# Electronic Supplementary Material (ESI) for Green Chemistry
# This journal is © The Royal Society of Chemistry 2013

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#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
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# 
#  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
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#  except for the purpose of generating routine backup copies
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#  from this site to visualise CIF-encoded structures and 
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data_cm11_0m
#TrackingRef '17301_web_deposit_cif_file_0_TomislavFriscic_1359468229.deposit.cif'


_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
Caffeinium Hydrogensulfate
;
_chemical_name_common            (HCaf)(HSO4)
_chemical_melting_point          ?
_chemical_formula_moiety         'C8 H12 N4 O6 S'
_chemical_formula_sum            'C8 H12 N4 O6 S'
_chemical_formula_weight         292.28

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'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_H-M   P2(1)2(1)2(1)

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

_cell_length_a                   6.4063(10)
_cell_length_b                   8.1667(13)
_cell_length_c                   23.311(4)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     1219.6(3)
_cell_formula_units_Z            4
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    2532
_cell_measurement_theta_min      2.64
_cell_measurement_theta_max      21.42

_exptl_crystal_description       hexagonal
_exptl_crystal_colour            colourless
_exptl_crystal_size_max          0.20
_exptl_crystal_size_mid          0.10
_exptl_crystal_size_min          0.10
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.592
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             608
_exptl_absorpt_coefficient_mu    0.297
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.6328
_exptl_absorpt_correction_T_max  0.7455
_exptl_absorpt_process_details   ?

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      293(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  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         0
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            13570
_diffrn_reflns_av_R_equivalents  0.0772
_diffrn_reflns_av_sigmaI/netI    0.0590
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_theta_min         1.75
_diffrn_reflns_theta_max         26.84
_reflns_number_total             2616
_reflns_number_gt                1846
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_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. All non-hydrogen atoms were
refined using the anisotropic model. Hydrogen atoms connected to carbon
and nitrogen atoms have been placed in positions calculated with respect
to the hybridization of the parent carbon and nitrogen atom.Hydrogen atoms
in the OH groups have been placed in positions generated by the SHELX
command AFIX 147. The hydrogensulfate ion was found to be disordered in
two positions with refined occupancies of 0.76 and 0.24. The disorder is
of rotational nature.
;

_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^)+(0.0480P)^2^+0.0418P] 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_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.08(11)
_refine_ls_number_reflns         2616
_refine_ls_number_parameters     210
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0712
_refine_ls_R_factor_gt           0.0430
_refine_ls_wR_factor_ref         0.1006
_refine_ls_wR_factor_gt          0.0897
_refine_ls_goodness_of_fit_ref   0.955
_refine_ls_restrained_S_all      0.955
_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
S1 S 0.63863(13) 0.91043(9) 0.23586(3) 0.0427(2) Uani 1 1 d . . .
O1 O -0.5662(4) 1.2613(3) 0.03256(11) 0.0695(8) Uani 1 1 d . . .
O2 O -0.0913(4) 0.8550(3) 0.05987(10) 0.0697(8) Uani 1 1 d . . .
N1 N -0.0373(5) 1.3534(4) 0.15842(12) 0.0568(8) Uani 1 1 d . . .
H1 H 0.0702 1.3417 0.1801 0.068 Uiso 1 1 calc R . .
N2 N -0.3067(5) 1.4643(3) 0.11682(11) 0.0463(7) Uani 1 1 d . . .
N3 N -0.3301(4) 1.0577(3) 0.04825(10) 0.0434(6) Uani 1 1 d . . .
N4 N -0.0423(4) 1.0862(3) 0.11096(11) 0.0466(7) Uani 1 1 d . . .
C1 C -0.2851(5) 1.3051(4) 0.09606(13) 0.0423(8) Uani 1 1 d . . .
C2 C -0.4098(5) 1.2156(4) 0.05622(13) 0.0444(8) Uani 1 1 d . . .
C3 C -0.4406(7) 0.9576(4) 0.00602(15) 0.0645(11) Uani 1 1 d . . .
H3A H -0.3741 0.8526 0.0030 0.097 Uiso 1 1 calc R . .
H3B H -0.4374 1.0113 -0.0306 0.097 Uiso 1 1 calc R . .
H3C H -0.5829 0.9433 0.0179 0.097 Uiso 1 1 calc R . .
C4 C -0.1510(6) 0.9908(4) 0.07251(13) 0.0458(8) Uani 1 1 d . . .
C5 C 0.1372(6) 1.0188(5) 0.14155(16) 0.0707(11) Uani 1 1 d . . .
H5A H 0.1642 0.9096 0.1282 0.106 Uiso 1 1 calc R . .
H5B H 0.1079 1.0162 0.1819 0.106 Uiso 1 1 calc R . .
H5C H 0.2573 1.0862 0.1347 0.106 Uiso 1 1 calc R . .
C6 C -0.1161(5) 1.2399(4) 0.12207(12) 0.0434(7) Uani 1 1 d . . .
C7 C -0.1573(7) 1.4872(4) 0.15444(15) 0.0591(10) Uani 1 1 d . . .
H7 H -0.1374 1.5828 0.1754 0.071 Uiso 1 1 calc R . .
C8 C -0.4674(7) 1.5796(4) 0.10122(16) 0.0688(11) Uani 1 1 d . . .
H8A H -0.5586 1.5307 0.0734 0.103 Uiso 1 1 calc R . .
H8B H -0.4044 1.6759 0.0852 0.103 Uiso 1 1 calc R . .
H8C H -0.5461 1.6090 0.1347 0.103 Uiso 1 1 calc R . .
O3 O 0.6013(5) 0.9305(4) 0.17630(11) 0.0597(9) Uani 0.76 1 d P A 1
O4 O 0.4371(12) 0.8509(10) 0.2648(3) 0.077(2) Uani 0.76 1 d P A 1
H4 H 0.4027 0.7625 0.2510 0.115 Uiso 0.76 1 calc PR A 1
O5 O 0.7929(8) 0.7865(6) 0.24753(16) 0.0628(14) Uani 0.76 1 d P A 1
O6 O 0.6864(6) 1.0591(4) 0.26635(18) 0.0631(9) Uani 0.76 1 d P A 1
O3A O 0.617(2) 1.0694(13) 0.2092(6) 0.091(4) Uani 0.24 1 d P A 2
O6A O 0.6858(19) 0.943(2) 0.2954(5) 0.096(4) Uani 0.24 1 d P A 2
O5A O 0.775(3) 0.801(2) 0.2108(9) 0.121(8) Uani 0.24 1 d P A 2
O4A O 0.412(3) 0.844(3) 0.2345(10) 0.080(7) Uani 0.24 1 d P A 2
H4A H 0.3951 0.7786 0.2606 0.121 Uiso 0.24 1 calc PR A 2

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
S1 0.0480(4) 0.0348(4) 0.0453(4) -0.0013(4) -0.0037(4) 0.0032(4)
O1 0.0821(19) 0.0553(15) 0.0711(17) -0.0026(13) -0.0366(15) 0.0066(14)
O2 0.080(2) 0.0536(15) 0.0751(18) -0.0195(13) -0.0034(15) 0.0140(13)
N1 0.0480(18) 0.0681(19) 0.0544(18) -0.0214(16) -0.0012(14) -0.0094(16)
N2 0.066(2) 0.0344(14) 0.0387(15) -0.0022(11) 0.0056(14) -0.0063(13)
N3 0.0574(17) 0.0370(15) 0.0358(14) -0.0029(11) -0.0034(13) -0.0102(13)
N4 0.0436(15) 0.0494(16) 0.0469(16) -0.0090(14) -0.0035(12) -0.0005(15)
C1 0.055(2) 0.0353(16) 0.0369(17) 0.0007(13) -0.0002(15) -0.0053(15)
C2 0.057(2) 0.0414(18) 0.0349(17) 0.0033(14) -0.0018(16) -0.0082(16)
C3 0.090(3) 0.048(2) 0.055(2) -0.0054(17) -0.015(2) -0.015(2)
C4 0.053(2) 0.0442(18) 0.0401(18) -0.0051(14) 0.0046(17) -0.0001(18)
C5 0.049(2) 0.087(3) 0.076(3) -0.009(2) -0.003(2) 0.015(2)
C6 0.0460(19) 0.0470(18) 0.0372(17) -0.0078(14) 0.0024(15) -0.0108(17)
C7 0.074(3) 0.047(2) 0.056(2) -0.0153(16) 0.009(2) -0.015(2)
C8 0.103(3) 0.0411(19) 0.063(2) 0.0034(19) 0.004(2) 0.009(2)
O3 0.072(2) 0.070(2) 0.0368(16) 0.0063(16) -0.0082(15) 0.004(2)
O4 0.090(5) 0.049(3) 0.091(4) -0.014(3) 0.052(4) -0.009(3)
O5 0.067(3) 0.053(2) 0.068(3) -0.009(2) -0.019(3) 0.0246(19)
O6 0.082(2) 0.0366(18) 0.071(2) -0.0100(17) -0.020(2) 0.0067(17)
O3A 0.093(9) 0.051(7) 0.130(11) 0.045(7) 0.037(9) 0.027(7)
O6A 0.065(8) 0.168(14) 0.053(7) -0.030(9) -0.020(6) 0.022(10)
O5A 0.113(15) 0.068(10) 0.18(2) -0.063(15) 0.101(16) -0.006(10)
O4A 0.031(6) 0.046(9) 0.16(2) 0.030(14) 0.011(12) 0.008(5)

_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
S1 O5A 1.378(15) . ?
S1 O3 1.418(3) . ?
S1 O6 1.440(3) . ?
S1 O5 1.441(5) . ?
S1 O6A 1.445(11) . ?
S1 O3A 1.446(10) . ?
S1 O4 1.535(8) . ?
S1 O4A 1.55(2) . ?
O1 C2 1.203(4) . ?
O2 C4 1.209(4) . ?
N1 C7 1.339(5) . ?
N1 C6 1.354(4) . ?
N1 H1 0.8600 . ?
N2 C7 1.312(4) . ?
N2 C1 1.394(4) . ?
N2 C8 1.442(4) . ?
N3 C4 1.391(4) . ?
N3 C2 1.399(4) . ?
N3 C3 1.462(4) . ?
N4 C6 1.366(4) . ?
N4 C4 1.377(4) . ?
N4 C5 1.461(4) . ?
C1 C6 1.351(4) . ?
C1 C2 1.426(4) . ?
C3 H3A 0.9600 . ?
C3 H3B 0.9600 . ?
C3 H3C 0.9600 . ?
C5 H5A 0.9600 . ?
C5 H5B 0.9600 . ?
C5 H5C 0.9600 . ?
C7 H7 0.9300 . ?
C8 H8A 0.9600 . ?
C8 H8B 0.9600 . ?
C8 H8C 0.9600 . ?
O4 H4 0.8200 . ?
O4A H4A 0.8200 . ?

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
O5A S1 O3 76.5(10) . . ?
O5A S1 O6 128.3(9) . . ?
O3 S1 O6 114.9(2) . . ?
O5A S1 O5 36.0(9) . . ?
O3 S1 O5 112.5(2) . . ?
O6 S1 O5 110.7(2) . . ?
O5A S1 O6A 113.2(11) . . ?
O3 S1 O6A 162.5(8) . . ?
O6 S1 O6A 47.6(7) . . ?
O5 S1 O6A 78.8(6) . . ?
O5A S1 O3A 117.4(10) . . ?
O3 S1 O3A 57.2(6) . . ?
O6 S1 O3A 58.4(6) . . ?
O5 S1 O3A 141.1(5) . . ?
O6A S1 O3A 105.5(10) . . ?
O5A S1 O4 121.0(8) . . ?
O3 S1 O4 108.9(3) . . ?
O6 S1 O4 103.2(3) . . ?
O5 S1 O4 105.7(4) . . ?
O6A S1 O4 79.2(6) . . ?
O3A S1 O4 113.0(6) . . ?
O5A S1 O4A 111.2(12) . . ?
O3 S1 O4A 82.0(9) . . ?
O6 S1 O4A 120.2(9) . . ?
O5 S1 O4A 113.8(8) . . ?
O6A S1 O4A 106.3(11) . . ?
O3A S1 O4A 102.2(9) . . ?
O4 S1 O4A 27.3(9) . . ?
C7 N1 C6 107.6(3) . . ?
C7 N1 H1 126.2 . . ?
C6 N1 H1 126.2 . . ?
C7 N2 C1 107.0(3) . . ?
C7 N2 C8 126.6(3) . . ?
C1 N2 C8 126.3(3) . . ?
C4 N3 C2 127.5(3) . . ?
C4 N3 C3 117.0(3) . . ?
C2 N3 C3 115.3(3) . . ?
C6 N4 C4 117.9(3) . . ?
C6 N4 C5 121.7(3) . . ?
C4 N4 C5 120.2(3) . . ?
C6 C1 N2 106.9(3) . . ?
C6 C1 C2 122.6(3) . . ?
N2 C1 C2 130.4(3) . . ?
O1 C2 N3 121.9(3) . . ?
O1 C2 C1 127.3(3) . . ?
N3 C2 C1 110.8(3) . . ?
N3 C3 H3A 109.5 . . ?
N3 C3 H3B 109.5 . . ?
H3A C3 H3B 109.5 . . ?
N3 C3 H3C 109.5 . . ?
H3A C3 H3C 109.5 . . ?
H3B C3 H3C 109.5 . . ?
O2 C4 N4 121.2(3) . . ?
O2 C4 N3 121.5(3) . . ?
N4 C4 N3 117.4(3) . . ?
N4 C5 H5A 109.5 . . ?
N4 C5 H5B 109.5 . . ?
H5A C5 H5B 109.5 . . ?
N4 C5 H5C 109.5 . . ?
H5A C5 H5C 109.5 . . ?
H5B C5 H5C 109.5 . . ?
C1 C6 N1 108.0(3) . . ?
C1 C6 N4 123.7(3) . . ?
N1 C6 N4 128.3(3) . . ?
N2 C7 N1 110.4(3) . . ?
N2 C7 H7 124.8 . . ?
N1 C7 H7 124.8 . . ?
N2 C8 H8A 109.5 . . ?
N2 C8 H8B 109.5 . . ?
H8A C8 H8B 109.5 . . ?
N2 C8 H8C 109.5 . . ?
H8A C8 H8C 109.5 . . ?
H8B C8 H8C 109.5 . . ?
S1 O4 H4 109.5 . . ?
S1 O4A H4A 109.5 . . ?

_diffrn_measured_fraction_theta_max 0.997
_diffrn_reflns_theta_full        26.84
_diffrn_measured_fraction_theta_full 0.997
_refine_diff_density_max         0.201
_refine_diff_density_min         -0.234
_refine_diff_density_rms         0.043

_vrf_PLAT_213_cm11_0m            
;
PROBLEM: Atom O5A has ADP max/min Ratio ..... 4.2 prola
RESPONSE: This atom is a part of a disordered hydrogensulfate unit.
We decided that using an anisotropic model is more justified than
isotropic refinement.
;


_database_code_depnum_ccdc_archive 'CCDC 922334'