Cyclo-hexane-1,4-dicarb-oxy-lic acid-pyridinium-4-olate (1/1).

In the title adduct, C5H5NO·C8H12O4, the heterocycle exists in its zwitterionic form. The cyclo-hexane ring exhibits a chair conformation with the carb-oxy-lic acid groups in equatorial and axial orientations. In the crystal, mol-ecules are linked through charge-assisted O-H⋯O(-), N(+)-H⋯O(-) and N(+)-H⋯O hydrogen bonds, and an additional series of C-H⋯O contacts, giving a pleated two-dimensional hydrogen-bonded network parallel to (-204).

Related literature

For reports on supra­molecular crystal engineering and potential applications of co-crystals, see: Desiraju (1995 ▶); Simon & Bassoul (2000 ▶); Weyna et al. (2009 ▶); Aakeröy et al. (2010 ▶); Yan et al. (2012 ▶). For related structures, see: Bhogala et al. (2005 ▶); Shattock et al. (2008 ▶); Yu (2012 ▶).

Experimental

Crystal data

C5H5NO·C8H12O4

M = 267.28

Monoclinic,

a = 11.749 (2) Å

b = 11.618 (2) Å

c = 10.8010 (19) Å

β = 115.383 (2)°

V = 1332.0 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 293 K

0.50 × 0.43 × 0.24 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.95, T max = 0.98

12552 measured reflections

2345 independent reflections

2229 reflections with I > 2σ(I)

R int = 0.041

Refinement

R[F 2 > 2σ(F 2)] = 0.072

wR(F 2) = 0.161

S = 1.02

2345 reflections

181 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.20 e Å−3

Δρmin = −0.27 e Å−3

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT-Plus-NT (Bruker, 2001 ▶); data reduction: SAINT-Plus-NT; program(s) used to solve structure: SHELXTL-NT (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL-NT; molecular graphics: ORTEP-3 (Farrugia, 2012 ▶) and Mercury (Macrae et al. 2008 ▶); software used to prepare material for publication: publCIF (Westrip, 2010) ▶.

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681300754X/pk2472sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681300754X/pk2472Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S160053681300754X/pk2472Isup3.cml

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

C5H5NO·C8H12O4	F(000) = 568
Mr = 267.28	Dx = 1.333 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5484 reflections
a = 11.749 (2) Å	θ = 2.6–27.4°
b = 11.618 (2) Å	µ = 0.10 mm−1
c = 10.8010 (19) Å	T = 293 K
β = 115.383 (2)°	Rectangular prism, yellow
V = 1332.0 (4) Å3	0.50 × 0.43 × 0.24 mm
Z = 4

Bruker SMART CCD area-detector diffractometer	2345 independent reflections
Radiation source: fine-focus sealed tube	2229 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
φ and ω scans	θmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→13
Tmin = 0.95, Tmax = 0.98	k = −13→13
12552 measured reflections	l = −12→12

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)] = 0.072	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.161	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.0623P)2 + 1.4075P] where P = (Fo2 + 2Fc2)/3
2345 reflections	(Δ/σ)max < 0.001
181 parameters	Δρmax = 0.20 e Å−3
3 restraints	Δρmin = −0.27 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
O1	0.2230 (2)	0.1930 (2)	0.0632 (2)	0.0663 (6)
H1'	0.162 (2)	0.198 (4)	0.085 (4)	0.099*
O2	0.3186 (2)	0.3059 (3)	0.2412 (3)	0.0898 (9)
O3	0.8439 (2)	0.3327 (2)	0.3413 (2)	0.0733 (7)
H3'	0.901 (3)	0.324 (4)	0.4210 (17)	0.110*
O4	0.7984 (2)	0.15562 (19)	0.3701 (2)	0.0805 (8)
C1	0.4258 (2)	0.2522 (2)	0.1037 (2)	0.0420 (6)
H1A	0.3892	0.2539	0.0033	0.050*
C2	0.5129 (3)	0.3552 (2)	0.1563 (3)	0.0489 (7)
H2A	0.4647	0.4256	0.1246	0.059*
H2B	0.5510	0.3555	0.2557	0.059*
C3	0.6155 (3)	0.3511 (3)	0.1063 (3)	0.0556 (8)
H3A	0.6718	0.4160	0.1442	0.067*
H3B	0.5773	0.3583	0.0073	0.067*
C4	0.6915 (3)	0.2400 (3)	0.1470 (3)	0.0497 (7)
H4	0.7428	0.2374	0.0955	0.060*
C5	0.6058 (3)	0.1347 (3)	0.1039 (3)	0.0557 (8)
H5A	0.5683	0.1283	0.0048	0.067*
H5B	0.6559	0.0662	0.1416	0.067*
C6	0.5018 (3)	0.1405 (2)	0.1514 (3)	0.0485 (7)
H6A	0.5384	0.1363	0.2506	0.058*
H6B	0.4460	0.0751	0.1152	0.058*
C7	0.3195 (3)	0.2542 (2)	0.1453 (3)	0.0471 (6)
C8	0.7822 (2)	0.2371 (2)	0.2978 (3)	0.0442 (6)
N1	0.0308 (3)	−0.0636 (2)	0.3628 (3)	0.0590 (7)
H1	0.041 (4)	−0.115 (2)	0.421 (3)	0.088*
O5	0.01175 (16)	0.18473 (15)	0.09311 (18)	0.0470 (5)
C9	0.0146 (2)	0.1065 (2)	0.1791 (2)	0.0384 (6)
C10	−0.0764 (3)	0.0194 (2)	0.1462 (3)	0.0495 (7)
H10	−0.1444	0.0185	0.0603	0.059*
C11	−0.0659 (3)	−0.0638 (2)	0.2390 (4)	0.0609 (8)
H11	−0.1266	−0.1213	0.2159	0.073*
C12	0.1179 (3)	0.0179 (3)	0.4004 (3)	0.0584 (8)
H12	0.1836	0.0165	0.4880	0.070*
C13	0.1124 (3)	0.1029 (2)	0.3127 (3)	0.0497 (7)
H13	0.1740	0.1599	0.3410	0.060*

	U11	U22	U33	U12	U13	U23
O1	0.0561 (13)	0.0868 (16)	0.0593 (13)	−0.0227 (12)	0.0280 (11)	−0.0188 (12)
O2	0.0729 (16)	0.130 (2)	0.0779 (16)	−0.0249 (15)	0.0433 (14)	−0.0510 (16)
O3	0.0722 (15)	0.0658 (14)	0.0532 (13)	−0.0221 (12)	−0.0005 (11)	0.0129 (11)
O4	0.1024 (19)	0.0580 (14)	0.0471 (12)	−0.0139 (13)	−0.0003 (12)	0.0119 (11)
C1	0.0442 (14)	0.0476 (15)	0.0296 (12)	−0.0022 (11)	0.0115 (11)	0.0003 (11)
C2	0.0532 (16)	0.0370 (14)	0.0506 (15)	0.0012 (12)	0.0166 (13)	0.0067 (12)
C3	0.0529 (16)	0.0624 (18)	0.0448 (15)	−0.0094 (14)	0.0146 (13)	0.0164 (13)
C4	0.0479 (15)	0.0695 (19)	0.0349 (13)	0.0017 (14)	0.0207 (12)	0.0011 (13)
C5	0.0569 (17)	0.0591 (18)	0.0447 (15)	0.0045 (14)	0.0157 (13)	−0.0176 (13)
C6	0.0550 (16)	0.0374 (14)	0.0483 (15)	−0.0063 (12)	0.0175 (13)	−0.0069 (12)
C7	0.0480 (15)	0.0490 (16)	0.0400 (14)	−0.0005 (12)	0.0146 (12)	0.0019 (12)
C8	0.0437 (14)	0.0500 (16)	0.0386 (13)	0.0008 (12)	0.0174 (11)	0.0004 (12)
N1	0.0757 (18)	0.0480 (15)	0.0647 (17)	0.0093 (13)	0.0411 (15)	0.0138 (12)
O5	0.0441 (10)	0.0454 (10)	0.0432 (10)	−0.0014 (8)	0.0109 (8)	0.0082 (8)
C9	0.0411 (13)	0.0345 (13)	0.0403 (13)	0.0048 (10)	0.0182 (11)	−0.0015 (10)
C10	0.0450 (15)	0.0467 (16)	0.0554 (16)	−0.0027 (12)	0.0202 (13)	−0.0062 (13)
C11	0.0667 (19)	0.0407 (16)	0.088 (2)	−0.0111 (14)	0.0458 (19)	−0.0066 (15)
C12	0.0672 (19)	0.0558 (18)	0.0488 (16)	0.0103 (16)	0.0217 (14)	0.0081 (14)
C13	0.0517 (15)	0.0439 (15)	0.0449 (14)	−0.0043 (12)	0.0125 (12)	−0.0001 (12)

O1—C7	1.310 (3)	C4—H4	0.9800
O1—H1'	0.8400 (10)	C5—C6	1.516 (4)
O2—C7	1.201 (3)	C5—H5A	0.9700
O3—C8	1.299 (3)	C5—H5B	0.9700
O3—H3'	0.8400 (11)	C6—H6A	0.9700
O4—C8	1.189 (3)	C6—H6B	0.9700
C1—C7	1.498 (4)	N1—C12	1.324 (4)
C1—C2	1.518 (4)	N1—C11	1.333 (4)
C1—C6	1.534 (4)	N1—H1	0.8400 (10)
C1—H1A	0.9800	O5—C9	1.289 (3)
C2—C3	1.518 (4)	C9—C10	1.403 (4)
C2—H2A	0.9700	C9—C13	1.408 (4)
C2—H2B	0.9700	C10—C11	1.359 (4)
C3—C4	1.524 (4)	C10—H10	0.9300
C3—H3A	0.9700	C11—H11	0.9300
C3—H3B	0.9700	C12—C13	1.351 (4)
C4—C8	1.517 (4)	C12—H12	0.9300
C4—C5	1.525 (4)	C13—H13	0.9300
C7—O1—H1'	112 (3)	H5A—C5—H5B	107.8
C8—O3—H3'	110 (3)	C5—C6—C1	111.2 (2)
C7—C1—C2	113.0 (2)	C5—C6—H6A	109.4
C7—C1—C6	110.6 (2)	C1—C6—H6A	109.4
C2—C1—C6	109.8 (2)	C5—C6—H6B	109.4
C7—C1—H1A	107.7	C1—C6—H6B	109.4
C2—C1—H1A	107.7	H6A—C6—H6B	108.0
C6—C1—H1A	107.7	O2—C7—O1	122.0 (3)
C3—C2—C1	110.7 (2)	O2—C7—C1	125.7 (3)
C3—C2—H2A	109.5	O1—C7—C1	112.3 (2)
C1—C2—H2A	109.5	O4—C8—O3	122.4 (2)
C3—C2—H2B	109.5	O4—C8—C4	124.3 (3)
C1—C2—H2B	109.5	O3—C8—C4	113.3 (2)
H2A—C2—H2B	108.1	C12—N1—C11	121.6 (3)
C2—C3—C4	112.4 (2)	C12—N1—H1	116 (3)
C2—C3—H3A	109.1	C11—N1—H1	122 (3)
C4—C3—H3A	109.1	O5—C9—C10	123.0 (2)
C2—C3—H3B	109.1	O5—C9—C13	121.1 (2)
C4—C3—H3B	109.1	C10—C9—C13	115.8 (2)
H3A—C3—H3B	107.9	C11—C10—C9	120.6 (3)
C8—C4—C3	112.5 (2)	C11—C10—H10	119.7
C8—C4—C5	112.2 (2)	C9—C10—H10	119.7
C3—C4—C5	111.2 (2)	N1—C11—C10	120.5 (3)
C8—C4—H4	106.8	N1—C11—H11	119.8
C3—C4—H4	106.8	C10—C11—H11	119.8
C5—C4—H4	106.8	N1—C12—C13	120.6 (3)
C6—C5—C4	112.6 (2)	N1—C12—H12	119.7
C6—C5—H5A	109.1	C13—C12—H12	119.7
C4—C5—H5A	109.1	C12—C13—C9	120.9 (3)
C6—C5—H5B	109.1	C12—C13—H13	119.6
C4—C5—H5B	109.1	C9—C13—H13	119.6
C7—C1—C2—C3	−177.7 (2)	C6—C1—C7—O1	−79.7 (3)
C6—C1—C2—C3	58.2 (3)	C3—C4—C8—O4	136.9 (3)
C1—C2—C3—C4	−56.6 (3)	C5—C4—C8—O4	10.5 (4)
C2—C3—C4—C8	−74.5 (3)	C3—C4—C8—O3	−44.6 (3)
C2—C3—C4—C5	52.4 (3)	C5—C4—C8—O3	−170.9 (2)
C8—C4—C5—C6	75.7 (3)	O5—C9—C10—C11	177.2 (2)
C3—C4—C5—C6	−51.4 (3)	C13—C9—C10—C11	−1.8 (4)
C4—C5—C6—C1	54.4 (3)	C12—N1—C11—C10	1.2 (4)
C7—C1—C6—C5	177.2 (2)	C9—C10—C11—N1	0.3 (4)
C2—C1—C6—C5	−57.4 (3)	C11—N1—C12—C13	−1.1 (5)
C2—C1—C7—O2	−22.5 (4)	N1—C12—C13—C9	−0.5 (4)
C6—C1—C7—O2	101.1 (3)	O5—C9—C13—C12	−177.1 (3)
C2—C1—C7—O1	156.7 (2)	C10—C9—C13—C12	1.9 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1′···O5	0.84	1.82	2.638 (3)	165
O3—H3′···O5i	0.84	1.76	2.594 (2)	175
N1—H1···O4ii	0.84	2.29	2.921 (3)	132
N1—H1···O5iii	0.84	2.39	3.038 (3)	134
C1—H1A···O2iv	0.98	2.67	3.625 (4)	162
C11—H11···O2iii	0.93	2.62	3.420 (5)	143
C12—H12···O4ii	0.93	2.47	3.014 (4)	117

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1′⋯O5	0.84	1.82	2.638 (3)	165
O3—H3′⋯O5i	0.84	1.76	2.594 (2)	175
N1—H1⋯O4ii	0.84	2.29	2.921 (3)	132
N1—H1⋯O5iii	0.84	2.39	3.038 (3)	134
C1—H1A⋯O2iv	0.98	2.67	3.625 (4)	162
C11—H11⋯O2iii	0.93	2.62	3.420 (5)	143
C12—H12⋯O4ii	0.93	2.47	3.014 (4)	117

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