# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2015

####################################################################### 
# 
# 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_1
_database_code_depnum_ccdc_archive 'CCDC 1430499'
_audit_update_record             
;
2015-10-09 deposited with the CCDC.
2015-12-22 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_PLAT780_1                   
;
PROBLEM: Coordinates do not Form a Properly Connected Set     Please Do !
RESPONSE: There are 1 and a half molecules in the unit cell connectivity is fine.
;

# Added during the CSD deposition process: Friday 9th of October 2015 01:11:37 PM
# end Validation Reply Form


_exptl_special_details           
; 
 The crystal was 
placed in the cold stream of an Oxford 
Cryosystems open-flow nitrogen cryostat (Cosier & 
Glazer, 1986) with a nominal stability of 0.1K. 
 
Cosier, J. & Glazer, A.M., 1986. J. Appl. Cryst. 105-107. 
;
_refine_special_details          
; 
? 
;
#--------------------------------------------------------------- 
# _oxford_ data items, April 2010: 
# There is some uncertainty about the correct way of forming local data 
# names, e.g. 

# _atom_site_special_shape_oxford 
# or 
# _oxford_atom_site_special_shape 

# see: 
# http://www.iucr.org/resources/cif/spec/version1.1/semantics#namespace 

# A reserved prefix, e.g. foo, must be used in the following way 
# " If the data file contains items defined in a DDL1 dictionary, the 
# local data names assigned under the reserved prefix must contain it as 
# their first component, e.g. _foo_atom_site_my_item. " 

# However, this seems to say the opposite: 
# http://www.iucr.org/__data/iucr/cif/standard/cifstd8.html 

# According to advice from the IUCr, CRYSTALS is correct 
#--------------------------------------------------------------- 
# End of 'script/refcif.dat' 
#end of refcif 
_cell_length_a                   9.78868(7)
_cell_length_b                   15.40415(13)
_cell_length_c                   17.09116(14)
_cell_angle_alpha                90
_cell_angle_beta                 90.7481(7)
_cell_angle_gamma                90
_cell_volume                     2576.89(4)

_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_H-M   'P 21/c '
_symmetry_space_group_name_Hall  ?
loop_
_symmetry_equiv_pos_as_xyz
x,y,z
-x,-y,-z
x,-y+1/2,z+1/2
-x,y+1/2,-z+1/2

loop_
_atom_type_symbol
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_Cromer_Mann_a1
_atom_type_scat_Cromer_Mann_b1
_atom_type_scat_Cromer_Mann_a2
_atom_type_scat_Cromer_Mann_b2
_atom_type_scat_Cromer_Mann_a3
_atom_type_scat_Cromer_Mann_b3
_atom_type_scat_Cromer_Mann_a4
_atom_type_scat_Cromer_Mann_b4
_atom_type_scat_Cromer_Mann_c
_atom_type_scat_source
C 0.0181 0.0091 2.3100 20.8439 1.0200 10.2075 1.5886 0.5687 0.8650 51.6512
0.2156 'International Tables Vol C 4.2.6.8 and 6.1.1.4'
H 0.0000 0.0000 0.4930 10.5109 0.3229 26.1257 0.1402 3.1424 0.0408 57.7998
0.0030 'International Tables Vol C 4.2.6.8 and 6.1.1.4'
N 0.0311 0.0180 12.2126 0.0057 3.1322 9.8933 2.0125 28.9975 1.1663 0.5826
-11.5290 'International Tables Vol C 4.2.6.8 and 6.1.1.4'
O 0.0492 0.0322 3.0485 13.2771 2.2868 5.7011 1.5463 0.3239 0.8670 32.9089
0.2508 'International Tables Vol C 4.2.6.8 and 6.1.1.4'
Cu -1.9646 0.5888 13.3380 3.5828 7.1676 0.2470 5.6158 11.3966 1.6735 64.8126
1.1910 'International Tables Vol C 4.2.6.8 and 6.1.1.4'
Br -0.6763 1.2805 17.1789 2.1723 5.2358 16.5796 5.6377 0.2609 3.9851 41.4328
2.9557 'International Tables Vol C 4.2.6.8 and 6.1.1.4'


_cell_formula_units_Z            4

# Given Formula = C18 H12 Br2 Cu1 N4 O2 
# Dc =      1.39 Fooo =   1578.00 Mu =     49.67 M =    539.67
# Found Formula = C27 H18 Br3 Cu1.50 N6 O3 
# Dc =      2.09 FOOO =   1578.00 Mu =     74.50 M =    809.51

_chemical_formula_sum            'C27 H18 Br3 Cu1.50 N6 O3'
_chemical_formula_moiety         'C27 H18 Br3 Cu1.50 N6 O3'
_chemical_compound_source        ?
_chemical_formula_weight         809.51


_cell_measurement_reflns_used    12116
_cell_measurement_theta_min      4
_cell_measurement_theta_max      76
_cell_measurement_temperature    120

_exptl_crystal_description       block
_exptl_crystal_colour            'translucent dark yellow'
_exptl_crystal_size_min          0.049
_exptl_crystal_size_mid          0.068
_exptl_crystal_size_max          0.098

_exptl_crystal_density_diffrn    2.086
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
# Non-dispersive F(000): 
_exptl_crystal_F_000             1578
_exptl_absorpt_coefficient_mu    7.450

# Sheldrick geometric approximatio 0.60 0.69 
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'CrysAlis, (Oxford Diffraction, 2002)'
_exptl_absorpt_correction_T_min  0.58
_exptl_absorpt_correction_T_max  0.69
_diffrn_measurement_device_type  'Oxford Diffraction SuperNova'
_diffrn_measurement_device       Area
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54180
_diffrn_measurement_method       ω

# If a reference occurs more than once, delete the author 
# and date from subsequent references. 
_computing_data_collection       'SuperNova, (Oxford Diffraction, 2010)'
_computing_cell_refinement       'CrysAlis, (Oxford Diffraction, 2002)'
_computing_data_reduction        'CrysAlis, (Oxford Diffraction, 2002)'
_computing_structure_solution    'Superflip (Palatinus & Chapuis, 2007)'
_computing_structure_refinement  'CRYSTALS (Betteridge et al., 2003)'
_computing_publication_material  'CRYSTALS (Betteridge et al., 2003)'
_computing_molecular_graphics    'CAMERON (Watkin et al., 1996)'

_diffrn_standards_interval_time  .
_diffrn_standards_interval_count .
_diffrn_standards_number         0
_diffrn_standards_decay_%        ?

_diffrn_ambient_temperature      120
_diffrn_reflns_number            21736
_reflns_number_total             5351
_diffrn_reflns_av_R_equivalents  0.029
# Number of reflections without Friedels Law is 0 
# Number of reflections with Friedels Law is 5351 
# Theoretical number of reflections is about 10790 


_diffrn_reflns_theta_min         3.863
_diffrn_reflns_theta_max         76.204
_diffrn_measured_fraction_theta_max 0.992

_diffrn_reflns_theta_full        74.680
_diffrn_measured_fraction_theta_full 0.998


_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_limit_l_max       18
_reflns_limit_h_min              -12
_reflns_limit_h_max              12
_reflns_limit_k_min              0
_reflns_limit_k_max              19
_reflns_limit_l_min              0
_reflns_limit_l_max              21

_oxford_diffrn_Wilson_B_factor   0.00
_oxford_diffrn_Wilson_scale      0.00

_atom_sites_solution_primary     Other #heavy,direct,difmap,geom
# _atom_sites_solution_secondary  difmap
_atom_sites_solution_hydrogens   difmap

_refine_diff_density_min         -0.58
_refine_diff_density_max         0.41


# The current dictionary definitions do not cover the 
# situation where the reflections used for refinement were 
# selected by a user-defined sigma threshold 


# The values actually used during refinement 
_oxford_reflns_threshold_expression_ref I>0.0\s(I)
_refine_ls_number_reflns         5333
_refine_ls_number_restraints     0
_refine_ls_number_parameters     439
_oxford_refine_ls_R_factor_ref   0.0250
_refine_ls_wR_factor_ref         0.0550
_refine_ls_goodness_of_fit_ref   0.9917
_refine_ls_shift/su_max          0.0012671
_refine_ls_shift/su_mean         0.0000364


# The values computed with all filters except I/sigma 
_oxford_reflns_number_all        5333
_refine_ls_R_factor_all          0.0250
_refine_ls_wR_factor_all         0.0550

# The values computed with a 2 sigma cutoff - a la SHELX 
_reflns_threshold_expression     I>2.0σ(I)
_reflns_number_gt                4908
_refine_ls_R_factor_gt           0.0219
_refine_ls_wR_factor_gt          0.0529

# choose from: rm (reference molecule of known chirality), 
# ad (anomolous dispersion - Flack), rmad (rm and ad), 
# syn (from synthesis), unk (unknown) or . (not applicable). 
_chemical_absolute_configuration .


_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_hydrogen_treatment    mixed #undef, noref, refall,
# refxyz, refU, constr or mixed
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
;
 Method= Modified Sheldrick 
 w=1/[σ²(F²) + ( 0.03P)² + 1.72P] 
 ,where P=(max(Fo²,0) + 2Fc²)/3 
;

# Uequiv = arithmetic mean of Ui i.e. Ueqiv = (U1+U2+U3)/3

# Replace last . with number of unfound hydrogen atoms attached to an atom.

# ..._refinement_flags_... 
# . no refinement constraints           S special position constraint on site
# G rigid group refinement of site      R riding atom
# D distance or angle restraint on site T thermal displacement constraints
# U Uiso or Uij restraint (rigid bond)  P partial occupancy constraint


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_occupancy
_atom_site_adp_type
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
_atom_site_attached_hydrogens
C13 C 1.3447(2) 0.42640(13) 0.36884(12) 0.0185 1.0000 Uani . . . . . .
C12 C 0.5977(2) 0.70883(13) 0.44982(11) 0.0169 1.0000 Uani . . . . . .
O13 O 1.35929(15) 0.48855(10) 0.42141(9) 0.0224 1.0000 Uani . . . . . .
C23 C 1.2174(2) 0.41612(14) 0.33038(12) 0.0207 1.0000 Uani . . . . . .
C33 C 1.1928(2) 0.35630(15) 0.27157(13) 0.0246 1.0000 Uani . . . . . .
C43 C 1.2973(3) 0.30161(15) 0.24853(13) 0.0269 1.0000 Uani . . . . . .
C53 C 1.4234(2) 0.30821(14) 0.28562(13) 0.0239 1.0000 Uani . . . . . .
C63 C 1.4494(2) 0.36882(14) 0.34523(12) 0.0195 1.0000 Uani . . . . . .
C73 C 1.5863(2) 0.37086(13) 0.38111(12) 0.0193 1.0000 Uani . . . . . .
C83 C 1.7042(2) 0.32342(14) 0.36156(13) 0.0222 1.0000 Uani . . . . . .
C93 C 1.8033(2) 0.34853(14) 0.41421(14) 0.0232 1.0000 Uani . . . . . .
N103 N 1.74781(18) 0.40787(12) 0.46174(11) 0.0204 1.0000 Uani . . . . . .
N113 N 1.61538(17) 0.42181(11) 0.44269(10) 0.0187 1.0000 Uani . . . . . .
O12 O 0.57255(14) 0.64874(10) 0.39691(9) 0.0211 1.0000 Uani . . . . . .
C72 C 0.3602(2) 0.77206(13) 0.44891(12) 0.0180 1.0000 Uani . . . . . .
C82 C 0.2499(2) 0.82510(14) 0.47173(13) 0.0226 1.0000 Uani . . . . . .
C92 C 0.1436(2) 0.80430(15) 0.42218(14) 0.0248 1.0000 Uani . . . . . .
N102 N 0.18795(18) 0.74275(13) 0.37315(12) 0.0221 1.0000 Uani . . . . . .
N112 N 0.31989(17) 0.72232(12) 0.38870(11) 0.0188 1.0000 Uani . . . . . .
Cu2 Cu 1.5000 0.5000 0.5000 0.0180 1.0000 Uani S . . . . .
C22 C 0.7312(2) 0.71552(14) 0.48150(12) 0.0195 1.0000 Uani . . . . . .
C32 C 0.7680(2) 0.77231(15) 0.54020(13) 0.0227 1.0000 Uani . . . . . .
C42 C 0.6704(2) 0.82820(15) 0.56976(13) 0.0252 1.0000 Uani . . . . . .
C52 C 0.5390(2) 0.82632(14) 0.53916(12) 0.0219 1.0000 Uani . . . . . .
C62 C 0.5007(2) 0.76861(13) 0.47951(12) 0.0175 1.0000 Uani . . . . . .
Cu1 Cu 0.41793(3) 0.637082(19) 0.329264(17) 0.0156 1.0000 Uani . . . . . .
Br2 Br 0.86542(2) 0.640022(16) 0.439904(14) 0.0249 1.0000 Uani . . . . . .
Br3 Br 1.07273(2) 0.490677(15) 0.361219(14) 0.0241 1.0000 Uani . . . . . .
Br1 Br -0.01727(2) 0.660657(16) 0.204931(13) 0.0242 1.0000 Uani . . . . . .
O11 O 0.27089(14) 0.63742(10) 0.25535(9) 0.0193 1.0000 Uani . . . . . .
C94 C 0.2450(2) 0.58213(13) 0.19889(12) 0.0178 1.0000 Uani . . . . . .
C21 C 0.1118(2) 0.58035(14) 0.16532(12) 0.0205 1.0000 Uani . . . . . .
C31 C 0.0724(2) 0.52343(15) 0.10648(13) 0.0247 1.0000 Uani . . . . . .
C41 C 0.1685(3) 0.46658(16) 0.07704(13) 0.0266 1.0000 Uani . . . . . .
C51 C 0.3004(2) 0.46654(14) 0.10691(13) 0.0226 1.0000 Uani . . . . . .
C61 C 0.3409(2) 0.52277(14) 0.16728(12) 0.0191 1.0000 Uani . . . . . .
C71 C 0.4814(2) 0.51806(13) 0.19806(12) 0.0182 1.0000 Uani . . . . . .
C81 C 0.5938(2) 0.46985(15) 0.17046(13) 0.0234 1.0000 Uani . . . . . .
C91 C 0.6998(2) 0.48715(15) 0.22104(14) 0.0243 1.0000 Uani . . . . . .
N101 N 0.65397(18) 0.54267(12) 0.27507(11) 0.0202 1.0000 Uani . . . . . .
N114 N 0.52082(17) 0.56206(11) 0.26207(10) 0.0180 1.0000 Uani . . . . . .
H1 H 0.689(2) 0.5672(16) 0.3121(15) 0.011(6) 1.0000 Uiso . . . . . .
H2 H 0.694(3) 0.8634(19) 0.6084(17) 0.025(7) 1.0000 Uiso . . . . . .
H3 H 0.859(3) 0.7707(18) 0.5599(16) 0.026(7) 1.0000 Uiso . . . . . .
H4 H 1.899(3) 0.3342(18) 0.4190(16) 0.024(7) 1.0000 Uiso . . . . . .
H5 H 0.056(3) 0.827(2) 0.4186(17) 0.032(8) 1.0000 Uiso . . . . . .
H6 H 0.599(3) 0.437(2) 0.1264(18) 0.030(7) 1.0000 Uiso . . . . . .
H7 H 1.285(3) 0.258(2) 0.2053(18) 0.031(7) 1.0000 Uiso . . . . . .
H8 H 1.106(3) 0.3555(18) 0.2454(17) 0.025(7) 1.0000 Uiso . . . . . .
H9 H 0.478(2) 0.8644(17) 0.5597(15) 0.015(6) 1.0000 Uiso . . . . . .
H11 H 0.358(3) 0.4312(19) 0.0881(17) 0.023(7) 1.0000 Uiso . . . . . .
H12 H 0.250(3) 0.868(2) 0.5119(18) 0.033(8) 1.0000 Uiso . . . . . .
H13 H 0.792(3) 0.472(2) 0.2241(18) 0.034(8) 1.0000 Uiso . . . . . .
H14 H 0.146(3) 0.427(2) 0.0351(18) 0.035(8) 1.0000 Uiso . . . . . .
H15 H 1.714(3) 0.283(2) 0.3251(18) 0.030(7) 1.0000 Uiso . . . . . .
H16 H 1.492(3) 0.271(2) 0.2713(17) 0.031(8) 1.0000 Uiso . . . . . .
H17 H -0.021(3) 0.524(2) 0.0887(18) 0.035(8) 1.0000 Uiso . . . . . .
H18 H 0.152(3) 0.720(2) 0.3377(18) 0.028(8) 1.0000 Uiso . . . . . .
H19 H 1.777(3) 0.436(2) 0.4974(19) 0.033(8) 1.0000 Uiso . . . . . .

_refine_ls_extinction_method     None
_oxford_refine_ls_scale          1.475(4)
loop_
_geom_bond_atom_site_label_1
_geom_bond_site_symmetry_1
_geom_bond_atom_site_label_2
_geom_bond_site_symmetry_2
_geom_bond_distance
_geom_bond_publ_flag
C13 . O13 . 1.319(3) yes
C13 . C23 . 1.410(3) yes
C13 . C63 . 1.418(3) yes
C12 . O12 . 1.315(2) yes
C12 . C22 . 1.412(3) yes
C12 . C62 . 1.421(3) yes
O13 . Cu2 . 1.9194(15) yes
C23 . C33 . 1.383(3) yes
C23 . Br3 . 1.903(2) yes
C33 . C43 . 1.386(3) yes
C33 . H8 . 0.95(3) no
C43 . C53 . 1.384(3) yes
C43 . H7 . 1.00(3) no
C53 . C63 . 1.403(3) yes
C53 . H16 . 0.92(3) no
C63 . C73 . 1.466(3) yes
C73 . C83 . 1.410(3) yes
C73 . N113 . 1.340(3) yes
C83 . C93 . 1.370(3) yes
C83 . H15 . 0.88(3) no
C93 . N103 . 1.342(3) yes
C93 . H4 . 0.97(3) no
N103 . N113 . 1.350(2) yes
N103 . H19 . 0.80(3) no
N113 . Cu2 . 1.9273(17) yes
O12 . Cu1 . 1.9011(15) yes
C72 . C82 . 1.413(3) yes
C72 . N112 . 1.338(3) yes
C72 . C62 . 1.466(3) yes
C82 . C92 . 1.371(3) yes
C82 . H12 . 0.95(3) no
C92 . N102 . 1.341(3) yes
C92 . H5 . 0.93(3) no
N102 . N112 . 1.352(2) yes
N102 . H18 . 0.78(3) no
N112 . Cu1 . 1.9242(17) yes
C22 . C32 . 1.375(3) yes
C22 . Br2 . 1.899(2) yes
C32 . C42 . 1.386(3) yes
C32 . H3 . 0.95(3) no
C42 . C52 . 1.383(3) yes
C42 . H2 . 0.88(3) no
C52 . C62 . 1.400(3) yes
C52 . H9 . 0.91(3) no
Cu1 . O11 . 1.9026(14) yes
Cu1 . N114 . 1.9233(17) yes
Br1 . C21 . 1.899(2) yes
O11 . C94 . 1.309(3) yes
C94 . C21 . 1.418(3) yes
C94 . C61 . 1.422(3) yes
C21 . C31 . 1.385(3) yes
C31 . C41 . 1.384(4) yes
C31 . H17 . 0.96(3) no
C41 . C51 . 1.383(3) yes
C41 . H14 . 0.96(3) no
C51 . C61 . 1.400(3) yes
C51 . H11 . 0.85(3) no
C61 . C71 . 1.468(3) yes
C71 . C81 . 1.413(3) yes
C71 . N114 . 1.340(3) yes
C81 . C91 . 1.368(3) yes
C81 . H6 . 0.91(3) no
C91 . N101 . 1.340(3) yes
C91 . H13 . 0.93(3) no
N101 . N114 . 1.353(2) yes
N101 . H1 . 0.81(3) no
loop_
_geom_angle_atom_site_label_1
_geom_angle_site_symmetry_1
_geom_angle_atom_site_label_2
_geom_angle_site_symmetry_2
_geom_angle_atom_site_label_3
_geom_angle_site_symmetry_3
_geom_angle
_geom_angle_publ_flag
O13 . C13 . C23 . 119.06(19) yes
O13 . C13 . C63 . 125.14(19) yes
C23 . C13 . C63 . 115.77(19) yes
O12 . C12 . C22 . 118.62(18) yes
O12 . C12 . C62 . 125.57(18) yes
C22 . C12 . C62 . 115.82(18) yes
C13 . O13 . Cu2 . 127.83(14) yes
C13 . C23 . C33 . 123.9(2) yes
C13 . C23 . Br3 . 117.35(16) yes
C33 . C23 . Br3 . 118.70(16) yes
C23 . C33 . C43 . 119.3(2) yes
C23 . C33 . H8 . 119.7(17) no
C43 . C33 . H8 . 121.0(17) no
C33 . C43 . C53 . 118.8(2) yes
C33 . C43 . H7 . 122.0(16) no
C53 . C43 . H7 . 119.2(16) no
C43 . C53 . C63 . 122.3(2) yes
C43 . C53 . H16 . 119.0(19) no
C63 . C53 . H16 . 118.8(19) no
C13 . C63 . C53 . 119.9(2) yes
C13 . C63 . C73 . 121.82(19) yes
C53 . C63 . C73 . 118.3(2) yes
C63 . C73 . C83 . 129.5(2) yes
C63 . C73 . N113 . 121.63(19) yes
C83 . C73 . N113 . 108.86(19) yes
C73 . C83 . C93 . 105.8(2) yes
C73 . C83 . H15 . 128.6(18) no
C93 . C83 . H15 . 125.5(18) no
C83 . C93 . N103 . 107.55(19) yes
C83 . C93 . H4 . 132.1(17) no
N103 . C93 . H4 . 120.2(17) no
C93 . N103 . N113 . 110.92(18) yes
C93 . N103 . H19 . 133(2) no
N113 . N103 . H19 . 116(2) no
N103 . N113 . C73 . 106.85(17) yes
N103 . N113 . Cu2 . 122.97(14) yes
C73 . N113 . Cu2 . 130.17(15) yes
C12 . O12 . Cu1 . 128.68(13) yes
C82 . C72 . N112 . 108.97(18) yes
C82 . C72 . C62 . 129.71(19) yes
N112 . C72 . C62 . 121.28(18) yes
C72 . C82 . C92 . 105.71(19) yes
C72 . C82 . H12 . 127.2(18) no
C92 . C82 . H12 . 127.1(18) no
C82 . C92 . N102 . 107.57(19) yes
C82 . C92 . H5 . 130.5(19) no
N102 . C92 . H5 . 122.0(19) no
C92 . N102 . N112 . 110.96(18) yes
C92 . N102 . H18 . 131(2) no
N112 . N102 . H18 . 118(2) no
N102 . N112 . C72 . 106.79(17) yes
N102 . N112 . Cu1 . 122.46(14) yes
C72 . N112 . Cu1 . 130.75(14) yes
N113 2_866 Cu2 . N113 . 179.994 yes
N113 2_866 Cu2 . O13 2_866 90.39(7) yes
N113 . Cu2 . O13 2_866 89.61(7) yes
N113 2_866 Cu2 . O13 . 89.61(7) yes
N113 . Cu2 . O13 . 90.39(7) yes
O13 2_866 Cu2 . O13 . 179.994 yes
C12 . C22 . C32 . 123.9(2) yes
C12 . C22 . Br2 . 116.94(15) yes
C32 . C22 . Br2 . 119.14(16) yes
C22 . C32 . C42 . 119.1(2) yes
C22 . C32 . H3 . 118.5(17) no
C42 . C32 . H3 . 122.3(17) no
C32 . C42 . C52 . 119.4(2) yes
C32 . C42 . H2 . 118.6(18) no
C52 . C42 . H2 . 121.9(18) no
C42 . C52 . C62 . 121.9(2) yes
C42 . C52 . H9 . 116.8(16) no
C62 . C52 . H9 . 121.4(16) no
C72 . C62 . C12 . 121.62(18) yes
C72 . C62 . C52 . 118.56(19) yes
C12 . C62 . C52 . 119.82(19) yes
N112 . Cu1 . O12 . 90.75(7) yes
N112 . Cu1 . O11 . 88.31(7) yes
O12 . Cu1 . O11 . 173.17(7) yes
N112 . Cu1 . N114 . 173.70(8) yes
O12 . Cu1 . N114 . 90.05(7) yes
O11 . Cu1 . N114 . 90.15(7) yes
Cu1 . O11 . C94 . 128.68(13) yes
O11 . C94 . C21 . 118.60(19) yes
O11 . C94 . C61 . 125.19(18) yes
C21 . C94 . C61 . 116.21(19) yes
Br1 . C21 . C94 . 117.11(16) yes
Br1 . C21 . C31 . 119.39(16) yes
C94 . C21 . C31 . 123.5(2) yes
C21 . C31 . C41 . 118.7(2) yes
C21 . C31 . H17 . 118.9(19) no
C41 . C31 . H17 . 122.3(19) no
C31 . C41 . C51 . 120.1(2) yes
C31 . C41 . H14 . 121.4(18) no
C51 . C41 . H14 . 118.5(18) no
C41 . C51 . C61 . 121.7(2) yes
C41 . C51 . H11 . 119.0(18) no
C61 . C51 . H11 . 119.3(19) no
C94 . C61 . C51 . 119.76(19) yes
C94 . C61 . C71 . 121.03(19) yes
C51 . C61 . C71 . 119.20(19) yes
C61 . C71 . C81 . 129.5(2) yes
C61 . C71 . N114 . 121.76(18) yes
C81 . C71 . N114 . 108.73(18) yes
C71 . C81 . C91 . 105.92(19) yes
C71 . C81 . H6 . 128.4(18) no
C91 . C81 . H6 . 125.5(18) no
C81 . C91 . N101 . 107.54(19) yes
C81 . C91 . H13 . 135.2(19) no
N101 . C91 . H13 . 117.1(19) no
C91 . N101 . N114 . 111.00(18) yes
C91 . N101 . H1 . 133.7(17) no
N114 . N101 . H1 . 115.3(17) no
N101 . N114 . C71 . 106.81(17) yes
N101 . N114 . Cu1 . 123.06(14) yes
C71 . N114 . Cu1 . 130.10(14) yes
loop_
_geom_hbond_atom_site_label_D
_geom_hbond_site_symmetry_D
_geom_hbond_atom_site_label_H
_geom_hbond_site_symmetry_H
_geom_hbond_atom_site_label_A
_geom_hbond_site_symmetry_A
_geom_hbond_angle_DHA
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_publ_flag
N101 . H1 . O12 . 123(2) 0.812 2.243 2.772(3) yes
N102 . H18 . O11 . 121(3) 0.781 2.237 2.718(3) yes
N103 . H19 . O13 2_866 123(3) 0.796 2.260 2.773(3) yes


_iucr_refine_instruction_details_constraints 
;
#
# Punched on 09/10/15 at 13:02:13
#
#LIST     12                                                                    
BLOCK 
CONT SCALE 
CONT C    (   13 ,X'S,U'S)  UNTIL N    (  114 ) 
CONT H    (    1 ,X'S,U[ISO])  UNTIL H    (   19 ) 
END                                                                             
;


_iucr_refine_instruction_details_restraints 
;
#
# Punched on 09/10/15 at 13:02:13
#
#LIST     16                                                                    
NO 
REM   HREST   START (DO NOT REMOVE THIS LINE) 
REM   HREST   END (DO NOT REMOVE THIS LINE) 
END                                                                             
;
####################################################################### 
# 
# 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_1
_database_code_depnum_ccdc_archive 'CCDC 1430501'
_audit_update_record             
;
2015-11-03 deposited with the CCDC.
2015-12-22 downloaded from the CCDC.
;

_exptl_special_details           
; 
 The crystal was 
placed in the cold stream of an Oxford 
Cryosystems open-flow nitrogen cryostat (Cosier & 
Glazer, 1986) with a nominal stability of 0.1K. 
 
Cosier, J. & Glazer, A.M., 1986. J. Appl. Cryst. 105-107. 
;
_refine_special_details          
; 
? 
;
#--------------------------------------------------------------- 
# _oxford_ data items, April 2010: 
# There is some uncertainty about the correct way of forming local data 
# names, e.g. 

# _atom_site_special_shape_oxford 
# or 
# _oxford_atom_site_special_shape 

# see: 
# http://www.iucr.org/resources/cif/spec/version1.1/semantics#namespace 

# A reserved prefix, e.g. foo, must be used in the following way 
# " If the data file contains items defined in a DDL1 dictionary, the 
# local data names assigned under the reserved prefix must contain it as 
# their first component, e.g. _foo_atom_site_my_item. " 

# However, this seems to say the opposite: 
# http://www.iucr.org/__data/iucr/cif/standard/cifstd8.html 

# According to advice from the IUCr, CRYSTALS is correct 
#--------------------------------------------------------------- 
# End of 'script/refcif.dat' 
#end of refcif 
_cell_length_a                   3.84135(10)
_cell_length_b                   9.9290(2)
_cell_length_c                   22.7560(6)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     867.94(4)

_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_H-M   'P 21 21 21 '
_symmetry_space_group_name_Hall  ?
loop_
_symmetry_equiv_pos_as_xyz
x,y,z
x+1/2,-y+1/2,-z
-x,y+1/2,-z+1/2
-x+1/2,-y,z+1/2

loop_
_atom_type_symbol
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_Cromer_Mann_a1
_atom_type_scat_Cromer_Mann_b1
_atom_type_scat_Cromer_Mann_a2
_atom_type_scat_Cromer_Mann_b2
_atom_type_scat_Cromer_Mann_a3
_atom_type_scat_Cromer_Mann_b3
_atom_type_scat_Cromer_Mann_a4
_atom_type_scat_Cromer_Mann_b4
_atom_type_scat_Cromer_Mann_c
_atom_type_scat_source
C 0.0181 0.0091 2.3100 20.8439 1.0200 10.2075 1.5886 0.5687 0.8650 51.6512
0.2156 'International Tables Vol C 4.2.6.8 and 6.1.1.4'
H 0.0000 0.0000 0.4930 10.5109 0.3229 26.1257 0.1402 3.1424 0.0408 57.7998
0.0030 'International Tables Vol C 4.2.6.8 and 6.1.1.4'
N 0.0311 0.0180 12.2126 0.0057 3.1322 9.8933 2.0125 28.9975 1.1663 0.5826
-11.5290 'International Tables Vol C 4.2.6.8 and 6.1.1.4'
O 0.0492 0.0322 3.0485 13.2771 2.2868 5.7011 1.5463 0.3239 0.8670 32.9089
0.2508 'International Tables Vol C 4.2.6.8 and 6.1.1.4'
Br -0.6763 1.2805 17.1789 2.1723 5.2358 16.5796 5.6377 0.2609 3.9851 41.4328
2.9557 'International Tables Vol C 4.2.6.8 and 6.1.1.4'


_cell_formula_units_Z            4

# Given Formula = C9 H7 Br1 N2 O1 
# Dc =      1.83 Fooo =    472.00 Mu =     61.13 M =    239.07
# Found Formula = C9 H7 Br1 N2 O1 
# Dc =      1.83 FOOO =    472.00 Mu =     61.13 M =    239.07

_chemical_formula_sum            'C9 H7 Br1 N2 O1'
_chemical_formula_moiety         'C9 H7 Br1 N2 O1'
_chemical_compound_source        ?
_chemical_formula_weight         239.07


_cell_measurement_reflns_used    8254
_cell_measurement_theta_min      4
_cell_measurement_theta_max      76
_cell_measurement_temperature    137

_exptl_crystal_description       lath
_exptl_crystal_colour            colourless
_exptl_crystal_size_min          0.020
_exptl_crystal_size_mid          0.063
_exptl_crystal_size_max          0.159

_exptl_crystal_density_diffrn    1.829
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
# Non-dispersive F(000): 
_exptl_crystal_F_000             472
_exptl_absorpt_coefficient_mu    6.113

# Sheldrick geometric approximatio 0.68 0.88 
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'CrysAlis, (Oxford Diffraction, 2002)'
_exptl_absorpt_correction_T_min  0.52
_exptl_absorpt_correction_T_max  0.88
_diffrn_measurement_device_type  'Oxford Diffraction SuperNova'
_diffrn_measurement_device       Area
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_measurement_method       ω

# If a reference occurs more than once, delete the author 
# and date from subsequent references. 
_computing_data_collection       'SuperNova, (Oxford Diffraction, 2010)'
_computing_cell_refinement       'CrysAlis, (Oxford Diffraction, 2002)'
_computing_data_reduction        'CrysAlis, (Oxford Diffraction, 2002)'
_computing_structure_solution    'SIR92 (Altomare et al., 1994)'
_computing_structure_refinement  'CRYSTALS (Betteridge et al., 2003)'
_computing_publication_material  'CRYSTALS (Betteridge et al., 2003)'
_computing_molecular_graphics    'CAMERON (Watkin et al., 1996)'

_diffrn_standards_interval_time  .
_diffrn_standards_interval_count .
_diffrn_standards_number         0
_diffrn_standards_decay_%        ?

_diffrn_ambient_temperature      137
_diffrn_reflns_number            15277
_reflns_number_total             1812
_diffrn_reflns_av_R_equivalents  0.035
# Number of reflections without Friedels Law is 1812 
# Number of reflections with Friedels Law is 1116 
# Theoretical number of reflections is about 909 


_diffrn_reflns_theta_min         3.885
_diffrn_reflns_theta_max         76.214
_diffrn_measured_fraction_theta_max 0.997

_diffrn_reflns_theta_full        76.214
_diffrn_measured_fraction_theta_full 0.997


_diffrn_reflns_limit_h_min       -4
_diffrn_reflns_limit_h_max       4
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_limit_l_max       28
_reflns_limit_h_min              -4
_reflns_limit_h_max              4
_reflns_limit_k_min              0
_reflns_limit_k_max              12
_reflns_limit_l_min              0
_reflns_limit_l_max              28

_oxford_diffrn_Wilson_B_factor   0.00
_oxford_diffrn_Wilson_scale      0.00

_atom_sites_solution_primary     direct #heavy,direct,difmap,geom
# _atom_sites_solution_secondary  difmap
_atom_sites_solution_hydrogens   difmap

_refine_diff_density_min         -0.41
_refine_diff_density_max         0.29


# The current dictionary definitions do not cover the 
# situation where the reflections used for refinement were 
# selected by a user-defined sigma threshold 


# The values actually used during refinement 
_oxford_reflns_threshold_expression_ref I>-3.0\s(I)
_refine_ls_number_reflns         1807
_refine_ls_number_restraints     4
_refine_ls_number_parameters     125
_oxford_refine_ls_R_factor_ref   0.0198
_refine_ls_wR_factor_ref         0.0465
_refine_ls_goodness_of_fit_ref   1.0189
_refine_ls_shift/su_max          0.0004730
_refine_ls_shift/su_mean         0.0000221


# The values computed with all filters except I/sigma 
_oxford_reflns_number_all        1807
_refine_ls_R_factor_all          0.0198
_refine_ls_wR_factor_all         0.0465

# The values computed with a 2 sigma cutoff - a la SHELX 
_reflns_threshold_expression     I>2.0σ(I)
_reflns_number_gt                1776
_refine_ls_R_factor_gt           0.0192
_refine_ls_wR_factor_gt          0.0463

_refine_ls_abs_structure_Flack   -0.01(2)
_refine_ls_abs_structure_details 'Flack (1983), 696 Friedel-pairs'
# choose from: rm (reference molecule of known chirality), 
# ad (anomolous dispersion - Flack), rmad (rm and ad), 
# syn (from synthesis), unk (unknown) or . (not applicable). 
_chemical_absolute_configuration ad


_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_hydrogen_treatment    mixed #undef, noref, refall,
# refxyz, refU, constr or mixed
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
;
 Method= Modified Sheldrick 
 w=1/[σ²(F²) + ( 0.02P)² + 0.71P] 
 ,where P=(max(Fo²,0) + 2Fc²)/3 
;

# Uequiv = arithmetic mean of Ui i.e. Ueqiv = (U1+U2+U3)/3

# Replace last . with number of unfound hydrogen atoms attached to an atom.

# ..._refinement_flags_... 
# . no refinement constraints           S special position constraint on site
# G rigid group refinement of site      R riding atom
# D distance or angle restraint on site T thermal displacement constraints
# U Uiso or Uij restraint (rigid bond)  P partial occupancy constraint


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_occupancy
_atom_site_adp_type
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
_atom_site_attached_hydrogens
Br1 Br -0.47101(6) -0.23876(2) -0.380330(9) 0.0284 1.0000 Uani . . . . . .
O11 O -0.4242(5) -0.50034(16) -0.31608(7) 0.0268 1.0000 Uani D . . . . .
C12 C -0.2871(6) -0.5148(2) -0.37095(9) 0.0215 1.0000 Uani . . . . . .
C21 C -0.2927(6) -0.4047(2) -0.40862(10) 0.0233 1.0000 Uani . . . . . .
C31 C -0.1637(6) -0.4130(2) -0.46546(10) 0.0256 1.0000 Uani . . . . . .
C41 C -0.0226(7) -0.5335(2) -0.48503(9) 0.0257 1.0000 Uani . . . . . .
C51 C -0.0105(7) -0.6438(2) -0.44749(8) 0.0227 1.0000 Uani . . . . . .
C61 C -0.1411(6) -0.6366(2) -0.39020(9) 0.0210 1.0000 Uani . . . . . .
C71 C -0.1215(5) -0.7541(2) -0.35091(8) 0.0210 1.0000 Uani . . . . . .
N81 N -0.2385(5) -0.7418(2) -0.29518(7) 0.0250 1.0000 Uani D . . . . .
N91 N -0.1878(6) -0.8642(2) -0.27080(9) 0.0278 1.0000 Uani D . . . . .
C101 C -0.0471(7) -0.9524(2) -0.30901(10) 0.0289 1.0000 Uani D . . . . .
C111 C -0.0010(7) -0.8855(2) -0.36124(9) 0.0258 1.0000 Uani . . . . . .
H511 H 0.0830 -0.7252 -0.4609 0.0268 1.0000 Uiso R . . . . .
H411 H 0.0692 -0.5389 -0.5250 0.0309 1.0000 Uiso R . . . . .
H1011 H 0.0043 -1.0433 -0.3000 0.0350 1.0000 Uiso R . . . . .
H1111 H 0.0874 -0.9210 -0.3959 0.0311 1.0000 Uiso R . . . . .
H311 H -0.1770 -0.3378 -0.4903 0.0300 1.0000 Uiso R . . . . .
H911 H -0.261(7) -0.8846(18) -0.2362(8) 0.0337 1.0000 Uiso D . . . . .
H111 H -0.388(8) -0.573(2) -0.2987(12) 0.0400 1.0000 Uiso D . . . . .

_refine_ls_extinction_method     None
_oxford_refine_ls_scale          6.28(9)
loop_
_geom_bond_atom_site_label_1
_geom_bond_site_symmetry_1
_geom_bond_atom_site_label_2
_geom_bond_site_symmetry_2
_geom_bond_distance
_geom_bond_publ_flag
Br1 . C21 . 1.897(2) yes
O11 . C12 . 1.363(3) yes
O11 . H111 . 0.832(17) no
C12 . C21 . 1.389(3) yes
C12 . C61 . 1.404(3) yes
C21 . C31 . 1.388(3) yes
C31 . C41 . 1.387(3) yes
C31 . H311 . 0.938 no
C41 . C51 . 1.390(3) yes
C41 . H411 . 0.976 no
C51 . C61 . 1.399(3) yes
C51 . H511 . 0.936 no
C61 . C71 . 1.472(3) yes
C71 . N81 . 1.351(3) yes
C71 . C111 . 1.404(3) yes
N81 . N91 . 1.350(3) yes
N91 . C101 . 1.347(3) yes
N91 . H911 . 0.859(17) no
C101 . C111 . 1.373(3) yes
C101 . H1011 . 0.946 no
C111 . H1111 . 0.929 no
loop_
_geom_angle_atom_site_label_1
_geom_angle_site_symmetry_1
_geom_angle_atom_site_label_2
_geom_angle_site_symmetry_2
_geom_angle_atom_site_label_3
_geom_angle_site_symmetry_3
_geom_angle
_geom_angle_publ_flag
C12 . O11 . H111 . 106(2) no
O11 . C12 . C21 . 118.5(2) yes
O11 . C12 . C61 . 122.1(2) yes
C21 . C12 . C61 . 119.5(2) yes
Br1 . C21 . C12 . 118.67(17) yes
Br1 . C21 . C31 . 119.78(18) yes
C12 . C21 . C31 . 121.5(2) yes
C21 . C31 . C41 . 119.3(2) yes
C21 . C31 . H311 . 119.7 no
C41 . C31 . H311 . 121.0 no
C31 . C41 . C51 . 119.7(2) yes
C31 . C41 . H411 . 119.2 no
C51 . C41 . H411 . 121.1 no
C41 . C51 . C61 . 121.4(2) yes
C41 . C51 . H511 . 119.5 no
C61 . C51 . H511 . 119.1 no
C12 . C61 . C51 . 118.56(19) yes
C12 . C61 . C71 . 120.92(19) yes
C51 . C61 . C71 . 120.51(19) yes
C61 . C71 . N81 . 118.8(2) yes
C61 . C71 . C111 . 130.65(19) yes
N81 . C71 . C111 . 110.6(2) yes
C71 . N81 . N91 . 104.83(19) yes
N81 . N91 . C101 . 112.20(18) yes
N81 . N91 . H911 . 122.8(12) no
C101 . N91 . H911 . 124.6(12) no
N91 . C101 . C111 . 107.20(19) yes
N91 . C101 . H1011 . 124.3 no
C111 . C101 . H1011 . 128.4 no
C71 . C111 . C101 . 105.20(19) yes
C71 . C111 . H1111 . 128.0 no
C101 . C111 . H1111 . 126.8 no
loop_
_geom_hbond_atom_site_label_D
_geom_hbond_site_symmetry_D
_geom_hbond_atom_site_label_H
_geom_hbond_site_symmetry_H
_geom_hbond_atom_site_label_A
_geom_hbond_site_symmetry_A
_geom_hbond_angle_DHA
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_publ_flag
N91 . H911 . O11 3_444 149(2) 0.859 2.050 2.821(3) yes
O11 . H111 . N81 . 153(3) 0.832 1.776 2.546(3) yes


_iucr_refine_instruction_details_constraints 
;
#
# Punched on 03/11/15 at 16:12:53
#
#LIST     12                                                                    
BLOCK 
CONT SCALE 
CONT BR   (    1 ,X'S,U'S)  UNTIL C    (  111 ) 
CONT H    (  911 ,X'S)  UNTIL H    (  111 ) 
CONT ENANTIO 
RIDE C   (  31,X'S) H   ( 311,X'S) 
RIDE C   (  41,X'S) H   ( 411,X'S) 
RIDE C   (  51,X'S) H   ( 511,X'S) 
RIDE C   ( 101,X'S) H   (1011,X'S) 
RIDE C   ( 111,X'S) H   (1111,X'S) 
END                                                                             
;


_iucr_refine_instruction_details_restraints 
;
#
# Punched on 03/11/15 at 16:12:53
#
#LIST     16                                                                    
NO 
REM   HREST   START (DO NOT REMOVE THIS LINE) 
REM NO H   NO #H U MULT DIST 
REM C-H 
REM >4           1.5    .96 DISORDER 
REM 1      1     1.2    .93 C C-H (ACETYLENE) 
REM 1      2     1.2    .93 C-C(H)-C 
REM 1      3     1.2    .98 (C)3-C-H 
REM 2      1     1.2    .93 C=C-H(2) 
REM 2      2     1.2    .97 (C)2-C-(H)2 
REM 3      1     1.5    .96 C-C-(H)3 
REM N-H 
REM >4           1.5    .89 DISORDER 
REM 1      1     1.2    .86 N-N/H 
REM 1      2     1.2    .86 (C)2-N-H 
REM 1      3     1.2    .89 (C)3-N-H 
REM 2      1     1.2    .86 C-N-(H)2 
REM 2      2     1.2    .89 (C)2-N-(H)2 
REM 3      1     1.2    .89 C-H-(H)3 
REM O-H 
REM 1      1     1.5    .82 O-H 
REM 
REM DIST      ESD = 0.02 
REM VIB       ESD = 0.002 
REM ANGLE     ESD = 2.0 
REM       H ON O-HETRO ATOM 
DIST 0.82, 0.02 = 
CONT O ( 11) TO H(111) 
REST 0.040, 0.002 = H(111,U[ISO]) 
REM            H1-N-R2 
DIST 0.86, 0.02 = 
CONT N ( 91) TO H(911) 
REST 0.033, 0.002 = H(911,U[ISO]) 
ANGLE 0.0, 2.0 = MEAN 
CONT H(911) TO N ( 91) TO N(81) 
CONT H(911) TO N ( 91) TO C(101) 
REM   HREST   END (DO NOT REMOVE THIS LINE) 
END                                                                             
;
