Bis­(di­cyclo­hexyl­ammonium) adipate monohydrate

In the asymmetric unit of the title compound, 2C₁₂H₂₄N⁺·C₆H₈O₄^2-·H₂O, the carboxyl­ate ion lies about an inversion center, the water mol­ecule is on a twofold axis and the sec-ammonium cation is in a general position. Cations link the oxy­gen ends of two adjacent carboxyl­ate anions to form an eight-membered ring [N...O 2.683 (3) and 2.711 (3) Å]. The ion pair propagates as a linear chain and adjacent chains are linked through the water mol­ecules [O...O 2.966 (3) Å] into layers.

S1. Comment

Dicyclohexylammonium monoalkanoates, [(cyclo-C₆H₁₁)₂NH₂] RCH₂CO₂] (R is an electron-withdrawing group), typically exist as dimeric ion pairs in which the two NH₂ units link two CO₂ units to form an eight-membered N···O≐C≐O···N···O≐C≐O··· ring, or as linear hydrogen-bonded chains (Ng et al., 1999). The ring architecture probably requires sterically bulky R groups; the R = (CH₃)₂NCS₂ derivative adopts the ring architecture, but the compound has water molecules that link adjacent dimers [O_water···O_carboxyl 2.784 (6) and 3.029 (7) Å; Ng, 1992]. In the title compound, both carboxyl ends of the centrosymmetric adipate dianion are engaged in a similar type of ring formation to give rise to a chain and adjacent chains are linked through the lattice water molecule [O_water···O 2.966 (3) Å] to form layers. The water molecule lies on a twofold axis.

A layer structure is also adopted by m-xylyleammonium adipate, which crystallizes as a monohydrate, but its N···O_carboxyl hydrogen bonds in the chains are somewhat longer. The chains are links into layers through the lattice water molecules (Moritani & Kashino, 1991). A chain structure is also adopted by anhydrous piperazinium adipate, which displays hydrogen bonds (Vanier & Brisse, 1983) that are somewhat longer than those in the dicyclohexylammonium salt. Slightly longer hydrogen bonds are also noted in hexamethylediammonium adipate (Brown, 1966).

S2. Experimental

Dicyclohexylamine, adipic acid and bis(tributyltin) oxide in a 2:2:1 molar stoichiometry was heated in a small volume of ethanol in an attempt to synthesize dicyclohexylammonium succinatotributylstannate. The procedure had been used to prepare the tributylstannate derivatives of oxalic (Ng et al., 1990), malonic (Ng et al., 1992) and succinic (Ng & Holecek, 1998) acids, but the reaction with adipic acid gave the organic salt as a hydrate. The Cu radiation powder diffractogram of the bulk compound is identical to the diffractogram that is calculated from the atomic coordinates by POWDIS (McArdle & Cunningham, 1998).

S3. Refinement

The N– and O-bonded H atoms were located and refined.

Computing details

Data collection: XSCANS (Siemens, 1990); cell refinement: XSCANS; data reduction: SHELXTL-Plus (Sheldrick, 1990); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97.

Bis(dicyclohexylammonium) adipate monohydrate

Crystal data

2C12H24N^+·C6H8O4^2^−·H2O	F(000) = 1168
Mr = 526.78	Dx = 1.132 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.155 (3) Å	Cell parameters from 25 reflections
b = 15.638 (5) Å	θ = 7.0–14.0°
c = 20.102 (6) Å	µ = 0.08 mm^−1
β = 104.56 (1)°	T = 298 K
V = 3089.8 (16) Å^3	Parallelepiped, colorless
Z = 4	0.50 × 0.50 × 0.40 mm

Data collection

Siemens R3m diffractometer	1461 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.089
Graphite monochromator	θmax = 25.0°, θmin = 2.1°
ω scans	h = 0→12
Absorption correction: empirical (using intensity measurements) ψ scan (North et al., 1968)	k = 0→18
Tmin = 0.912, Tmax = 1.000	l = −23→23
2879 measured reflections	2 standard reflections every 118 reflections
2715 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.059	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.159	w = 1/[σ^2(Fo^2) + (0.0754P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.98	(Δ/σ)max = 0.001
2715 reflections	Δρmax = 0.18 e Å^−3
181 parameters	Δρmin = −0.18 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.017 (1)

Special details

Refinement. Riding, U(H) = 1.5U_eq(C). The N– and O-bonded H-atoms were located and refined.

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

	x	y	z	Uiso*/Ueq
O1	0.4503 (2)	0.2493 (2)	0.3782 (1)	0.060 (1)
O2	0.2711 (2)	0.2268 (2)	0.2918 (1)	0.066 (1)
O3	0.0000	0.3095 (3)	0.2500	0.083 (1)
N1	0.6777 (2)	0.2361 (2)	0.3340 (1)	0.033 (1)
C1	0.3262 (3)	0.2382 (2)	0.3538 (1)	0.036 (1)
C2	0.2333 (2)	0.2380 (2)	0.4022 (1)	0.037 (1)
C3	0.2995 (2)	0.2516 (2)	0.4775 (1)	0.039 (1)
C4	0.7297 (2)	0.1542 (2)	0.3695 (1)	0.034 (1)
C5	0.6401 (3)	0.0821 (2)	0.3342 (2)	0.050 (1)
C6	0.6864 (3)	−0.0038 (2)	0.3674 (2)	0.063 (1)
C7	0.8353 (4)	−0.0201 (2)	0.3721 (2)	0.069 (1)
C8	0.9224 (3)	0.0538 (2)	0.4071 (2)	0.071 (1)
C9	0.8772 (3)	0.1379 (2)	0.3709 (2)	0.052 (1)
C10	0.7601 (2)	0.3155 (2)	0.3564 (1)	0.033 (1)
C11	0.7927 (3)	0.3307 (2)	0.4334 (1)	0.044 (1)
C12	0.8804 (3)	0.4107 (2)	0.4507 (2)	0.051 (1)
C13	0.8098 (3)	0.4889 (2)	0.4126 (2)	0.062 (1)
C14	0.7664 (3)	0.4730 (2)	0.3359 (2)	0.063 (1)
C15	0.6831 (3)	0.3913 (2)	0.3181 (2)	0.049 (1)
H1a	0.590 (3)	0.247 (2)	0.343 (1)	0.055 (8)*
H1b	0.674 (3)	0.230 (2)	0.287 (1)	0.040 (7)*
H3w	0.069 (5)	0.268 (3)	0.263 (3)	0.17 (2)*
H2a	0.1651	0.2821	0.3874	0.055*
H2b	0.1862	0.1835	0.3973	0.055*
H3a	0.3446	0.3068	0.4832	0.058*
H3b	0.3686	0.2081	0.4928	0.058*
H4	0.7218	0.1579	0.4170	0.051*
H5a	0.6414	0.0805	0.2861	0.075*
H5b	0.5472	0.0926	0.3364	0.075*
H6a	0.6326	−0.0488	0.3403	0.094*
H6b	0.6710	−0.0056	0.4130	0.094*
H7a	0.8634	−0.0722	0.3979	0.103*
H7b	0.8484	−0.0279	0.3263	0.103*
H8a	0.9170	0.0575	0.4545	0.106*
H8b	1.0166	0.0430	0.4072	0.106*
H9a	0.8880	0.1359	0.3243	0.079*
H9b	0.9332	0.1840	0.3951	0.079*
H10	0.8462	0.3097	0.3432	0.049*
H11a	0.8407	0.2818	0.4576	0.066*
H11b	0.7091	0.3382	0.4477	0.066*
H12a	0.9004	0.4209	0.4998	0.076*
H12b	0.9659	0.4014	0.4386	0.076*
H13a	0.8712	0.5374	0.4221	0.093*
H13b	0.7303	0.5025	0.4290	0.093*
H14a	0.7129	0.5212	0.3136	0.094*
H14b	0.8469	0.4689	0.3184	0.094*
H15a	0.5970	0.3979	0.3303	0.074*
H15b	0.6639	0.3809	0.2691	0.074*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.030 (1)	0.101 (2)	0.057 (1)	−0.003 (1)	0.026 (1)	−0.008 (2)
O2	0.056 (1)	0.117 (2)	0.029 (1)	−0.004 (1)	0.019 (1)	−0.005 (1)
O3	0.056 (2)	0.119 (4)	0.072 (2)	0.000	0.014 (2)	0.000
N1	0.022 (1)	0.051 (2)	0.026 (1)	0.000 (1)	0.009 (1)	0.001 (1)
C1	0.036 (2)	0.041 (2)	0.036 (2)	0.003 (1)	0.017 (1)	0.001 (1)
C2	0.027 (1)	0.055 (2)	0.033 (1)	−0.002 (1)	0.014 (1)	0.002 (1)
C3	0.026 (1)	0.061 (2)	0.030 (1)	0.002 (1)	0.011 (1)	0.004 (1)
C4	0.027 (1)	0.047 (2)	0.031 (2)	−0.001 (1)	0.009 (1)	0.001 (1)
C5	0.036 (2)	0.055 (2)	0.056 (2)	−0.006 (2)	0.008 (2)	−0.011 (2)
C6	0.063 (2)	0.047 (2)	0.080 (2)	−0.011 (2)	0.020 (2)	−0.007 (2)
C7	0.069 (2)	0.056 (2)	0.083 (3)	0.017 (2)	0.023 (2)	0.004 (2)
C8	0.043 (2)	0.063 (2)	0.099 (3)	0.012 (2)	0.006 (2)	0.011 (2)
C9	0.026 (2)	0.058 (2)	0.072 (2)	0.003 (2)	0.010 (2)	0.007 (2)
C10	0.025 (1)	0.046 (2)	0.030 (1)	−0.001 (1)	0.011 (1)	0.003 (1)
C11	0.041 (2)	0.056 (2)	0.035 (2)	−0.004 (2)	0.010 (1)	−0.001 (1)
C12	0.041 (2)	0.059 (2)	0.049 (2)	−0.011 (2)	0.005 (2)	−0.007 (2)
C13	0.046 (2)	0.056 (2)	0.079 (2)	−0.001 (2)	0.006 (2)	−0.011 (2)
C14	0.062 (2)	0.048 (2)	0.072 (2)	−0.005 (2)	0.004 (2)	0.014 (2)
C15	0.047 (2)	0.049 (2)	0.047 (2)	0.004 (2)	0.004 (2)	0.007 (2)

Geometric parameters (Å, º)

O1—C1	1.244 (3)	C3—H3a	0.9700
O2—C1	1.243 (3)	C3—H3b	0.9700
N1—C4	1.496 (3)	C4—H4	0.9800
N1—C10	1.501 (3)	C5—H5a	0.9702
C1—C2	1.515 (3)	C5—H5b	0.9700
C2—C3	1.509 (3)	C6—H6a	0.9700
C3—C3^i	1.514 (5)	C6—H6b	0.9700
C4—C5	1.509 (4)	C7—H7a	0.9700
C4—C9	1.513 (4)	C7—H7b	0.9699
C5—C6	1.522 (4)	C8—H8a	0.9701
C6—C7	1.512 (5)	C8—H8b	0.9699
C7—C8	1.516 (4)	C9—H9a	0.9698
C8—C9	1.518 (4)	C9—H9b	0.9700
C10—C11	1.517 (3)	C10—H10	0.9800
C10—C15	1.519 (4)	C11—H11a	0.9700
C11—C12	1.523 (4)	C11—H11b	0.9700
C12—C13	1.524 (4)	C12—H12a	0.9698
C13—C14	1.513 (4)	C12—H12b	0.9701
C14—C15	1.525 (4)	C13—H13a	0.9700
O3—H3w	0.95 (4)	C13—H13b	0.9700
N1—H1a	0.97 (3)	C14—H14a	0.9700
N1—H1b	0.94 (3)	C14—H14b	0.9701
C2—H2a	0.9700	C15—H15a	0.9701
C2—H2b	0.9700	C15—H15b	0.9699
C4—N1—C10	117.5 (2)	C7—C6—H6b	109.5
O2—C1—O1	124.8 (2)	C5—C6—H6b	109.6
O2—C1—C2	116.5 (2)	H6a—C6—H6b	107.9
O1—C1—C2	118.6 (2)	C6—C7—H7a	109.3
C3—C2—C1	116.8 (2)	C8—C7—H7a	109.4
C2—C3—C3^i	113.6 (3)	C6—C7—H7b	109.6
N1—C4—C5	108.5 (2)	C8—C7—H7b	109.5
N1—C4—C9	112.5 (2)	H7a—C7—H7b	108.0
C5—C4—C9	111.1 (2)	C7—C8—H8a	109.4
C4—C5—C6	111.7 (2)	C9—C8—H8a	109.5
C7—C6—C5	111.7 (3)	C7—C8—H8b	109.2
C6—C7—C8	111.0 (3)	C9—C8—H8b	109.3
C7—C8—C9	111.5 (3)	H8a—C8—H8b	107.9
C4—C9—C8	109.5 (2)	C4—C9—H9a	109.8
N1—C10—C11	113.5 (2)	C8—C9—H9a	110.0
N1—C10—C15	108.4 (2)	C4—C9—H9b	109.7
C11—C10—C15	110.3 (2)	C8—C9—H9b	109.6
C10—C11—C12	109.2 (2)	H9a—C9—H9b	108.2
C11—C12—C13	111.7 (2)	N1—C10—H10	108.1
C14—C13—C12	111.1 (3)	C11—C10—H10	108.1
C13—C14—C15	112.3 (3)	C15—C10—H10	108.3
C10—C15—C14	110.5 (2)	C10—C11—H11a	109.9
C4—N1—H1a	108 (2)	C12—C11—H11a	110.0
C10—N1—H1a	106 (2)	C10—C11—H11b	109.8
C4—N1—H1b	108 (2)	C12—C11—H11b	109.7
C10—N1—H1b	105 (2)	H11a—C11—H11b	108.3
H1a—N1—H1b	113 (2)	C11—C12—H12a	109.2
C3—C2—H2a	108.1	C13—C12—H12a	109.4
C1—C2—H2a	108.3	C11—C12—H12b	109.2
C3—C2—H2b	108.0	C13—C12—H12b	109.3
C1—C2—H2b	108.0	H12a—C12—H12b	108.0
H2a—C2—H2b	107.3	C14—C13—H13a	109.7
C2—C3—H3a	108.8	C12—C13—H13a	109.4
C3^i—C3—H3a	108.9	C14—C13—H13b	109.2
C2—C3—H3b	108.8	C12—C13—H13b	109.4
C3^i—C3—H3b	108.9	H13a—C13—H13b	108.0
H3a—C3—H3b	107.7	C13—C14—H14a	109.2
N1—C4—H4	108.0	C15—C14—H14a	109.2
C5—C4—H4	108.4	C13—C14—H14b	109.0
C9—C4—H4	108.3	C15—C14—H14b	109.2
C4—C5—H5a	109.3	H14a—C14—H14b	107.9
C6—C5—H5a	109.5	C10—C15—H15a	109.7
C4—C5—H5b	109.3	C14—C15—H15a	109.5
C6—C5—H5b	109.1	C10—C15—H15b	109.3
H5a—C5—H5b	107.9	C14—C15—H15b	109.7
C7—C6—H6a	109.1	H15a—C15—H15b	108.1
C5—C6—H6a	109.0

Symmetry code: (i) −x+1/2, −y+1/2, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1a···O1	0.97 (3)	1.74 (3)	2.683 (3)	165 (2)
N1—H1b···O2^ii	0.94 (2)	1.81 (2)	2.711 (3)	160 (3)
O3—H3w···O2	0.94 (5)	2.09 (5)	2.966 (3)	154 (4)

Symmetry code: (ii) −x+1, y, −z+1/2.