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

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#
#                 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.
#
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#  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:
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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_added_by_encifer


_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            (Zn(DMF))2(TTFTC)(DPNI)
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C43 H26 N7 O15 S4 Zn2'
_chemical_formula_weight         1139.69

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'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Zn Zn 0.2839 1.4301 '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'
N N 0.0061 0.0033 '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/c'

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

_cell_length_a                   8.3800(4)
_cell_length_b                   20.9662(9)
_cell_length_c                   13.0999(6)
_cell_angle_alpha                90.00
_cell_angle_beta                 95.038(3)
_cell_angle_gamma                90.00
_cell_volume                     2292.72(18)
_cell_formula_units_Z            2
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    4082
_cell_measurement_theta_min      2.6345
_cell_measurement_theta_max      23.076

_exptl_crystal_description       prismatic
_exptl_crystal_colour            green
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.04
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.651
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1154
_exptl_absorpt_coefficient_mu    1.307
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.8068
_exptl_absorpt_correction_T_max  0.8621
_exptl_absorpt_process_details   
; 
 SADABS (Sheldrick, 1996)
;

_diffrn_crystal_treatment        
;
attached with Exxon Paratone N, to a short length 
of fibre supported on a thin piece of copper wire 
inserted in a copper mounting pin.  The crystal was 
quenched in a cold nitrogen gas stream from an 
Oxford Cryosystems Cryostream. 
;

_diffrn_ambient_temperature      150(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'rotating anode'
_diffrn_radiation_monochromator  mirror
_diffrn_measurement_device_type  APEXII-FR591
_diffrn_measurement_method       ω+φ
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            67862
_diffrn_reflns_av_R_equivalents  0.1261
_diffrn_reflns_av_sigmaI/netI    0.0742
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_theta_min         1.84
_diffrn_reflns_theta_max         28.30
_reflns_number_total             5676
_reflns_number_gt                3543
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'APEX (Bruker-AXS,2012)'
_computing_cell_refinement       'SAINT (Bruker-AXS,2012)'
_computing_data_reduction        'SAINT and XPREP (Bruker-AXS,2012)'
_computing_structure_solution    'Superflip (Palatinus, et. al. 2007)'
_computing_structure_refinement  'SHELXL-13 (Sheldrick, 2013)'
_computing_molecular_graphics    
;
 WinGX (Farrugia, 1999)
 POV-Ray v3.6 with XSEED v2.0 
;
_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 metal-organic framework was refined anisotropically. The 
N,N'-dimethylformamide solvent molecule was disordered over two positions 
and hence the occupancies of the disordered components were refined 
as a free variable, adding up to unity. The following restraints were used:
DFIX 1.4 N4 C54 N4 C55
DANG 2.5 C54 C55
SADI 0.01 N4 C54 N4 C55
FLAT 0.100 N4 C53 C55 O8 C54

Due to distortions in the rings of the TTFTC and DPNI, the following
restraints were applied: 
FLAT 0.01 N1 C2 C4 C5 C3 C1
FLAT 0.01 C10 N2 C6 C7 C8 C9
;

_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)+(0.1438P)²+10.0416P] 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         5676
_refine_ls_number_parameters     318
_refine_ls_number_restraints     12
_refine_ls_R_factor_all          0.1548
_refine_ls_R_factor_gt           0.0937
_refine_ls_wR_factor_ref         0.2816
_refine_ls_wR_factor_gt          0.2380
_refine_ls_goodness_of_fit_ref   1.074
_refine_ls_restrained_S_all      1.073
_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
Zn1 Zn 0.63770(11) 0.29106(4) 0.85556(6) 0.0359(3) Uani 1 1 d . . .
O3 O 0.4095(7) 0.2812(3) 0.8070(4) 0.0497(14) Uani 1 1 d . . .
O6 O 0.3425(7) 0.3657(3) 1.2769(4) 0.0480(14) Uani 1 1 d . . .
C10 C 0.5012(6) 0.4892(3) 1.4487(4) 0.0266(13) Uani 1 1 d D . .
O5 O 0.6902(6) 0.5236(2) 1.2153(4) 0.0382(12) Uani 1 1 d . . .
O2 O 0.7347(7) 0.3120(2) 0.7290(4) 0.0435(13) Uani 1 1 d . . .
O1 O 0.6649(8) 0.4105(3) 0.7660(4) 0.0541(15) Uani 1 1 d . . .
O4 O 0.7524(7) 0.2127(2) 0.9022(4) 0.0417(12) Uani 1 1 d . . .
N2 N 0.5216(5) 0.4430(2) 1.2493(4) 0.0325(13) Uani 1 1 d D . .
N1 N 0.6171(6) 0.3475(2) 0.9797(4) 0.0326(13) Uani 1 1 d D . .
N3 N 0.2192(9) 0.2576(4) 0.6771(7) 0.059(2) Uani 1 1 d . . .
C5 C 0.5554(8) 0.4118(3) 1.1556(5) 0.0301(14) Uani 1 1 d D . .
C6 C 0.6104(7) 0.4981(3) 1.2762(5) 0.0316(15) Uani 1 1 d D . .
C17 C 0.7953(8) 0.3946(3) 0.6156(5) 0.0273(13) Uani 1 1 d . . .
C7 C 0.4226(7) 0.4091(3) 1.3134(5) 0.0343(15) Uani 1 1 d D . .
C8 C 0.5989(7) 0.5229(3) 1.3828(5) 0.0302(14) Uani 1 1 d D . .
C11 C 0.6785(9) 0.5773(3) 1.4146(5) 0.0326(15) Uani 1 1 d . . .
H11 H 0.7369 0.6000 1.3695 0.039 Uiso 1 1 calc R . .
C9 C 0.4147(7) 0.4339(3) 1.4168(5) 0.0288(14) Uani 1 1 d D . .
C12 C 0.6716(8) 0.5985(3) 1.5152(5) 0.0321(15) Uani 1 1 d . . .
H12 H 0.7265 0.6354 1.5366 0.039 Uiso 1 1 calc R . .
C16 C 0.7228(8) 0.3707(3) 0.7117(5) 0.0331(15) Uani 1 1 d . . .
C14 C 0.1820(15) 0.2391(7) 0.5721(10) 0.095(4) Uani 1 1 d . . .
H14A H 0.0685 0.2329 0.5592 0.142 Uiso 1 1 calc R . .
H14B H 0.2366 0.2000 0.5591 0.142 Uiso 1 1 calc R . .
H14C H 0.2160 0.2719 0.5279 0.142 Uiso 1 1 calc R . .
C3 C 0.6729(9) 0.3650(3) 1.1594(6) 0.0429(18) Uani 1 1 d D . .
H3 H 0.7320 0.3549 1.2207 0.052 Uiso 1 1 calc R . .
C13 C 0.3679(10) 0.2688(4) 0.7136(7) 0.049(2) Uani 1 1 d . . .
H13 H 0.4472 0.2676 0.6682 0.058 Uiso 1 1 calc R . .
C2 C 0.5049(8) 0.3927(3) 0.9773(5) 0.0445(19) Uani 1 1 d D . .
H2 H 0.4477 0.4022 0.9151 0.053 Uiso 1 1 calc R . .
C1 C 0.6990(8) 0.3344(3) 1.0702(6) 0.0412(17) Uani 1 1 d D . .
H1 H 0.7774 0.3030 1.0723 0.049 Uiso 1 1 calc R . .
C4 C 0.4700(9) 0.4264(3) 1.0640(6) 0.047(2) Uani 1 1 d D . .
H4 H 0.3914 0.4579 1.0603 0.056 Uiso 1 1 calc R . .
C15 C 0.0948(13) 0.2523(8) 0.7492(12) 0.105(5) Uani 1 1 d . . .
H15A H -0.0069 0.2441 0.7119 0.157 Uiso 1 1 calc R . .
H15B H 0.0892 0.2914 0.7868 0.157 Uiso 1 1 calc R . .
H15C H 0.1208 0.2179 0.7961 0.157 Uiso 1 1 calc R . .
S1 S 0.8992(2) 0.08877(8) 0.93084(13) 0.0323(4) Uani 1 1 d . . .
S2 S 0.9054(2) 0.46472(8) 0.64046(12) 0.0331(4) Uani 1 1 d . . .
C18 C 0.7911(8) 0.1291(3) 1.0206(5) 0.0298(14) Uani 1 1 d . . .
C19 C 0.9600(8) 0.0256(3) 1.0145(5) 0.0284(14) Uani 1 1 d . . .
O7 O 0.5751(6) 0.2028(2) 1.0180(4) 0.0432(13) Uani 1 1 d . . .
C20 C 0.6960(8) 0.1863(3) 0.9794(5) 0.0314(14) Uani 1 1 d . . .
N4 N 1.022(2) 0.4708(8) 0.9919(13) 0.087(6) Uiso 0.50 1 d PD A -1
C53 C 1.019(3) 0.4291(13) 0.931(2) 0.087(7) Uiso 0.50 1 d PD A -1
C55 C 1.035(5) 0.5301(14) 0.944(3) 0.155(16) Uiso 0.50 1 d PD A -1
O8 O 1.001(3) 0.3690(15) 0.947(2) 0.164(10) Uiso 0.50 1 d PD A -1
C54 C 1.023(4) 0.4615(16) 1.0979(16) 0.120(11) Uiso 0.50 1 d PD A -1


_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
Zn1 O2 1.959(5) . ?
Zn1 O4 1.972(5) . ?
Zn1 O3 1.973(6) . ?
Zn1 N1 2.030(5) . ?
O3 C13 1.269(10) . ?
O6 C7 1.204(8) . ?
C10 C9 1.412(9) . ?
C10 C10 1.420(12) 3_668 ?
C10 C8 1.428(9) . ?
O5 C6 1.208(8) . ?
O2 C16 1.254(8) . ?
O1 C16 1.224(9) . ?
O4 C20 1.280(8) . ?
N2 C6 1.403(8) . ?
N2 C7 1.423(9) . ?
N2 C5 1.441(8) . ?
N1 C2 1.334(9) . ?
N1 C1 1.345(9) . ?
N3 C13 1.316(11) . ?
N3 C14 1.437(15) . ?
N3 C15 1.471(14) . ?
C5 C4 1.376(10) . ?
C5 C3 1.387(10) . ?
C6 C8 1.501(9) . ?
C17 C18 1.336(9) 4_565 ?
C17 C16 1.530(9) . ?
C17 S2 1.752(6) . ?
C7 C9 1.457(9) . ?
C8 C11 1.368(9) . ?
C11 C12 1.397(9) . ?
C9 C12 1.375(9) 3_668 ?
C12 C9 1.375(9) 3_668 ?
C3 C1 1.368(10) . ?
C2 C4 1.390(10) . ?
S1 C18 1.762(7) . ?
S1 C19 1.765(6) . ?
S2 C19 1.762(6) 4_565 ?
C18 C17 1.336(9) 4_566 ?
C18 C20 1.513(9) . ?
C19 C19 1.340(12) 3_757 ?
C19 S2 1.762(6) 4_566 ?
O7 C20 1.222(9) . ?
N4 C53 1.18(3) . ?
N4 C55 1.400(13) . ?
N4 C54 1.403(13) . ?
C53 O8 1.29(4) . ?

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 Zn1 O4 102.8(2) . . ?
O2 Zn1 O3 102.3(2) . . ?
O4 Zn1 O3 116.4(2) . . ?
O2 Zn1 N1 128.2(2) . . ?
O4 Zn1 N1 108.1(2) . . ?
O3 Zn1 N1 99.9(2) . . ?
C13 O3 Zn1 120.6(5) . . ?
C9 C10 C10 119.6(7) . 3_668 ?
C9 C10 C8 122.3(6) . . ?
C10 C10 C8 118.1(7) 3_668 . ?
C16 O2 Zn1 109.9(5) . . ?
C20 O4 Zn1 113.7(4) . . ?
C6 N2 C7 126.0(5) . . ?
C6 N2 C5 116.6(5) . . ?
C7 N2 C5 116.4(5) . . ?
C2 N1 C1 118.0(6) . . ?
C2 N1 Zn1 120.3(5) . . ?
C1 N1 Zn1 121.0(4) . . ?
C13 N3 C14 121.0(9) . . ?
C13 N3 C15 118.9(9) . . ?
C14 N3 C15 119.2(10) . . ?
C4 C5 C3 120.2(6) . . ?
C4 C5 N2 121.0(6) . . ?
C3 C5 N2 118.8(6) . . ?
O5 C6 N2 120.7(6) . . ?
O5 C6 C8 123.1(6) . . ?
N2 C6 C8 116.2(6) . . ?
C18 C17 C16 131.7(6) 4_565 . ?
C18 C17 S2 117.1(5) 4_565 . ?
C16 C17 S2 111.2(5) . . ?
O6 C7 N2 118.5(6) . . ?
O6 C7 C9 124.7(6) . . ?
N2 C7 C9 116.5(6) . . ?
C11 C8 C10 121.2(6) . . ?
C11 C8 C6 120.1(6) . . ?
C10 C8 C6 118.6(6) . . ?
C8 C11 C12 119.6(6) . . ?
C12 C9 C10 119.9(6) 3_668 . ?
C12 C9 C7 119.7(6) 3_668 . ?
C10 C9 C7 120.3(6) . . ?
C9 C12 C11 121.4(6) 3_668 . ?
O1 C16 O2 126.4(7) . . ?
O1 C16 C17 117.5(6) . . ?
O2 C16 C17 116.0(6) . . ?
C1 C3 C5 117.8(7) . . ?
O3 C13 N3 123.9(8) . . ?
N1 C2 C4 122.7(7) . . ?
N1 C1 C3 123.4(7) . . ?
C5 C4 C2 117.9(7) . . ?
C18 S1 C19 94.7(3) . . ?
C17 S2 C19 95.6(3) . 4_565 ?
C17 C18 C20 126.6(6) 4_566 . ?
C17 C18 S1 118.1(5) 4_566 . ?
C20 C18 S1 115.3(5) . . ?
C19 C19 S2 122.3(7) 3_757 4_566 ?
C19 C19 S1 123.4(7) 3_757 . ?
S2 C19 S1 114.3(3) 4_566 . ?
O7 C20 O4 125.6(6) . . ?
O7 C20 C18 120.5(6) . . ?
O4 C20 C18 114.0(6) . . ?
C53 N4 C55 111(3) . . ?
C53 N4 C54 124(2) . . ?
C55 N4 C54 125(3) . . ?
N4 C53 O8 128(3) . . ?

_diffrn_measured_fraction_theta_max 0.997
_diffrn_reflns_theta_full        28.30
_diffrn_measured_fraction_theta_full 0.997
_refine_diff_density_max         2.041
_refine_diff_density_min         -0.930
_refine_diff_density_rms         0.340
_database_code_depnum_ccdc_archive 'CCDC 997130'
