1,4-Diazo­niabicyclo­[2.2.2]octane terephthalate

Yang, E.; Song, X.-C.; Zhu, J.-W.

doi:10.1107/S1600536808025312

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 64| Part 9| September 2008| Page o1764

doi:10.1107/S1600536808025312

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1,4-Diazoniabicyclo[2.2.2]octane terephthalate

E Yang,^a ^* Xu-Chun Song ^a and Jian-Wei Zhu ^b

^aCollege of Chemistry and Materials Science, Fujian Normal University, Fuzhou 350007, People's Republic of China, and ^bCollege of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, People's Republic of China
^*Correspondence e-mail: yangeli66@yahoo.com.cn

(Received 18 July 2008; accepted 6 August 2008; online 16 August 2008)

In the title compound, C₆H₁₄N²⁺·C₈H₄O₄²⁻, the protonated 1,4-diazoniabicyclo[2.2.2]octane cations and the deprotonated terephthalate anions are alternately linked by N—H⋯O hydrogen bonds into chains.

Experimental

Crystal data

C₆H₁₄N₂²⁺·C₈H₄O₄²⁻
M_r = 278.30
Triclinic, $[P \overline 1]$
a = 7.8046 (10) Å
b = 9.5482 (2) Å
c = 10.8075 (2) Å
α = 65.900 (10)°
β = 78.360 (10)°
γ = 66.800 (10)°
V = 672.39 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 (2) K
0.23 × 0.13 × 0.08 mm

Data collection

Siemens SMART 1K CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.900, T_max = 0.950
7312 measured reflections
2377 independent reflections
1779 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.125
S = 1.04
2377 reflections
188 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O2	0.954 (15)	1.623 (15)	2.5757 (19)	176.8 (17)
N2—H2N⋯O4ⁱ	0.959 (15)	1.600 (15)	2.5589 (19)	177.9 (18)
Symmetry code: (i) x-2, y+1, z.

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Bergerhoff et al., 1996 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808025312/pv2092sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808025312/pv2092Isup2.hkl

checkCIF report

Comment top

The asymmetric unit of the title compound, (I), consists of a protonated 1,4-diazoniabicyclo[2.2.2]octane cation, C₆H₁₄N²⁺, and a deprotonated terephthalate anion, C₈H₄O₄^2-, (Figure 1). Single N—H···O hydrogen bond was formed between the protonated N end of the cation and the deprotonated carboxylate group of the anion, which generates the hydrogen bonding chains (Table 1 & Figure 2).

Related literature top

Please supply any relevant related literature.

Experimental top

A mixture of 1,4-diazoniabicyclo[2.2.2]octane (0.072 g), terephthalic acid (0.08 g) and H₂O (10 ml) was sealed in a 25 ml stainless-steel reactor with a Teflon-lined stainless steel reactor and was heated at 373 K for 3 d. On completion of the reaction, the reactor was cooled slowly to room temperature and the mixture was filtered, giving collorless single crystals suitable for X-ray analysis.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Bergerhoff et al., 1996); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the title compound, showing 30% probability displacement ellipsoids.
	Fig. 2. The unit-cell packing of the title compound, showing the hydrogen bonding chains (symmetry code: a = 2 + x, -1 + y, z).

1,4-Diazoniabicyclo[2.2.2]octane terephthalate top

Crystal data top

C₆H₁₄N₂²⁺·C₈H₄O₄²⁻	Z = 2
M_r = 278.30	F(000) = 296
Triclinic, P1	D_x = 1.375 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.8046 (10) Å	Cell parameters from 98 reflections
b = 9.5482 (2) Å	θ = 2.1–25.0°
c = 10.8075 (2) Å	µ = 0.10 mm⁻¹
α = 65.99 (1)°	T = 293 K
β = 78.436 (10)°	Prism, colorless
γ = 66.18 (1)°	0.23 × 0.13 × 0.08 mm
V = 672.39 (2) Å³

Data collection top

Siemens SMART 1K CCD area-detector diffractometer	2377 independent reflections
Radiation source: fine-focus sealed tube	1779 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.900, T_max = 0.950	k = −11→11
7312 measured reflections	l = −12→12

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.125	w = 1/[σ²(F_o²) + (0.0633P)² + 0.1475P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.002
2377 reflections	Δρ_max = 0.21 e Å⁻³
188 parameters	Δρ_min = −0.27 e Å⁻³
2 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.023 (4)

Crystal data top

C₆H₁₄N₂²⁺·C₈H₄O₄²⁻	γ = 66.18 (1)°
M_r = 278.30	V = 672.39 (2) Å³
Triclinic, P1	Z = 2
a = 7.8046 (10) Å	Mo Kα radiation
b = 9.5482 (2) Å	µ = 0.10 mm⁻¹
c = 10.8075 (2) Å	T = 293 K
α = 65.99 (1)°	0.23 × 0.13 × 0.08 mm
β = 78.436 (10)°

Data collection top

Siemens SMART 1K CCD area-detector diffractometer	2377 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1779 reflections with I > 2σ(I)
T_min = 0.900, T_max = 0.950	R_int = 0.026
7312 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	2 restraints
wR(F²) = 0.125	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.21 e Å⁻³
2377 reflections	Δρ_min = −0.27 e Å⁻³
188 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.2883 (2)	0.8953 (2)	0.60534 (16)	0.0691 (5)
O2	0.25555 (18)	0.84559 (17)	0.82616 (14)	0.0489 (4)
O3	1.1805 (2)	0.27977 (19)	0.89737 (15)	0.0629 (5)
O4	1.23265 (18)	0.40326 (18)	0.67751 (14)	0.0519 (4)
N1	−0.0871 (2)	1.03609 (18)	0.77218 (15)	0.0328 (4)
H1N	0.040 (2)	0.964 (2)	0.7898 (18)	0.039*
N2	−0.4239 (2)	1.21700 (18)	0.72154 (14)	0.0317 (4)
H2N	−0.553 (2)	1.285 (2)	0.7069 (18)	0.038*
C1	0.5526 (2)	0.7124 (2)	0.73811 (18)	0.0315 (4)
C2	0.6233 (2)	0.6175 (2)	0.86638 (18)	0.0345 (4)
H2A	0.5455	0.6256	0.9425	0.041*
C3	0.8080 (3)	0.5111 (2)	0.88253 (18)	0.0354 (4)
H3A	0.8524	0.4464	0.9692	0.042*
C4	0.9270 (2)	0.5006 (2)	0.77020 (17)	0.0303 (4)
C5	0.8571 (3)	0.5980 (2)	0.64181 (18)	0.0352 (4)
H5A	0.9362	0.5932	0.5657	0.042*
C6	0.6722 (3)	0.7017 (2)	0.62577 (19)	0.0376 (5)
H6A	0.6273	0.7649	0.5391	0.045*
C7	0.3509 (3)	0.8265 (2)	0.71843 (19)	0.0376 (5)
C8	1.1275 (3)	0.3846 (2)	0.78670 (19)	0.0356 (4)
C9	−0.3943 (3)	1.0480 (2)	0.7369 (2)	0.0389 (5)
H9A	−0.4315	1.0493	0.6559	0.047*
H9B	−0.4709	1.0034	0.8132	0.047*
C10	−0.1869 (3)	0.9399 (2)	0.7601 (2)	0.0407 (5)
H10A	−0.1752	0.8438	0.8422	0.049*
H10B	−0.1322	0.9032	0.6847	0.049*
C11	−0.3778 (3)	1.2165 (3)	0.84800 (19)	0.0419 (5)
H11A	−0.4643	1.1827	0.9213	0.050*
H11B	−0.3897	1.3264	0.8360	0.050*
C12	−0.1769 (3)	1.0977 (2)	0.88353 (18)	0.0377 (5)
H12A	−0.1062	1.1538	0.8965	0.045*
H12B	−0.1781	1.0064	0.9672	0.045*
C13	−0.3010 (3)	1.2820 (2)	0.60835 (19)	0.0404 (5)
H13A	−0.3256	1.3954	0.5939	0.048*
H13B	−0.3262	1.2783	0.5256	0.048*
C14	−0.0959 (3)	1.1773 (2)	0.64345 (19)	0.0411 (5)
H14A	−0.0299	1.1377	0.5711	0.049*
H14B	−0.0356	1.2435	0.6526	0.049*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0381 (9)	0.0919 (13)	0.0523 (10)	0.0164 (8)	−0.0141 (7)	−0.0364 (9)
O2	0.0265 (7)	0.0596 (10)	0.0459 (8)	0.0020 (7)	0.0000 (6)	−0.0230 (7)
O3	0.0341 (8)	0.0626 (10)	0.0484 (9)	0.0015 (7)	−0.0034 (7)	0.0032 (8)
O4	0.0259 (7)	0.0630 (10)	0.0413 (8)	0.0009 (7)	0.0016 (6)	−0.0126 (7)
N1	0.0195 (8)	0.0335 (9)	0.0379 (9)	−0.0030 (7)	−0.0017 (6)	−0.0122 (7)
N2	0.0203 (8)	0.0342 (9)	0.0353 (8)	−0.0016 (7)	−0.0034 (6)	−0.0145 (7)
C1	0.0242 (9)	0.0320 (10)	0.0394 (10)	−0.0070 (8)	−0.0002 (8)	−0.0177 (8)
C2	0.0277 (10)	0.0387 (11)	0.0348 (10)	−0.0085 (8)	0.0063 (8)	−0.0181 (8)
C3	0.0316 (10)	0.0363 (10)	0.0305 (9)	−0.0076 (8)	−0.0022 (8)	−0.0091 (8)
C4	0.0248 (9)	0.0272 (9)	0.0360 (10)	−0.0076 (8)	0.0007 (8)	−0.0116 (8)
C5	0.0270 (10)	0.0388 (11)	0.0329 (10)	−0.0059 (8)	0.0043 (8)	−0.0149 (8)
C6	0.0297 (10)	0.0403 (11)	0.0325 (10)	−0.0027 (8)	−0.0048 (8)	−0.0115 (8)
C7	0.0270 (10)	0.0403 (11)	0.0456 (11)	−0.0045 (8)	−0.0033 (9)	−0.0226 (9)
C8	0.0263 (10)	0.0344 (10)	0.0399 (11)	−0.0069 (8)	−0.0030 (8)	−0.0108 (9)
C9	0.0333 (11)	0.0375 (11)	0.0475 (11)	−0.0130 (9)	−0.0045 (9)	−0.0156 (9)
C10	0.0378 (11)	0.0316 (10)	0.0518 (12)	−0.0081 (9)	−0.0050 (9)	−0.0173 (9)
C11	0.0308 (11)	0.0532 (13)	0.0422 (11)	−0.0041 (9)	−0.0019 (8)	−0.0285 (10)
C12	0.0311 (10)	0.0438 (11)	0.0365 (10)	−0.0076 (9)	−0.0059 (8)	−0.0170 (9)
C13	0.0360 (11)	0.0348 (11)	0.0397 (10)	−0.0087 (9)	−0.0027 (8)	−0.0068 (9)
C14	0.0303 (10)	0.0420 (11)	0.0414 (11)	−0.0105 (9)	0.0028 (8)	−0.0104 (9)

Geometric parameters (Å, º) top

O1—C7	1.221 (2)	C4—C8	1.503 (2)
O2—C7	1.288 (2)	C5—C6	1.378 (3)
O3—C8	1.222 (2)	C5—H5A	0.9300
O4—C8	1.287 (2)	C6—H6A	0.9300
N1—C10	1.478 (2)	C9—C10	1.533 (3)
N1—C12	1.480 (2)	C9—H9A	0.9700
N1—C14	1.482 (2)	C9—H9B	0.9700
N1—H1N	0.954 (15)	C10—H10A	0.9700
N2—C9	1.477 (2)	C10—H10B	0.9700
N2—C11	1.479 (2)	C11—C12	1.531 (3)
N2—C13	1.481 (2)	C11—H11A	0.9700
N2—H2N	0.959 (15)	C11—H11B	0.9700
C1—C6	1.388 (2)	C12—H12A	0.9700
C1—C2	1.388 (3)	C12—H12B	0.9700
C1—C7	1.507 (2)	C13—C14	1.532 (3)
C2—C3	1.383 (3)	C13—H13A	0.9700
C2—H2A	0.9300	C13—H13B	0.9700
C3—C4	1.385 (2)	C14—H14A	0.9700
C3—H3A	0.9300	C14—H14B	0.9700
C4—C5	1.390 (2)

C10—N1—C12	109.46 (14)	N2—C9—C10	109.63 (14)
C10—N1—C14	109.60 (14)	N2—C9—H9A	109.7
C12—N1—C14	109.29 (14)	C10—C9—H9A	109.7
C10—N1—H1N	106.8 (11)	N2—C9—H9B	109.7
C12—N1—H1N	111.5 (11)	C10—C9—H9B	109.7
C14—N1—H1N	110.1 (11)	H9A—C9—H9B	108.2
C9—N2—C11	109.82 (14)	N1—C10—C9	109.09 (14)
C9—N2—C13	109.48 (14)	N1—C10—H10A	109.9
C11—N2—C13	109.17 (15)	C9—C10—H10A	109.9
C9—N2—H2N	109.9 (11)	N1—C10—H10B	109.9
C11—N2—H2N	106.9 (11)	C9—C10—H10B	109.9
C13—N2—H2N	111.5 (11)	H10A—C10—H10B	108.3
C6—C1—C2	118.69 (16)	N2—C11—C12	109.40 (14)
C6—C1—C7	119.60 (16)	N2—C11—H11A	109.8
C2—C1—C7	121.71 (16)	C12—C11—H11A	109.8
C3—C2—C1	120.90 (16)	N2—C11—H11B	109.8
C3—C2—H2A	119.6	C12—C11—H11B	109.8
C1—C2—H2A	119.6	H11A—C11—H11B	108.2
C2—C3—C4	120.26 (17)	N1—C12—C11	109.31 (14)
C2—C3—H3A	119.9	N1—C12—H12A	109.8
C4—C3—H3A	119.9	C11—C12—H12A	109.8
C3—C4—C5	118.80 (16)	N1—C12—H12B	109.8
C3—C4—C8	120.66 (16)	C11—C12—H12B	109.8
C5—C4—C8	120.54 (16)	H12A—C12—H12B	108.3
C6—C5—C4	120.92 (16)	N2—C13—C14	108.99 (15)
C6—C5—H5A	119.5	N2—C13—H13A	109.9
C4—C5—H5A	119.5	C14—C13—H13A	109.9
C5—C6—C1	120.40 (17)	N2—C13—H13B	109.9
C5—C6—H6A	119.8	C14—C13—H13B	109.9
C1—C6—H6A	119.8	H13A—C13—H13B	108.3
O1—C7—O2	124.21 (17)	N1—C14—C13	109.66 (14)
O1—C7—C1	120.01 (17)	N1—C14—H14A	109.7
O2—C7—C1	115.77 (16)	C13—C14—H14A	109.7
O3—C8—O4	124.30 (17)	N1—C14—H14B	109.7
O3—C8—C4	120.41 (17)	C13—C14—H14B	109.7
O4—C8—C4	115.28 (16)	H14A—C14—H14B	108.2

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2	0.95 (2)	1.62 (2)	2.5757 (19)	177 (2)
N2—H2N···O4ⁱ	0.96 (2)	1.60 (2)	2.5589 (19)	178 (2)

Symmetry code: (i) x−2, y+1, z.

Experimental details

Crystal data
Chemical formula	C₆H₁₄N₂²⁺·C₈H₄O₄²⁻
M_r	278.30
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.8046 (10), 9.5482 (2), 10.8075 (2)
α, β, γ (°)	65.99 (1), 78.436 (10), 66.18 (1)
V (Å³)	672.39 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.23 × 0.13 × 0.08

Data collection
Diffractometer	Siemens SMART 1K CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.900, 0.950
No. of measured, independent and observed [I > 2σ(I)] reflections	7312, 2377, 1779
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.125, 1.04
No. of reflections	2377
No. of parameters	188
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.27

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Bergerhoff et al., 1996), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2	0.954 (15)	1.623 (15)	2.5757 (19)	176.8 (17)
N2—H2N···O4ⁱ	0.959 (15)	1.600 (15)	2.5589 (19)	177.9 (18)

Symmetry code: (i) x−2, y+1, z.

Acknowledgements

The authors acknowledge the financial support from the Natural Science Foundation of Fujian Province (No. 2006 F3042).

References

Bergerhoff, G., Berndt, M. & Brandenburg, K. (1996). J. Res. Natl Inst. Stand. Technol. 101, 221–225. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar