4-Amino-pyridinium cis-2-carb-oxy-cyclo-hexane-1-carboxyl-ate.

In the structure of the title molecular salt, C(5)H(7)N(2) (+)·C(8)H(11)O(4) (-), the cis monoanions associate through short O-H⋯O hydrogen bonds in the carb-oxy-lic acid groups [graph set C(7)], forming zigzag chains which extend along the c axis. These are inter-linked through pyridinium and amine N-H⋯O hydrogen bonds, giving a three-dimensional network structure.

Related literature

For the structure of racemic cis-cyclo­hexane-1,2-dicarb­oxy­lic acid, see: Benedetti et al. (1970 ▶). For the structure of the racemic ammonium and 2-amino­pyridinium salts of cis-2-carb­oxy­cyclo­hexane-1-carboxyl­ate, see: Smith & Wermuth (2011a ▶,b ▶). For graph-set analysis, see Etter et al. (1990 ▶).

Experimental

Crystal data

C5H7N2 +·C8H11O4 −

M = 266.29

Orthorhombic,

a = 12.1359 (3) Å

b = 9.8351 (3) Å

c = 11.1850 (3) Å

V = 1335.02 (6) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 200 K

0.30 × 0.25 × 0.20 mm

Data collection

Oxford Diffraction Gemini-S CCD-detector diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T min = 0.948, T max = 0.990

9670 measured reflections

1709 independent reflections

1448 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.028

wR(F 2) = 0.060

S = 0.99

1709 reflections

188 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.15 e Å−3

Δρmin = −0.16 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) within WinGX (Farrugia, 1999 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811039547/fj2453sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811039547/fj2453Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811039547/fj2453Isup3.cml

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

C5H7N2+·C8H11O4−	F(000) = 568
Mr = 266.29	Dx = 1.325 Mg m−3
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 4840 reflections
a = 12.1359 (3) Å	θ = 3.2–28.7°
b = 9.8351 (3) Å	µ = 0.10 mm−1
c = 11.1850 (3) Å	T = 200 K
V = 1335.02 (6) Å3	Block, colourless
Z = 4	0.30 × 0.25 × 0.20 mm

Oxford Diffraction Gemini-S CCD-detector diffractometer	1709 independent reflections
Radiation source: Enhance (Mo) X-ray source	1448 reflections with I > 2σ(I)
graphite	Rint = 0.029
Detector resolution: 16.077 pixels mm-1	θmax = 28.8°, θmin = 3.2°
ω scans	h = −16→15
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −12→13
Tmin = 0.948, Tmax = 0.990	l = −13→15
9670 measured reflections

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.060	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	w = 1/[σ2(Fo2) + (0.0357P)2] where P = (Fo2 + 2Fc2)/3
1709 reflections	(Δ/σ)max < 0.001
188 parameters	Δρmax = 0.15 e Å−3
1 restraint	Δρmin = −0.16 e Å−3

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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
O11	−0.08623 (9)	0.42384 (12)	0.16082 (11)	0.0293 (4)
O12	0.08627 (8)	0.38250 (12)	0.21757 (10)	0.0262 (3)
O21	0.01171 (10)	0.40723 (12)	0.51058 (12)	0.0285 (3)
O22	0.17703 (9)	0.30714 (12)	0.50187 (12)	0.0296 (3)
C1	−0.06239 (12)	0.25883 (16)	0.31330 (14)	0.0202 (4)
C2	0.02258 (13)	0.20096 (16)	0.40246 (15)	0.0223 (5)
C3	0.10393 (14)	0.10098 (18)	0.34520 (18)	0.0311 (5)
C4	0.04378 (15)	−0.01169 (19)	0.2767 (2)	0.0410 (6)
C5	−0.03704 (15)	0.04676 (19)	0.18597 (18)	0.0340 (6)
C6	−0.11879 (14)	0.14099 (17)	0.24603 (17)	0.0272 (5)
C11	−0.01574 (12)	0.36284 (16)	0.22481 (14)	0.0200 (5)
C21	0.07930 (13)	0.30994 (17)	0.47466 (14)	0.0222 (5)
N1A	0.16603 (12)	0.28917 (15)	0.99803 (15)	0.0301 (4)
N41A	0.30073 (13)	0.14997 (18)	0.68510 (15)	0.0320 (5)
C2A	0.14635 (14)	0.35553 (19)	0.89470 (16)	0.0306 (5)
C3A	0.18908 (13)	0.31222 (17)	0.78984 (16)	0.0285 (5)
C4A	0.25659 (12)	0.19462 (16)	0.78670 (15)	0.0236 (5)
C5A	0.27516 (14)	0.12848 (18)	0.89698 (16)	0.0289 (5)
C6A	0.22940 (14)	0.17671 (18)	0.99826 (17)	0.0309 (5)
H1	−0.11940	0.30510	0.36020	0.0240*
H2	−0.02010	0.14740	0.46010	0.0270*
H21	0.046 (2)	0.473 (3)	0.561 (3)	0.069 (8)*
H31B	0.15200	0.14990	0.29080	0.0370*
H32B	0.14940	0.06050	0.40700	0.0370*
H41B	0.09730	−0.06800	0.23550	0.0490*
H42B	0.00420	−0.06880	0.33280	0.0490*
H51B	0.00320	0.09640	0.12510	0.0410*
H52B	−0.07640	−0.02690	0.14720	0.0410*
H61B	−0.16300	0.08910	0.30200	0.0330*
H62B	−0.16790	0.17830	0.18600	0.0330*
H1A	0.1408 (18)	0.319 (2)	1.0674 (19)	0.038 (6)*
H2A	0.10230	0.43290	0.89560	0.0370*
H3A	0.17420	0.35960	0.71970	0.0340*
H5A	0.31920	0.05120	0.89970	0.0350*
H6A	0.24190	0.13130	1.06990	0.0370*
H41A	0.3409 (18)	0.078 (2)	0.687 (2)	0.047 (6)*
H42A	0.2841 (16)	0.193 (2)	0.615 (2)	0.038 (6)*

	U11	U22	U33	U12	U13	U23
O11	0.0297 (6)	0.0270 (6)	0.0312 (7)	0.0010 (5)	−0.0051 (5)	0.0106 (6)
O12	0.0244 (6)	0.0291 (6)	0.0251 (6)	−0.0047 (5)	0.0004 (5)	0.0028 (5)
O21	0.0321 (6)	0.0263 (6)	0.0272 (6)	0.0042 (5)	−0.0021 (6)	−0.0066 (6)
O22	0.0304 (6)	0.0316 (6)	0.0269 (6)	0.0036 (5)	−0.0062 (5)	−0.0019 (6)
C1	0.0205 (7)	0.0188 (8)	0.0212 (8)	0.0009 (6)	0.0009 (6)	−0.0003 (7)
C2	0.0267 (8)	0.0193 (8)	0.0209 (8)	−0.0009 (7)	0.0007 (7)	0.0046 (7)
C3	0.0325 (9)	0.0253 (9)	0.0354 (10)	0.0084 (8)	−0.0064 (8)	−0.0016 (8)
C4	0.0439 (10)	0.0247 (9)	0.0543 (13)	0.0080 (8)	−0.0046 (10)	−0.0118 (9)
C5	0.0387 (10)	0.0270 (9)	0.0363 (11)	−0.0064 (8)	−0.0040 (9)	−0.0106 (8)
C6	0.0269 (8)	0.0226 (8)	0.0322 (10)	−0.0068 (7)	−0.0053 (7)	0.0039 (8)
C11	0.0254 (8)	0.0166 (8)	0.0179 (8)	−0.0006 (6)	−0.0006 (6)	−0.0031 (6)
C21	0.0287 (8)	0.0222 (8)	0.0157 (8)	0.0017 (7)	−0.0004 (6)	0.0051 (7)
N1A	0.0318 (7)	0.0344 (8)	0.0240 (8)	0.0016 (6)	0.0021 (7)	−0.0067 (8)
N41A	0.0366 (8)	0.0293 (9)	0.0302 (9)	0.0098 (7)	0.0024 (7)	−0.0044 (7)
C2A	0.0324 (9)	0.0258 (9)	0.0335 (10)	0.0077 (8)	0.0012 (8)	−0.0007 (9)
C3A	0.0334 (9)	0.0241 (9)	0.0281 (9)	0.0057 (7)	−0.0019 (8)	0.0023 (8)
C4A	0.0225 (7)	0.0209 (8)	0.0275 (9)	−0.0010 (6)	−0.0021 (7)	−0.0032 (8)
C5A	0.0305 (9)	0.0233 (9)	0.0329 (10)	0.0054 (7)	−0.0085 (8)	−0.0012 (8)
C6A	0.0334 (9)	0.0328 (9)	0.0264 (9)	−0.0001 (8)	−0.0080 (8)	0.0013 (9)

O11—C11	1.2665 (19)	C1—H1	0.9800
O12—C11	1.2556 (18)	C2—H2	0.9800
O21—C21	1.323 (2)	C3—H32B	0.9700
O22—C21	1.2248 (19)	C3—H31B	0.9700
O21—H21	0.95 (3)	C4—H42B	0.9700
N1A—C6A	1.347 (2)	C4—H41B	0.9700
N1A—C2A	1.349 (2)	C5—H51B	0.9700
N41A—C4A	1.331 (2)	C5—H52B	0.9700
N1A—H1A	0.88 (2)	C6—H61B	0.9700
N41A—H41A	0.86 (2)	C6—H62B	0.9700
N41A—H42A	0.91 (2)	C2A—C3A	1.351 (2)
C1—C2	1.543 (2)	C3A—C4A	1.418 (2)
C1—C11	1.532 (2)	C4A—C5A	1.413 (2)
C1—C6	1.542 (2)	C5A—C6A	1.348 (3)
C2—C3	1.534 (2)	C2A—H2A	0.9300
C2—C21	1.508 (2)	C3A—H3A	0.9300
C3—C4	1.532 (3)	C5A—H5A	0.9300
C4—C5	1.524 (3)	C6A—H6A	0.9300
C5—C6	1.515 (3)
C21—O21—H21	113.6 (15)	C2—C3—H31B	109.00
C2A—N1A—C6A	120.01 (16)	C2—C3—H32B	109.00
C6A—N1A—H1A	117.9 (13)	C5—C4—H41B	109.00
C2A—N1A—H1A	122.0 (13)	C5—C4—H42B	109.00
H41A—N41A—H42A	122 (2)	C3—C4—H42B	109.00
C4A—N41A—H41A	118.6 (15)	C3—C4—H41B	109.00
C4A—N41A—H42A	119.4 (13)	H41B—C4—H42B	108.00
C2—C1—C6	109.55 (13)	C6—C5—H51B	109.00
C2—C1—C11	114.64 (12)	C4—C5—H52B	109.00
C6—C1—C11	110.53 (13)	C6—C5—H52B	109.00
C1—C2—C21	112.88 (13)	H51B—C5—H52B	108.00
C1—C2—C3	113.38 (14)	C4—C5—H51B	109.00
C3—C2—C21	112.67 (13)	C5—C6—H62B	109.00
C2—C3—C4	111.46 (14)	H61B—C6—H62B	108.00
C3—C4—C5	111.52 (15)	C1—C6—H61B	109.00
C4—C5—C6	110.92 (16)	C1—C6—H62B	109.00
C1—C6—C5	112.68 (14)	C5—C6—H61B	109.00
O11—C11—C1	115.58 (13)	N1A—C2A—C3A	121.56 (17)
O11—C11—O12	123.82 (14)	C2A—C3A—C4A	120.03 (16)
O12—C11—C1	120.59 (13)	N41A—C4A—C3A	121.53 (16)
O21—C21—C2	113.18 (13)	C3A—C4A—C5A	116.50 (15)
O22—C21—C2	123.99 (15)	N41A—C4A—C5A	121.97 (15)
O21—C21—O22	122.77 (15)	C4A—C5A—C6A	120.41 (16)
C6—C1—H1	107.00	N1A—C6A—C5A	121.50 (17)
C2—C1—H1	107.00	N1A—C2A—H2A	119.00
C11—C1—H1	107.00	C3A—C2A—H2A	119.00
C1—C2—H2	106.00	C2A—C3A—H3A	120.00
C3—C2—H2	106.00	C4A—C3A—H3A	120.00
C21—C2—H2	106.00	C4A—C5A—H5A	120.00
C4—C3—H32B	109.00	C6A—C5A—H5A	120.00
H31B—C3—H32B	108.00	N1A—C6A—H6A	119.00
C4—C3—H31B	109.00	C5A—C6A—H6A	119.00
C6A—N1A—C2A—C3A	−0.2 (3)	C3—C2—C21—O21	171.15 (14)
C2A—N1A—C6A—C5A	0.6 (3)	C3—C2—C21—O22	−11.6 (2)
C6—C1—C2—C3	51.98 (17)	C1—C2—C21—O21	41.13 (19)
C11—C1—C2—C21	56.73 (18)	C1—C2—C21—O22	−141.58 (16)
C6—C1—C2—C21	−178.36 (13)	C2—C3—C4—C5	53.7 (2)
C11—C1—C2—C3	−72.93 (17)	C3—C4—C5—C6	−56.2 (2)
C2—C1—C11—O11	−171.66 (14)	C4—C5—C6—C1	57.4 (2)
C2—C1—C11—O12	9.2 (2)	N1A—C2A—C3A—C4A	−0.2 (3)
C6—C1—C11—O11	63.95 (18)	C2A—C3A—C4A—N41A	−179.40 (16)
C6—C1—C11—O12	−115.22 (16)	C2A—C3A—C4A—C5A	0.0 (2)
C11—C1—C6—C5	72.82 (18)	N41A—C4A—C5A—C6A	179.81 (17)
C2—C1—C6—C5	−54.43 (19)	C3A—C4A—C5A—C6A	0.4 (2)
C21—C2—C3—C4	177.72 (15)	C4A—C5A—C6A—N1A	−0.7 (3)
C1—C2—C3—C4	−52.5 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···O12i	0.88 (2)	1.91 (2)	2.795 (2)	180 (3)
N41A—H41A···O12ii	0.86 (2)	2.14 (2)	2.989 (2)	168 (2)
N41A—H42A···O22	0.91 (2)	2.13 (2)	2.974 (2)	152.6 (18)
O21—H21···O11iii	0.95 (3)	1.59 (3)	2.5302 (17)	170 (3)
C2A—H2A···O21iii	0.93	2.46	3.287 (2)	149
C3A—H3A···O22	0.93	2.49	3.225 (2)	136
C3A—H3A···O11iii	0.93	2.47	3.222 (2)	138
C6A—H6A···O11iv	0.93	2.38	3.048 (2)	128
C3—H31B···O12	0.97	2.56	3.123 (2)	117

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1A—H1A⋯O12i	0.88 (2)	1.91 (2)	2.795 (2)	180 (3)
N41A—H41A⋯O12ii	0.86 (2)	2.14 (2)	2.989 (2)	168 (2)
N41A—H42A⋯O22	0.91 (2)	2.13 (2)	2.974 (2)	152.6 (18)
O21—H21⋯O11iii	0.95 (3)	1.59 (3)	2.5302 (17)	170 (3)

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