# Electronic Supplementary Material (ESI) for Journal of Materials Chemistry
# This journal is © The Royal Society of Chemistry 2012


data_global
_journal_name_full               J.Mater.Chem.

_journal_coden_Cambridge         1145
_journal_volume                  ?
_journal_page_first              ?
_journal_year                    ?

_publ_contact_author_name        'Dr Rahul Banerjee'
_publ_contact_author_address     
;
Physical/Materials Chemistry Division
National Chemical Laboratory
Dr. Homi Bhaba Road
Pune 411008, India
;

_publ_contact_author_email       r.banerjee@ncl.res.in
_publ_contact_author_phone       '91 020 2590 2535'

_publ_contact_author_fax         '91 020 2590 2636'

_publ_section_title              
;
Fine-Tuning the Balance between Crystallization and Gelation
and Enhancement of CO2 Uptake on Functionalized
Calcium Based MOFs and Metallogels

;
loop_
_publ_author_name
R.Banerjee
A.Mallick
E.Schon
D.Diaz
T.Panda
Sreenivas

# Attachment '- cif_Ca-5TIA-MOF.txt'

data_Ca-5TIA-MOF
_database_code_depnum_ccdc_archive 'CCDC 846548'
#TrackingRef '- cif_Ca-5TIA-MOF.txt'

_audit_creation_method           SHELXL-97

_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C10 H4 Ca N3 O5'
_chemical_formula_sum            'C10 H4 Ca N3 O5'
_chemical_formula_weight         286.24

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'
Ca Ca 0.2262 0.3064 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Orthorhombic
_symmetry_space_group_name_H-M   'C m c a'

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

_cell_length_a                   19.346(2)
_cell_length_b                   24.081(3)
_cell_length_c                   14.2543(15)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     6640.7(12)
_cell_formula_units_Z            16
_cell_measurement_temperature    273(2)
_cell_measurement_reflns_used    7330
_cell_measurement_theta_min      2.21
_cell_measurement_theta_max      27.52

_exptl_crystal_description       Plate
_exptl_crystal_colour            colorless
_exptl_crystal_size_max          0.29
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.12
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.145
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             2320
_exptl_absorpt_coefficient_mu    0.392
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.9544
_exptl_absorpt_correction_T_max  0.9723
_exptl_absorpt_process_details   'Blessing, Acta Cryst. (1995) A51 33-58'

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      273(2)
_diffrn_radiation_wavelength     0.71073
_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            31141
_diffrn_reflns_av_R_equivalents  0.1096
_diffrn_reflns_av_sigmaI/netI    0.0460
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_theta_min         1.69
_diffrn_reflns_theta_max         24.99
_reflns_number_total             3022
_reflns_number_gt                2456
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SMART'
_computing_structure_solution    'Bruker SHELXTL'
_computing_structure_refinement  'Bruker SHELXTL'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_refine_special_details          
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ 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/[\s^2^(Fo^2^)+(0.1152P)^2^+1.3161P] where P=(Fo^2^+2Fc^2^)/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         3022
_refine_ls_number_parameters     178
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0642
_refine_ls_R_factor_gt           0.0567
_refine_ls_wR_factor_ref         0.1728
_refine_ls_wR_factor_gt          0.1671
_refine_ls_goodness_of_fit_ref   1.083
_refine_ls_restrained_S_all      1.083
_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
C1 C 0.25502(13) 0.15241(11) -0.07310(18) 0.0250(6) Uani 1 1 d . . .
C2 C 0.2500 0.15065(15) -0.2500 0.0220(8) Uani 1 2 d S . .
H2 H 0.2500 0.1893 -0.2500 0.026 Uiso 1 2 calc SR . .
C3 C 0.25378(14) 0.06417(12) -0.16558(19) 0.0308(7) Uani 1 1 d . . .
H3 H 0.2566 0.0447 -0.1094 0.037 Uiso 1 1 calc R . .
C4 C 0.25334(13) 0.12199(11) -0.16548(17) 0.0232(6) Uani 1 1 d . . .
C5 C 0.2500 0.03595(16) -0.2500 0.0297(9) Uani 1 2 d S . .
C6 C 0.37077(13) 0.22683(11) 0.18837(19) 0.0290(6) Uani 1 1 d . . .
C7 C 0.5000 0.23224(18) 0.1842(3) 0.0343(9) Uani 1 2 d S . .
H7 H 0.5000 0.2105 0.1302 0.041 Uiso 1 2 calc SR . .
C8 C 0.24926(18) 0.05868(13) 0.1756(2) 0.0457(9) Uani 1 1 d . . .
H8 H 0.2491 0.0470 0.1134 0.055 Uiso 1 1 calc R . .
C9 C 0.5000 0.30469(18) 0.3350(3) 0.0410(11) Uani 1 2 d S . .
C10 C 0.43787(13) 0.24884(12) 0.2254(2) 0.0326(7) Uani 1 1 d . . .
C11 C 0.43796(14) 0.28494(13) 0.2996(2) 0.0389(7) Uani 1 1 d . . .
H11 H 0.3964 0.2962 0.3262 0.047 Uiso 1 1 calc R . .
C12 C 0.5535(3) 0.3702(3) 0.4461(6) 0.146(3) Uani 1 1 d . . .
Ca1 Ca 0.23962(3) 0.20080(2) 0.11082(4) 0.0209(2) Uani 1 1 d . . .
N1 N 0.24873(14) 0.11023(10) 0.20176(18) 0.0433(7) Uani 1 1 d . . .
N2 N 0.5000 0.34582(17) 0.4069(3) 0.0566(11) Uani 1 2 d S . .
N3 N 0.5336(2) 0.4104(2) 0.5037(4) 0.135(2) Uani 1 1 d . . .
N4 N 0.2500 -0.02405(14) -0.2500 0.0344(9) Uani 1 2 d S . .
O1 O 0.32141(9) 0.22139(8) 0.24543(10) 0.0270(5) Uani 1 1 d . . .
O2 O 0.36553(10) 0.21477(10) 0.10247(13) 0.0419(6) Uani 1 1 d . . .
O3 O 0.25148(12) 0.12498(9) 0.00021(15) 0.0477(7) Uani 1 1 d . . .
O4 O 0.23949(10) 0.29544(7) 0.07366(15) 0.0298(5) Uani 1 1 d . . .
O5 O 0.12527(12) 0.20546(10) 0.04066(17) 0.0601(7) Uani 1 1 d . . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
C1 0.0436(16) 0.0140(13) 0.0173(15) -0.0009(11) -0.0022(11) 0.0019(10)
C2 0.036(2) 0.0120(17) 0.0182(19) 0.000 0.0012(14) 0.000
C3 0.0608(19) 0.0140(14) 0.0176(15) 0.0022(11) -0.0008(11) -0.0010(11)
C4 0.0394(15) 0.0144(13) 0.0157(14) -0.0009(10) 0.0000(10) 0.0019(10)
C5 0.056(3) 0.0105(18) 0.022(2) 0.000 0.0017(16) 0.000
C6 0.0276(15) 0.0305(14) 0.0291(15) 0.0018(12) -0.0028(12) 0.0035(11)
C7 0.029(2) 0.045(2) 0.029(2) -0.0027(18) 0.000 0.000
C8 0.104(3) 0.0147(14) 0.0186(15) 0.0007(12) 0.0016(14) 0.0015(14)
C9 0.033(2) 0.040(2) 0.050(3) -0.010(2) 0.000 0.000
C10 0.0189(13) 0.0344(16) 0.0445(16) -0.0005(13) -0.0004(12) 0.0020(11)
C11 0.0251(15) 0.0456(17) 0.0459(19) -0.0013(14) 0.0024(13) 0.0002(12)
C12 0.065(3) 0.156(6) 0.216(7) -0.144(6) -0.012(4) 0.005(3)
Ca1 0.0341(4) 0.0120(3) 0.0166(4) -0.00022(18) -0.00089(19) -0.00089(19)
N1 0.097(2) 0.0154(12) 0.0172(12) 0.0002(10) -0.0008(11) 0.0008(11)
N2 0.036(2) 0.059(3) 0.075(3) -0.033(2) 0.000 0.000
N3 0.079(3) 0.134(4) 0.193(5) -0.116(4) -0.005(3) -0.002(2)
N4 0.075(3) 0.0116(17) 0.0168(17) 0.000 -0.0019(14) 0.000
O1 0.0218(9) 0.0336(11) 0.0256(10) 0.0012(7) 0.0034(7) -0.0034(8)
O2 0.0297(11) 0.0638(14) 0.0324(12) -0.0029(9) -0.0010(8) -0.0002(10)
O3 0.110(2) 0.0172(11) 0.0155(10) -0.0002(9) 0.0015(10) 0.0005(10)
O4 0.0530(13) 0.0123(10) 0.0241(11) -0.0029(7) -0.0025(8) 0.0005(7)
O5 0.0408(14) 0.0867(19) 0.0529(15) 0.0072(13) -0.0070(11) -0.0115(11)

_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
C1 O3 1.238(3) . ?
C1 O4 1.260(3) 13 ?
C1 C4 1.507(4) . ?
C1 Ca1 2.884(3) . ?
C2 C4 1.390(3) 7_544 ?
C2 C4 1.390(3) . ?
C3 C5 1.384(3) . ?
C3 C4 1.392(4) . ?
C5 C3 1.384(3) 7_544 ?
C5 N4 1.445(5) . ?
C6 O1 1.261(3) . ?
C6 O2 1.262(3) . ?
C6 C10 1.498(4) . ?
C6 Ca1 2.838(3) . ?
C7 C10 1.396(3) 12_655 ?
C7 C10 1.396(3) . ?
C8 N1 1.296(4) . ?
C8 N4 1.349(4) 6_545 ?
C9 C11 1.386(3) . ?
C9 C11 1.386(3) 12_655 ?
C9 N2 1.425(5) . ?
C10 C11 1.369(4) . ?
C12 N2 1.315(5) . ?
C12 N3 1.328(6) . ?
Ca1 O4 2.3399(18) . ?
Ca1 O1 2.4164(16) 7_545 ?
Ca1 O3 2.423(2) . ?
Ca1 O5 2.430(2) . ?
Ca1 O2 2.462(2) . ?
Ca1 O1 2.5360(17) . ?
Ca1 N1 2.543(3) . ?
Ca1 O4 2.662(2) 13 ?
Ca1 Ca1 3.9698(11) 13 ?
Ca1 Ca1 3.9880(11) 7_545 ?
N1 N1 1.376(5) 7_545 ?
N2 C12 1.315(5) 12_655 ?
N3 N3 1.299(8) 12_655 ?
N4 C8 1.349(4) 6_544 ?
N4 C8 1.349(4) 4 ?
O1 Ca1 2.4163(16) 7_545 ?
O4 C1 1.260(3) 13 ?
O4 Ca1 2.662(2) 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
O3 C1 O4 122.8(3) . 13 ?
O3 C1 C4 118.5(2) . . ?
O4 C1 C4 118.7(2) 13 . ?
O3 C1 Ca1 56.12(14) . . ?
O4 C1 Ca1 67.16(15) 13 . ?
C4 C1 Ca1 171.20(18) . . ?
C4 C2 C4 120.5(3) 7_544 . ?
C5 C3 C4 119.4(3) . . ?
C2 C4 C3 119.7(2) . . ?
C2 C4 C1 121.1(2) . . ?
C3 C4 C1 119.1(2) . . ?
C3 C5 C3 121.2(4) 7_544 . ?
C3 C5 N4 119.41(18) 7_544 . ?
C3 C5 N4 119.41(18) . . ?
O1 C6 O2 122.7(2) . . ?
O1 C6 C10 117.7(2) . . ?
O2 C6 C10 119.5(2) . . ?
O1 C6 Ca1 63.34(13) . . ?
O2 C6 Ca1 59.98(14) . . ?
C10 C6 Ca1 171.93(19) . . ?
C10 C7 C10 118.8(4) 12_655 . ?
N1 C8 N4 111.5(3) . 6_545 ?
C11 C9 C11 119.9(4) . 12_655 ?
C11 C9 N2 120.0(2) . . ?
C11 C9 N2 120.0(2) 12_655 . ?
C11 C10 C7 120.4(3) . . ?
C11 C10 C6 119.9(2) . . ?
C7 C10 C6 119.8(3) . . ?
C10 C11 C9 120.0(3) . . ?
N2 C12 N3 111.0(4) . . ?
O4 Ca1 O1 89.52(7) . 7_545 ?
O4 Ca1 O3 125.92(8) . . ?
O1 Ca1 O3 138.82(7) 7_545 . ?
O4 Ca1 O5 82.00(8) . . ?
O1 Ca1 O5 83.96(8) 7_545 . ?
O3 Ca1 O5 81.56(8) . . ?
O4 Ca1 O2 81.78(7) . . ?
O1 Ca1 O2 119.76(7) 7_545 . ?
O3 Ca1 O2 88.72(8) . . ?
O5 Ca1 O2 150.97(7) . . ?
O4 Ca1 O1 88.94(7) . . ?
O1 Ca1 O1 67.86(7) 7_545 . ?
O3 Ca1 O1 125.49(7) . . ?
O5 Ca1 O1 150.49(8) . . ?
O2 Ca1 O1 52.59(6) . . ?
O4 Ca1 N1 161.95(8) . . ?
O1 Ca1 N1 77.15(8) 7_545 . ?
O3 Ca1 N1 71.27(8) . . ?
O5 Ca1 N1 108.21(9) . . ?
O2 Ca1 N1 94.20(8) . . ?
O1 Ca1 N1 74.86(8) . . ?
O4 Ca1 O4 75.13(7) . 13 ?
O1 Ca1 O4 154.81(6) 7_545 13 ?
O3 Ca1 O4 50.84(6) . 13 ?
O5 Ca1 O4 74.34(7) . 13 ?
O2 Ca1 O4 78.31(6) . 13 ?
O1 Ca1 O4 130.24(6) . 13 ?
N1 Ca1 O4 121.48(7) . 13 ?
O4 Ca1 C6 82.76(7) . . ?
O1 Ca1 C6 93.51(7) 7_545 . ?
O3 Ca1 C6 109.58(8) . . ?
O5 Ca1 C6 164.57(8) . . ?
O2 Ca1 C6 26.36(7) . . ?
O1 Ca1 C6 26.39(6) . . ?
N1 Ca1 C6 85.93(8) . . ?
O4 Ca1 C6 103.97(7) 13 . ?
O4 Ca1 C1 100.83(8) . . ?
O1 Ca1 C1 154.71(7) 7_545 . ?
O3 Ca1 C1 25.10(7) . . ?
O5 Ca1 C1 74.85(8) . . ?
O2 Ca1 C1 84.78(7) . . ?
O1 Ca1 C1 134.60(7) . . ?
N1 Ca1 C1 96.29(8) . . ?
O4 Ca1 C1 25.87(6) 13 . ?
C6 Ca1 C1 110.54(8) . . ?
O4 Ca1 Ca1 40.40(5) . 13 ?
O1 Ca1 Ca1 127.00(5) 7_545 13 ?
O3 Ca1 Ca1 85.54(5) . 13 ?
O5 Ca1 Ca1 74.75(6) . 13 ?
O2 Ca1 Ca1 77.28(5) . 13 ?
O1 Ca1 Ca1 114.98(5) . 13 ?
N1 Ca1 Ca1 155.58(6) . 13 ?
O4 Ca1 Ca1 34.73(4) 13 13 ?
C6 Ca1 Ca1 95.03(6) . 13 ?
C1 Ca1 Ca1 60.48(5) . 13 ?
O4 Ca1 Ca1 103.02(6) . 7_545 ?
O1 Ca1 Ca1 37.39(4) 7_545 7_545 ?
O3 Ca1 Ca1 129.63(5) . 7_545 ?
O5 Ca1 Ca1 120.07(6) . 7_545 ?
O2 Ca1 Ca1 87.05(5) . 7_545 ?
O1 Ca1 Ca1 35.36(4) . 7_545 ?
N1 Ca1 Ca1 59.07(6) . 7_545 ?
O4 Ca1 Ca1 165.35(5) 13 7_545 ?
C6 Ca1 Ca1 61.47(6) . 7_545 ?
C1 Ca1 Ca1 153.37(5) . 7_545 ?
Ca1 Ca1 Ca1 141.410(16) 13 7_545 ?
C8 N1 N1 106.68(19) . 7_545 ?
C8 N1 Ca1 132.5(2) . . ?
N1 N1 Ca1 120.79(6) 7_545 . ?
C12 N2 C12 104.0(5) . 12_655 ?
C12 N2 C9 128.0(3) . . ?
C12 N2 C9 128.0(3) 12_655 . ?
N3 N3 C12 106.9(3) 12_655 . ?
C8 N4 C8 103.6(3) 6_544 4 ?
C8 N4 C5 128.18(17) 6_544 . ?
C8 N4 C5 128.18(17) 4 . ?
C6 O1 Ca1 159.75(16) . 7_545 ?
C6 O1 Ca1 90.28(14) . . ?
Ca1 O1 Ca1 107.25(7) 7_545 . ?
C6 O2 Ca1 93.66(16) . . ?
C1 O3 Ca1 98.78(17) . . ?
C1 O4 Ca1 166.4(2) 13 . ?
C1 O4 Ca1 86.97(16) 13 13 ?
Ca1 O4 Ca1 104.87(7) . 13 ?

_diffrn_measured_fraction_theta_max 1.000
_diffrn_reflns_theta_full        24.99
_diffrn_measured_fraction_theta_full 1.000
_refine_diff_density_max         1.197
_refine_diff_density_min         -0.407
_refine_diff_density_rms         0.093