meso-1,2-Diphenyl­ethyl­enediammonium adipate

In the title mol­ecular salt, C₁₄H₁₈N₂²⁺·C₆H₈O₄²⁻, both the dication and the dianion lie on inversion centers. There is an approximate 61:39 disorder in the central linkage of the cation. In the crystal structure, the components associate via N—H...O and C—H...O inter­actions, resulting in R₂²(9) rings.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.003 Å
• Disorder in main residue
• R factor = 0.061
• wR factor = 0.165
• Data-to-parameter ratio = 19.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT031_ALERT_4_C Refined Extinction Parameter within Range ......       3.22 Sigma
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)       2000 Deg.
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         C6
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C5B
PLAT301_ALERT_3_C Main Residue  Disorder .........................      13.00 Perc.

Alert level G
PLAT793_ALERT_1_G Check the Absolute Configuration of C4A    = ...          R
PLAT793_ALERT_1_G Check the Absolute Configuration of C4B    = ...          S

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

From the viewpoint of crystal engineering (Desiraju, 1995), adipic acid is a useful species for constructing crystalline architectures because of its proton donating capability to generate hydrogen bonding accepting sites (Roy et al., 2005, Bu˘car et al., 2007), leading to a solid state array with defined dimensionality.

The survey of Khokhar & Lumetta (1989) suggests that meso-1,2-diphenylethylenediamine might be useful as a chemotherapeutic agent. This species and its organic and inorganic salts or complexes can develop supramolecular structures by self assembly of components which contain two hydrogen bonding donor sites (Ferguson et al., 1992; Kuroda & Mason, 1977).

As part of our ongoing studies of this species (Ramasubramanian et al.,2007), we now report the synthesis and structure of the title compound, (I), (Fig. 1). Double proton transfer from acid to amine has occurred. Both anion and cation are generated by inversion and there is a 61:39 disorder in the central fragment of the cation.

The C—O bond lengths in the adipate moiety indicate delocalization of charge [C—O = 1.244 (1) Å and 1.283 (1) Å] as they are intermediate between single and double bond lengths (Bruno et al., 2004; Allen, 2002).

The species interact by way of N—H···O and C—H···O interactions (Table 1, Fig. 2) such that each cation forms a R₂²(9) ring (Etter, 1990) with its neighbouring adipate anion. Several other hydrogen-bonded rings are apparent in the crystal packing and they are designated as R₄⁴(28), R₂³(10) R₂⁴(12), and R₂¹(6). The R₄⁴(28) ring forms an infinite ladder in the crystal by N—H···O interactions (Fig. 3).

Related literature

For related literature, see: Allen (2002); Bruno et al. (2004); Desiraju (1995); Etter (1990); Ferguson et al. (1992); Khokhar & Lumetta (1989); Kuroda & Mason (1977); Ramasubramanian et al. (2007); Roy et al. (2005).

For related literature, see: Bu˘car et al. (2007).

S2. Experimental

Stoichiometric quantities of adipic acid and meso-1,2-diphenylethylene diamine were separately dissolved in methanol. These solutions were warmed to 343 K and slowly mixed in a 1:1 molar ratio of acid to amine. The resulting mixture was kept at room temperature for slow evaporation of the solvent. Colourless crystals of (I) appeared after two days and were washed with water and dried in vacuo.

S3. Refinement

The H atoms were placed in idealized positions (C—H = 0.95–1.00 Å, N—H = 0.91 Å) and refined as riding with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(N). In the disordered central portion of the cation, the populations of the two conformers [0.613 (8):0.387 (8)] were contrained to sum to unity.

Computing details

Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO and SCALEPACK; data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. A view of (I) with displacement ellipsoids shown at the 50% probability level (arbitrary spheres for the H aotms), and only the major orientation of the cation shown. Symmetry codes: (a) -x, 1 - y, -z; (b) 1 - x, 1 - y, 1 - z.
	Fig. 2. A view of (I) showing the hydrogen bonds as dashed lines.
	Fig. 3. The hydrogen-bonding interactions of (I) in the crystal packing.

meso-1,2-Diphenylethylenediammonium adipate

Crystal data

C14H18N2^2+·C6H8O4^2^−	Z = 1
Mr = 358.43	F(000) = 192
Triclinic, P1	Dx = 1.310 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.361 (3) Å	Cell parameters from 2369 reflections
b = 6.931 (3) Å	θ = 2.5–30.0°
c = 11.820 (5) Å	µ = 0.09 mm^−1
α = 105.35 (2)°	T = 100 K
β = 92.05 (2)°	Shard, colourless
γ = 113.64 (2)°	0.18 × 0.17 × 0.15 mm
V = 454.4 (4) Å^3

Data collection

Nonius KappaCCD diffractometer	1727 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.040
Graphite monochromator	θmax = 30.1°, θmin = 3.3°
ω scans with κ offsets	h = −8→8
8038 measured reflections	k = −9→9
2643 independent reflections	l = −16→16

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)] = 0.061	H-atom parameters constrained
wR(F^2) = 0.165	w = 1/[σ^2(Fo^2) + (0.0671P)^2 + 0.226P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
2643 reflections	Δρmax = 0.32 e Å^−3
138 parameters	Δρmin = −0.35 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: 0.029 (9)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.2968 (2)	0.6691 (2)	0.29572 (11)	0.0219 (3)
O2	0.0766 (2)	0.8389 (2)	0.37116 (10)	0.0222 (3)
C1	0.1389 (3)	0.7285 (3)	0.28460 (15)	0.0172 (4)
C2	0.0067 (3)	0.6698 (3)	0.16156 (15)	0.0189 (4)
H2A	0.0321	0.8088	0.1441	0.023*
H2B	−0.1614	0.5914	0.1631	0.023*
C3	0.0716 (3)	0.5271 (3)	0.06021 (14)	0.0204 (4)
H3A	0.0472	0.3874	0.0767	0.024*
H3B	0.2387	0.6055	0.0564	0.024*
N1	0.3377 (3)	0.2390 (2)	0.54090 (14)	0.0210 (4)
H1N	0.2729	0.3005	0.5989	0.031*	0.613 (8)
H2N	0.4619	0.2284	0.5746	0.031*	0.613 (8)
H3N	0.2306	0.1017	0.4977	0.031*	0.613 (8)
H4N	0.3499	0.1461	0.4735	0.031*	0.387 (8)
H5N	0.1921	0.1784	0.5588	0.031*	0.387 (8)
H6N	0.4440	0.2603	0.6019	0.031*	0.387 (8)
C4A	0.4175 (5)	0.3837 (5)	0.4595 (3)	0.0162 (9)	0.613 (8)
H4A	0.2786	0.3923	0.4229	0.019*	0.613 (8)
C5A	0.5268 (8)	0.2904 (7)	0.3605 (3)	0.0156 (8)	0.613 (8)
C4B	0.3833 (8)	0.4618 (8)	0.5214 (5)	0.0158 (14)	0.387 (8)
H4B	0.2628	0.4322	0.4545	0.019*	0.387 (8)
C5B	0.6303 (13)	0.3637 (10)	0.3729 (4)	0.0150 (12)	0.387 (8)
C6	0.7312 (4)	0.2447 (3)	0.38574 (18)	0.0350 (5)
H6	0.8136	0.2963	0.4642	0.042*
C7	0.7970 (3)	0.1269 (3)	0.29318 (16)	0.0222 (4)
H7	0.9117	0.0774	0.3076	0.027*
C8	0.6942 (4)	0.0812 (4)	0.17879 (18)	0.0352 (5)
H8	0.7372	−0.0020	0.1139	0.042*
C9	0.5293 (4)	0.1554 (3)	0.15777 (18)	0.0303 (5)
H9	0.4608	0.1242	0.0785	0.036*
C10	0.4644 (4)	0.2733 (4)	0.25008 (18)	0.0314 (5)
H10	0.3718	0.3446	0.2340	0.038*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0225 (7)	0.0251 (7)	0.0179 (6)	0.0129 (6)	0.0003 (5)	0.0023 (5)
O2	0.0251 (7)	0.0265 (7)	0.0134 (6)	0.0137 (6)	0.0021 (5)	−0.0004 (5)
C1	0.0178 (8)	0.0164 (8)	0.0152 (8)	0.0056 (7)	0.0028 (6)	0.0042 (6)
C2	0.0194 (9)	0.0215 (8)	0.0144 (8)	0.0099 (7)	0.0013 (6)	0.0014 (6)
C3	0.0211 (9)	0.0246 (9)	0.0140 (8)	0.0109 (8)	0.0014 (7)	0.0020 (7)
N1	0.0176 (7)	0.0203 (7)	0.0240 (8)	0.0060 (6)	0.0016 (6)	0.0089 (6)
C4A	0.0167 (14)	0.0177 (14)	0.0126 (17)	0.0073 (12)	0.0018 (11)	0.0022 (12)
C5A	0.0159 (19)	0.0112 (16)	0.0156 (15)	0.0046 (14)	0.0025 (14)	−0.0004 (12)
C4B	0.018 (2)	0.019 (2)	0.014 (3)	0.0102 (19)	0.0033 (17)	0.006 (2)
C5B	0.019 (3)	0.012 (3)	0.008 (2)	0.004 (2)	0.002 (2)	−0.0007 (19)
C6	0.0673 (16)	0.0301 (10)	0.0156 (9)	0.0320 (11)	−0.0003 (9)	0.0026 (8)
C7	0.0203 (9)	0.0239 (9)	0.0235 (9)	0.0101 (8)	0.0059 (7)	0.0074 (7)
C8	0.0468 (14)	0.0465 (13)	0.0190 (10)	0.0334 (12)	0.0045 (9)	−0.0013 (9)
C9	0.0374 (12)	0.0315 (11)	0.0199 (9)	0.0199 (10)	−0.0031 (8)	−0.0029 (8)
C10	0.0459 (13)	0.0395 (11)	0.0295 (11)	0.0319 (11)	0.0193 (9)	0.0196 (9)

Geometric parameters (Å, º)

O1—C1	1.244 (2)	C4A—H4A	1.0000
O2—C1	1.283 (2)	C5A—C10	1.311 (4)
C1—C2	1.521 (2)	C5A—C6	1.494 (4)
C2—C3	1.523 (2)	C4B—C4B^ii	1.518 (9)
C2—H2A	0.9900	C4B—C5B^ii	1.524 (8)
C2—H2B	0.9900	C4B—H4B	1.0000
C3—C3^i	1.532 (3)	C5B—C6	1.264 (6)
C3—H3A	0.9900	C5B—C4B^ii	1.524 (8)
C3—H3B	0.9900	C5B—C10	1.579 (6)
N1—C4A	1.525 (3)	C6—C7	1.368 (3)
N1—C4B	1.535 (5)	C6—H6	0.9500
N1—H1N	0.9100	C7—C8	1.378 (3)
N1—H2N	0.9100	C7—H7	0.9500
N1—H3N	0.9100	C8—C9	1.382 (3)
N1—H4N	0.9100	C8—H8	0.9500
N1—H5N	0.9100	C9—C10	1.364 (3)
N1—H6N	0.9100	C9—H9	0.9500
C4A—C5A	1.513 (5)	C10—H10	0.9500
C4A—C4A^ii	1.540 (6)
O1—C1—O2	124.40 (16)	C4A^ii—C4A—H4A	108.3
O1—C1—C2	119.49 (15)	C10—C5A—C6	117.1 (3)
O2—C1—C2	116.11 (15)	C10—C5A—C4A	120.7 (3)
C1—C2—C3	115.80 (15)	C6—C5A—C4A	121.6 (3)
C1—C2—H2A	108.3	C4B^ii—C4B—C5B^ii	112.9 (6)
C3—C2—H2A	108.3	C4B^ii—C4B—N1	106.0 (5)
C1—C2—H2B	108.3	C5B^ii—C4B—N1	115.8 (4)
C3—C2—H2B	108.3	C4B^ii—C4B—H4B	107.2
H2A—C2—H2B	107.4	C5B^ii—C4B—H4B	107.2
C2—C3—C3^i	112.47 (18)	N1—C4B—H4B	107.2
C2—C3—H3A	109.1	C6—C5B—C4B^ii	121.6 (4)
C3^i—C3—H3A	109.1	C6—C5B—C10	114.3 (4)
C2—C3—H3B	109.1	C4B^ii—C5B—C10	122.0 (4)
C3^i—C3—H3B	109.1	C5B—C6—C7	123.0 (3)
H3A—C3—H3B	107.8	C7—C6—C5A	118.5 (2)
C4A—N1—H1N	109.5	C5B—C6—H6	110.9
C4A—N1—H2N	109.5	C7—C6—H6	120.8
H1N—N1—H2N	109.5	C5A—C6—H6	120.8
C4A—N1—H3N	109.5	C6—C7—C8	119.01 (18)
H1N—N1—H3N	109.5	C6—C7—H7	120.5
H2N—N1—H3N	109.5	C8—C7—H7	120.5
C4B—N1—H4N	109.5	C7—C8—C9	120.51 (18)
C4B—N1—H5N	109.5	C7—C8—H8	119.7
H4N—N1—H5N	109.5	C9—C8—H8	119.7
C4B—N1—H6N	109.5	C10—C9—C8	120.41 (19)
H4N—N1—H6N	109.5	C10—C9—H9	119.8
H5N—N1—H6N	109.5	C8—C9—H9	119.8
C5A—C4A—N1	112.2 (2)	C5A—C10—C9	121.5 (2)
C5A—C4A—C4A^ii	113.4 (4)	C9—C10—C5B	114.8 (3)
N1—C4A—C4A^ii	106.2 (3)	C5A—C10—H10	119.3
C5A—C4A—H4A	108.3	C9—C10—H10	119.3
N1—C4A—H4A	108.3	C5B—C10—H10	120.9
O1—C1—C2—C3	3.6 (2)	C10—C5A—C6—C7	−19.3 (5)
O2—C1—C2—C3	−176.46 (15)	C4A—C5A—C6—C7	169.2 (3)
C1—C2—C3—C3^i	179.22 (19)	C5B—C6—C7—C8	−19.5 (5)
C4B—N1—C4A—C5A	168.8 (5)	C5A—C6—C7—C8	8.8 (4)
C4B—N1—C4A—C4A^ii	44.4 (4)	C6—C7—C8—C9	0.8 (3)
N1—C4A—C5A—C10	131.7 (3)	C7—C8—C9—C10	−0.6 (4)
C4A^ii—C4A—C5A—C10	−108.0 (4)	C6—C5A—C10—C9	20.1 (5)
N1—C4A—C5A—C6	−57.1 (4)	C4A—C5A—C10—C9	−168.3 (3)
C4A^ii—C4A—C5A—C6	63.2 (5)	C6—C5A—C10—C5B	−59.2 (7)
C4A—N1—C4B—C4B^ii	−45.1 (4)	C4A—C5A—C10—C5B	112.4 (8)
C4A—N1—C4B—C5B^ii	−171.2 (6)	C8—C9—C10—C5A	−10.8 (4)
C4B^ii—C5B—C6—C7	−163.5 (4)	C8—C9—C10—C5B	14.2 (4)
C10—C5B—C6—C7	32.9 (7)	C6—C5B—C10—C5A	82.6 (8)
C4B^ii—C5B—C6—C5A	109.4 (10)	C4B^ii—C5B—C10—C5A	−80.8 (8)
C10—C5B—C6—C5A	−54.1 (6)	C6—C5B—C10—C9	−30.0 (6)
C10—C5A—C6—C5B	88.3 (8)	C4B^ii—C5B—C10—C9	166.5 (4)
C4A—C5A—C6—C5B	−83.2 (7)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H5N···O2^iii	0.91	1.90	2.769 (2)	159
N1—H6N···O1^ii	0.91	1.82	2.717 (2)	167
N1—H3N···O2^iv	0.91	1.88	2.756 (2)	161
C6—H6···O2^ii	0.95	2.56	3.359 (3)	142
C7—H7···O2^v	0.95	2.53	3.421 (3)	157
C10—H10···O1	0.95	2.42	3.249 (3)	146

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