1,4-Diaza-bicyclo-[2.2.2]octa-ne-trans,trans-hexa-2,4-dienedioic acid (1/1).

The title 1:1 co-crystal, C(6)H(12)N(2)·C(6)H(6)O(4), the dicarb-oxy-lic acid mol-ecule is close to planar [r.m.s. deviation from the mean plane = 0.07 (1) Å]. In the crystal, the two mol-ecules are arranged alternately and are linked by O-H⋯N hydrogen bonds, leading to the formation of a chain along the [20-1] direction. The chains are assembled into a two-dimensional framework parallel to the (102) plane through weak C-H⋯O hydrogen bonds between the two types of mol-ecules.

Related literature

For background to the applications of co-crystals, see: Bhogala & Nangia (2003 ▶); Gao et al. (2004 ▶); Hori et al. (2009 ▶); Weyna et al. (2009 ▶). For a related structure, see: Moon & Park (2012 ▶).

Experimental

Crystal data

C6H12N2·C6H6O4

M = 254.28

Triclinic,

a = 8.1547 (2) Å

b = 8.9321 (2) Å

c = 9.4028 (2) Å

α = 86.258 (1)°

β = 67.376 (1)°

γ = 80.719 (1)°

V = 623.90 (2) Å3

Z = 2

Mo Kα radiation

μ = 0.10 mm−1

T = 173 K

0.20 × 0.12 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.980, T max = 0.990

10893 measured reflections

2719 independent reflections

2382 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.125

S = 1.06

2719 reflections

163 parameters

H-atom parameters constrained

Δρmax = 0.39 e Å−3

Δρmin = −0.37 e Å−3

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and DIAMOND (Brandenburg, 1998 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681202942X/wn2482sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681202942X/wn2482Isup2.hkl

Supplementary material file. DOI: 10.1107/S160053681202942X/wn2482Isup3.cml

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

C6H12N2·C6H6O4	Z = 2
Mr = 254.28	F(000) = 272
Triclinic, P1	Dx = 1.354 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.1547 (2) Å	Cell parameters from 5075 reflections
b = 8.9321 (2) Å	θ = 3.3–28.4°
c = 9.4028 (2) Å	µ = 0.10 mm−1
α = 86.258 (1)°	T = 173 K
β = 67.376 (1)°	Plate, colourless
γ = 80.719 (1)°	0.20 × 0.12 × 0.10 mm
V = 623.90 (2) Å3

Bruker APEXII CCD diffractometer	2719 independent reflections
Radiation source: fine-focus sealed tube	2382 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
φ and ω scans	θmax = 27.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→9
Tmin = 0.980, Tmax = 0.990	k = −11→11
10893 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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.125	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0641P)2 + 0.2432P] where P = (Fo2 + 2Fc2)/3
2719 reflections	(Δ/σ)max < 0.001
163 parameters	Δρmax = 0.39 e Å−3
0 restraints	Δρmin = −0.37 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	0.76168 (14)	0.35311 (12)	0.48540 (14)	0.0383 (3)
H1	0.8660	0.3185	0.4255	0.046*
O2	0.70091 (14)	0.13027 (12)	0.44151 (14)	0.0356 (3)
O3	−0.25828 (14)	0.13485 (13)	0.96677 (14)	0.0384 (3)
H3	−0.3611	0.1718	1.0276	0.046*
O4	−0.20125 (14)	0.37072 (12)	0.96904 (14)	0.0370 (3)
C1	0.65577 (17)	0.25426 (15)	0.50280 (15)	0.0231 (3)
C2	0.46734 (18)	0.30803 (16)	0.60830 (16)	0.0253 (3)
H2	0.4375	0.4100	0.6432	0.030*
C3	0.33925 (17)	0.22026 (15)	0.65586 (15)	0.0221 (3)
H3A	0.3679	0.1191	0.6190	0.027*
C4	0.15787 (17)	0.27194 (16)	0.76141 (15)	0.0234 (3)
H4	0.1279	0.3750	0.7929	0.028*
C5	0.03082 (18)	0.18318 (16)	0.81672 (16)	0.0257 (3)
H5	0.0598	0.0800	0.7857	0.031*
C6	−0.15544 (18)	0.23910 (16)	0.92551 (16)	0.0250 (3)
N1	1.08788 (14)	0.27644 (12)	0.31399 (13)	0.0215 (3)
N2	1.41841 (14)	0.22012 (13)	0.14620 (13)	0.0230 (3)
C7	1.11006 (18)	0.27117 (17)	0.15051 (16)	0.0261 (3)
H7A	1.0583	0.3700	0.1199	0.031*
H7B	1.0455	0.1919	0.1366	0.031*
C8	1.31022 (19)	0.23589 (17)	0.04914 (16)	0.0279 (3)
H8A	1.3332	0.1406	−0.0081	0.033*
H8B	1.3454	0.3187	−0.0267	0.033*
C9	1.18363 (18)	0.39594 (16)	0.33479 (16)	0.0252 (3)
H9A	1.1706	0.3982	0.4438	0.030*
H9B	1.1302	0.4963	0.3087	0.030*
C10	1.38327 (18)	0.36395 (16)	0.23055 (17)	0.0273 (3)
H10A	1.4159	0.4484	0.1563	0.033*
H10B	1.4575	0.3558	0.2936	0.033*
C11	1.16529 (18)	0.12776 (15)	0.35852 (16)	0.0252 (3)
H11A	1.1041	0.0467	0.3432	0.030*
H11B	1.1471	0.1290	0.4688	0.030*
C12	1.36674 (19)	0.09588 (16)	0.25949 (17)	0.0274 (3)
H12A	1.4366	0.0877	0.3263	0.033*
H12B	1.3943	−0.0016	0.2047	0.033*

	U11	U22	U33	U12	U13	U23
O1	0.0164 (5)	0.0337 (6)	0.0531 (7)	−0.0076 (4)	0.0034 (5)	−0.0147 (5)
O2	0.0232 (5)	0.0290 (5)	0.0455 (7)	−0.0053 (4)	−0.0009 (5)	−0.0109 (5)
O3	0.0190 (5)	0.0351 (6)	0.0470 (7)	−0.0081 (4)	0.0059 (5)	−0.0094 (5)
O4	0.0240 (5)	0.0287 (6)	0.0456 (7)	−0.0033 (4)	0.0006 (5)	−0.0012 (5)
C1	0.0176 (6)	0.0246 (7)	0.0252 (7)	−0.0034 (5)	−0.0058 (5)	−0.0002 (5)
C2	0.0195 (7)	0.0242 (6)	0.0289 (7)	−0.0022 (5)	−0.0056 (5)	−0.0027 (5)
C3	0.0177 (6)	0.0254 (6)	0.0218 (6)	−0.0017 (5)	−0.0065 (5)	−0.0001 (5)
C4	0.0178 (6)	0.0272 (7)	0.0235 (6)	−0.0019 (5)	−0.0067 (5)	0.0001 (5)
C5	0.0191 (7)	0.0291 (7)	0.0256 (7)	−0.0029 (5)	−0.0047 (5)	−0.0024 (5)
C6	0.0179 (6)	0.0302 (7)	0.0243 (7)	−0.0040 (5)	−0.0052 (5)	0.0016 (5)
N1	0.0163 (5)	0.0238 (6)	0.0222 (6)	−0.0039 (4)	−0.0041 (4)	−0.0029 (4)
N2	0.0168 (5)	0.0262 (6)	0.0222 (6)	−0.0035 (4)	−0.0030 (4)	−0.0017 (4)
C7	0.0216 (7)	0.0325 (7)	0.0252 (7)	−0.0033 (5)	−0.0101 (5)	−0.0015 (5)
C8	0.0245 (7)	0.0358 (8)	0.0206 (6)	−0.0039 (6)	−0.0054 (5)	−0.0026 (5)
C9	0.0201 (6)	0.0252 (7)	0.0273 (7)	−0.0042 (5)	−0.0043 (5)	−0.0066 (5)
C10	0.0197 (6)	0.0287 (7)	0.0320 (7)	−0.0079 (5)	−0.0055 (6)	−0.0052 (6)
C11	0.0218 (7)	0.0260 (7)	0.0246 (7)	−0.0059 (5)	−0.0049 (5)	0.0024 (5)
C12	0.0229 (7)	0.0245 (7)	0.0295 (7)	−0.0007 (5)	−0.0057 (6)	0.0024 (5)

O1—C1	1.2925 (16)	N2—C8	1.4812 (18)
O1—H1	0.8400	N2—C12	1.4815 (18)
O2—C1	1.2177 (17)	N2—C10	1.4836 (17)
O3—C6	1.2944 (17)	C7—C8	1.5324 (18)
O3—H3	0.8400	C7—H7A	0.9900
O4—C6	1.2217 (18)	C7—H7B	0.9900
C1—C2	1.4924 (18)	C8—H8A	0.9900
C2—C3	1.3284 (19)	C8—H8B	0.9900
C2—H2	0.9500	C9—C10	1.5335 (18)
C3—C4	1.4477 (18)	C9—H9A	0.9900
C3—H3A	0.9500	C9—H9B	0.9900
C4—C5	1.3301 (19)	C10—H10A	0.9900
C4—H4	0.9500	C10—H10B	0.9900
C5—C6	1.4931 (18)	C11—C12	1.5342 (18)
C5—H5	0.9500	C11—H11A	0.9900
N1—C7	1.4800 (17)	C11—H11B	0.9900
N1—C11	1.4825 (17)	C12—H12A	0.9900
N1—C9	1.4835 (16)	C12—H12B	0.9900
C1—O1—H1	109.5	H7A—C7—H7B	108.2
C6—O3—H3	109.5	N2—C8—C7	109.89 (11)
O2—C1—O1	125.03 (13)	N2—C8—H8A	109.7
O2—C1—C2	122.44 (12)	C7—C8—H8A	109.7
O1—C1—C2	112.53 (12)	N2—C8—H8B	109.7
C3—C2—C1	123.21 (12)	C7—C8—H8B	109.7
C3—C2—H2	118.4	H8A—C8—H8B	108.2
C1—C2—H2	118.4	N1—C9—C10	109.92 (10)
C2—C3—C4	122.93 (13)	N1—C9—H9A	109.7
C2—C3—H3A	118.5	C10—C9—H9A	109.7
C4—C3—H3A	118.5	N1—C9—H9B	109.7
C5—C4—C3	123.67 (13)	C10—C9—H9B	109.7
C5—C4—H4	118.2	H9A—C9—H9B	108.2
C3—C4—H4	118.2	N2—C10—C9	109.32 (10)
C4—C5—C6	122.70 (13)	N2—C10—H10A	109.8
C4—C5—H5	118.7	C9—C10—H10A	109.8
C6—C5—H5	118.7	N2—C10—H10B	109.8
O4—C6—O3	125.06 (13)	C9—C10—H10B	109.8
O4—C6—C5	121.79 (12)	H10A—C10—H10B	108.3
O3—C6—C5	113.15 (12)	N1—C11—C12	109.41 (10)
C7—N1—C11	109.23 (10)	N1—C11—H11A	109.8
C7—N1—C9	109.70 (11)	C12—C11—H11A	109.8
C11—N1—C9	108.99 (10)	N1—C11—H11B	109.8
C8—N2—C12	109.88 (11)	C12—C11—H11B	109.8
C8—N2—C10	109.04 (11)	H11A—C11—H11B	108.2
C12—N2—C10	108.85 (11)	N2—C12—C11	109.83 (11)
N1—C7—C8	109.49 (11)	N2—C12—H12A	109.7
N1—C7—H7A	109.8	C11—C12—H12A	109.7
C8—C7—H7A	109.8	N2—C12—H12B	109.7
N1—C7—H7B	109.8	C11—C12—H12B	109.7
C8—C7—H7B	109.8	H12A—C12—H12B	108.2
O2—C1—C2—C3	7.1 (2)	N1—C7—C8—N2	−0.71 (16)
O1—C1—C2—C3	−172.87 (14)	C7—N1—C9—C10	−58.31 (14)
C1—C2—C3—C4	178.33 (12)	C11—N1—C9—C10	61.24 (14)
C2—C3—C4—C5	−176.16 (14)	C8—N2—C10—C9	61.06 (14)
C3—C4—C5—C6	−179.99 (12)	C12—N2—C10—C9	−58.81 (14)
C4—C5—C6—O4	0.4 (2)	N1—C9—C10—N2	−2.11 (16)
C4—C5—C6—O3	−179.44 (13)	C7—N1—C11—C12	61.50 (14)
C11—N1—C7—C8	−59.61 (14)	C9—N1—C11—C12	−58.35 (14)
C9—N1—C7—C8	59.80 (14)	C8—N2—C12—C11	−57.63 (14)
C12—N2—C8—C7	59.59 (14)	C10—N2—C12—C11	61.71 (14)
C10—N2—C8—C7	−59.64 (14)	N1—C11—C12—N2	−2.54 (15)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.84	1.70	2.5299 (14)	170
O3—H3···N2i	0.84	1.71	2.5447 (15)	170
C3—H3A···O2ii	0.95	2.53	3.4182 (17)	155
C8—H8A···O3ii	0.99	2.60	3.4255 (18)	141
C9—H9A···O1iii	0.99	2.56	3.0789 (17)	113

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.84	1.70	2.5299 (14)	170
O3—H3⋯N2i	0.84	1.71	2.5447 (15)	170
C3—H3A⋯O2ii	0.95	2.53	3.4182 (17)	155
C8—H8A⋯O3ii	0.99	2.60	3.4255 (18)	141
C9—H9A⋯O1iii	0.99	2.56	3.0789 (17)	113

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