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

#######################################################################
#
#                 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
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  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.
#
data_caf-BA
#TrackingRef 'CCDC_898406-12.cif'



_diffrn_source                   'sealed X-ray tube'
_diffrn_source_target            Cu
_diffrn_source_type              ?
_diffrn_radiation_type           'Cu K\a'
_diffrn_measurement_device_type  "Panalytical X'pert PRO"
_diffrn_detector                 ?
_diffrn_detector_type            "X'Celerator RTMS"

_exptl_special_details           ?
_pd_meas_scan_method             cont
_pd_meas_special_details         ?
_pd_spec_size_axial              14
_pd_spec_size_equat              10
_pd_spec_size_thick              0.5
_pd_spec_mounting                'packed powder pellet'
_pd_spec_mount_mode              reflection
_pd_spec_shape                   flat_sheet
_pd_char_colour                  white
_pd_prep_temperature             293

# The following six items are used for angular dispersive measurements only.


_diffrn_radiation_monochromator  none

# The following four items give details of the measured (not processed)
# powder pattern. Angles are in degrees.

_pd_meas_number_of_points        1726
_pd_meas_2theta_range_min        3
_pd_meas_2theta_range_max        60
_pd_meas_2theta_range_inc        0.033

#==============================================================================
_pd_proc_ls_profile_function     'Fundamental parameters'
_pd_proc_ls_background_function  'Chebyshev polynomial'
_pd_proc_ls_pref_orient_corr     'Spherical harmonics, 4th order'

_computing_data_collection       "X'Pert Data Collector (Panalytical)"
_computing_cell_refinement       'TOPAS (Bruker 2009)'
_computing_structure_solution    'TOPAS (Bruker 2009)'
_computing_structure_refinement  'TOPAS (Bruker 2009)'
_computing_molecular_graphics    ?
_computing_publication_material  ?


_chemical_formula_moiety         'C8 H10 N4 O2, C7 H6 O2'
_chemical_formula_sum            'C15 H16 N4 O4'
_chemical_formula_weight         316.32
_cell_formula_units_Z            4

_symmetry_cell_setting           monoclinic

_diffrn_ambient_temperature      293
_diffrn_radiation_wavelength     1.5418
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     ?
_refine_ls_hydrogen_treatment    refall
_exptl_crystal_density_diffrn    1.334
_exptl_crystal_description       'microcrystaline powder'
_exptl_crystal_colour            white
_refine_ls_shift/su_max          <0.01
_refine_ls_number_parameters     165
_pd_proc_ls_prof_R_factor        0.062
_pd_proc_ls_prof_wR_factor       0.081
_pd_proc_ls_prof_wR_expected     2.61
_refine_ls_R_Fsqd_factor         0.016
_refine_ls_goodness_of_fit_all   3.11
_cell_measurement_temperature    293
_refine_ls_structure_factor_coef Fsqd
_refine_special_details          
;
Both caffeine and benzoic acid (BA) were refined as rigid bodies with
six degrees of freedom (three translational and three rotational degrees of
freedom for each molecule). The carboxylic acid group of BA was allowed to
rotate around its C-C bond during structure solution and refinement. The
hydrogen atoms of the caffeine methyl groups were modelled to minimise
the occurence of unreasonably short contacts in the crystal structure.
The structure model was finally refined using restraints on bond lenghts
and angles, as well as planarity restraints.
;

_cell_length_a                   11.2358(13)
_cell_length_b                   9.1056(10)
_cell_length_c                   15.9131(18)
_cell_angle_alpha                90
_cell_angle_beta                 104.5787(42)
_cell_angle_gamma                90
_cell_volume                     1575.64(31)
_symmetry_space_group_name_H-M   P21/c
_symmetry_space_group_name_Hall  '-P 2ybc'
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'
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_symmetry_multiplicity
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_occupancy
_atom_site_B_iso_or_equiv
C1 C 4 -0.02886(29) 0.21531(40) 0.46825(23) 1 7.30(32)
C2 C 4 -0.12020(30) 0.14561(50) 0.50163(17) 1 7.30(32)
C3 C 4 -0.19998(30) 0.03061(48) 0.45348(22) 1 7.30(32)
N1 N 4 -0.17584(35) -0.00446(42) 0.37351(22) 1 7.30(32)
C4 C 4 -0.08310(37) 0.06494(47) 0.34195(17) 1 7.30(32)
N2 N 4 -0.00833(33) 0.17502(46) 0.39234(21) 1 7.30(32)
N3 N 4 0.03428(41) 0.31756(57) 0.52724(30) 1 7.30(32)
C5 C 4 -0.02173(30) 0.31299(48) 0.59289(19) 1 7.30(32)
N4 N 4 -0.11554(33) 0.21161(41) 0.58120(19) 1 7.30(32)
O1 O 4 -0.06747(65) 0.02984(90) 0.27098(54) 1 7.30(32)
O2 O 4 -0.28117(88) -0.03497(84) 0.47912(42) 1 7.30(32)
C6 C 4 0.08526(22) 0.24746(30) 0.36178(16) 1 7.30(32)
C7 C 4 -0.24931(23) -0.11571(28) 0.32191(16) 1 7.30(32)
C8 C 4 -0.19079(20) 0.17824(26) 0.63969(15) 1 7.30(32)
H1 H 4 0.0012(10) 0.3720(14) 0.64344(64) 1 7.30(32)
H2 H 4 0.0877(11) 0.2058(17) 0.30599(64) 1 7.30(32)
H3 H 4 0.0661(11) 0.3515(14) 0.35540(66) 1 7.30(32)
H4 H 4 0.16440(91) 0.2328(13) 0.40384(65) 1 7.30(32)
H5 H 4 -0.22240(91) -0.1290(13) 0.26882(68) 1 7.30(32)
H6 H 4 -0.2394(10) -0.2076(14) 0.35507(73) 1 7.30(32)
H7 H 4 -0.33507(95) -0.0845(14) 0.30789(76) 1 7.30(32)
H8 H 4 -0.2494(10) 0.1019(12) 0.61384(70) 1 7.30(32)
H9 H 4 -0.1376(10) 0.1433(15) 0.69494(75) 1 7.30(32)
H10 H 4 -0.2350(10) 0.2671(14) 0.64937(73) 1 7.30(32)
C11 C 4 0.40707(29) 0.73887(47) 0.70116(18) 1 7.30(32)
C12 C 4 0.50580(28) 0.83308(47) 0.71020(19) 1 7.30(32)
C13 C 4 0.57098(31) 0.83875(45) 0.64547(18) 1 7.30(32)
C14 C 4 0.53394(30) 0.75050(45) 0.56986(18) 1 7.30(32)
C15 C 4 0.43524(27) 0.65562(47) 0.56059(19) 1 7.30(32)
C16 C 4 0.36918(30) 0.65240(42) 0.62547(18) 1 7.30(32)
C17 C 4 0.26541(28) 0.55435(40) 0.61414(19) 1 7.30(32)
O11 O 4 0.19748(71) 0.53245(64) 0.66256(36) 1 7.30(32)
O12 O 4 0.23877(37) 0.47258(63) 0.53874(26) 1 7.30(32)
H16 H 4 0.3626(10) 0.7327(16) 0.74616(70) 1 7.30(32)
H11 H 4 0.5334(11) 0.8909(16) 0.76339(83) 1 7.30(32)
H12 H 4 0.64133(94) 0.9036(14) 0.65246(64) 1 7.30(32)
H13 H 4 0.5781(10) 0.7557(12) 0.52454(84) 1 7.30(32)
H14 H 4 0.4062(10) 0.5967(14) 0.50725(80) 1 7.30(32)
H15 H 4 0.16804(92) 0.4107(13) 0.53768(72) 1 7.30(32)

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance

O1 C4 1.228(8)
O2 C3 1.242(10)
O11 C17 1.230(8)
O12 C17 1.380(6)
O12 H15 0.972(12)
N1 C3 1.404(5)
N1 C4 1.414(6)
N1 C7 1.428(4)
N2 C4 1.419(6)
N2 C1 1.339(5)
N2 C6 1.427(4)
N3 C1 1.384(6)
N3 C5 1.350(6)
N4 C8 1.439(4)
N4 C5 1.378(5)
N4 C2 1.391(4)
C1 C2 1.418(5)
C2 C3 1.463(6)
C5 H1 0.947(11)
C6 H2 0.972(11)
C6 H3 0.971(13)
C6 H4 0.978(11)
C7 H7 0.976(12)
C7 H6 0.981(13)
C7 H5 0.974(11)
C8 H8 0.974(11)
C8 H9 0.983(13)
C8 H10 0.982(13)
C11 C16 1.412(5)
C11 C12 1.381(6)
C12 C13 1.407(4)
C13 C14 1.420(4)
C14 C15 1.384(5)
C15 C16 1.415(4)
C16 C17 1.443(5)
C11 H16 0.973(12)
C12 H11 0.979(14)
C13 H12 0.970(12)
C14 H13 0.975(12)
C15 H14 0.987(13)

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle

C17 O12 H15 108.9(8)
C3 N1 C4 123.3(3)
C4 N1 C7 118.9(3)
C3 N1 C7 117.8(3)
C1 N2 C4 119.4(3)
C1 N2 C6 119.4(3)
C4 N2 C6 121.2(3)
C1 N3 C5 104.1(4)
C2 N4 C5 105.4(3)
C5 N4 C8 127.5(3)
C2 N4 C8 127.2(3)
N2 C1 C2 121.4(3)
N3 C1 C2 110.1(3)
N2 C1 N3 128.4(4)
N4 C2 C3 131.6(3)
C1 C2 C3 122.0(3)
N4 C2 C1 106.4(3)
O2 C3 C2 125.2(4)
N1 C3 C2 113.9(3)
O2 C3 N1 120.9(4)
O1 C4 N1 119.9(5)
N1 C4 N2 120.0(3)
O1 C4 N2 120.1(5)
N3 C5 N4 114.0(4)
N4 C5 H1 122.0(8)
N3 C5 H1 124.0(8)
N2 C6 H3 108.9(8)
N2 C6 H4 109.0(7)
C16 C11 H16 119.7(8)
C11 C12 H11 119.7(8)
C13 C12 H11 120.2(8)
C12 C13 H12 119.8(7)
C14 C13 H12 120.0(6)
H2 C6 H3 110.0(11)
H2 C6 H4 110.0(10)
H3 C6 H4 110.2(10)
N2 C6 H2 108.8(9)
N1 C7 H5 109.0(7)
N1 C7 H7 108.7(8)
H5 C7 H6 110.1(10)
H5 C7 H7 110.0(10)
H6 C7 H7 110.1(10)
N1 C7 H6 108.9(7)
N4 C8 H8 108.8(7)
N4 C8 H9 108.8(7)
H8 C8 H9 110.0(10)
H8 C8 H10 109.9(10)
H9 C8 H10 110.1(10)
N4 C8 H10 109.3(7)
C12 C11 C16 119.8(3)
C11 C12 C13 120.0(3)
C12 C13 C14 120.2(3)
C13 C14 C15 120.0(3)
C14 C15 C16 119.2(3)
C11 C16 C17 120.8(3)
C15 C16 C17 118.5(3)
C11 C16 C15 120.7(3)
O11 C17 C16 129.1(4)
O12 C17 C16 115.7(3)
O11 C17 O12 115.2(4)
C12 C11 H16 120.5(8)
C13 C14 H13 120.3(8)
C15 C14 H13 119.7(7)
C14 C15 H14 120.9(8)
C16 C15 H14 119.7(8)


_vrf_ATOM006_caf-BA              
;
PROBLEM: _atom_site_U_iso_or_equiv is missing
RESPONSE: The atomic displacement parameters are reported as B(iso),
rather than U(iso).
;
_database_code_depnum_ccdc_archive 'CCDC 898406'
#######################################################################
#
#                 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
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  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.
#
data_caf-2FBA
#TrackingRef 'CCDC_898406-12.cif'


_diffrn_source                   'sealed X-ray tube'
_diffrn_source_target            Cu
_diffrn_source_type              ?
_diffrn_radiation_type           'Cu K\a'
_diffrn_measurement_device_type  "Panalytical X'pert PRO"
_diffrn_detector                 ?
_diffrn_detector_type            "X'Celerator RTMS"

_exptl_special_details           ?
_pd_meas_scan_method             cont
_pd_meas_special_details         ?
_pd_spec_size_axial              14
_pd_spec_size_equat              10
_pd_spec_size_thick              0.5
_pd_spec_mounting                'packed powder pellet'
_pd_spec_mount_mode              reflection
_pd_spec_shape                   flat_sheet
_pd_char_colour                  white
_pd_prep_temperature             293

# The following six items are used for angular dispersive measurements only.


_diffrn_radiation_monochromator  none

# The following four items give details of the measured (not processed)
# powder pattern. Angles are in degrees.

_pd_meas_number_of_points        1726
_pd_meas_2theta_range_min        3
_pd_meas_2theta_range_max        60
_pd_meas_2theta_range_inc        0.033

#==============================================================================
_pd_proc_ls_profile_function     'Fundamental parameters'
_pd_proc_ls_background_function  'Chebyshev polynomial'
_pd_proc_ls_pref_orient_corr     'Spherical harmonics, 4th order'

_computing_data_collection       "X'Pert Data Collector (Panalytical)"
_computing_cell_refinement       'TOPAS (Bruker 2009)'
_computing_structure_solution    'TOPAS (Bruker 2009)'
_computing_structure_refinement  'TOPAS (Bruker 2009)'
_computing_molecular_graphics    ?
_computing_publication_material  ?



_chemical_formula_moiety         'C8 H10 N4 O2, C7 H5 F1 O2'
_chemical_formula_sum            'C15 H15 F1 N4 O4'
_chemical_formula_weight         334.31
_cell_formula_units_Z            4

_symmetry_cell_setting           monoclinic

_diffrn_radiation_wavelength     1.5418
_diffrn_ambient_temperature      293
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     ?
_refine_ls_hydrogen_treatment    refall
_exptl_crystal_density_diffrn    1.408
_exptl_crystal_description       'microcrystaline powder'
_exptl_crystal_colour            white
_refine_ls_shift/su_max          <0.001
_refine_ls_number_parameters     173
_pd_proc_ls_prof_R_factor        0.042
_pd_proc_ls_prof_wR_factor       0.056
_pd_proc_ls_prof_wR_expected     1.11
_refine_ls_R_Fsqd_factor         0.017
_refine_ls_goodness_of_fit_all   5.01
_cell_measurement_temperature    293
_refine_ls_structure_factor_coef Fsqd
_refine_special_details          
;
Both caffeine and 2-fluorobenzoic acid (2FBA) were refined as rigid bodies with
six degrees of freedom (three translational and three rotational degrees of
freedom for each molecule). The carboxylic acid group of 2FBA was allowed to
rotate around its C-C bond during structure solution and refinement. The
hydrogen atoms of the caffeine methyl groups were modelled to minimise
the occurence of unreasonably short contacts in the crystal structure.
The structure model was finally refined using restraints on bond lenghts
and angles, as well as planarity restraints.
;

_cell_length_a                   11.30697(76)
_cell_length_b                   9.06586(42)
_cell_length_c                   15.94455(91)
_cell_angle_alpha                90
_cell_angle_beta                 105.2800(33)
_cell_angle_gamma                90
_cell_volume                     1576.66(16)
_symmetry_space_group_name_H-M   P21/c
_symmetry_space_group_name_Hall  '-P 2ybc'
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'
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_symmetry_multiplicity
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_occupancy
_atom_site_B_iso_or_equiv
C1 C 4 -0.02521(19) 0.21377(30) 0.47102(17) 1 7.79(27)
C2 C 4 -0.11965(22) 0.14847(37) 0.50056(14) 1 7.79(27)
C3 C 4 -0.20071(26) 0.03929(35) 0.44980(15) 1 7.79(27)
N1 N 4 -0.17704(24) 0.00693(32) 0.36979(15) 1 7.79(27)
C4 C 4 -0.07910(20) 0.07174(36) 0.34256(12) 1 7.79(27)
N2 N 4 -0.00245(22) 0.17318(30) 0.39607(15) 1 7.79(27)
N3 N 4 0.04132(28) 0.31083(43) 0.53384(22) 1 7.79(27)
C5 C 4 -0.01936(19) 0.31065(34) 0.59654(13) 1 7.79(27)
N4 N 4 -0.11210(23) 0.21034(33) 0.58304(13) 1 7.79(27)
O1 O 4 -0.06228(43) 0.04052(73) 0.27149(39) 1 7.79(27)
O2 O 4 -0.28467(56) -0.02217(63) 0.47210(29) 1 7.79(27)
C6 C 4 0.09605(16) 0.23988(22) 0.36989(11) 1 7.79(27)
C7 C 4 -0.25496(16) -0.10129(20) 0.31375(11) 1 7.79(27)
C8 C 4 -0.19176(16) 0.18570(21) 0.63745(10) 1 7.79(27)
H1 H 4 0.00675(74) 0.3636(10) 0.64949(51) 1 9.35(32)
H2 H 4 0.10022(73) 0.1969(12) 0.31458(51) 1 9.35(32)
H3 H 4 0.08116(76) 0.34537(99) 0.36326(51) 1 9.35(32)
H4 H 4 0.17303(65) 0.2212(11) 0.41462(51) 1 9.35(32)
H5 H 4 -0.22493(64) -0.11766(96) 0.26261(49) 1 9.35(32)
H6 H 4 -0.25251(73) -0.1933(10) 0.34585(56) 1 9.35(32)
H7 H 4 -0.33859(67) -0.0635(11) 0.29622(58) 1 9.35(32)
H8 H 4 -0.18196(70) 0.08450(99) 0.65844(56) 1 9.35(32)
H9 H 4 -0.17003(65) 0.2535(11) 0.68623(61) 1 9.35(32)
H10 H 4 -0.27686(74) 0.2033(11) 0.60351(55) 1 9.35(32)
C11 C 4 0.42554(18) 0.65392(33) 0.53962(13) 1 8.92(31)
C12 C 4 0.52128(20) 0.74587(31) 0.53843(12) 1 8.92(31)
C13 C 4 0.57671(24) 0.83375(34) 0.61221(11) 1 8.92(31)
C14 C 4 0.52962(19) 0.83611(34) 0.68413(14) 1 8.92(31)
C15 C 4 0.43293(25) 0.74349(39) 0.68660(14) 1 8.92(31)
C16 C 4 0.37582(23) 0.65511(35) 0.61076(12) 1 8.92(31)
C17 C 4 0.27408(21) 0.55871(33) 0.61117(14) 1 8.92(31)
O11 O 4 0.22052(50) 0.53720(52) 0.66784(39) 1 8.92(31)
O12 O 4 0.23235(33) 0.47906(55) 0.53756(18) 1 8.92(31)
F11 F 4 0.39170(53) 0.74272(60) 0.75886(38) 1 8.92(31)
H11 H 4 0.38362(71) 0.5995(12) 0.48712(61) 1 10.71(37)
H12 H 4 0.55040(79) 0.75119(99) 0.48654(55) 1 10.71(37)
H13 H 4 0.64505(66) 0.8965(11) 0.61103(53) 1 10.71(37)
H14 H 4 0.57027(77) 0.8918(12) 0.73643(57) 1 10.71(37)
H15 H 4 0.16481(65) 0.4184(11) 0.54367(58) 1 10.71(37)


loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance

F11 C15 1.352(7)
O1 C4 1.230(6)
O2 C3 1.232(7)
O11 C17 1.228(6)
O12 C17 1.352(4)
O12 H15 0.968(10)
N1 C7 1.457(3)
N1 C4 1.419(4)
N1 C3 1.402(3)
N2 C4 1.391(4)
N2 C6 1.424(3)
N2 C1 1.338(3)
N3 C1 1.394(4)
N3 C5 1.354(4)
N4 C8 1.423(3)
N4 C2 1.411(3)
N4 C5 1.362(4)
C1 C2 1.407(4)
C2 C3 1.443(4)
C5 H1 0.948(8)
C6 H2 0.976(8)
C6 H3 0.972(9)
C6 H4 0.983(8)
C7 H5 0.974(8)
C7 H7 0.975(9)
C7 H6 0.976(9)
C8 H9 0.970(10)
C8 H10 0.985(8)
C8 H8 0.973(9)
C11 C16 1.393(3)
C11 C12 1.371(3)
C12 C13 1.422(3)
C13 C14 1.386(3)
C14 C15 1.387(4)
C15 C16 1.453(4)
C16 C17 1.446(4)
C11 H11 0.980(10)
C12 H12 0.969(8)
C13 H13 0.964(9)
C14 H14 0.979(10)

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle

C17 O12 H15 108.7(6)
C3 N1 C7 118.0(2)
C4 N1 C7 119.1(2)
C3 N1 C4 122.9(2)
C1 N2 C6 119.6(2)
C4 N2 C6 120.7(2)
C1 N2 C4 119.6(2)
C1 N3 C5 104.3(3)
C2 N4 C8 127.8(2)
C5 N4 C8 126.4(2)
C2 N4 C5 105.5(2)
N2 C1 C2 121.6(2)
N3 C1 C2 109.8(2)
N2 C1 N3 128.3(2)
N4 C2 C1 106.3(2)
N4 C2 C3 132.0(2)
C1 C2 C3 121.8(2)
O2 C3 N1 121.0(3)
O2 C3 C2 124.9(3)
N1 C3 C2 114.1(3)
O1 C4 N2 119.7(3)
N1 C4 N2 119.8(2)
O1 C4 N1 120.6(3)
N3 C5 N4 113.7(2)
N3 C5 H1 123.9(6)
N4 C5 H1 121.7(5)
N2 C6 H3 108.9(6)
N2 C6 H4 109.0(5)
O11 C17 O12 115.3(4)
C12 C11 H11 120.0(6)
C16 C11 H11 119.5(6)
C11 C12 H12 119.3(6)
C13 C12 H12 120.3(6)
H2 C6 H3 110.1(8)
H2 C6 H4 110.0(7)
H3 C6 H4 110.0(8)
N2 C6 H2 108.8(6)
N1 C7 H6 108.9(6)
N1 C7 H7 108.9(6)
N1 C7 H5 109.2(5)
H5 C7 H7 109.8(7)
H6 C7 H7 110.0(8)
H5 C7 H6 110.0(8)
N4 C8 H8 108.9(5)
N4 C8 H10 108.9(5)
H8 C8 H9 109.9(8)
N4 C8 H9 108.8(5)
H9 C8 H10 110.0(8)
H8 C8 H10 110.3(8)
C12 C11 C16 119.8(2)
C11 C12 C13 120.5(2)
C12 C13 C14 120.8(2)
C13 C14 C15 119.5(2)
F11 C15 C14 118.6(3)
F11 C15 C16 122.0(4)
C14 C15 C16 119.4(2)
C11 C16 C17 119.4(2)
C15 C16 C17 120.6(2)
C11 C16 C15 119.7(2)
O11 C17 C16 130.3(3)
O12 C17 C16 114.5(2)
C12 C13 H13 119.6(5)
C14 C13 H13 119.5(5)
C13 C14 H14 121.0(6)
C15 C14 H14 119.0(6)

_vrf_ATOM006_caf-2FBA            
;
PROBLEM: _atom_site_U_iso_or_equiv is missing
RESPONSE: The atomic displacement parameters are reported as B(iso),
rather than U(iso).
;
_database_code_depnum_ccdc_archive 'CCDC 898407'
#######################################################################
#
#                 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
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  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.
#
data_caf-3FBA
#TrackingRef 'CCDC_898406-12.cif'


_diffrn_source                   'sealed X-ray tube'
_diffrn_source_target            Cu
_diffrn_source_type              ?
_diffrn_radiation_type           'Cu K\a'
_diffrn_measurement_device_type  "Panalytical X'pert PRO"
_diffrn_detector                 ?
_diffrn_detector_type            "X'Celerator RTMS"

_exptl_special_details           ?
_pd_meas_scan_method             cont
_pd_meas_special_details         ?
_pd_spec_size_axial              14
_pd_spec_size_equat              10
_pd_spec_size_thick              0.5
_pd_spec_mounting                'packed powder pellet'
_pd_spec_mount_mode              reflection
_pd_spec_shape                   flat_sheet
_pd_char_colour                  white
_pd_prep_temperature             293

# The following six items are used for angular dispersive measurements only.


_diffrn_radiation_monochromator  none

# The following four items give details of the measured (not processed)
# powder pattern. Angles are in degrees.

_pd_meas_number_of_points        1726
_pd_meas_2theta_range_min        3
_pd_meas_2theta_range_max        60
_pd_meas_2theta_range_inc        0.033

#==============================================================================
_pd_proc_ls_profile_function     'Fundamental parameters'
_pd_proc_ls_background_function  'Chebyshev polynomial'
_pd_proc_ls_pref_orient_corr     'Spherical harmonics, 4th order'

_computing_data_collection       "X'Pert Data Collector (Panalytical)"
_computing_cell_refinement       'TOPAS (Bruker 2009)'
_computing_structure_solution    'TOPAS (Bruker 2009)'
_computing_structure_refinement  'TOPAS (Bruker 2009)'
_computing_molecular_graphics    ?
_computing_publication_material  ?


_chemical_formula_moiety         'C8 H10 N4 O2, C7 H5 F1 O2'
_chemical_formula_sum            'C15 H15 F1 N4 O4'
_chemical_formula_weight         334.31
_cell_formula_units_Z            2



_symmetry_cell_setting           triclinic

_diffrn_ambient_temperature      293
_diffrn_radiation_wavelength     1.5418
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     ?
_refine_ls_hydrogen_treatment    refall
_exptl_crystal_density_diffrn    1.442
_exptl_crystal_description       'microcrystaline powder'
_exptl_crystal_colour            white
_refine_ls_shift/su_max          <0.01
_refine_ls_number_parameters     167
_pd_proc_ls_prof_R_factor        0.059
_pd_proc_ls_prof_wR_factor       0.078
_pd_proc_ls_prof_wR_expected     1.03
_refine_ls_R_Fsqd_factor         0.021
_refine_ls_goodness_of_fit_all   7.53
_cell_measurement_temperature    293
_refine_ls_structure_factor_coef Fsqd
_refine_special_details          
;
Both caffeine and 3-fluorobenzoic acid (3FBA) were refined as rigid bodies with
six degrees of freedom (three translational and three rotational degrees of
freedom for each molecule). The carboxylic acid group of 3FBA was allowed to
rotate around its C-C bond during structure solution and refinement. The
hydrogen atoms of the caffeine methyl groups were modelled to minimise the
occurence of unreasonably short contacts in the crystal structure. The
structure model was finally refined using restraints on bond lenghts and
angles, as well as planarity restraints.
;


_cell_length_a                   8.78113(87)
_cell_length_b                   10.06607(56)
_cell_length_c                   10.5609(14)
_cell_angle_alpha                105.8710(58)
_cell_angle_beta                 72.7172(63)
_cell_angle_gamma                71.1516(63)
_cell_volume                     769.83(16)
_symmetry_space_group_name_H-M   P-1
_symmetry_space_group_name_Hall  '-P 1'
loop_
_symmetry_equiv_pos_as_xyz
'-x, -y, -z'
'x, y, z'
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_symmetry_multiplicity
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_occupancy
_atom_site_B_iso_or_equiv
C1 C 2 0.27285(30) -0.23651(67) 0.06279(31) 1 5.51(25)
C2 C 2 0.40003(37) -0.33127(62) -0.08613(24) 1 5.51(25)
C3 C 2 0.58843(37) -0.40793(77) -0.12638(29) 1 5.51(25)
N1 N 2 0.63475(35) -0.37914(54) -0.00856(26) 1 5.51(25)
C4 C 2 0.50568(31) -0.28625(89) 0.13972(28) 1 5.51(25)
N2 N 2 0.32603(36) -0.21703(56) 0.17210(28) 1 5.51(25)
N3 N 2 0.10229(47) -0.1760(15) 0.07016(49) 1 5.51(25)
C5 C 2 0.12683(37) -0.23449(70) -0.07188(28) 1 5.51(25)
N4 N 2 0.30256(33) -0.32899(53) -0.17054(29) 1 5.51(25)
O1 O 2 0.55302(84) -0.2704(14) 0.23958(80) 1 5.51(25)
O2 O 2 0.70250(64) -0.4898(13) -0.25088(68) 1 5.51(25)
C6 C 2 0.19430(25) -0.12421(24) 0.32233(21) 1 5.51(25)
C7 C 2 0.82127(26) -0.44784(25) -0.03946(23) 1 5.51(25)
C8 C 2 0.37125(26) -0.41185(24) -0.32928(21) 1 5.51(25)
H1 H 2 0.0335(16) -0.2164(20) -0.1019(13) 1 5.51(25)
H2 H 2 0.2551(14) -0.1176(10) 0.3852(12) 1 5.51(25)
H3 H 2 0.1155(13) -0.1724(10) 0.3494(13) 1 5.51(25)
H4 H 2 0.1250(14) -0.0213(11) 0.3307(12) 1 5.51(25)
H5 H 2 0.8345(12) -0.4197(11) 0.0512(15) 1 5.51(25)
H6 H 2 0.8837(12) -0.40995(94) -0.1034(10) 1 5.51(25)
H7 H 2 0.8688(11) -0.5593(11) -0.0873(11) 1 5.51(25)
H8 H 2 0.3182(13) -0.4838(11) -0.3490(12) 1 5.51(25)
H9 H 2 0.5012(16) -0.4696(12) -0.3707(11) 1 5.51(25)
H10 H 2 0.3383(12) -0.33640(95) -0.3718(12) 1 5.51(25)
C11 C 2 -0.58941(31) 0.17525(61) 0.45061(26) 1 5.51(25)
C12 C 2 -0.76458(30) 0.27074(63) 0.54873(23) 1 5.51(25)
C13 C 2 -0.89549(35) 0.30928(65) 0.49977(26) 1 5.51(25)
C14 C 2 -0.85012(32) 0.25101(75) 0.34722(25) 1 5.51(25)
C15 C 2 -0.67340(34) 0.15547(61) 0.24815(23) 1 5.51(25)
C16 C 2 -0.53987(36) 0.11595(54) 0.29907(24) 1 5.51(25)
C17 C 2 -0.35604(34) 0.01973(35) 0.20342(24) 1 5.51(25)
O11 O 2 -0.28680(58) -0.04396(80) 0.06992(76) 1 5.51(25)
O12 O 2 -0.24559(62) -0.00355(70) 0.27100(35) 1 5.51(25)
F11 F 2 -0.97505(90) 0.2913(12) 0.29557(59) 1 5.51(25)
H11 H 2 -0.4982(17) 0.1486(15) 0.4850(12) 1 5.51(25)
H12 H 2 -0.7961(14) 0.3100(15) 0.6521(13) 1 5.51(25)
H13 H 2 -1.0203(15) 0.3768(15) 0.5702(11) 1 5.51(25)
H14 H 2 -0.6424(13) 0.1157(15) 0.1440(11) 1 5.51(25)
H15 H 2 -0.1227(15) -0.0710(12) 0.1971(13) 1 5.51(25)

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance

F11 C14 1.362(10)
O1 C4 1.234(9)
O2 C3 1.226(8)
O11 C17 1.230(8)
O12 C17 1.364(6)
O12 H15 0.985(14)
N1 C7 1.447(5)
N1 C4 1.439(4)
N1 C3 1.406(5)
N2 C4 1.390(7)
N2 C6 1.459(4)
N2 C1 1.358(5)
N3 C1 1.391(9)
N3 C5 1.374(6)
N4 C8 1.477(3)
N4 C2 1.406(5)
N4 C5 1.388(5)
C1 C2 1.441(4)
C2 C3 1.446(7)
C5 H1 0.946(17)
C6 H2 0.970(13)
C6 H3 0.986(12)
C6 H4 0.981(12)
C7 H5 0.975(14)
C7 H7 0.975(11)
C7 H6 0.978(10)
C8 H9 0.983(14)
C8 H10 0.992(11)
C8 H8 0.989(12)
C11 C16 1.415(3)
C11 C12 1.384(5)
C12 C13 1.383(6)
C13 C14 1.432(4)
C14 C15 1.396(5)
C15 C16 1.418(5)
C16 C17 1.432(4)
C11 H11 0.966(16)
C12 H12 0.969(12)
C13 H13 0.987(13)
C15 H14 0.978(10)

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle

C17 O12 H15 109.1(8)
C3 N1 C7 117.8(3)
C4 N1 C7 119.2(3)
C3 N1 C4 123.0(4)
C1 N2 C6 119.9(4)
C4 N2 C6 120.6(3)
C1 N2 C4 119.6(3)
C1 N3 C5 104.1(5)
C2 N4 C8 127.6(3)
C5 N4 C8 127.2(3)
C2 N4 C5 105.1(3)
N2 C1 C2 120.9(4)
N3 C1 C2 110.0(3)
N2 C1 N3 129.1(3)
N4 C2 C1 106.6(3)
N4 C2 C3 131.3(2)
C1 C2 C3 122.1(3)
O2 C3 N1 120.9(5)
O2 C3 C2 125.0(5)
N1 C3 C2 114.1(3)
O1 C4 N2 119.3(5)
N1 C4 N2 120.3(3)
O1 C4 N1 120.4(6)
N3 C5 N4 114.2(5)
N3 C5 H1 124.1(9)
N4 C5 H1 121.6(8)
N2 C6 H3 109.8(7)
N2 C6 H4 108.4(7)
O11 C17 O12 116.8(4)
C12 C11 H11 120.1(7)
C16 C11 H11 118.7(8)
C11 C12 H12 120.0(9)
C13 C12 H12 119.7(9)
H2 C6 H3 109.5(10)
H2 C6 H4 110.1(10)
H3 C6 H4 110.1(10)
N2 C6 H2 109.0(7)
N1 C7 H6 108.9(7)
N1 C7 H7 108.8(7)
N1 C7 H5 109.3(8)
H5 C7 H7 109.8(10)
H6 C7 H7 110.0(8)
H5 C7 H6 110.0(10)
N4 C8 H8 108.9(7)
N4 C8 H10 109.1(7)
H8 C8 H9 109.8(10)
N4 C8 H9 109.0(7)
H9 C8 H10 110.2(10)
H8 C8 H10 109.9(10)
C12 C11 C16 121.2(3)
C11 C12 C13 120.3(2)
C12 C13 C14 120.0(3)
F11 C14 C15 118.8(4)
C13 C14 C15 119.8(4)
F11 C14 C13 121.4(4)
C14 C15 C16 119.9(2)
C11 C16 C17 118.4(3)
C15 C16 C17 122.8(2)
C11 C16 C15 118.9(3)
O11 C17 C16 128.4(4)
O12 C17 C16 114.9(2)
C12 C13 H13 119.9(8)
C14 C13 H13 120.0(8)
C14 C15 H14 119.8(9)
C16 C15 H14 120.3(8)

_vrf_ATOM006_caf-3FBA            
;
PROBLEM: _atom_site_U_iso_or_equiv is missing
RESPONSE: The atomic displacement parameters are reported as B(iso),
rather than U(iso).
;
_database_code_depnum_ccdc_archive 'CCDC 898408'
#######################################################################
#
#                 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
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  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.
#
data_caf-23diFBA
#TrackingRef 'CCDC_898406-12.cif'


_diffrn_source                   'sealed X-ray tube'
_diffrn_source_target            Cu
_diffrn_source_type              ?
_diffrn_radiation_type           'Cu K\a'
_diffrn_measurement_device_type  "Panalytical X'pert PRO"
_diffrn_detector                 ?
_diffrn_detector_type            "X'Celerator RTMS"

_exptl_special_details           ?
_pd_meas_scan_method             cont
_pd_meas_special_details         ?
_pd_spec_size_axial              14
_pd_spec_size_equat              10
_pd_spec_size_thick              0.5
_pd_spec_mounting                'packed powder pellet'
_pd_spec_mount_mode              reflection
_pd_spec_shape                   flat_sheet
_pd_char_colour                  white
_pd_prep_temperature             293

# The following six items are used for angular dispersive measurements only.


_diffrn_radiation_monochromator  none

# The following four items give details of the measured (not processed)
# powder pattern. Angles are in degrees.

_pd_meas_number_of_points        1726
_pd_meas_2theta_range_min        3
_pd_meas_2theta_range_max        60
_pd_meas_2theta_range_inc        0.033

#==============================================================================
_pd_proc_ls_profile_function     'Fundamental parameters'
_pd_proc_ls_background_function  'Chebyshev polynomial'
_pd_proc_ls_pref_orient_corr     'Spherical harmonics, 4th order'

_computing_data_collection       "X'Pert Data Collector (Panalytical)"
_computing_cell_refinement       'TOPAS (Bruker 2009)'
_computing_structure_solution    'TOPAS (Bruker 2009)'
_computing_structure_refinement  'TOPAS (Bruker 2009)'
_computing_molecular_graphics    ?
_computing_publication_material  ?



_chemical_formula_moiety         'C8 H10 N4 O2, C7 H4 F2 O2'
_chemical_formula_sum            'C15 H14 F2 N4 O4'
_chemical_formula_weight         352.30
_cell_formula_units_Z            4

_symmetry_cell_setting           monoclinic

_diffrn_ambient_temperature      293
_diffrn_radiation_wavelength     1.5418
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     ?
_refine_ls_hydrogen_treatment    refall
_exptl_crystal_density_diffrn    1.456
_exptl_crystal_description       'microcrystaline powder'
_exptl_crystal_colour            white
_refine_ls_shift/su_max          <0.01
_refine_ls_number_parameters     157
_pd_proc_ls_prof_R_factor        0.052
_pd_proc_ls_prof_wR_factor       0.072
_pd_proc_ls_prof_wR_expected     1.08
_refine_ls_R_Fsqd_factor         0.022
_refine_ls_goodness_of_fit_all   6.67
_cell_measurement_temperature    293
_refine_ls_structure_factor_coef Fsqd
_refine_special_details          
;
Both caffeine and 2,3-difluorobenzoic acid (23diFBA) were refined as rigid
bodies with six degrees of freedom (three translational and three rotational
degrees of freedom for each molecule). The carboxylic acid group of 23diFBA
was allowed to rotate around its C-C bond during structure solution and
refinement. The hydrogen atoms of the caffeine methyl groups were modelled
to minimise the occurence of unreasonably short contacts in the crystal
structure. The structure model was finally refined using restraints on bond
lenghts and angles, as well as planarity restraints.
;


_cell_length_a                   11.39598(91)
_cell_length_b                   9.15968(51)
_cell_length_c                   15.8701(12)
_cell_angle_alpha                90
_cell_angle_beta                 104.0247(43)
_cell_angle_gamma                90
_cell_volume                     1607.19(20)
_symmetry_space_group_name_H-M   P21/c
_symmetry_space_group_name_Hall  '-P 2ybc'
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'
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_symmetry_multiplicity
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_occupancy
_atom_site_B_iso_or_equiv
C1 C 4 -0.03104(29) 0.20938(37) -0.03239(21) 1 4.34(26)
C2 C 4 -0.12154(27) 0.13907(46) 0.00102(15) 1 4.34(26)
C3 C 4 -0.20219(27) 0.02690(42) -0.04883(16) 1 4.34(26)
N1 N 4 -0.17817(26) -0.00549(40) -0.12850(20) 1 4.34(26)
C4 C 4 -0.08600(28) 0.06276(48) -0.16051(20) 1 4.34(26)
N2 N 4 -0.01146(25) 0.17127(43) -0.10987(16) 1 4.34(26)
N3 N 4 0.03283(37) 0.30803(55) 0.02828(28) 1 4.34(26)
C5 C 4 -0.02565(28) 0.30679(44) 0.09328(18) 1 4.34(26)
N4 N 4 -0.11783(30) 0.20325(37) 0.08155(18) 1 4.34(26)
O1 O 4 -0.06763(49) 0.02491(73) -0.23222(52) 1 4.34(26)
O2 O 4 -0.28286(80) -0.04171(82) -0.02278(30) 1 4.34(26)
C6 C 4 0.08241(19) 0.24125(28) -0.14147(14) 1 4.34(26)
C7 C 4 -0.25183(18) -0.11406(26) -0.18005(15) 1 4.34(26)
C8 C 4 -0.19555(18) 0.16927(24) 0.14019(14) 1 4.34(26)
H1 H 4 0.0012(10) 0.3599(12) 0.14694(78) 1 4.34(26)
H2 H 4 0.08722(93) 0.1956(14) -0.19639(70) 1 4.34(26)
H3 H 4 0.15929(85) 0.2297(12) -0.09838(74) 1 4.34(26)
H4 H 4 0.0630(10) 0.3441(12) -0.15052(78) 1 4.34(26)
H5 H 4 -0.22280(92) -0.1318(11) -0.23276(71) 1 4.34(26)
H6 H 4 -0.33558(89) -0.0787(12) -0.19577(82) 1 4.34(26)
H7 H 4 -0.24665(98) -0.2048(12) -0.14569(77) 1 4.34(26)
H8 H 4 -0.14410(93) 0.1384(12) 0.19737(77) 1 4.34(26)
H9 H 4 -0.25111(89) 0.0895(11) 0.11459(75) 1 4.34(26)
H10 H 4 -0.24231(97) 0.2562(12) 0.14765(74) 1 4.34(26)
C11 C 4 0.42068(25) 0.64951(43) 0.03770(18) 1 4.34(26)
C12 C 4 0.51637(28) 0.74066(41) 0.03915(15) 1 4.34(26)
C13 C 4 0.56145(30) 0.82718(45) 0.10999(17) 1 4.34(26)
C14 C 4 0.50667(33) 0.82685(46) 0.18191(17) 1 4.34(26)
C15 C 4 0.40997(31) 0.73939(50) 0.18123(18) 1 4.34(26)
C16 C 4 0.36209(30) 0.64902(41) 0.10754(17) 1 4.34(26)
C17 C 4 0.25789(28) 0.55159(41) 0.10196(19) 1 4.34(26)
O11 O 4 0.18985(66) 0.54313(63) 0.15116(49) 1 4.34(26)
O12 O 4 0.23448(33) 0.45708(69) 0.03223(22) 1 4.34(26)
F11 F 4 0.36461(68) 0.73995(85) 0.25209(49) 1 4.34(26)
F12 F 4 0.54766(56) 0.9130(10) 0.25059(44) 1 4.34(26)
H12 H 4 0.38536(89) 0.5902(13) -0.01524(82) 1 4.34(26)
H13 H 4 0.55474(96) 0.7417(11) -0.00902(70) 1 4.34(26)
H14 H 4 0.62980(86) 0.8897(12) 0.11074(80) 1 4.34(26)
H15 H 4 0.16474(82) 0.3967(12) 0.03429(82) 1 4.34(26)


loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance

F11 C15 1.347(8)
F12 C14 1.335(8)
O1 C4 1.255(8)
O2 C3 1.263(9)
O11 C17 1.229(9)
O12 C17 1.380(6)
O12 H15 0.976(11)
N1 C3 1.389(4)
N1 C4 1.418(5)
N1 C7 1.425(4)
N2 C6 1.438(4)
N2 C1 1.347(4)
N2 C4 1.423(5)
N3 C5 1.357(6)
N3 C1 1.390(6)
N4 C2 1.398(4)
N4 C5 1.393(5)
N4 C8 1.466(4)
C1 C2 1.423(5)
C2 C3 1.475(5)
C5 H1 0.963(12)
C6 H3 0.978(11)
C6 H2 0.980(11)
C6 H4 0.970(11)
C7 H5 0.985(11)
C7 H6 0.982(11)
C7 H7 0.988(12)
C8 H9 0.988(11)
C8 H10 0.981(11)
C8 H8 0.995(12)
C11 C16 1.426(4)
C11 C12 1.370(5)
C12 C13 1.370(4)
C13 C14 1.428(4)
C14 C15 1.361(6)
C15 C16 1.429(5)
C16 C17 1.471(5)
C11 H12 0.999(12)
C12 H13 0.968(12)
C13 H14 0.964(11)

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle


C17 O12 H15 109.2(8)
C3 N1 C4 123.9(3)
C3 N1 C7 117.0(3)
C4 N1 C7 119.1(3)
C1 N2 C4 119.3(3)
C1 N2 C6 120.3(3)
C4 N2 C6 120.5(2)
C1 N3 C5 104.5(4)
C2 N4 C5 105.3(3)
C2 N4 C8 127.0(3)
C5 N4 C8 127.7(3)
N2 C1 N3 128.8(4)
N2 C1 C2 121.2(3)
N3 C1 C2 109.9(3)
N4 C2 C3 131.3(3)
C1 C2 C3 122.0(3)
N4 C2 C1 106.6(3)
O2 C3 N1 120.7(4)
N1 C3 C2 113.7(3)
O2 C3 C2 125.5(3)
O1 C4 N1 120.2(4)
N1 C4 N2 119.9(3)
O1 C4 N2 119.8(4)
N3 C5 N4 113.4(3)
N3 C5 H1 123.9(8)
N4 C5 H1 122.0(8)
N2 C6 H2 109.0(7)
N2 C6 H3 108.9(7)
O11 C17 C16 128.6(4)
O12 C17 C16 115.2(3)
O11 C17 O12 116.2(4)
C12 C11 H12 120.2(7)
C16 C11 H12 118.8(7)
H2 C6 H3 110.0(9)
H2 C6 H4 110.1(11)
H3 C6 H4 110.0(10)
N2 C6 H4 108.8(7)
N1 C7 H5 109.3(6)
N1 C7 H6 108.5(7)
H5 C7 H6 110.1(10)
H5 C7 H7 110.1(9)
N1 C7 H7 108.8(7)
H6 C7 H7 110.0(10)
N4 C8 H9 108.8(7)
N4 C8 H10 109.5(7)
N4 C8 H8 109.1(7)
H8 C8 H10 109.7(9)
H9 C8 H10 109.7(9)
H8 C8 H9 110.0(9)
C12 C11 C16 120.7(3)
C11 C12 C13 120.4(3)
C12 C13 C14 120.4(3)
F12 C14 C13 121.2(4)
F12 C14 C15 118.5(4)
C13 C14 C15 120.3(3)
F11 C15 C14 117.7(4)
F11 C15 C16 122.5(5)
C14 C15 C16 119.7(3)
C11 C16 C17 118.6(3)
C15 C16 C17 122.9(3)
C11 C16 C15 118.5(3)
C11 C12 H13 120.2(7)
C13 C12 H13 119.4(7)
C12 C13 H14 119.6(8)
C14 C13 H14 120.0(8)

_vrf_ATOM006_caf-23diFBA         
;
PROBLEM: _atom_site_U_iso_or_equiv is missing
RESPONSE: The atomic displacement parameters are reported as B(iso),
rather than U(iso).
;
_database_code_depnum_ccdc_archive 'CCDC 898409'
#######################################################################
#
#                 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
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  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.
#
data_caf-25diFBA
#TrackingRef 'CCDC_898406-12.cif'


_diffrn_source                   'sealed X-ray tube'
_diffrn_source_target            Cu
_diffrn_source_type              ?
_diffrn_radiation_type           'Cu K\a'
_diffrn_measurement_device_type  "Panalytical X'pert PRO"
_diffrn_detector                 ?
_diffrn_detector_type            "X'Celerator RTMS"

_exptl_special_details           ?
_pd_meas_scan_method             cont
_pd_meas_special_details         ?
_pd_spec_size_axial              14
_pd_spec_size_equat              10
_pd_spec_size_thick              0.5
_pd_spec_mounting                'packed powder pellet'
_pd_spec_mount_mode              reflection
_pd_spec_shape                   flat_sheet
_pd_char_colour                  white
_pd_prep_temperature             293

# The following six items are used for angular dispersive measurements only.


_diffrn_radiation_monochromator  none

# The following four items give details of the measured (not processed)
# powder pattern. Angles are in degrees.

_pd_meas_number_of_points        1726
_pd_meas_2theta_range_min        3
_pd_meas_2theta_range_max        60
_pd_meas_2theta_range_inc        0.033

#==============================================================================
_pd_proc_ls_profile_function     'Fundamental parameters'
_pd_proc_ls_background_function  'Chebyshev polynomial'
_pd_proc_ls_pref_orient_corr     'Spherical harmonics, 4th order'

_computing_data_collection       "X'Pert Data Collector (Panalytical)"
_computing_cell_refinement       'TOPAS (Bruker 2009)'
_computing_structure_solution    'TOPAS (Bruker 2009)'
_computing_structure_refinement  'TOPAS (Bruker 2009)'
_computing_molecular_graphics    ?
_computing_publication_material  ?



_chemical_formula_moiety         'C8 H10 N4 O2, C7 H4 F2 O2'
_chemical_formula_sum            'C15 H14 F2 N4 O4'
_chemical_formula_weight         352.30
_cell_formula_units_Z            4

_symmetry_cell_setting           monoclinic

_diffrn_ambient_temperature      293
_diffrn_radiation_wavelength     1.5418
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     ?
_refine_ls_hydrogen_treatment    refall
_exptl_crystal_density_diffrn    1.453
_exptl_crystal_description       'microcrystaline powder'
_exptl_crystal_colour            white
_refine_ls_shift/su_max          <0.01
_refine_ls_number_parameters     156
_pd_proc_ls_prof_R_factor        0.047
_pd_proc_ls_prof_wR_factor       0.062
_pd_proc_ls_prof_wR_expected     1.17
_refine_ls_R_Fsqd_factor         0.021
_refine_ls_goodness_of_fit_all   5.28
_cell_measurement_temperature    293
_refine_ls_structure_factor_coef Fsqd
_refine_special_details          
;
Both caffeine and 2,5-difluorobenzoic acid (25diFBA) were refined as rigid
bodies with six degrees of freedom (three translational and three rotational
degrees of freedom for each molecule). The carboxylic acid group of 25diFBA
was allowed to rotate around its C-C bond during structure solution and
refinement.The hydrogen atoms of the caffeine methyl groups were modelled to
minimise the occurence of unreasonably short contacts in the crystal structure.
The structure model was finally refined using restraints on bond lenghts
and angles, as well as planarity restraints.
;

_cell_length_a                   11.36104(82)
_cell_length_b                   9.11522(46)
_cell_length_c                   15.8828(13)
_cell_angle_alpha                90
_cell_angle_beta                 101.7770(41)
_cell_angle_gamma                90
_cell_volume                     1610.18(19)
_symmetry_space_group_name_H-M   P21/c
_symmetry_space_group_name_Hall  '-P 2ybc'
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'
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_symmetry_multiplicity
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_occupancy
_atom_site_B_iso_or_equiv
C1 C 4 -0.02560(23) 0.20621(42) -0.03295(19) 1 8.73(30)
C2 C 4 -0.11688(25) 0.14318(43) 0.00305(14) 1 8.73(30)
C3 C 4 -0.19987(30) 0.03394(43) -0.04331(15) 1 8.73(30)
N1 N 4 -0.18097(23) 0.00111(37) -0.12393(14) 1 8.73(30)
C4 C 4 -0.08842(30) 0.06313(42) -0.15880(17) 1 8.73(30)
N2 N 4 -0.00851(26) 0.16606(35) -0.11024(18) 1 8.73(30)
N3 N 4 0.04356(33) 0.30137(51) 0.02618(25) 1 8.73(30)
C5 C 4 -0.01281(25) 0.30243(41) 0.09311(13) 1 8.73(30)
N4 N 4 -0.10764(26) 0.20732(36) 0.08438(16) 1 8.73(30)
O1 O 4 -0.07634(50) 0.02699(81) -0.23238(45) 1 8.73(30)
O2 O 4 -0.28215(66) -0.02470(87) -0.01620(35) 1 8.73(30)
C6 C 4 0.08716(18) 0.23597(25) -0.14600(13) 1 8.73(30)
C7 C 4 -0.26233(16) -0.09971(23) -0.17493(13) 1 8.73(30)
C8 C 4 -0.18570(16) 0.18526(23) 0.14448(12) 1 8.73(30)
H1 H 4 0.0157(10) 0.3538(12) 0.14497(57) 1 8.73(30)
H2 H 4 0.08855(89) 0.1933(15) -0.20162(60) 1 8.73(30)
H3 H 4 0.16510(80) 0.2197(13) -0.10623(58) 1 8.73(30)
H4 H 4 0.07106(83) 0.3401(12) -0.15242(59) 1 8.73(30)
H5 H 4 -0.23407(77) -0.1211(11) -0.22820(61) 1 8.73(30)
H6 H 4 -0.34303(81) -0.0545(14) -0.18869(63) 1 8.73(30)
H7 H 4 -0.26489(87) -0.1902(12) -0.14206(59) 1 8.73(30)
H8 H 4 -0.13767(79) 0.1532(13) 0.19900(60) 1 8.73(30)
H9 H 4 -0.24514(80) 0.1109(11) 0.12162(57) 1 8.73(30)
H10 H 4 -0.22606(84) 0.2772(12) 0.15204(60) 1 8.73(30)
C11 C 4 0.40059(24) 0.71192(38) 0.19793(13) 1 8.73(30)
C12 C 4 0.49617(27) 0.80844(45) 0.21019(15) 1 8.73(30)
C13 C 4 0.55600(28) 0.83820(45) 0.14421(13) 1 8.73(30)
C14 C 4 0.51758(25) 0.77367(38) 0.06372(14) 1 8.73(30)
C15 C 4 0.42374(28) 0.67813(44) 0.05033(15) 1 8.73(30)
C16 C 4 0.36090(27) 0.64891(42) 0.11936(15) 1 8.73(30)
C17 C 4 0.25597(27) 0.54873(38) 0.10795(15) 1 8.73(30)
O11 O 4 0.19588(60) 0.51648(60) 0.15940(42) 1 8.73(30)
O12 O 4 0.22268(32) 0.48181(61) 0.02809(17) 1 8.73(30)
F11 F 4 0.38852(52) 0.61900(81) -0.02911(39) 1 8.73(30)
F12 F 4 0.53402(49) 0.86767(97) 0.28625(42) 1 8.73(30)
H12 H 4 0.36133(82) 0.6885(13) 0.24533(61) 1 8.73(30)
H13 H 4 0.62316(78) 0.9053(12) 0.15455(58) 1 8.73(30)
H14 H 4 0.55664(89) 0.7957(11) 0.01639(66) 1 8.73(30)
H15 H 4 0.15352(72) 0.4196(14) 0.02822(68) 1 8.73(30)


loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance

F11 C15 1.355(7)
F12 C12 1.314(7)
O1 C4 1.249(7)
O2 C3 1.229(8)
O11 C17 1.203(7)
O12 C17 1.389(4)
O12 H15 0.970(11)
N1 C3 1.374(3)
N1 C4 1.404(4)
N1 C7 1.431(3)
N2 C6 1.470(4)
N2 C1 1.333(4)
N2 C4 1.419(4)
N3 C5 1.348(5)
N3 C1 1.397(5)
N4 C2 1.402(4)
N4 C5 1.367(5)
N4 C8 1.444(4)
C1 C2 1.405(4)
C2 C3 1.463(5)
C5 H1 0.946(10)
C6 H3 0.989(10)
C6 H2 0.968(10)
C6 H4 0.968(11)
C7 H5 0.984(10)
C7 H6 0.988(10)
C7 H7 0.980(11)
C8 H9 0.973(10)
C8 H10 0.974(11)
C8 H8 0.970(10)
C11 C16 1.364(4)
C11 C12 1.380(5)
C12 C13 1.387(4)
C13 C14 1.394(3)
C14 C15 1.360(5)
C15 C16 1.450(4)
C16 C17 1.483(5)
C11 H12 0.974(10)
C13 H13 0.966(11)
C14 H14 0.968(11)

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle


C17 O12 H15 109.0(7)
C3 N1 C4 123.5(3)
C3 N1 C7 117.5(2)
C4 N1 C7 119.0(2)
C1 N2 C4 119.0(3)
C1 N2 C6 119.7(3)
C4 N2 C6 121.2(2)
C1 N3 C5 104.0(3)
C2 N4 C5 105.5(3)
C2 N4 C8 127.6(3)
C5 N4 C8 126.8(2)
N2 C1 N3 128.5(3)
N2 C1 C2 121.4(3)
N3 C1 C2 109.9(3)
N4 C2 C3 131.9(3)
C1 C2 C3 121.8(2)
N4 C2 C1 106.4(3)
O2 C3 N1 120.5(4)
N1 C3 C2 114.2(3)
O2 C3 C2 125.3(4)
O1 C4 N1 119.9(4)
N1 C4 N2 120.0(3)
O1 C4 N2 120.2(4)
N3 C5 N4 114.0(3)
N3 C5 H1 123.8(8)
N4 C5 H1 121.7(7)
N2 C6 H2 109.2(7)
N2 C6 H3 108.9(6)
O11 C17 C16 128.4(4)
O12 C17 C16 116.4(3)
O11 C17 O12 115.3(4)
C12 C11 H12 120.2(7)
C16 C11 H12 119.8(7)
H2 C6 H3 110.1(9)
H2 C6 H4 109.7(10)
H3 C6 H4 109.9(9)
N2 C6 H4 109.1(6)
N1 C7 H5 109.1(6)
N1 C7 H6 108.7(7)
H5 C7 H6 110.1(8)
H5 C7 H7 110.0(8)
N1 C7 H7 109.0(6)
H6 C7 H7 110.0(9)
N4 C8 H9 108.8(6)
N4 C8 H10 109.3(6)
N4 C8 H8 108.8(6)
H8 C8 H10 110.1(9)
H9 C8 H10 109.7(8)
H8 C8 H9 110.1(9)
C12 C11 C16 120.1(2)
F12 C12 C13 119.7(4)
C11 C12 C13 120.7(2)
F12 C12 C11 119.5(4)
C12 C13 C14 120.0(3)
C13 C14 C15 120.2(3)
F11 C15 C14 118.3(4)
F11 C15 C16 122.3(4)
C14 C15 C16 119.4(2)
C11 C16 C17 118.6(2)
C15 C16 C17 121.9(2)
C11 C16 C15 119.5(3)
C12 C13 H13 119.1(6)
C14 C13 H13 120.8(6)
C13 C14 H14 121.2(7)
C15 C14 H14 118.7(7)

_vrf_ATOM006_caf-25diFBA         
;
PROBLEM: _atom_site_U_iso_or_equiv is missing
RESPONSE: The atomic displacement parameters are reported as B(iso),
rather than U(iso).
;
_database_code_depnum_ccdc_archive 'CCDC 898410'
#######################################################################
#
#                 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
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  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.
#
data_caf-26diFBA
#TrackingRef 'CCDC_898406-12.cif'


_diffrn_source                   'sealed X-ray tube'
_diffrn_source_target            Cu
_diffrn_source_type              ?
_diffrn_radiation_type           'Cu K\a'
_diffrn_measurement_device_type  "Panalytical X'pert PRO"
_diffrn_detector                 ?
_diffrn_detector_type            "X'Celerator RTMS"

_exptl_special_details           ?
_pd_meas_scan_method             cont
_pd_meas_special_details         ?
_pd_spec_size_axial              14
_pd_spec_size_equat              10
_pd_spec_size_thick              0.5
_pd_spec_mounting                'packed powder pellet'
_pd_spec_mount_mode              reflection
_pd_spec_shape                   flat_sheet
_pd_char_colour                  white
_pd_prep_temperature             293

# The following six items are used for angular dispersive measurements only.


_diffrn_radiation_monochromator  none

# The following four items give details of the measured (not processed)
# powder pattern. Angles are in degrees.

_pd_meas_number_of_points        1726
_pd_meas_2theta_range_min        3
_pd_meas_2theta_range_max        60
_pd_meas_2theta_range_inc        0.033

#==============================================================================
_pd_proc_ls_profile_function     'Fundamental parameters'
_pd_proc_ls_background_function  'Chebyshev polynomial'
_pd_proc_ls_pref_orient_corr     'Spherical harmonics, 4th order'

_computing_data_collection       "X'Pert Data Collector (Panalytical)"
_computing_cell_refinement       'TOPAS (Bruker 2009)'
_computing_structure_solution    'TOPAS (Bruker 2009)'
_computing_structure_refinement  'TOPAS (Bruker 2009)'
_computing_molecular_graphics    ?
_computing_publication_material  ?



_chemical_formula_moiety         'C8 H10 N4 O2, C7 H4 F2 O2'
_chemical_formula_sum            'C15 H14 F2 N4 O4'
_chemical_formula_weight         352.30
_cell_formula_units_Z            4

_symmetry_cell_setting           monoclinic

_diffrn_ambient_temperature      293
_diffrn_radiation_wavelength     1.5418
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     ?
_refine_ls_hydrogen_treatment    refall
_exptl_crystal_density_diffrn    1.464
_exptl_crystal_description       'microcrystaline powder'
_exptl_crystal_colour            white
_refine_ls_shift/su_max          <0.01
_refine_ls_number_parameters     156
_pd_proc_ls_prof_R_factor        0.045
_pd_proc_ls_prof_wR_factor       0.058
_pd_proc_ls_prof_wR_expected     1.13
_refine_ls_R_Fsqd_factor         0.019
_refine_ls_goodness_of_fit_all   5.12
_cell_measurement_temperature    293
_refine_ls_structure_factor_coef Fsqd
_refine_special_details          
;
Both caffeine and 2,6-difluorobenzoic acid (26diFBA) were refined as rigid
bodies with six degrees of freedom (three translational and three rotational
degrees of freedom for each molecule). The carboxylic acid group of 26diFBA
was allowed to rotate around its C-C bond during structure solution and
refinement. The hydrogen atoms of the caffeine methyl groups were modelled to
minimise the occurence of unreasonably short contacts in the crystal structure.
The structure model was finally refined using restraints on bond lenghts
and angles, as well as planarity restraints.
;

_cell_length_a                   11.33562(74)
_cell_length_b                   9.12362(42)
_cell_length_c                   15.9442(11)
_cell_angle_alpha                90
_cell_angle_beta                 104.2599(39)
_cell_angle_gamma                90
_cell_volume                     1598.17(17)
_symmetry_space_group_name_H-M   P21/c
_symmetry_space_group_name_Hall  '-P 2ybc'
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'
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_symmetry_multiplicity
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_occupancy
_atom_site_B_iso_or_equiv
C1 C 4 -0.02695(20) 0.21337(30) -0.02813(16) 1 6.92(20)
C2 C 4 -0.11950(21) 0.14477(32) 0.00265(15) 1 6.92(20)
C3 C 4 -0.20039(21) 0.03736(35) -0.04854(15) 1 6.92(20)
N1 N 4 -0.17735(20) 0.00998(32) -0.12910(12) 1 6.92(20)
C4 C 4 -0.08147(21) 0.07609(36) -0.15790(12) 1 6.92(20)
N2 N 4 -0.00628(23) 0.17842(35) -0.10526(12) 1 6.92(20)
N3 N 4 0.03930(29) 0.30679(45) 0.03498(22) 1 6.92(20)
C5 C 4 -0.02115(19) 0.30455(34) 0.09861(13) 1 6.92(20)
N4 N 4 -0.11369(23) 0.20504(34) 0.08501(13) 1 6.92(20)
O1 O 4 -0.06417(38) 0.04420(61) -0.23044(40) 1 6.92(20)
O2 O 4 -0.28329(55) -0.02657(66) -0.02584(30) 1 6.92(20)
C6 C 4 0.09147(16) 0.24742(22) -0.13352(11) 1 6.92(20)
C7 C 4 -0.25415(16) -0.09247(20) -0.18428(11) 1 6.92(20)
C8 C 4 -0.19061(16) 0.17245(20) 0.14246(10) 1 6.92(20)
H1 H 4 0.00585(72) 0.3544(11) 0.15251(56) 1 6.92(20)
H2 H 4 0.09921(66) 0.2009(12) -0.18681(54) 1 6.92(20)
H3 H 4 0.16718(57) 0.2358(11) -0.08858(54) 1 6.92(20)
H4 H 4 0.07281(72) 0.3509(10) -0.14383(54) 1 6.92(20)
H5 H 4 -0.22076(60) -0.11296(94) -0.23437(52) 1 6.92(20)
H6 H 4 -0.33567(62) -0.0500(10) -0.20365(70) 1 6.92(20)
H7 H 4 -0.25771(69) -0.18324(96) -0.15171(61) 1 6.92(20)
H8 H 4 -0.19211(63) 0.25683(99) 0.17993(63) 1 6.92(20)
H9 H 4 -0.15768(64) 0.0871(10) 0.17793(63) 1 6.92(20)
H10 H 4 -0.27314(68) 0.15124(98) 0.10733(58) 1 6.92(20)
C11 C 4 0.43091(25) 0.67089(35) 0.04042(13) 1 6.92(20)
C12 C 4 0.52432(22) 0.77258(33) 0.04305(13) 1 6.92(20)
C13 C 4 0.57101(25) 0.85104(36) 0.11783(13) 1 6.92(20)
C14 C 4 0.52410(21) 0.83454(32) 0.18998(11) 1 6.92(20)
C15 C 4 0.43211(24) 0.73330(39) 0.18869(14) 1 6.92(20)
C16 C 4 0.38191(25) 0.65116(34) 0.11320(12) 1 6.92(20)
C17 C 4 0.27940(21) 0.54963(32) 0.11141(14) 1 6.92(20)
O11 O 4 0.22388(48) 0.52586(52) 0.16684(40) 1 6.92(20)
O12 O 4 0.24145(28) 0.47086(54) 0.03784(18) 1 6.92(20)
F11 F 4 0.39161(52) 0.71534(58) 0.26050(39) 1 6.92(20)
F12 F 4 0.38831(43) 0.59061(72) -0.03328(29) 1 6.92(20)
H12 H 4 0.55610(74) 0.78538(96) -0.00748(58) 1 6.92(20)
H13 H 4 0.63599(67) 0.9202(11) 0.11958(57) 1 6.92(20)
H14 H 4 0.55892(72) 0.8877(12) 0.24339(61) 1 6.92(20)
H15 H 4 0.17455(60) 0.4086(11) 0.04343(58) 1 6.92(20)


loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance


F11 C15 1.345(6)
F12 C11 1.368(6)
O1 C4 1.253(6)
O2 C3 1.234(6)
O11 C17 1.223(6)
O12 C17 1.352(4)
O12 H15 0.969(9)
N1 C3 1.395(3)
N1 C4 1.415(3)
N1 C7 1.424(3)
N2 C6 1.440(3)
N2 C1 1.346(3)
N2 C4 1.396(4)
N3 C5 1.357(4)
N3 C1 1.390(4)
N4 C2 1.410(3)
N4 C5 1.364(4)
N4 C8 1.442(3)
C1 C2 1.409(3)
C2 C3 1.449(4)
C5 H1 0.953(10)
C6 H3 0.979(8)
C6 H2 0.973(9)
C6 H4 0.973(9)
C7 H5 0.983(8)
C7 H6 0.980(8)
C7 H7 0.983(9)
C8 H9 0.981(9)
C8 H10 0.984(9)
C8 H8 0.976(9)
C11 C16 1.416(4)
C11 C12 1.401(4)
C12 C13 1.379(3)
C13 C14 1.389(3)
C14 C15 1.389(4)
C15 C16 1.413(3)
C16 C17 1.481(4)
C12 H12 0.968(9)
C13 H13 0.965(10)
C14 H14 0.975(10)
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle

C17 O12 H15 108.7(6)
C3 N1 C4 123.7(2)
C3 N1 C7 117.5(2)
C4 N1 C7 118.7(2)
C1 N2 C4 119.3(2)
C1 N2 C6 120.2(2)
C4 N2 C6 120.5(2)
C1 N3 C5 104.5(3)
C2 N4 C5 105.4(2)
C2 N4 C8 127.9(2)
C5 N4 C8 126.7(2)
N2 C1 N3 128.5(3)
N2 C1 C2 121.7(2)
N3 C1 C2 109.6(2)
N4 C2 C3 131.8(2)
C1 C2 C3 121.8(2)
N4 C2 C1 106.5(2)
O2 C3 N1 121.0(3)
N1 C3 C2 113.8(2)
O2 C3 C2 125.2(3)
O1 C4 N1 120.5(3)
N1 C4 N2 119.6(2)
O1 C4 N2 119.9(3)
N3 C5 N4 113.7(2)
N3 C5 H1 123.9(6)
N4 C5 H1 121.7(6)
N2 C6 H2 108.9(6)
N2 C6 H3 109.1(5)
O11 C17 C16 129.6(3)
O12 C17 C16 115.4(2)
O11 C17 O12 115.0(4)
C11 C12 H12 119.3(6)
C13 C12 H12 121.0(6)
H2 C6 H3 109.9(7)
H2 C6 H4 109.8(8)
H3 C6 H4 110.1(8)
N2 C6 H4 109.0(5)
N1 C7 H5 109.2(5)
N1 C7 H6 108.7(6)
H5 C7 H6 109.9(8)
H5 C7 H7 110.1(7)
N1 C7 H7 108.9(6)
H6 C7 H7 110.0(7)
N4 C8 H9 109.0(5)
N4 C8 H10 108.5(5)
N4 C8 H8 109.3(5)
H8 C8 H10 110.3(7)
H9 C8 H10 110.2(7)
H8 C8 H9 109.6(8)
F12 C11 C16 120.6(3)
C12 C11 C16 120.4(2)
F12 C11 C12 119.0(3)
C11 C12 C13 119.7(2)
C12 C13 C14 121.1(3)
C13 C14 C15 119.9(2)
F11 C15 C14 118.8(3)
F11 C15 C16 120.7(3)
C14 C15 C16 120.6(2)
C11 C16 C17 121.9(2)
C15 C16 C17 119.8(2)
C11 C16 C15 118.3(3)
C12 C13 H13 119.5(6)
C14 C13 H13 119.5(6)
C13 C14 H14 121.0(6)
C15 C14 H14 119.0(6)

_vrf_ATOM006_caf-26diFBA         
;
PROBLEM: _atom_site_U_iso_or_equiv is missing
RESPONSE: The atomic displacement parameters reported as B(iso),
rather than U(iso).
;
_database_code_depnum_ccdc_archive 'CCDC 898411'
#######################################################################
#
#                 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
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  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.
#
data_caf-2345tetraFBA
#TrackingRef 'CCDC_898406-12.cif'


_diffrn_source                   'sealed X-ray tube'
_diffrn_source_target            Cu
_diffrn_source_type              ?
_diffrn_radiation_type           'Cu K\a'
_diffrn_measurement_device_type  "Panalytical X'pert PRO"
_diffrn_detector                 ?
_diffrn_detector_type            "X'Celerator RTMS"

_exptl_special_details           ?
_pd_meas_scan_method             cont
_pd_meas_special_details         ?
_pd_spec_size_axial              14
_pd_spec_size_equat              10
_pd_spec_size_thick              0.5
_pd_spec_mounting                'packed powder pellet'
_pd_spec_mount_mode              reflection
_pd_spec_shape                   flat_sheet
_pd_char_colour                  white
_pd_prep_temperature             293

# The following six items are used for angular dispersive measurements only.


_diffrn_radiation_monochromator  none

# The following four items give details of the measured (not processed)
# powder pattern. Angles are in degrees.

_pd_meas_number_of_points        1726
_pd_meas_2theta_range_min        3
_pd_meas_2theta_range_max        60
_pd_meas_2theta_range_inc        0.033

#==============================================================================
_pd_proc_ls_profile_function     'Fundamental parameters'
_pd_proc_ls_background_function  'Chebyshev polynomial'
_pd_proc_ls_pref_orient_corr     'Spherical harmonics, 4th order'

_computing_data_collection       "X'Pert Data Collector (Panalytical)"
_computing_cell_refinement       'TOPAS (Bruker 2009)'
_computing_structure_solution    'TOPAS (Bruker 2009)'
_computing_structure_refinement  'TOPAS (Bruker 2009)'
_computing_molecular_graphics    ?
_computing_publication_material  ?



_chemical_formula_moiety         'C8 H10 N4 O2, C7 H2 F4 O2'
_chemical_formula_sum            'C15 H12 F4 N4 O4'
_chemical_formula_weight         388.29
_cell_formula_units_Z            4

_symmetry_cell_setting           monoclinic

_diffrn_ambient_temperature      293
_diffrn_radiation_wavelength     1.5418
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     ?
_refine_ls_hydrogen_treatment    refall
_exptl_crystal_density_diffrn    1.623
_exptl_crystal_description       'microcrystaline powder'
_exptl_crystal_colour            white
_refine_ls_shift/su_max          <0.01
_refine_ls_number_parameters     173
_pd_proc_ls_prof_R_factor        0.042
_pd_proc_ls_prof_wR_factor       0.056
_pd_proc_ls_prof_wR_expected     1.11
_refine_ls_R_Fsqd_factor         0.017
_refine_ls_goodness_of_fit_all   5.01
_cell_measurement_temperature    293
_refine_ls_structure_factor_coef Fsqd
_refine_special_details          
;
Both caffeine and 2,3,4,5-tetrafluorobenzoic acid (2345tetraFBA) were
refined as rigid bodies with six degrees of freedom (three translational
and three rotational degrees of freedom for each molecule). The carboxylic
acid group of 2345tetraFBA was allowed torotate around its C-C bond during
structure solution and refinement. The hydrogen atoms of the caffeine methyl
groups were modelled to minimise the occurence of unreasonably short contacts
in the crystal structure. The structure model was finally refined using
restraints on bond lenghts and angles, as well as planarity restraints.
;

_cell_length_a                   14.2630(11)
_cell_length_b                   8.13716(48)
_cell_length_c                   16.0129(16)
_cell_angle_alpha                90
_cell_angle_beta                 121.2142(35)
_cell_angle_gamma                90
_cell_volume                     1589.42(23)

_symmetry_space_group_name_H-M   P21/c
_symmetry_space_group_name_Hall  '-P 2ybc'

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'
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_symmetry_multiplicity
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_occupancy
_atom_site_B_iso_or_equiv
C1 C 4 0.40346(15) 0.66648(37) 0.86301(13) 1 8.22(24)
C2 C 4 0.31944(15) 0.56348(33) 0.859103(96) 1 8.22(24)
C3 C 4 0.23597(14) 0.48624(36) 0.76887(12) 1 8.22(24)
N1 N 4 0.24702(14) 0.52093(36) 0.687824(99) 1 8.22(24)
C4 C 4 0.33140(15) 0.62473(39) 0.69328(12) 1 8.22(24)
N2 N 4 0.41022(14) 0.69481(34) 0.78302(12) 1 8.22(24)
N3 N 4 0.47290(21) 0.72557(54) 0.95883(19) 1 8.22(24)
C5 C 4 0.43166(13) 0.65596(36) 1.01023(10) 1 8.22(24)
N4 N 4 0.33582(16) 0.56160(36) 0.95217(12) 1 8.22(24)
O1 O 4 0.33569(34) 0.65362(70) 0.61884(33) 1 8.22(24)
O2 O 4 0.16148(45) 0.3953(11) 0.76072(23) 1 8.22(24)
C6 C 4 0.49544(10) 0.79729(21) 0.789427(86) 1 8.22(24)
C7 C 4 0.16631(11) 0.45164(21) 0.594250(95) 1 8.22(24)
C8 C 4 0.27020(10) 0.47844(17) 0.983271(82) 1 8.22(24)
H1 H 4 0.46018(46) 0.6751(16) 1.07820(42) 1 8.22(24)
H2 H 4 0.54178(52) 0.8360(15) 0.85656(44) 1 8.22(24)
H3 H 4 0.46200(58) 0.8901(16) 0.74580(65) 1 8.22(24)
H4 H 4 0.53863(62) 0.7341(14) 0.77005(66) 1 8.22(24)
H5 H 4 0.18472(47) 0.4829(13) 0.54612(46) 1 8.22(24)
H6 H 4 0.09419(58) 0.4938(14) 0.57557(63) 1 8.22(24)
H7 H 4 0.16703(51) 0.3329(17) 0.59994(52) 1 8.22(24)
H8 H 4 0.31866(56) 0.4040(12) 1.03845(48) 1 8.22(24)
H9 H 4 0.21151(59) 0.4138(12) 0.92722(53) 1 8.22(24)
H10 H 4 0.23670(62) 0.5599(11) 1.00447(50) 1 8.22(24)
C11 C 4 0.81606(14) 1.10748(34) 1.14545(10) 1 8.22(24)
C12 C 4 0.91259(16) 1.20449(39) 1.19818(11) 1 8.22(24)
C13 C 4 0.96376(16) 1.22073(36) 1.29995(11) 1 8.22(24)
C14 C 4 0.91891(18) 1.13947(39) 1.34914(11) 1 8.22(24)
C15 C 4 0.82469(15) 1.04223(37) 1.29718(11) 1 8.22(24)
C16 C 4 0.77314(16) 1.02699(33) 1.19435(11) 1 8.22(24)
C17 C 4 0.67527(16) 0.92637(31) 1.14074(10) 1 8.22(24)
O11 O 4 0.62414(37) 0.85384(60) 1.17227(20) 1 8.22(24)
O12 O 4 0.63637(18) 0.91060(40) 1.04229(14) 1 8.22(24)
F11 F 4 0.78712(40) 0.96684(87) 1.34692(31) 1 8.22(24)
F12 F 4 0.96631(28) 1.15394(65) 1.44545(33) 1 8.22(24)
F13 F 4 1.05405(39) 1.31302(85) 1.35014(21) 1 8.22(24)
F14 F 4 0.95673(39) 1.28177(83) 1.15252(33) 1 8.22(24)
H14 H 4 0.78166(66) 1.0951(12) 1.07563(49) 1 8.22(24)
H15 H 4 0.57098(52) 0.8424(15) 1.01258(57) 1 8.22(24)

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance


F11 C15 1.319(6)
F12 C14 1.331(4)
F13 C13 1.340(6)
F14 C12 1.343(6)
O1 C4 1.248(5)
O2 C3 1.244(8)
O11 C17 1.233(6)
O12 C17 1.380(2)
O12 H15 0.972(10)
N1 C4 1.435(4)
N1 C3 1.415(3)
N1 C7 1.449(2)
N2 C1 1.353(3)
N2 C6 1.433(3)
N2 C4 1.407(3)
N3 C5 1.359(4)
N3 C1 1.411(3)
N4 C8 1.437(3)
N4 C2 1.384(2)
N4 C5 1.416(3)
C1 C2 1.437(4)
C2 C3 1.455(3)
C5 H1 0.957(6)
C6 H3 0.970(12)
C6 H2 0.978(7)
C6 H4 0.968(11)
C7 H5 0.968(8)
C7 H6 0.973(10)
C7 H7 0.970(14)
C8 H8 0.997(8)
C8 H10 0.976(9)
C8 H9 1.002(8)
C11 C16 1.383(3)
C11 C12 1.424(3)
C12 C13 1.405(2)
C13 C14 1.410(4)
C14 C15 1.402(4)
C15 C16 1.419(2)
C16 C17 1.454(3)
C11 H14 0.966(7)

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle


C17 O12 H15 109.2(5)
C3 N1 C7 117.7(2)
C4 N1 C7 118.9(2)
C3 N1 C4 123.4(2)
C1 N2 C6 120.4(2)
C4 N2 C6 120.5(2)
C1 N2 C4 119.1(2)
C1 N3 C5 103.7(3)
C2 N4 C5 105.5(2)
C2 N4 C8 127.0(2)
C5 N4 C8 127.5(2)
N2 C1 C2 121.7(2)
N3 C1 C2 110.2(2)
N2 C1 N3 128.1(3)
N4 C2 C3 131.2(2)
C1 C2 C3 122.0(2)
N4 C2 C1 106.7(2)
O2 C3 C2 125.2(2)
N1 C3 C2 113.7(2)
O2 C3 N1 121.1(2)
O1 C4 N1 120.5(3)
O1 C4 N2 119.4(3)
N1 C4 N2 120.1(2)
N3 C5 N4 113.7(2)
N3 C5 H1 124.0(7)
N4 C5 H1 122.1(6)
N2 C6 H3 108.6(6)
N2 C6 H4 108.9(7)
C14 C15 C16 119.9(2)
C11 C16 C17 120.2(1)
C15 C16 C17 119.7(2)
C11 C16 C15 120.0(2)
O11 C17 C16 128.3(2)
N2 C6 H2 109.3(5)
H2 C6 H4 110.1(8)
H3 C6 H4 109.9(9)
H2 C6 H3 110.0(9)
N1 C7 H6 109.1(6)
N1 C7 H7 109.1(4)
H5 C7 H6 110.0(7)
H5 C7 H7 110.0(8)
H6 C7 H7 109.8(8)
N1 C7 H5 108.9(5)
N4 C8 H9 109.2(5)
N4 C8 H10 109.0(6)
N4 C8 H8 108.5(6)
H8 C8 H10 110.1(7)
H9 C8 H10 109.6(7)
H8 C8 H9 110.5(7)
C12 C11 C16 120.2(1)
F14 C12 C13 118.7(3)
C11 C12 C13 120.1(2)
F14 C12 C11 121.3(2)
F13 C13 C14 120.1(2)
C12 C13 C14 119.4(2)
F13 C13 C12 120.5(3)
F12 C14 C13 120.1(3)
F12 C14 C15 119.5(3)
C13 C14 C15 120.4(2)
F11 C15 C14 118.0(3)
F11 C15 C16 122.1(3)
O12 C17 C16 114.9(2)
O11 C17 O12 116.8(2)
C12 C11 H14 119.9(7)
C16 C11 H14 119.9(7)

_vrf_ATOM006_caf-2345tetraFBA    
;
PROBLEM: _atom_site_U_iso_or_equiv is missing
RESPONSE: The atomic displacement parameters are reported as B(iso),
rather than U(iso).
;









_database_code_depnum_ccdc_archive 'CCDC 898412'