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Acta Crystallogr Sect E Struct Rep Online. 2008 December 1; 64(Pt 12): o2354–o2355.
Published online 2008 November 13. doi:  10.1107/S1600536808037409
PMCID: PMC2959848

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

Abstract

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 [triangle]); Hübschle et al. (2007 [triangle]); Hansen & Coppens (1978 [triangle]). For the original structure determination and background information on quinolone anti­bacterial agents, see: Turel et al. (1997 [triangle]); Turel (2002 [triangle]); Mitscher (2005 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o2354-scheme1.jpg

Experimental

Crystal data

  • C17H18FN3O3·6H2O
  • M r = 439.44
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o2354-efi1.jpg
  • 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 [triangle]) T min = 0.918, T max = 0.996
  • 35927 measured reflections
  • 7766 independent reflections
  • 6705 reflections with F > 3σ(F)
  • R int = 0.037

Refinement

  • R[F 2 > 2σ(F 2)] = 0.024
  • wR(F 2) = 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

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

Table 1
Hydrogen-bond geometry (Å, °)
Table 2
Invarioms and model compounds used for aspherical refinement of the title compound

Supplementary Material

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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.

supplementary crystallographic information

Comment

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.

Experimental

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

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.

Figures

Fig. 1.
The title compound with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as spheres of arbitrary radius.

Crystal data

C17H18FN3O3·6H2OZ = 2.0
Mr = 439.44F000 = 468
Triclinic, P1Dx = 1.426 Mg m3
Hall symbol: -P 1Mo Kα radiation λ = 0.71073 Å
a = 9.5079 (3) ÅCell parameters from 9906 reflections
b = 9.9437 (3) Åθ = 2.6–35.8º
c = 11.0391 (3) ŵ = 0.12 mm1
α = 94.227 (2)ºT = 120 K
β = 100.206 (2)ºPlate, colourless
γ = 91.327 (2)º0.30 × 0.25 × 0.03 mm
V = 1023.66 (6) Å3

Data collection

Bruker APEXII diffractometer7766 independent reflections
Radiation source: Mo microsource6705 reflections with F > 3σ(F)
Monochromator: graphiteRint = 0.037
T = 120 Kθmax = 33.1º
ω scansθmin = 2.1º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)h = −14→14
Tmin = 0.918, Tmax = 0.996k = −15→15
35927 measured reflectionsl = 0→16

Refinement

Refinement on FSecondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.024All H-atom parameters refined
wR(F2) = 0.032  w1 = 1/[s2(Fo)]
S = 2.09(Δ/σ)max < 0.001
6705 reflectionsΔρmax = 0.22 e Å3
391 parametersΔρmin = −0.29 e Å3
Primary atom site location: noneExtinction correction: none

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

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)

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, °)

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, °)

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.

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

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BI2314).

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