(m-Carboxy­phenyl)­ammonium perchlorate at 223 K

The title compound, C₇H₈N⁺·ClO₄^-, is built up from (m-carboxy­phenyl)­ammonium cations and perchlorate anions. Crystal cohesion is ensured by strong cation-anion and cation-cation hydrogen bonds, between the carboxyl­ic acid groups of the organic cations and the O atoms of the anions, and also between amine groups and carboxyl­ic acid groups.

Key indicators

• Single-crystal X-ray study
• T = 223 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.036
• wR factor = 0.140
• Data-to-parameter ratio = 11.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level B:



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           26.35
         From the CIF: _reflns_number_total               1629
         TEST2: Reflns within _diffrn_reflns_theta_max
         Count of symmetry unique reflns         1870
         Completeness (_total/calc)             87.11%
          Alert B: < 90% complete (theta max?)

General Notes



FORMU_01  There is a discrepancy between the atom counts in the
          _chemical_formula_sum and _chemical_formula_moiety. This is
          usually due to the moiety formula being in the wrong format.
          Atom count from _chemical_formula_sum:   C7 H8 Cl1 N1 O6
          Atom count from _chemical_formula_moiety:C7 H8 Cl1 N1 O4


 0 Alert Level A = Potentially serious problem

 1 Alert Level B = Potential problem

 0 Alert Level C = Please check

---

S1. Comment

During the past few decades, organic–inorganic hybrid materials have been receiving increasing attention (Mazeaud et al., 2000; Soghomonian et al., 1995; Mayer et al., 1999) owing to their electrical, magnetic and optical properties (Kagan et al., 1999; Hill, 1998). This study is a part of systematic investigation on organic–inorganic hybrid materials including amino acids and various nitric: (m-carboxyphenyl)ammonium nitrate (Benali-Cherif, Cherouana et al., 2002) and L-histidinium dinitrate (Benali-Cherif, Benguedouar et al., 2002); phosphoric: (m-carboxyphenyl)ammonium phosphate (Benali-Cherif, Bendheif et al., 2002) and (p-carboxyphenyl)ammonuim dihydrogenmonophosphate monohydrate (Benali-Cherif, Abouimrane et al., 2002), and hydrochloride: 3-aminibenzoic acid hydrochloride (Arora et al., 1973) acids. The (m-carboxyphenyl)ammonium perchlorate structure, (I), is constituted by cationic (HCOO-C₆H₄—NH₃⁺) and anionic (ClO₄⁻) layers alternating along the c axis. All bond lengths and angles of the organic cation are within normal ranges and are in good agreement with those observed in (m-carboxyphenyl)ammonium nitrate, (m-carboxyphenyl)ammonium phosphate and 3-aminobenzoic acid hydrochloride. In the title compound, perchlorate anion is not disordered at 223 K, it is stabilized by strong interactions with its environment. The average Cl—O bond distances and O—Cl—O bond angles are 1.4384 (15) and 109.47 (10)°, respectively, confirming a tetrahedral symmetry (Table 1), similar to those observed in perchlorate studied at low temperature. Perchlorate anions (ClO₄⁻), surrounded by four (m-carboxyphenyl)ammonium residues via N—H2N···O3, N—H3N···O4, N—H3N···O6 and O1—H1···O5 hydrogen bonds, plays an important role in stabilizing the crystal structure.

Two types of hydrogen bonds are observed in this structure, viz. cation–cation and anion–cation interactions.

For the cation–cation interactions, each (m-carboxyphenyl)ammonium cation is connected to its neighbour, parallel to the bc diagonal, by a strong hydrogen bond [N—H1N···O2 = 2.822 (2) Å)].

For the anion–cation interactions, two H atoms of the ammonium group are linked through hydrogen bonds to O3, O4 and O6 atoms of perchlorate, while the third is linked to atom O2 of the carboxylic acid group. The carboxylic acid group is not deprotonated and its H atom is involved in the strongest interaction with the perchlorate anion via O1—H1···O5 = 2.748 (2) Å.

S2. Experimental

The title compound was crystallized from a 1:1 aqueous solution of 3-aminobenzoic acid and perchlorate acid. Brown crystals grew after a few days.

Computing details

Data collection: KappaCCD Reference Manual (Nonius, 1998); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and PARST (Nardelli, 1995).

Figures

	Fig. 1. ORTEP-3 (Farrugia, 1997) view of the ionic structure of (I), with the atom-numbering scheme and 50% probability displacement ellipsoids.
	Fig. 2. View of the ionic stacking, showing the three-dimensional network of hydrogen bonds.

(I)

Crystal data

C7H8N^+·ClO4^−	Z = 2
Mr = 237.59	F(000) = 244
Triclinic, P1	Dx = 1.727 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.0886 (2) Å	Cell parameters from 1629 reflections
b = 9.3338 (7) Å	θ = 2.1–26.4°
c = 10.1159 (7) Å	µ = 0.43 mm^−1
α = 103.904 (3)°	T = 223 K
β = 95.153 (5)°	Prism, brown
γ = 98.779 (5)°	0.4 × 0.3 × 0.3 mm
V = 456.90 (5) Å^3

Data collection

KappaCCD diffractometer	Rint = 0.034
Radiation source: fine-focus sealed tube	θmax = 26.4°, θmin = 2.1°
ϕ scans	h = −5→5
3143 measured reflections	k = −11→10
1629 independent reflections	l = −12→12
1532 reflections with I > 2σ(I)

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.140	H-atom parameters constrained
S = 1.27	w = 1/[σ^2(Fo^2) + (0.0849P)^2 + 0.1634P] where P = (Fo^2 + 2Fc^2)/3
1629 reflections	(Δ/σ)max < 0.001
138 parameters	Δρmax = 0.46 e Å^−3
0 restraints	Δρmin = −0.62 e Å^−3

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.

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

	x	y	z	Uiso*/Ueq
C1	0.2555 (4)	0.5124 (2)	0.24451 (19)	0.0179 (5)
C2	0.5086 (4)	0.6226 (2)	0.28069 (19)	0.0171 (5)
C3	0.6341 (4)	0.6623 (2)	0.17409 (19)	0.0167 (5)
H3	0.5581	0.6208	0.0832	0.020*
C4	0.8707 (4)	0.7632 (2)	0.20531 (19)	0.0169 (5)
C5	0.9900 (4)	0.8282 (2)	0.3398 (2)	0.0208 (5)
H5	1.1510	0.8961	0.3587	0.025*
C6	0.8628 (5)	0.7890 (2)	0.4453 (2)	0.0247 (5)
H6	0.9392	0.8317	0.5360	0.030*
C7	0.6240 (5)	0.6874 (2)	0.4171 (2)	0.0213 (5)
H7	0.5404	0.6622	0.4885	0.026*
N	1.0000 (4)	0.80275 (19)	0.09166 (17)	0.0202 (4)
H1N	1.0099	0.7194	0.0289	0.030*
H2N	1.1645	0.8547	0.1236	0.030*
H3N	0.9041	0.8582	0.0537	0.030*
O1	0.1563 (3)	0.47873 (18)	0.35230 (15)	0.0265 (4)
H1	0.0171	0.4170	0.3263	0.032*
O2	0.1465 (3)	0.45929 (17)	0.12658 (15)	0.0258 (4)
O3	0.5380 (3)	0.96472 (18)	−0.23006 (17)	0.0304 (4)
O4	0.5053 (4)	0.82644 (19)	−0.06366 (16)	0.0310 (4)
O5	0.3314 (3)	0.71150 (17)	−0.29431 (16)	0.0296 (4)
O6	0.1201 (3)	0.89145 (17)	−0.16085 (16)	0.0264 (4)
Cl	0.37506 (9)	0.84948 (5)	−0.18688 (4)	0.0173 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0197 (12)	0.0173 (9)	0.0194 (10)	0.0053 (8)	0.0065 (8)	0.0071 (7)
C2	0.0194 (12)	0.0165 (9)	0.0173 (9)	0.0045 (8)	0.0052 (8)	0.0062 (7)
C3	0.0196 (13)	0.0161 (9)	0.0149 (9)	0.0030 (8)	0.0036 (8)	0.0043 (7)
C4	0.0188 (12)	0.0164 (9)	0.0180 (9)	0.0045 (8)	0.0060 (8)	0.0074 (7)
C5	0.0194 (13)	0.0185 (10)	0.0226 (10)	−0.0002 (8)	0.0017 (8)	0.0045 (8)
C6	0.0303 (14)	0.0245 (10)	0.0161 (9)	−0.0008 (9)	0.0007 (8)	0.0039 (8)
C7	0.0262 (13)	0.0223 (10)	0.0164 (9)	0.0024 (8)	0.0054 (8)	0.0073 (7)
N	0.0186 (11)	0.0221 (9)	0.0204 (9)	−0.0008 (7)	0.0055 (7)	0.0079 (7)
O1	0.0243 (11)	0.0303 (9)	0.0229 (8)	−0.0078 (6)	0.0066 (6)	0.0100 (6)
O2	0.0245 (10)	0.0276 (8)	0.0215 (8)	−0.0036 (6)	0.0027 (6)	0.0044 (6)
O3	0.0261 (10)	0.0294 (9)	0.0342 (9)	−0.0091 (7)	0.0079 (7)	0.0128 (7)
O4	0.0312 (11)	0.0389 (10)	0.0259 (8)	0.0090 (7)	−0.0017 (7)	0.0142 (7)
O5	0.0290 (11)	0.0266 (9)	0.0267 (8)	−0.0041 (7)	0.0116 (7)	−0.0028 (7)
O6	0.0180 (10)	0.0292 (8)	0.0340 (9)	0.0065 (6)	0.0078 (6)	0.0091 (6)
Cl	0.0144 (4)	0.0195 (3)	0.0177 (3)	−0.0004 (2)	0.0035 (2)	0.0055 (2)

Geometric parameters (Å, º)

C1—O2	1.220 (2)	C4—N	1.469 (2)
C1—O1	1.326 (2)	C5—C6	1.390 (3)
C1—C2	1.477 (3)	C6—C7	1.383 (3)
C2—C3	1.397 (3)	O3—Cl	1.4330 (15)
C2—C7	1.400 (3)	O4—Cl	1.4364 (15)
C3—C4	1.371 (3)	O5—Cl	1.4442 (15)
C4—C5	1.389 (3)	O6—Cl	1.4399 (16)
O2—C1—O1	123.4 (2)	C4—C5—C6	118.3 (2)
O2—C1—C2	123.00 (18)	C7—C6—C5	120.82 (19)
O1—C1—C2	113.63 (17)	C6—C7—C2	119.81 (19)
C3—C2—C7	119.73 (19)	O3—Cl—O4	110.46 (11)
C3—C2—C1	118.15 (17)	O3—Cl—O6	109.93 (10)
C7—C2—C1	122.13 (18)	O4—Cl—O6	108.97 (10)
C4—C3—C2	119.11 (18)	O3—Cl—O5	109.10 (10)
C3—C4—C5	122.20 (18)	O4—Cl—O5	109.21 (10)
C3—C4—N	118.23 (17)	O6—Cl—O5	109.15 (9)
C5—C4—N	119.56 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N—H1N···O2^i	0.89	2.00	2.822 (2)	153
N—H2N···O3^ii	0.89	2.09	2.931 (3)	158
N—H3N···O4	0.89	2.20	2.912 (3)	137
N—H3N···O6^iii	0.89	2.36	2.943 (2)	124
O1—H1···O5^iv	0.82	1.94	2.748 (2)	170

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