4-Aza-1-azoniabicyclo-[2.2.2]octa-ne-2-amino-benzoate-2-amino-benzoic acid (1/1/1).

A 4-aza-1-azoniabicyclo-[2.2.2]octane cation, a 2-amino-benzoate anion and a neutral 2-amino-benzoic acid mol-ecule comprise the asymmetric unit of the title compound, C(6)H(13)N(2) (+)·C(7)H(6)NO(2) (-)·C(7)H(7)NO(2). An intra-molecular N-H⋯O hydrogen bond occurs in the anion and in the neutral 2-amino-benzoic acid mol-ecule. The cation provides a charge-assisted N-H⋯O hydrogen bond to the anion, and the 2-amino-benzoic acid mol-ecule 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-carboxyl-ate 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 +·C7H6n class="Chemical">NO2 −·C7H7NO2

M = 386.45

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.056

wR(F 2) = 0.128

S = 1.13

4440 reflections

268 parameters

7 restraints

H-atom parameters constrained

Δρmax = 0.30 e Å−3

Δρmin = −0.23 e Å−3

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 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811041559/hb6440sup1.cif

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

Supplementary material file. DOI: 10.1107/S1600536811041559/hb6440Isup3.cml

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

C6H13N2+·C7H6NO2−·C7H7NO2	F(000) = 824
Mr = 386.45	Dx = 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

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

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(Fo2) + (0.0473P)2 + 0.9109P] where P = (Fo2 + 2Fc2)/3
4440 reflections	(Δ/σ)max < 0.001
268 parameters	Δρmax = 0.30 e Å−3
7 restraints	Δρmin = −0.23 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	0.73506 (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*

	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)

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)

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

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) ; (ii) .