# Supplementary Information (SI) for CrystEngComm.
# This journal is © The Royal Society of Chemistry 2025

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_x
_database_code_depnum_ccdc_archive 'CCDC 2466544'
loop_
_audit_author_name
_audit_author_address
'XiaoYing Huang'
;Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences
China
;
_audit_update_record             
;
2025-06-23 deposited with the CCDC.	2025-09-22 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2018/3
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C2 H8 N, Zr P O4 F2'
_chemical_formula_sum            'C2 H8 F2 N O4 P Zr'
_chemical_formula_weight         270.28

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'
F F 0.0171 0.0103 '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'
P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Zr Zr -2.9673 0.5597 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      monoclinic
_space_group_IT_number           11
_space_group_name_H-M_alt        'P 21/m'
_space_group_name_Hall           '-P 2yb'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

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

_cell_length_a                   6.5946(10)
_cell_length_b                   6.5775(11)
_cell_length_c                   9.962(3)
_cell_angle_alpha                90
_cell_angle_beta                 98.763(18)
_cell_angle_gamma                90
_cell_volume                     427.07(16)
_cell_formula_units_Z            2
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    1410
_cell_measurement_theta_min      3.0970
_cell_measurement_theta_max      29.6271

_exptl_crystal_description       plate
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    2.102
_exptl_crystal_F_000             264
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.150
_exptl_crystal_size_mid          0.100
_exptl_crystal_size_min          0.100
_exptl_absorpt_coefficient_mu    1.480
_shelx_estimated_absorpt_T_min   0.26351
_shelx_estimated_absorpt_T_max   1.00000
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.26351
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.42.63a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_measurement_device_type  
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean 10.3468
_diffrn_reflns_number            3341
_diffrn_reflns_av_unetI/netI     0.1033
_diffrn_reflns_av_R_equivalents  0.1117
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_theta_min         3.126
_diffrn_reflns_theta_max         26.365
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_point_group_measured_fraction_full 0.999
_reflns_number_total             951
_reflns_number_gt                792
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;

_computing_data_collection       'CrysAlisPro 1.171.42.63a (Rigaku OD, 2022)'
_computing_cell_refinement       'CrysAlisPro 1.171.42.63a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.63a (Rigaku OD, 2022)'
_computing_structure_solution    ?
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_molecular_graphics    'DIAMOND. Version 3.0. Crystal Impact'
_computing_publication_material  'Microsoft Word 2016'
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0733P)²+0.0750P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         951
_refine_ls_number_parameters     75
_refine_ls_number_restraints     20
_refine_ls_R_factor_all          0.0714
_refine_ls_R_factor_gt           0.0559
_refine_ls_wR_factor_ref         0.1477
_refine_ls_wR_factor_gt          0.1330
_refine_ls_goodness_of_fit_ref   1.097
_refine_ls_restrained_S_all      1.115
_refine_ls_shift/su_max          0.028
_refine_ls_shift/su_mean         0.002

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_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Zr1 Zr 0.23189(9) 0.250000 0.40645(8) 0.0129(3) Uani 1 2 d S T P . .
P1 P 0.2478(3) 0.750000 0.5009(3) 0.0184(6) Uani 1 2 d S T P . .
F1 F 0.2730(8) 0.250000 0.6068(6) 0.0318(15) Uani 1 2 d S T P . .
F2 F 0.1687(8) 0.250000 0.2029(7) 0.0375(15) Uani 1 2 d S T P . .
O1 O 0.2266(5) 0.5621(7) 0.4096(5) 0.0220(11) Uani 1 1 d . . . . .
O2 O 0.0837(8) 0.750000 0.5947(7) 0.0243(16) Uani 1 2 d S T P . .
O3 O 0.4563(8) 0.750000 0.5919(7) 0.0240(16) Uani 1 2 d S T P . .
N1 N 0.093(4) 0.212(4) 0.861(3) 0.156(15) Uani 0.5 1 d D U P A -1
H1A H -0.006297 0.161876 0.796448 0.187 Uiso 0.5 1 calc R U P A -1
H1B H 0.036945 0.225094 0.938757 0.187 Uiso 0.5 1 calc R U P A -1
C1 C 0.262(5) 0.053(5) 0.887(4) 0.19(2) Uani 0.5 1 d D U P A -1
H1C H 0.220525 -0.068997 0.834218 0.281 Uiso 0.5 1 calc R U P A -1
H1D H 0.286954 0.019163 0.984198 0.281 Uiso 0.5 1 calc R U P A -1
H1E H 0.388525 0.107885 0.860431 0.281 Uiso 0.5 1 calc R U P A -1
C2 C 0.144(3) 0.418(3) 0.819(2) 0.065(7) Uani 0.5 1 d D U P A -1
H2A H 0.032959 0.511359 0.830609 0.097 Uiso 0.5 1 calc R U P A -1
H2B H 0.162047 0.415119 0.722649 0.097 Uiso 0.5 1 calc R U P A -1
H2C H 0.271863 0.463239 0.873848 0.097 Uiso 0.5 1 calc R U P A -1

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
Zr1 0.0058(4) 0.0092(5) 0.0247(6) 0.000 0.0054(3) 0.000
P1 0.0075(10) 0.0111(11) 0.0375(17) 0.000 0.0061(9) 0.000
F1 0.037(3) 0.039(4) 0.019(3) 0.000 0.005(2) 0.000
F2 0.039(3) 0.041(4) 0.030(4) 0.000 -0.001(3) 0.000
O1 0.018(2) 0.013(2) 0.036(3) -0.0027(17) 0.006(2) 0.0001(14)
O2 0.008(3) 0.026(3) 0.039(5) 0.000 0.005(3) 0.000
O3 0.006(2) 0.025(3) 0.041(5) 0.000 0.004(3) 0.000
N1 0.28(3) 0.05(3) 0.11(2) 0.04(2) -0.058(19) -0.05(2)
C1 0.34(6) 0.15(4) 0.07(3) 0.01(2) 0.04(3) -0.16(4)
C2 0.085(14) 0.072(16) 0.028(13) 0.002(11) -0.021(10) 0.032(12)

_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
Zr1 F1 1.972(6) . ?
Zr1 F2 2.007(6) . ?
Zr1 O1 2.054(4) 4_565 ?
Zr1 O1 2.054(4) . ?
Zr1 O3 2.054(5) 3_666 ?
Zr1 O2 2.079(5) 3_566 ?
P1 O3 1.527(5) . ?
P1 O1 1.528(4) . ?
P1 O1 1.528(4) 4_575 ?
P1 O2 1.534(7) . ?
N1 C2 1.471(19) . ?
N1 C1 1.52(2) . ?
N1 H1A 0.9100 . ?
N1 H1B 0.9100 . ?
C1 H1C 0.9800 . ?
C1 H1D 0.9800 . ?
C1 H1E 0.9800 . ?
C2 H2A 0.9800 . ?
C2 H2B 0.9800 . ?
C2 H2C 0.9800 . ?

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
F1 Zr1 F2 176.0(2) . . ?
F1 Zr1 O1 89.10(13) . 4_565 ?
F2 Zr1 O1 90.82(13) . 4_565 ?
F1 Zr1 O1 89.10(13) . . ?
F2 Zr1 O1 90.82(13) . . ?
O1 Zr1 O1 177.2(3) 4_565 . ?
F1 Zr1 O3 90.5(2) . 3_666 ?
F2 Zr1 O3 93.5(3) . 3_666 ?
O1 Zr1 O3 91.11(10) 4_565 3_666 ?
O1 Zr1 O3 91.11(10) . 3_666 ?
F1 Zr1 O2 89.4(2) . 3_566 ?
F2 Zr1 O2 86.6(3) . 3_566 ?
O1 Zr1 O2 88.89(10) 4_565 3_566 ?
O1 Zr1 O2 88.89(10) . 3_566 ?
O3 Zr1 O2 179.9(3) 3_666 3_566 ?
O3 P1 O1 110.3(2) . . ?
O3 P1 O1 110.2(2) . 4_575 ?
O1 P1 O1 108.0(4) . 4_575 ?
O3 P1 O2 107.0(4) . . ?
O1 P1 O2 110.7(2) . . ?
O1 P1 O2 110.7(2) 4_575 . ?
P1 O1 Zr1 144.8(3) . . ?
P1 O2 Zr1 142.6(4) . 3_566 ?
P1 O3 Zr1 144.5(5) . 3_666 ?
C2 N1 C1 119(3) . . ?
C2 N1 H1A 107.6 . . ?
C1 N1 H1A 107.6 . . ?
C2 N1 H1B 107.6 . . ?
C1 N1 H1B 107.5 . . ?
H1A N1 H1B 107.0 . . ?
N1 C1 H1C 109.5 . . ?
N1 C1 H1D 109.5 . . ?
H1C C1 H1D 109.5 . . ?
N1 C1 H1E 109.5 . . ?
H1C C1 H1E 109.5 . . ?
H1D C1 H1E 109.5 . . ?
N1 C2 H2A 109.5 . . ?
N1 C2 H2B 109.5 . . ?
H2A C2 H2B 109.5 . . ?
N1 C2 H2C 109.5 . . ?
H2A C2 H2C 109.5 . . ?
H2B C2 H2C 109.5 . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
O3 P1 O1 Zr1 57.6(5) . . . . ?
O1 P1 O1 Zr1 178.06(18) 4_575 . . . ?
O2 P1 O1 Zr1 -60.7(5) . . . . ?
O3 P1 O2 Zr1 180.000(1) . . . 3_566 ?
O1 P1 O2 Zr1 -59.8(2) . . . 3_566 ?
O1 P1 O2 Zr1 59.8(2) 4_575 . . 3_566 ?
O1 P1 O3 Zr1 59.6(2) . . . 3_666 ?
O1 P1 O3 Zr1 -59.6(2) 4_575 . . 3_666 ?
O2 P1 O3 Zr1 180.000(1) . . . 3_666 ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
_geom_hbond_publ_flag
N1^a H1B^a F2 0.91 2.65 3.37(4) 137.3 1_556 yes
C1^a H1C^a O2 0.98 2.70 3.58(4) 150.4 1_545 yes
C2^a H2A^a F2 0.98 2.05 2.99(2) 160.1 3_566 yes
C2^a H2B^a F1 0.98 1.82 2.63(3) 138.4 . yes

_refine_diff_density_max         1.183
_refine_diff_density_min         -1.139
_refine_diff_density_rms         0.224

_shelx_res_file                  
;
TITL x                P 21         R = 0.07 New:P21/m
    x.res
    created by SHELXL-2018/3 at 11:39:28 on 12-Sep-2024
CELL  0.71073    6.5946    6.5775    9.9620    90.000    98.763    90.000
ZERR        2    0.0010    0.0011    0.0030     0.000     0.018     0.000
LATT   1
SYMM               - X ,    0.50000 + Y ,            - Z
SFAC  C  H  F  N  O  P Zr
UNIT    4 16   4   2   8   2   2
TEMP  -173.15
L.S. 25
FMAP 2
PLAN 10
ACTA
CONF
dfix 1.42 0.02 n1 c1 n1 c2
BOND $H
isor 0.05 $n $c
htab
shel 999 0.8
EQIV $5 x, y, z+1
HTAB N1 F2_$5
EQIV $6 x, y-1, z
HTAB C1 O2_$6
EQIV $1 -x, -y+1, -z+1
HTAB C2 F2_$1
HTAB C2 F1
rem EXTI    0.008339
WGHT    0.073300    0.075000
FVAR       0.85327
ZR1   7    0.231889    0.250000    0.406450    10.50000    0.00585    0.00923 =
         0.02466    0.00000    0.00542    0.00000
P1    6    0.247850    0.750000    0.500882    10.50000    0.00747    0.01112 =
         0.03750    0.00000    0.00610    0.00000
F1    3    0.272963    0.250000    0.606752    10.50000    0.03702    0.03950 =
         0.01927    0.00000    0.00527    0.00000
F2    3    0.168732    0.250000    0.202921    10.50000    0.03948    0.04140 =
         0.02972    0.00000   -0.00124    0.00000
O1    5    0.226556    0.562132    0.409646    11.00000    0.01829    0.01261 =
         0.03580   -0.00267    0.00650    0.00014
O2    5    0.083707    0.750000    0.594739    10.50000    0.00753    0.02650 =
         0.03946    0.00000    0.00510    0.00000
O3    5    0.456318    0.750000    0.591922    10.50000    0.00593    0.02518 =
         0.04095    0.00000    0.00400    0.00000
PART  -1
N1    4    0.093190    0.212292    0.861251    10.50000    0.27611    0.05037 =
         0.11356    0.03877   -0.05774   -0.05004
AFIX  23
H1A   2   -0.006297    0.161876    0.796448    10.50000   -1.20000
H1B   2    0.036945    0.225094    0.938757    10.50000   -1.20000
AFIX   0
C1    1    0.262351    0.053451    0.887347    10.50000    0.34108    0.15442 =
         0.06755    0.01047    0.03719   -0.15682
AFIX 137
H1C   2    0.220525   -0.068997    0.834218    10.50000   -1.50000
H1D   2    0.286954    0.019163    0.984198    10.50000   -1.50000
H1E   2    0.388525    0.107885    0.860431    10.50000   -1.50000
AFIX   0
C2    1    0.144275    0.417625    0.818526    10.50000    0.08516    0.07201 =
         0.02782    0.00208   -0.02116    0.03214
AFIX 137
H2A   2    0.032959    0.511359    0.830609    10.50000   -1.50000
H2B   2    0.162047    0.415119    0.722649    10.50000   -1.50000
H2C   2    0.271863    0.463239    0.873848    10.50000   -1.50000
PART   0

AFIX   0
HKLF 4




REM  x                P 21         R = 0.07 New:P21/m
REM wR2 = 0.1477, GooF = S = 1.097, Restrained GooF = 1.115 for all data
REM R1 = 0.0559 for 792 Fo > 4sig(Fo) and 0.0714 for all 951 data
REM 75 parameters refined using 20 restraints

END

WGHT      0.0729      0.0616

REM Instructions for potential hydrogen bonds
EQIV $7 -x, y-1/2, -z+1
HTAB N1 O1_$7
HTAB C2 F2_$1
HTAB C2 F1
HTAB C2 O2

REM Highest difference peak  1.183,  deepest hole -1.139,  1-sigma level  0.224
Q1    1  -0.0812  0.2500  0.8750  10.50000  0.05    1.18
Q2    1   0.2139  0.7500  0.3137  10.50000  0.05    1.05
Q3    1   0.1829  0.4140  0.3947  11.00000  0.05    0.99
Q4    1   0.3553  0.5654  0.8806  11.00000  0.05    0.99
Q5    1   0.2985  0.2500  0.7856  10.50000  0.05    0.94
Q6    1   0.2974  0.4226  0.4207  11.00000  0.05    0.85
Q7    1  -0.0500  0.2500  0.6577  10.50000  0.05    0.78
Q8    1   0.2680  0.7500  0.6834  10.50000  0.05    0.76
Q9    1   0.0142  0.9373  0.5538  11.00000  0.05    0.73
Q10   1   0.2583  0.5728  0.4821  11.00000  0.05    0.72
;
_shelx_res_checksum              53589
