1-Cyclo-propyl-6-fluoro-7-(4-nitro-so-piperazin-1-yl)-4-oxo-1,4-dihydro-quinoline-3-carboxylic acid.

The title compound, C(17)H(17)FN(4)O(4), is a derivative of ciprofloxacin [1-cyclo-propyl-6-fluoro-4-oxo-7-(1-piperazin-yl)-1,4-dihydro-quinoline-3-carboxylic acid]. The crystal packing is stabilized by inter-molecular C-H⋯O hydrogen bonds together with π-π electron ring inter-actions [centroid-centroid separations between quinoline rings of 3.5864 (11) and 3.9339 (13) Å]. A strong intra-molecular O-H⋯O hydrogen bonds is present as well as an intra-molecular C-H⋯F inter-action.

Related literature

For the biological activity of ciprofloxacin compounds, see: n class="Gene">Neu (1987 ▶). For related structures, see: Turel et al. (1996 ▶); Drevenšek et al. (2003 ▶); Li et al. (2005 ▶); Lou et al. (2007 ▶). The nitroso-group geometry is similar to that observed in 1,4-dinitro­sopiperazine, see: Sekido et al. (1985 ▶).

Experimental

Crystal data

C17H17FN4O4

M = 360.35

Triclinic,

a = 8.378 (3) Å

b = 9.625 (4) Å

c = 10.328 (4) Å

α = 102.99 (2)°

β = 96.089 (14)°

γ = 97.392 (16)°

V = 797.0 (6) Å3

Z = 2

Mo Kα radiation

μ = 0.12 mm−1

T = 293 K

0.2 × 0.2 × 0.2 mm

Data collection

Rigaku Mercury n class="Disease">CCD/AFC diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2007 ▶) T min = 0.976, T max = 0.977

6267 measured reflections

3631 independent reflections

2568 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.067

wR(F 2) = 0.207

S = 1.06

3631 reflections

236 parameters

H-atom parameters constrained

Δρmax = 0.52 e Å−3

Δρmin = −0.35 e Å−3

Data collection: CrystalClear (Rigaku, 2007 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXL97 and DIAMOND (Brandenburg, 2005 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809029729/fb2160sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809029729/fb2160Isup2.hkl

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

C17H17FN4O4	Z = 2
Mr = 360.35	F(000) = 376
Triclinic, P1	Dx = 1.502 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.378 (3) Å	Cell parameters from 771 reflections
b = 9.625 (4) Å	θ = 2.0–27.4°
c = 10.328 (4) Å	µ = 0.12 mm−1
α = 102.99 (2)°	T = 293 K
β = 96.089 (14)°	Block, yellow
γ = 97.392 (16)°	0.2 × 0.2 × 0.2 mm
V = 797.0 (6) Å3

Rigaku Mercury CCD/AFC diffractometer	3631 independent reflections
Radiation source: fine-focus sealed tube	2568 reflections with I > 2σ(I)
graphite	Rint = 0.031
φ and ω scans	θmax = 27.4°, θmin = 2.5°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007)	h = −10→10
Tmin = 0.976, Tmax = 0.977	k = −12→12
6267 measured reflections	l = −13→11

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.067	Hydrogen site location: difference Fourier map
wR(F2) = 0.207	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.1165P)2 + 0.047P] where P = (Fo2 + 2Fc2)/3
3631 reflections	(Δ/σ)max < 0.001
236 parameters	Δρmax = 0.52 e Å−3
0 restraints	Δρmin = −0.35 e Å−3
67 constraints

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.

	x	y	z	Uiso*/Ueq
N1	0.14474 (19)	0.38921 (17)	0.16119 (15)	0.0330 (4)
O2	−0.1340 (2)	0.09746 (18)	−0.25939 (15)	0.0561 (5)
H18	−0.0827	0.1674	−0.2814	0.084*
O3	0.0676 (2)	0.32428 (17)	−0.25086 (13)	0.0472 (4)
C8	0.2117 (2)	0.4611 (2)	−0.03990 (18)	0.0331 (4)
F1	0.51960 (16)	0.74426 (14)	−0.07933 (12)	0.0505 (4)
C13	0.2335 (2)	0.48548 (19)	0.10118 (18)	0.0318 (4)
C11	0.4372 (2)	0.6987 (2)	0.1245 (2)	0.0342 (4)
C5	0.0120 (2)	0.2477 (2)	−0.05450 (19)	0.0356 (5)
O1	−0.1742 (2)	0.03235 (18)	−0.07173 (17)	0.0580 (5)
C12	0.3415 (2)	0.6063 (2)	0.18211 (19)	0.0344 (4)
H12A	0.3488	0.6247	0.2770	0.041*
C9	0.3081 (3)	0.5551 (2)	−0.0978 (2)	0.0372 (5)
H9A	0.2962	0.5415	−0.1925	0.045*
N2	0.5528 (2)	0.81427 (18)	0.20147 (16)	0.0380 (4)
C7	0.0944 (2)	0.3414 (2)	−0.1242 (2)	0.0361 (5)
C10	0.4184 (3)	0.6654 (2)	−0.0179 (2)	0.0361 (5)
C4	0.0408 (2)	0.2758 (2)	0.0830 (2)	0.0359 (5)
H4A	−0.0163	0.2111	0.1257	0.043*
C6	−0.1066 (3)	0.1168 (2)	−0.1269 (2)	0.0428 (5)
N3	0.7368 (3)	1.0685 (2)	0.37104 (18)	0.0492 (5)
C3	0.1612 (3)	0.4155 (2)	0.30774 (19)	0.0373 (5)
H3A	0.1132	0.4997	0.3544	0.045*
C14	0.5794 (3)	0.8301 (2)	0.3473 (2)	0.0473 (6)
H14A	0.5869	0.7346	0.3663	0.057*
H14B	0.4859	0.8666	0.3870	0.057*
C2	0.3112 (3)	0.3878 (3)	0.3816 (2)	0.0512 (6)
H2A	0.3549	0.4545	0.4696	0.061*
H2B	0.3943	0.3493	0.3283	0.061*
C15	0.7354 (3)	0.9344 (2)	0.4114 (2)	0.0487 (6)
H15A	0.7434	0.9535	0.5103	0.058*
H15B	0.8306	0.8901	0.3840	0.058*
C16	0.5548 (3)	0.9558 (3)	0.1687 (2)	0.0570 (7)
H16A	0.4633	1.0008	0.2039	0.068*
H16B	0.5390	0.9417	0.0700	0.068*
C17	0.7110 (3)	1.0550 (3)	0.2268 (2)	0.0574 (7)
H17A	0.8022	1.0156	0.1856	0.069*
H17B	0.7058	1.1509	0.2082	0.069*
C1	0.1525 (3)	0.2910 (3)	0.3709 (2)	0.0551 (7)
H1A	0.1379	0.1929	0.3111	0.066*
H1B	0.0986	0.2981	0.4524	0.066*
N4	0.7544 (3)	1.1903 (2)	0.4635 (2)	0.0654 (7)
O4	0.7463 (3)	1.3001 (2)	0.4211 (2)	0.0895 (7)

	U11	U22	U33	U12	U13	U23
N1	0.0369 (9)	0.0264 (8)	0.0303 (8)	−0.0042 (6)	−0.0015 (7)	0.0040 (6)
O2	0.0664 (11)	0.0464 (10)	0.0397 (9)	−0.0092 (8)	−0.0087 (8)	−0.0047 (7)
O3	0.0588 (10)	0.0433 (9)	0.0306 (8)	−0.0015 (7)	−0.0052 (7)	0.0012 (6)
C8	0.0372 (10)	0.0277 (9)	0.0302 (10)	0.0036 (8)	−0.0017 (8)	0.0023 (7)
F1	0.0587 (8)	0.0475 (8)	0.0438 (7)	−0.0084 (6)	0.0111 (6)	0.0155 (6)
C13	0.0359 (10)	0.0249 (9)	0.0310 (10)	0.0015 (8)	0.0008 (8)	0.0029 (7)
C11	0.0373 (10)	0.0278 (9)	0.0340 (10)	0.0004 (8)	−0.0015 (8)	0.0061 (8)
C5	0.0382 (10)	0.0268 (10)	0.0348 (11)	0.0003 (8)	−0.0037 (8)	−0.0008 (8)
O1	0.0590 (11)	0.0456 (10)	0.0569 (10)	−0.0192 (8)	−0.0103 (8)	0.0103 (8)
C12	0.0416 (11)	0.0270 (9)	0.0295 (10)	−0.0019 (8)	0.0003 (8)	0.0025 (7)
C9	0.0455 (11)	0.0354 (10)	0.0293 (10)	0.0065 (9)	0.0029 (8)	0.0057 (8)
N2	0.0446 (10)	0.0308 (9)	0.0329 (9)	−0.0071 (7)	−0.0044 (7)	0.0074 (7)
C7	0.0390 (11)	0.0306 (10)	0.0336 (10)	0.0058 (8)	−0.0010 (8)	−0.0002 (8)
C10	0.0395 (10)	0.0312 (10)	0.0375 (11)	0.0008 (8)	0.0039 (8)	0.0115 (8)
C4	0.0361 (10)	0.0284 (10)	0.0380 (11)	−0.0023 (8)	−0.0013 (8)	0.0043 (8)
C6	0.0426 (11)	0.0340 (11)	0.0436 (12)	0.0024 (9)	−0.0064 (9)	0.0002 (9)
N3	0.0662 (13)	0.0354 (10)	0.0359 (9)	−0.0088 (9)	−0.0016 (9)	0.0013 (7)
C3	0.0473 (12)	0.0311 (10)	0.0294 (10)	−0.0022 (8)	0.0031 (8)	0.0045 (8)
C14	0.0608 (14)	0.0394 (12)	0.0337 (11)	−0.0112 (10)	−0.0030 (10)	0.0075 (9)
C2	0.0527 (14)	0.0551 (14)	0.0393 (12)	−0.0017 (11)	−0.0041 (10)	0.0086 (10)
C15	0.0607 (15)	0.0401 (12)	0.0364 (11)	−0.0056 (10)	−0.0068 (10)	0.0051 (9)
C16	0.0679 (16)	0.0395 (13)	0.0546 (14)	−0.0137 (11)	−0.0191 (12)	0.0179 (11)
C17	0.0767 (18)	0.0424 (13)	0.0451 (13)	−0.0128 (12)	−0.0004 (12)	0.0104 (10)
C1	0.0709 (16)	0.0458 (13)	0.0420 (12)	−0.0121 (12)	−0.0059 (11)	0.0150 (10)
N4	0.0859 (17)	0.0430 (12)	0.0536 (13)	−0.0081 (11)	0.0084 (12)	−0.0059 (10)
O4	0.132 (2)	0.0383 (11)	0.0856 (16)	0.0046 (12)	0.0002 (14)	0.0002 (10)

N1—C4	1.346 (2)	C4—H4A	0.9500
N1—C13	1.405 (2)	N3—N4	1.315 (3)
N1—C3	1.466 (2)	N3—C15	1.442 (3)
O2—C6	1.330 (3)	N3—C17	1.456 (3)
O2—H18	0.8400	C3—C1	1.485 (3)
O3—C7	1.273 (2)	C3—C2	1.485 (3)
C8—C9	1.410 (3)	C3—H3A	1.0000
C8—C13	1.411 (3)	C14—C15	1.528 (3)
C8—C7	1.458 (3)	C14—H14A	0.9900
F1—C10	1.365 (2)	C14—H14B	0.9900
C13—C12	1.414 (3)	C2—C1	1.501 (3)
C11—C12	1.394 (3)	C2—H2A	0.9900
C11—N2	1.404 (2)	C2—H2B	0.9900
C11—C10	1.420 (3)	C15—H15A	0.9900
C5—C4	1.373 (3)	C15—H15B	0.9900
C5—C7	1.431 (3)	C16—C17	1.496 (3)
C5—C6	1.493 (3)	C16—H16A	0.9900
O1—C6	1.210 (3)	C16—H16B	0.9900
C12—H12A	0.9500	C17—H17A	0.9900
C9—C10	1.361 (3)	C17—H17B	0.9900
C9—H9A	0.9500	C1—H1A	0.9900
N2—C14	1.469 (3)	C1—H1B	0.9900
N2—C16	1.474 (3)	N4—O4	1.238 (3)
C4—N1—C13	119.38 (16)	C1—C3—C2	60.70 (16)
C4—N1—C3	120.52 (15)	N1—C3—H3A	115.5
C13—N1—C3	120.07 (15)	C1—C3—H3A	115.5
C6—O2—H18	109.5	C2—C3—H3A	115.5
C9—C8—C13	118.03 (17)	N2—C14—C15	110.91 (17)
C9—C8—C7	120.60 (17)	N2—C14—H14A	109.5
C13—C8—C7	121.36 (18)	C15—C14—H14A	109.5
N1—C13—C8	119.20 (16)	N2—C14—H14B	109.5
N1—C13—C12	120.02 (17)	C15—C14—H14B	109.5
C8—C13—C12	120.77 (17)	H14A—C14—H14B	108.0
C12—C11—N2	122.48 (18)	C3—C2—C1	59.64 (15)
C12—C11—C10	116.46 (17)	C3—C2—H2A	117.8
N2—C11—C10	120.98 (17)	C1—C2—H2A	117.8
C4—C5—C7	120.37 (17)	C3—C2—H2B	117.8
C4—C5—C6	117.68 (18)	C1—C2—H2B	117.8
C7—C5—C6	121.95 (18)	H2A—C2—H2B	114.9
C11—C12—C13	120.90 (18)	N3—C15—C14	110.6 (2)
C11—C12—H12A	119.6	N3—C15—H15A	109.5
C13—C12—H12A	119.6	C14—C15—H15A	109.5
C10—C9—C8	119.97 (18)	N3—C15—H15B	109.5
C10—C9—H9A	120.0	C14—C15—H15B	109.5
C8—C9—H9A	120.0	H15A—C15—H15B	108.1
C11—N2—C14	117.59 (15)	N2—C16—C17	111.9 (2)
C11—N2—C16	117.81 (17)	N2—C16—H16A	109.2
C14—N2—C16	111.17 (17)	C17—C16—H16A	109.2
O3—C7—C5	123.16 (18)	N2—C16—H16B	109.2
O3—C7—C8	121.43 (18)	C17—C16—H16B	109.2
C5—C7—C8	115.41 (17)	H16A—C16—H16B	107.9
C9—C10—F1	117.51 (17)	N3—C17—C16	108.62 (19)
C9—C10—C11	123.63 (18)	N3—C17—H17A	110.0
F1—C10—C11	118.81 (17)	C16—C17—H17A	110.0
N1—C4—C5	124.20 (18)	N3—C17—H17B	110.0
N1—C4—H4A	117.9	C16—C17—H17B	110.0
C5—C4—H4A	117.9	H17A—C17—H17B	108.3
O1—C6—O2	121.06 (19)	C3—C1—C2	59.66 (15)
O1—C6—C5	123.8 (2)	C3—C1—H1A	117.8
O2—C6—C5	115.15 (19)	C2—C1—H1A	117.8
N4—N3—C15	119.31 (19)	C3—C1—H1B	117.8
N4—N3—C17	125.3 (2)	C2—C1—H1B	117.8
C15—N3—C17	115.35 (18)	H1A—C1—H1B	114.9
N1—C3—C1	119.44 (18)	O4—N4—N3	115.6 (2)
N1—C3—C2	119.07 (18)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H18···O3	0.84	1.78	2.562 (2)	153
C4—H4A···O1	0.95	2.48	2.812 (3)	101
C15—H15A···O2i	0.99	2.50	3.405 (3)	151
C15—H15B···O3ii	0.99	2.51	3.385 (3)	147
C16—H16A···O1iii	0.99	2.60	3.264 (3)	125
C16—H16B···F1	0.99	2.14	2.852 (3)	128
C17—H17B···O4	0.99	2.30	2.692 (3)	102

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H18⋯O3	0.84	1.78	2.562 (2)	153
C15—H15A⋯O2i	0.99	2.50	3.405 (3)	151
C15—H15B⋯O3ii	0.99	2.51	3.385 (3)	147
C16—H16A⋯O1iii	0.99	2.60	3.264 (3)	125
C16—H16B⋯F1	0.99	2.14	2.852 (3)	128

Symmetry codes: (i) ; (ii) ; (iii) .