# 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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#  Bona fide researchers may freely download Mercury and enCIFer
#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
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data_www

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C12 H12 Cu Mo4 N4 O14'
_chemical_formula_sum            'C12 H12 Cu Mo4 N4 O14 '
_chemical_formula_weight         883.55

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'
Mo Mo -1.6832 0.6857 '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                   13.526(5)
_cell_length_b                   11.743(5)
_cell_length_c                   13.885(5)
_cell_angle_alpha                90.000(5)
_cell_angle_beta                 107.129(5)
_cell_angle_gamma                90.000(5)
_cell_volume                     2107.6(14)
_cell_formula_units_Z            4
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    9528
_cell_measurement_theta_min      2.32
_cell_measurement_theta_max      28.32

_exptl_crystal_description       block
_exptl_crystal_colour            blue
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.18
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    2.778
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1676.0
_exptl_absorpt_coefficient_mu    3.389
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.479
_exptl_absorpt_correction_T_max  0.543
_exptl_absorpt_process_details   '(SADABS; Sheldrick, 2003)'

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71069
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  ?
_diffrn_measurement_method       ?
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            15247
_diffrn_reflns_av_R_equivalents  0.0160
_diffrn_reflns_av_sigmaI/netI    0.0177
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_theta_min         1.85
_diffrn_reflns_theta_max         28.32
_reflns_number_total             5254
_reflns_number_gt                4803
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SMART'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'Bruker SMART'
_computing_publication_material  'Bruker SMART'

_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)+(0.0200P)²+1.7247P] 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         5255
_refine_ls_number_parameters     316
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0203
_refine_ls_R_factor_gt           0.0170
_refine_ls_wR_factor_ref         0.0426
_refine_ls_wR_factor_gt          0.0414
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_restrained_S_all      1.042
_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
Mo1 Mo 0.389561(14) -0.021164(16) 0.209854(13) 0.01761(5) Uani 1 1 d . . .
Mo2 Mo 0.351977(14) 0.154496(15) 0.023100(13) 0.01562(4) Uani 1 1 d . . .
Mo3 Mo 0.625209(14) -0.051201(16) 0.198656(13) 0.01548(4) Uani 1 1 d . . .
Mo4 Mo 0.581935(13) 0.123820(15) 0.010412(13) 0.01399(4) Uani 1 1 d . . .
Cu1 Cu 0.60397(2) 0.16770(2) 0.371127(18) 0.01759(6) Uani 1 1 d . . .
O12 O 0.65481(12) 0.07071(14) 0.27244(11) 0.0221(3) Uani 1 1 d . . .
O11 O 0.61975(13) 0.23614(14) 0.08819(12) 0.0241(3) Uani 1 1 d . . .
O10 O 0.24699(12) 0.21841(14) -0.05812(12) 0.0233(3) Uani 1 1 d . . .
O9 O 0.48417(11) 0.03785(12) 0.08809(11) 0.0151(3) Uani 1 1 d . . .
O8 O 0.44022(13) 0.09240(15) 0.28665(12) 0.0252(4) Uani 1 1 d . . .
O7 O 0.35782(12) -0.14491(13) 0.08400(11) 0.0204(3) Uani 1 1 d . . .
O6 O 0.40754(12) 0.26052(14) 0.10573(12) 0.0235(3) Uani 1 1 d . . .
O5 O 0.29249(12) 0.06256(14) 0.10357(11) 0.0213(3) Uani 1 1 d . . .
O4 O 0.51677(12) -0.10790(13) 0.24349(11) 0.0200(3) Uani 1 1 d . . .
O3 O 0.31390(14) -0.09060(16) 0.26816(13) 0.0307(4) Uani 1 1 d . . .
O2 O 0.44358(11) 0.17030(12) -0.06676(11) 0.0159(3) Uani 1 1 d . . .
O1 O 0.67256(11) 0.00331(13) 0.08294(10) 0.0159(3) Uani 1 1 d . . .
N2 N 0.53717(15) 0.26074(17) 0.45572(14) 0.0211(4) Uani 1 1 d . . .
C12 C 0.43097(19) 0.3835(2) 0.49814(18) 0.0261(5) Uani 1 1 d . . .
H12 H 0.3778 0.4350 0.4947 0.031 Uiso 1 1 calc R . .
N3 N 0.78530(15) -0.05156(16) 0.57894(14) 0.0206(4) Uani 1 1 d . . .
C11 C 0.7617(2) 0.0434(2) 0.52373(18) 0.0275(5) Uani 1 1 d . . .
H11 H 0.8090 0.1005 0.5228 0.033 Uiso 1 1 calc R . .
C10 C 0.98848(18) -0.12522(19) 0.81389(17) 0.0211(4) Uani 1 1 d . . .
C9 C 0.89140(18) -0.1047(2) 0.74732(17) 0.0222(5) Uani 1 1 d . . .
H9 H 0.8323 -0.1097 0.7683 0.027 Uiso 1 1 calc R . .
N4 N 0.50327(15) 0.34392(17) 0.58428(14) 0.0219(4) Uani 1 1 d . . .
C8 C 1.0683(2) -0.0885(3) 0.6849(2) 0.0340(6) Uani 1 1 d . . .
H8 H 1.1273 -0.0825 0.6639 0.041 Uiso 1 1 calc R . .
C7 C 0.45333(19) 0.3321(2) 0.42020(18) 0.0250(5) Uani 1 1 d . . .
H7 H 0.4175 0.3432 0.3526 0.030 Uiso 1 1 calc R . .
C6 C 0.6971(2) -0.1139(3) 0.5599(2) 0.0440(8) Uani 1 1 d . . .
H6 H 0.6894 -0.1844 0.5875 0.053 Uiso 1 1 calc R . .
C5 C 0.56540(18) 0.2707(2) 0.55472(16) 0.0216(4) Uani 1 1 d . . .
H5 H 0.6208 0.2323 0.5983 0.026 Uiso 1 1 calc R . .
C4 C 0.6225(2) -0.0537(3) 0.4929(2) 0.0397(7) Uani 1 1 d . . .
H4 H 0.5541 -0.0767 0.4659 0.048 Uiso 1 1 calc R . .
C3 C 0.88458(18) -0.07642(19) 0.64849(17) 0.0210(4) Uani 1 1 d . . .
N1 N 0.66329(15) 0.04636(16) 0.47089(14) 0.0207(4) Uani 1 1 d . . .
O13 O 0.72310(13) -0.14296(15) 0.24877(12) 0.0274(4) Uani 1 1 d . . .
C2 C 1.07730(19) -0.1165(2) 0.78407(19) 0.0289(5) Uani 1 1 d . . .
H2 H 1.1420 -0.1292 0.8299 0.035 Uiso 1 1 calc R . .
C1 C 0.9718(2) -0.0694(2) 0.61707(19) 0.0296(5) Uani 1 1 d . . .
H1 H 0.9660 -0.0520 0.5503 0.035 Uiso 1 1 calc R . .
O1W O 0.57538(12) 0.29394(14) 0.27112(11) 0.0220(3) Uani 1 1 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
Mo1 O3 1.6899(17) . ?
Mo1 O8 1.7189(17) . ?
Mo1 O5 1.9305(16) . ?
Mo1 O4 1.9346(17) . ?
Mo1 O7 2.2154(17) . ?
Mo1 O9 2.5000(16) . ?
Mo2 O10 1.7053(16) . ?
Mo2 O6 1.7098(16) . ?
Mo2 O5 1.8950(17) . ?
Mo2 O2 2.0092(16) . ?
Mo2 O9 2.2220(15) . ?
Mo2 O1 2.3289(16) 3_655 ?
Mo2 Mo4 3.1872(12) . ?
Mo3 O13 1.6899(17) . ?
Mo3 O12 1.7371(17) . ?
Mo3 O4 1.8761(17) . ?
Mo3 O1 2.0020(16) . ?
Mo3 O2 2.2741(16) 3_655 ?
Mo3 O9 2.3161(15) . ?
Mo4 O11 1.6859(16) . ?
Mo4 O7 1.7530(16) 3_655 ?
Mo4 O2 1.9409(15) . ?
Mo4 O1 1.9474(15) . ?
Mo4 O9 2.1844(16) . ?
Mo4 O9 2.3567(16) 3_655 ?
Cu1 N1 1.985(2) . ?
Cu1 O1W 1.9897(17) . ?
Cu1 N2 2.004(2) . ?
Cu1 O12 2.0501(17) . ?
Cu1 O10 2.3188(17) 4_666 ?
Cu1 O8 2.3523(18) . ?
O10 Cu1 2.3188(17) 4_565 ?
O9 Mo4 2.3567(16) 3_655 ?
O7 Mo4 1.7530(16) 3_655 ?
O2 Mo3 2.2741(16) 3_655 ?
O1 Mo2 2.3289(16) 3_655 ?
N2 C5 1.319(3) . ?
N2 C7 1.379(3) . ?
C12 C7 1.349(3) . ?
C12 N4 1.383(3) . ?
N3 C11 1.337(3) . ?
N3 C6 1.358(3) . ?
N3 C3 1.434(3) . ?
C11 N1 1.317(3) . ?
C10 C2 1.385(3) . ?
C10 C9 1.386(3) . ?
C10 N4 1.432(3) 2_646 ?
C9 C3 1.388(3) . ?
N4 C5 1.348(3) . ?
N4 C10 1.432(3) 2_656 ?
C8 C2 1.386(4) . ?
C8 C1 1.384(4) . ?
C6 C4 1.353(4) . ?
C4 N1 1.370(3) . ?
C3 C1 1.376(3) . ?

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
O3 Mo1 O8 105.32(9) . . ?
O3 Mo1 O5 103.91(8) . . ?
O8 Mo1 O5 97.83(8) . . ?
O3 Mo1 O4 104.56(8) . . ?
O8 Mo1 O4 95.45(8) . . ?
O5 Mo1 O4 143.99(7) . . ?
O3 Mo1 O7 93.29(8) . . ?
O8 Mo1 O7 161.35(7) . . ?
O5 Mo1 O7 78.52(7) . . ?
O4 Mo1 O7 78.29(6) . . ?
O3 Mo1 O9 163.85(7) . . ?
O8 Mo1 O9 90.83(7) . . ?
O5 Mo1 O9 73.16(6) . . ?
O4 Mo1 O9 73.33(6) . . ?
O7 Mo1 O9 70.57(6) . . ?
O10 Mo2 O6 103.83(8) . . ?
O10 Mo2 O5 103.01(8) . . ?
O6 Mo2 O5 101.43(8) . . ?
O10 Mo2 O2 95.42(7) . . ?
O6 Mo2 O2 96.89(7) . . ?
O5 Mo2 O2 149.92(7) . . ?
O10 Mo2 O9 162.48(7) . . ?
O6 Mo2 O9 91.96(7) . . ?
O5 Mo2 O9 80.79(7) . . ?
O2 Mo2 O9 74.90(6) . . ?
O10 Mo2 O1 89.79(7) . 3_655 ?
O6 Mo2 O1 162.99(7) . 3_655 ?
O5 Mo2 O1 85.02(7) . 3_655 ?
O2 Mo2 O1 71.34(6) . 3_655 ?
O9 Mo2 O1 73.38(5) . 3_655 ?
O10 Mo2 Mo4 130.49(6) . . ?
O6 Mo2 Mo4 82.89(6) . . ?
O5 Mo2 Mo4 123.98(5) . . ?
O2 Mo2 Mo4 35.49(4) . . ?
O9 Mo2 Mo4 43.21(4) . . ?
O1 Mo2 Mo4 80.49(4) 3_655 . ?
O13 Mo3 O12 105.43(8) . . ?
O13 Mo3 O4 103.38(8) . . ?
O12 Mo3 O4 99.42(7) . . ?
O13 Mo3 O1 97.89(8) . . ?
O12 Mo3 O1 97.88(7) . . ?
O4 Mo3 O1 147.77(6) . . ?
O13 Mo3 O2 91.41(7) . 3_655 ?
O12 Mo3 O2 161.86(6) . 3_655 ?
O4 Mo3 O2 82.79(6) . 3_655 ?
O1 Mo3 O2 72.66(6) . 3_655 ?
O13 Mo3 O9 162.43(7) . . ?
O12 Mo3 O9 91.18(7) . . ?
O4 Mo3 O9 78.95(6) . . ?
O1 Mo3 O9 73.71(6) . . ?
O2 Mo3 O9 71.47(6) 3_655 . ?
O11 Mo4 O7 104.38(8) . 3_655 ?
O11 Mo4 O2 101.24(7) . . ?
O7 Mo4 O2 97.61(7) 3_655 . ?
O11 Mo4 O1 102.20(8) . . ?
O7 Mo4 O1 97.41(7) 3_655 . ?
O2 Mo4 O1 147.95(6) . . ?
O11 Mo4 O9 99.14(7) . . ?
O7 Mo4 O9 156.48(6) 3_655 . ?
O2 Mo4 O9 77.12(6) . . ?
O1 Mo4 O9 77.83(6) . . ?
O11 Mo4 O9 173.55(7) . 3_655 ?
O7 Mo4 O9 81.97(7) 3_655 3_655 ?
O2 Mo4 O9 76.51(6) . 3_655 ?
O1 Mo4 O9 77.77(6) . 3_655 ?
O9 Mo4 O9 74.51(6) . 3_655 ?
O11 Mo4 Mo2 89.60(6) . . ?
O7 Mo4 Mo2 134.55(5) 3_655 . ?
O2 Mo4 Mo2 36.94(5) . . ?
O1 Mo4 Mo2 121.97(5) . . ?
O9 Mo4 Mo2 44.14(4) . . ?
O9 Mo4 Mo2 85.04(4) 3_655 . ?
N1 Cu1 O1W 167.85(7) . . ?
N1 Cu1 N2 98.15(8) . . ?
O1W Cu1 N2 88.53(8) . . ?
N1 Cu1 O12 85.49(8) . . ?
O1W Cu1 O12 88.97(7) . . ?
N2 Cu1 O12 173.07(7) . . ?
N1 Cu1 O10 90.17(7) . 4_666 ?
O1W Cu1 O10 80.35(6) . 4_666 ?
N2 Cu1 O10 84.32(7) . 4_666 ?
O12 Cu1 O10 101.62(7) . 4_666 ?
N1 Cu1 O8 101.89(7) . . ?
O1W Cu1 O8 88.35(7) . . ?
N2 Cu1 O8 88.64(7) . . ?
O12 Cu1 O8 84.83(6) . . ?
O10 Cu1 O8 166.81(6) 4_666 . ?
Mo3 O12 Cu1 141.96(10) . . ?
Mo2 O10 Cu1 164.22(9) . 4_565 ?
Mo4 O9 Mo2 92.65(6) . . ?
Mo4 O9 Mo3 92.05(6) . . ?
Mo2 O9 Mo3 162.69(7) . . ?
Mo4 O9 Mo4 105.49(6) . 3_655 ?
Mo2 O9 Mo4 97.96(6) . 3_655 ?
Mo3 O9 Mo4 96.81(6) . 3_655 ?
Mo4 O9 Mo1 165.22(7) . . ?
Mo2 O9 Mo1 86.25(5) . . ?
Mo3 O9 Mo1 84.97(5) . . ?
Mo4 O9 Mo1 89.25(5) 3_655 . ?
Mo1 O8 Cu1 138.22(9) . . ?
Mo4 O7 Mo1 118.19(8) 3_655 . ?
Mo2 O5 Mo1 115.44(8) . . ?
Mo3 O4 Mo1 117.37(8) . . ?
Mo4 O2 Mo2 107.57(7) . . ?
Mo4 O2 Mo3 111.77(7) . 3_655 ?
Mo2 O2 Mo3 105.21(7) . 3_655 ?
Mo4 O1 Mo3 110.24(7) . . ?
Mo4 O1 Mo2 107.49(7) . 3_655 ?
Mo3 O1 Mo2 103.49(7) . 3_655 ?
C5 N2 C7 105.90(19) . . ?
C5 N2 Cu1 128.11(16) . . ?
C7 N2 Cu1 125.94(15) . . ?
C7 C12 N4 106.0(2) . . ?
C11 N3 C6 106.9(2) . . ?
C11 N3 C3 125.0(2) . . ?
C6 N3 C3 128.0(2) . . ?
N1 C11 N3 111.9(2) . . ?
C2 C10 C9 121.5(2) . . ?
C2 C10 N4 119.5(2) . 2_646 ?
C9 C10 N4 119.0(2) . 2_646 ?
C10 C9 C3 118.4(2) . . ?
C5 N4 C12 107.23(19) . . ?
C5 N4 C10 126.0(2) . 2_656 ?
C12 N4 C10 126.8(2) . 2_656 ?
C2 C8 C1 120.3(2) . . ?
C12 C7 N2 109.9(2) . . ?
C4 C6 N3 106.6(2) . . ?
N2 C5 N4 111.0(2) . . ?
C6 C4 N1 109.5(2) . . ?
C1 C3 C9 120.9(2) . . ?
C1 C3 N3 119.7(2) . . ?
C9 C3 N3 119.4(2) . . ?
C11 N1 C4 105.1(2) . . ?
C11 N1 Cu1 122.84(16) . . ?
C4 N1 Cu1 131.65(17) . . ?
C8 C2 C10 119.0(2) . . ?
C3 C1 C8 119.9(2) . . ?

_diffrn_measured_fraction_theta_max 1.000
_diffrn_reflns_theta_full        28.32
_diffrn_measured_fraction_theta_full 1.000
_refine_diff_density_max         0.704
_refine_diff_density_min         -0.488
_refine_diff_density_rms         0.095
_database_code_depnum_ccdc_archive 'CCDC 1012514'
