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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 64| Part 12| December 2008| Pages o2354-o2355
doi:10.1107/S1600536808037409

Redetermination and invariom refinement of 1-cyclo­propyl-6-fluoro-4-oxo-7-(piperazin-4-ium-1-yl)-1,4-di­hydro­quinoline-3-carboxyl­ate hexa­hydrate at 120 K

Francesca P. A. Fabbiania* and Birger Dittrichb

aGeorg-August Universität Göttingen, GZG, Abteilung Kristallographie, Goldschmidtstrasse 1, 37077 Göttingen, Germany, and bGeorg-August Universität Göttingen, Institut für Anorganische Chemie, Tammannstrasse 4, 37077 Göttingen, Germany
*Correspondence e-mail: ffabbia@gwdg.de

(Received 17 October 2008; accepted 11 November 2008; online 13 November 2008)

The structure of the title compound, C17H18FN3O3·6H2O, has been redetermined at 120 K. An invariom refinement, a structural refinement using aspherical scattering factors from theoretically predicted multipole population parameters, yields accurate geometry and anisotropic displacement parameters, including hydrogen-bonding parameters. All potential hydrogen-bond donors and acceptors are involved in hydrogen bonding, forming an intricate three-dimensional network of N—H⋯O and O—H⋯O bonds.

Related literature

For related literature on the invariom refinement procedure, see: Dittrich et al. (2005[Dittrich, B., Hübschle, C. B., Messerschmidt, M., Kalinowski, R., Girnt, D. & Luger, P. (2005). Acta Cryst. A61, 314-320.]); Hübschle et al. (2007[Hübschle, C. B., Luger, P. & Dittrich, B. (2007). J. Appl. Cryst. 40, 623-627.]); Hansen & Coppens (1978[Hansen, N. K. & Coppens, P. (1978). Acta Cryst. A34, 909-921.]). For the original structure determination and background information on quinolone anti­bacterial agents, see: Turel et al. (1997[Turel, I., Bukovec, P. & Quirós, M. (1997). Int. J. Pharm. 152, 59-65.]); Turel (2002[Turel, I. (2002). Coord. Chem. Rev. 232, 27-47.]); Mitscher (2005[Mitscher, L. A. (2005). Chem. Rev. 105, 559-592.]).

[Scheme 1]

Experimental

Crystal data

  • C17H18FN3O3·6H2O

  • Mr = 439.44

  • Triclinic, [P \overline 1]

  • a = 9.5079 (3) Å

  • b = 9.9437 (3) Å

  • c = 11.0391 (3) Å

  • α = 94.227 (2)°

  • β = 100.206 (2)°

  • γ = 91.327 (2)°

  • V = 1023.66 (6) Å3

  • Z = 2.0

  • Mo Kα radiation

  • μ = 0.12 mm−1

  • T = 120 K

  • 0.30 × 0.25 × 0.03 mm
Data collection

  • Bruker APEXII diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.918, Tmax = 0.996

  • 35927 measured reflections

  • 7766 independent reflections

  • 6705 reflections with F > 3σ(F)

  • Rint = 0.037
Refinement

  • R[F2 > 2σ(F2)] = 0.024

  • wR(F2) = 0.032

  • S = 2.09

  • 6705 reflections

  • 391 parameters

  • All H-atom parameters refined

  • Δρmax = 0.22 e Å−3

  • Δρmin = −0.29 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N3—H311⋯O51i 1.02 (1) 2.53 (1) 3.0458 (8) 110 (1)
N3—H311⋯O41ii 1.02 (1) 1.98 (1) 2.8063 (7) 136 (1)
N3—H312⋯O91 1.02 (1) 1.81 (1) 2.8153 (7) 165 (1)
O41—H412⋯O1 0.96 (1) 1.84 (1) 2.8064 (6) 175 (1)
O41—H411⋯O81iii 0.93 (1) 1.89 (1) 2.8055 (8) 168 (1)
O51—H511⋯O81iii 0.96 (1) 1.87 (1) 2.8032 (8) 163 (1)
O51—H512⋯O1 0.90 (1) 1.94 (1) 2.8265 (7) 167 (1)
O61—H611⋯O71iv 0.95 (1) 1.87 (1) 2.8150 (8) 172 (1)
O61—H612⋯O71v 0.97 (1) 1.93 (1) 2.8842 (8) 168 (1)
O71—H711⋯O2 0.94 (1) 2.04 (1) 2.8392 (7) 141 (1)
O71—H711⋯O3 0.94 (1) 2.30 (1) 3.0702 (7) 138 (1)
O71—H712⋯O51vi 0.92 (1) 1.92 (1) 2.8272 (8) 166 (1)
O81—H811⋯O2vii 0.90 (1) 2.05 (1) 2.8624 (7) 149 (1)
O81—H811⋯O3vii 0.90 (1) 2.50 (1) 3.1874 (7) 133 (1)
O81—H812⋯O3 0.95 (1) 1.76 (1) 2.7104 (7) 172 (1)
O91—H911⋯O61 0.92 (1) 1.91 (1) 2.8085 (7) 168 (1)
O91—H912⋯O2v 0.94 (1) 1.79 (1) 2.7102 (6) 164 (1)
Symmetry codes: (i) x-1, y-1, z-1; (ii) -x, -y, -z+1; (iii) x+1, y, z; (iv) x, y-1, z-1; (v) -x, -y+1, -z+1; (vi) x-1, y, z; (vii) -x, -y+1, -z+2.

Table 2
Invarioms and model compounds used for aspherical refinement of the title compound

Atom label Invariom assigned Model compound
F1 F1c fluoromethane
O1, O2, O3 O1.5c[1.5o1c]− acetic acid anion
O41–O91 O1h1h water
N1, N2 N1c1c1c trimethylamine
N3 N1c1c1h1h+ N,N-dimethylammonium
C1 C1n1c1c1h 2-aminopropane
C2, C3 C1c1c1h1h propane
C4 C1.5c[1.5c1c]1.5c[1.5c1h]1n o-methylaniline
C5 C1.5n[1.5c1c]1.5c[1.5c1c]1h+ N-meth­yl-3-methylpyridinium
C6 C1.5c[1.5n1h]1.5c[1.5c1o]1c+ 3-meth­yl-4-hydroxypyridinium
C7 C1.5o1.5o1c− acetic acid anion
C8 C2o1c1c acetone
C9 C1.5c[1.5c1n]1.5c[1.5c1h]1c o-methylaniline
C10 C1.5c[1.5c1f]1.5c[1.5c1c]1h 1-fluoro-3-methylbenzene
C11 C1.5c[1.5c1n]1.5c[1.5c1h]1f 2-fluoroaniline
C12 C1.5c[1.5c1f]1.5c[1.5c1h]1n 2-fluoroaniline
C13–C16 C1n1c1h1h aminoethane
C17 C1.5c[1.5c1n]1.5c[1.5c1n]1h m-phenylenediamine
H312, H322 H1n[1c1c1h]+ dimethylammonium
H11 H1c[1n1c1c] 2-aminopropane
H21–H32 H1c[1c1c1h] propane
H51 H1c[1.5n1.5c] pyridine
H101, H171 H1c[1.5c1.5c] benzene
H131–H162 H1c[1n1c1h] aminoethane
H411–H912 H1o[1h] water

Data collection: APEX2 (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; method used to solve structure: from known coordinates (Turel et al., 1997[Turel, I., Bukovec, P. & Quirós, M. (1997). Int. J. Pharm. 152, 59-65.]); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003[Betteridge, P. W., Carruthers, J. R., Cooper, R. I., Prout, K. & Watkin, D. J. (2003). J. Appl. Cryst. 36, 1487.]) and XD (Koritsánszky et al., 2003[Koritsánszky, T., Richter, T., Macchi, P., Volkov, A., Gatti, C., Howard, S., Mallinson, P. R., Farrugia, L., Su, Z. W. & Hansen, N. K. (2003). XD. Freie Universität Berlin, Germany.]); molecular graphics: ORTEPIII (Burnett & Johnson, 1996[Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA.]); software used to prepare material for publication: XDCIF (Koritsánszky et al., 2003[Koritsánszky, T., Richter, T., Macchi, P., Volkov, A., Gatti, C., Howard, S., Mallinson, P. R., Farrugia, L., Su, Z. W. & Hansen, N. K. (2003). XD. Freie Universität Berlin, Germany.]) and publCIF (Westrip, 2008[Westrip, S. P. (2008). publCIF. In preparation.]).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808037409/bi2314sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808037409/bi2314Isup2.hkl

checkCIF report


Comment top

The title compound, commonly known as ciprofloxacin hexahydrate, belongs to the quinolone family of synthetic antibiotics (Turel, 2002; Mitscher, 2005). In this study, the structure of ciprofloxacin hexahydrate (Fig. 1), has been redetermined at 120 K using a 30 W microfocus Mo sealed tube. An invariom refinement (Dittrich et al., 2005), a structural refinement using aspherical scattering factors from theoretically predicted multipole population parameters, yields accurate ADPs and molecular geometries, including hydrogen-bonding parameters. All primary bond lengths and angles are in good agreement with those of the previously reported room-temperature structure (Turel et al.,1997), but are more precise. The crystal structure exhibits an intricate 3-D hydrogen-bonding pattern. All potential hydrogen-bond donors and acceptors are involved in hydrogen bonding: water O41, O61 and O91 accept one hydrogen bond; O51, O71, O81 and carboxyl O1 accept two; both carboxyl O2 and carbonyl O3 accept three. The majority of hydrogen bonds are linear; N3—H311, O71—H711 and O8—H811 form bifurcated ones.

Related literature top

For related literature on the invariom refinement procedure, see: Dittrich et al. (2005); Hübschle et al. (2007); Hansen & Coppens (1978). For the original structure determination and background information on quinolone antibacterial agents, see: Turel et al. (1997); Turel (2002); Mitscher (2005).

Experimental top

Ciprofloxacin (Sigma Aldrich) was used as received. Single crystals suitable for X-ray measurements were obtained by recrystallization from water by slow evaporation at room temperature.

Refinement top

The refinement was initiated with the original structure determined at ambient temperature by Turel et al. (1997) (CSD refcode COVPIN). We note that the numbering scheme in the original paper differs from that of the deposited structure. We used the same numbering scheme as in COVPIN. We also note that although the original paper reports refined H atom positions, these are not present in the deposited structure. An Independent Atom Model (IAM) refinement with CRYSTALS (Betteridge et al., 2003) provided starting values for subsequent invariom refinement (Dittrich et al., 2005), which is based on the Hansen & Coppens multipole formalism (Hansen & Coppens, 1978). This non-spherical atom refinement, which included reflections with [F > 3 σ(F)], was performed with XDLSM as included in the XD package (Koritsánszky et al., 2003). XD input files were processed with the program InvariomTool (Hübschle et al., 2007). For invariom refinement, non-spherical valence scattering contributions for atoms in an environment of simple bonds were obtained from theoretical calculations on model compounds that included nearest-neighbour atoms, whereas for H-atoms and atoms in a delocalized chemical environment, model compounds also included the next-nearest neighbour atoms (see table in the Supplementary Information). Full details for the general invariom modelling procedure of organic molecules can be found in Hübschle et al. (2007). Since in the invariom refinement the multipole parameters are fixed at theoretically predicted values, only the positional and displacement parameters were refined. Bond distances to H-atoms were freely refined due to the high quality of the data set, but can optionally be set to the values found in the model compounds, which are very close to those obtained from neutron diffraction.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: from known coordinates (Turel et al., 1997); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003) and XD (Koritsánszky et al., 2003); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: XDCIF (Koritsánszky et al., 2003) and publCIF (Westrip, 2008).

Figures top
[Figure 1] Fig. 1. The title compound with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as spheres of arbitrary radius.
1-cyclopropyl-6-fluoro-4-oxo-7-(piperazin-4-ium-1-yl)-1,4-dihydroquinoline- 3-carboxylate hexahydrate top
Crystal data top
C17H18FN3O3·6H2OZ = 2.0
Mr = 439.44F(000) = 468
Triclinic, P1Dx = 1.426 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 9.5079 (3) ÅCell parameters from 9906 reflections
b = 9.9437 (3) Åθ = 2.6–35.8°
c = 11.0391 (3) ŵ = 0.12 mm−1
α = 94.227 (2)°T = 120 K
β = 100.206 (2)°Plate, colourless
γ = 91.327 (2)°0.30 × 0.25 × 0.03 mm
V = 1023.66 (6) Å3
Data collection top
Bruker APEXII
diffractometer		7766 independent reflections
Radiation source: Mo microsource6705 reflections with F > 3σ(F)
Graphite monochromatorRint = 0.037
ω scansθmax = 33.1°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −14→14
Tmin = 0.918, Tmax = 0.996k = −15→15
35927 measured reflectionsl = 0→16
Refinement top
Refinement on FPrimary atom site location: none
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.024Hydrogen site location: difference Fourier map
wR(F2) = 0.032All H-atom parameters refined
S = 2.09 w1 = 1/[s2(Fo)]
6705 reflections(Δ/σ)max < 0.001
391 parametersΔρmax = 0.22 e Å−3
0 restraintsΔρmin = −0.29 e Å−3
Crystal data top
C17H18FN3O3·6H2Oγ = 91.327 (2)°
Mr = 439.44V = 1023.66 (6) Å3
Triclinic, P1Z = 2.0
a = 9.5079 (3) ÅMo Kα radiation
b = 9.9437 (3) ŵ = 0.12 mm−1
c = 11.0391 (3) ÅT = 120 K
α = 94.227 (2)°0.30 × 0.25 × 0.03 mm
β = 100.206 (2)°
Data collection top
Bruker APEXII
diffractometer		7766 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		6705 reflections with F > 3σ(F)
Tmin = 0.918, Tmax = 0.996Rint = 0.037
35927 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0240 restraints
wR(F2) = 0.032All H-atom parameters refined
S = 2.09Δρmax = 0.22 e Å−3
6705 reflectionsΔρmin = −0.29 e Å−3
391 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
F(1)−0.33045 (4)0.12852 (4)0.58299 (3)0.017
O(1)0.40535 (4)0.62476 (4)0.78894 (4)0.016
O(2)0.20874 (4)0.70663 (4)0.84664 (4)0.017
O(3)−0.01084 (5)0.50635 (4)0.80861 (4)0.018
O(41)0.51207 (6)0.36492 (5)0.80865 (6)0.032
O(51)0.67335 (6)0.70056 (6)0.93720 (5)0.026
O(61)−0.12179 (6)0.06543 (6)−0.12561 (5)0.028
O(71)−0.05227 (6)0.79577 (5)0.91011 (5)0.027
O(81)−0.21443 (5)0.44232 (6)0.94044 (5)0.024
O(91)−0.35014 (5)0.08636 (5)0.00415 (4)0.017
N(1)0.17346 (5)0.36898 (5)0.51490 (4)0.011
N(2)−0.22506 (5)0.04178 (5)0.37452 (4)0.011
N(3)−0.37382 (5)−0.12031 (5)0.16130 (5)0.012
C(1)0.23877 (6)0.33110 (6)0.40859 (5)0.012
C(2)0.39731 (6)0.31298 (7)0.42941 (6)0.018
C(3)0.29514 (6)0.19203 (6)0.39590 (6)0.016
C(4)0.04233 (5)0.31170 (5)0.52812 (5)0.01
C(5)0.23769 (6)0.46656 (5)0.59958 (5)0.011
C(6)0.18357 (6)0.51677 (5)0.70044 (5)0.011
C(7)0.27219 (6)0.62394 (5)0.78547 (5)0.012
C(8)0.04741 (6)0.46515 (6)0.72033 (5)0.012
C(9)−0.02011 (5)0.35741 (5)0.62955 (5)0.01
C(10)−0.14985 (6)0.29436 (6)0.64428 (5)0.012
C(11)−0.21170 (6)0.19255 (6)0.56113 (5)0.012
C(12)−0.15499 (6)0.14755 (5)0.45515 (5)0.011
C(13)−0.14735 (6)−0.01330 (6)0.27971 (5)0.012
C(14)−0.22196 (6)−0.14286 (6)0.21485 (5)0.013
C(15)−0.44960 (6)−0.06561 (6)0.26046 (5)0.013
C(16)−0.37577 (6)0.06451 (6)0.32136 (5)0.012
C(17)−0.02664 (6)0.20945 (5)0.44071 (5)0.011
H(311)−0.4250 (10)−0.2100 (10)0.1250 (10)0.043 (3)
H(312)−0.3779 (9)−0.0550 (9)0.0933 (9)0.027 (2)
H(11)0.1918 (9)0.3733 (8)0.3296 (8)0.029 (2)
H(21)0.4516 (9)0.3257 (8)0.5233 (8)0.029 (2)
H(22)0.4485 (9)0.3462 (9)0.3602 (9)0.037 (2)
H(31)0.2831 (9)0.1433 (9)0.3068 (9)0.033 (2)
H(32)0.2849 (9)0.1304 (9)0.4675 (8)0.035 (2)
H(51)0.3399 (9)0.5067 (9)0.5852 (7)0.028 (2)
H(101)−0.1957 (9)0.3228 (9)0.7198 (8)0.031 (2)
H(131)−0.0424 (9)−0.0394 (9)0.3266 (8)0.029 (2)
H(132)−0.1367 (9)0.0571 (9)0.2100 (8)0.028 (2)
H(141)−0.1715 (9)−0.1792 (9)0.1422 (8)0.030 (2)
H(142)−0.2228 (9)−0.2200 (9)0.2761 (8)0.028 (2)
H(151)−0.4442 (9)−0.1406 (9)0.3245 (8)0.034 (2)
H(152)−0.5590 (10)−0.0490 (10)0.2190 (10)0.039 (2)
H(161)−0.3774 (9)0.1389 (9)0.2537 (8)0.030 (2)
H(162)−0.4302 (9)0.0975 (8)0.3918 (8)0.031 (2)
H(171)0.0170 (8)0.1819 (8)0.3589 (8)0.022 (2)
H(411)0.6040 (10)0.3780 (10)0.8550 (10)0.039 (3)
H(412)0.4720 (10)0.4530 (10)0.8050 (10)0.041 (3)
H(511)0.7020 (10)0.6100 (10)0.9510 (10)0.041 (3)
H(512)0.5850 (10)0.6900 (10)0.8910 (10)0.039 (3)
H(611)−0.0920 (10)−0.0250 (10)−0.1190 (10)0.043 (3)
H(612)−0.0550 (10)0.1170 (10)−0.0610 (10)0.047 (3)
H(711)0.0040 (10)0.7320 (10)0.8750 (10)0.049 (3)
H(712)−0.1410 (10)0.7550 (10)0.9080 (10)0.045 (3)
H(811)−0.1790 (10)0.4090 (10)1.0130 (10)0.044 (3)
H(812)−0.1370 (10)0.4600 (10)0.8990 (10)0.040 (3)
H(911)−0.2840 (10)0.0710 (10)−0.0460 (10)0.032 (3)
H(912)−0.3176 (9)0.1646 (10)0.0559 (9)0.031 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
F(1)0.0139 (2)0.0189 (2)0.0175 (2)−0.00660 (10)0.00720 (10)−0.00390 (10)
O(1)0.0106 (2)0.0146 (2)0.0204 (2)−0.00230 (10)0.0016 (2)−0.0033 (2)
O(2)0.0155 (2)0.0133 (2)0.0198 (2)−0.0025 (2)0.0049 (2)−0.0062 (2)
O(3)0.0158 (2)0.0208 (2)0.0180 (2)−0.0067 (2)0.0095 (2)−0.0096 (2)
O(41)0.0217 (2)0.0143 (2)0.0567 (4)−0.0022 (2)0.0038 (2)0.0000 (2)
O(51)0.0192 (2)0.0240 (3)0.0313 (3)−0.0029 (2)−0.0015 (2)−0.0065 (2)
O(61)0.0268 (3)0.0282 (3)0.0281 (3)0.0032 (2)0.0103 (2)0.0013 (2)
O(71)0.0217 (2)0.0201 (2)0.0372 (3)0.0010 (2)0.0076 (2)−0.0060 (2)
O(81)0.0186 (2)0.0314 (3)0.0240 (3)0.0036 (2)0.0081 (2)0.0086 (2)
O(91)0.0157 (2)0.0172 (2)0.0161 (2)−0.0035 (2)0.0008 (2)0.0002 (2)
N(1)0.0100 (2)0.0119 (2)0.0094 (2)−0.0008 (2)0.0026 (2)0.0000 (2)
N(2)0.0087 (2)0.0111 (2)0.0125 (2)−0.0006 (2)0.0021 (2)−0.0019 (2)
N(3)0.0105 (2)0.0127 (2)0.0129 (2)−0.0005 (2)0.0007 (2)−0.0020 (2)
C(1)0.0107 (2)0.0133 (2)0.0121 (2)−0.0001 (2)0.0039 (2)−0.0003 (2)
C(2)0.0110 (2)0.0197 (3)0.0217 (3)−0.0010 (2)0.0069 (2)−0.0033 (2)
C(3)0.0140 (2)0.0145 (3)0.0196 (3)0.0016 (2)0.0053 (2)−0.0019 (2)
C(4)0.0087 (2)0.0105 (2)0.0107 (2)−0.0005 (2)0.0023 (2)−0.0009 (2)
C(5)0.0095 (2)0.0107 (2)0.0133 (2)−0.0014 (2)0.0028 (2)−0.0007 (2)
C(6)0.0097 (2)0.0102 (2)0.0123 (2)−0.0016 (2)0.0026 (2)−0.0019 (2)
C(7)0.0108 (2)0.0099 (2)0.0134 (2)−0.0012 (2)0.0022 (2)−0.0012 (2)
C(8)0.0105 (2)0.0117 (2)0.0119 (2)−0.0011 (2)0.0033 (2)−0.0032 (2)
C(9)0.0092 (2)0.0106 (2)0.0111 (2)−0.0010 (2)0.0024 (2)−0.0019 (2)
C(10)0.0101 (2)0.0139 (2)0.0130 (2)−0.0022 (2)0.0045 (2)−0.0028 (2)
C(11)0.0100 (2)0.0133 (2)0.0127 (2)−0.0022 (2)0.0041 (2)−0.0018 (2)
C(12)0.0089 (2)0.0109 (2)0.0112 (2)−0.0006 (2)0.0025 (2)−0.0016 (2)
C(13)0.0092 (2)0.0122 (2)0.0137 (2)−0.0001 (2)0.0026 (2)−0.0025 (2)
C(14)0.0111 (2)0.0114 (2)0.0153 (3)0.0009 (2)0.0006 (2)−0.0022 (2)
C(15)0.0096 (2)0.0145 (3)0.0136 (2)−0.0019 (2)0.0020 (2)−0.0016 (2)
C(16)0.0090 (2)0.0121 (2)0.0146 (3)0.0007 (2)0.0016 (2)−0.0018 (2)
C(17)0.0090 (2)0.0111 (2)0.0118 (2)−0.0013 (2)0.0019 (2)−0.0016 (2)
Geometric parameters (Å, º) top
F(1)—C(11)1.3504 (6)C(2)—C(3)1.5098 (9)
O(1)—C(7)1.2595 (7)C(2)—H(21)1.070 (9)
O(2)—C(7)1.2577 (7)C(2)—H(22)1.045 (10)
O(3)—C(8)1.2520 (7)C(3)—H(31)1.050 (9)
O(41)—H(411)0.931 (11)C(3)—H(32)1.051 (9)
O(41)—H(412)0.965 (11)C(4)—C(9)1.4093 (8)
O(51)—H(511)0.957 (11)C(4)—C(17)1.4125 (8)
O(51)—H(512)0.903 (11)C(5)—C(6)1.3738 (8)
O(61)—H(611)0.948 (12)C(5)—H(51)1.084 (9)
O(61)—H(612)0.969 (12)C(6)—C(7)1.5023 (8)
O(71)—H(711)0.941 (12)C(6)—C(8)1.4400 (7)
O(71)—H(712)0.922 (11)C(8)—C(9)1.4650 (8)
O(81)—H(811)0.904 (11)C(9)—C(10)1.4110 (7)
O(81)—H(812)0.952 (11)C(10)—C(11)1.3629 (8)
O(91)—H(911)0.919 (10)C(10)—H(101)1.031 (9)
O(91)—H(912)0.943 (10)C(11)—C(12)1.4205 (8)
N(1)—C(1)1.4523 (7)C(12)—C(17)1.3933 (7)
N(1)—C(4)1.3940 (7)C(13)—C(14)1.5222 (8)
N(1)—C(5)1.3509 (7)C(13)—H(131)1.086 (9)
N(2)—C(12)1.4006 (7)C(13)—H(132)1.094 (9)
N(2)—C(13)1.4663 (7)C(14)—H(141)1.052 (9)
N(3)—H(311)1.026 (12)C(14)—H(142)1.060 (9)
N(3)—H(312)1.025 (10)C(15)—C(16)1.5103 (8)
N(2)—C(16)1.4782 (7)C(15)—H(151)1.061 (9)
N(3)—C(14)1.4889 (7)C(15)—H(152)1.084 (10)
N(3)—C(15)1.4910 (8)C(16)—H(161)1.087 (9)
C(1)—C(2)1.5010 (8)C(16)—H(162)1.046 (9)
C(1)—C(3)1.5004 (8)C(17)—H(171)1.079 (8)
C(1)—H(11)1.030 (9)
H(411)—O(41)—H(412)105.7 (8)O(3)—C(8)—C(9)121.14 (5)
H(511)—O(51)—H(512)104.1 (8)C(6)—C(8)—C(9)115.11 (5)
H(611)—O(61)—H(612)103.5 (8)C(4)—C(9)—C(8)121.95 (5)
H(711)—O(71)—H(712)107.6 (8)C(4)—C(9)—C(10)118.27 (5)
H(811)—O(81)—H(812)108.2 (8)C(8)—C(9)—C(10)119.77 (5)
H(911)—O(91)—H(912)106.5 (7)C(9)—C(10)—C(11)119.92 (5)
C(1)—N(1)—C(4)121.37 (5)C(9)—C(10)—H(101)120.0 (5)
C(1)—N(1)—C(5)119.24 (4)C(11)—C(10)—H(101)120.1 (5)
C(4)—N(1)—C(5)119.30 (5)F(1)—C(11)—C(10)118.14 (5)
C(12)—N(2)—C(13)116.04 (4)F(1)—C(11)—C(12)118.45 (5)
H(311)—N(3)—H(312)109.3 (7)C(10)—C(11)—C(12)123.38 (5)
N(1)—C(1)—C(2)118.16 (5)N(2)—C(12)—C(11)119.72 (5)
N(1)—C(1)—C(3)118.70 (5)N(2)—C(12)—C(17)123.50 (5)
N(1)—C(1)—H(11)113.4 (5)C(11)—C(12)—C(17)116.72 (5)
C(2)—C(1)—C(3)60.40 (4)N(2)—C(13)—C(14)110.41 (4)
C(2)—C(1)—H(11)118.3 (5)N(2)—C(13)—H(131)107.3 (4)
C(3)—C(1)—H(11)118.1 (5)N(2)—C(13)—H(132)113.1 (4)
C(1)—C(2)—C(3)59.78 (4)C(14)—C(13)—H(131)107.3 (4)
C(1)—C(2)—H(21)116.0 (4)C(14)—C(13)—H(132)108.5 (4)
C(1)—C(2)—H(22)114.8 (5)H(131)—C(13)—H(132)110.1 (6)
C(3)—C(2)—H(21)116.1 (4)C(13)—C(14)—H(141)111.0 (5)
C(3)—C(2)—H(22)117.3 (5)C(13)—C(14)—H(142)112.0 (4)
H(21)—C(2)—H(22)119.0 (6)H(141)—C(14)—H(142)108.1 (6)
C(1)—C(3)—C(2)59.82 (4)N(3)—C(14)—C(13)111.14 (5)
C(1)—C(3)—H(31)117.8 (5)N(3)—C(14)—H(141)107.5 (4)
C(1)—C(3)—H(32)115.7 (5)N(3)—C(14)—H(142)106.9 (4)
C(2)—C(3)—H(31)118.9 (5)N(3)—C(15)—C(16)109.86 (5)
C(2)—C(3)—H(32)116.4 (5)N(3)—C(15)—H(151)105.8 (5)
H(31)—C(3)—H(32)116.3 (7)N(3)—C(15)—H(152)108.2 (5)
N(1)—C(4)—C(9)119.07 (5)C(16)—C(15)—H(151)110.8 (5)
N(1)—C(4)—C(17)120.24 (5)C(16)—C(15)—H(152)111.0 (5)
C(9)—C(4)—C(17)120.69 (5)H(151)—C(15)—H(152)111.1 (7)
N(1)—C(5)—C(6)125.09 (5)N(2)—C(16)—C(15)110.46 (5)
N(1)—C(5)—H(51)116.1 (4)N(2)—C(16)—H(161)108.3 (4)
C(6)—C(5)—H(51)118.8 (4)N(2)—C(16)—H(162)109.6 (5)
C(5)—C(6)—C(7)117.23 (5)C(15)—C(16)—H(161)110.0 (4)
C(5)—C(6)—C(8)119.45 (5)C(15)—C(16)—H(162)107.3 (5)
C(7)—C(6)—C(8)123.32 (5)H(161)—C(16)—H(162)111.2 (6)
O(1)—C(7)—O(2)124.85 (5)C(4)—C(17)—C(12)120.94 (5)
O(1)—C(7)—C(6)117.03 (5)C(4)—C(17)—H(171)120.0 (4)
O(2)—C(7)—C(6)118.12 (5)C(12)—C(17)—H(171)119.0 (4)
O(3)—C(8)—C(6)123.75 (5)
C(4)—N(1)—C(1)—C(2)−139.1 (1)N(1)—C(4)—C(17)—C(12)177.5 (1)
C(4)—N(1)—C(1)—C(3)−69.3 (1)N(1)—C(4)—C(17)—H(171)−5.7 (5)
C(1)—N(1)—C(4)—C(9)−176.5 (1)C(17)—C(4)—C(9)—C(8)−178.7 (1)
C(1)—N(1)—C(4)—C(17)3.4 (1)C(17)—C(4)—C(9)—C(10)2.7 (1)
C(4)—N(1)—C(1)—H(11)76.0 (6)C(9)—C(4)—C(17)—C(12)−2.6 (1)
C(5)—N(1)—C(1)—C(2)44.2 (1)C(9)—C(4)—C(17)—H(171)174.2 (5)
C(5)—N(1)—C(1)—C(3)114.0 (1)N(1)—C(5)—C(6)—C(7)179.0 (1)
C(1)—N(1)—C(5)—C(6)176.3 (1)N(1)—C(5)—C(6)—C(8)−0.6 (1)
C(5)—N(1)—C(1)—H(11)−100.6 (6)H(51)—C(5)—C(6)—C(7)−0.8 (6)
C(1)—N(1)—C(5)—H(51)−3.9 (6)H(51)—C(5)—C(6)—C(8)179.5 (6)
C(4)—N(1)—C(5)—C(6)−0.4 (1)C(5)—C(6)—C(7)—O(1)−26.4 (1)
C(5)—N(1)—C(4)—C(9)0.1 (1)C(5)—C(6)—C(7)—O(2)152.9 (1)
C(5)—N(1)—C(4)—C(17)−179.9 (1)C(5)—C(6)—C(8)—O(3)−178.9 (1)
C(4)—N(1)—C(5)—H(51)179.4 (6)C(5)—C(6)—C(8)—C(9)1.8 (1)
C(13)—N(2)—C(12)—C(11)−170.1 (1)C(8)—C(6)—C(7)—O(1)153.3 (1)
C(12)—N(2)—C(13)—C(14)169.4 (1)C(8)—C(6)—C(7)—O(2)−27.5 (1)
C(13)—N(2)—C(12)—C(17)7.0 (1)C(7)—C(6)—C(8)—O(3)1.4 (1)
C(12)—N(2)—C(13)—H(131)52.8 (5)C(7)—C(6)—C(8)—C(9)−177.9 (1)
C(12)—N(2)—C(13)—H(132)−68.8 (5)O(3)—C(8)—C(9)—C(4)178.6 (1)
N(1)—C(1)—C(2)—C(3)108.8 (1)O(3)—C(8)—C(9)—C(10)−2.9 (1)
N(1)—C(1)—C(2)—H(21)2.4 (6)C(6)—C(8)—C(9)—C(4)−2.1 (1)
N(1)—C(1)—C(2)—H(22)−142.7 (6)C(6)—C(8)—C(9)—C(10)176.4 (1)
N(1)—C(1)—C(3)—C(2)−107.9 (1)C(4)—C(9)—C(10)—C(11)−0.3 (1)
N(1)—C(1)—C(3)—H(31)143.1 (6)C(4)—C(9)—C(10)—H(101)177.3 (6)
N(1)—C(1)—C(3)—H(32)−1.1 (6)C(8)—C(9)—C(10)—C(11)−178.9 (1)
C(2)—C(1)—C(3)—C(2)0.0 (1)C(8)—C(9)—C(10)—H(101)−1.3 (6)
C(3)—C(1)—C(2)—C(3)0.0 (1)C(9)—C(10)—C(11)—F(1)175.5 (1)
C(3)—C(1)—C(2)—H(21)−106.5 (6)C(9)—C(10)—C(11)—C(12)−2.3 (1)
C(3)—C(1)—C(2)—H(22)108.4 (6)H(101)—C(10)—C(11)—F(1)−2.1 (6)
C(2)—C(1)—C(3)—H(31)−109.0 (6)H(101)—C(10)—C(11)—C(12)−179.9 (6)
C(2)—C(1)—C(3)—H(32)106.9 (6)F(1)—C(11)—C(12)—N(2)1.9 (1)
H(11)—C(1)—C(2)—C(3)−108.1 (6)F(1)—C(11)—C(12)—C(17)−175.4 (1)
H(11)—C(1)—C(2)—H(21)145.5 (8)C(10)—C(11)—C(12)—N(2)179.8 (1)
H(11)—C(1)—C(2)—H(22)0.4 (8)C(10)—C(11)—C(12)—C(17)2.4 (1)
H(11)—C(1)—C(3)—C(2)108.3 (6)N(2)—C(12)—C(17)—C(4)−177.2 (1)
H(11)—C(1)—C(3)—H(31)−0.7 (8)N(2)—C(12)—C(17)—H(171)6.0 (5)
H(11)—C(1)—C(3)—H(32)−144.8 (8)C(11)—C(12)—C(17)—C(4)0.1 (1)
C(1)—C(2)—C(3)—C(1)0.0 (1)C(11)—C(12)—C(17)—H(171)−176.8 (5)
C(1)—C(2)—C(3)—H(31)107.1 (6)N(2)—C(13)—C(14)—H(141)175.7 (6)
C(1)—C(2)—C(3)—H(32)−105.8 (6)N(2)—C(13)—C(14)—H(142)−63.4 (5)
H(21)—C(2)—C(3)—C(1)106.2 (6)H(131)—C(13)—C(14)—H(141)−67.7 (7)
H(21)—C(2)—C(3)—H(31)−146.6 (8)H(131)—C(13)—C(14)—H(142)53.2 (7)
H(21)—C(2)—C(3)—H(32)0.4 (8)H(132)—C(13)—C(14)—H(141)51.3 (7)
H(22)—C(2)—C(3)—C(1)−104.2 (6)H(132)—C(13)—C(14)—H(142)172.2 (7)
H(22)—C(2)—C(3)—H(31)2.9 (9)H(151)—C(15)—C(16)—H(161)177.2 (7)
H(22)—C(2)—C(3)—H(32)150.0 (8)H(151)—C(15)—C(16)—H(162)−61.7 (8)
N(1)—C(4)—C(9)—C(8)1.2 (1)H(152)—C(15)—C(16)—H(161)−58.9 (8)
N(1)—C(4)—C(9)—C(10)−177.4 (1)H(152)—C(15)—C(16)—H(162)62.2 (8)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N(3)—H(311)···O(51)i1.03 (1)2.53 (1)3.0458 (8)110 (1)
N(3)—H(311)···O(41)ii1.03 (1)1.98 (1)2.8063 (7)136 (1)
N(3)—H(312)···O(91)1.02 (1)1.81 (1)2.8153 (7)165 (1)
O(41)—H(412)···O(1)0.96 (1)1.85 (1)2.8064 (6)175 (1)
O(41)—H(411)···O(81)iii0.93 (1)1.89 (1)2.8055 (8)168 (1)
O(51)—H(511)···O(81)iii0.96 (1)1.87 (1)2.8032 (8)163 (1)
O(51)—H(512)···O(1)0.90 (1)1.94 (1)2.8265 (7)167 (1)
O(61)—H(611)···O(71)iv0.95 (1)1.87 (1)2.8150 (8)172 (1)
O(61)—H(612)···O(71)v0.97 (1)1.93 (1)2.8842 (8)168 (1)
O(71)—H(711)···O(2)0.94 (1)2.04 (1)2.8392 (7)141 (1)
O(71)—H(711)···O(3)0.94 (1)2.30 (1)3.0702 (7)138 (1)
O(71)—H(712)···O(51)vi0.92 (1)1.92 (1)2.8272 (8)166 (1)
O(81)—H(811)···O(2)vii0.90 (1)2.05 (1)2.8624 (7)149 (1)
O(81)—H(811)···O(3)vii0.90 (1)2.50 (1)3.1874 (7)133 (1)
O(81)—H(812)···O(3)0.95 (1)1.76 (1)2.7104 (7)172 (1)
O(91)—H(911)···O(61)0.92 (1)1.91 (1)2.8085 (7)168 (1)
O(91)—H(912)···O(2)v0.94 (1)1.79 (1)2.7102 (6)164 (1)
Symmetry codes: (i) x−1, y−1, z−1; (ii) −x, −y, −z+1; (iii) x+1, y, z; (iv) x, y−1, z−1; (v) −x, −y+1, −z+1; (vi) x−1, y, z; (vii) −x, −y+1, −z+2.

Experimental details

Crystal data
Chemical formulaC17H18FN3O3·6H2O
Mr439.44
Crystal system, space groupTriclinic, P1
Temperature (K)120
a, b, c (Å)9.5079 (3), 9.9437 (3), 11.0391 (3)
α, β, γ (°)94.227 (2), 100.206 (2), 91.327 (2)
V (Å3)1023.66 (6)
Z2.0
Radiation typeMo Kα
µ (mm−1)0.12
Crystal size (mm)0.30 × 0.25 × 0.03
Data collection
DiffractometerBruker APEXII
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.918, 0.996
No. of measured, independent and
observed [F > 3σ(F)] reflections		35927, 7766, 6705
Rint0.037
(sin θ/λ)max (Å−1)0.769
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.024, 0.032, 2.09
No. of reflections6705
No. of parameters391
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å−3)0.22, −0.29

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), from known coordinates (Turel et al., 1997), CRYSTALS (Betteridge et al., 2003) and XD (Koritsánszky et al., 2003), ORTEPIII (Burnett & Johnson, 1996), XDCIF (Koritsánszky et al., 2003) and publCIF (Westrip, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N(3)—H(311)···O(51)i1.025 (10)2.533 (10)3.0458 (8)110.4 (7)
N(3)—H(311)···O(41)ii1.025 (10)1.979 (10)2.8063 (7)135.8 (9)
N(3)—H(312)···O(91)1.024 (9)1.814 (9)2.8153 (7)164.6 (8)
O(41)—H(412)···O(1)0.964 (10)1.845 (10)2.8064 (6)175.2 (9)
O(41)—H(411)···O(81)iii0.932 (10)1.887 (10)2.8055 (8)168.0 (9)
O(51)—H(511)···O(81)iii0.962 (10)1.868 (10)2.8032 (8)163.4 (9)
O(51)—H(512)···O(1)0.902 (10)1.941 (10)2.8265 (7)167.1 (9)
O(61)—H(611)···O(71)iv0.953 (10)1.869 (10)2.8150 (8)171.6 (9)
O(61)—H(612)···O(71)v0.972 (10)1.927 (11)2.8842 (8)167.8 (9)
O(71)—H(711)···O(2)0.944 (10)2.044 (10)2.8392 (7)140.8 (8)
O(71)—H(711)···O(3)0.944 (10)2.302 (10)3.0702 (7)138.1 (8)
O(71)—H(712)···O(51)vi0.923 (10)1.922 (10)2.8272 (8)166.2 (9)
O(81)—H(811)···O(2)vii0.902 (11)2.050 (10)2.8624 (7)149.1 (9)
O(81)—H(811)···O(3)vii0.902 (11)2.504 (10)3.1874 (7)132.9 (8)
O(81)—H(812)···O(3)0.953 (10)1.764 (10)2.7104 (7)171.8 (9)
O(91)—H(911)···O(61)0.917 (10)1.906 (10)2.8085 (7)167.9 (9)
O(91)—H(912)···O(2)v0.942 (10)1.791 (10)2.7102 (6)164.1 (8)
Symmetry codes: (i) x−1, y−1, z−1; (ii) −x, −y, −z+1; (iii) x+1, y, z; (iv) x, y−1, z−1; (v) −x, −y+1, −z+1; (vi) x−1, y, z; (vii) −x, −y+1, −z+2.
Invarioms and model compounds used for aspherical refinement of the title compound top
Atom labelInvariom assignedModel compound
F1F1cfluoromethane
O1, O2, O3O1.5c[1.5o1c]-acetic acid anion
O41–O91O1h1hwater
N1, N2N1c1c1ctrimethylamine
N3N1c1c1h1h+N,N-dimethylammonium
C1C1n1c1c1h2-aminopropane
C2, C3C1c1c1h1hpropane
C4C1.5c[1.5c1c]1.5c[1.5c1h]1no-methylaniline
C5C1.5n[1.5c1c]1.5c[1.5c1c]1h+N-methyl-3-methylpyridinium
C6C1.5c[1.5n1h]1.5c[1.5c1o]1c+3-methyl-4-hydroxypyridinium
C7C1.5o1.5o1c-acetic acid anion
C8C2o1c1cacetone
C9C1.5c[1.5c1n]1.5c[1.5c1h]1co-methylaniline
C10C1.5c[1.5c1f]1.5c[1.5c1c]1h1-fluoro-3-methylbenzene
C11C1.5c[1.5c1n]1.5c[1.5c1h]1f2-fluoroaniline
C12C1.5c[1.5c1f]1.5c[1.5c1h]1n2-fluoroaniline
C13–C16C1n1c1h1haminoethane
C17C1.5c[1.5c1n]1.5c[1.5c1n]1hm-phenylenediamine
H312, H322H1n[1c1c1h]+dimethylammonium
H11H1c[1n1c1c]2-aminopropane
H21–H32H1c[1c1c1h]propane
H51H1c[1.5n1.5c]pyridine
H101, H171H1c[1.5c1.5c]benzene
H131–H162H1c[1n1c1h]aminoethane
H411–H912H1o[1h]water
 

Acknowledgements

FPAF thanks the Alexander von Humboldt Foundation for the award of a Postdoctoral Fellowship. BD thanks the DFG for the award of an Emmy Noether Fellowship (DI 921/3–1). We also thank Professor Dietmar Stalke (Göttingen) for diffractometer time and Professor Alastair Florence (Strathclyde) for providing the starting material.

References

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ISSN: 2056-9890
Volume 64| Part 12| December 2008| Pages o2354-o2355
doi:10.1107/S1600536808037409
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