Bis(4-carboxy-piperidinium) 5-nitro-isophthalate.

Cocrystallization of 4-carboxypiperdine with 5-nitro-isophthalic acid afforded the title salt, 2C(6)H(12N)O(2) (+)·C(8)H(3)NO(6) (2-), in which the heterocyclic N atoms are protonated and the carboxylic acid groups are deprotonated. In the crystal, inter-molecular N-H⋯O and O-H⋯O hydrogen-bonding inter-actions assemble the ions into a three-dimensional network.

Related literature

For mol­ecular self-assembly by non-covalent inter­actions and its potential applications, see: Remenar et al. (2003 ▶); Oxtoby et al. (2005 ▶); Zaworotko (2001 ▶); Wang et al. (2009 ▶). For 4-piperdinecarboxylic acid as a zwitterion in aqueous solution, see: Mora et al. (2002 ▶) and for its ability to act selectively as a bridging or terminal ligand, see: Inomata et al. (2002 ▶). For related structures, see: Adams et al. (2006 ▶); Podesta & Orpen (2002 ▶); Delgado et al. (2001 ▶); Zhang et al. (2009 ▶).

Experimental

Crystal data

2C6H12NO2 +·n class="Chemical">C8H3NO6 2−

M = 469.45

Monoclinic,

a = 23.6865 (12) Å

b = 8.2478 (4) Å

c = 22.5140 (11) Å

β = 92.396 (1)°

V = 4394.5 (4) Å3

Z = 8

Mo Kα radiation

μ = 0.12 mm−1

T = 296 K

0.25 × 0.24 × 0.20 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.972, T max = 0.977

10813 measured reflections

3855 independent reflections

3272 reflections with I > 2σ(I)

R int = 0.016

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.101

S = 1.04

3855 reflections

300 parameters

H-atom parameters constrained

Δρmax = 0.30 e Å−3

Δρmin = −0.23 e Å−3

Data collection: APEX2 (Bruker, 2003 ▶); 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 ▶) and n class="Disease">DIAMOND (Brandenburg & Berndt, 1999 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810017927/bt5271sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810017927/bt5271Isup2.hkl

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

2C6H12NO2+·C8H3NO62−	F(000) = 1984
Mr = 469.45	Dx = 1.419 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 23.6865 (12) Å	Cell parameters from 5783 reflections
b = 8.2478 (4) Å	θ = 2.6–27.7°
c = 22.5140 (11) Å	µ = 0.12 mm−1
β = 92.396 (1)°	T = 296 K
V = 4394.5 (4) Å3	Block, colourless
Z = 8	0.25 × 0.24 × 0.20 mm

Bruker APEXII CCD area-detector diffractometer	3855 independent reflections
Radiation source: fine-focus sealed tube	3272 reflections with I > 2σ(I)
graphite	Rint = 0.016
phi and ω scans	θmax = 25.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −26→28
Tmin = 0.972, Tmax = 0.977	k = −6→9
10813 measured reflections	l = −26→25

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.101	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0446P)2 + 3.6101P] where P = (Fo2 + 2Fc2)/3
3855 reflections	(Δ/σ)max = 0.001
300 parameters	Δρmax = 0.30 e Å−3
0 restraints	Δρmin = −0.23 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
O1	0.05079 (5)	0.70916 (18)	−0.03056 (5)	0.0496 (3)
O2	0.08990 (5)	0.83618 (18)	−0.10541 (5)	0.0508 (3)
O3	0.16282 (6)	0.63183 (16)	0.15592 (5)	0.0497 (3)
O4	0.22886 (5)	0.81433 (15)	0.18158 (5)	0.0431 (3)
O5	0.31864 (6)	1.0750 (2)	0.00708 (7)	0.0634 (4)
O6	0.26236 (6)	1.1471 (2)	−0.06513 (7)	0.0702 (5)
O7	1.00128 (5)	0.77960 (18)	0.83217 (6)	0.0561 (4)
H7	1.0273	0.8104	0.8546	0.084*
O8	0.96201 (7)	1.0009 (2)	0.86340 (11)	0.1136 (9)
O9	0.89526 (5)	0.40628 (18)	0.75229 (5)	0.0520 (4)
H9	0.8714	0.3961	0.7774	0.078*
O10	0.82217 (6)	0.3599 (3)	0.69185 (7)	0.0915 (7)
N1	0.27300 (6)	1.07054 (18)	−0.01985 (7)	0.0410 (3)
N2	0.78899 (5)	0.87733 (17)	0.76390 (6)	0.0333 (3)
H2A	0.7801	0.9650	0.7854	0.040*
H2B	0.7578	0.8468	0.7426	0.040*
N3	0.99531 (6)	0.26082 (18)	0.57233 (6)	0.0410 (3)
H3A	1.0170	0.2687	0.5406	0.049*
H3B	1.0025	0.1645	0.5898	0.049*
C1	0.14080 (6)	0.83039 (19)	−0.01316 (7)	0.0310 (3)
C2	0.14657 (6)	0.77035 (19)	0.04446 (7)	0.0314 (3)
H2	0.1191	0.7006	0.0582	0.038*
C3	0.19210 (6)	0.81163 (19)	0.08202 (6)	0.0304 (3)
C4	0.23391 (6)	0.9130 (2)	0.06152 (7)	0.0324 (4)
H4	0.2646	0.9434	0.0861	0.039*
C5	0.22846 (6)	0.96748 (19)	0.00345 (7)	0.0314 (3)
C6	0.18275 (6)	0.92973 (19)	−0.03393 (7)	0.0326 (3)
H6	0.1801	0.9704	−0.0725	0.039*
C7	0.08946 (6)	0.7881 (2)	−0.05230 (7)	0.0350 (4)
C8	0.19502 (7)	0.7475 (2)	0.14504 (7)	0.0335 (4)
C9	0.90789 (6)	0.8298 (2)	0.79810 (8)	0.0386 (4)
H9A	0.9167	0.7345	0.7742	0.046*
C10	0.88790 (7)	0.9662 (2)	0.75661 (8)	0.0424 (4)
H10A	0.8819	1.0635	0.7797	0.051*
H10B	0.9170	0.9894	0.7288	0.051*
C11	0.83367 (7)	0.9221 (2)	0.72253 (8)	0.0426 (4)
H11A	0.8210	1.0135	0.6983	0.051*
H11B	0.8405	0.8317	0.6962	0.051*
C12	0.80657 (7)	0.7439 (2)	0.80488 (8)	0.0411 (4)
H12A	0.8121	0.6456	0.7822	0.049*
H12B	0.7769	0.7236	0.8323	0.049*
C13	0.86074 (7)	0.7858 (2)	0.83956 (8)	0.0422 (4)
H13A	0.8725	0.6940	0.8640	0.051*
H13B	0.8540	0.8766	0.8657	0.051*
C14	0.96009 (7)	0.8790 (2)	0.83435 (9)	0.0433 (4)
C15	0.91160 (7)	0.3924 (2)	0.64910 (7)	0.0358 (4)
H15	0.9051	0.4959	0.6286	0.043*
C16	0.89746 (7)	0.2580 (2)	0.60467 (7)	0.0405 (4)
H16A	0.9024	0.1536	0.6240	0.049*
H16B	0.8582	0.2674	0.5910	0.049*
C17	0.93479 (7)	0.2668 (2)	0.55192 (8)	0.0436 (4)
H17A	0.9264	0.1766	0.5253	0.052*
H17B	0.9273	0.3666	0.5302	0.052*
C18	1.01064 (7)	0.3933 (2)	0.61503 (8)	0.0448 (4)
H18A	1.0056	0.4974	0.5955	0.054*
H18B	1.0501	0.3830	0.6280	0.054*
C19	0.97391 (7)	0.3853 (2)	0.66851 (8)	0.0418 (4)
H19A	0.9830	0.4754	0.6949	0.050*
H19B	0.9815	0.2855	0.6901	0.050*
C20	0.87172 (7)	0.3847 (2)	0.69963 (8)	0.0406 (4)

	U11	U22	U33	U12	U13	U23
O1	0.0375 (7)	0.0741 (9)	0.0371 (7)	−0.0206 (6)	0.0007 (5)	−0.0047 (6)
O2	0.0380 (7)	0.0776 (10)	0.0356 (7)	−0.0124 (6)	−0.0110 (5)	0.0119 (6)
O3	0.0657 (8)	0.0494 (8)	0.0343 (6)	−0.0115 (7)	0.0051 (6)	0.0055 (6)
O4	0.0462 (7)	0.0512 (7)	0.0311 (6)	0.0052 (6)	−0.0100 (5)	0.0004 (5)
O5	0.0413 (8)	0.0816 (11)	0.0667 (9)	−0.0263 (7)	−0.0037 (7)	−0.0034 (8)
O6	0.0663 (10)	0.0886 (12)	0.0559 (9)	−0.0231 (8)	0.0044 (7)	0.0300 (8)
O7	0.0410 (7)	0.0657 (9)	0.0596 (9)	0.0117 (7)	−0.0218 (6)	−0.0146 (7)
O8	0.0655 (11)	0.0722 (12)	0.198 (2)	0.0142 (9)	−0.0592 (13)	−0.0777 (14)
O9	0.0445 (7)	0.0722 (9)	0.0398 (7)	−0.0102 (7)	0.0066 (6)	−0.0009 (7)
O10	0.0310 (8)	0.191 (2)	0.0526 (9)	−0.0075 (10)	0.0066 (6)	−0.0059 (11)
N1	0.0385 (8)	0.0437 (8)	0.0414 (8)	−0.0086 (6)	0.0070 (6)	−0.0033 (7)
N2	0.0262 (6)	0.0404 (8)	0.0328 (7)	−0.0002 (6)	−0.0040 (5)	−0.0028 (6)
N3	0.0386 (8)	0.0470 (9)	0.0379 (8)	0.0116 (6)	0.0060 (6)	0.0081 (7)
C1	0.0268 (7)	0.0360 (9)	0.0301 (8)	0.0001 (6)	−0.0015 (6)	−0.0016 (7)
C2	0.0283 (8)	0.0356 (9)	0.0305 (8)	−0.0024 (6)	0.0026 (6)	−0.0003 (7)
C3	0.0302 (8)	0.0342 (8)	0.0268 (7)	0.0035 (6)	0.0008 (6)	−0.0020 (6)
C4	0.0278 (8)	0.0370 (9)	0.0320 (8)	0.0006 (6)	−0.0041 (6)	−0.0049 (7)
C5	0.0294 (8)	0.0321 (8)	0.0329 (8)	−0.0026 (6)	0.0024 (6)	−0.0015 (7)
C6	0.0325 (8)	0.0372 (9)	0.0278 (8)	0.0023 (7)	−0.0004 (6)	0.0022 (7)
C7	0.0298 (8)	0.0441 (10)	0.0308 (8)	−0.0005 (7)	−0.0018 (6)	−0.0029 (7)
C8	0.0350 (8)	0.0373 (9)	0.0282 (8)	0.0077 (7)	−0.0007 (7)	−0.0014 (7)
C9	0.0287 (8)	0.0333 (9)	0.0532 (10)	0.0005 (7)	−0.0052 (7)	−0.0104 (8)
C10	0.0339 (9)	0.0461 (10)	0.0475 (10)	−0.0069 (8)	0.0057 (7)	0.0022 (8)
C11	0.0378 (9)	0.0546 (11)	0.0353 (9)	−0.0019 (8)	0.0032 (7)	0.0060 (8)
C12	0.0329 (9)	0.0461 (10)	0.0438 (9)	−0.0079 (7)	−0.0041 (7)	0.0103 (8)
C13	0.0375 (9)	0.0449 (10)	0.0433 (10)	−0.0045 (8)	−0.0096 (7)	0.0089 (8)
C14	0.0325 (9)	0.0369 (10)	0.0597 (11)	−0.0035 (7)	−0.0073 (8)	−0.0068 (9)
C15	0.0326 (8)	0.0371 (9)	0.0380 (9)	0.0023 (7)	0.0030 (7)	0.0068 (7)
C16	0.0319 (9)	0.0490 (10)	0.0403 (9)	−0.0024 (7)	−0.0016 (7)	0.0028 (8)
C17	0.0399 (9)	0.0539 (11)	0.0366 (9)	0.0026 (8)	−0.0026 (7)	−0.0001 (8)
C18	0.0303 (9)	0.0591 (12)	0.0453 (10)	−0.0017 (8)	0.0031 (7)	0.0017 (9)
C19	0.0326 (9)	0.0549 (11)	0.0379 (9)	−0.0021 (8)	0.0011 (7)	−0.0015 (8)
C20	0.0329 (9)	0.0459 (10)	0.0431 (10)	0.0039 (7)	0.0035 (7)	0.0036 (8)

O1—C7	1.241 (2)	C5—C6	1.379 (2)
O2—C7	1.260 (2)	C6—H6	0.9300
O3—C8	1.252 (2)	C9—C14	1.508 (2)
O4—C8	1.2524 (19)	C9—C10	1.525 (2)
O5—N1	1.2177 (19)	C9—C13	1.529 (2)
O6—N1	1.216 (2)	C9—H9A	0.9800
O7—C14	1.277 (2)	C10—C11	1.513 (2)
O7—H7	0.8200	C10—H10A	0.9700
O8—C14	1.199 (2)	C10—H10B	0.9700
O9—C20	1.301 (2)	C11—H11A	0.9700
O9—H9	0.8200	C11—H11B	0.9700
O10—C20	1.197 (2)	C12—C13	1.514 (2)
N1—C5	1.469 (2)	C12—H12A	0.9700
N2—C12	1.485 (2)	C12—H12B	0.9700
N2—C11	1.485 (2)	C13—H13A	0.9700
N2—H2A	0.9000	C13—H13B	0.9700
N2—H2B	0.9000	C15—C20	1.510 (2)
N3—C17	1.488 (2)	C15—C16	1.521 (2)
N3—C18	1.490 (2)	C15—C19	1.523 (2)
N3—H3A	0.9000	C15—H15	0.9800
N3—H3B	0.9000	C16—C17	1.512 (2)
C1—C6	1.384 (2)	C16—H16A	0.9700
C1—C2	1.390 (2)	C16—H16B	0.9700
C1—C7	1.512 (2)	C17—H17A	0.9700
C2—C3	1.385 (2)	C17—H17B	0.9700
C2—H2	0.9300	C18—C19	1.516 (2)
C3—C4	1.390 (2)	C18—H18A	0.9700
C3—C8	1.513 (2)	C18—H18B	0.9700
C4—C5	1.383 (2)	C19—H19A	0.9700
C4—H4	0.9300	C19—H19B	0.9700
C14—O7—H7	109.5	N2—C11—H11A	109.5
C20—O9—H9	109.5	C10—C11—H11A	109.5
O6—N1—O5	123.39 (15)	N2—C11—H11B	109.5
O6—N1—C5	118.22 (14)	C10—C11—H11B	109.5
O5—N1—C5	118.38 (15)	H11A—C11—H11B	108.1
C12—N2—C11	112.66 (13)	N2—C12—C13	111.15 (14)
C12—N2—H2A	109.1	N2—C12—H12A	109.4
C11—N2—H2A	109.1	C13—C12—H12A	109.4
C12—N2—H2B	109.1	N2—C12—H12B	109.4
C11—N2—H2B	109.1	C13—C12—H12B	109.4
H2A—N2—H2B	107.8	H12A—C12—H12B	108.0
C17—N3—C18	112.38 (13)	C12—C13—C9	111.37 (14)
C17—N3—H3A	109.1	C12—C13—H13A	109.4
C18—N3—H3A	109.1	C9—C13—H13A	109.4
C17—N3—H3B	109.1	C12—C13—H13B	109.4
C18—N3—H3B	109.1	C9—C13—H13B	109.4
H3A—N3—H3B	107.9	H13A—C13—H13B	108.0
C6—C1—C2	118.83 (14)	O8—C14—O7	123.21 (17)
C6—C1—C7	120.71 (14)	O8—C14—C9	122.15 (17)
C2—C1—C7	120.46 (14)	O7—C14—C9	114.63 (15)
C3—C2—C1	121.73 (14)	C20—C15—C16	109.74 (14)
C3—C2—H2	119.1	C20—C15—C19	114.31 (14)
C1—C2—H2	119.1	C16—C15—C19	110.20 (14)
C2—C3—C4	119.53 (14)	C20—C15—H15	107.4
C2—C3—C8	119.36 (14)	C16—C15—H15	107.4
C4—C3—C8	121.11 (14)	C19—C15—H15	107.4
C5—C4—C3	118.01 (14)	C17—C16—C15	111.22 (14)
C5—C4—H4	121.0	C17—C16—H16A	109.4
C3—C4—H4	121.0	C15—C16—H16A	109.4
C6—C5—C4	122.91 (14)	C17—C16—H16B	109.4
C6—C5—N1	118.04 (14)	C15—C16—H16B	109.4
C4—C5—N1	119.05 (14)	H16A—C16—H16B	108.0
C5—C6—C1	118.94 (14)	N3—C17—C16	110.08 (14)
C5—C6—H6	120.5	N3—C17—H17A	109.6
C1—C6—H6	120.5	C16—C17—H17A	109.6
O1—C7—O2	125.10 (15)	N3—C17—H17B	109.6
O1—C7—C1	118.68 (14)	C16—C17—H17B	109.6
O2—C7—C1	116.22 (14)	H17A—C17—H17B	108.2
O3—C8—O4	125.83 (15)	N3—C18—C19	110.39 (14)
O3—C8—C3	116.47 (14)	N3—C18—H18A	109.6
O4—C8—C3	117.70 (15)	C19—C18—H18A	109.6
C14—C9—C10	111.07 (14)	N3—C18—H18B	109.6
C14—C9—C13	109.67 (15)	C19—C18—H18B	109.6
C10—C9—C13	109.44 (13)	H18A—C18—H18B	108.1
C14—C9—H9A	108.9	C18—C19—C15	110.60 (14)
C10—C9—H9A	108.9	C18—C19—H19A	109.5
C13—C9—H9A	108.9	C15—C19—H19A	109.5
C11—C10—C9	111.62 (14)	C18—C19—H19B	109.5
C11—C10—H10A	109.3	C15—C19—H19B	109.5
C9—C10—H10A	109.3	H19A—C19—H19B	108.1
C11—C10—H10B	109.3	O10—C20—O9	122.47 (17)
C9—C10—H10B	109.3	O10—C20—C15	122.50 (16)
H10A—C10—H10B	108.0	O9—C20—C15	115.03 (14)
N2—C11—C10	110.73 (14)
C6—C1—C2—C3	2.2 (2)	C14—C9—C10—C11	−176.73 (15)
C7—C1—C2—C3	−177.66 (14)	C13—C9—C10—C11	−55.51 (19)
C1—C2—C3—C4	−1.3 (2)	C12—N2—C11—C10	−55.94 (19)
C1—C2—C3—C8	177.74 (14)	C9—C10—C11—N2	56.0 (2)
C2—C3—C4—C5	−0.8 (2)	C11—N2—C12—C13	55.84 (19)
C8—C3—C4—C5	−179.84 (14)	N2—C12—C13—C9	−55.4 (2)
C3—C4—C5—C6	2.1 (2)	C14—C9—C13—C12	177.09 (15)
C3—C4—C5—N1	−178.06 (14)	C10—C9—C13—C12	55.02 (19)
O6—N1—C5—C6	16.3 (2)	C10—C9—C14—O8	53.3 (3)
O5—N1—C5—C6	−163.70 (16)	C13—C9—C14—O8	−67.8 (3)
O6—N1—C5—C4	−163.54 (17)	C10—C9—C14—O7	−127.69 (18)
O5—N1—C5—C4	16.5 (2)	C13—C9—C14—O7	111.21 (18)
C4—C5—C6—C1	−1.3 (2)	C20—C15—C16—C17	177.29 (14)
N1—C5—C6—C1	178.86 (14)	C19—C15—C16—C17	−55.98 (19)
C2—C1—C6—C5	−0.8 (2)	C18—N3—C17—C16	−57.40 (19)
C7—C1—C6—C5	178.99 (14)	C15—C16—C17—N3	56.3 (2)
C6—C1—C7—O1	−174.49 (16)	C17—N3—C18—C19	57.68 (19)
C2—C1—C7—O1	5.3 (2)	N3—C18—C19—C15	−56.3 (2)
C6—C1—C7—O2	6.0 (2)	C20—C15—C19—C18	179.86 (15)
C2—C1—C7—O2	−174.16 (15)	C16—C15—C19—C18	55.7 (2)
C2—C3—C8—O3	15.5 (2)	C16—C15—C20—O10	−42.0 (3)
C4—C3—C8—O3	−165.40 (15)	C19—C15—C20—O10	−166.3 (2)
C2—C3—C8—O4	−164.12 (15)	C16—C15—C20—O9	137.65 (16)
C4—C3—C8—O4	15.0 (2)	C19—C15—C20—O9	13.3 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7···O2i	0.82	1.72	2.5204 (16)	166
O9—H9···O3ii	0.82	1.75	2.5495 (17)	164
N2—H2A···O4iii	0.90	1.98	2.8629 (19)	166
N2—H2B···O4iv	0.90	2.01	2.7823 (17)	143
N3—H3A···O1v	0.90	1.83	2.7220 (18)	171
N3—H3B···O8vi	0.90	1.89	2.755 (2)	161

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H7⋯O2i	0.82	1.72	2.5204 (16)	166
O9—H9⋯O3ii	0.82	1.75	2.5495 (17)	164
N2—H2A⋯O4iii	0.90	1.98	2.8629 (19)	166
N2—H2B⋯O4iv	0.90	2.01	2.7823 (17)	143
N3—H3A⋯O1v	0.90	1.83	2.7220 (18)	171
N3—H3B⋯O8vi	0.90	1.89	2.755 (2)	161

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .