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The title compound, C6H10N3O2+·C2F3O2, crystallizes with two histidine cations and two trifluoro­acetate anions in the asymmetric unit. The protonated cations and deprotonated anions are linked by a number of inter­molecular N—H...O hydrogen bonds to form a three-dimensional network.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805038791/su6250sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805038791/su6250Isup2.hkl
Contains datablock I

CCDC reference: 281106

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.005 Å
  • R factor = 0.038
  • wR factor = 0.108
  • Data-to-parameter ratio = 5.4

checkCIF/PLATON results

No syntax errors found



Alert level B PLAT089_ALERT_3_B Poor Data / Parameter Ratio (Zmax .LT. 18) ..... 5.40
Alert level C PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature . 293 K PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.33 Ratio PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C7 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C15 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C16 PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 5 PLAT352_ALERT_3_C Short N-H Bond (0.87A) N4 - H4 ... 0.76 Ang. PLAT432_ALERT_2_C Short Inter X...Y Contact O6 .. C6 .. 2.94 Ang. PLAT731_ALERT_1_C Bond Calc 0.85(4), Rep 0.847(11) ...... 3.64 su-Rat C2 -H2' 1.555 1.555 PLAT735_ALERT_1_C D-H Calc 0.94(4), Rep 0.935(11) ...... 3.64 su-Rat N3 -H3A 1.555 1.555 PLAT735_ALERT_1_C D-H Calc 0.93(4), Rep 0.932(11) ...... 3.64 su-Rat N3 -H3C 1.555 1.555 PLAT735_ALERT_1_C D-H Calc 0.93(3), Rep 0.926(11) ...... 2.73 su-Rat N6 -H6A 1.555 1.555 PLAT735_ALERT_1_C D-H Calc 0.93(3), Rep 0.932(11) ...... 2.73 su-Rat N6 -H6B 1.555 1.555 PLAT736_ALERT_1_C H...A Calc 1.85(4), Rep 1.855(13) ...... 3.08 su-Rat H3A -O4 1.555 1.555 PLAT736_ALERT_1_C H...A Calc 1.98(5), Rep 1.98(2) ...... 2.50 su-Rat H3B -O1 1.555 1.455 PLAT736_ALERT_1_C H...A Calc 1.81(3), Rep 1.806(14) ...... 2.14 su-Rat H6B -O3 1.555 1.565 PLAT736_ALERT_1_C H...A Calc 1.92(5), Rep 1.92(2) ...... 2.50 su-Rat H6C -O8 1.555 1.555 PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 1 C6 H10 N3 O2 PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 4 C2 F3 O2
Alert level G FORMU01_ALERT_1_G There is a discrepancy between the atom counts in the _chemical_formula_sum and _chemical_formula_moiety. This is usually due to the moiety formula being in the wrong format. Atom count from _chemical_formula_sum: C8 H10 F3 N3 O4 Atom count from _chemical_formula_moiety:C8 H10 F3 N3 O3 REFLT03_ALERT_4_G WARNING: CuKa measured Friedel data can be used to determine absolute structure in a light-atom study only if the Friedel fraction is large. From the CIF: _diffrn_reflns_theta_max 67.95 From the CIF: _reflns_number_total 2063 Count of symmetry unique reflns 1971 Completeness (_total/calc) 104.67% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 92 Fraction of Friedel pairs measured 0.047 Are heavy atom types Z>Si present no
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 20 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 12 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 4 ALERT type 2 Indicator that the structure model may be wrong or deficient 4 ALERT type 3 Indicator that the structure quality may be low 3 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

Histidine is an interesting molecule from a crystal engineering point of view. It can act as a proton donor, a proton acceptor, a nucleophilic agent and a ligand for complexation with various metal ions. It exists as both orthorhombic and monclinic polymorphic forms. The crystal structures of L-histidine (Madden, McGandy & Seeman, 1972; Madden, McGandy, Seeman, Harding & Hoy, 1972) and its complexes, such as L-histidinium hydrochloride (Fuess & Bartunik 1976; Donohue & Caron 1964), L-histidinium dinitrate (Benali-Cherif et al., 2002), L-histidinium sulfate (Kumar et al., 2005) and L-histidinium tetrafluorosuccinate (Akkurt et al., 2004), have been reported, and recently the crystal structure of L-histidinium trichloroacetate (Gokulraj et al., 2005) has also been published. In the present study, we report the crystal structure of L-histidinium trifluoroacetate, (I).

The molecular structure of (I) is illustrated in Fig. 1, and selected bond distances and angles are given in Table 1. Compound (I) crystallizes with two histidine cations (A and B) and two trifluoroacetate anions in the unit cell of the non-centrosymmetric triclinic space group P1. The α-amino and imidazole groups of the L-histidine cations are protonated and positively charged, while the carboxyl groups are in the ionized state and are negatively charged. Moreover, the zwitterionic cation carries a net positive charge. The conformation angles of the histidine side chain (IUPAC–IUB Commission on Biochemical Nomenclature, 1970) are χ1 [−68.5 (4) and −69.9 (4)°], χ21 [−54.5 (5) and 54.1 (5)°] and χ22 [126.2 (4) and 132.0 (4)° for cations A and B, respectively]. The conformation ψ1 is such that it is in a gauche II form for both molecules, having a closed conformation (Pratap et al., 2000) (see Table 1). The difference in the absolute values of χ21 and χ22 is about 180°, indicating the planarity of the imidazole group. The deviations in the preferred torsion angles of χ21 at −90 and 90° are due to the interactions of the imidazole ring with other groups in the structure. The imidazole group of L-histidine is in a trans conformation, for both A [C3—C4—C5—C6 = 170.3 (3)°] and B [C11—C12—C13—C14 = 168.9 (3)°], with respect to the carboxyl group, and gauche with respect to the amino N atom. The corresponding gauche II conformation angles observed in other complexes are −60 and −60.9° in L-histidine formate formic acid, −60 and −67.5° in DL-histidine formate monohydrate, −60.2 (3)° in L-histidine dinitrate, 58.2 and −96.8° in L-histidine glycolate, −61.2 (5) and 99.2 (5)° in monoclinic L-histidine acetate and 37.1 (6) and −78.8 (6)° in L-histidinium trichloroacetate.

The trifluoroacetate anions play a vital role in the hydrogen bonding with the histidinium cation via the amine N atom and the N atom of the imidazole ring. The three-dimensional network of N—H···O bonds links the cations and trifluoroacetate anions stabilizing the crystal packing as shown in Fig. 2.

Experimental top

Crystals of the title compound, (I), were grown from a mixture of L-histidine and trifluoroacetic acid, in the stoichiometric ratio of 1:1, by slow evaporation at room temperature.

Refinement top

The tertiary CH and secondary CH2 H atoms of the histidinium cations were included in calculated positions and treated as riding atoms, with C—H = 0.97–0.98 Å and Uiso(H) = 1.2Ueq(parent C atom). All other H atoms were located in difference Fourier maps and refined freely [N—H = 0.75 (7)–1.00 (6) Å and C—H = 0.847 (11)–0.85 (6) Å].

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1997); cell refinement: CAD-4 Software; data reduction: XCAD4 in WinGX (Farrugia, 1999); program(s) used to solve structure: SIR92 (Burla et al., 1989); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-32 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with the atomic numbering scheme and 50% probability displacement ellipsoids. H atoms have been omitted.
[Figure 2] Fig. 2. The crystal packing of (I), viewed down the b axis. The intramolecular N—H···O bonds are shown as broken lines.
L-Histidinium trifluoroacetate top
Crystal data top
C6H10N3O2+·C2F3O2Z = 2
Mr = 269.19F(000) = 276
Triclinic, P1Dx = 1.649 Mg m3
Hall symbol: P 1Cu Kα radiation, λ = 1.54180 Å
a = 5.1724 (6) ÅCell parameters from 25 reflections
b = 8.8183 (12) Åθ = 20–30°
c = 12.481 (3) ŵ = 1.46 mm1
α = 96.193 (17)°T = 293 K
β = 99.853 (13)°Block, brown
γ = 102.106 (13)°0.2 × 0.2 × 0.1 mm
V = 542.26 (16) Å3
Data collection top
Enraf–Nonius CAD-4
diffractometer
2053 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.001
Graphite monochromatorθmax = 68.0°, θmin = 3.6°
ω/2θ scansh = 66
Absorption correction: ψ scan
(North et al., 1968)
k = 1010
Tmin = 0.790, Tmax = 0.864l = 1415
2064 measured reflections2 standard reflections every 60 min
2063 independent reflections intensity decay: none
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.038 w = 1/[σ2(Fo2) + (0.0775P)2 + 0.22P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.108(Δ/σ)max < 0.001
S = 1.01Δρmax = 0.42 e Å3
2063 reflectionsΔρmin = 0.32 e Å3
382 parametersExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
13 restraintsExtinction coefficient: 0.055 (4)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 92 Friedel pairs
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.04 (2)
Crystal data top
C6H10N3O2+·C2F3O2γ = 102.106 (13)°
Mr = 269.19V = 542.26 (16) Å3
Triclinic, P1Z = 2
a = 5.1724 (6) ÅCu Kα radiation
b = 8.8183 (12) ŵ = 1.46 mm1
c = 12.481 (3) ÅT = 293 K
α = 96.193 (17)°0.2 × 0.2 × 0.1 mm
β = 99.853 (13)°
Data collection top
Enraf–Nonius CAD-4
diffractometer
2053 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.001
Tmin = 0.790, Tmax = 0.8642 standard reflections every 60 min
2064 measured reflections intensity decay: none
2063 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.038H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.108Δρmax = 0.42 e Å3
S = 1.01Δρmin = 0.32 e Å3
2063 reflectionsAbsolute structure: Flack (1983), 92 Friedel pairs
382 parametersAbsolute structure parameter: 0.04 (2)
13 restraints
Special details top

Experimental. psi-scan absorption correction: North et al. (1968) Number of psi-scan sets used was 4 Theta correction was applied. Averaged transmission function was used. No Fourier smoothing was applied.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.8441 (8)0.2285 (5)0.2787 (4)0.0460 (9)
C21.1001 (11)0.1445 (4)0.1522 (4)0.0524 (11)
C31.0878 (7)0.3327 (4)0.2536 (3)0.0331 (7)
C41.1832 (8)0.4790 (4)0.2996 (3)0.0379 (8)
H4A1.03290.49720.35070.045*
H4B1.31990.46260.34110.045*
C51.3010 (6)0.6273 (3)0.2138 (3)0.0272 (6)
H5A1.43810.60520.15680.033*
C61.4345 (6)0.7612 (4)0.2695 (3)0.0289 (6)
C71.0914 (8)0.4240 (4)0.0842 (3)0.0412 (8)
C80.8156 (7)0.3716 (4)0.0061 (3)0.0369 (7)
C90.9856 (9)0.9431 (6)0.5115 (4)0.0523 (10)
C100.6365 (9)0.7805 (5)0.4043 (4)0.0467 (9)
C110.8024 (8)0.8432 (4)0.3391 (3)0.0402 (8)
C120.7871 (10)0.8073 (4)0.2184 (3)0.0462 (9)
H12A0.61220.73870.18580.055*
H12B0.92280.74970.20670.055*
C130.8268 (6)0.9487 (4)0.1569 (3)0.0303 (6)
H130.99021.02590.19580.036*
C140.8615 (7)0.8969 (4)0.0390 (3)0.0345 (7)
C150.7585 (11)1.3651 (5)0.3768 (5)0.0661 (14)
C160.5426 (10)1.2437 (6)0.4187 (4)0.0568 (12)
N10.8581 (8)0.1136 (4)0.2154 (4)0.0566 (10)
N21.2439 (7)0.2766 (3)0.1733 (3)0.0378 (6)
N31.0882 (6)0.6752 (3)0.1614 (2)0.0313 (6)
N41.0179 (8)0.9436 (5)0.4079 (3)0.0476 (8)
N50.7568 (8)0.8435 (5)0.5115 (3)0.0503 (9)
N60.5937 (6)1.0230 (3)0.1517 (2)0.0339 (6)
O11.6392 (5)0.7386 (3)0.3067 (2)0.0394 (6)
O21.3431 (5)0.8785 (3)0.2730 (2)0.0411 (6)
O30.6610 (6)0.2548 (4)0.0239 (3)0.0614 (9)
O40.7704 (5)0.4498 (3)0.0692 (2)0.0475 (7)
O51.0912 (5)0.8762 (4)0.0320 (2)0.0484 (7)
O60.6702 (6)0.8824 (4)0.0369 (2)0.0556 (8)
O70.4911 (11)1.2820 (8)0.5071 (3)0.1013 (17)
O80.4445 (7)1.1223 (4)0.3506 (3)0.0530 (7)
F11.0849 (7)0.5183 (4)0.1742 (2)0.0693 (8)
F21.2823 (5)0.5032 (3)0.0376 (2)0.0600 (7)
F31.1793 (6)0.3021 (3)0.1180 (3)0.0637 (7)
F40.9327 (8)1.2950 (5)0.3359 (5)0.1025 (14)
F50.6422 (8)1.4234 (5)0.2938 (3)0.0916 (11)
F60.8936 (13)1.4847 (5)0.4500 (4)0.130 (2)
H10.710 (12)0.017 (7)0.223 (5)0.058 (14)*
H1'0.694 (9)0.218 (10)0.323 (6)0.11 (3)*
H21.407 (11)0.327 (6)0.141 (4)0.044 (12)*
H2'1.183 (9)0.101 (6)0.104 (3)0.050 (13)*
H3A0.996 (8)0.596 (4)0.128 (3)0.036 (10)*
H3B0.970 (9)0.714 (6)0.210 (4)0.063 (15)*
H3C1.163 (10)0.758 (4)0.104 (3)0.059 (14)*
H41.141 (12)0.986 (7)0.389 (5)0.057 (16)*
H50.727 (11)0.816 (6)0.567 (5)0.055 (14)*
H6A0.440 (5)0.965 (4)0.103 (3)0.033 (10)*
H6B0.614 (9)1.110 (3)0.115 (3)0.037 (10)*
H6C0.578 (15)1.067 (8)0.221 (3)0.09 (2)*
H9'1.104 (10)0.982 (7)0.569 (3)0.075 (18)*
H10'0.489 (6)0.713 (5)0.377 (4)0.054 (14)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.040 (2)0.0367 (18)0.052 (2)0.0070 (15)0.0130 (18)0.0066 (16)
C20.084 (3)0.0276 (17)0.055 (3)0.0163 (19)0.029 (2)0.0160 (17)
C30.0343 (16)0.0264 (14)0.0362 (17)0.0007 (12)0.0120 (13)0.0009 (13)
C40.050 (2)0.0297 (16)0.0325 (17)0.0021 (14)0.0119 (15)0.0039 (13)
C50.0297 (14)0.0246 (14)0.0265 (14)0.0023 (11)0.0062 (11)0.0082 (11)
C60.0275 (14)0.0292 (14)0.0252 (14)0.0027 (11)0.0011 (11)0.0088 (11)
C70.0461 (19)0.0408 (18)0.042 (2)0.0143 (15)0.0142 (16)0.0109 (16)
C80.0408 (18)0.0362 (17)0.0415 (19)0.0124 (14)0.0183 (15)0.0174 (15)
C90.057 (2)0.074 (3)0.0308 (19)0.018 (2)0.0151 (18)0.0149 (19)
C100.059 (2)0.044 (2)0.045 (2)0.0155 (18)0.0230 (19)0.0195 (17)
C110.059 (2)0.0395 (17)0.0339 (18)0.0221 (16)0.0195 (16)0.0208 (15)
C120.076 (3)0.0374 (18)0.0330 (18)0.0198 (18)0.0196 (18)0.0114 (15)
C130.0346 (15)0.0320 (15)0.0250 (15)0.0060 (12)0.0091 (12)0.0054 (12)
C140.0380 (17)0.0360 (16)0.0265 (16)0.0012 (13)0.0086 (13)0.0025 (12)
C150.072 (3)0.045 (2)0.067 (3)0.012 (2)0.017 (3)0.001 (2)
C160.067 (3)0.075 (3)0.036 (2)0.039 (2)0.0035 (19)0.002 (2)
N10.064 (2)0.0285 (15)0.072 (3)0.0132 (15)0.032 (2)0.0000 (16)
N20.0411 (16)0.0304 (13)0.0410 (16)0.0032 (12)0.0113 (13)0.0069 (12)
N30.0371 (14)0.0268 (12)0.0321 (14)0.0051 (10)0.0120 (11)0.0101 (11)
N40.054 (2)0.064 (2)0.0331 (17)0.0189 (17)0.0187 (15)0.0212 (15)
N50.068 (2)0.064 (2)0.0354 (17)0.0283 (18)0.0267 (16)0.0268 (16)
N60.0382 (14)0.0367 (14)0.0284 (14)0.0082 (12)0.0094 (11)0.0079 (11)
O10.0350 (12)0.0497 (14)0.0389 (13)0.0068 (10)0.0166 (10)0.0215 (11)
O20.0462 (13)0.0314 (11)0.0503 (14)0.0079 (10)0.0146 (11)0.0208 (11)
O30.0518 (16)0.0565 (18)0.080 (2)0.0037 (13)0.0146 (16)0.0421 (17)
O40.0412 (13)0.0536 (15)0.0528 (16)0.0075 (11)0.0136 (12)0.0299 (13)
O50.0405 (13)0.0647 (17)0.0360 (14)0.0072 (12)0.0134 (11)0.0089 (12)
O60.0502 (16)0.083 (2)0.0282 (13)0.0158 (15)0.0020 (12)0.0051 (13)
O70.115 (3)0.161 (5)0.0402 (19)0.070 (3)0.017 (2)0.010 (2)
O80.0631 (17)0.0536 (16)0.0461 (15)0.0097 (14)0.0271 (14)0.0060 (13)
F10.0872 (19)0.0697 (17)0.0504 (15)0.0236 (15)0.0151 (14)0.0059 (13)
F20.0432 (13)0.0721 (17)0.0599 (15)0.0005 (11)0.0103 (11)0.0160 (13)
F30.0614 (15)0.0599 (15)0.0738 (18)0.0265 (12)0.0020 (13)0.0210 (13)
F40.078 (2)0.079 (2)0.160 (4)0.0144 (18)0.047 (3)0.031 (3)
F50.107 (3)0.082 (2)0.070 (2)0.0078 (19)0.0181 (19)0.0230 (17)
F60.189 (5)0.072 (2)0.079 (3)0.006 (3)0.047 (3)0.0087 (19)
Geometric parameters (Å, º) top
C1—N11.357 (6)C10—H10'0.85 (5)
C1—C31.360 (5)C11—N41.363 (6)
C1—H1'0.85 (6)C11—C121.491 (5)
C2—N11.317 (7)C12—C131.530 (5)
C2—N21.323 (5)C12—H12A0.9700
C2—H2'0.847 (11)C12—H12B0.9700
C3—N21.378 (5)C13—N61.483 (4)
C3—C41.492 (5)C13—C141.544 (4)
C4—C51.539 (4)C13—H130.9800
C4—H4A0.9700C14—O61.222 (5)
C4—H4B0.9700C14—O51.255 (5)
C5—N31.483 (4)C15—F61.303 (6)
C5—C61.535 (4)C15—F51.316 (6)
C5—H5A0.9800C15—F41.333 (7)
C6—O21.226 (4)C15—C161.577 (8)
C6—O11.270 (4)C16—O71.208 (6)
C7—F31.333 (5)C16—O81.247 (6)
C7—F11.333 (5)N1—H11.00 (6)
C7—F21.340 (5)N2—H20.87 (5)
C7—C81.533 (5)N3—H3A0.93 (5)
C8—O31.231 (5)N3—H3B0.93 (5)
C8—O41.243 (5)N3—H3C0.93 (5)
C9—N51.318 (7)N4—H40.75 (7)
C9—N41.332 (6)N5—H50.79 (6)
C9—H9'0.85 (5)N6—H6A0.93 (5)
C10—C111.357 (6)N6—H6B0.93 (5)
C10—N51.377 (6)N6—H6C0.93 (5)
N1—C1—C3107.6 (4)C11—C12—H12B108.3
N1—C1—H1'115 (6)C13—C12—H12B108.3
C3—C1—H1'137 (6)H12A—C12—H12B107.4
N1—C2—N2108.7 (4)N6—C13—C12111.0 (3)
N1—C2—H2'136 (4)N6—C13—C14109.4 (3)
N2—C2—H2'115 (4)C12—C13—C14109.9 (3)
C1—C3—N2105.8 (3)N6—C13—H13108.8
C1—C3—C4129.9 (4)C12—C13—H13108.8
N2—C3—C4124.3 (3)C14—C13—H13108.8
C3—C4—C5115.1 (3)O6—C14—O5126.7 (3)
C3—C4—H4A108.5O6—C14—C13118.4 (3)
C5—C4—H4A108.5O5—C14—C13114.9 (3)
C3—C4—H4B108.5F6—C15—F5106.3 (4)
C5—C4—H4B108.5F6—C15—F4108.7 (6)
H4A—C4—H4B107.5F5—C15—F4104.6 (5)
N3—C5—C6109.6 (2)F6—C15—C16115.0 (5)
N3—C5—C4111.1 (3)F5—C15—C16110.5 (4)
C6—C5—C4109.4 (3)F4—C15—C16111.1 (4)
N3—C5—H5A108.9O7—C16—O8130.2 (6)
C6—C5—H5A108.9O7—C16—C15117.4 (5)
C4—C5—H5A108.9O8—C16—C15112.4 (4)
O2—C6—O1125.9 (3)C2—N1—C1109.0 (3)
O2—C6—C5119.4 (3)C2—N1—H1127 (3)
O1—C6—C5114.6 (3)C1—N1—H1124 (3)
F3—C7—F1106.8 (3)C2—N2—C3108.9 (3)
F3—C7—F2106.8 (3)C2—N2—H2128 (3)
F1—C7—F2106.2 (3)C3—N2—H2123 (3)
F3—C7—C8111.7 (3)C5—N3—H3A113 (3)
F1—C7—C8112.3 (3)C5—N3—H3B112 (4)
F2—C7—C8112.7 (3)H3A—N3—H3B112 (4)
O3—C8—O4126.4 (4)C5—N3—H3C111 (3)
O3—C8—C7116.4 (3)H3A—N3—H3C104 (4)
O4—C8—C7117.2 (3)H3B—N3—H3C105 (5)
N5—C9—N4108.4 (4)C9—N4—C11109.5 (4)
N5—C9—H9'123 (5)C9—N4—H4126 (5)
N4—C9—H9'127 (5)C11—N4—H4124 (4)
C11—C10—N5107.4 (4)C9—N5—C10108.4 (3)
C11—C10—H10'121 (4)C9—N5—H5120 (4)
N5—C10—H10'132 (4)C10—N5—H5130 (4)
C10—C11—N4106.2 (4)C13—N6—H6A113 (3)
C10—C11—C12130.8 (4)C13—N6—H6B113 (3)
N4—C11—C12122.8 (4)H6A—N6—H6B96 (4)
C11—C12—C13116.0 (3)C13—N6—H6C112 (5)
C11—C12—H12A108.3H6A—N6—H6C119 (5)
C13—C12—H12A108.3H6B—N6—H6C102 (5)
N1—C1—C3—N20.5 (4)C11—C12—C13—C14168.9 (3)
N1—C1—C3—C4179.2 (3)N6—C13—C14—O619.2 (4)
C1—C3—C4—C5126.2 (4)C12—C13—C14—O6102.9 (4)
N2—C3—C4—C554.1 (5)N6—C13—C14—O5159.8 (3)
C3—C4—C5—N368.5 (4)C12—C13—C14—O578.1 (4)
C3—C4—C5—C6170.3 (3)F6—C15—C16—O711.0 (7)
N3—C5—C6—O25.9 (4)F5—C15—C16—O7109.4 (5)
C4—C5—C6—O2116.2 (3)F4—C15—C16—O7135.0 (5)
N3—C5—C6—O1172.8 (3)F6—C15—C16—O8171.2 (5)
C4—C5—C6—O165.1 (3)F5—C15—C16—O868.4 (5)
F3—C7—C8—O333.6 (5)F4—C15—C16—O847.2 (5)
F1—C7—C8—O386.3 (4)N2—C2—N1—C10.2 (5)
F2—C7—C8—O3153.9 (4)C3—C1—N1—C20.5 (5)
F3—C7—C8—O4145.9 (4)N1—C2—N2—C30.1 (4)
F1—C7—C8—O494.2 (4)C1—C3—N2—C20.4 (4)
F2—C7—C8—O425.6 (5)C4—C3—N2—C2179.3 (3)
N5—C10—C11—N40.5 (4)N5—C9—N4—C110.9 (5)
N5—C10—C11—C12173.7 (4)C10—C11—N4—C90.2 (5)
C10—C11—C12—C13132.0 (4)C12—C11—N4—C9175.0 (4)
N4—C11—C12—C1354.6 (5)N4—C9—N5—C101.2 (5)
C11—C12—C13—N669.9 (4)C11—C10—N5—C91.0 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O2i1.00 (6)1.99 (6)2.935 (4)157 (5)
N2—H2···O4ii0.87 (5)1.97 (6)2.838 (4)178 (4)
N3—H3A···O40.94 (1)1.86 (1)2.784 (4)172 (4)
N3—H3B···O1iii0.93 (5)1.98 (2)2.884 (4)162 (5)
N3—H3C···O50.93 (1)2.03 (3)2.832 (4)144 (5)
N4—H4···O8ii0.75 (7)1.93 (7)2.681 (5)172 (6)
N5—H5···O1iv0.79 (6)1.87 (6)2.657 (4)176 (6)
N6—H6A···O5iii0.93 (1)1.84 (2)2.740 (4)165 (4)
N6—H6B···O3v0.93 (1)1.81 (1)2.728 (4)170 (4)
N6—H6C···O80.93 (5)1.92 (2)2.827 (4)164 (7)
Symmetry codes: (i) x1, y1, z; (ii) x+1, y, z; (iii) x1, y, z; (iv) x1, y, z+1; (v) x, y+1, z.

Experimental details

Crystal data
Chemical formulaC6H10N3O2+·C2F3O2
Mr269.19
Crystal system, space groupTriclinic, P1
Temperature (K)293
a, b, c (Å)5.1724 (6), 8.8183 (12), 12.481 (3)
α, β, γ (°)96.193 (17), 99.853 (13), 102.106 (13)
V3)542.26 (16)
Z2
Radiation typeCu Kα
µ (mm1)1.46
Crystal size (mm)0.2 × 0.2 × 0.1
Data collection
DiffractometerEnraf–Nonius CAD-4
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.790, 0.864
No. of measured, independent and
observed [I > 2σ(I)] reflections
2064, 2063, 2053
Rint0.001
(sin θ/λ)max1)0.601
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.108, 1.01
No. of reflections2063
No. of parameters382
No. of restraints13
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.42, 0.32
Absolute structureFlack (1983), 92 Friedel pairs
Absolute structure parameter0.04 (2)

Computer programs: CAD-4 Software (Enraf–Nonius, 1997), CAD-4 Software, XCAD4 in WinGX (Farrugia, 1999), SIR92 (Burla et al., 1989), SHELXL97 (Sheldrick, 1997), ORTEP-32 (Farrugia, 1997), SHELXL97.

Selected geometric parameters (Å, º) top
C1—N11.357 (6)C6—O11.270 (4)
C2—N11.317 (7)C7—F31.333 (5)
C2—N21.323 (5)C7—F11.333 (5)
C3—N21.378 (5)C7—F21.340 (5)
C5—N31.483 (4)C8—O31.231 (5)
C6—O21.226 (4)C8—O41.243 (5)
N1—C1—C3107.6 (4)F3—C7—F2106.8 (3)
N1—C2—N2108.7 (4)F1—C7—F2106.2 (3)
C1—C3—N2105.8 (3)F3—C7—C8111.7 (3)
N2—C3—C4124.3 (3)F1—C7—C8112.3 (3)
N3—C5—C6109.6 (2)F2—C7—C8112.7 (3)
N3—C5—C4111.1 (3)O3—C8—O4126.4 (4)
O2—C6—O1125.9 (3)O3—C8—C7116.4 (3)
O2—C6—C5119.4 (3)O4—C8—C7117.2 (3)
O1—C6—C5114.6 (3)C2—N1—C1109.0 (3)
F3—C7—F1106.8 (3)C2—N2—C3108.9 (3)
C1—C3—C4—C5126.2 (4)C3—C4—C5—C6170.3 (3)
N2—C3—C4—C554.1 (5)C11—C12—C13—C14168.9 (3)
C3—C4—C5—N368.5 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O2i1.00 (6)1.99 (6)2.935 (4)157 (5)
N2—H2···O4ii0.87 (5)1.97 (6)2.838 (4)178 (4)
N3—H3A···O40.935 (11)1.855 (13)2.784 (4)172 (4)
N3—H3B···O1iii0.93 (5)1.98 (2)2.884 (4)162 (5)
N3—H3C···O50.932 (11)2.03 (3)2.832 (4)144 (5)
N4—H4···O8ii0.75 (7)1.93 (7)2.681 (5)172 (6)
N5—H5···O1iv0.79 (6)1.87 (6)2.657 (4)176 (6)
N6—H6A···O5iii0.926 (11)1.835 (16)2.740 (4)165 (4)
N6—H6B···O3v0.932 (11)1.806 (14)2.728 (4)170 (4)
N6—H6C···O80.93 (5)1.92 (2)2.827 (4)164 (7)
Symmetry codes: (i) x1, y1, z; (ii) x+1, y, z; (iii) x1, y, z; (iv) x1, y, z+1; (v) x, y+1, z.
 

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