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

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.

Key indicators

• Single-crystal X-ray study
• T = 120 K
• Mean [sigma](C-C) = 0.001 Å
• R factor = 0.024
• wR factor = 0.032
• Data-to-parameter ratio = 17.1

checkCIF/PLATON results

No syntax errors found



Alert level A
DIFF020_ALERT_1_A  _diffrn_standards_interval_count and
            _diffrn_standards_interval_time are missing. Number of measurements
            between standards or time (min) between standards.
DIFF022_ALERT_1_A  _diffrn_standards_decay_% is missing
            Percentage decrease in standards intensity.

Alert level C
            Value of measurement temperature given =   120.000
            Value of melting point given =     0.000
GOODF01_ALERT_2_C  The least squares goodness of fit parameter lies
            outside the range 0.80 <> 2.00
            Goodness of fit given =      2.089
PLAT087_ALERT_2_C Unsatisfactory S value (Too High) ..............       2.09
PLAT353_ALERT_3_C Long    N-H Bond (0.87A)   N3     -   H311   ...       1.02 Ang.
PLAT353_ALERT_3_C Long    N-H Bond (0.87A)   N3     -   H312   ...       1.02 Ang.
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT153_ALERT_1_C The su's on the Cell Axes   are Equal (x 100000)         30 Ang.
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)        200 Deg.
PLAT703_ALERT_1_C Torsion Calc   153.24(5), Rep  153.30(10), Dev..       1.20 Sigma
              C(8)-C(6)-C(7)-O(1)   1.555   1.555   1.555   1.555
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          4
              H2 O
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          6
              H2 O
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          7
              H2 O

   2 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
  11 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   6 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. 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.

Related literature

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).

S2. 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.

S3. 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.

Computing details

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

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

Crystal data

C17H18FN3O3·6H2O	Z = 2.0
Mr = 439.44	F(000) = 468
Triclinic, P1	Dx = 1.426 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.5079 (3) Å	Cell parameters from 9906 reflections
b = 9.9437 (3) Å	θ = 2.6–35.8°
c = 11.0391 (3) Å	µ = 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) Å^3

Data collection

Bruker APEXII diffractometer	7766 independent reflections
Radiation source: Mo microsource	6705 reflections with F > 3σ(F)
Graphite monochromator	Rint = 0.037
ω scans	θmax = 33.1°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→14
Tmin = 0.918, Tmax = 0.996	k = −15→15
35927 measured reflections	l = 0→16

Refinement

Refinement on F	Primary atom site location: none
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.024	Hydrogen site location: difference Fourier map
wR(F^2) = 0.032	All H-atom parameters refined
S = 2.09	w1 = 1/[s^2(Fo)]
6705 reflections	(Δ/σ)max < 0.001
391 parameters	Δρmax = 0.22 e Å^−3
0 restraints	Δρmin = −0.29 e Å^−3

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

	x	y	z	Uiso*/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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

D—H···A	D—H	H···A	D···A	D—H···A
N(3)—H(311)···O(51)^i	1.03 (1)	2.53 (1)	3.0458 (8)	110 (1)
N(3)—H(311)···O(41)^ii	1.03 (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)^iii	0.93 (1)	1.89 (1)	2.8055 (8)	168 (1)
O(51)—H(511)···O(81)^iii	0.96 (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)^iv	0.95 (1)	1.87 (1)	2.8150 (8)	172 (1)
O(61)—H(612)···O(71)^v	0.97 (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)^vi	0.92 (1)	1.92 (1)	2.8272 (8)	166 (1)
O(81)—H(811)···O(2)^vii	0.90 (1)	2.05 (1)	2.8624 (7)	149 (1)
O(81)—H(811)···O(3)^vii	0.90 (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)^v	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.