7-[(7S)-7-Aza­niumyl-5-aza­spiro­[2.4]hept-5-yl]-8-chloro-6-fluoro-1-[(1S,2R)-2-fluoro­cyclo­prop­yl]-4-oxo-1,4-dihydroquinoline-3-carboxyl­ate methanol monosolvate

Xu, W.-J.; Qiu, X.-H.; Hua, H.-J.; Tan, S.-D.; Ding, H.-Y.

doi:10.1107/S160053681203632X

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 9| September 2012| Page o2794

doi:10.1107/S160053681203632X

Open

access

7-[(7S)-7-Azaniumyl-5-azaspiro[2.4]hept-5-yl]-8-chloro-6-fluoro-1-[(1S,2R)-2-fluorocyclopropyl]-4-oxo-1,4-dihydroquinoline-3-carboxylate methanol monosolvate

Wen-jie Xu,^a Xue-hui Qiu,^a Huai-jie Hua,^a Song-de Tan ^a and Hai-yan Ding ^b ^*

^aShenzhen Salubris Pharmaceuticals Co. Ltd, Guangdong Shenzhen 361021, People's Republic of China, and ^bGuangzhou Institutes of Biomedicine and Health, Chinese Academy of Sciences, Guanzhou, Guangdong 510530, People's Republic of China
^*Correspondence e-mail: ding_haiyan@gibh.ac.cn

(Received 17 August 2012; accepted 20 August 2012; online 25 August 2012)

Sitafloxacin is a newly developed fluoroquinolone antibacterial drug. The crystal studied, C₁₉H₁₈ClF₂N₃O₃·CH₃OH, consists of one molecule of sitafloxacin and one methanol solvent molecule. The molecule of sitafloxacin is a zwitterion with a protonated primary amine group and a deprotonated carboxylate group. The cyclopropane ring and the CO₂ group make dihedral angles of 79.5 (3) and 35.4 (4)°, respectively, with the fused ring system. The supramolecular structure is defined by N—H⋯O and O—H⋯O hydrogen bonds.

Related literature

For the synthesis, applications and pseudopolymorphic structure of the title compound, see: Yamazaki et al. (1998 ), Suzuki et al. (2000 ) and Suzuki et al. (2010 ), respectively.

Experimental

Crystal data

C₁₉H₁₈ClF₂N₃O₃·CH₄O
M_r = 441.86
Monoclinic, P 2₁
a = 8.7455 (3) Å
b = 8.2968 (3) Å
c = 14.0638 (4) Å
β = 104.474 (3)°
V = 988.07 (5) Å³
Z = 2
Cu Kα radiation
μ = 2.18 mm⁻¹
T = 293 K
0.2 × 0.1 × 0.05 mm

Data collection

Agilent Xcalibur Sapphire3 Gemini ultra diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ) T_min = 0.990, T_max = 1.000
5115 measured reflections
2745 independent reflections
2537 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.100
S = 1.08
2745 reflections
273 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.21 e Å⁻³
Absolute structure: Flack, (1983 ), 856 Friedel pairs
Flack parameter: −0.024 (19)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O3ⁱ	0.89	2.07	2.929 (3)	161
N3—H3A⋯O2ⁱ	0.89	2.43	3.022 (3)	124
O4—H4O⋯O3ⁱⁱ	0.82	1.84	2.654 (4)	173
N3—H3C⋯O2ⁱⁱⁱ	0.89	1.82	2.675 (4)	159
N3—H3B⋯O4	0.89	1.91	2.788 (4)	171
Symmetry codes: (i) x+1, y, z+1; (ii) $[-x+1, y-{\script{1\over 2}}, -z+1]$ ; (iii) $[-x+1, y+{\script{1\over 2}}, -z+1]$ .

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: OLEX2 (Dolomanov et al., 2009 ); program(s) used to refine structure: OLEX2; molecular graphics: OLEX2; software used to prepare material for publication: OLEX2.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681203632X/go2064sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681203632X/go2064Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681203632X/go2064Isup3.cml

checkCIF report

Comment top

Three hydrate forms (hemihydrate, monohydrade and sesqiuhydrate) and three anhydrate forms (alpha,beta and gamma forms) of sitafloxacin crystals have been found so far. The polymorphic and pseudopolymorphic crystals show different physicochemical properties (Yamazaki et al., 1998, Suzuki et al., 2000). The crystal structures of the beta form, the monohydrate and the sesquihydrate have been already reported (Yamazaki et al., 1998, Suzuki et al., 2000). Preparation of the title compound has been reported earlier (Suzuki et al., 2010). In this paper, we report the X-ray crystal structure of the title compound. All donor H atoms are involved in the hydrogen bonding as well as all acceptor O atoms with exception made for O1, Table 1.

Related literature top

For the synthesis, applications and pseudopolymorphic structure of the title compound, see: Yamazaki et al. (1998), Suzuki et al. (2000) and Suzuki et al. (2010), respectively.

Experimental top

The preparation of the titled compound was made following a similar procedure described earlier (Suzuki et al., 2010). The 7-[(7S)-7-Boc-NH-5-azaspiro[2.4]hept-5-yl]-6-fluoro-1-[(1S,2R)-2- fluorocyclopropyl]-1,4-dihydro-4-oxo-3-quinolinecarboxylic acid reacted with thionyl chloride in dichloromethane for 8 h. The yield was 78%. The Boc functional group was removed with trifluoroacetic acid,. The resulting solution was concentrated, washed giving the colorless crystals of the title compound, yield: 68%. 0.2g of this material was dissolved in 20 ml of methanol at 323K. Slow evaporation gave needle-like crystals suitable for X-ray analysis.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: OLEX2 (Dolomanov et al., 2009); program(s) used to refine structure: OLEX2 (Dolomanov et al., 2009); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top

Figure 1. The molecular structure of the title compound showing the atom numbering scheme. Hydrogen bonds are shown as dashed lines and displacement ellipsoids are drawn at the 50% probability level.

7-[(7S)-7-Azaniumyl-5-azaspiro[2.4]hept-5-yl]-8-chloro-6-fluoro-1- [(1S,2R)-2-fluorocyclopropyl]-4-oxo-1,4-dihydroquinoline- 3-carboxylate methanol monosolvate top

Crystal data top

C₁₉H₁₈ClF₂N₃O₃·CH₄O	F(000) = 460
M_r = 441.86	D_x = 1.485 Mg m⁻³
Monoclinic, P2₁	Cu Kα radiation, λ = 1.54184 Å
a = 8.7455 (3) Å	θ = 3.3–66.9°
b = 8.2968 (3) Å	µ = 2.18 mm⁻¹
c = 14.0638 (4) Å	T = 293 K
β = 104.474 (3)°	Block, colourless
V = 988.07 (5) Å³	0.2 × 0.1 × 0.05 mm
Z = 2

Data collection top

Agilent Xcalibur Sapphire3 Gemini ultra diffractometer	2745 independent reflections
Radiation source: fine-focus sealed tube	2537 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
ω scans	θ_max = 66.9°, θ_min = 3.3°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	h = −9→10
T_min = 0.990, T_max = 1.000	k = −9→9
5115 measured reflections	l = −15→16

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.038	H-atom parameters constrained
wR(F²) = 0.100	w = 1/[σ²(F_o²) + (0.0582P)² + 0.0956P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
2745 reflections	Δρ_max = 0.21 e Å⁻³
273 parameters	Δρ_min = −0.21 e Å⁻³
1 restraint	Absolute structure: Flack, (1983), 856 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.024 (19)

Crystal data top

C₁₉H₁₈ClF₂N₃O₃·CH₄O	V = 988.07 (5) Å³
M_r = 441.86	Z = 2
Monoclinic, P2₁	Cu Kα radiation
a = 8.7455 (3) Å	µ = 2.18 mm⁻¹
b = 8.2968 (3) Å	T = 293 K
c = 14.0638 (4) Å	0.2 × 0.1 × 0.05 mm
β = 104.474 (3)°

Data collection top

Agilent Xcalibur Sapphire3 Gemini ultra diffractometer	2745 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	2537 reflections with I > 2σ(I)
T_min = 0.990, T_max = 1.000	R_int = 0.033
5115 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	H-atom parameters constrained
wR(F²) = 0.100	Δρ_max = 0.21 e Å⁻³
S = 1.08	Δρ_min = −0.21 e Å⁻³
2745 reflections	Absolute structure: Flack, (1983), 856 Friedel pairs
273 parameters	Absolute structure parameter: −0.024 (19)
1 restraint

Special details top

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

	x	y	z	U_iso*/U_eq
Cl1	0.85678 (8)	0.70137 (11)	0.46653 (5)	0.02508 (19)
F1	0.4439 (2)	0.5006 (3)	0.63177 (12)	0.0273 (5)
F2	0.7157 (2)	0.3005 (3)	0.33304 (16)	0.0357 (5)
N1	0.5964 (3)	0.6077 (3)	0.27925 (18)	0.0203 (6)
N2	0.7559 (3)	0.5849 (4)	0.63790 (17)	0.0230 (6)
N3	0.9156 (3)	0.6914 (4)	0.89555 (17)	0.0243 (6)
H3A	1.0152	0.6728	0.9281	0.036*
H3B	0.8519	0.6240	0.9165	0.036*
H3C	0.8899	0.7925	0.9060	0.036*
O1	0.1338 (2)	0.5512 (3)	0.28669 (16)	0.0259 (5)
O2	0.0906 (2)	0.5100 (3)	0.07641 (15)	0.0263 (5)
O3	0.2332 (2)	0.6989 (3)	0.02739 (14)	0.0258 (5)
C1	0.4763 (4)	0.6164 (4)	0.1961 (2)	0.0210 (7)
H1A	0.5039	0.6322	0.1371	0.025*
C2	0.3199 (4)	0.6040 (4)	0.1921 (2)	0.0225 (7)
C3	0.2715 (3)	0.5742 (4)	0.2817 (2)	0.0211 (7)
C4	0.3635 (4)	0.5465 (4)	0.4621 (2)	0.0228 (7)
H4A	0.2589	0.5322	0.4642	0.027*
C5	0.4807 (4)	0.5417 (4)	0.5467 (2)	0.0209 (7)
C6	0.6391 (4)	0.5778 (4)	0.5504 (2)	0.0225 (7)
C7	0.6742 (3)	0.6140 (4)	0.4608 (2)	0.0213 (7)
C8	0.5596 (4)	0.5974 (4)	0.3706 (2)	0.0200 (7)
C9	0.4007 (3)	0.5730 (4)	0.3720 (2)	0.0205 (7)
C10	0.8951 (4)	0.4780 (5)	0.6564 (2)	0.0253 (8)
H10A	0.9615	0.5022	0.6124	0.030*
H10B	0.8639	0.3656	0.6490	0.030*
C11	0.9791 (3)	0.5169 (4)	0.7627 (2)	0.0208 (7)
C12	0.8986 (3)	0.6661 (4)	0.7881 (2)	0.0202 (7)
H12A	0.9402	0.7607	0.7612	0.024*
C13	0.7270 (4)	0.6385 (4)	0.7308 (2)	0.0232 (7)
H13A	0.6757	0.5561	0.7607	0.028*
H13B	0.6655	0.7371	0.7233	0.028*
C14	1.0352 (4)	0.3823 (4)	0.8350 (2)	0.0243 (7)
H14A	1.0215	0.2725	0.8107	0.029*
H14B	1.0249	0.3966	0.9016	0.029*
C15	1.1523 (4)	0.4884 (5)	0.8009 (2)	0.0275 (8)
H15A	1.2122	0.5658	0.8472	0.033*
H15B	1.2088	0.4418	0.7564	0.033*
C16	0.7537 (3)	0.5663 (4)	0.2680 (2)	0.0207 (7)
H16A	0.8311	0.6541	0.2790	0.025*
C17	0.8167 (4)	0.4026 (5)	0.3007 (2)	0.0255 (8)
H17A	0.9297	0.3938	0.3324	0.031*
C18	0.7710 (4)	0.4402 (5)	0.1939 (2)	0.0274 (8)
H18A	0.6755	0.3911	0.1543	0.033*
H18B	0.8549	0.4544	0.1607	0.033*
C19	0.2061 (4)	0.6049 (4)	0.0915 (2)	0.0226 (7)
O4	0.6931 (2)	0.5098 (3)	0.96034 (16)	0.0306 (6)
H4O	0.7168	0.4143	0.9593	0.046*
C20	0.5279 (4)	0.5273 (6)	0.9249 (3)	0.0400 (10)
H20A	0.4963	0.4929	0.8577	0.060*
H20B	0.4996	0.6383	0.9293	0.060*
H20C	0.4755	0.4625	0.9638	0.060*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0194 (3)	0.0357 (5)	0.0191 (3)	−0.0057 (3)	0.0029 (3)	−0.0007 (4)
F1	0.0257 (10)	0.0426 (13)	0.0147 (9)	−0.0042 (9)	0.0073 (7)	0.0033 (9)
F2	0.0397 (11)	0.0307 (12)	0.0426 (12)	−0.0026 (9)	0.0213 (9)	0.0067 (10)
N1	0.0178 (12)	0.0267 (17)	0.0157 (12)	0.0005 (11)	0.0029 (10)	0.0018 (12)
N2	0.0193 (13)	0.0366 (17)	0.0124 (12)	0.0030 (12)	0.0027 (10)	−0.0009 (12)
N3	0.0237 (12)	0.0302 (16)	0.0159 (12)	0.0016 (13)	−0.0004 (10)	−0.0028 (14)
O1	0.0216 (11)	0.0337 (15)	0.0212 (11)	−0.0012 (10)	0.0031 (9)	0.0013 (11)
O2	0.0255 (12)	0.0295 (14)	0.0201 (11)	−0.0029 (10)	−0.0018 (9)	−0.0025 (11)
O3	0.0270 (11)	0.0330 (14)	0.0167 (10)	0.0022 (12)	0.0040 (8)	0.0017 (12)
C1	0.0234 (15)	0.0207 (18)	0.0179 (14)	0.0015 (13)	0.0030 (12)	0.0016 (14)
C2	0.0239 (16)	0.0204 (19)	0.0212 (16)	0.0015 (13)	0.0019 (13)	0.0007 (15)
C3	0.0208 (16)	0.0220 (17)	0.0193 (15)	0.0005 (13)	0.0027 (12)	−0.0016 (14)
C4	0.0181 (15)	0.030 (2)	0.0202 (15)	0.0001 (13)	0.0051 (12)	−0.0003 (15)
C5	0.0241 (16)	0.0242 (19)	0.0159 (14)	0.0005 (13)	0.0079 (12)	−0.0003 (13)
C6	0.0219 (15)	0.0264 (19)	0.0182 (14)	0.0011 (13)	0.0032 (12)	−0.0011 (15)
C7	0.0184 (15)	0.0281 (19)	0.0173 (15)	−0.0009 (13)	0.0039 (12)	0.0014 (14)
C8	0.0223 (15)	0.0203 (18)	0.0170 (14)	0.0000 (13)	0.0043 (12)	0.0003 (14)
C9	0.0200 (15)	0.0235 (18)	0.0168 (14)	0.0009 (13)	0.0026 (12)	−0.0018 (14)
C10	0.0273 (18)	0.030 (2)	0.0175 (15)	0.0056 (14)	0.0036 (13)	0.0011 (15)
C11	0.0193 (15)	0.0259 (18)	0.0160 (14)	−0.0018 (13)	0.0024 (12)	−0.0002 (14)
C12	0.0192 (14)	0.027 (2)	0.0139 (13)	0.0003 (12)	0.0023 (11)	0.0019 (13)
C13	0.0230 (16)	0.0320 (19)	0.0136 (14)	0.0012 (14)	0.0030 (12)	−0.0001 (14)
C14	0.0294 (17)	0.0232 (18)	0.0191 (15)	0.0027 (14)	0.0042 (13)	0.0013 (14)
C15	0.0248 (18)	0.028 (2)	0.0273 (17)	0.0037 (14)	0.0030 (13)	−0.0040 (16)
C16	0.0190 (15)	0.0270 (18)	0.0161 (14)	−0.0009 (13)	0.0043 (11)	0.0002 (14)
C17	0.0239 (16)	0.031 (2)	0.0233 (16)	0.0005 (14)	0.0089 (13)	0.0045 (15)
C18	0.0276 (18)	0.035 (2)	0.0195 (16)	0.0015 (15)	0.0064 (13)	−0.0025 (16)
C19	0.0217 (16)	0.024 (2)	0.0214 (16)	0.0034 (14)	0.0046 (13)	−0.0009 (15)
O4	0.0255 (12)	0.0366 (15)	0.0283 (12)	0.0029 (11)	0.0040 (9)	0.0031 (12)
C20	0.0300 (19)	0.055 (3)	0.036 (2)	0.0090 (18)	0.0104 (16)	0.005 (2)

Geometric parameters (Å, º) top

Cl1—C7	1.737 (3)	C10—C11	1.526 (4)
F1—C5	1.358 (3)	C10—H10A	0.9700
F2—C17	1.381 (4)	C10—H10B	0.9700
N1—C1	1.364 (4)	C11—C15	1.494 (4)
N1—C8	1.402 (4)	C11—C14	1.507 (5)
N1—C16	1.464 (4)	C11—C12	1.510 (5)
N2—C6	1.390 (4)	C12—C13	1.533 (4)
N2—C13	1.460 (4)	C12—H12A	0.9800
N2—C10	1.476 (4)	C13—H13A	0.9700
N3—C12	1.496 (4)	C13—H13B	0.9700
N3—H3A	0.8900	C14—C15	1.516 (5)
N3—H3B	0.8900	C14—H14A	0.9700
N3—H3C	0.8900	C14—H14B	0.9700
O1—C3	1.239 (4)	C15—H15A	0.9700
O2—C19	1.256 (4)	C15—H15B	0.9700
O3—C19	1.258 (4)	C16—C17	1.494 (5)
C1—C2	1.359 (4)	C16—C18	1.511 (5)
C1—H1A	0.9300	C16—H16A	0.9800
C2—C3	1.448 (4)	C17—C18	1.488 (5)
C2—C19	1.513 (4)	C17—H17A	0.9800
C3—C9	1.474 (4)	C18—H18A	0.9700
C4—C5	1.363 (4)	C18—H18B	0.9700
C4—C9	1.402 (4)	O4—C20	1.414 (4)
C4—H4A	0.9300	O4—H4O	0.8200
C5—C6	1.406 (4)	C20—H20A	0.9600
C6—C7	1.401 (4)	C20—H20B	0.9600
C7—C8	1.414 (4)	C20—H20C	0.9600
C8—C9	1.409 (4)

C1—N1—C8	118.9 (3)	N3—C12—C13	112.9 (2)
C1—N1—C16	117.6 (2)	C11—C12—C13	101.9 (3)
C8—N1—C16	121.5 (2)	N3—C12—H12A	109.0
C6—N2—C13	123.5 (3)	C11—C12—H12A	109.0
C6—N2—C10	121.4 (3)	C13—C12—H12A	109.0
C13—N2—C10	110.1 (2)	N2—C13—C12	98.7 (2)
C12—N3—H3A	109.5	N2—C13—H13A	112.0
C12—N3—H3B	109.5	C12—C13—H13A	112.0
H3A—N3—H3B	109.5	N2—C13—H13B	112.0
C12—N3—H3C	109.5	C12—C13—H13B	112.0
H3A—N3—H3C	109.5	H13A—C13—H13B	109.7
H3B—N3—H3C	109.5	C11—C14—C15	59.2 (2)
C2—C1—N1	125.7 (3)	C11—C14—H14A	117.9
C2—C1—H1A	117.2	C15—C14—H14A	117.9
N1—C1—H1A	117.2	C11—C14—H14B	117.9
C1—C2—C3	119.1 (3)	C15—C14—H14B	117.9
C1—C2—C19	117.3 (3)	H14A—C14—H14B	115.0
C3—C2—C19	123.2 (3)	C11—C15—C14	60.1 (2)
O1—C3—C2	125.2 (3)	C11—C15—H15A	117.8
O1—C3—C9	119.8 (3)	C14—C15—H15A	117.8
C2—C3—C9	115.0 (3)	C11—C15—H15B	117.8
C5—C4—C9	120.0 (3)	C14—C15—H15B	117.8
C5—C4—H4A	120.0	H15A—C15—H15B	114.9
C9—C4—H4A	120.0	N1—C16—C17	117.6 (3)
F1—C5—C4	119.0 (3)	N1—C16—C18	119.7 (3)
F1—C5—C6	118.0 (3)	C17—C16—C18	59.4 (2)
C4—C5—C6	123.0 (3)	N1—C16—H16A	116.1
N2—C6—C7	120.6 (3)	C17—C16—H16A	116.1
N2—C6—C5	122.7 (3)	C18—C16—H16A	116.1
C7—C6—C5	116.6 (3)	F2—C17—C18	115.4 (3)
C6—C7—C8	121.4 (3)	F2—C17—C16	116.3 (3)
C6—C7—Cl1	116.9 (2)	C18—C17—C16	60.9 (2)
C8—C7—Cl1	121.3 (2)	F2—C17—H17A	117.4
N1—C8—C9	118.3 (2)	C18—C17—H17A	117.4
N1—C8—C7	122.8 (3)	C16—C17—H17A	117.4
C9—C8—C7	118.8 (3)	C17—C18—C16	59.8 (2)
C4—C9—C8	119.2 (3)	C17—C18—H18A	117.8
C4—C9—C3	118.6 (3)	C16—C18—H18A	117.8
C8—C9—C3	122.2 (3)	C17—C18—H18B	117.8
N2—C10—C11	102.7 (3)	C16—C18—H18B	117.8
N2—C10—H10A	111.2	H18A—C18—H18B	114.9
C11—C10—H10A	111.2	O2—C19—O3	123.7 (3)
N2—C10—H10B	111.2	O2—C19—C2	117.9 (3)
C11—C10—H10B	111.2	O3—C19—C2	118.4 (3)
H10A—C10—H10B	109.1	C20—O4—H4O	109.5
C15—C11—C14	60.7 (2)	O4—C20—H20A	109.5
C15—C11—C12	122.4 (3)	O4—C20—H20B	109.5
C14—C11—C12	122.7 (3)	H20A—C20—H20B	109.5
C15—C11—C10	121.0 (3)	O4—C20—H20C	109.5
C14—C11—C10	120.0 (3)	H20A—C20—H20C	109.5
C12—C11—C10	105.4 (2)	H20B—C20—H20C	109.5
N3—C12—C11	114.8 (3)

C8—N1—C1—C2	−5.3 (5)	O1—C3—C9—C4	−0.4 (5)
C16—N1—C1—C2	158.7 (3)	C2—C3—C9—C4	179.4 (3)
N1—C1—C2—C3	−2.0 (5)	O1—C3—C9—C8	179.6 (3)
N1—C1—C2—C19	−175.7 (3)	C2—C3—C9—C8	−0.6 (5)
C1—C2—C3—O1	−175.5 (3)	C6—N2—C10—C11	−174.7 (3)
C19—C2—C3—O1	−2.2 (6)	C13—N2—C10—C11	−18.7 (3)
C1—C2—C3—C9	4.7 (5)	N2—C10—C11—C15	−155.8 (3)
C19—C2—C3—C9	178.1 (3)	N2—C10—C11—C14	132.4 (3)
C9—C4—C5—F1	−173.7 (3)	N2—C10—C11—C12	−11.3 (3)
C9—C4—C5—C6	6.4 (6)	C15—C11—C12—N3	−58.4 (4)
C13—N2—C6—C7	144.3 (4)	C14—C11—C12—N3	15.2 (4)
C10—N2—C6—C7	−62.9 (5)	C10—C11—C12—N3	157.7 (3)
C13—N2—C6—C5	−32.8 (5)	C15—C11—C12—C13	179.1 (3)
C10—N2—C6—C5	120.0 (4)	C14—C11—C12—C13	−107.2 (3)
F1—C5—C6—N2	−5.0 (5)	C10—C11—C12—C13	35.3 (3)
C4—C5—C6—N2	174.8 (3)	C6—N2—C13—C12	−164.6 (3)
F1—C5—C6—C7	177.7 (3)	C10—N2—C13—C12	40.0 (3)
C4—C5—C6—C7	−2.4 (5)	N3—C12—C13—N2	−168.4 (3)
N2—C6—C7—C8	175.9 (3)	C11—C12—C13—N2	−44.7 (3)
C5—C6—C7—C8	−6.8 (5)	C12—C11—C14—C15	−111.7 (3)
N2—C6—C7—Cl1	−11.2 (5)	C10—C11—C14—C15	111.0 (3)
C5—C6—C7—Cl1	166.1 (3)	C12—C11—C15—C14	112.2 (3)
C1—N1—C8—C9	9.1 (5)	C10—C11—C15—C14	−109.3 (4)
C16—N1—C8—C9	−154.2 (3)	C1—N1—C16—C17	−108.0 (3)
C1—N1—C8—C7	−169.5 (3)	C8—N1—C16—C17	55.5 (4)
C16—N1—C8—C7	27.1 (5)	C1—N1—C16—C18	−39.3 (4)
C6—C7—C8—N1	−169.6 (3)	C8—N1—C16—C18	124.2 (3)
Cl1—C7—C8—N1	17.8 (5)	N1—C16—C17—F2	4.1 (4)
C6—C7—C8—C9	11.8 (5)	C18—C16—C17—F2	−105.8 (3)
Cl1—C7—C8—C9	−160.8 (3)	N1—C16—C17—C18	109.9 (3)
C5—C4—C9—C8	−1.2 (5)	F2—C17—C18—C16	107.2 (3)
C5—C4—C9—C3	178.8 (3)	N1—C16—C18—C17	−106.4 (3)
N1—C8—C9—C4	173.8 (3)	C1—C2—C19—O2	139.6 (3)
C7—C8—C9—C4	−7.6 (5)	C3—C2—C19—O2	−33.9 (5)
N1—C8—C9—C3	−6.2 (5)	C1—C2—C19—O3	−39.5 (4)
C7—C8—C9—C3	172.4 (3)	C3—C2—C19—O3	147.1 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O3ⁱ	0.89	2.07	2.929 (3)	161
N3—H3A···O2ⁱ	0.89	2.43	3.022 (3)	124
O4—H4O···O3ⁱⁱ	0.82	1.84	2.654 (4)	173
N3—H3C···O2ⁱⁱⁱ	0.89	1.82	2.675 (4)	159
N3—H3B···O4	0.89	1.91	2.788 (4)	171

Symmetry codes: (i) x+1, y, z+1; (ii) −x+1, y−1/2, −z+1; (iii) −x+1, y+1/2, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₉H₁₈ClF₂N₃O₃·CH₄O
M_r	441.86
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	293
a, b, c (Å)	8.7455 (3), 8.2968 (3), 14.0638 (4)
β (°)	104.474 (3)
V (Å³)	988.07 (5)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	2.18
Crystal size (mm)	0.2 × 0.1 × 0.05

Data collection
Diffractometer	Agilent Xcalibur Sapphire3 Gemini ultra diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.990, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	5115, 2745, 2537
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.100, 1.08
No. of reflections	2745
No. of parameters	273
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.21
Absolute structure	Flack, (1983), 856 Friedel pairs
Absolute structure parameter	−0.024 (19)

Computer programs: CrysAlis PRO (Agilent, 2011), OLEX2 (Dolomanov et al., 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O3ⁱ	0.89	2.07	2.929 (3)	161
N3—H3A···O2ⁱ	0.89	2.43	3.022 (3)	124
O4—H4O···O3ⁱⁱ	0.82	1.84	2.654 (4)	173
N3—H3C···O2ⁱⁱⁱ	0.89	1.82	2.675 (4)	159
N3—H3B···O4	0.89	1.91	2.788 (4)	171

Symmetry codes: (i) x+1, y, z+1; (ii) −x+1, y−1/2, −z+1; (iii) −x+1, y+1/2, −z+1.

Acknowledgements

This work was supported by grants from the Major Science and Technology Projects of Guangdong Province (No. 2011 A080504007).

References

Agilent (2011). CrysAlis PRO. Agilent Technologies UK Ltd, Yarnton, England. Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Suzuki, T., Araki, T., Kitaoka, H. & Tereda, K. (2010). Int. J. Pharm. 402, 110–116. Web of Science CrossRef CAS PubMed Google Scholar
Suzuki, M., Kitaoka, H., Miwa, Y. & Taga, T. (2000). Anal. Sci. 16, 343–344. Web of Science CSD CrossRef CAS Google Scholar
Yamazaki, K. & Suzuki, M. (1998). Anal. Sci. 14, 463–464. Web of Science CSD CrossRef CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 9| September 2012| Page o2794

doi:10.1107/S160053681203632X

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

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

7-[(7S)-7-Aza­niumyl-5-aza­spiro­[2.4]hept-5-yl]-8-chloro-6-fluoro-1-[(1S,2R)-2-fluoro­cyclo­prop­yl]-4-oxo-1,4-di­hydro­quinoline-3-carboxyl­ate methanol monosolvate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

7-[(7S)-7-Azaniumyl-5-azaspiro[2.4]hept-5-yl]-8-chloro-6-fluoro-1-[(1S,2R)-2-fluorocyclopropyl]-4-oxo-1,4-dihydroquinoline-3-carboxylate methanol monosolvate