# 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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#  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.
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data_7032
#TrackingRef '1996_web_deposit_cif_file_0_V.M.Manikandamathavan_1280752737.cif'


_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C20 H18 Cu N5 O3, N O3, 2(H2O)'
_chemical_formula_sum            'C20 H22 Cu N6 O8'
_chemical_formula_weight         537.98

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'
Cu Cu 0.3201 1.2651 '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'

_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_H-M   'P 21/n'

loop_
_symmetry_equiv_pos_as_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                   7.0908(13)
_cell_length_b                   22.814(4)
_cell_length_c                   14.215(3)
_cell_angle_alpha                90.00
_cell_angle_beta                 102.509(3)
_cell_angle_gamma                90.00
_cell_volume                     2244.9(7)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    9298
_cell_measurement_theta_min      2.9426
_cell_measurement_theta_max      34.9928

loop_
_exptl_crystal_face_index_h
_exptl_crystal_face_index_k
_exptl_crystal_face_index_l
_exptl_crystal_face_perp_dist
0.00 1.00 -1.00 0.0200
0.00 -1.00 1.00 0.0200
1.00 0.00 0.00 0.0200
-1.00 0.00 0.00 0.0100
0.00 2.00 1.00 0.0200
0.00 -1.00 0.00 0.0300

_exptl_crystal_description       'transparent block'
_exptl_crystal_colour            green
_exptl_crystal_size_max          0.05
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.03
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.592
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1108
_exptl_absorpt_coefficient_mu    1.034
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details   'SADABS (Bruker AXS, 2008)'
_exptl_absorpt_correction_T_min  0.94899
_exptl_absorpt_correction_T_max  0.97261

_exptl_special_details           
;
Crystal mounted on a MiTeGen loop using Perfluoropolyether PFO-XR75
;

_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         '0.2 x 2mm^2^ focus rotating anode'
_diffrn_radiation_monochromator  'Incoatec Helios mirrors'
_diffrn_measurement_device_type  'Bruker-AXS Kappa Mach3 APEX-II'
_diffrn_measurement_method       'CCD φ- and ω-scans'
_diffrn_detector_area_resol_mean 66.67
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            70422
_diffrn_reflns_av_R_equivalents  0.0311
_diffrn_reflns_av_sigmaI/netI    0.0175
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_k_min       -36
_diffrn_reflns_limit_k_max       36
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_theta_min         1.79
_diffrn_reflns_theta_max         35.00
_reflns_number_total             9892
_reflns_number_gt                8835
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'APEX2 (Bruker AXS, 2008)'
_computing_cell_refinement       'SAINT software (Bruker AXS, 2004)'
_computing_data_reduction        'SAINT software (Bruker AXS, 2004)'
_computing_structure_solution    'SHELXS-97 (G. M. Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-97 (G. M. Sheldrick, 2008)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_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.

The minimum and maximum estimated transmissions from the multi-scan
scaling are 0.8589 and 1.0000 (SADABS).
;

_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)+(0.0472P)²+0.7456P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         9892
_refine_ls_number_parameters     335
_refine_ls_number_restraints     6
_refine_ls_R_factor_all          0.0335
_refine_ls_R_factor_gt           0.0288
_refine_ls_wR_factor_ref         0.0828
_refine_ls_wR_factor_gt          0.0792
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_restrained_S_all      1.039
_refine_ls_shift/su_max          0.001
_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 0.175528(15) 0.120374(5) 0.305919(7) 0.01247(3) Uani 1 1 d . . .
N1 N 0.06585(11) 0.17233(3) 0.18887(5) 0.01412(12) Uani 1 1 d . . .
C2 C -0.01406(14) 0.22516(4) 0.18930(7) 0.01768(15) Uani 1 1 d . . .
H2 H -0.0264 0.2416 0.2491 0.021 Uiso 1 1 calc R . .
C3 C -0.08013(15) 0.25716(4) 0.10528(7) 0.02017(16) Uani 1 1 d . . .
H3 H -0.1381 0.2945 0.1075 0.024 Uiso 1 1 calc R . .
C4 C -0.05971(15) 0.23340(4) 0.01817(7) 0.02005(16) Uani 1 1 d . . .
H4 H -0.1037 0.2544 -0.0402 0.024 Uiso 1 1 calc R . .
C5 C 0.02575(14) 0.17860(4) 0.01722(6) 0.01703(15) Uani 1 1 d . . .
H5 H 0.0430 0.1618 -0.0415 0.020 Uiso 1 1 calc R . .
C6 C 0.08523(12) 0.14898(4) 0.10373(6) 0.01336(13) Uani 1 1 d . . .
C7 C 0.16352(12) 0.08873(4) 0.11174(6) 0.01221(12) Uani 1 1 d . . .
C8 C 0.19524(12) 0.05394(4) 0.03641(6) 0.01317(13) Uani 1 1 d . . .
H8 H 0.1721 0.0688 -0.0275 0.016 Uiso 1 1 calc R . .
C9 C 0.26205(12) -0.00346(4) 0.05671(6) 0.01237(12) Uani 1 1 d . . .
C10 C 0.29159(13) -0.02441(4) 0.15154(6) 0.01410(13) Uani 1 1 d . . .
H10 H 0.3345 -0.0634 0.1667 0.017 Uiso 1 1 calc R . .
C11 C 0.25687(12) 0.01304(4) 0.22267(6) 0.01296(13) Uani 1 1 d . . .
N12 N 0.19755(10) 0.06803(3) 0.20192(5) 0.01268(11) Uani 1 1 d . . .
C13 C 0.27093(13) -0.00210(4) 0.32512(6) 0.01395(13) Uani 1 1 d . . .
C14 C 0.30886(15) -0.05818(4) 0.36206(6) 0.01800(15) Uani 1 1 d . . .
H14 H 0.3372 -0.0892 0.3227 0.022 Uiso 1 1 calc R . .
C15 C 0.30435(15) -0.06798(4) 0.45827(7) 0.02046(17) Uani 1 1 d . . .
H15 H 0.3290 -0.1060 0.4855 0.025 Uiso 1 1 calc R . .
C16 C 0.26355(15) -0.02166(5) 0.51411(7) 0.02007(16) Uani 1 1 d . . .
H16 H 0.2576 -0.0277 0.5795 0.024 Uiso 1 1 calc R . .
C17 C 0.23160(14) 0.03359(4) 0.47269(6) 0.01745(15) Uani 1 1 d . . .
H17 H 0.2070 0.0655 0.5113 0.021 Uiso 1 1 calc R . .
N18 N 0.23440(11) 0.04332(3) 0.37998(5) 0.01461(12) Uani 1 1 d . . .
C19 C 0.29880(12) -0.04224(4) -0.01883(6) 0.01301(13) Uani 1 1 d . . .
N20 N 0.26149(11) -0.02785(3) -0.11392(5) 0.01462(12) Uani 1 1 d . . .
H20 H 0.2135 0.0056 -0.1393 0.018 Uiso 1 1 calc R . .
C21 C 0.31215(13) -0.07481(4) -0.16301(6) 0.01693(15) Uani 1 1 d . . .
H21 H 0.3023 -0.0779 -0.2305 0.020 Uiso 1 1 calc R . .
C22 C 0.37993(14) -0.11652(4) -0.09476(7) 0.01748(15) Uani 1 1 d . . .
H22 H 0.4261 -0.1541 -0.1078 0.021 Uiso 1 1 calc R . .
N23 N 0.37158(11) -0.09621(3) -0.00475(6) 0.01543(13) Uani 1 1 d . . .
O41 O 0.13632(10) 0.17002(3) 0.40902(5) 0.01790(12) Uani 1 1 d . . .
C42 C -0.03962(13) 0.17042(4) 0.41810(6) 0.01522(14) Uani 1 1 d . . .
O43 O -0.16439(10) 0.13747(3) 0.37028(5) 0.01917(12) Uani 1 1 d . . .
C44 C -0.08728(17) 0.21271(6) 0.48946(9) 0.0283(2) Uani 1 1 d . . .
H44A H -0.2278 0.2168 0.4792 0.042 Uiso 1 1 calc R . .
H44B H -0.0298 0.2509 0.4813 0.042 Uiso 1 1 calc R . .
H44C H -0.0356 0.1982 0.5548 0.042 Uiso 1 1 calc R . .
O30 O 0.45751(11) 0.16426(4) 0.30699(7) 0.02428(15) Uani 1 1 d D . .
H30A H 0.5704(15) 0.1584(9) 0.3302(13) 0.036 Uiso 1 1 d D . .
H30B H 0.451(3) 0.1995(4) 0.2995(14) 0.036 Uiso 1 1 d D . .
N50 N 0.18002(14) 0.09180(4) 0.74132(6) 0.02167(16) Uani 1 1 d . . .
O51 O 0.19161(16) 0.14377(5) 0.71379(9) 0.0399(2) Uani 1 1 d . . .
O52 O 0.2521(2) 0.05111(5) 0.70458(8) 0.0500(3) Uani 1 1 d . . .
O53 O 0.09617(13) 0.08197(4) 0.80891(6) 0.02516(15) Uani 1 1 d . . .
O60 O 0.41876(15) -0.16590(4) 0.16417(7) 0.02948(17) Uani 1 1 d D . .
H60A H 0.5317(15) -0.1632(9) 0.1923(14) 0.044 Uiso 1 1 d D . .
H60B H 0.417(3) -0.1492(8) 0.1128(9) 0.044 Uiso 1 1 d D . .
O70 O 0.40474(15) 0.28318(4) 0.27502(8) 0.03306(19) Uani 1 1 d D . .
H70A H 0.485(2) 0.3067(8) 0.2635(16) 0.050 Uiso 1 1 d D . .
H70B H 0.313(2) 0.3006(8) 0.2887(15) 0.050 Uiso 1 1 d D . .


_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 O41 1.9196(7) . ?
Cu1 N12 1.9329(8) . ?
Cu1 N18 2.0451(8) . ?
Cu1 N1 2.0536(8) . ?
Cu1 O30 2.2333(8) . ?
N1 C2 1.3325(12) . ?
N1 C6 1.3562(11) . ?
C2 C3 1.3915(14) . ?
C3 C4 1.3877(15) . ?
C4 C5 1.3906(13) . ?
C5 C6 1.3864(12) . ?
C6 C7 1.4776(12) . ?
C7 N12 1.3380(11) . ?
C7 C8 1.3898(11) . ?
C8 C9 1.4012(12) . ?
C9 C10 1.4026(12) . ?
C9 C19 1.4576(12) . ?
C10 C11 1.3859(12) . ?
C11 N12 1.3356(11) . ?
C11 C13 1.4790(12) . ?
C13 N18 1.3552(11) . ?
C13 C14 1.3871(13) . ?
C14 C15 1.3931(13) . ?
C15 C16 1.3891(15) . ?
C16 C17 1.3890(14) . ?
C17 N18 1.3408(11) . ?
C19 N23 1.3334(12) . ?
C19 N20 1.3601(11) . ?
N20 C21 1.3682(12) . ?
C21 C22 1.3697(14) . ?
C22 N23 1.3740(12) . ?
O41 C42 1.2818(11) . ?
C42 O43 1.2447(11) . ?
C42 C44 1.4907(14) . ?
N50 O52 1.2293(13) . ?
N50 O53 1.2548(11) . ?
N50 O51 1.2568(13) . ?

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
O41 Cu1 N12 176.01(3) . . ?
O41 Cu1 N18 99.28(3) . . ?
N12 Cu1 N18 79.71(3) . . ?
O41 Cu1 N1 100.72(3) . . ?
N12 Cu1 N1 79.40(3) . . ?
N18 Cu1 N1 155.84(3) . . ?
O41 Cu1 O30 90.44(3) . . ?
N12 Cu1 O30 93.54(3) . . ?
N18 Cu1 O30 107.41(3) . . ?
N1 Cu1 O30 85.88(3) . . ?
C2 N1 C6 118.99(8) . . ?
C2 N1 Cu1 127.24(6) . . ?
C6 N1 Cu1 113.74(6) . . ?
N1 C2 C3 122.35(9) . . ?
C4 C3 C2 118.69(9) . . ?
C3 C4 C5 119.33(9) . . ?
C6 C5 C4 118.62(8) . . ?
N1 C6 C5 122.01(8) . . ?
N1 C6 C7 113.92(7) . . ?
C5 C6 C7 123.98(8) . . ?
N12 C7 C8 120.72(8) . . ?
N12 C7 C6 112.89(7) . . ?
C8 C7 C6 126.35(7) . . ?
C7 C8 C9 118.62(7) . . ?
C8 C9 C10 119.32(7) . . ?
C8 C9 C19 121.46(7) . . ?
C10 C9 C19 119.21(8) . . ?
C11 C10 C9 118.55(8) . . ?
N12 C11 C10 121.01(8) . . ?
N12 C11 C13 112.81(7) . . ?
C10 C11 C13 126.13(8) . . ?
C11 N12 C7 121.73(7) . . ?
C11 N12 Cu1 119.02(6) . . ?
C7 N12 Cu1 119.15(6) . . ?
N18 C13 C14 122.21(8) . . ?
N18 C13 C11 114.05(8) . . ?
C14 C13 C11 123.67(8) . . ?
C13 C14 C15 118.41(9) . . ?
C16 C15 C14 119.40(9) . . ?
C17 C16 C15 118.89(8) . . ?
N18 C17 C16 122.08(9) . . ?
C17 N18 C13 118.98(8) . . ?
C17 N18 Cu1 127.12(7) . . ?
C13 N18 Cu1 113.84(6) . . ?
N23 C19 N20 110.96(7) . . ?
N23 C19 C9 125.10(8) . . ?
N20 C19 C9 123.95(8) . . ?
C19 N20 C21 107.57(8) . . ?
N20 C21 C22 105.87(8) . . ?
C21 C22 N23 110.24(8) . . ?
C19 N23 C22 105.37(8) . . ?
C42 O41 Cu1 112.71(6) . . ?
O43 C42 O41 122.20(8) . . ?
O43 C42 C44 121.56(9) . . ?
O41 C42 C44 116.24(8) . . ?
O52 N50 O53 119.99(10) . . ?
O52 N50 O51 121.26(11) . . ?
O53 N50 O51 118.73(10) . . ?

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
N20 H20 O53 0.88 2.00 2.8805(12) 176.8 1_554
O30 H30A O43 0.808(9) 1.904(10) 2.7067(12) 172(2) 1_655
O30 H30B O70 0.811(9) 1.955(9) 2.7628(13) 173.8(19) .
O60 H60A O51 0.817(9) 2.166(10) 2.9701(16) 168(2) 3_656
O60 H60B N23 0.821(9) 2.031(10) 2.8386(12) 168(2) .
O70 H70A O51 0.825(9) 2.090(10) 2.9050(15) 170(2) 4_665
O70 H70B O60 0.818(9) 2.054(10) 2.8666(15) 172(2) 2

_diffrn_measured_fraction_theta_max 1.000
_diffrn_reflns_theta_full        35.00
_diffrn_measured_fraction_theta_full 1.000
_refine_diff_density_max         0.996
_refine_diff_density_min         -0.322
_refine_diff_density_rms         0.076


_database_code_depnum_ccdc_archive 'CCDC 787339'
