_measured_fraction_theta_max 0.747
_diffrn_measured_fraction_theta_full 0.747
_diffrn_reflns_Laue_measured_fraction_max 0.747
_diffrn_reflns_Laue_measured_fraction_full 0.747
_diffrn_reflns_point_group_measured_fraction_max 0.747
_diffrn_reflns_point_group_measured_fraction_full 0.747
_reflns_number_total             2055
_reflns_number_gt                866
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;

_computing_data_collection       'APEX3(Bruker, 2016)'
_computing_cell_refinement       'APEX3/SAINT (Bruker, 2016)'
_computing_data_reduction        'SAINT/XPREP (Bruker, 2016)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_molecular_graphics    'ORTEP3 (Farrugia, 2012)'
_computing_publication_material  'SHELXL-2018/3 (Sheldrick, 2018)'
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.2000P)²] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         2055
_refine_ls_number_parameters     214
_refine_ls_number_restraints     3
_refine_ls_R_factor_all          0.2503
_refine_ls_R_factor_gt           0.1300
_refine_ls_wR_factor_ref         0.4030
_refine_ls_wR_factor_gt          0.3196
_refine_ls_goodness_of_fit_ref   1.203
_refine_ls_restrained_S_all      1.202
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
C1 C 0.157(3) 0.5501(14) 0.661(2) 0.088(7) Uani 1 1 d . . . . .
H1 H 0.122345 0.577671 0.724464 0.106 Uiso 1 1 calc R U . . .
C2 C 0.130(3) 0.4750(15) 0.662(2) 0.097(7) Uani 1 1 d . . . . .
H2 H 0.078863 0.453345 0.725633 0.117 Uiso 1 1 calc R U . . .
C3 C 0.178(3) 0.4350(14) 0.571(3) 0.107(9) Uani 1 1 d . . . . .
H3 H 0.156095 0.385581 0.569314 0.128 Uiso 1 1 calc R U . . .
C4 C 0.264(3) 0.4668(14) 0.474(3) 0.100(8) Uani 1 1 d . . . . .
C5 C 0.322(3) 0.4293(15) 0.374(3) 0.102(8) Uani 1 1 d . . . . .
H5 H 0.313377 0.379161 0.368121 0.122 Uiso 1 1 calc R U . . .
C6 C 0.389(3) 0.4676(16) 0.288(3) 0.102(8) Uani 1 1 d . . . . .
H6 H 0.427995 0.442567 0.223742 0.122 Uiso 1 1 calc R U . . .
C7 C 0.405(2) 0.5432(14) 0.2891(19) 0.082(7) Uani 1 1 d . . . . .
H7 H 0.453324 0.567163 0.227139 0.099 Uiso 1 1 calc R U . . .
C8 C 0.347(3) 0.5810(13) 0.383(3) 0.090(7) Uani 1 1 d . . . . .
C9 C 0.277(3) 0.5410(14) 0.478(2) 0.083(7) Uani 1 1 d . . . . .
C10 C 0.373(3) 0.7025(15) 0.327(3) 0.093(8) Uani 1 1 d . . . . .
C11 C 0.354(3) 0.7838(13) 0.368(3) 0.099(8) Uani 1 1 d . . . . .
H11A H 0.444614 0.812692 0.338748 0.119 Uiso 1 1 calc R U . . .
H11B H 0.247046 0.803156 0.334167 0.119 Uiso 1 1 calc R U . . .
C12 C 0.546(3) 0.8010(10) 0.547(2) 0.086(7) Uani 1 1 d . . . . .
H12A H 0.558085 0.790787 0.632922 0.104 Uiso 1 1 calc R U . . .
H12B H 0.618123 0.767395 0.508101 0.104 Uiso 1 1 calc R U . . .
C13 C 0.606(3) 0.8767(11) 0.527(2) 0.090(7) Uani 1 1 d . . . . .
H13A H 0.721773 0.881734 0.561565 0.108 Uiso 1 1 calc R U . . .
H13B H 0.605414 0.885407 0.441080 0.108 Uiso 1 1 calc R U . . .
C14 C 0.336(3) 0.9225(12) 0.520(2) 0.102(8) Uani 1 1 d . . . . .
H14A H 0.340184 0.929457 0.433699 0.122 Uiso 1 1 calc R U . . .
H14B H 0.264288 0.960314 0.548907 0.122 Uiso 1 1 calc R U . . .
C15 C 0.258(3) 0.8507(11) 0.542(2) 0.099(8) Uani 1 1 d . . . . .
H15A H 0.146068 0.848749 0.500114 0.119 Uiso 1 1 calc R U . . .
H15B H 0.246393 0.845358 0.627029 0.119 Uiso 1 1 calc R U . . .
N1 N 0.231(2) 0.5833(9) 0.5743(19) 0.081(5) Uani 1 1 d . . . . .
N2 N 0.352(2) 0.6552(11) 0.4091(16) 0.078(5) Uani 1 1 d . . . . .
N3 N 0.362(2) 0.7886(9) 0.4999(19) 0.083(6) Uani 1 1 d . . . . .
O1 O 0.406(2) 0.6964(8) 0.2213(19) 0.103(6) Uani 1 1 d . . . . .
O2 O 0.504(2) 0.9290(7) 0.5780(15) 0.096(5) Uani 1 1 d . . . . .
Cu1 Cu 0.2835(4) 0.68889(16) 0.5597(3) 0.0861(15) Uani 1 1 d . . . . .
Br1 Br 0.3361(3) 0.71069(14) 0.7768(3) 0.1001(14) Uani 1 1 d . . . . .
O3 O 0.0063(19) 0.7178(6) 0.5435(17) 0.089(5) Uani 1 1 d D . . . .
H3A H 0.04(3) 0.752(7) 0.587(15) 0.133 Uiso 1 1 d D U . . .
H3B H -0.04(3) 0.733(10) 0.479(10) 0.133 Uiso 1 1 d D U . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
C1 N1 1.32(2) . ?
C1 C2 1.40(3) . ?
C1 H1 0.9300 . ?
C2 C3 1.34(3) . ?
C2 H2 0.9300 . ?
C3 C4 1.44(3) . ?
C3 H3 0.9300 . ?
C4 C9 1.37(3) . ?
C4 C5 1.42(3) . ?
C5 C6 1.33(3) . ?
C5 H5 0.9300 . ?
C6 C7 1.40(3) . ?
C6 H6 0.9300 . ?
C7 C8 1.36(3) . ?
C7 H7 0.9300 . ?
C8 N2 1.40(3) . ?
C8 C9 1.44(3) . ?
C9 N1 1.41(2) . ?
C10 O1 1.23(3) . ?
C10 N2 1.29(3) . ?
C10 C11 1.58(3) . ?
C11 N3 1.47(3) . ?
C11 H11A 0.9700 . ?
C11 H11B 0.9700 . ?
C12 C13 1.50(2) . ?
C12 N3 1.53(3) . ?
C12 H12A 0.9700 . ?
C12 H12B 0.9700 . ?
C13 O2 1.41(2) . ?
C13 H13A 0.9700 . ?
C13 H13B 0.9700 . ?
C14 O2 1.44(2) . ?
C14 C15 1.49(3) . ?
C14 H14A 0.9700 . ?
C14 H14B 0.9700 . ?
C15 N3 1.50(2) . ?
C15 H15A 0.9700 . ?
C15 H15B 0.9700 . ?
N1 Cu1 2.004(16) . ?
N2 Cu1 1.909(17) . ?
N3 Cu1 2.070(16) . ?
Cu1 O3 2.251(16) . ?
Cu1 Br1 2.456(5) . ?
O3 H3A 0.82(2) . ?
O3 H3B 0.82(2) . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
N1 C1 C2 123(2) . . ?
N1 C1 H1 118.5 . . ?
C2 C1 H1 118.5 . . ?
C3 C2 C1 119(2) . . ?
C3 C2 H2 120.6 . . ?
C1 C2 H2 120.6 . . ?
C2 C3 C4 122(3) . . ?
C2 C3 H3 119.1 . . ?
C4 C3 H3 119.1 . . ?
C9 C4 C5 119(3) . . ?
C9 C4 C3 115(3) . . ?
C5 C4 C3 126(3) . . ?
C6 C5 C4 118(3) . . ?
C6 C5 H5 120.8 . . ?
C4 C5 H5 120.8 . . ?
C5 C6 C7 124(3) . . ?
C5 C6 H6 117.8 . . ?
C7 C6 H6 117.8 . . ?
C8 C7 C6 119(2) . . ?
C8 C7 H7 120.7 . . ?
C6 C7 H7 120.7 . . ?
C7 C8 N2 131(2) . . ?
C7 C8 C9 118(2) . . ?
N2 C8 C9 111(2) . . ?
C4 C9 N1 124(2) . . ?
C4 C9 C8 122(2) . . ?
N1 C9 C8 115(2) . . ?
O1 C10 N2 132(2) . . ?
O1 C10 C11 114(2) . . ?
N2 C10 C11 115(2) . . ?
N3 C11 C10 111(2) . . ?
N3 C11 H11A 109.5 . . ?
C10 C11 H11A 109.5 . . ?
N3 C11 H11B 109.5 . . ?
C10 C11 H11B 109.5 . . ?
H11A C11 H11B 108.1 . . ?
C13 C12 N3 113.1(17) . . ?
C13 C12 H12A 109.0 . . ?
N3 C12 H12A 109.0 . . ?
C13 C12 H12B 109.0 . . ?
N3 C12 H12B 109.0 . . ?
H12A C12 H12B 107.8 . . ?
O2 C13 C12 112.3(16) . . ?
O2 C13 H13A 109.1 . . ?
C12 C13 H13A 109.1 . . ?
O2 C13 H13B 109.1 . . ?
C12 C13 H13B 109.1 . . ?
H13A C13 H13B 107.9 . . ?
O2 C14 C15 112.1(19) . . ?
O2 C14 H14A 109.2 . . ?
C15 C14 H14A 109.2 . . ?
O2 C14 H14B 109.2 . . ?
C15 C14 H14B 109.2 . . ?
H14A C14 H14B 107.9 . . ?
C14 C15 N3 112.8(16) . . ?
C14 C15 H15A 109.0 . . ?
N3 C15 H15A 109.0 . . ?
C14 C15 H15B 109.0 . . ?
N3 C15 H15B 109.0 . . ?
H15A C15 H15B 107.8 . . ?
C1 N1 C9 118(2) . . ?
C1 N1 Cu1 128.2(17) . . ?
C9 N1 Cu1 114.2(16) . . ?
C10 N2 C8 121(2) . . ?
C10 N2 Cu1 117.9(18) . . ?
C8 N2 Cu1 119.9(16) . . ?
C11 N3 C15 112.1(19) . . ?
C11 N3 C12 108.5(17) . . ?
C15 N3 C12 107.8(16) . . ?
C11 N3 Cu1 106.3(13) . . ?
C15 N3 Cu1 113.2(12) . . ?
C12 N3 Cu1 109.0(13) . . ?
C13 O2 C14 107.5(17) . . ?
N2 Cu1 N1 80.2(9) . . ?
N2 Cu1 N3 83.8(8) . . ?
N1 Cu1 N3 164.0(8) . . ?
N2 Cu1 O3 110.4(7) . . ?
N1 Cu1 O3 91.7(6) . . ?
N3 Cu1 O3 94.5(6) . . ?
N2 Cu1 Br1 152.0(6) . . ?
N1 Cu1 Br1 95.7(6) . . ?
N3 Cu1 Br1 98.1(6) . . ?
O3 Cu1 Br1 97.3(5) . . ?
Cu1 O3 H3A 84(10) . . ?
Cu1 O3 H3B 119(10) . . ?
H3A O3 H3B 110(4) . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
N1 C1 C2 C3 -1(4) . . . . ?
C1 C2 C3 C4 3(4) . . . . ?
C2 C3 C4 C9 -6(4) . . . . ?
C2 C3 C4 C5 179(2) . . . . ?
C9 C4 C5 C6 1(4) . . . . ?
C3 C4 C5 C6 176(2) . . . . ?
C4 C5 C6 C7 -1(4) . . . . ?
C5 C6 C7 C8 -1(4) . . . . ?
C6 C7 C8 N2 177(2) . . . . ?
C6 C7 C8 C9 2(3) . . . . ?
C5 C4 C9 N1 -177(2) . . . . ?
C3 C4 C9 N1 7(4) . . . . ?
C5 C4 C9 C8 0(4) . . . . ?
C3 C4 C9 C8 -175(2) . . . . ?
C7 C8 C9 C4 -2(4) . . . . ?
N2 C8 C9 C4 -178(2) . . . . ?
C7 C8 C9 N1 176.0(19) . . . . ?
N2 C8 C9 N1 0(3) . . . . ?
O1 C10 C11 N3 -164(2) . . . . ?
N2 C10 C11 N3 15(3) . . . . ?
N3 C12 C13 O2 57(3) . . . . ?
O2 C14 C15 N3 -58(3) . . . . ?
C2 C1 N1 C9 2(3) . . . . ?
C2 C1 N1 Cu1 -178.9(16) . . . . ?
C4 C9 N1 C1 -6(3) . . . . ?
C8 C9 N1 C1 176.3(19) . . . . ?
C4 C9 N1 Cu1 175.0(19) . . . . ?
C8 C9 N1 Cu1 -3(2) . . . . ?
O1 C10 N2 C8 -7(4) . . . . ?
C11 C10 N2 C8 173.3(18) . . . . ?
O1 C10 N2 Cu1 -175(2) . . . . ?
C11 C10 N2 Cu1 5(3) . . . . ?
C7 C8 N2 C10 20(4) . . . . ?
C9 C8 N2 C10 -164(2) . . . . ?
C7 C8 N2 Cu1 -172(2) . . . . ?
C9 C8 N2 Cu1 3(2) . . . . ?
C10 C11 N3 C15 -149.5(17) . . . . ?
C10 C11 N3 C12 91.5(19) . . . . ?
C10 C11 N3 Cu1 -25(2) . . . . ?
C14 C15 N3 C11 -71(3) . . . . ?
C14 C15 N3 C12 48(3) . . . . ?
C14 C15 N3 Cu1 168.5(17) . . . . ?
C13 C12 N3 C11 75(2) . . . . ?
C13 C12 N3 C15 -47(3) . . . . ?
C13 C12 N3 Cu1 -170.2(15) . . . . ?
C12 C13 O2 C14 -62(2) . . . . ?
C15 C14 O2 C13 63(2) . . . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
_geom_hbond_publ_flag
C1 H1 Br1 0.93 3.01 3.49(3) 113.4 . yes
C2 H2 O2 0.93 2.38 3.27(3) 161.3 2_546 yes
C7 H7 O1 0.93 2.42 2.93(3) 114.6 . yes
C12 H12A Br1 0.97 2.88 3.57(2) 129.3 . yes
C13 H13A O1 0.97 2.64 3.37(3) 132.1 4_676 yes
C15 H15B Br1 0.97 3.05 3.70(3) 125.7 . yes
O3 H3A O1 0.82(2) 2.12(19) 2.71(2) 129(22) 4_576 yes
O3 H3A Br1 0.82(2) 3.14(19) 3.536(17) 113(16) . yes
O3 H3B Br1 0.82(2) 2.61(3) 3.430(18) 177(19) 4_575 yes

_refine_diff_density_max         1.043
_refine_diff_density_min         -1.342
_refine_diff_density_rms         0.170



# start Validation Reply Form
_vrf_PLAT029_shelx               
;
PROBLEM: _diffrn_measured_fraction_theta_full value Low .      0.747 Why?  
RESPONSE: Although diffraction data were collected upto 0.81 Angstrom,
the crystal showed very weak diffraction at higher Bragg angles. The
higher angle data have not been omitted from the refinement. 
;
_vrf_PLAT084_shelx               
;
PROBLEM: High wR2 Value (i.e. > 0.25) ...................       0.40 Report
RESPONSE: The crystal did not diffract appreciably at higher Bragg angles
and hence, the data and the structure are of suboptimal quality.
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_vrf_PLAT341_shelx               
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PROBLEM: Low Bond Precision on  C-C Bonds ...............    0.03833 Ang.  
RESPONSE: The crystal did not diffract appreciably at higher Bragg angles
and hence, the data and the structure are of suboptimal quality.
;
_vrf_PLAT911_shelx               
;
PROBLEM: Missing FCF Refl Between Thmin & STh/L=    0.587        521 Report
RESPONSE: Although diffraction data were collected upto 0.81 Angstrom,
the crystal showed very weak diffraction at higher Bragg angles. 
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# end Validation Reply Form
