2-(4-Carb-oxy-piperidinium-1-yl)pyridine-3-carboxyl-ate.

The title compound, C(12)H(14)N(2)O(4), crystallizes as a zwitterion. A negative charge is delocalized in the deprotonated carboxyl group attached to the pyridine ring. The piperidine N atom accepts a proton and the ring is transformed into a piperidinium cation. There is an intra-molecular N-H⋯O hydrogen bond between the protonated NH and a carboxyl-ate O atom. In the crystal, an O-H⋯O hydrogen bond between the carboxyl group and the carboxyl-ate O atom of another mol-ecule generates a helix along the b axis.

Related literature

For the synthesis, see: Shreder et al. (2009 ▶); Léost et al. (1997 ▶); Bonnet et al. (2002 ▶).

Experimental

Crystal data

C12H14N2O4

M = 250.25

Monoclinic,

a = 7.1094 (14) Å

b = 18.667 (4) Å

c = 8.6603 (17) Å

β = 93.57 (3)°

V = 1147.1 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.11 mm−1

T = 293 K

0.20 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.964, T max = 0.983

6010 measured reflections

2237 independent reflections

1841 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.118

S = 1.09

2237 reflections

168 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.22 e Å−3

Δρmin = −0.34 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); 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: SHELXL97.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812005752/kp2382sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812005752/kp2382Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812005752/kp2382Isup3.cml

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

C12H14N2O4	F(000) = 528
Mr = 250.25	Dx = 1.449 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P2ybc	Cell parameters from 361 reflections
a = 7.1094 (14) Å	θ = 2.5–22.7°
b = 18.667 (4) Å	µ = 0.11 mm−1
c = 8.6603 (17) Å	T = 293 K
β = 93.57 (3)°	Block, colourless
V = 1147.1 (4) Å3	0.20 × 0.20 × 0.20 mm
Z = 4

Bruker SMART CCD area-detector diffractometer	2237 independent reflections
Radiation source: fine-focus sealed tube	1841 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
φ and ω scans	θmax = 26.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −8→8
Tmin = 0.964, Tmax = 0.983	k = −23→21
6010 measured reflections	l = −10→7

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.118	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ2(Fo2) + (0.0685P)2 + 0.1385P] where P = (Fo2 + 2Fc2)/3
2237 reflections	(Δ/σ)max = 0.001
168 parameters	Δρmax = 0.22 e Å−3
0 restraints	Δρmin = −0.34 e Å−3

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
O4	0.06398 (16)	0.42630 (6)	0.56128 (13)	0.0431 (3)
N2	0.41209 (16)	0.63507 (6)	0.81715 (14)	0.0291 (3)
O3	−0.10491 (16)	0.44848 (6)	0.76521 (13)	0.0445 (3)
H3	−0.1719	0.4164	0.7277	0.067*
N1	0.68999 (17)	0.64666 (6)	0.98026 (15)	0.0373 (3)
O2	0.26774 (16)	0.75408 (6)	0.70841 (13)	0.0466 (3)
C3	0.55581 (18)	0.68088 (7)	0.89789 (16)	0.0278 (3)
C8	0.1114 (2)	0.56996 (8)	0.83901 (18)	0.0355 (4)
H8A	0.0488	0.6001	0.7604	0.043*
H8B	0.0187	0.5552	0.9102	0.043*
C12	0.0444 (2)	0.45637 (7)	0.68272 (17)	0.0314 (3)
O1	0.36031 (17)	0.85729 (6)	0.82086 (15)	0.0534 (4)
C7	0.2667 (2)	0.61218 (8)	0.92594 (17)	0.0357 (4)
H7A	0.2134	0.6541	0.9730	0.043*
H7B	0.3256	0.5828	1.0077	0.043*
C9	0.19275 (19)	0.50397 (7)	0.76289 (16)	0.0301 (3)
H9	0.2557	0.4754	0.8458	0.036*
C10	0.3436 (2)	0.52666 (8)	0.65609 (17)	0.0376 (4)
H10A	0.4004	0.4843	0.6136	0.045*
H10B	0.2858	0.5541	0.5707	0.045*
C2	0.53838 (18)	0.75479 (7)	0.88389 (16)	0.0288 (3)
C11	0.4954 (2)	0.57139 (8)	0.74008 (19)	0.0369 (4)
H11A	0.5636	0.5422	0.8174	0.044*
H11B	0.5842	0.5877	0.6670	0.044*
C1	0.3745 (2)	0.79174 (8)	0.79697 (18)	0.0352 (4)
C5	0.8281 (2)	0.76099 (9)	1.03995 (19)	0.0411 (4)
H5	0.9268	0.7873	1.0871	0.049*
C6	0.6822 (2)	0.79468 (8)	0.95705 (18)	0.0358 (4)
H6	0.6801	0.8444	0.9501	0.043*
C4	0.8245 (2)	0.68742 (9)	1.05140 (19)	0.0402 (4)
H4	0.9201	0.6649	1.1114	0.048*
H2A	0.344 (3)	0.6686 (11)	0.742 (2)	0.063 (6)*

	U11	U22	U33	U12	U13	U23
O4	0.0449 (6)	0.0350 (6)	0.0484 (7)	0.0028 (5)	−0.0044 (5)	−0.0133 (5)
N2	0.0281 (6)	0.0229 (6)	0.0362 (7)	−0.0020 (5)	−0.0001 (5)	0.0017 (5)
O3	0.0428 (6)	0.0447 (7)	0.0460 (7)	−0.0203 (5)	0.0027 (5)	−0.0074 (5)
N1	0.0333 (7)	0.0290 (7)	0.0483 (8)	0.0023 (5)	−0.0067 (6)	0.0049 (5)
O2	0.0421 (7)	0.0400 (6)	0.0551 (7)	0.0019 (5)	−0.0171 (6)	0.0043 (5)
C3	0.0244 (7)	0.0251 (7)	0.0340 (7)	−0.0014 (5)	0.0014 (6)	0.0008 (5)
C8	0.0297 (7)	0.0333 (8)	0.0438 (9)	−0.0055 (6)	0.0053 (6)	−0.0074 (6)
C12	0.0356 (8)	0.0207 (7)	0.0370 (8)	0.0022 (6)	−0.0039 (6)	0.0021 (6)
O1	0.0497 (7)	0.0295 (6)	0.0787 (9)	0.0131 (5)	−0.0153 (6)	−0.0008 (5)
C7	0.0333 (8)	0.0342 (8)	0.0404 (8)	−0.0071 (6)	0.0090 (6)	−0.0082 (6)
C9	0.0318 (7)	0.0257 (7)	0.0323 (7)	−0.0019 (6)	−0.0016 (6)	0.0019 (6)
C10	0.0390 (8)	0.0356 (8)	0.0389 (8)	−0.0056 (6)	0.0078 (7)	−0.0078 (6)
C2	0.0264 (7)	0.0252 (7)	0.0350 (8)	0.0014 (5)	0.0036 (6)	0.0008 (5)
C11	0.0328 (7)	0.0331 (8)	0.0457 (9)	−0.0026 (6)	0.0089 (6)	−0.0053 (7)
C1	0.0325 (7)	0.0302 (8)	0.0426 (8)	0.0039 (6)	−0.0006 (6)	0.0039 (6)
C5	0.0309 (8)	0.0379 (9)	0.0532 (10)	−0.0054 (6)	−0.0082 (7)	−0.0037 (7)
C6	0.0327 (7)	0.0257 (7)	0.0488 (9)	−0.0022 (6)	0.0006 (7)	−0.0010 (6)
C4	0.0303 (7)	0.0396 (9)	0.0491 (9)	0.0048 (6)	−0.0105 (7)	0.0037 (7)

O4—C12	1.2079 (18)	C7—H7A	0.9700
N2—C3	1.4749 (17)	C7—H7B	0.9700
N2—C11	1.5030 (18)	C9—C10	1.519 (2)
N2—C7	1.5031 (18)	C9—H9	0.9800
N2—H2A	1.01 (2)	C10—C11	1.515 (2)
O3—C12	1.3240 (18)	C10—H10A	0.9700
O3—H3	0.8200	C10—H10B	0.9700
N1—C3	1.3200 (18)	C2—C6	1.386 (2)
N1—C4	1.342 (2)	C2—C1	1.514 (2)
O2—C1	1.2593 (18)	C11—H11A	0.9700
C3—C2	1.3897 (19)	C11—H11B	0.9700
C8—C7	1.518 (2)	C5—C6	1.376 (2)
C8—C9	1.528 (2)	C5—C4	1.377 (2)
C8—H8A	0.9700	C5—H5	0.9300
C8—H8B	0.9700	C6—H6	0.9300
C12—C9	1.5142 (19)	C4—H4	0.9300
O1—C1	1.2462 (18)
C3—N2—C11	112.86 (11)	C10—C9—H9	106.9
C3—N2—C7	110.53 (11)	C8—C9—H9	106.9
C11—N2—C7	111.03 (11)	C11—C10—C9	111.73 (12)
C3—N2—H2A	103.8 (11)	C11—C10—H10A	109.3
C11—N2—H2A	113.0 (11)	C9—C10—H10A	109.3
C7—N2—H2A	105.2 (11)	C11—C10—H10B	109.3
C12—O3—H3	109.5	C9—C10—H10B	109.3
C3—N1—C4	116.38 (13)	H10A—C10—H10B	107.9
N1—C3—C2	125.81 (13)	C6—C2—C3	115.73 (13)
N1—C3—N2	115.57 (12)	C6—C2—C1	120.38 (12)
C2—C3—N2	118.61 (12)	C3—C2—C1	123.88 (13)
C7—C8—C9	110.46 (12)	N2—C11—C10	111.12 (12)
C7—C8—H8A	109.6	N2—C11—H11A	109.4
C9—C8—H8A	109.6	C10—C11—H11A	109.4
C7—C8—H8B	109.6	N2—C11—H11B	109.4
C9—C8—H8B	109.6	C10—C11—H11B	109.4
H8A—C8—H8B	108.1	H11A—C11—H11B	108.0
O4—C12—O3	123.91 (14)	O1—C1—O2	126.68 (14)
O4—C12—C9	123.86 (13)	O1—C1—C2	115.64 (13)
O3—C12—C9	112.14 (12)	O2—C1—C2	117.68 (12)
N2—C7—C8	110.12 (12)	C6—C5—C4	118.46 (14)
N2—C7—H7A	109.6	C6—C5—H5	120.8
C8—C7—H7A	109.6	C4—C5—H5	120.8
N2—C7—H7B	109.6	C5—C6—C2	120.24 (14)
C8—C7—H7B	109.6	C5—C6—H6	119.9
H7A—C7—H7B	108.1	C2—C6—H6	119.9
C12—C9—C10	112.48 (11)	N1—C4—C5	123.25 (14)
C12—C9—C8	113.54 (12)	N1—C4—H4	118.4
C10—C9—C8	109.78 (11)	C5—C4—H4	118.4
C12—C9—H9	106.9

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O1i	0.82	1.77	2.566 (2)	166
N2—H2A···O2	1.01 (2)	1.71 (2)	2.599 (2)	146.0 (16)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O1i	0.82	1.77	2.566 (2)	166
N2—H2A⋯O2	1.01 (2)	1.71 (2)	2.599 (2)	146.0 (16)

Symmetry code: (i) .