4-Aza-1-azoniabicyclo­[2.2.2]octa­ne–2-amino­benzoate–2-amino­benzoic acid (1/1/1)

Arman, H.D.; Kaulgud, T.; Tiekink, E.R.T.

doi:10.1107/S1600536811041559

organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page o2933

doi:10.1107/S1600536811041559

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4-Aza-1-azoniabicyclo[2.2.2]octane–2-aminobenzoate–2-aminobenzoic acid (1/1/1)

Hadi D. Arman,^a Trupta Kaulgud ^a and Edward R. T. Tiekink ^b ^*

^aDepartment of Chemistry, The University of Texas at San Antonio, One UTSA Circle, San Antonio, Texas 78249-0698, USA, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 7 October 2011; accepted 10 October 2011; online 12 October 2011)

A 4-aza-1-azoniabicyclo[2.2.2]octane cation, a 2-aminobenzoate anion and a neutral 2-aminobenzoic acid molecule comprise the asymmetric unit of the title compound, C₆H₁₃N₂⁺·C₇H₆NO₂⁻·C₇H₇NO₂. An intramolecular N—H⋯O hydrogen bond occurs in the anion and in the neutral 2-aminobenzoic acid molecule. The cation provides a charge-assisted N—H⋯O hydrogen bond to the anion, and the 2-aminobenzoic acid molecule forms an O—H⋯N hydrogen bond to the unprotonated amino N atom in the cation. In this way, a three-component aggregate is formed. These are connected into a three-dimensional network by amino–carboxylate N—H⋯O hydrogen bonds. N—H⋯N hydrogen bonds are also observed.

Related literature

For related studies on co-crystal formation, see: Arman et al. (2010 ); Arman & Tiekink (2010 ); Wardell & Tiekink (2011 ). For examples of multi-component crystals containing the 2-aminobenzoate anion, see: Lynch et al. (1998 ); Chen & Peng (2011 ). For a description of the Cambridge Structural Database, see: Allen (2002 ).

Experimental

Crystal data

C₆H₁₃N₂⁺·C₇H₆NO₂⁻·C₇H₇NO₂
M_r = 386.45
Monoclinic, P 2₁ /c
a = 9.285 (3) Å
b = 16.843 (5) Å
c = 12.660 (4) Å
β = 102.127 (6)°
V = 1935.7 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 98 K
0.34 × 0.17 × 0.07 mm

Data collection

Rigaku AFC12/SATURN724 diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.731, T_max = 1.000
16911 measured reflections
4440 independent reflections
3929 reflections with I > 2σ(I)
R_int = 0.054

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.128
S = 1.13
4440 reflections
268 parameters
7 restraints
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯N3	0.84	1.77	2.597 (2)	168
N4—H5n⋯O3	0.93	1.64	2.546 (2)	166
N1—H2n⋯O2	0.88	2.03	2.725 (2)	135
N2—H3n⋯O3	0.88	2.04	2.696 (2)	131
N1—H1n⋯O4ⁱ	0.88	2.08	2.941 (2)	165
N2—H4n⋯N1ⁱⁱ	0.88	2.38	3.256 (2)	171
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2005 ); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976 ) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811041559/hb6440sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811041559/hb6440Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811041559/hb6440Isup3.cml

checkCIF report

Comment top

As a part of on-going studies into co-crystallization experiments of carboxylic acids with N-containing molecules (Arman et al. 2010; Arman & Tiekink, 2010; Wardell & Tiekink, 2011), the 1:2 co-crystallization of 1,4-diazabicyclo[2.2.2]octane (DABCO) and 2-aminobenzoic was investigated, leading to the isolation of (I).

The crystallographic asymmetric unit of (I) comprises a 4-aza-1-azoniabicyclo(2.2.2)octane cation, Fig. 1, a 2-aminobenzoate anion, Fig. 2, and a neutral 2-aminobenzoic acid molecule, Fig. 3. While there are many examples of 4-aza-1-azoniabicyclo(2.2.2)octane cations and neutral 2-aminobenzoic acid molecules in the crystallographic literature (Allen, 2002), examples of 2-aminobenzoate anions are comparatively rare in all-organic molecules (Lynch et al., 1998; Chen & Peng, 2011). The ions and neutral benzoic acid derivative associate into a three-molecule aggregate via N⁺—H···O and O—H···N hydrogen bonds formed by and to the cation, Fig. 4 and Table 1; intramolecular N—H···O hydrogen bonds are also noted in the benzoate and benzoic acid species, Table 1.

The three component aggregates are connected into the three-dimensional architecture by hydrogen bonds involving the amino-H atoms not participating in intramolecular N—H···O interactions, Fig. 5 and Table 1.

Related literature top

For related studies on co-crystal formation, see: Arman et al. (2010); Arman & Tiekink (2010); Wardell & Tiekink (2011). For examples of multi-component crystals containing the 2-aminobenzoate anion, see: Lynch et al. (1998); Chen & Peng (2011). For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental top

Colourless crystals of (I) were isolated from the 1:2 co-crystallization of 1,4-diazabicyclo[2.2.2]octane (Sigma-Aldrich, 0.089 mmol) and anthranilic acid (Sigma-Aldrich, 0.19 mmol) in chloroform solution (6 ml); M.pt. 427–430 K.

Computing details top

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2005); cell refinement: CrystalClear (Molecular Structure Corporation & Rigaku, 2005); data reduction: CrystalClear (Molecular Structure Corporation & Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Molecular structure of the 4-aza-1-azoniabicyclo(2.2.2)octane cation in (I) showing atom-labelling scheme and displacement ellipsoids at the 50% probability level.
	Fig. 2. Molecular structure of the 2-aminobenzoate anion in (I) showing atom-labelling scheme and displacement ellipsoids at the 50% probability level.
	Fig. 3. Molecular structure of the neutral 2-aminobenzoic acid molecule in (I) showing atom-labelling scheme and displacement ellipsoids at the 50% probability level.
	Fig. 4. Three component aggregate in (I) held together by O—H···N and N—H···O hydrogen bonds shown as orange and blue dashed lines, respectively.
	Fig. 5. View in projection down the a axis of the unit-cell contents of (I). The O—H···N and N—H···O hydrogen bonds are shown as orange and blue dashed lines, respectively.

4-Aza-1-azoniabicyclo[2.2.2]octane–2-aminobenzoate–2-aminobenzoic acid (1/1/1) top

Crystal data top

C₆H₁₃N₂⁺·C₇H₆NO₂⁻·C₇H₇NO₂	F(000) = 824
M_r = 386.45	D_x = 1.326 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8162 reflections
a = 9.285 (3) Å	θ = 2.0–40.6°
b = 16.843 (5) Å	µ = 0.09 mm⁻¹
c = 12.660 (4) Å	T = 98 K
β = 102.127 (6)°	Block, colourless
V = 1935.7 (10) Å³	0.34 × 0.17 × 0.07 mm
Z = 4

Data collection top

Rigaku AFC12K/SATURN724 diffractometer	4440 independent reflections
Radiation source: fine-focus sealed tube	3929 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.054
ω scans	θ_max = 27.5°, θ_min = 2.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −12→12
T_min = 0.731, T_max = 1.000	k = −19→21
16911 measured reflections	l = −15→16

Refinement top

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.128	H-atom parameters constrained
S = 1.13	w = 1/[σ²(F_o²) + (0.0473P)² + 0.9109P] where P = (F_o² + 2F_c²)/3
4440 reflections	(Δ/σ)_max < 0.001
268 parameters	Δρ_max = 0.30 e Å⁻³
7 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₆H₁₃N₂⁺·C₇H₆NO₂⁻·C₇H₇NO₂	V = 1935.7 (10) Å³
M_r = 386.45	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.285 (3) Å	µ = 0.09 mm⁻¹
b = 16.843 (5) Å	T = 98 K
c = 12.660 (4) Å	0.34 × 0.17 × 0.07 mm
β = 102.127 (6)°

Data collection top

Rigaku AFC12K/SATURN724 diffractometer	4440 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	3929 reflections with I > 2σ(I)
T_min = 0.731, T_max = 1.000	R_int = 0.054
16911 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	7 restraints
wR(F²) = 0.128	H-atom parameters constrained
S = 1.13	Δρ_max = 0.30 e Å⁻³
4440 reflections	Δρ_min = −0.23 e Å⁻³
268 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	0.73506 (15)	0.46965 (8)	1.01396 (10)	0.0286 (3)
H1o	0.7433	0.4752	0.9495	0.043*
O2	0.63182 (15)	0.35565 (8)	0.94734 (10)	0.0280 (3)
O3	0.87552 (13)	0.60731 (8)	0.46906 (9)	0.0255 (3)
O4	0.63909 (13)	0.62403 (7)	0.38987 (10)	0.0245 (3)
N1	0.58477 (16)	0.24385 (8)	1.09196 (12)	0.0225 (3)
H1n	0.5262	0.2075	1.1100	0.034*
H2n	0.5710	0.2596	1.0243	0.034*
N2	1.07213 (17)	0.69313 (11)	0.38788 (13)	0.0320 (4)
H3n	1.0547	0.6697	0.4460	0.048*
H4n	1.1631	0.7060	0.3850	0.048*
N3	0.76627 (15)	0.50739 (8)	0.82113 (11)	0.0203 (3)
N4	0.79912 (15)	0.55587 (8)	0.63832 (11)	0.0207 (3)
H5n	0.8114	0.5735	0.5712	0.025*
C1	0.61784 (17)	0.30546 (9)	1.16546 (13)	0.0184 (3)
C2	0.66288 (17)	0.38151 (9)	1.13704 (12)	0.0175 (3)
C3	0.69563 (17)	0.44053 (10)	1.21593 (13)	0.0200 (3)
H3	0.7229	0.4918	1.1959	0.024*
C4	0.68936 (19)	0.42613 (11)	1.32282 (13)	0.0232 (3)
H4	0.7110	0.4671	1.3754	0.028*
C5	0.65063 (18)	0.35033 (10)	1.35151 (13)	0.0228 (3)
H5	0.6493	0.3392	1.4249	0.027*
C6	0.61417 (17)	0.29115 (10)	1.27466 (13)	0.0209 (3)
H6	0.5863	0.2402	1.2957	0.025*
C7	0.67418 (17)	0.40032 (10)	1.02372 (13)	0.0192 (3)
C8	0.96688 (18)	0.68766 (10)	0.29348 (13)	0.0211 (3)
C9	0.82171 (17)	0.66015 (9)	0.29093 (13)	0.0185 (3)
C10	0.72053 (18)	0.65777 (10)	0.19229 (13)	0.0211 (3)
H10	0.6227	0.6407	0.1912	0.025*
C11	0.7582 (2)	0.67941 (10)	0.09614 (14)	0.0253 (4)
H11	0.6883	0.6759	0.0298	0.030*
C12	0.9008 (2)	0.70645 (10)	0.09858 (14)	0.0259 (4)
H12	0.9283	0.7215	0.0333	0.031*
C13	1.00247 (19)	0.71146 (10)	0.19520 (14)	0.0243 (4)
H13	1.0983	0.7313	0.1955	0.029*
C14	0.77248 (18)	0.62962 (9)	0.38957 (13)	0.0190 (3)
C15	0.92485 (19)	0.50551 (11)	0.81698 (14)	0.0254 (4)
H15A	0.9641	0.4512	0.8332	0.031*
H15B	0.9806	0.5420	0.8721	0.031*
C16	0.94441 (19)	0.53077 (12)	0.70394 (15)	0.0289 (4)
H16A	1.0154	0.5753	0.7103	0.035*
H16B	0.9837	0.4858	0.6682	0.035*
C17	0.71221 (19)	0.58987 (10)	0.80251 (14)	0.0241 (4)
H17A	0.7639	0.6242	0.8620	0.029*
H17B	0.6055	0.5916	0.8022	0.029*
C18	0.7387 (2)	0.62134 (10)	0.69428 (14)	0.0262 (4)
H18A	0.6450	0.6406	0.6491	0.031*
H18B	0.8091	0.6662	0.7070	0.031*
C19	0.6829 (2)	0.45573 (11)	0.73500 (13)	0.0255 (4)
H19A	0.5780	0.4541	0.7403	0.031*
H19B	0.7224	0.4010	0.7443	0.031*
C20	0.6952 (2)	0.48755 (11)	0.62315 (14)	0.0294 (4)
H20A	0.7318	0.4452	0.5813	0.035*
H20B	0.5972	0.5048	0.5826	0.035*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0416 (7)	0.0283 (7)	0.0170 (6)	−0.0134 (5)	0.0084 (5)	0.0005 (5)
O2	0.0388 (7)	0.0268 (7)	0.0190 (6)	−0.0089 (5)	0.0072 (5)	−0.0038 (5)
O3	0.0244 (6)	0.0334 (7)	0.0195 (6)	−0.0001 (5)	0.0065 (5)	0.0052 (5)
O4	0.0217 (6)	0.0242 (6)	0.0305 (7)	0.0010 (5)	0.0116 (5)	0.0023 (5)
N1	0.0269 (7)	0.0176 (7)	0.0247 (7)	−0.0022 (5)	0.0093 (6)	−0.0011 (6)
N2	0.0226 (7)	0.0477 (10)	0.0253 (8)	−0.0078 (7)	0.0038 (6)	0.0046 (7)
N3	0.0226 (7)	0.0212 (7)	0.0176 (6)	−0.0018 (5)	0.0052 (5)	0.0014 (5)
N4	0.0224 (7)	0.0229 (7)	0.0181 (6)	0.0010 (5)	0.0072 (5)	0.0027 (5)
C1	0.0162 (7)	0.0179 (8)	0.0214 (8)	0.0017 (6)	0.0048 (6)	0.0006 (6)
C2	0.0168 (7)	0.0196 (8)	0.0164 (7)	0.0012 (6)	0.0044 (6)	0.0009 (6)
C3	0.0210 (7)	0.0192 (8)	0.0203 (8)	−0.0014 (6)	0.0057 (6)	0.0006 (6)
C4	0.0265 (8)	0.0257 (9)	0.0179 (8)	−0.0038 (6)	0.0055 (6)	−0.0018 (7)
C5	0.0230 (8)	0.0286 (9)	0.0173 (8)	0.0001 (6)	0.0051 (6)	0.0046 (7)
C6	0.0213 (8)	0.0185 (8)	0.0236 (8)	0.0013 (6)	0.0067 (7)	0.0049 (6)
C7	0.0195 (7)	0.0191 (8)	0.0193 (8)	0.0001 (6)	0.0046 (6)	0.0001 (6)
C8	0.0225 (8)	0.0192 (8)	0.0226 (8)	0.0023 (6)	0.0069 (6)	0.0009 (6)
C9	0.0220 (8)	0.0151 (7)	0.0199 (8)	0.0015 (6)	0.0074 (6)	0.0004 (6)
C10	0.0233 (8)	0.0164 (8)	0.0237 (8)	0.0013 (6)	0.0053 (6)	−0.0014 (6)
C11	0.0321 (9)	0.0232 (9)	0.0199 (8)	0.0047 (7)	0.0040 (7)	0.0001 (7)
C12	0.0362 (9)	0.0215 (8)	0.0229 (8)	0.0053 (7)	0.0127 (7)	0.0044 (7)
C13	0.0254 (8)	0.0220 (8)	0.0283 (9)	0.0011 (6)	0.0117 (7)	0.0035 (7)
C14	0.0226 (8)	0.0150 (7)	0.0206 (8)	0.0006 (6)	0.0073 (6)	−0.0009 (6)
C15	0.0221 (8)	0.0312 (9)	0.0215 (8)	0.0024 (7)	0.0011 (7)	0.0047 (7)
C16	0.0202 (8)	0.0394 (11)	0.0284 (9)	0.0058 (7)	0.0084 (7)	0.0089 (8)
C17	0.0294 (9)	0.0230 (8)	0.0222 (8)	0.0026 (7)	0.0106 (7)	0.0007 (7)
C18	0.0319 (9)	0.0216 (8)	0.0288 (9)	0.0050 (7)	0.0146 (8)	0.0047 (7)
C19	0.0305 (9)	0.0251 (9)	0.0203 (8)	−0.0082 (7)	0.0036 (7)	−0.0004 (7)
C20	0.0396 (10)	0.0300 (10)	0.0173 (8)	−0.0114 (8)	0.0028 (7)	−0.0022 (7)

Geometric parameters (Å, º) top

O1—C7	1.315 (2)	C6—H6	0.9500
O1—H1O	0.8402	C8—C13	1.411 (2)
O2—C7	1.223 (2)	C8—C9	1.419 (2)
O3—C14	1.290 (2)	C9—C10	1.397 (2)
O4—C14	1.243 (2)	C9—C14	1.507 (2)
N1—C1	1.384 (2)	C10—C11	1.384 (2)
N1—H1N	0.8800	C10—H10	0.9500
N1—H2N	0.8802	C11—C12	1.394 (3)
N2—C8	1.379 (2)	C11—H11	0.9500
N2—H3N	0.8800	C12—C13	1.382 (3)
N2—H4N	0.8799	C12—H12	0.9500
N3—C17	1.479 (2)	C13—H13	0.9500
N3—C19	1.480 (2)	C15—C16	1.540 (2)
N3—C15	1.485 (2)	C15—H15A	0.9900
N4—C18	1.483 (2)	C15—H15B	0.9900
N4—C20	1.488 (2)	C16—H16A	0.9900
N4—C16	1.489 (2)	C16—H16B	0.9900
N4—H5N	0.9300	C17—C18	1.536 (2)
C1—C6	1.411 (2)	C17—H17A	0.9900
C1—C2	1.417 (2)	C17—H17B	0.9900
C2—C3	1.397 (2)	C18—H18A	0.9900
C2—C7	1.494 (2)	C18—H18B	0.9900
C3—C4	1.388 (2)	C19—C20	1.541 (2)
C3—H3	0.9500	C19—H19A	0.9900
C4—C5	1.395 (2)	C19—H19B	0.9900
C4—H4	0.9500	C20—H20A	0.9900
C5—C6	1.384 (2)	C20—H20B	0.9900
C5—H5	0.9500

C7—O1—H1O	108.5	C10—C11—H11	120.6
C1—N1—H1N	114.1	C12—C11—H11	120.6
C1—N1—H2N	113.2	C13—C12—C11	120.57 (16)
H1N—N1—H2N	119.4	C13—C12—H12	119.7
C8—N2—H3N	118.3	C11—C12—H12	119.7
C8—N2—H4N	119.5	C12—C13—C8	121.35 (16)
H3N—N2—H4N	119.5	C12—C13—H13	119.3
C17—N3—C19	109.10 (14)	C8—C13—H13	119.3
C17—N3—C15	108.67 (13)	O4—C14—O3	123.47 (15)
C19—N3—C15	109.31 (14)	O4—C14—C9	120.27 (15)
C18—N4—C20	109.67 (14)	O3—C14—C9	116.19 (14)
C18—N4—C16	109.51 (14)	N3—C15—C16	109.79 (13)
C20—N4—C16	109.83 (14)	N3—C15—H15A	109.7
C18—N4—H5N	109.3	C16—C15—H15A	109.7
C20—N4—H5N	109.3	N3—C15—H15B	109.7
C16—N4—H5N	109.3	C16—C15—H15B	109.7
N1—C1—C6	118.89 (15)	H15A—C15—H15B	108.2
N1—C1—C2	122.85 (14)	N4—C16—C15	109.08 (13)
C6—C1—C2	118.18 (15)	N4—C16—H16A	109.9
C3—C2—C1	119.56 (14)	C15—C16—H16A	109.9
C3—C2—C7	119.14 (14)	N4—C16—H16B	109.9
C1—C2—C7	121.29 (14)	C15—C16—H16B	109.9
C4—C3—C2	121.70 (15)	H16A—C16—H16B	108.3
C4—C3—H3	119.2	N3—C17—C18	110.71 (13)
C2—C3—H3	119.2	N3—C17—H17A	109.5
C3—C4—C5	118.66 (16)	C18—C17—H17A	109.5
C3—C4—H4	120.7	N3—C17—H17B	109.5
C5—C4—H4	120.7	C18—C17—H17B	109.5
C6—C5—C4	120.95 (15)	H17A—C17—H17B	108.1
C6—C5—H5	119.5	N4—C18—C17	108.48 (13)
C4—C5—H5	119.5	N4—C18—H18A	110.0
C5—C6—C1	120.87 (15)	C17—C18—H18A	110.0
C5—C6—H6	119.6	N4—C18—H18B	110.0
C1—C6—H6	119.6	C17—C18—H18B	110.0
O2—C7—O1	123.04 (15)	H18A—C18—H18B	108.4
O2—C7—C2	123.56 (15)	N3—C19—C20	110.12 (14)
O1—C7—C2	113.39 (14)	N3—C19—H19A	109.6
N2—C8—C13	119.39 (16)	C20—C19—H19A	109.6
N2—C8—C9	122.57 (15)	N3—C19—H19B	109.6
C13—C8—C9	118.03 (15)	C20—C19—H19B	109.6
C10—C9—C8	119.14 (15)	H19A—C19—H19B	108.2
C10—C9—C14	117.83 (15)	N4—C20—C19	108.78 (14)
C8—C9—C14	122.98 (15)	N4—C20—H20A	109.9
C11—C10—C9	122.13 (16)	C19—C20—H20A	109.9
C11—C10—H10	118.9	N4—C20—H20B	109.9
C9—C10—H10	118.9	C19—C20—H20B	109.9
C10—C11—C12	118.74 (16)	H20A—C20—H20B	108.3

N1—C1—C2—C3	−179.44 (14)	C11—C12—C13—C8	1.6 (3)
C6—C1—C2—C3	−2.8 (2)	N2—C8—C13—C12	179.51 (17)
N1—C1—C2—C7	1.4 (2)	C9—C8—C13—C12	−1.6 (2)
C6—C1—C2—C7	178.02 (14)	C10—C9—C14—O4	−19.9 (2)
C1—C2—C3—C4	1.9 (2)	C8—C9—C14—O4	162.91 (15)
C7—C2—C3—C4	−178.95 (15)	C10—C9—C14—O3	157.33 (15)
C2—C3—C4—C5	0.6 (2)	C8—C9—C14—O3	−19.9 (2)
C3—C4—C5—C6	−2.2 (3)	C17—N3—C15—C16	−62.35 (18)
C4—C5—C6—C1	1.2 (3)	C19—N3—C15—C16	56.62 (19)
N1—C1—C6—C5	178.09 (15)	C18—N4—C16—C15	57.55 (19)
C2—C1—C6—C5	1.3 (2)	C20—N4—C16—C15	−62.94 (19)
C3—C2—C7—O2	−171.35 (16)	N3—C15—C16—N4	5.0 (2)
C1—C2—C7—O2	7.8 (2)	C19—N3—C17—C18	−62.15 (18)
C3—C2—C7—O1	9.0 (2)	C15—N3—C17—C18	56.95 (18)
C1—C2—C7—O1	−171.82 (15)	C20—N4—C18—C17	57.54 (18)
N2—C8—C9—C10	178.78 (16)	C16—N4—C18—C17	−63.04 (18)
C13—C8—C9—C10	−0.1 (2)	N3—C17—C18—N4	4.8 (2)
N2—C8—C9—C14	−4.0 (3)	C17—N3—C19—C20	55.90 (18)
C13—C8—C9—C14	177.12 (15)	C15—N3—C19—C20	−62.81 (18)
C8—C9—C10—C11	1.8 (2)	C18—N4—C20—C19	−63.53 (19)
C14—C9—C10—C11	−175.57 (15)	C16—N4—C20—C19	56.86 (19)
C9—C10—C11—C12	−1.8 (3)	N3—C19—C20—N4	5.3 (2)
C10—C11—C12—C13	0.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···N3	0.84	1.77	2.597 (2)	168
N4—H5n···O3	0.93	1.64	2.546 (2)	166
N1—H2n···O2	0.88	2.03	2.725 (2)	135
N2—H3n···O3	0.88	2.04	2.696 (2)	131
N1—H1n···O4ⁱ	0.88	2.08	2.941 (2)	165
N2—H4n···N1ⁱⁱ	0.88	2.38	3.256 (2)	171

Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+2, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₆H₁₃N₂⁺·C₇H₆NO₂⁻·C₇H₇NO₂
M_r	386.45
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	98
a, b, c (Å)	9.285 (3), 16.843 (5), 12.660 (4)
β (°)	102.127 (6)
V (Å³)	1935.7 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.34 × 0.17 × 0.07

Data collection
Diffractometer	Rigaku AFC12K/SATURN724 diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.731, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	16911, 4440, 3929
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.128, 1.13
No. of reflections	4440
No. of parameters	268
No. of restraints	7
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.23

Computer programs: CrystalClear (Molecular Structure Corporation & Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPII (Johnson, 1976) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···N3	0.84	1.77	2.597 (2)	168
N4—H5n···O3	0.93	1.64	2.546 (2)	166
N1—H2n···O2	0.88	2.03	2.725 (2)	135
N2—H3n···O3	0.88	2.04	2.696 (2)	131
N1—H1n···O4ⁱ	0.88	2.08	2.941 (2)	165
N2—H4n···N1ⁱⁱ	0.88	2.38	3.256 (2)	171

Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+2, y+1/2, −z+3/2.

Acknowledgements

The Ministry of Higher Education, Malaysia, is thanked for the award of a research grant in crystal engineering (RG125/10AFR).

References

Allen, F. H. (2002). Acta Cryst. B58, 380–388. Web of Science CrossRef CAS IUCr Journals Google Scholar
Arman, H. D., Kaulgud, T. & Tiekink, E. R. T. (2010). Acta Cryst. E66, o2117. Web of Science CSD CrossRef IUCr Journals Google Scholar
Arman, H. D. & Tiekink, E. R. T. (2010). Acta Cryst. E66, o2188. Web of Science CSD CrossRef IUCr Journals Google Scholar
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Chen, Z.-Y. & Peng, M.-X. (2011). J. Chem. Crystallogr. 41, 137–142. Web of Science CSD CrossRef CAS Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Lynch, D. E., Smith, G., Byriel, K. A. & Kennard, C. H. L. (1998). Aust. J. Chem. 51, 587–592. Web of Science CSD CrossRef CAS Google Scholar
Molecular Structure Corporation & Rigaku (2005). CrystalClear. MSC, The Woodlands, Texas, USA, and Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wardell, J. L. & Tiekink, E. R. T. (2011). J. Chem. Crystallogr. 41, 1418–1424. Web of Science CSD CrossRef CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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Volume 67| Part 11| November 2011| Page o2933

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

4-Aza-1-azoniabi­cyclo­[2.2.2]octa­ne–2-amino­benzoate–2-amino­benzoic acid (1/1/1)

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

4-Aza-1-azoniabicyclo[2.2.2]octane–2-aminobenzoate–2-aminobenzoic acid (1/1/1)