# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2014

#######################################################################
#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
#######################################################################
# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
#
#  This CIF is provided on the understanding that it is used for bona
#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
#  disseminated in any form, whether machine-readable or not,
#  except for the purpose of generating routine backup copies
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# 
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#  data retrieval see:
#                         www.ccdc.cam.ac.uk
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#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
#
data_ns16

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C24 H36 Cu2 N8 O10, 4(Cl O4), 4(H2O)'
_chemical_formula_sum            'C24 H40 Cl4 Cu2 N8 O30'
_chemical_formula_weight         1185.47

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 '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 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cu Cu 0.3201 1.2651 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Orthorhombic
_symmetry_space_group_name_H-M   Pnnm

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

_cell_length_a                   12.9191(5)
_cell_length_b                   14.6740(6)
_cell_length_c                   11.9279(4)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     2261.23(15)
_cell_formula_units_Z            2
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    4213
_cell_measurement_theta_min      2.71
_cell_measurement_theta_max      26.00

_exptl_crystal_description       needles
_exptl_crystal_colour            blue-green
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.4
_exptl_crystal_density_meas      'not measured'
_exptl_crystal_density_diffrn    1.738
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1200
_exptl_absorpt_coefficient_mu    1.283
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.85
_exptl_absorpt_correction_T_max  0.87
_exptl_absorpt_process_details   'SADABS; (sheldrick, 2003)'

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'INCOATEC Imus micro-focus source'
_diffrn_radiation_monochromator  mirrors
_diffrn_measurement_device_type  'Bruker D8 Venture PHOTON 100 CMOS'
_diffrn_measurement_method       'phi scan'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         0
_diffrn_standards_interval_count 0
_diffrn_standards_interval_time  0
_diffrn_standards_decay_%        0
_diffrn_reflns_number            37305
_diffrn_reflns_av_R_equivalents  0.0255
_diffrn_reflns_av_sigmaI/netI    0.0102
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_theta_min         2.71
_diffrn_reflns_theta_max         26.00
_reflns_number_total             2327
_reflns_number_gt                2042
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'APEX2 (Bruker, 2010)'
_computing_cell_refinement       'APEX2 (Bruker, 2010); SAINT (Bruker, 2009)'
_computing_data_reduction        'SAINT (Bruker, 2009);XPREP(Sheldrick,2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXTL (Sheldrick, 2008), OLEX2 (2009)'
_computing_molecular_graphics    'XP (Siemens)'
_computing_publication_material  SHELXL-97

_refine_special_details          
;
 Refinement of F² against ALL reflections.  The weighted R-factor wR and
 goodness of fit S are based on F², conventional R-factors R are based
 on F, with F set to zero for negative F². The threshold expression of
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is
 not relevant to the choice of reflections for refinement.  R-factors based
 on F² are statistically about twice as large as those based on F, and R-
 factors based on ALL data will be even larger.
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[σ²(Fo²)+(0.1152P)²+5.8064P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         2327
_refine_ls_number_parameters     207
_refine_ls_number_restraints     10
_refine_ls_R_factor_all          0.0644
_refine_ls_R_factor_gt           0.0584
_refine_ls_wR_factor_ref         0.1814
_refine_ls_wR_factor_gt          0.1747
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_restrained_S_all      1.081
_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_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Cu1 Cu 0.00033(4) -0.40999(4) 0.0000 0.0183(3) Uani 1 2 d S . .
O1 O -0.10513(19) -0.42583(15) -0.1175(2) 0.0227(5) Uani 1 1 d . . .
O2 O -0.10844(19) -0.57911(15) -0.1152(2) 0.0243(6) Uani 1 1 d . . .
O3 O 0.0089(4) -0.2628(3) 0.0000 0.0559(14) Uani 1 2 d S . .
N1 N -0.2680(2) -0.58643(18) -0.2624(3) 0.0239(7) Uani 1 1 d . . .
N2 N -0.3749(3) -0.6981(2) -0.2480(3) 0.0370(8) Uani 1 1 d . . .
C1 C -0.3538(3) -0.6142(3) -0.2123(4) 0.0342(9) Uani 1 1 d . . .
H1A H -0.3926 -0.5808 -0.1611 0.041 Uiso 1 1 calc R . .
C2 C -0.2323(3) -0.6550(2) -0.3313(3) 0.0302(8) Uani 1 1 d . . .
H2A H -0.1730 -0.6535 -0.3755 0.036 Uiso 1 1 calc R . .
C3 C -0.2999(3) -0.7246(3) -0.3223(3) 0.0317(8) Uani 1 1 d . . .
H3A H -0.2963 -0.7802 -0.3595 0.038 Uiso 1 1 calc R . .
C4 C -0.4643(5) -0.7534(4) -0.2150(5) 0.075(2) Uani 1 1 d . . .
H4A H -0.4696 -0.7545 -0.1348 0.112 Uiso 1 1 calc R . .
H4B H -0.4556 -0.8144 -0.2425 0.112 Uiso 1 1 calc R . .
H4C H -0.5262 -0.7276 -0.2462 0.112 Uiso 1 1 calc R . .
C5 C -0.2174(3) -0.4990(2) -0.2429(3) 0.0251(8) Uani 1 1 d . . .
H5A H -0.2695 -0.4540 -0.2238 0.030 Uiso 1 1 calc R . .
H5B H -0.1841 -0.4794 -0.3116 0.030 Uiso 1 1 calc R . .
C6 C -0.1372(3) -0.5024(2) -0.1499(3) 0.0209(7) Uani 1 1 d . . .
Cl1 Cl 0.0000 -0.5000 -0.5000 0.0599(8) Uani 1 4 d SD . .
O4 O 0.0045(8) -0.4595(10) -0.6073(9) 0.119(6) Uani 0.50 1 d PD . 1
O5 O 0.0515(17) -0.4156(10) -0.5000 0.126(8) Uani 0.50 2 d SPD . 2
O6 O -0.1110(7) -0.4654(12) -0.5000 0.082(4) Uani 0.50 2 d SPD . 3
Cl2 Cl -0.61455(13) -0.59638(12) 0.0000 0.0617(6) Uani 1 2 d SD . .
O7 O -0.5736(7) -0.5851(5) 0.1145(7) 0.090(4) Uani 0.50 1 d PD A 1
O8 O -0.5058(5) -0.6099(8) 0.0000 0.158(6) Uani 1 2 d SD A 2
O9 O -0.6675(4) -0.6799(3) 0.0000 0.0599(14) Uani 1 2 d SD A 3
O10 O -0.6790(5) -0.5168(3) 0.0000 0.0635(16) Uani 1 2 d SD A 4
Cl3 Cl 0.0000 0.0000 0.0000 0.1118(19) Uani 1 4 d SD . .
O11 O -0.011(2) 0.0653(13) 0.0876(15) 0.240(17) Uani 0.50 1 d PD B 1
O12 O 0.1107(7) -0.0145(15) 0.0000 0.221(19) Uani 0.50 2 d SPD B 2
O13 O 0.052(2) 0.0834(11) 0.0000 0.26(3) Uani 0.50 2 d SPD B 3
O14 O 0.1929(11) -0.1875(9) -0.0608(10) 0.106(4) Uani 0.50 1 d P . 1
O15 O 0.2637(15) -0.227(2) 0.0000 0.144(8) Uani 0.50 2 d SP C 2
O16 O 0.155(4) -0.235(4) 0.0000 0.31(3) Uani 0.50 2 d SP D 3


_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
Cu1 O2 1.966(3) 5_545 ?
Cu1 O2 1.966(3) 2_545 ?
Cu1 O1 1.968(2) . ?
Cu1 O1 1.968(2) 6 ?
Cu1 O3 2.163(5) . ?
Cu1 Cu1 2.6416(11) 5_545 ?
O1 C6 1.258(4) . ?
O2 C6 1.255(4) . ?
O2 Cu1 1.966(3) 5_545 ?
N1 C1 1.323(5) . ?
N1 C2 1.378(4) . ?
N1 C5 1.459(4) . ?
N2 C1 1.331(5) . ?
N2 C3 1.370(5) . ?
N2 C4 1.466(5) . ?
C2 C3 1.348(5) . ?
C5 C6 1.519(5) . ?
Cl1 O5 1.406(8) 5_544 ?
Cl1 O5 1.406(8) . ?
Cl1 O4 1.412(8) 6_554 ?
Cl1 O4 1.412(8) 5_544 ?
Cl1 O4 1.412(8) . ?
Cl1 O4 1.412(8) 2_545 ?
Cl1 O6 1.522(7) 5_544 ?
Cl1 O6 1.522(7) . ?
O4 O4 1.19(3) 2_545 ?
Cl2 O9 1.403(4) . ?
Cl2 O8 1.419(7) . ?
Cl2 O10 1.434(5) . ?
Cl2 O7 1.474(6) . ?
Cl2 O7 1.474(6) 6 ?
Cl3 O13 1.400(9) . ?
Cl3 O13 1.400(9) 5 ?
Cl3 O11 1.426(9) 2 ?
Cl3 O11 1.426(9) . ?
Cl3 O11 1.426(9) 5 ?
Cl3 O11 1.426(9) 6 ?
Cl3 O12 1.446(9) . ?
Cl3 O12 1.446(9) 5 ?
O14 O14 1.45(2) 6 ?

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
O2 Cu1 O2 88.69(16) 5_545 2_545 ?
O2 Cu1 O1 168.48(11) 5_545 . ?
O2 Cu1 O1 89.12(12) 2_545 . ?
O2 Cu1 O1 89.12(12) 5_545 6 ?
O2 Cu1 O1 168.48(11) 2_545 6 ?
O1 Cu1 O1 90.78(15) . 6 ?
O2 Cu1 O3 92.57(11) 5_545 . ?
O2 Cu1 O3 92.57(11) 2_545 . ?
O1 Cu1 O3 98.83(11) . . ?
O1 Cu1 O3 98.83(11) 6 . ?
O2 Cu1 Cu1 85.46(7) 5_545 5_545 ?
O2 Cu1 Cu1 85.46(7) 2_545 5_545 ?
O1 Cu1 Cu1 83.09(7) . 5_545 ?
O1 Cu1 Cu1 83.09(7) 6 5_545 ?
O3 Cu1 Cu1 177.24(13) . 5_545 ?
C6 O1 Cu1 123.5(2) . . ?
C6 O2 Cu1 120.9(2) . 5_545 ?
C1 N1 C2 108.9(3) . . ?
C1 N1 C5 125.0(3) . . ?
C2 N1 C5 126.0(3) . . ?
C1 N2 C3 109.0(3) . . ?
C1 N2 C4 126.1(3) . . ?
C3 N2 C4 125.0(3) . . ?
N1 C1 N2 108.2(3) . . ?
C3 C2 N1 106.8(3) . . ?
C2 C3 N2 107.1(3) . . ?
N1 C5 C6 113.2(3) . . ?
O2 C6 O1 127.0(3) . . ?
O2 C6 C5 118.2(3) . . ?
O1 C6 C5 114.8(3) . . ?
O5 Cl1 O5 180.000(4) 5_544 . ?
O5 Cl1 O4 113.0(6) 5_544 6_554 ?
O5 Cl1 O4 67.0(6) . 6_554 ?
O5 Cl1 O4 67.0(6) 5_544 5_544 ?
O5 Cl1 O4 113.0(6) . 5_544 ?
O4 Cl1 O4 50.0(13) 6_554 5_544 ?
O5 Cl1 O4 113.0(6) 5_544 . ?
O5 Cl1 O4 67.0(6) . . ?
O4 Cl1 O4 130.0(13) 6_554 . ?
O4 Cl1 O4 180.0(11) 5_544 . ?
O5 Cl1 O4 67.0(6) 5_544 2_545 ?
O5 Cl1 O4 113.0(6) . 2_545 ?
O4 Cl1 O4 180.000(2) 6_554 2_545 ?
O4 Cl1 O4 130.0(13) 5_544 2_545 ?
O4 Cl1 O4 50.0(13) . 2_545 ?
O5 Cl1 O6 98.8(11) 5_544 5_544 ?
O5 Cl1 O6 81.2(11) . 5_544 ?
O4 Cl1 O6 95.8(5) 6_554 5_544 ?
O4 Cl1 O6 84.2(5) 5_544 5_544 ?
O4 Cl1 O6 95.8(5) . 5_544 ?
O4 Cl1 O6 84.2(5) 2_545 5_544 ?
O5 Cl1 O6 81.2(11) 5_544 . ?
O5 Cl1 O6 98.8(11) . . ?
O4 Cl1 O6 84.2(5) 6_554 . ?
O4 Cl1 O6 95.8(5) 5_544 . ?
O4 Cl1 O6 84.2(5) . . ?
O4 Cl1 O6 95.8(5) 2_545 . ?
O6 Cl1 O6 180.000(3) 5_544 . ?
O4 O4 Cl1 65.0(7) 2_545 . ?
O9 Cl2 O8 111.1(6) . . ?
O9 Cl2 O10 115.3(4) . . ?
O8 Cl2 O10 133.5(6) . . ?
O9 Cl2 O7 105.9(4) . . ?
O8 Cl2 O7 70.1(4) . . ?
O10 Cl2 O7 96.7(3) . . ?
O9 Cl2 O7 105.9(4) . 6 ?
O8 Cl2 O7 70.1(4) . 6 ?
O10 Cl2 O7 96.7(3) . 6 ?
O7 Cl2 O7 135.8(9) . 6 ?
O13 Cl3 O13 180.0(15) . 5 ?
O13 Cl3 O11 122.5(13) . 2 ?
O13 Cl3 O11 57.5(13) 5 2 ?
O13 Cl3 O11 57.5(13) . . ?
O13 Cl3 O11 122.5(13) 5 . ?
O11 Cl3 O11 85.7(19) 2 . ?
O13 Cl3 O11 122.5(13) . 5 ?
O13 Cl3 O11 57.5(13) 5 5 ?
O11 Cl3 O11 94.3(19) 2 5 ?
O11 Cl3 O11 180(2) . 5 ?
O13 Cl3 O11 57.5(13) . 6 ?
O13 Cl3 O11 122.5(13) 5 6 ?
O11 Cl3 O11 180.0(7) 2 6 ?
O11 Cl3 O11 94.3(19) . 6 ?
O11 Cl3 O11 85.7(19) 5 6 ?
O13 Cl3 O12 69.5(15) . . ?
O13 Cl3 O12 110.5(15) 5 . ?
O11 Cl3 O12 78.4(11) 2 . ?
O11 Cl3 O12 101.6(11) . . ?
O11 Cl3 O12 78.4(11) 5 . ?
O11 Cl3 O12 101.6(11) 6 . ?
O13 Cl3 O12 110.5(15) . 5 ?
O13 Cl3 O12 69.5(15) 5 5 ?
O11 Cl3 O12 101.6(11) 2 5 ?
O11 Cl3 O12 78.4(11) . 5 ?
O11 Cl3 O12 101.6(11) 5 5 ?
O11 Cl3 O12 78.4(11) 6 5 ?
O12 Cl3 O12 180.0(17) . 5 ?

_diffrn_measured_fraction_theta_max 0.996
_diffrn_reflns_theta_full        26.00
_diffrn_measured_fraction_theta_full 0.996
_refine_diff_density_max         0.986
_refine_diff_density_min         -0.976
_refine_diff_density_rms         0.117
_database_code_depnum_ccdc_archive 'CCDC 1003339'
