Six two- and three-component ammonium carboxyl­ate salt structures with a ladder-type hydrogen-bonding motif, three incorporating neutral carb­oxy­lic acid mol­ecules

Six ammonium carboxylate salts are synthesized and reported, namely 2-propyl­ammonium benzoate, C₃H₁₀N⁺·C₇H₅O₂⁻, (I), benzyl­ammonium (R)-2-phenyl­propion­ate, C₆H₁₀N⁺·C₉H₉O₂⁻, (II), (RS)-1-phenyl­ethyl­ammonium naphthalene-1-car­box­yl­ate, C₈H₁₂N⁺·C₁₁H₇O₂⁻, (III), benzyl­ammonium–benzoate–benzoic acid (1/1/1), C₆H₁₀N⁺·C₇H₅O₂⁻·C₇H₆O₂, (IV), cyclo­propyl­ammonium–benzoate–benzoic acid (1/1/1), C₃H₈N⁺·C₇H₅O₂⁻·C₇H₆O₂, (V), and cyclo­propyl­ammonium–ea-cis-cyclo­hexane-1,4-dicarboxyl­ate–ee-trans-cyclo­hexane-1,4-dicarb­oxy­lic acid (2/1/1), 2C₃H₈N⁺·C₈H₁₀O₄²⁻·C₈H₁₂O₄, (VI). Salts (I)–(III) all have a 1:1 ratio of cation to anion and feature three N⁺—H...O⁻ hydrogen bonds which form one-dimensional hydrogen-bonded ladders. Salts (I) and (II) have type II ladders, consisting of repeating R₄³(10) rings, while (III) has type III ladders, in this case consisting of alternating R₄²(8) and R₄⁴(12) rings. Salts (IV) and (V) have a 1:1:1 ratio of cation to anion to benzoic acid. They have type III ladders formed by three N⁺—H...O⁻ hydrogen bonds, while the benzoic acid mol­ecules are pendant to the ladders and hydrogen bond to them via O—H...O⁻ hydrogen bonds. Salt (VI) has a 2:1:1 ratio of cation to anion to acid and does not feature any hydrogen-bonded ladders; instead, the ionized and un-ionized components form a three-dimensional network of hydrogen-bonded rings. The two-component 1:1 salts are formed from a 1:1 ratio of amine to acid. To create the three-component salts (IV)–(VI), the ratio of amine to acid was reduced so as to deprotonate only half of the acid mol­ecules, and then to observe how the un-ionized acid mol­ecules are incorporated into the ladder motif. For (IV) and (V), the ratio of amine to acid was reduced to 1:2, while for (VI) the ratio of amine to acid required to deprotonate only half the diacid mol­ecules was 1:1.

S1. Comment

Ammonium carboxylate salts of the general formula (R-NH₃⁺).(R'-COO^-) are known to form hydrogen-bonded one-dimensional ladders in the solid state, among other motifs (Lemmerer et al., 2008a, 2010). The ladders are formed by hydrogen-bonded rings formed from four N—H···O hydrogen bonds and consist of two cation–anion pairs (Odendal et al., 2010). The ladders are predominantly of two types, as classified by Nagahama et al. (2003): type II consists of repeating hydrogen-bonded rings, described using graph-set notation (Bernstein et al., 1995) as R₄³(10), and type III consists of the repetition of two differently sized rings, described as R₄²(8) and R₄⁴(12) (Fig. 1). Together with the ladder concept used to describe the hydrogen-bonded pattern of ammonium carboxylate salts, the four hydrogen bonds forming the rings can be divided into legs and rungs (Fig. 1). These two ladders have also been described as robust heterosynthons (Lemmerer et al., 2008b), as they form even in the presence of other hydrogen-bonding functional groups. The type of ladder observed is also dependent on the presence of a chiral ion. If either of the ions is present as the optically active enantiomer only (either R or S), then a type II ladder is formed almost exclusively, while if the ion is present as the racemate (RS), type III ladders form (with a minority of type II) (Lemmerer et al., 2008a).

When combining an amine and an acid, the difference in pK_a can be indicative of whether a salt or a neutral complex is formed. Generally, a difference of 3 units should result in a salt (Bhogala et al., 2005). However, it has been observed that salts formed with succinic and fumaric acids often include un-ionized acid molecules, even with large differences in pK_a (Haynes & Pietersen, 2008). We have observed the inclusion of un-ionized acid molecules together with ionized acid and amine molecules in the salt (4-pyridylmethyl)ammonium.m-iodobenzoate.m-iodobenzoic acid (Lemmerer et al., 2008c). In this salt, the peripheral un-ionized m-iodobenzoic acid molecule forms hydrogen bonds to the pyridine N atom of the (4-pyridylmethyl)ammonium cation, thus forming a type II salt. This 1:1:1 salt was synthesized from a 1:1 ratio of amine to acid (with a large difference in pK_a), and the 1:1 salt (containing no un-ionized acid) was not obtained. The 1:1:1 salt was successfully synthesized using a ratio of amine to acid of 1:2, by having an excess of acid available which is then unable to undergo proton transfer to the amine. This had led us to believe that we might selectively prepare these three-component salts by controlling the molecular ratio in the crystallization synthesis. In this study, we wished to include un-ionized acid molecules into the salt structure, in order to observe if the ladders are still formed and how the un-ionized acid molecule becomes incorporated. In addition, three related 1:1 salts have been synthesized that illustrate the different types of ladders and how their formation is controlled. The six salts synthesized and reported here are 2-propylammonium benzoate, (I), benzylammonium (R)-2-phenylpropyl-1-carboxylate, (II), (RS)-1-phenylethylammonium naphthalene-1-carboxylate, (III), benzylammonium benzoate–benzoic acid (1/1), (IV), cyclopropylammonium benzoate–benzoic acid (1/1), (V), and bis(cyclopropylammonium) ea-cis-cyclohexane-1,4-dicarboxylate–ee-trans-cyclohexane-1,4-dicarboxylic acid (1/1), (VI).

The molecular structure and atomic numbering scheme of the asymmetric unit of the 1:1 salt (I) are shown in Fig. 2. The asymmetric unit consists of one disordered 2-propylammonium cation and one benzoate anion, both on general positions. The ammonium group forms three charge-assisted hydrogen bonds to form a ring, graph-set notation R₄³(10), consisting of two ammonium cations and two carboxylate anions, one involving both atoms O1 and O2 and the second involving only atom O1 (see Fig. 3). This hydrogen-bonded pattern has translational symmetry via a twofold screw axis along the crystallographic a axis inherent in the space group P2₁2₁2₁. All three ammonium H atoms are used to form the ring and atom O1 acts as a bifurcated hydrogen-bond acceptor. Salt (I) thus forms a type II hydrogen-bonded ladder.

The molecular structure and atomic numbering scheme of the asymmetric unit of the 1:1 salt (II) are shown in Fig. 4. The asymmetric unit consists of one benzylammonium cation and one (R)-2-phenyl-propane-1-carboxylate anion, both on general positions. The salt crystallizes in the chiral space group C2 and features a type II ladder, extending along the twofold rotation axis in the direction of the b axis (Fig. 5).

The molecular structure and atomic numbering scheme of the asymmetric unit of the 1:1 salt (III) are shown in Fig. 6. The asymmetric unit consists of one (S)-1-phenylethylammonium cation (labelled N1), one (R)-1-phenylethylammonium cation (N2) and two naphthalene-1-carboxylate anions, labelled O1/O2 and O3/O4, all on general positions. Both N1 and N2 cations form two charge-assisted hydrogen bonds to form a ring, graph-set notation R₄²(8), consisting of the two ammonium cations and the two carboxylate anions, involving atoms O1 and O3 (see Fig. 7). A second type of ring is formed by two N1 cations and two O3/O4 anions, again using four N⁺—H···O^- hydrogen bonds, to generate an R₄⁴(12) ring. Another similar R₄⁴(12) ring is present, this time involving two N2 cations and two O1/O2 anions. The sequence of these three unique rings generates a type III hydrogen-bonded ladder along the a axis.

The molecular structure and atomic numbering scheme of the asymmetric unit of the 1:1:1 salt (IV) are shown in Fig. 8. The asymmetric unit consists of one (un-ionized) benzoic acid molecule, one benzylammonium cation and one benzoate anion, all on general positions. The cation and anion form a type III ladder via N⁺—H···O^- hydrogen bonds along the b axis. The benzoic acid molecule forms O—H···O^- hydrogen bonds to one of the carboxylate O atoms of the ladder (Fig. 9).

The molecular structure and atomic numbering scheme of the asymmetric unit of the 1:1:1 salt (V) are shown in Fig. 10. The asymmetric unit consists of one neutral benzoic acid molecule, one cyclopropylammonium cation and one benzoate anion, all on general positions. The cation and anion form a type III ladder via N⁺—H···O^- hydrogen bonds along the b axis. The benzoic acid molecule forms O—H···O^- hydrogen bonds to one of the carboxylate O atoms of the ladder (Fig. 11).

The molecular structure and atomic numbering scheme of the asymmetric unit of the 1:2:1 salt (VI) are shown in Fig. 12. The asymmetric unit consists of one neutral ee-trans-1,4-cyclohexanedicarboxylic acid molecule, two cyclopropylammonium cations and one ea-cis-1,4-cyclohexanedicarboxylate anion, all on general positions. The hydrogen-bonding pattern does not correspond to any of the three rings described above. Each of the two cyclopentylammonium cations forms hydrogen bonds to two separate cations (to one of their O atoms). The third hydrogen bond from the cations is to the carbonyl O atom of the neutral dicarboxylic acid molecule. In addition, the neutral dicarboxylic acid molecule forms hydrogen bonds to the carboxylate anion via an O—H···O^- hydrogen bond. A number of larger hydrogen-bonded rings are formed through this combination of un-ionized and ionized species (Fig. 13). The two rings R⁴₆(16) and R⁵₅(21) are formed using all three species, whereas the R₄⁴(22) ring is formed using only the ionized species.

The 1:1 salts (I)–(III) form type II and III ladders in accordance with previous studies (Lemmerer, 2008). The type II ladder was found to be the most common motif observed in general ammonium carboxylate salts deposited in the Cambridge Structural Database (CSD; Version ?; Allen, 2002). According to a detailed CSD analysis of 317 primary ammonium carboxylate salts performed by Yuge et al. (2008), 185 of the salts have a type II ladder (58%). Type II ladders are helical in nature and frequently crystallize in space groups with twofold screw axes. This is also observed for (I). If any of the ions are chiral in nature, and only the optically active enantiomer is present, then the chance of forming a type II ladder increases considerably (Lemmerer et al., 2010, and references therein), and hence a type II ladder is again observed in salt (II), which has the R enantiomer of the 2-phenylpropyl-1-carboxylate cation. In salt (III), which contains the racemate of the 1-phenthylammonium cation, a type III ladder forms, and the hydrogen-bonded rings are all centrosymmetric. It was observed previously that the racemate of the 1-phenylethylammonium cation often produces a type III ladder (Lemmerer et al., 2008a).

The 1:1:1 salts (IV)–(VI) were prepared by including un-ionized acid molecules in the crystallization solution. This does not necessarily guarantee that they will be incorporated into the crystallized salts, but nonetheless they were incorporated in all three. A reason for this is the increased acceptor potential of the O atoms on the carboxylate anions. As they are now negatively charged, the electrostatic interaction is stronger between the un-ionized acid molecules and the ionized anions hydrogen-bonding to each other. In salts (IV) and (V), the ladder motif is still observed, in this case a type III ladder. The benzoic acid molecules form hydrogen bonds to the O atoms of the carboxylate anions, as they are the only acceptor atoms available, and they are arranged as pendant molecules to the ladders. In the 1:2:1 salt (VI), the un-ionized and ionized acid molecules have different conformations. The 1,4-cyclohexanedicarboxylic acid used consisted of a cis/trans mixture. In (VI), while the cis conformer underwent proton transfer to the two cyclopropylamine molecules, the trans conformer remained un-ionized. It is not clear at this stage why the cis conformer underwent proton transfer and the trans isomer did not. In contrast with the 1:1:1 salts of (IV) and (V), no ladder motif is formed in (VI) and the un-ionized acid molecules are incorporated into the rings formed by the ionized species. Previous work has shown that ammonium carboxylate salts that have two carboxylate functional groups on one ion form two-dimensional networks by joining two ladders together (Lemmerer et al., 2008a; Lemmerer, 2011). It was hoped that the two-dimensional network would be retained and that the un-ionized diacid species would connect the two-dimensional networks into three-dimensional networks.

In conclusion, we have shown that is it possible to create three-component salt structures with a ladder motif by reducing the ratio of amine to acid in the synthesis.

Related literature

For related literature, see: Allen (2002); Bernstein et al. (1995); Bhogala et al. (2005); Haynes & Pietersen (2008); Lemmerer (2008, 2011); Lemmerer et al. (2008a, 2008b, 2008c, 2010); Nagahama et al. (2003); Odendal et al. (2010); Yuge et al. (2008).

S2. Experimental

All chemicals were purchased from commercial sources and used as received. Crystals were grown by slow evaporation, under ambient conditions, of methanol solutions containing a 1:1 ratio of amine and acid for (I)–(III) and (VI), and a ratio of 1:2 for (IV) and (V). Detailed masses and volumes are as follows. For (I): 2-propylamine (0.050 g, 0.85 mmol) and benzoic acid (0.103 g, 0.846 mmol) in methanol (5 ml); for (II): benzylamine (0.050 g, 0.47 mmol) and 2-phenylpropionic acid (0.070 g, 0.47 mmol) in methanol (5 ml); for (III): (RS)-1-phenylethylamine (0.050 g, 0.41 mmol) and 1-naphthalenecarboxylic acid (0.085 g, 0.41 mmol) in methanol (10 ml); for (IV): benzylamine (0.050 g, 0.047 mmol) and benzoic acid (0.114 g, 0.92 mmol) in methanol (10 ml); for (V): cyclopropylamine (0.050 g, 0.088 mmol) and benzoic acid (0.214 g, 0.18 mmol) in methanol (15 ml); and for (VI): cyclopropylamine (0.050 g, 0.088 mmol) and (cis/trans)-1,4-cyclohexanedicarboxylic acid (0.151 g, 0.088 mmol) in methanol (10 ml).

S3. Refinement

For compound (I), the C-bound H atoms were positioned geometrically, with C—H = 0.99 (methine CH), 0.97 (methylene CH₃) or 0.94 Å (Ar—H), and refined as riding, with U_iso(H) = 1.2 or 1.5U_eq(C). The N-bound H atoms were positioned geometrically, with N—H = 0.91 Å, and refined as riding, with U_iso(H) = 1.5U_eq(N). The disorder of the 2-propylammonium cation was resolved by finding alternate positions for atom C9 in the difference Fourier map. These two atoms, C9A and C9B, were then refined anisotropically together with their site occupancy, such that the sum of the occupancies equalled one.

For compounds (II)–(VI), the C-bound H atoms were positioned geometrically, with C—H = 1.00 (methine CH), 0.99 (ethylene CH₂), 0.98 (methylene CH₃) or 0.95 Å (Ar—H), and refined as riding, with U_iso(H) = 1.2 or 1.5U_eq(C). The N-bound H atoms were positioned geometrically, with N—H = 0.91 Å, and refined as riding, with U_iso(H) = 1.5U_eq(N).

Computing details

For all compounds, data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus (Bruker, 2004) and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures

	Fig. 1. The two types of ladder formed by ammonium carboxylate salts. Type II has repeating R4^3(10) rings, whereas type III has alternating R4^2(8) and R4^4(12) rings. The three hydrogen bonds from the –NH3^+ cation consist of two legs and one rung.
	Fig. 2. A perspective view of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. The 2-propylammonium cation is disordered and both occupied sites are shown. The dashed line indicates the symmetry-independent N^+—H···O^- hydrogen bond.
	Fig. 3. A partial packing diagram of the type II ladder for (I). N^+—H···O^- hydrogen bonds are shown as dashed lines. The 2-propylammonium cation is disordered and only the major occupied site is shown. H atoms not involved in hydrogen bonding have been omitted for clarity. [Symmetry code: (i) x + 1/2, -y + 3/2, -z + 1.]
	Fig. 4. A perspective view of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. The dashed line indicates the symmetry-independent N^+—H···O^- hydrogen bond.
	Fig. 5. A partial packing diagram of the type II ladder for (II). N^+—H···O^- hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity.
	Fig. 6. A perspective view of (III), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. The dashed lines indicate the symmetry-independent N^+—H···O^- hydrogen bonds.
	Fig. 7. A partial packing diagram of the type III ladder for (III). N^+—H···O^- hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity. [Symmetry codes: (i) -x + 1, -y + 1, -z + 1; (ii) -x + 1, -y + 2, -z + 1; (iii) x, y + 1, z; (iv) -x + 2, -y + 1, -z + 1; (v) x + 1, y, z.]
	Fig. 8. A perspective view of (IV), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. The dashed lines indicate the symmetry-independent O—H···O^- and N^+—H···O^- hydrogen bonds.
	Fig. 9. A partial packing diagram of the type III ladder for (IV). N^+—H···O^- and O—H···O^- hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity, together with the hydrocarbon part of the ammonium cation.
	Fig. 10. A perspective view of (V), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. The dashed lines indicate the symmetry-independent O—H···O^- and N^+—H···O^- hydrogen bonds.
	Fig. 11. A partial packing diagram of the type III ladder for (V). N^+—H···O^- and O—H···O^- hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity, together with the hydrocarbon part of the ammonium cation.
	Fig. 12. A perspective view of (VI), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. The dashed lines indicate the symmetry-independent O—H···O^- and N^+—H···O^- hydrogen bonds.
	Fig. 13. A partial packing diagram of the hydrogen-bonded interactions for (VI). N^+—H···O^- and O—H···O^- hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity, together with the hydrocarbon part of the ammonium cation. [Symmetry codes: (i) x + 1/2, -y + 3/2, z; (ii) -x + 1, -y + 1, z - 1/2.]

(I) 2-propylammonium benzoate

Crystal data

C3H10N^+·C7H5O2^−	F(000) = 392
Mr = 181.23	Dx = 1.065 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1643 reflections
a = 6.3823 (7) Å	θ = 0.4–27.5°
b = 9.0629 (5) Å	µ = 0.07 mm^−1
c = 19.5457 (13) Å	T = 243 K
V = 1130.57 (16) Å^3	Needle, colourless
Z = 4	0.26 × 0.16 × 0.1 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	869 reflections with I > 2σ(I)
ω scans	Rint = 0.081
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	θmax = 25.5°, θmin = 3.1°
Tmin = 0.981, Tmax = 0.993	h = −7→7
9482 measured reflections	k = −10→8
1232 independent reflections	l = −23→22

Refinement

Refinement on F^2	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.1081P)^2 + 0.123P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.061	(Δ/σ)max < 0.001
wR(F^2) = 0.181	Δρmax = 0.20 e Å^−3
S = 1.04	Δρmin = −0.19 e Å^−3
1232 reflections	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
133 parameters	Extinction coefficient: 0.043 (12)
23 restraints	Absolute structure: Flack (1983), with 854 Friedel pairs

Special details

Experimental. Absorption corrections were made using the program SADABS (Sheldrick, 1996)

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.8635 (5)	0.4588 (3)	0.34254 (15)	0.0535 (8)
C2	0.6604 (6)	0.4581 (6)	0.3213 (2)	0.0861 (13)
H2	0.5614	0.5182	0.3435	0.103*
C3	0.5987 (8)	0.3692 (9)	0.2671 (3)	0.131 (3)
H3	0.4584	0.3686	0.2525	0.157*
C4	0.7434 (12)	0.2829 (8)	0.2353 (3)	0.141 (3)
H4	0.7021	0.2223	0.1987	0.169*
C5	0.9443 (11)	0.2832 (7)	0.2556 (3)	0.131 (2)
H5	1.0435	0.2237	0.2332	0.158*
C6	1.0036 (6)	0.3716 (5)	0.3095 (2)	0.0854 (12)
H6	1.1442	0.3715	0.3238	0.103*
C7	0.9392 (6)	0.5571 (4)	0.39933 (17)	0.0629 (9)
O1	0.8073 (5)	0.6296 (4)	0.43234 (16)	0.1001 (11)
O2	1.1284 (4)	0.5656 (4)	0.40924 (15)	0.1023 (11)
C8	0.4373 (9)	0.4896 (6)	0.5529 (2)	0.1035 (15)
H8A	0.5502	0.5104	0.5863	0.124*	0.654 (12)
H8B	0.4486	0.397	0.5263	0.124*	0.346 (12)
C9A	0.490 (2)	0.3545 (9)	0.5162 (5)	0.160 (5)	0.654 (12)
H9A	0.6235	0.3672	0.4931	0.24*	0.654 (12)
H9B	0.3821	0.3333	0.4828	0.24*	0.654 (12)
H9C	0.5003	0.2733	0.5484	0.24*	0.654 (12)
C9B	0.633 (3)	0.503 (2)	0.5926 (10)	0.145 (7)	0.346 (12)
H9D	0.752	0.494	0.5621	0.218*	0.346 (12)
H9E	0.6384	0.4252	0.6267	0.218*	0.346 (12)
H9F	0.6366	0.5982	0.6152	0.218*	0.346 (12)
C10	0.2311 (13)	0.4831 (9)	0.5910 (3)	0.146 (2)
H10A	0.2373	0.406	0.6254	0.219*
H10B	0.1188	0.4619	0.559	0.219*
H10C	0.205	0.5773	0.613	0.219*
N1	0.4289 (4)	0.6138 (3)	0.50249 (14)	0.0686 (9)
H1A	0.5494	0.6169	0.4786	0.103*
H1B	0.4112	0.6996	0.5249	0.103*
H1C	0.321	0.5996	0.4736	0.103*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0547 (18)	0.0550 (16)	0.0509 (16)	−0.0060 (13)	0.0076 (14)	−0.0036 (14)
C2	0.065 (2)	0.127 (3)	0.066 (2)	−0.005 (2)	0.0018 (18)	−0.019 (2)
C3	0.088 (3)	0.219 (7)	0.087 (3)	−0.044 (4)	0.000 (3)	−0.051 (4)
C4	0.139 (5)	0.180 (6)	0.105 (4)	−0.071 (5)	0.027 (4)	−0.077 (4)
C5	0.133 (5)	0.122 (4)	0.139 (5)	−0.021 (4)	0.051 (4)	−0.081 (4)
C6	0.074 (3)	0.093 (3)	0.090 (3)	−0.004 (2)	0.015 (2)	−0.027 (2)
C7	0.064 (2)	0.0684 (19)	0.0562 (17)	−0.0085 (18)	0.0081 (16)	−0.0026 (17)
O1	0.0820 (19)	0.107 (2)	0.111 (2)	−0.0111 (16)	0.0232 (17)	−0.0544 (19)
O2	0.0666 (17)	0.152 (3)	0.088 (2)	−0.0107 (17)	−0.0149 (15)	−0.031 (2)
C8	0.118 (3)	0.106 (3)	0.086 (3)	0.020 (3)	0.005 (3)	0.019 (2)
C9A	0.250 (12)	0.080 (4)	0.151 (7)	0.046 (6)	0.060 (8)	0.034 (4)
C9B	0.162 (7)	0.145 (14)	0.128 (14)	0.026 (12)	−0.049 (8)	0.023 (12)
C10	0.161 (5)	0.159 (5)	0.118 (4)	0.002 (5)	0.044 (4)	0.028 (4)
N1	0.0621 (16)	0.0755 (18)	0.0683 (17)	0.0024 (14)	−0.0043 (14)	−0.0155 (14)

Geometric parameters (Å, º)

C1—C6	1.357 (5)	C8—C10	1.513 (9)
C1—C2	1.361 (5)	C8—H8A	0.99
C1—C7	1.503 (5)	C8—H8B	0.99
C2—C3	1.388 (6)	C9A—H8B	0.5074
C2—H2	0.94	C9A—H9A	0.97
C3—C4	1.361 (9)	C9A—H9B	0.97
C3—H3	0.94	C9A—H9C	0.97
C4—C5	1.342 (10)	C9B—H9D	0.97
C4—H4	0.94	C9B—H9E	0.97
C5—C6	1.377 (7)	C9B—H9F	0.97
C5—H5	0.94	C10—H10A	0.97
C6—H6	0.94	C10—H10B	0.97
C7—O2	1.226 (4)	C10—H10C	0.97
C7—O1	1.247 (4)	N1—H1A	0.9
C8—C9A	1.458 (10)	N1—H1B	0.9
C8—C9B	1.474 (18)	N1—H1C	0.9
C8—N1	1.497 (5)
C6—C1—C2	118.7 (4)	C9B—C8—H8B	106.6
C6—C1—C7	119.0 (3)	N1—C8—H8B	107.1
C2—C1—C7	122.3 (3)	C10—C8—H8B	106.8
C1—C2—C3	120.4 (4)	H8A—C8—H8B	117.1
C1—C2—H2	119.8	C8—C9A—H9A	109.5
C3—C2—H2	119.8	H8B—C9A—H9A	123.4
C4—C3—C2	119.3 (5)	C8—C9A—H9B	109.5
C4—C3—H3	120.3	H8B—C9A—H9B	92.2
C2—C3—H3	120.3	C8—C9A—H9C	109.5
C5—C4—C3	120.8 (5)	H8B—C9A—H9C	111
C5—C4—H4	119.6	C8—C9B—H9D	109.5
C3—C4—H4	119.6	C8—C9B—H9E	109.5
C4—C5—C6	119.3 (5)	H9D—C9B—H9E	109.5
C4—C5—H5	120.3	C8—C9B—H9F	109.5
C6—C5—H5	120.3	H9D—C9B—H9F	109.5
C1—C6—C5	121.5 (4)	H9E—C9B—H9F	109.5
C1—C6—H6	119.3	C8—C10—H10A	109.5
C5—C6—H6	119.3	C8—C10—H10B	109.5
O2—C7—O1	123.4 (4)	H10A—C10—H10B	109.5
O2—C7—C1	118.1 (3)	C8—C10—H10C	109.5
O1—C7—C1	118.5 (3)	H10A—C10—H10C	109.5
C9A—C8—N1	108.4 (4)	H10B—C10—H10C	109.5
C9B—C8—N1	108.4 (10)	C8—N1—H1A	109.5
C9A—C8—C10	114.3 (7)	C8—N1—H1B	109.5
C9B—C8—C10	118.7 (8)	H1A—N1—H1B	109.5
N1—C8—C10	108.8 (4)	C8—N1—H1C	109.5
C9A—C8—H8A	108.4	H1A—N1—H1C	109.5
N1—C8—H8A	108.4	H1B—N1—H1C	109.5
C10—C8—H8A	108.4
C6—C1—C2—C3	0.3 (7)	C7—C1—C6—C5	−177.7 (4)
C7—C1—C2—C3	177.8 (4)	C4—C5—C6—C1	−0.2 (9)
C1—C2—C3—C4	−0.1 (9)	C6—C1—C7—O2	7.1 (5)
C2—C3—C4—C5	−0.2 (11)	C2—C1—C7—O2	−170.5 (4)
C3—C4—C5—C6	0.4 (11)	C6—C1—C7—O1	−175.3 (4)
C2—C1—C6—C5	−0.1 (7)	C2—C1—C7—O1	7.1 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.9	1.88	2.781 (4)	177
N1—H1B···O1^i	0.9	1.88	2.763 (4)	167
N1—H1C···O2^ii	0.9	1.79	2.681 (4)	174

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

(II) benzylammonium (R)-2-phenylpropyl-1-carboxylate

Crystal data

C7H10N^+·C9H9O2^−	F(000) = 552
Mr = 257.32	Dx = 1.217 Mg m^−3 Dm = 0 Mg m^−3 Dm measured by not measured
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2y	Cell parameters from 4876 reflections
a = 30.970 (2) Å	θ = 2.7–28.1°
b = 5.8832 (4) Å	µ = 0.08 mm^−1
c = 7.8239 (5) Å	T = 173 K
β = 99.825 (2)°	Plate, colourless
V = 1404.63 (16) Å^3	0.63 × 0.26 × 0.09 mm
Z = 4

Data collection

Bruker APEXII CCD area-detector diffractometer	1660 reflections with I > 2σ(I)
ω scans	Rint = 0.068
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	θmax = 28°, θmin = 1.3°
Tmin = 0.951, Tmax = 0.993	h = −40→40
16064 measured reflections	k = −7→7
1863 independent reflections	l = −10→10

Refinement

Refinement on F^2	1 restraint
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.035	w = 1/[σ^2(Fo^2) + (0.0504P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.086	(Δ/σ)max < 0.001
S = 1.09	Δρmax = 0.21 e Å^−3
1863 reflections	Δρmin = −0.15 e Å^−3
174 parameters	Absolute structure: Flack (1983), with 1534 Friedel pairs

Special details

Experimental. Absorption corrections were made using the program SADABS (Sheldrick, 1996)

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.30330 (5)	0.6853 (3)	0.7906 (2)	0.0261 (3)
C2	0.31586 (5)	0.5265 (3)	0.9455 (2)	0.0299 (4)
H2	0.3085	0.3672	0.9062	0.036*
C3	0.28863 (6)	0.5874 (4)	1.0844 (2)	0.0392 (4)
H3A	0.298	0.4938	1.1877	0.059*
H3B	0.2576	0.5591	1.0396	0.059*
H3C	0.2929	0.7484	1.1149	0.059*
C4	0.36465 (5)	0.5402 (3)	1.01108 (19)	0.0292 (4)
C5	0.38331 (6)	0.7262 (3)	1.1045 (2)	0.0366 (4)
H5	0.3652	0.8496	1.1264	0.044*
C6	0.42782 (6)	0.7347 (4)	1.1664 (2)	0.0448 (5)
H6	0.44	0.8627	1.2312	0.054*
C7	0.45445 (6)	0.5584 (4)	1.1342 (2)	0.0494 (5)
H7	0.4851	0.564	1.1766	0.059*
C8	0.43641 (6)	0.3738 (4)	1.0402 (2)	0.0482 (5)
H8	0.4548	0.2525	1.0167	0.058*
C9	0.39188 (6)	0.3632 (3)	0.9796 (2)	0.0386 (4)
H9	0.3798	0.2339	0.916	0.046*
O1	0.29267 (4)	0.5987 (2)	0.64142 (14)	0.0328 (3)
O2	0.30422 (4)	0.8926 (2)	0.82038 (14)	0.0339 (3)
C10	0.12920 (5)	0.5775 (3)	0.49970 (19)	0.0321 (4)
C11	0.10961 (6)	0.4026 (4)	0.3950 (2)	0.0392 (4)
H11	0.1263	0.273	0.3745	0.047*
C12	0.06590 (7)	0.4164 (4)	0.3205 (2)	0.0477 (5)
H12	0.0527	0.2975	0.2477	0.057*
C13	0.04147 (6)	0.6034 (4)	0.3522 (2)	0.0491 (5)
H13	0.0113	0.6124	0.3019	0.059*
C14	0.06063 (7)	0.7761 (4)	0.4559 (3)	0.0492 (5)
H14	0.0438	0.9046	0.4773	0.059*
C15	0.10445 (6)	0.7636 (4)	0.5296 (2)	0.0403 (4)
H15	0.1176	0.8839	0.6012	0.048*
C16	0.17665 (6)	0.5610 (3)	0.5796 (2)	0.0351 (4)
H16A	0.1817	0.6474	0.6898	0.042*
H16B	0.1841	0.3999	0.6071	0.042*
N1	0.20620 (4)	0.6503 (2)	0.46383 (17)	0.0294 (3)
H1A	0.2344	0.6447	0.52	0.044*
H1B	0.1989	0.7968	0.4348	0.044*
H1C	0.2033	0.5641	0.366	0.044*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0210 (7)	0.0288 (9)	0.0277 (8)	0.0001 (6)	0.0018 (6)	0.0004 (6)
C2	0.0338 (8)	0.0256 (8)	0.0286 (8)	−0.0023 (7)	0.0009 (6)	0.0018 (7)
C3	0.0379 (9)	0.0444 (11)	0.0361 (9)	−0.0017 (9)	0.0088 (7)	0.0086 (8)
C4	0.0343 (9)	0.0295 (9)	0.0228 (7)	0.0022 (7)	0.0021 (6)	0.0043 (7)
C5	0.0394 (10)	0.0338 (10)	0.0351 (9)	−0.0020 (8)	0.0023 (7)	0.0002 (8)
C6	0.0422 (11)	0.0472 (12)	0.0418 (10)	−0.0100 (9)	−0.0023 (8)	0.0024 (9)
C7	0.0311 (9)	0.0718 (16)	0.0425 (10)	0.0001 (10)	−0.0017 (7)	0.0110 (11)
C8	0.0415 (10)	0.0611 (14)	0.0414 (10)	0.0183 (10)	0.0050 (8)	0.0042 (10)
C9	0.0438 (10)	0.0402 (11)	0.0294 (8)	0.0095 (8)	−0.0005 (7)	−0.0016 (8)
O1	0.0366 (6)	0.0306 (6)	0.0277 (5)	−0.0007 (5)	−0.0049 (4)	−0.0027 (5)
O2	0.0474 (7)	0.0244 (6)	0.0302 (6)	0.0039 (6)	0.0072 (5)	0.0007 (5)
C10	0.0396 (9)	0.0342 (9)	0.0229 (7)	−0.0021 (8)	0.0067 (6)	0.0022 (7)
C11	0.0437 (10)	0.0368 (9)	0.0391 (9)	−0.0053 (9)	0.0130 (8)	−0.0037 (9)
C12	0.0448 (11)	0.0553 (13)	0.0432 (10)	−0.0156 (11)	0.0083 (8)	−0.0090 (10)
C13	0.0336 (10)	0.0679 (15)	0.0455 (10)	−0.0025 (11)	0.0063 (8)	0.0066 (11)
C14	0.0473 (12)	0.0536 (13)	0.0484 (11)	0.0098 (10)	0.0127 (9)	0.0010 (11)
C15	0.0503 (11)	0.0368 (11)	0.0342 (9)	0.0007 (9)	0.0087 (8)	−0.0042 (8)
C16	0.0441 (10)	0.0339 (10)	0.0257 (7)	−0.0007 (8)	0.0014 (6)	0.0023 (7)
N1	0.0317 (7)	0.0249 (7)	0.0282 (6)	−0.0003 (6)	−0.0041 (5)	−0.0005 (6)

Geometric parameters (Å, º)

C1—O2	1.241 (2)	C9—H9	0.95
C1—O1	1.2644 (19)	C10—C15	1.379 (3)
C1—C2	1.527 (2)	C10—C11	1.389 (3)
C2—C4	1.513 (2)	C10—C16	1.499 (2)
C2—C3	1.527 (2)	C11—C12	1.382 (3)
C2—H2	1	C11—H11	0.95
C3—H3A	0.98	C12—C13	1.381 (3)
C3—H3B	0.98	C12—H12	0.95
C3—H3C	0.98	C13—C14	1.371 (3)
C4—C5	1.386 (2)	C13—H13	0.95
C4—C9	1.388 (3)	C14—C15	1.383 (3)
C5—C6	1.381 (3)	C14—H14	0.95
C5—H5	0.95	C15—H15	0.95
C6—C7	1.375 (3)	C16—N1	1.489 (2)
C6—H6	0.95	C16—H16A	0.99
C7—C8	1.376 (3)	C16—H16B	0.99
C7—H7	0.95	N1—H1A	0.91
C8—C9	1.381 (3)	N1—H1B	0.91
C8—H8	0.95	N1—H1C	0.91
O2—C1—O1	124.28 (15)	C4—C9—H9	119.8
O2—C1—C2	117.23 (14)	C15—C10—C11	119.26 (17)
O1—C1—C2	118.49 (15)	C15—C10—C16	120.96 (16)
C4—C2—C3	112.77 (13)	C11—C10—C16	119.79 (16)
C4—C2—C1	109.92 (13)	C12—C11—C10	120.21 (19)
C3—C2—C1	108.91 (14)	C12—C11—H11	119.9
C4—C2—H2	108.4	C10—C11—H11	119.9
C3—C2—H2	108.4	C13—C12—C11	119.90 (19)
C1—C2—H2	108.4	C13—C12—H12	120.1
C2—C3—H3A	109.5	C11—C12—H12	120.1
C2—C3—H3B	109.5	C14—C13—C12	120.10 (18)
H3A—C3—H3B	109.5	C14—C13—H13	119.9
C2—C3—H3C	109.5	C12—C13—H13	119.9
H3A—C3—H3C	109.5	C13—C14—C15	120.2 (2)
H3B—C3—H3C	109.5	C13—C14—H14	119.9
C5—C4—C9	118.33 (16)	C15—C14—H14	119.9
C5—C4—C2	121.57 (15)	C10—C15—C14	120.38 (18)
C9—C4—C2	120.09 (15)	C10—C15—H15	119.8
C6—C5—C4	120.97 (18)	C14—C15—H15	119.8
C6—C5—H5	119.5	N1—C16—C10	112.59 (12)
C4—C5—H5	119.5	N1—C16—H16A	109.1
C7—C6—C5	120.16 (19)	C10—C16—H16A	109.1
C7—C6—H6	119.9	N1—C16—H16B	109.1
C5—C6—H6	119.9	C10—C16—H16B	109.1
C6—C7—C8	119.47 (17)	H16A—C16—H16B	107.8
C6—C7—H7	120.3	C16—N1—H1A	109.5
C8—C7—H7	120.3	C16—N1—H1B	109.5
C7—C8—C9	120.66 (19)	H1A—N1—H1B	109.5
C7—C8—H8	119.7	C16—N1—H1C	109.5
C9—C8—H8	119.7	H1A—N1—H1C	109.5
C8—C9—C4	120.41 (18)	H1B—N1—H1C	109.5
C8—C9—H9	119.8
O2—C1—C2—C4	−71.75 (18)	C7—C8—C9—C4	0.7 (3)
O1—C1—C2—C4	108.31 (16)	C5—C4—C9—C8	−0.1 (3)
O2—C1—C2—C3	52.26 (19)	C2—C4—C9—C8	−179.50 (16)
O1—C1—C2—C3	−127.67 (16)	C15—C10—C11—C12	0.6 (3)
C3—C2—C4—C5	−47.4 (2)	C16—C10—C11—C12	−179.88 (16)
C1—C2—C4—C5	74.37 (18)	C10—C11—C12—C13	−0.9 (3)
C3—C2—C4—C9	132.03 (17)	C11—C12—C13—C14	0.6 (3)
C1—C2—C4—C9	−106.23 (17)	C12—C13—C14—C15	−0.1 (3)
C9—C4—C5—C6	−0.6 (2)	C11—C10—C15—C14	−0.1 (3)
C2—C4—C5—C6	178.81 (16)	C16—C10—C15—C14	−179.60 (16)
C4—C5—C6—C7	0.7 (3)	C13—C14—C15—C10	−0.2 (3)
C5—C6—C7—C8	0.0 (3)	C15—C10—C16—N1	−93.06 (18)
C6—C7—C8—C9	−0.7 (3)	C11—C10—C16—N1	87.43 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.91	1.91	2.8152 (16)	174
N1—H1B···O1^i	0.91	1.91	2.7652 (18)	157
N1—H1C···O2^ii	0.91	1.76	2.6651 (18)	178

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

(III) (RS)-1-phenylethylammonium naphthalene-1-carboxylate

Crystal data

C8H12N^+·C11H7O2^−	Z = 4
Mr = 293.35	F(000) = 624
Triclinic, P1	Dx = 1.188 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.8979 (9) Å	Cell parameters from 12505 reflections
b = 12.0013 (8) Å	θ = 0.4–27.1°
c = 16.0498 (15) Å	µ = 0.08 mm^−1
α = 100.213 (5)°	T = 173 K
β = 103.102 (3)°	Needle, colourless
γ = 90.652 (5)°	0.51 × 0.35 × 0.12 mm
V = 1640.5 (3) Å^3

Data collection

Bruker APEXII CCD area-detector diffractometer	3917 reflections with I > 2σ(I)
ω scans	Rint = 0.075
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	θmax = 27.1°, θmin = 2.4°
Tmin = 0.962, Tmax = 0.991	h = −11→11
27233 measured reflections	k = −15→14
7082 independent reflections	l = −19→20

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.050	w = 1/[σ^2(Fo^2) + (0.068P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.135	(Δ/σ)max < 0.001
S = 1.00	Δρmax = 0.22 e Å^−3
7082 reflections	Δρmin = −0.25 e Å^−3
401 parameters

Special details

Experimental. Absorption corrections were made using the program SADABS (Sheldrick, 1996)

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	−0.0372 (2)	0.66878 (13)	0.33043 (11)	0.0291 (4)
C2	0.0736 (2)	0.60999 (15)	0.37703 (12)	0.0379 (4)
H2	0.1306	0.6457	0.4331	0.046*
C3	0.1044 (2)	0.49875 (16)	0.34374 (13)	0.0478 (5)
H3	0.1799	0.4593	0.3775	0.057*
C4	0.0254 (2)	0.44756 (16)	0.26283 (13)	0.0465 (5)
H4	0.0483	0.3728	0.24	0.056*
C5	−0.0896 (2)	0.50338 (14)	0.21235 (11)	0.0368 (4)
C6	−0.1722 (3)	0.45001 (16)	0.12847 (13)	0.0502 (5)
H6	−0.1505	0.3747	0.1061	0.06*
C7	−0.2815 (3)	0.50399 (17)	0.07935 (13)	0.0540 (6)
H7	−0.3358	0.4666	0.0231	0.065*
C8	−0.3144 (3)	0.61509 (17)	0.11169 (13)	0.0481 (5)
H8	−0.3906	0.6528	0.0768	0.058*
C9	−0.2385 (2)	0.66975 (15)	0.19248 (11)	0.0363 (4)
H9	−0.263	0.7449	0.2131	0.044*
C10	−0.1238 (2)	0.61658 (14)	0.24634 (11)	0.0304 (4)
C11	−0.0576 (2)	0.78893 (14)	0.37164 (11)	0.0300 (4)
O1	0.06319 (14)	0.84530 (10)	0.41804 (8)	0.0357 (3)
O2	−0.18822 (14)	0.82804 (10)	0.35959 (8)	0.0419 (3)
C13	0.5803 (2)	0.32449 (14)	0.37054 (12)	0.0378 (4)
H13	0.6408	0.3152	0.4255	0.045*
C14	0.6114 (2)	0.41975 (16)	0.33680 (13)	0.0475 (5)
H14	0.6914	0.4743	0.3687	0.057*
C15	0.5263 (3)	0.43367 (16)	0.25806 (13)	0.0476 (5)
H15	0.5481	0.4981	0.2351	0.057*
C16	0.4062 (2)	0.35450 (15)	0.20974 (12)	0.0369 (4)
C17	0.3170 (3)	0.36900 (18)	0.12836 (13)	0.0531 (6)
H17	0.338	0.4339	0.1056	0.064*
C18	0.2017 (3)	0.29252 (19)	0.08146 (13)	0.0569 (6)
H18	0.143	0.3042	0.0267	0.068*
C19	0.1693 (2)	0.19631 (17)	0.11410 (12)	0.0473 (5)
H19	0.0889	0.1428	0.081	0.057*
C20	0.2525 (2)	0.17877 (15)	0.19322 (11)	0.0360 (4)
H20	0.2291	0.113	0.2142	0.043*
C21	0.3727 (2)	0.25709 (13)	0.24417 (11)	0.0296 (4)
C22	0.4653 (2)	0.24406 (13)	0.32678 (11)	0.0296 (4)
C23	0.4452 (2)	0.14361 (14)	0.36902 (11)	0.0296 (4)
O3	0.56591 (14)	0.11208 (10)	0.41573 (7)	0.0365 (3)
O4	0.31428 (15)	0.09705 (10)	0.35766 (8)	0.0425 (3)
C24	0.3880 (2)	0.80597 (15)	0.26047 (12)	0.0365 (4)
C25	0.2674 (3)	0.72691 (19)	0.22057 (14)	0.0538 (6)
H25	0.2298	0.6802	0.2542	0.065*
C26	0.2003 (3)	0.7146 (2)	0.13242 (15)	0.0641 (6)
H26	0.1178	0.6597	0.1059	0.077*
C27	0.2540 (3)	0.7824 (2)	0.08352 (14)	0.0620 (7)
H27	0.2076	0.7754	0.0232	0.074*
C28	0.3747 (3)	0.8602 (2)	0.12225 (14)	0.0617 (6)
H28	0.4129	0.9064	0.0885	0.074*
C29	0.4402 (3)	0.87160 (17)	0.20931 (13)	0.0484 (5)
H29	0.5237	0.926	0.2351	0.058*
C30	0.4621 (2)	0.82355 (15)	0.35694 (12)	0.0371 (4)
H30	0.5603	0.8706	0.3676	0.045*
C31	0.5024 (2)	0.71338 (16)	0.39042 (13)	0.0478 (5)
H31A	0.5507	0.731	0.4528	0.072*
H31B	0.5745	0.6733	0.3592	0.072*
H31C	0.408	0.6653	0.3807	0.072*
N1	0.35936 (17)	0.88833 (11)	0.40702 (9)	0.0329 (4)
H1A	0.2658	0.8501	0.3947	0.049*
H1B	0.3468	0.9579	0.392	0.049*
H1C	0.4027	0.8967	0.465	0.049*
C32	0.8890 (2)	0.06757 (15)	0.25853 (12)	0.0379 (4)
C33	0.7690 (3)	0.12616 (19)	0.21794 (14)	0.0541 (6)
H33	0.7329	0.1895	0.251	0.065*
C34	0.7008 (3)	0.0942 (2)	0.13029 (14)	0.0644 (7)
H34	0.619	0.1355	0.1035	0.077*
C35	0.7522 (3)	0.0019 (2)	0.08197 (14)	0.0636 (7)
H35	0.7053	−0.0212	0.0218	0.076*
C36	0.8722 (3)	−0.05630 (19)	0.12179 (14)	0.0623 (7)
H36	0.9087	−0.1193	0.0886	0.075*
C37	0.9394 (3)	−0.02401 (16)	0.20894 (13)	0.0479 (5)
H37	1.0215	−0.0653	0.2354	0.057*
C38	0.9640 (2)	0.09944 (15)	0.35446 (12)	0.0366 (4)
H38	1.0606	0.0573	0.3657	0.044*
C39	1.0088 (2)	0.22533 (16)	0.38598 (13)	0.0465 (5)
H39A	0.9168	0.2692	0.3736	0.07*
H39B	1.0849	0.2482	0.3558	0.07*
H39C	1.0536	0.2396	0.4488	0.07*
N2	0.85974 (17)	0.06125 (12)	0.40619 (9)	0.0321 (3)
H2A	0.7663	0.0919	0.3923	0.048*
H2B	0.9025	0.0843	0.464	0.048*
H2C	0.847	−0.0157	0.3938	0.048*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0311 (10)	0.0265 (9)	0.0283 (9)	−0.0055 (7)	0.0058 (8)	0.0034 (7)
C2	0.0418 (11)	0.0334 (10)	0.0344 (11)	−0.0009 (9)	0.0009 (9)	0.0054 (8)
C3	0.0545 (13)	0.0336 (11)	0.0508 (13)	0.0079 (10)	−0.0004 (11)	0.0121 (9)
C4	0.0624 (14)	0.0280 (10)	0.0481 (13)	0.0072 (10)	0.0126 (11)	0.0045 (9)
C5	0.0502 (12)	0.0263 (9)	0.0326 (10)	−0.0027 (8)	0.0092 (9)	0.0028 (8)
C6	0.0738 (16)	0.0339 (11)	0.0370 (12)	−0.0036 (10)	0.0095 (11)	−0.0041 (9)
C7	0.0752 (16)	0.0483 (13)	0.0286 (11)	−0.0095 (11)	−0.0005 (11)	−0.0022 (9)
C8	0.0576 (14)	0.0457 (12)	0.0358 (11)	−0.0043 (10)	−0.0033 (10)	0.0126 (9)
C9	0.0400 (11)	0.0325 (10)	0.0348 (11)	−0.0022 (8)	0.0054 (9)	0.0070 (8)
C10	0.0348 (10)	0.0274 (9)	0.0300 (10)	−0.0052 (8)	0.0089 (8)	0.0066 (7)
C11	0.0320 (11)	0.0295 (9)	0.0280 (10)	−0.0043 (8)	0.0064 (8)	0.0050 (7)
O1	0.0326 (7)	0.0340 (7)	0.0344 (7)	−0.0077 (6)	0.0036 (6)	−0.0036 (5)
O2	0.0316 (8)	0.0329 (7)	0.0551 (9)	−0.0002 (6)	0.0065 (6)	−0.0036 (6)
C13	0.0392 (11)	0.0325 (10)	0.0375 (11)	−0.0003 (8)	0.0012 (9)	0.0053 (8)
C14	0.0525 (13)	0.0327 (10)	0.0519 (13)	−0.0092 (9)	0.0044 (11)	0.0043 (9)
C15	0.0643 (14)	0.0305 (10)	0.0510 (13)	−0.0030 (10)	0.0157 (11)	0.0133 (9)
C16	0.0491 (12)	0.0309 (10)	0.0334 (10)	0.0046 (9)	0.0123 (9)	0.0091 (8)
C17	0.0782 (17)	0.0481 (12)	0.0370 (12)	0.0041 (12)	0.0128 (12)	0.0191 (10)
C18	0.0752 (17)	0.0649 (15)	0.0285 (11)	0.0063 (13)	0.0020 (11)	0.0161 (11)
C19	0.0561 (14)	0.0489 (12)	0.0303 (11)	0.0007 (10)	0.0012 (10)	0.0011 (9)
C20	0.0411 (11)	0.0338 (10)	0.0322 (10)	0.0034 (9)	0.0068 (9)	0.0059 (8)
C21	0.0351 (10)	0.0263 (9)	0.0285 (9)	0.0078 (8)	0.0096 (8)	0.0044 (7)
C22	0.0306 (10)	0.0279 (9)	0.0315 (10)	0.0053 (8)	0.0089 (8)	0.0062 (7)
C23	0.0304 (11)	0.0293 (9)	0.0283 (10)	0.0056 (8)	0.0067 (8)	0.0033 (7)
O3	0.0327 (7)	0.0436 (7)	0.0344 (7)	0.0092 (6)	0.0035 (6)	0.0157 (6)
O4	0.0320 (8)	0.0436 (7)	0.0555 (9)	0.0014 (6)	0.0051 (6)	0.0250 (6)
C24	0.0367 (11)	0.0374 (10)	0.0341 (10)	0.0067 (9)	0.0087 (9)	0.0026 (8)
C25	0.0539 (14)	0.0634 (14)	0.0452 (13)	−0.0040 (11)	0.0127 (11)	0.0119 (11)
C26	0.0639 (16)	0.0702 (16)	0.0459 (14)	−0.0107 (12)	0.0003 (12)	−0.0046 (12)
C27	0.0839 (19)	0.0654 (15)	0.0312 (12)	0.0110 (14)	0.0061 (12)	0.0032 (11)
C28	0.0879 (19)	0.0596 (14)	0.0384 (13)	−0.0029 (13)	0.0130 (13)	0.0136 (11)
C29	0.0611 (14)	0.0427 (11)	0.0399 (12)	−0.0026 (10)	0.0089 (11)	0.0075 (9)
C30	0.0331 (10)	0.0404 (10)	0.0399 (11)	0.0073 (8)	0.0089 (9)	0.0122 (8)
C31	0.0519 (13)	0.0446 (12)	0.0488 (13)	0.0137 (10)	0.0106 (10)	0.0140 (10)
N1	0.0347 (9)	0.0316 (8)	0.0316 (8)	−0.0002 (7)	0.0045 (7)	0.0077 (6)
C32	0.0429 (11)	0.0397 (11)	0.0343 (10)	−0.0025 (9)	0.0135 (9)	0.0095 (8)
C33	0.0570 (14)	0.0657 (14)	0.0412 (13)	0.0139 (11)	0.0157 (11)	0.0076 (10)
C34	0.0635 (16)	0.0844 (18)	0.0469 (15)	0.0144 (13)	0.0080 (12)	0.0213 (13)
C35	0.0820 (18)	0.0738 (16)	0.0304 (12)	−0.0061 (14)	0.0030 (12)	0.0111 (11)
C36	0.097 (2)	0.0521 (13)	0.0370 (13)	0.0069 (13)	0.0177 (13)	0.0042 (10)
C37	0.0673 (15)	0.0396 (11)	0.0380 (12)	0.0044 (10)	0.0138 (11)	0.0080 (9)
C38	0.0346 (11)	0.0358 (10)	0.0408 (11)	−0.0023 (8)	0.0119 (9)	0.0065 (8)
C39	0.0528 (13)	0.0383 (11)	0.0480 (13)	−0.0077 (9)	0.0142 (10)	0.0041 (9)
N2	0.0341 (8)	0.0298 (8)	0.0305 (8)	0.0014 (6)	0.0050 (7)	0.0040 (6)

Geometric parameters (Å, º)

C1—C2	1.378 (2)	C24—C29	1.380 (3)
C1—C10	1.423 (2)	C24—C25	1.383 (3)
C1—C11	1.507 (2)	C24—C30	1.515 (2)
C2—C3	1.402 (3)	C25—C26	1.386 (3)
C2—H2	0.95	C25—H25	0.95
C3—C4	1.361 (3)	C26—C27	1.376 (3)
C3—H3	0.95	C26—H26	0.95
C4—C5	1.409 (3)	C27—C28	1.371 (3)
C4—H4	0.95	C27—H27	0.95
C5—C6	1.413 (3)	C28—C29	1.368 (3)
C5—C10	1.434 (2)	C28—H28	0.95
C6—C7	1.355 (3)	C29—H29	0.95
C6—H6	0.95	C30—N1	1.488 (2)
C7—C8	1.402 (3)	C30—C31	1.530 (2)
C7—H7	0.95	C30—H30	1
C8—C9	1.364 (3)	C31—H31A	0.98
C8—H8	0.95	C31—H31B	0.98
C9—C10	1.416 (2)	C31—H31C	0.98
C9—H9	0.95	N1—H1A	0.91
C11—O2	1.245 (2)	N1—H1B	0.91
C11—O1	1.269 (2)	N1—H1C	0.91
C13—C22	1.373 (2)	C32—C37	1.380 (3)
C13—C14	1.399 (3)	C32—C33	1.387 (3)
C13—H13	0.95	C32—C38	1.510 (3)
C14—C15	1.357 (3)	C33—C34	1.382 (3)
C14—H14	0.95	C33—H33	0.95
C15—C16	1.409 (3)	C34—C35	1.379 (3)
C15—H15	0.95	C34—H34	0.95
C16—C17	1.407 (3)	C35—C36	1.380 (3)
C16—C21	1.434 (2)	C35—H35	0.95
C17—C18	1.359 (3)	C36—C37	1.374 (3)
C17—H17	0.95	C36—H36	0.95
C18—C19	1.402 (3)	C37—H37	0.95
C18—H18	0.95	C38—N2	1.494 (2)
C19—C20	1.370 (3)	C38—C39	1.524 (3)
C19—H19	0.95	C38—H38	1
C20—C21	1.416 (2)	C39—H39A	0.98
C20—H20	0.95	C39—H39B	0.98
C21—C22	1.429 (2)	C39—H39C	0.98
C22—C23	1.511 (2)	N2—H2A	0.91
C23—O4	1.247 (2)	N2—H2B	0.91
C23—O3	1.2666 (19)	N2—H2C	0.91
C2—C1—C10	119.99 (15)	C24—C25—C26	121.2 (2)
C2—C1—C11	117.08 (15)	C24—C25—H25	119.4
C10—C1—C11	122.91 (15)	C26—C25—H25	119.4
C1—C2—C3	121.62 (17)	C27—C26—C25	119.6 (2)
C1—C2—H2	119.2	C27—C26—H26	120.2
C3—C2—H2	119.2	C25—C26—H26	120.2
C4—C3—C2	119.64 (18)	C28—C27—C26	119.7 (2)
C4—C3—H3	120.2	C28—C27—H27	120.2
C2—C3—H3	120.2	C26—C27—H27	120.2
C3—C4—C5	121.22 (17)	C29—C28—C27	120.3 (2)
C3—C4—H4	119.4	C29—C28—H28	119.9
C5—C4—H4	119.4	C27—C28—H28	119.9
C4—C5—C6	121.23 (17)	C28—C29—C24	121.6 (2)
C4—C5—C10	119.61 (16)	C28—C29—H29	119.2
C6—C5—C10	119.16 (17)	C24—C29—H29	119.2
C7—C6—C5	121.36 (18)	N1—C30—C24	109.71 (14)
C7—C6—H6	119.3	N1—C30—C31	110.06 (14)
C5—C6—H6	119.3	C24—C30—C31	113.80 (16)
C6—C7—C8	119.84 (19)	N1—C30—H30	107.7
C6—C7—H7	120.1	C24—C30—H30	107.7
C8—C7—H7	120.1	C31—C30—H30	107.7
C9—C8—C7	120.90 (19)	C30—C31—H31A	109.5
C9—C8—H8	119.5	C30—C31—H31B	109.5
C7—C8—H8	119.5	H31A—C31—H31B	109.5
C8—C9—C10	121.28 (17)	C30—C31—H31C	109.5
C8—C9—H9	119.4	H31A—C31—H31C	109.5
C10—C9—H9	119.4	H31B—C31—H31C	109.5
C9—C10—C1	124.62 (15)	C30—N1—H1A	109.5
C9—C10—C5	117.45 (16)	C30—N1—H1B	109.5
C1—C10—C5	117.90 (15)	H1A—N1—H1B	109.5
O2—C11—O1	123.32 (15)	C30—N1—H1C	109.5
O2—C11—C1	120.10 (15)	H1A—N1—H1C	109.5
O1—C11—C1	116.58 (15)	H1B—N1—H1C	109.5
C22—C13—C14	122.15 (17)	C37—C32—C33	118.18 (18)
C22—C13—H13	118.9	C37—C32—C38	119.39 (17)
C14—C13—H13	118.9	C33—C32—C38	122.43 (17)
C15—C14—C13	119.46 (18)	C34—C33—C32	121.3 (2)
C15—C14—H14	120.3	C34—C33—H33	119.4
C13—C14—H14	120.3	C32—C33—H33	119.4
C14—C15—C16	121.35 (17)	C35—C34—C33	119.7 (2)
C14—C15—H15	119.3	C35—C34—H34	120.2
C16—C15—H15	119.3	C33—C34—H34	120.2
C17—C16—C15	121.55 (17)	C34—C35—C36	119.4 (2)
C17—C16—C21	118.89 (18)	C34—C35—H35	120.3
C15—C16—C21	119.57 (16)	C36—C35—H35	120.3
C18—C17—C16	121.66 (18)	C37—C36—C35	120.6 (2)
C18—C17—H17	119.2	C37—C36—H36	119.7
C16—C17—H17	119.2	C35—C36—H36	119.7
C17—C18—C19	119.86 (19)	C36—C37—C32	120.9 (2)
C17—C18—H18	120.1	C36—C37—H37	119.6
C19—C18—H18	120.1	C32—C37—H37	119.6
C20—C19—C18	120.64 (19)	N2—C38—C32	109.65 (14)
C20—C19—H19	119.7	N2—C38—C39	109.90 (14)
C18—C19—H19	119.7	C32—C38—C39	114.30 (15)
C19—C20—C21	121.05 (17)	N2—C38—H38	107.6
C19—C20—H20	119.5	C32—C38—H38	107.6
C21—C20—H20	119.5	C39—C38—H38	107.6
C20—C21—C22	124.26 (15)	C38—C39—H39A	109.5
C20—C21—C16	117.90 (15)	C38—C39—H39B	109.5
C22—C21—C16	117.83 (16)	H39A—C39—H39B	109.5
C13—C22—C21	119.63 (15)	C38—C39—H39C	109.5
C13—C22—C23	117.23 (15)	H39A—C39—H39C	109.5
C21—C22—C23	123.13 (15)	H39B—C39—H39C	109.5
O4—C23—O3	123.43 (15)	C38—N2—H2A	109.5
O4—C23—C22	119.95 (15)	C38—N2—H2B	109.5
O3—C23—C22	116.61 (16)	H2A—N2—H2B	109.5
C29—C24—C25	117.69 (18)	C38—N2—H2C	109.5
C29—C24—C30	119.59 (17)	H2A—N2—H2C	109.5
C25—C24—C30	122.72 (17)	H2B—N2—H2C	109.5
C10—C1—C2—C3	0.1 (3)	C15—C16—C21—C20	−179.26 (16)
C11—C1—C2—C3	−178.48 (17)	C17—C16—C21—C22	179.79 (17)
C1—C2—C3—C4	1.2 (3)	C15—C16—C21—C22	−0.7 (2)
C2—C3—C4—C5	−1.4 (3)	C14—C13—C22—C21	−0.3 (3)
C3—C4—C5—C6	−179.69 (19)	C14—C13—C22—C23	178.68 (17)
C3—C4—C5—C10	0.4 (3)	C20—C21—C22—C13	179.28 (16)
C4—C5—C6—C7	−179.2 (2)	C16—C21—C22—C13	0.8 (2)
C10—C5—C6—C7	0.7 (3)	C20—C21—C22—C23	0.4 (2)
C5—C6—C7—C8	0.0 (3)	C16—C21—C22—C23	−178.09 (15)
C6—C7—C8—C9	−0.5 (3)	C13—C22—C23—O4	148.21 (17)
C7—C8—C9—C10	0.2 (3)	C21—C22—C23—O4	−32.8 (2)
C8—C9—C10—C1	178.48 (17)	C13—C22—C23—O3	−31.1 (2)
C8—C9—C10—C5	0.5 (3)	C21—C22—C23—O3	147.86 (16)
C2—C1—C10—C9	−179.02 (17)	C29—C24—C25—C26	−0.5 (3)
C11—C1—C10—C9	−0.5 (3)	C30—C24—C25—C26	178.71 (19)
C2—C1—C10—C5	−1.1 (2)	C24—C25—C26—C27	−0.3 (3)
C11—C1—C10—C5	177.40 (15)	C25—C26—C27—C28	1.0 (4)
C4—C5—C10—C9	178.92 (17)	C26—C27—C28—C29	−0.9 (4)
C6—C5—C10—C9	−1.0 (2)	C27—C28—C29—C24	0.1 (3)
C4—C5—C10—C1	0.8 (2)	C25—C24—C29—C28	0.6 (3)
C6—C5—C10—C1	−179.05 (17)	C30—C24—C29—C28	−178.65 (19)
C2—C1—C11—O2	−145.61 (17)	C29—C24—C30—N1	103.07 (19)
C10—C1—C11—O2	35.9 (2)	C25—C24—C30—N1	−76.1 (2)
C2—C1—C11—O1	34.2 (2)	C29—C24—C30—C31	−133.13 (19)
C10—C1—C11—O1	−144.34 (16)	C25—C24—C30—C31	47.6 (2)
C22—C13—C14—C15	−0.4 (3)	C37—C32—C33—C34	0.1 (3)
C13—C14—C15—C16	0.5 (3)	C38—C32—C33—C34	−179.00 (19)
C14—C15—C16—C17	179.5 (2)	C32—C33—C34—C35	0.3 (3)
C14—C15—C16—C21	0.1 (3)	C33—C34—C35—C36	−0.7 (4)
C15—C16—C17—C18	179.7 (2)	C34—C35—C36—C37	0.7 (4)
C21—C16—C17—C18	−0.8 (3)	C35—C36—C37—C32	−0.3 (3)
C16—C17—C18—C19	0.0 (3)	C33—C32—C37—C36	−0.1 (3)
C17—C18—C19—C20	0.3 (3)	C38—C32—C37—C36	179.04 (18)
C18—C19—C20—C21	0.1 (3)	C37—C32—C38—N2	−103.52 (19)
C19—C20—C21—C22	−179.38 (17)	C33—C32—C38—N2	75.6 (2)
C19—C20—C21—C16	−0.9 (3)	C37—C32—C38—C39	132.58 (19)
C17—C16—C21—C20	1.2 (2)	C33—C32—C38—C39	−48.3 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.91	1.92	2.7305 (19)	147
N1—H1B···O4^i	0.91	1.86	2.7650 (17)	178
N1—H1C···O3^ii	0.91	1.89	2.7716 (18)	162
N2—H2A···O3	0.91	1.91	2.7232 (18)	147
N2—H2B···O1^ii	0.91	1.89	2.7695 (19)	163
N2—H2C···O2^iii	0.91	1.86	2.7678 (18)	175

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

(IV) benzylammonium benzoate–benzoic acid (1/1)

Crystal data

C7H10N^+·C7H5O2^−·C7H6O2	F(000) = 744
Mr = 351.39	Dx = 1.263 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 24815 reflections
a = 12.3249 (11) Å	θ = 0.4–27.1°
b = 6.0804 (6) Å	µ = 0.09 mm^−1
c = 24.7669 (17) Å	T = 173 K
β = 95.526 (5)°	Block, colourless
V = 1847.4 (3) Å^3	0.5 × 0.08 × 0.06 mm
Z = 4

Data collection

Bruker APEXII CCD area-detector diffractometer	4004 independent reflections
Radiation source: fine-focus sealed tube	2214 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.094
ω scans	θmax = 27°, θmin = 3.1°
Absorption correction: integration (XPREP; Bruker, 2004)	h = −15→15
Tmin = 0.957, Tmax = 0.995	k = −7→7
22843 measured reflections	l = −31→30

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.045	w = 1/[σ^2(Fo^2) + (0.0545P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.114	(Δ/σ)max = 0.002
S = 0.96	Δρmax = 0.21 e Å^−3
4004 reflections	Δρmin = −0.22 e Å^−3
237 parameters

Special details

Experimental. Numerical integration absorption corrections based on indexed crystal faces were applied using the XPREP routine (Bruker, 2004)

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.72097 (13)	0.1218 (3)	0.39195 (6)	0.0243 (4)
C2	0.77136 (13)	−0.0759 (3)	0.40748 (7)	0.0301 (4)
H2	0.7654	−0.132	0.4429	0.036*
C3	0.83019 (14)	−0.1920 (3)	0.37203 (7)	0.0382 (5)
H3A	0.8634	−0.3278	0.383	0.046*
C4	0.84071 (15)	−0.1112 (4)	0.32093 (8)	0.0436 (6)
H4	0.8817	−0.1902	0.2967	0.052*
C5	0.79147 (16)	0.0850 (4)	0.30498 (8)	0.0472 (6)
H5	0.7983	0.1409	0.2697	0.057*
C6	0.73197 (14)	0.2009 (3)	0.34033 (7)	0.0365 (5)
H6	0.6984	0.3361	0.329	0.044*
C7	0.65643 (13)	0.2460 (3)	0.43049 (7)	0.0236 (4)
O1	0.63819 (9)	0.15715 (19)	0.47483 (4)	0.0261 (3)
O2	0.62322 (9)	0.4378 (2)	0.41757 (4)	0.0305 (3)
C8	0.44262 (14)	0.9390 (3)	0.29160 (6)	0.0282 (4)
C9	0.45026 (15)	0.8606 (3)	0.23976 (7)	0.0402 (5)
H9	0.4851	0.7239	0.2346	0.048*
C10	0.40736 (18)	0.9804 (4)	0.19535 (7)	0.0535 (6)
H10	0.412	0.9248	0.1598	0.064*
C11	0.35791 (17)	1.1800 (4)	0.20240 (8)	0.0468 (6)
H11	0.3293	1.2624	0.1717	0.056*
C12	0.34980 (16)	1.2598 (4)	0.25331 (8)	0.0456 (6)
H12	0.3158	1.3977	0.2581	0.055*
C13	0.39134 (17)	1.1390 (3)	0.29801 (7)	0.0415 (5)
H13	0.3846	1.1937	0.3335	0.05*
C14	0.48561 (14)	0.8134 (3)	0.34045 (7)	0.0305 (5)
O3	0.54779 (11)	0.6453 (2)	0.32883 (4)	0.0401 (4)
H3	0.573	0.5836	0.3577	0.048*
O4	0.46587 (10)	0.8575 (2)	0.38636 (4)	0.0421 (4)
C15	0.25443 (13)	0.2956 (3)	0.44232 (6)	0.0234 (4)
C16	0.18925 (14)	0.4720 (3)	0.45402 (6)	0.0284 (4)
H16	0.2217	0.6088	0.4648	0.034*
C17	0.07698 (15)	0.4491 (4)	0.45003 (7)	0.0346 (5)
H17	0.0325	0.5705	0.4579	0.042*
C18	0.02966 (15)	0.2506 (4)	0.43475 (7)	0.0407 (5)
H18	−0.0473	0.2346	0.4325	0.049*
C19	0.09366 (16)	0.0757 (3)	0.42269 (7)	0.0407 (5)
H19	0.0608	−0.0607	0.4119	0.049*
C20	0.20618 (15)	0.0977 (3)	0.42617 (7)	0.0321 (5)
H20	0.2501	−0.0231	0.4174	0.039*
C21	0.37664 (13)	0.3184 (3)	0.44681 (6)	0.0280 (4)
H21A	0.4068	0.2182	0.4205	0.034*
H21B	0.396	0.4708	0.4375	0.034*
N1	0.42661 (11)	0.2654 (2)	0.50288 (5)	0.0249 (4)
H1A	0.5003	0.2555	0.5028	0.037*
H1B	0.3998	0.1349	0.5138	0.037*
H1C	0.4101	0.3736	0.5261	0.037*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0201 (9)	0.0252 (11)	0.0272 (9)	−0.0020 (8)	0.0001 (7)	−0.0032 (8)
C2	0.0240 (10)	0.0296 (12)	0.0364 (10)	−0.0010 (9)	0.0020 (8)	−0.0002 (9)
C3	0.0275 (11)	0.0332 (13)	0.0536 (13)	0.0059 (9)	0.0022 (9)	−0.0062 (11)
C4	0.0324 (11)	0.0545 (16)	0.0438 (13)	0.0082 (11)	0.0035 (9)	−0.0173 (11)
C5	0.0445 (13)	0.0664 (17)	0.0318 (11)	0.0133 (12)	0.0094 (9)	−0.0005 (11)
C6	0.0361 (11)	0.0419 (13)	0.0317 (10)	0.0103 (10)	0.0039 (8)	0.0027 (10)
C7	0.0208 (9)	0.0240 (11)	0.0248 (9)	−0.0034 (8)	−0.0047 (7)	−0.0023 (9)
O1	0.0289 (7)	0.0262 (7)	0.0232 (6)	0.0005 (6)	0.0024 (5)	0.0016 (6)
O2	0.0397 (8)	0.0239 (8)	0.0280 (7)	0.0066 (6)	0.0040 (5)	0.0019 (6)
C8	0.0299 (10)	0.0310 (12)	0.0232 (9)	0.0003 (9)	0.0003 (7)	0.0002 (9)
C9	0.0478 (13)	0.0445 (13)	0.0282 (10)	0.0112 (11)	0.0039 (9)	−0.0007 (10)
C10	0.0722 (16)	0.0654 (18)	0.0230 (11)	0.0152 (14)	0.0054 (10)	0.0040 (11)
C11	0.0496 (13)	0.0572 (16)	0.0328 (11)	0.0062 (12)	−0.0002 (9)	0.0162 (11)
C12	0.0564 (14)	0.0371 (13)	0.0420 (12)	0.0125 (11)	−0.0023 (10)	0.0052 (10)
C13	0.0593 (14)	0.0358 (13)	0.0281 (10)	0.0092 (11)	−0.0034 (9)	−0.0033 (10)
C14	0.0309 (11)	0.0304 (12)	0.0293 (10)	0.0012 (9)	−0.0021 (8)	−0.0035 (9)
O3	0.0528 (9)	0.0408 (9)	0.0257 (7)	0.0187 (7)	−0.0005 (6)	0.0019 (7)
O4	0.0572 (9)	0.0486 (9)	0.0202 (7)	0.0161 (7)	0.0017 (6)	−0.0010 (6)
C15	0.0263 (10)	0.0276 (11)	0.0156 (8)	−0.0027 (9)	−0.0019 (7)	0.0015 (8)
C16	0.0346 (11)	0.0279 (11)	0.0223 (9)	−0.0019 (9)	0.0011 (8)	−0.0005 (8)
C17	0.0323 (11)	0.0425 (13)	0.0299 (10)	0.0051 (10)	0.0072 (8)	0.0028 (10)
C18	0.0249 (11)	0.0558 (16)	0.0411 (11)	−0.0071 (11)	0.0010 (9)	0.0111 (11)
C19	0.0383 (13)	0.0335 (13)	0.0479 (12)	−0.0137 (11)	−0.0073 (10)	0.0023 (10)
C20	0.0347 (11)	0.0277 (12)	0.0323 (10)	−0.0001 (9)	−0.0054 (8)	−0.0010 (9)
C21	0.0294 (10)	0.0352 (12)	0.0192 (9)	−0.0027 (9)	0.0011 (7)	0.0004 (8)
N1	0.0251 (8)	0.0251 (9)	0.0239 (7)	−0.0011 (7)	−0.0001 (6)	0.0000 (7)

Geometric parameters (Å, º)

C1—C6	1.385 (2)	C12—H12	0.95
C1—C2	1.390 (2)	C13—H13	0.95
C1—C7	1.504 (2)	C14—O4	1.2152 (19)
C2—C3	1.385 (2)	C14—O3	1.326 (2)
C2—H2	0.95	O3—H3	0.84
C3—C4	1.375 (2)	C15—C20	1.384 (2)
C3—H3A	0.95	C15—C16	1.387 (2)
C4—C5	1.379 (3)	C15—C21	1.506 (2)
C4—H4	0.95	C16—C17	1.385 (2)
C5—C6	1.388 (3)	C16—H16	0.95
C5—H5	0.95	C17—C18	1.378 (3)
C6—H6	0.95	C17—H17	0.95
C7—O1	1.2633 (19)	C18—C19	1.374 (3)
C7—O2	1.267 (2)	C18—H18	0.95
C8—C9	1.381 (2)	C19—C20	1.388 (3)
C8—C13	1.386 (3)	C19—H19	0.95
C8—C14	1.485 (2)	C20—H20	0.95
C9—C10	1.381 (3)	C21—N1	1.4989 (19)
C9—H9	0.95	C21—H21A	0.99
C10—C11	1.377 (3)	C21—H21B	0.99
C10—H10	0.95	N1—H1A	0.91
C11—C12	1.364 (3)	N1—H1B	0.91
C11—H11	0.95	N1—H1C	0.91
C12—C13	1.385 (3)
C6—C1—C2	118.37 (16)	C12—C13—H13	119.6
C6—C1—C7	121.07 (16)	C8—C13—H13	119.6
C2—C1—C7	120.56 (15)	O4—C14—O3	123.03 (16)
C3—C2—C1	120.83 (17)	O4—C14—C8	124.13 (17)
C3—C2—H2	119.6	O3—C14—C8	112.83 (15)
C1—C2—H2	119.6	C14—O3—H3	109.5
C4—C3—C2	120.20 (19)	C20—C15—C16	119.41 (16)
C4—C3—H3A	119.9	C20—C15—C21	120.01 (16)
C2—C3—H3A	119.9	C16—C15—C21	120.58 (16)
C3—C4—C5	119.64 (18)	C17—C16—C15	120.16 (17)
C3—C4—H4	120.2	C17—C16—H16	119.9
C5—C4—H4	120.2	C15—C16—H16	119.9
C4—C5—C6	120.24 (19)	C18—C17—C16	120.08 (18)
C4—C5—H5	119.9	C18—C17—H17	120
C6—C5—H5	119.9	C16—C17—H17	120
C1—C6—C5	120.70 (19)	C19—C18—C17	120.07 (17)
C1—C6—H6	119.6	C19—C18—H18	120
C5—C6—H6	119.6	C17—C18—H18	120
O1—C7—O2	122.22 (16)	C18—C19—C20	120.21 (18)
O1—C7—C1	119.09 (16)	C18—C19—H19	119.9
O2—C7—C1	118.69 (15)	C20—C19—H19	119.9
C9—C8—C13	118.80 (17)	C15—C20—C19	120.05 (18)
C9—C8—C14	121.93 (17)	C15—C20—H20	120
C13—C8—C14	119.26 (15)	C19—C20—H20	120
C10—C9—C8	120.22 (19)	N1—C21—C15	111.56 (13)
C10—C9—H9	119.9	N1—C21—H21A	109.3
C8—C9—H9	119.9	C15—C21—H21A	109.3
C11—C10—C9	120.25 (18)	N1—C21—H21B	109.3
C11—C10—H10	119.9	C15—C21—H21B	109.3
C9—C10—H10	119.9	H21A—C21—H21B	108
C12—C11—C10	120.24 (18)	C21—N1—H1A	109.5
C12—C11—H11	119.9	C21—N1—H1B	109.5
C10—C11—H11	119.9	H1A—N1—H1B	109.5
C11—C12—C13	119.7 (2)	C21—N1—H1C	109.5
C11—C12—H12	120.1	H1A—N1—H1C	109.5
C13—C12—H12	120.1	H1B—N1—H1C	109.5
C12—C13—C8	120.74 (17)
C6—C1—C2—C3	−0.7 (2)	C11—C12—C13—C8	1.0 (3)
C7—C1—C2—C3	179.48 (15)	C9—C8—C13—C12	−0.9 (3)
C1—C2—C3—C4	0.8 (3)	C14—C8—C13—C12	−179.64 (18)
C2—C3—C4—C5	−0.6 (3)	C9—C8—C14—O4	−167.81 (18)
C3—C4—C5—C6	0.3 (3)	C13—C8—C14—O4	10.9 (3)
C2—C1—C6—C5	0.3 (3)	C9—C8—C14—O3	11.7 (2)
C7—C1—C6—C5	−179.85 (16)	C13—C8—C14—O3	−169.57 (17)
C4—C5—C6—C1	−0.1 (3)	C20—C15—C16—C17	0.6 (2)
C6—C1—C7—O1	172.24 (15)	C21—C15—C16—C17	−179.68 (15)
C2—C1—C7—O1	−7.9 (2)	C15—C16—C17—C18	0.4 (2)
C6—C1—C7—O2	−8.6 (2)	C16—C17—C18—C19	−0.9 (3)
C2—C1—C7—O2	171.30 (15)	C17—C18—C19—C20	0.4 (3)
C13—C8—C9—C10	0.0 (3)	C16—C15—C20—C19	−1.1 (2)
C14—C8—C9—C10	178.72 (18)	C21—C15—C20—C19	179.17 (15)
C8—C9—C10—C11	0.8 (3)	C18—C19—C20—C15	0.6 (3)
C9—C10—C11—C12	−0.8 (3)	C20—C15—C21—N1	−91.71 (18)
C10—C11—C12—C13	−0.1 (3)	C16—C15—C21—N1	88.60 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2	0.84	1.79	2.6255 (16)	177
N1—H1A···O1	0.91	1.99	2.8399 (18)	155
N1—H1B···O1^i	0.91	1.87	2.7620 (18)	168
N1—H1C···O2^ii	0.91	1.88	2.7835 (17)	171

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

(V) cyclopropylammonium benzoate–benzoic acid (1/1)

Crystal data

C3H8N^+·C7H5O2^−·C7H6O2	F(000) = 640
Mr = 301.33	Dx = 1.248 Mg m^−3 Dm = 0 Mg m^−3 Dm measured by not measured
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1969 reflections
a = 15.3307 (10) Å	θ = 2.9–27.6°
b = 6.3703 (3) Å	µ = 0.09 mm^−1
c = 17.9989 (11) Å	T = 173 K
β = 114.199 (2)°	Block, colourless
V = 1603.33 (16) Å^3	0.34 × 0.2 × 0.1 mm
Z = 4

Data collection

Bruker APEXII CCD area-detector diffractometer	2461 reflections with I > 2σ(I)
ω scans	Rint = 0.028
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	θmax = 28.0°, θmin = 1.5°
Tmin = 0.970, Tmax = 0.991	h = −14→20
9730 measured reflections	k = −7→8
3876 independent reflections	l = −23→21

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.044	w = 1/[σ^2(Fo^2) + (0.0437P)^2 + 0.2204P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.11	(Δ/σ)max = 0.006
S = 1.00	Δρmax = 0.19 e Å^−3
3876 reflections	Δρmin = −0.19 e Å^−3
200 parameters

Special details

Experimental. Absorption corrections were made using the program SADABS (Sheldrick, 1996)

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.78280 (10)	0.1676 (2)	0.57876 (9)	0.0314 (3)
C2	0.86076 (12)	0.2719 (3)	0.63506 (11)	0.0472 (4)
H2	0.8528	0.4085	0.6525	0.057*
C3	0.95012 (14)	0.1798 (3)	0.66630 (12)	0.0609 (5)
H3A	1.0031	0.2535	0.705	0.073*
C4	0.96290 (14)	−0.0170 (3)	0.64184 (12)	0.0581 (5)
H4	1.0246	−0.0795	0.6631	0.07*
C5	0.88607 (14)	−0.1231 (3)	0.58644 (14)	0.0562 (5)
H5	0.8943	−0.2604	0.5698	0.067*
C6	0.79663 (12)	−0.0313 (2)	0.55471 (12)	0.0448 (4)
H6	0.7439	−0.1056	0.5159	0.054*
C7	0.68468 (11)	0.2651 (2)	0.54413 (9)	0.0311 (3)
O1	0.67544 (8)	0.45045 (15)	0.56561 (7)	0.0443 (3)
O2	0.61583 (7)	0.16305 (15)	0.49517 (7)	0.0365 (3)
C8	0.76369 (10)	0.9573 (2)	0.77606 (9)	0.0323 (3)
C9	0.83615 (12)	0.8712 (3)	0.84356 (11)	0.0450 (4)
H9	0.8564	0.7312	0.8416	0.054*
C10	0.87921 (14)	0.9873 (3)	0.91361 (12)	0.0588 (5)
H10	0.9293	0.9273	0.9597	0.071*
C11	0.85028 (14)	1.1892 (3)	0.91732 (12)	0.0566 (5)
H11	0.88	1.2686	0.9659	0.068*
C12	0.77849 (14)	1.2758 (3)	0.85077 (12)	0.0522 (5)
H12	0.7584	1.4156	0.8534	0.063*
C13	0.73478 (12)	1.1614 (2)	0.77958 (10)	0.0400 (4)
H13	0.6852	1.2227	0.7334	0.048*
C14	0.71382 (11)	0.8330 (2)	0.70051 (10)	0.0334 (3)
O3	0.75692 (9)	0.65301 (16)	0.70143 (7)	0.0496 (3)
H3	0.7265	0.5879	0.6578	0.074*
O4	0.64141 (8)	0.88983 (16)	0.64465 (7)	0.0418 (3)
C15	0.52382 (12)	0.7411 (2)	0.38333 (10)	0.0389 (4)
H15	0.4869	0.862	0.3497	0.047*
C16	0.59417 (14)	0.6443 (3)	0.35686 (12)	0.0518 (5)
H16A	0.6539	0.5879	0.3995	0.062*
H16B	0.6012	0.706	0.3091	0.062*
C17	0.50236 (13)	0.5329 (3)	0.34255 (11)	0.0509 (5)
H17A	0.4528	0.5263	0.286	0.061*
H17B	0.5056	0.4082	0.3764	0.061*
N1	0.54718 (9)	0.75446 (18)	0.47059 (8)	0.0335 (3)
H1A	0.5832	0.6415	0.4965	0.05*
H1B	0.4922	0.7558	0.4785	0.05*
H1C	0.5807	0.8744	0.4911	0.05*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0332 (8)	0.0275 (7)	0.0386 (8)	0.0015 (6)	0.0199 (7)	0.0018 (6)
C2	0.0374 (10)	0.0518 (10)	0.0524 (11)	0.0007 (8)	0.0183 (9)	−0.0137 (9)
C3	0.0375 (11)	0.0867 (15)	0.0537 (12)	0.0043 (10)	0.0138 (9)	−0.0147 (11)
C4	0.0419 (11)	0.0736 (13)	0.0646 (13)	0.0224 (10)	0.0276 (10)	0.0162 (11)
C5	0.0542 (12)	0.0368 (9)	0.0930 (16)	0.0112 (8)	0.0458 (12)	0.0070 (10)
C6	0.0400 (10)	0.0290 (8)	0.0731 (13)	−0.0017 (7)	0.0309 (9)	−0.0052 (8)
C7	0.0362 (9)	0.0238 (7)	0.0372 (8)	0.0000 (6)	0.0191 (7)	−0.0016 (6)
O1	0.0470 (7)	0.0273 (5)	0.0518 (7)	0.0073 (5)	0.0135 (6)	−0.0102 (5)
O2	0.0338 (6)	0.0269 (5)	0.0474 (7)	−0.0024 (4)	0.0153 (5)	−0.0058 (5)
C8	0.0319 (8)	0.0314 (7)	0.0367 (8)	−0.0034 (6)	0.0173 (7)	−0.0025 (6)
C9	0.0403 (10)	0.0418 (9)	0.0465 (11)	0.0012 (7)	0.0111 (8)	−0.0013 (8)
C10	0.0504 (12)	0.0685 (13)	0.0426 (11)	−0.0042 (10)	0.0039 (9)	−0.0027 (10)
C11	0.0583 (13)	0.0671 (13)	0.0436 (11)	−0.0208 (10)	0.0202 (10)	−0.0218 (10)
C12	0.0608 (13)	0.0410 (9)	0.0587 (12)	−0.0085 (9)	0.0286 (11)	−0.0171 (9)
C13	0.0437 (10)	0.0332 (8)	0.0418 (9)	−0.0020 (7)	0.0161 (8)	−0.0042 (7)
C14	0.0373 (9)	0.0284 (7)	0.0375 (9)	0.0006 (6)	0.0185 (8)	−0.0003 (7)
O3	0.0580 (8)	0.0351 (6)	0.0466 (7)	0.0120 (5)	0.0122 (6)	−0.0084 (5)
O4	0.0403 (7)	0.0395 (6)	0.0402 (7)	0.0038 (5)	0.0111 (6)	−0.0062 (5)
C15	0.0409 (10)	0.0313 (8)	0.0432 (9)	0.0071 (7)	0.0157 (8)	−0.0023 (7)
C16	0.0576 (12)	0.0535 (11)	0.0557 (12)	0.0132 (9)	0.0349 (10)	0.0058 (9)
C17	0.0601 (12)	0.0408 (9)	0.0470 (10)	0.0037 (8)	0.0171 (9)	−0.0121 (8)
N1	0.0292 (7)	0.0244 (6)	0.0470 (8)	−0.0014 (5)	0.0158 (6)	−0.0084 (6)

Geometric parameters (Å, º)

C1—C2	1.380 (2)	C11—C12	1.367 (3)
C1—C6	1.383 (2)	C11—H11	0.95
C1—C7	1.506 (2)	C12—C13	1.385 (2)
C2—C3	1.380 (2)	C12—H12	0.95
C2—H2	0.95	C13—H13	0.95
C3—C4	1.369 (3)	C14—O4	1.2081 (18)
C3—H3A	0.95	C14—O3	1.3200 (17)
C4—C5	1.369 (3)	O3—H3	0.84
C4—H4	0.95	C15—N1	1.463 (2)
C5—C6	1.381 (2)	C15—C16	1.480 (2)
C5—H5	0.95	C15—C17	1.486 (2)
C6—H6	0.95	C15—H15	1
C7—O2	1.2454 (17)	C16—C17	1.501 (3)
C7—O1	1.2682 (16)	C16—H16A	0.99
C8—C9	1.380 (2)	C16—H16B	0.99
C8—C13	1.383 (2)	C17—H17A	0.99
C8—C14	1.486 (2)	C17—H17B	0.99
C9—C10	1.375 (2)	N1—H1A	0.91
C9—H9	0.95	N1—H1B	0.91
C10—C11	1.371 (3)	N1—H1C	0.91
C10—H10	0.95
C2—C1—C6	118.24 (15)	C11—C12—H12	119.7
C2—C1—C7	121.51 (13)	C13—C12—H12	119.7
C6—C1—C7	120.24 (14)	C12—C13—C8	119.62 (17)
C1—C2—C3	120.72 (16)	C12—C13—H13	120.2
C1—C2—H2	119.6	C8—C13—H13	120.2
C3—C2—H2	119.6	O4—C14—O3	123.73 (14)
C4—C3—C2	120.46 (19)	O4—C14—C8	123.66 (13)
C4—C3—H3A	119.8	O3—C14—C8	112.61 (14)
C2—C3—H3A	119.8	C14—O3—H3	109.5
C3—C4—C5	119.49 (17)	N1—C15—C16	118.66 (14)
C3—C4—H4	120.3	N1—C15—C17	119.31 (14)
C5—C4—H4	120.3	C16—C15—C17	60.80 (11)
C4—C5—C6	120.27 (17)	N1—C15—H15	115.7
C4—C5—H5	119.9	C16—C15—H15	115.7
C6—C5—H5	119.9	C17—C15—H15	115.7
C5—C6—C1	120.81 (17)	C15—C16—C17	59.78 (11)
C5—C6—H6	119.6	C15—C16—H16A	117.8
C1—C6—H6	119.6	C17—C16—H16A	117.8
O2—C7—O1	122.25 (14)	C15—C16—H16B	117.8
O2—C7—C1	119.36 (12)	C17—C16—H16B	117.8
O1—C7—C1	118.39 (13)	H16A—C16—H16B	114.9
C9—C8—C13	119.39 (15)	C15—C17—C16	59.42 (11)
C9—C8—C14	121.35 (14)	C15—C17—H17A	117.8
C13—C8—C14	119.24 (14)	C16—C17—H17A	117.8
C10—C9—C8	120.29 (16)	C15—C17—H17B	117.8
C10—C9—H9	119.9	C16—C17—H17B	117.8
C8—C9—H9	119.9	H17A—C17—H17B	115
C11—C10—C9	120.39 (18)	C15—N1—H1A	109.5
C11—C10—H10	119.8	C15—N1—H1B	109.5
C9—C10—H10	119.8	H1A—N1—H1B	109.5
C12—C11—C10	119.75 (17)	C15—N1—H1C	109.5
C12—C11—H11	120.1	H1A—N1—H1C	109.5
C10—C11—H11	120.1	H1B—N1—H1C	109.5
C11—C12—C13	120.57 (17)
C6—C1—C2—C3	0.1 (3)	C14—C8—C9—C10	−177.98 (16)
C7—C1—C2—C3	179.85 (16)	C8—C9—C10—C11	0.4 (3)
C1—C2—C3—C4	0.0 (3)	C9—C10—C11—C12	−0.3 (3)
C2—C3—C4—C5	−0.5 (3)	C10—C11—C12—C13	−0.1 (3)
C3—C4—C5—C6	0.8 (3)	C11—C12—C13—C8	0.4 (3)
C4—C5—C6—C1	−0.7 (3)	C9—C8—C13—C12	−0.3 (2)
C2—C1—C6—C5	0.2 (2)	C14—C8—C13—C12	177.63 (15)
C7—C1—C6—C5	−179.53 (15)	C9—C8—C14—O4	168.67 (15)
C2—C1—C7—O2	−178.00 (15)	C13—C8—C14—O4	−9.3 (2)
C6—C1—C7—O2	1.7 (2)	C9—C8—C14—O3	−10.8 (2)
C2—C1—C7—O1	2.6 (2)	C13—C8—C14—O3	171.22 (14)
C6—C1—C7—O1	−177.69 (14)	N1—C15—C16—C17	109.49 (16)
C13—C8—C9—C10	0.0 (2)	N1—C15—C17—C16	−108.45 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O1	0.84	1.75	2.5881 (16)	173
N1—H1A···O1	0.91	1.89	2.7901 (16)	168
N1—H1B···O2^i	0.91	1.97	2.8573 (16)	165
N1—H1C···O2^ii	0.91	1.91	2.7743 (15)	158

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

(VI) bis(cyclopropylammonium) ea-cis-cyclohexane-1,4-dicarboxylate– ee-trans-cyclohexane-1,4-dicarboxylic acid (1/1)

Crystal data

2C3H8N^+·C8H10O4^2^−·C8H12O4	F(000) = 992
Mr = 458.54	Dx = 1.297 Mg m^−3 Dm = 0 Mg m^−3 Dm measured by not measured
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 8893 reflections
a = 10.2478 (4) Å	θ = 2.3–28.1°
b = 9.6134 (4) Å	µ = 0.10 mm^−1
c = 23.8354 (9) Å	T = 173 K
V = 2348.17 (16) Å^3	Triangle, colourless
Z = 4	0.56 × 0.4 × 0.07 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	2735 reflections with I > 2σ(I)
ω scans	Rint = 0.037
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	θmax = 28.0°, θmin = 1.7°
Tmin = 0.947, Tmax = 0.993	h = −13→13
27099 measured reflections	k = −12→11
2909 independent reflections	l = −26→31

Refinement

Refinement on F^2	1 restraint
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.035	w = 1/[σ^2(Fo^2) + (0.0621P)^2 + 0.3462P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.094	(Δ/σ)max = 0.001
S = 1.04	Δρmax = 0.33 e Å^−3
2909 reflections	Δρmin = −0.18 e Å^−3
293 parameters	Absolute structure: Flack (1983), with 2122 Friedel pairs

Special details

Experimental. Absorption corrections were made using the program SADABS (Sheldrick, 1996)

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.53031 (18)	0.8886 (2)	0.61593 (8)	0.0159 (4)
H1	0.459	0.9243	0.6407	0.019*
C2	0.47606 (19)	0.76215 (19)	0.58481 (8)	0.0170 (4)
H2D	0.4449	0.6928	0.6124	0.02*
H2E	0.5467	0.7186	0.5625	0.02*
C3	0.36322 (19)	0.8022 (2)	0.54561 (8)	0.0184 (4)
H3A	0.3341	0.7189	0.5247	0.022*
H3B	0.2887	0.836	0.5683	0.022*
C4	0.40401 (18)	0.9149 (2)	0.50418 (8)	0.0172 (4)
H4	0.3245	0.9434	0.4827	0.021*
C5	0.4519 (2)	1.0418 (2)	0.53664 (9)	0.0226 (4)
H5A	0.3792	1.08	0.5593	0.027*
H5B	0.4799	1.1146	0.5098	0.027*
C6	0.5656 (2)	1.0056 (2)	0.57531 (8)	0.0212 (4)
H6A	0.591	1.0893	0.5969	0.025*
H6B	0.6415	0.9769	0.5524	0.025*
C7	0.64613 (18)	0.8536 (2)	0.65394 (8)	0.0161 (4)
C8	0.50671 (18)	0.8663 (2)	0.46154 (8)	0.0170 (4)
O1	0.65311 (14)	0.72828 (15)	0.67225 (6)	0.0213 (3)
O2	0.72535 (16)	0.94572 (16)	0.66630 (7)	0.0276 (3)
O3	0.50529 (14)	0.73805 (15)	0.44698 (6)	0.0217 (3)
O4	0.58416 (15)	0.95240 (16)	0.44247 (6)	0.0261 (3)
C9	0.78798 (18)	0.5424 (2)	0.31075 (8)	0.0171 (4)
H9	0.7624	0.5184	0.2714	0.021*
C10	0.83307 (18)	0.4084 (2)	0.34001 (9)	0.0195 (4)
H10A	0.8568	0.4292	0.3794	0.023*
H10B	0.7609	0.34	0.3403	0.023*
C11	0.95106 (19)	0.3465 (2)	0.30950 (9)	0.0193 (4)
H11A	0.9813	0.2625	0.3297	0.023*
H11B	0.9253	0.3185	0.2711	0.023*
C12	1.06206 (18)	0.4521 (2)	0.30630 (8)	0.0161 (4)
H12	1.0886	0.4761	0.3455	0.019*
C13	1.01603 (19)	0.5862 (2)	0.27744 (9)	0.0197 (4)
H13A	1.0882	0.6547	0.2769	0.024*
H13B	0.9916	0.5657	0.2381	0.024*
C14	0.89913 (19)	0.6479 (2)	0.30821 (9)	0.0193 (4)
H14A	0.8692	0.7328	0.2885	0.023*
H14B	0.9251	0.6745	0.3467	0.023*
C15	1.18106 (18)	0.4006 (2)	0.27562 (8)	0.0168 (4)
C16	0.66857 (18)	0.5964 (2)	0.34083 (8)	0.0173 (4)
O5	0.69379 (14)	0.67242 (17)	0.38507 (7)	0.0270 (3)
H5	0.6239	0.6901	0.4021	0.04*
O6	0.55794 (14)	0.56647 (16)	0.32570 (6)	0.0227 (3)
O7	1.15657 (15)	0.31369 (17)	0.23494 (7)	0.0261 (3)
H7	1.2259	0.2964	0.2174	0.039*
O8	1.29028 (14)	0.44374 (16)	0.28676 (6)	0.0227 (3)
C17	0.5095 (2)	0.3923 (2)	0.67976 (11)	0.0304 (5)
H17	0.4443	0.3155	0.6835	0.036*
C18	0.5772 (4)	0.4002 (3)	0.62473 (11)	0.0460 (8)
H18A	0.6013	0.4934	0.6104	0.055*
H18B	0.5523	0.3319	0.5955	0.055*
C19	0.6470 (3)	0.3474 (3)	0.67527 (12)	0.0398 (6)
H19A	0.6656	0.2465	0.6773	0.048*
H19B	0.7145	0.4079	0.6922	0.048*
N1	0.47602 (17)	0.52266 (19)	0.70892 (8)	0.0223 (4)
H1B	0.479	0.5087	0.7467	0.033*
H1C	0.3942	0.5497	0.6989	0.033*
H1A	0.5342	0.59	0.6993	0.033*
C20	0.3644 (2)	0.4084 (2)	0.43062 (10)	0.0277 (5)
H20	0.3104	0.3268	0.419	0.033*
C21	0.4022 (3)	0.4101 (3)	0.48986 (12)	0.0447 (7)
H21A	0.3705	0.3335	0.514	0.054*
H21B	0.4095	0.5016	0.5087	0.054*
C22	0.4998 (3)	0.3756 (3)	0.44567 (14)	0.0451 (7)
H22A	0.5677	0.4458	0.437	0.054*
H22B	0.5286	0.2777	0.4424	0.054*
N2	0.33162 (17)	0.54013 (18)	0.40263 (7)	0.0216 (4)
H2A	0.3863	0.6082	0.4149	0.032*
H2B	0.2478	0.5637	0.4108	0.032*
H2C	0.3405	0.5299	0.3649	0.032*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0178 (8)	0.0186 (9)	0.0112 (8)	0.0024 (7)	−0.0012 (7)	0.0022 (7)
C2	0.0209 (8)	0.0167 (8)	0.0136 (8)	0.0001 (7)	−0.0020 (7)	0.0041 (7)
C3	0.0165 (8)	0.0264 (9)	0.0124 (8)	−0.0005 (7)	0.0014 (7)	0.0015 (7)
C4	0.0172 (8)	0.0234 (9)	0.0109 (8)	0.0058 (7)	0.0001 (7)	0.0021 (7)
C5	0.0344 (11)	0.0177 (9)	0.0157 (9)	0.0088 (8)	0.0005 (9)	0.0036 (8)
C6	0.0316 (10)	0.0151 (8)	0.0171 (9)	−0.0031 (8)	−0.0037 (8)	−0.0011 (7)
C7	0.0170 (8)	0.0215 (9)	0.0099 (8)	0.0019 (7)	−0.0008 (7)	−0.0011 (7)
C8	0.0164 (8)	0.0261 (9)	0.0084 (8)	0.0036 (7)	−0.0015 (6)	−0.0008 (7)
O1	0.0204 (7)	0.0243 (7)	0.0191 (7)	0.0006 (5)	−0.0048 (6)	0.0071 (6)
O2	0.0270 (8)	0.0271 (8)	0.0287 (8)	−0.0032 (6)	−0.0097 (7)	0.0009 (7)
O3	0.0216 (7)	0.0254 (7)	0.0181 (7)	−0.0008 (6)	0.0038 (6)	−0.0058 (6)
O4	0.0266 (8)	0.0290 (8)	0.0227 (7)	−0.0031 (6)	0.0082 (6)	0.0024 (6)
C9	0.0154 (8)	0.0228 (9)	0.0132 (8)	0.0014 (7)	0.0008 (7)	−0.0041 (7)
C10	0.0183 (9)	0.0179 (9)	0.0223 (10)	−0.0015 (7)	0.0065 (8)	−0.0011 (8)
C11	0.0190 (9)	0.0159 (9)	0.0229 (9)	0.0004 (7)	0.0057 (8)	−0.0017 (7)
C12	0.0149 (8)	0.0208 (9)	0.0127 (8)	0.0007 (7)	0.0011 (7)	−0.0036 (7)
C13	0.0191 (9)	0.0185 (9)	0.0214 (10)	0.0007 (7)	0.0053 (8)	−0.0001 (8)
C14	0.0205 (9)	0.0164 (9)	0.0210 (9)	0.0016 (7)	0.0045 (8)	0.0000 (7)
C15	0.0169 (8)	0.0204 (9)	0.0132 (8)	0.0018 (7)	0.0017 (7)	0.0001 (7)
C16	0.0176 (9)	0.0188 (9)	0.0157 (9)	0.0017 (7)	0.0017 (7)	−0.0019 (7)
O5	0.0182 (7)	0.0388 (9)	0.0239 (8)	0.0000 (6)	0.0036 (6)	−0.0160 (7)
O6	0.0162 (6)	0.0304 (8)	0.0214 (7)	0.0012 (6)	0.0004 (6)	−0.0065 (6)
O7	0.0188 (7)	0.0370 (8)	0.0225 (7)	0.0000 (6)	0.0044 (6)	−0.0125 (7)
O8	0.0172 (7)	0.0297 (8)	0.0212 (7)	−0.0006 (6)	0.0013 (6)	−0.0065 (6)
C17	0.0320 (11)	0.0210 (10)	0.0381 (13)	−0.0020 (9)	−0.0056 (10)	0.0058 (10)
C18	0.083 (2)	0.0281 (12)	0.0274 (13)	0.0166 (13)	−0.0013 (14)	−0.0006 (10)
C19	0.0429 (14)	0.0381 (13)	0.0385 (15)	0.0114 (11)	−0.0079 (12)	−0.0103 (12)
N1	0.0186 (8)	0.0280 (9)	0.0203 (8)	0.0000 (7)	−0.0017 (7)	0.0063 (7)
C20	0.0342 (11)	0.0180 (9)	0.0310 (11)	0.0006 (8)	0.0078 (9)	−0.0012 (9)
C21	0.073 (2)	0.0315 (12)	0.0298 (13)	0.0163 (13)	0.0050 (13)	0.0104 (11)
C22	0.0383 (13)	0.0430 (15)	0.0540 (18)	0.0129 (12)	0.0069 (13)	0.0234 (14)
N2	0.0208 (8)	0.0242 (8)	0.0198 (8)	0.0003 (7)	0.0024 (7)	0.0000 (7)

Geometric parameters (Å, º)

C1—C6	1.528 (3)	C13—C14	1.525 (3)
C1—C2	1.528 (3)	C13—H13A	0.99
C1—C7	1.530 (3)	C13—H13B	0.99
C1—H1	1	C14—H14A	0.99
C2—C3	1.536 (3)	C14—H14B	0.99
C2—H2D	0.99	C15—O8	1.223 (2)
C2—H2E	0.99	C15—O7	1.305 (2)
C3—C4	1.525 (3)	C16—O6	1.224 (2)
C3—H3A	0.99	C16—O5	1.309 (2)
C3—H3B	0.99	O5—H5	0.84
C4—C5	1.526 (3)	O7—H7	0.84
C4—C8	1.536 (3)	C17—N1	1.474 (3)
C4—H4	1	C17—C19	1.477 (4)
C5—C6	1.526 (3)	C17—C18	1.485 (4)
C5—H5A	0.99	C17—H17	1
C5—H5B	0.99	C18—C19	1.490 (4)
C6—H6A	0.99	C18—H18A	0.99
C6—H6B	0.99	C18—H18B	0.99
C7—O2	1.237 (3)	C19—H19A	0.99
C7—O1	1.283 (2)	C19—H19B	0.99
C8—O4	1.234 (3)	N1—H1B	0.91
C8—O3	1.281 (2)	N1—H1C	0.91
C9—C16	1.510 (3)	N1—H1A	0.91
C9—C14	1.527 (3)	C20—C21	1.464 (4)
C9—C10	1.535 (3)	C20—C22	1.468 (4)
C9—H9	1	C20—N2	1.470 (3)
C10—C11	1.531 (3)	C20—H20	1
C10—H10A	0.99	C21—C22	1.490 (4)
C10—H10B	0.99	C21—H21A	0.99
C11—C12	1.527 (3)	C21—H21B	0.99
C11—H11A	0.99	C22—H22A	0.99
C11—H11B	0.99	C22—H22B	0.99
C12—C15	1.506 (2)	N2—H2A	0.91
C12—C13	1.535 (3)	N2—H2B	0.91
C12—H12	1	N2—H2C	0.91
C6—C1—C2	111.36 (15)	C14—C13—H13A	109.5
C6—C1—C7	110.68 (16)	C12—C13—H13A	109.5
C2—C1—C7	113.25 (15)	C14—C13—H13B	109.5
C6—C1—H1	107.1	C12—C13—H13B	109.5
C2—C1—H1	107.1	H13A—C13—H13B	108.1
C7—C1—H1	107.1	C13—C14—C9	110.28 (16)
C1—C2—C3	111.71 (15)	C13—C14—H14A	109.6
C1—C2—H2D	109.3	C9—C14—H14A	109.6
C3—C2—H2D	109.3	C13—C14—H14B	109.6
C1—C2—H2E	109.3	C9—C14—H14B	109.6
C3—C2—H2E	109.3	H14A—C14—H14B	108.1
H2D—C2—H2E	107.9	O8—C15—O7	123.68 (18)
C4—C3—C2	111.46 (15)	O8—C15—C12	121.63 (18)
C4—C3—H3A	109.3	O7—C15—C12	114.58 (16)
C2—C3—H3A	109.3	O6—C16—O5	123.47 (18)
C4—C3—H3B	109.3	O6—C16—C9	121.99 (18)
C2—C3—H3B	109.3	O5—C16—C9	114.49 (16)
H3A—C3—H3B	108	C16—O5—H5	109.5
C3—C4—C5	109.15 (16)	C15—O7—H7	109.5
C3—C4—C8	113.59 (16)	N1—C17—C19	120.3 (2)
C5—C4—C8	111.00 (17)	N1—C17—C18	118.8 (2)
C3—C4—H4	107.6	C19—C17—C18	60.4 (2)
C5—C4—H4	107.6	N1—C17—H17	115.4
C8—C4—H4	107.6	C19—C17—H17	115.4
C4—C5—C6	111.69 (15)	C18—C17—H17	115.4
C4—C5—H5A	109.3	C17—C18—C19	59.53 (18)
C6—C5—H5A	109.3	C17—C18—H18A	117.8
C4—C5—H5B	109.3	C19—C18—H18A	117.8
C6—C5—H5B	109.3	C17—C18—H18B	117.8
H5A—C5—H5B	107.9	C19—C18—H18B	117.8
C5—C6—C1	111.70 (16)	H18A—C18—H18B	115
C5—C6—H6A	109.3	C17—C19—C18	60.08 (19)
C1—C6—H6A	109.3	C17—C19—H19A	117.8
C5—C6—H6B	109.3	C18—C19—H19A	117.8
C1—C6—H6B	109.3	C17—C19—H19B	117.8
H6A—C6—H6B	107.9	C18—C19—H19B	117.8
O2—C7—O1	123.67 (18)	H19A—C19—H19B	114.9
O2—C7—C1	119.52 (18)	C17—N1—H1B	109.5
O1—C7—C1	116.79 (17)	C17—N1—H1C	109.5
O4—C8—O3	123.59 (18)	H1B—N1—H1C	109.5
O4—C8—C4	118.72 (18)	C17—N1—H1A	109.5
O3—C8—C4	117.68 (17)	H1B—N1—H1A	109.5
C16—C9—C14	113.25 (16)	H1C—N1—H1A	109.5
C16—C9—C10	108.45 (16)	C21—C20—C22	61.1 (2)
C14—C9—C10	110.54 (16)	C21—C20—N2	119.2 (2)
C16—C9—H9	108.2	C22—C20—N2	120.8 (2)
C14—C9—H9	108.2	C21—C20—H20	115
C10—C9—H9	108.2	C22—C20—H20	115
C11—C10—C9	110.36 (16)	N2—C20—H20	115
C11—C10—H10A	109.6	C20—C21—C22	59.57 (18)
C9—C10—H10A	109.6	C20—C21—H21A	117.8
C11—C10—H10B	109.6	C22—C21—H21A	117.8
C9—C10—H10B	109.6	C20—C21—H21B	117.8
H10A—C10—H10B	108.1	C22—C21—H21B	117.8
C12—C11—C10	110.70 (16)	H21A—C21—H21B	115
C12—C11—H11A	109.5	C20—C22—C21	59.33 (18)
C10—C11—H11A	109.5	C20—C22—H22A	117.8
C12—C11—H11B	109.5	C21—C22—H22A	117.8
C10—C11—H11B	109.5	C20—C22—H22B	117.8
H11A—C11—H11B	108.1	C21—C22—H22B	117.8
C15—C12—C11	114.14 (16)	H22A—C22—H22B	115
C15—C12—C13	107.90 (16)	C20—N2—H2A	109.5
C11—C12—C13	110.60 (16)	C20—N2—H2B	109.5
C15—C12—H12	108	H2A—N2—H2B	109.5
C11—C12—H12	108	C20—N2—H2C	109.5
C13—C12—H12	108	H2A—N2—H2C	109.5
C14—C13—C12	110.64 (16)	H2B—N2—H2C	109.5
C6—C1—C2—C3	−52.5 (2)	C9—C10—C11—C12	56.9 (2)
C7—C1—C2—C3	−178.03 (15)	C10—C11—C12—C15	−178.60 (17)
C1—C2—C3—C4	55.8 (2)	C10—C11—C12—C13	−56.7 (2)
C2—C3—C4—C5	−57.7 (2)	C15—C12—C13—C14	−177.33 (16)
C2—C3—C4—C8	66.8 (2)	C11—C12—C13—C14	57.2 (2)
C3—C4—C5—C6	58.0 (2)	C12—C13—C14—C9	−57.7 (2)
C8—C4—C5—C6	−68.0 (2)	C16—C9—C14—C13	179.89 (17)
C4—C5—C6—C1	−56.2 (2)	C10—C9—C14—C13	58.0 (2)
C2—C1—C6—C5	52.7 (2)	C11—C12—C15—O8	−151.41 (19)
C7—C1—C6—C5	179.63 (16)	C13—C12—C15—O8	85.2 (2)
C6—C1—C7—O2	29.9 (2)	C11—C12—C15—O7	32.2 (2)
C2—C1—C7—O2	155.77 (18)	C13—C12—C15—O7	−91.2 (2)
C6—C1—C7—O1	−151.58 (17)	C14—C9—C16—O6	143.5 (2)
C2—C1—C7—O1	−25.7 (2)	C10—C9—C16—O6	−93.4 (2)
C3—C4—C8—O4	−150.54 (18)	C14—C9—C16—O5	−38.9 (2)
C5—C4—C8—O4	−27.1 (2)	C10—C9—C16—O5	84.1 (2)
C3—C4—C8—O3	30.7 (2)	N1—C17—C18—C19	110.5 (2)
C5—C4—C8—O3	154.18 (17)	N1—C17—C19—C18	−108.0 (3)
C16—C9—C10—C11	177.79 (16)	N2—C20—C21—C22	−111.2 (3)
C14—C9—C10—C11	−57.5 (2)	N2—C20—C22—C21	108.7 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···O3	0.84	1.68	2.511 (2)	168
O7—H7···O1^i	0.84	1.66	2.490 (2)	169
N1—H1A···O1	0.91	1.91	2.822 (2)	175
N1—H1B···O6^ii	0.91	2.05	2.933 (2)	162
N1—H1C···O2^iii	0.91	1.9	2.779 (2)	163
N2—H2A···O3	0.91	1.91	2.812 (2)	174
N2—H2B···O4^iii	0.91	1.85	2.709 (2)	158
N2—H2C···O8^iv	0.91	2.1	2.944 (2)	153

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