tert-Butyl 4-carbamoyl-3-methoxy-imino-4-methyl-piperidine-1-carboxyl-ate.

The title compound, C(13)H(23)N(3)O(4), was prepared starting from ethyl N-benzyl-3-oxopiperidine-4-carboxyl-ate through a nine-step reaction, including hydrogenation, Boc (tert-butoxy-carbon-yl) protection, methyl-ation, oximation, hydrolysis, esterification and ammonolysis. In the crystal structure, mol-ecules are linked by inter-molecular N-H⋯O hydrogen bonds to form a porous three-dimensional network with solvent-free hydro-phobic channels extending along the c axis.

Related literature

For the synthesis and properties of quinolone derivatives, see: Ray et al. (2005 ▶); Ball et al. (1998 ▶); Bryskier (1997 ▶); De Sarro & De Sarro (2001 ▶); Anderson & Osheroff (2001 ▶); Dang et al. (2007 ▶); Wang et al. (2008 ▶).

Experimental

Crystal data

C13H23N3O4

M = 285.34

Tetragonal,

a = 22.813 (2) Å

c = 12.0742 (16) Å

V = 6283.8 (11) Å3

Z = 16

Mo Kα radiation

μ = 0.09 mm−1

T = 293 (2) K

0.48 × 0.46 × 0.45 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.957, T max = 0.963

16003 measured reflections

2763 independent reflections

1794 reflections with I > 2σ(I)

R int = 0.049

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.113

S = 1.01

2763 reflections

181 parameters

H-atom parameters constrained

Δρmax = 0.19 e Å−3

Δρmin = −0.12 e Å−3

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1999 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808036106/rz2260sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808036106/rz2260Isup2.hkl

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

C13H23N3O4	Z = 16
Mr = 285.34	F000 = 2464
Tetragonal, I41/a	Dx = 1.206 Mg m−3
Hall symbol: -I 4ad	Mo Kα radiation λ = 0.71073 Å
a = 22.813 (2) Å	Cell parameters from 3595 reflections
b = 22.813 (2) Å	θ = 2.5–22.6º
c = 12.0742 (16) Å	µ = 0.09 mm−1
α = 90º	T = 293 (2) K
β = 90º	Block, colorless
γ = 90º	0.48 × 0.46 × 0.45 mm
V = 6283.8 (11) Å3

Bruker SMART APEX CCD diffractometer	2763 independent reflections
Radiation source: fine-focus sealed tube	1794 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.049
T = 293(2) K	θmax = 25.0º
φ and ω scans	θmin = 1.8º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)	h = −27→27
Tmin = 0.957, Tmax = 0.963	k = −27→18
16003 measured reflections	l = −14→14

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)] = 0.039	H-atom parameters constrained
wR(F2) = 0.113	w = 1/[σ2(Fo2) + (0.0607P)2] where P = (Fo2 + 2Fc2)/3
S = 1.01	(Δ/σ)max < 0.001
2763 reflections	Δρmax = 0.19 e Å−3
181 parameters	Δρmin = −0.12 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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	0.38925 (6)	0.53733 (7)	0.27764 (13)	0.0504 (4)
N2	0.29390 (6)	0.58484 (6)	0.05570 (12)	0.0430 (4)
N3	0.41951 (6)	0.51996 (6)	−0.00791 (13)	0.0484 (4)
H3A	0.4432	0.4941	−0.0342	0.058*
H3B	0.3830	0.5189	−0.0253	0.058*
O1	0.46173 (5)	0.48101 (5)	0.33671 (11)	0.0554 (4)
O2	0.37946 (6)	0.43856 (6)	0.26866 (13)	0.0694 (4)
O3	0.24359 (5)	0.55589 (5)	0.09853 (10)	0.0501 (4)
O4	0.49117 (5)	0.56448 (5)	0.08658 (12)	0.0570 (4)
C1	0.33172 (8)	0.54686 (10)	0.23109 (17)	0.0558 (5)
H1A	0.3080	0.5692	0.2828	0.067*
H1B	0.3126	0.5094	0.2189	0.067*
C2	0.33613 (7)	0.57937 (7)	0.12372 (14)	0.0400 (4)
C3	0.39477 (7)	0.60751 (7)	0.09840 (14)	0.0405 (4)
C4	0.41585 (8)	0.63467 (8)	0.20750 (15)	0.0502 (5)
H4A	0.4531	0.6541	0.1949	0.060*
H4B	0.3879	0.6642	0.2309	0.060*
C5	0.42325 (9)	0.58985 (8)	0.30031 (16)	0.0558 (5)
H5A	0.4643	0.5796	0.3074	0.067*
H5B	0.4105	0.6069	0.3698	0.067*
C6	0.40799 (8)	0.48163 (10)	0.29224 (16)	0.0503 (5)
C7	0.49544 (8)	0.42673 (9)	0.34839 (16)	0.0544 (5)
C8	0.50169 (11)	0.39737 (11)	0.2370 (2)	0.0890 (8)
H8A	0.4643	0.3824	0.2138	0.134*
H8B	0.5292	0.3657	0.2426	0.134*
H8C	0.5155	0.4254	0.1837	0.134*
C9	0.55329 (9)	0.44949 (10)	0.3911 (2)	0.0709 (6)
H9A	0.5703	0.4754	0.3372	0.106*
H9B	0.5794	0.4172	0.4041	0.106*
H9C	0.5471	0.4704	0.4590	0.106*
C10	0.46678 (10)	0.38805 (11)	0.4341 (2)	0.0861 (8)
H10A	0.4619	0.4096	0.5017	0.129*
H10B	0.4910	0.3544	0.4475	0.129*
H10C	0.4291	0.3755	0.4076	0.129*
C11	0.19775 (8)	0.55590 (9)	0.01807 (17)	0.0588 (6)
H11A	0.1818	0.5947	0.0115	0.088*
H11B	0.1674	0.5293	0.0408	0.088*
H11C	0.2132	0.5437	−0.0522	0.088*
C12	0.43929 (8)	0.56124 (7)	0.05932 (14)	0.0401 (4)
C13	0.39064 (9)	0.65416 (8)	0.00759 (16)	0.0529 (5)
H13A	0.3761	0.6366	−0.0593	0.079*
H13B	0.4288	0.6705	−0.0057	0.079*
H13C	0.3644	0.6847	0.0308	0.079*

	U11	U22	U33	U12	U13	U23
N1	0.0401 (9)	0.0565 (10)	0.0546 (10)	0.0059 (8)	−0.0052 (7)	0.0066 (8)
N2	0.0373 (9)	0.0459 (9)	0.0457 (9)	0.0019 (7)	0.0041 (7)	−0.0026 (7)
N3	0.0342 (8)	0.0456 (9)	0.0655 (11)	0.0027 (7)	0.0014 (7)	−0.0195 (8)
O1	0.0444 (8)	0.0558 (8)	0.0661 (9)	0.0102 (6)	−0.0121 (6)	0.0019 (7)
O2	0.0574 (9)	0.0617 (10)	0.0890 (11)	−0.0071 (7)	−0.0152 (8)	0.0097 (8)
O3	0.0346 (7)	0.0627 (8)	0.0529 (8)	−0.0010 (6)	0.0000 (6)	0.0073 (6)
O4	0.0338 (7)	0.0607 (9)	0.0766 (10)	0.0034 (6)	−0.0029 (6)	−0.0254 (7)
C1	0.0360 (11)	0.0753 (14)	0.0560 (13)	0.0088 (9)	0.0019 (9)	0.0136 (10)
C2	0.0345 (10)	0.0412 (10)	0.0442 (10)	0.0093 (8)	0.0030 (8)	−0.0041 (8)
C3	0.0398 (10)	0.0369 (10)	0.0447 (10)	0.0042 (8)	0.0025 (8)	−0.0042 (8)
C4	0.0525 (12)	0.0423 (11)	0.0559 (12)	0.0054 (9)	−0.0005 (9)	−0.0119 (9)
C5	0.0593 (13)	0.0571 (13)	0.0509 (12)	0.0100 (10)	−0.0094 (10)	−0.0106 (10)
C6	0.0433 (12)	0.0622 (14)	0.0453 (12)	0.0027 (10)	−0.0009 (9)	0.0055 (10)
C7	0.0512 (12)	0.0570 (13)	0.0549 (13)	0.0139 (9)	0.0011 (10)	0.0058 (10)
C8	0.0959 (19)	0.0966 (19)	0.0744 (17)	0.0334 (15)	−0.0017 (14)	−0.0162 (14)
C9	0.0470 (13)	0.0821 (16)	0.0837 (17)	0.0128 (11)	−0.0020 (11)	0.0093 (13)
C10	0.0726 (16)	0.0894 (18)	0.0962 (19)	0.0002 (13)	−0.0024 (14)	0.0364 (15)
C11	0.0409 (11)	0.0714 (14)	0.0641 (13)	−0.0025 (9)	−0.0097 (10)	0.0085 (11)
C12	0.0345 (10)	0.0393 (10)	0.0467 (11)	−0.0006 (8)	0.0024 (8)	−0.0035 (8)
C13	0.0551 (12)	0.0464 (11)	0.0571 (12)	0.0021 (9)	0.0057 (9)	0.0021 (9)

N1—C6	1.352 (2)	C4—H4B	0.9700
N1—C1	1.444 (2)	C5—H5A	0.9700
N1—C5	1.453 (2)	C5—H5B	0.9700
N2—C2	1.272 (2)	C7—C10	1.509 (3)
N2—O3	1.4217 (17)	C7—C9	1.509 (3)
N3—C12	1.323 (2)	C7—C8	1.509 (3)
N3—H3A	0.8600	C8—H8A	0.9600
N3—H3B	0.8600	C8—H8B	0.9600
O1—C6	1.339 (2)	C8—H8C	0.9600
O1—C7	1.465 (2)	C9—H9A	0.9600
O2—C6	1.213 (2)	C9—H9B	0.9600
O3—C11	1.427 (2)	C9—H9C	0.9600
O4—C12	1.2308 (19)	C10—H10A	0.9600
C1—C2	1.497 (2)	C10—H10B	0.9600
C1—H1A	0.9700	C10—H10C	0.9600
C1—H1B	0.9700	C11—H11A	0.9600
C2—C3	1.515 (2)	C11—H11B	0.9600
C3—C13	1.531 (2)	C11—H11C	0.9600
C3—C4	1.533 (2)	C13—H13A	0.9600
C3—C12	1.539 (2)	C13—H13B	0.9600
C4—C5	1.526 (3)	C13—H13C	0.9600
C4—H4A	0.9700
C6—N1—C1	118.66 (17)	O1—C7—C10	109.46 (16)
C6—N1—C5	125.56 (16)	O1—C7—C9	101.60 (15)
C1—N1—C5	115.73 (16)	C10—C7—C9	110.25 (18)
C2—N2—O3	109.33 (14)	O1—C7—C8	109.82 (17)
C12—N3—H3A	120.0	C10—C7—C8	113.1 (2)
C12—N3—H3B	120.0	C9—C7—C8	111.98 (17)
H3A—N3—H3B	120.0	C7—C8—H8A	109.5
C6—O1—C7	121.90 (15)	C7—C8—H8B	109.5
N2—O3—C11	110.11 (13)	H8A—C8—H8B	109.5
N1—C1—C2	110.52 (15)	C7—C8—H8C	109.5
N1—C1—H1A	109.5	H8A—C8—H8C	109.5
C2—C1—H1A	109.5	H8B—C8—H8C	109.5
N1—C1—H1B	109.5	C7—C9—H9A	109.5
C2—C1—H1B	109.5	C7—C9—H9B	109.5
H1A—C1—H1B	108.1	H9A—C9—H9B	109.5
N2—C2—C1	123.83 (16)	C7—C9—H9C	109.5
N2—C2—C3	119.79 (16)	H9A—C9—H9C	109.5
C1—C2—C3	116.37 (15)	H9B—C9—H9C	109.5
C2—C3—C13	112.63 (14)	C7—C10—H10A	109.5
C2—C3—C4	105.95 (14)	C7—C10—H10B	109.5
C13—C3—C4	110.71 (14)	H10A—C10—H10B	109.5
C2—C3—C12	110.73 (13)	C7—C10—H10C	109.5
C13—C3—C12	107.33 (14)	H10A—C10—H10C	109.5
C4—C3—C12	109.49 (14)	H10B—C10—H10C	109.5
C5—C4—C3	113.25 (14)	O3—C11—H11A	109.5
C5—C4—H4A	108.9	O3—C11—H11B	109.5
C3—C4—H4A	108.9	H11A—C11—H11B	109.5
C5—C4—H4B	108.9	O3—C11—H11C	109.5
C3—C4—H4B	108.9	H11A—C11—H11C	109.5
H4A—C4—H4B	107.7	H11B—C11—H11C	109.5
N1—C5—C4	110.80 (15)	O4—C12—N3	122.35 (15)
N1—C5—H5A	109.5	O4—C12—C3	120.75 (15)
C4—C5—H5A	109.5	N3—C12—C3	116.84 (15)
N1—C5—H5B	109.5	C3—C13—H13A	109.5
C4—C5—H5B	109.5	C3—C13—H13B	109.5
H5A—C5—H5B	108.1	H13A—C13—H13B	109.5
O2—C6—O1	125.26 (19)	C3—C13—H13C	109.5
O2—C6—N1	124.14 (18)	H13A—C13—H13C	109.5
O1—C6—N1	110.60 (17)	H13B—C13—H13C	109.5
C2—N2—O3—C11	−173.54 (15)	C1—N1—C5—C4	−40.4 (2)
C6—N1—C1—C2	−118.26 (19)	C3—C4—C5—N1	−20.9 (2)
C5—N1—C1—C2	59.1 (2)	C7—O1—C6—O2	8.3 (3)
O3—N2—C2—C1	0.3 (2)	C7—O1—C6—N1	−172.16 (15)
O3—N2—C2—C3	−178.79 (13)	C1—N1—C6—O2	0.0 (3)
N1—C1—C2—N2	167.35 (16)	C5—N1—C6—O2	−177.08 (19)
N1—C1—C2—C3	−13.5 (2)	C1—N1—C6—O1	−179.54 (15)
N2—C2—C3—C13	16.4 (2)	C5—N1—C6—O1	3.4 (3)
C1—C2—C3—C13	−162.72 (16)	C6—O1—C7—C10	−68.6 (2)
N2—C2—C3—C4	137.60 (16)	C6—O1—C7—C9	174.80 (16)
C1—C2—C3—C4	−41.54 (19)	C6—O1—C7—C8	56.1 (2)
N2—C2—C3—C12	−103.77 (18)	C2—C3—C12—O4	−142.74 (17)
C1—C2—C3—C12	77.10 (19)	C13—C3—C12—O4	93.96 (19)
C2—C3—C4—C5	59.91 (19)	C4—C3—C12—O4	−26.3 (2)
C13—C3—C4—C5	−177.69 (15)	C2—C3—C12—N3	40.0 (2)
C12—C3—C4—C5	−59.54 (19)	C13—C3—C12—N3	−83.25 (19)
C6—N1—C5—C4	136.72 (18)	C4—C3—C12—N3	156.51 (15)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O4i	0.86	2.11	2.9607 (18)	173
N3—H3B···O3ii	0.86	2.34	3.1334 (19)	153

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O4i	0.86	2.11	2.9607 (18)	173
N3—H3B⋯O3ii	0.86	2.34	3.1334 (19)	153

Symmetry codes: (i) ; (ii) .