Cyclo­propylammonium 4-iodo­benzoate

Abstract

In the title mol­ecular salt, C₃H₈N⁺·C₇H₄IO₂ ⁻, the cyclo­propanaminium cation forms three hydrogen bonds to the 4-iodo­benzoate anion, forming two unique repeating R ₄ ⁴(12) hydrogen-bonding rings that result in one-dimensional hydrogen-bonded columns along the crystallographic c axis.

Related literature  

For proton-transfer compounds, see: Kinbara et al. (1996 ▶). For hydrogen bonds between primary ammonium cations and a carboxyl­ate anion, see: Lemmerer (2011 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental  

Crystal data  

• C₃H₈N⁺·C₇H₄IO₂ ⁻

• M _r = 305.11

• Orthorhombic,

• a = 30.7877 (6) Å

• b = 9.7608 (2) Å

• c = 7.4757 (2) Å

• V = 2246.54 (9) ų

• Z = 8

• Mo Kα radiation

• μ = 2.83 mm⁻¹

• T = 173 K

• 0.5 × 0.15 × 0.11 mm

Data collection  

• Bruker APEXII CCD area-detector diffractometer

• Absorption correction: integration (XPREP; Bruker, 2004 ▶) T _min = 0.332, T _max = 0.746

• 11693 measured reflections

• 2705 independent reflections

• 2103 reflections with I > 2σ(I)

• R _int = 0.037

Refinement  

• R[F ² > 2σ(F ²)] = 0.023

• wR(F ²) = 0.047

• S = 0.97

• 2705 reflections

• 139 parameters

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.42 e Å⁻³

• Δρ_min = −0.79 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT-Plus (Bruker, 2004 ▶); data reduction: SAINT-Plus 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 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S160053681202449X/bt5937Isup3.mol

Supplementary material file. DOI: 10.1107/S160053681202449X/bt5937Isup4.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1	0.86 (3)	1.95 (3)	2.807 (3)	173 (2)
N1—H1B⋯O1i	0.95 (2)	1.90 (2)	2.807 (2)	161 (2)
N1—H1C⋯O2ii	0.83 (3)	1.92 (3)	2.739 (2)	171 (2)

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Comment

Ammonium carboxylate salts are molecular salts formed by mixing a primary amine and a carboxylic acid containing molecule, thus resulting in proton transfer from the acid to the amine (Kinbara et al., 1996). This forms a primary ammonium cation and a carboxylate anion. The three H atoms on the cation can then form three charge-assisted hydrogen bonds to the two O atoms on the anion. In the literature, three kinds of hydrogen bonded rings are most commonly formed by these hydrogen bonds, described using graph-set notation (Bernstein et al., 1995): R²₄(8), R³₄(10) and R⁴₄(12) (Lemmerer, 2011).

In molecular salt (I), shown in Fig. 1, formed by dissolving cyclopropylamine and p-iodobenzoic acid in methanol, only a R⁴₄(12) ring is formed. However, two such rings are formed, one by using the N1—H1A···O1 and N1—H1B···O1 hydrogen bonds, and the second one by using the N1—H1B···O1 and N1—H1C···O2 hydrogen bonds. As the N1—H1B···O1 hydrogen bond is common to both rings, a repetition of the two types of rings results, forming a 1-D hydrogen bonded column along the c axis (Fig. 2).

Experimental

All chemicals were purchased from commercial sources and used as received. (I) was prepared by slowly evaporating a solution of cyclopropylamine (0.050 g, 0.88 mmol) and p-iodobenzoic acid (0.217 g, 0.886 mmol) dissolved in 5 ml methanol.

Refinement

All C—H atoms were refined using a riding model, with a distance of 0.95 Å (Ar—H), 0.99 Å, (CH₂) and 1.00 Å, (CH) and U_iso(H) = 1.2U_eq(C). N—H atoms on the ammonium group were located in the difference Fourier map and their coordinates and isotropic displacement parameters were refined freely.

Figures

Fig. 1.

The asymmetric unit and atom numbering scheme of the title compound. Displacement ellipsoids are shown at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.

Fig. 2.

The hydrogen bonding pattern of the title compound. H atoms not involved in hydrogen bonding are omitted for clarity. Atoms marked with superscript i and ii are at the symmetry positions (-x, -y + 1, z - 1/2) and (-x, y, -z + 1/2) respectively.

Crystal data

C3H8N+·C7H4IO2−	F(000) = 1184
Mr = 305.11	Dx = 1.804 Mg m−3
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 4806 reflections
a = 30.7877 (6) Å	θ = 2.7–28.1°
b = 9.7608 (2) Å	µ = 2.83 mm−1
c = 7.4757 (2) Å	T = 173 K
V = 2246.54 (9) Å3	Needle, colourless
Z = 8	0.5 × 0.15 × 0.11 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	2103 reflections with I > 2σ(I)
ω scans	Rint = 0.037
Absorption correction: integration (XPREP; Bruker, 2004)	θmax = 28°, θmin = 2.2°
Tmin = 0.332, Tmax = 0.746	h = −37→40
11693 measured reflections	k = −12→11
2705 independent reflections	l = −9→9

Refinement

Refinement on F2	0 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.023	w = 1/[σ2(Fo2) + (0.0206P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.047	(Δ/σ)max = 0.001
S = 0.97	Δρmax = 0.42 e Å−3
2705 reflections	Δρmin = −0.79 e Å−3
139 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	0.12089 (7)	0.65046 (19)	0.5124 (3)	0.0213 (4)
C2	0.14737 (7)	0.5436 (2)	0.4583 (3)	0.0247 (5)
H2	0.1355	0.4708	0.3895	0.03*
C3	0.19096 (7)	0.5418 (2)	0.5035 (3)	0.0268 (5)
H3	0.2089	0.4674	0.4683	0.032*
C4	0.20809 (7)	0.6497 (2)	0.6003 (3)	0.0225 (4)
C5	0.18231 (7)	0.7577 (2)	0.6552 (3)	0.0262 (5)
H5	0.1944	0.8312	0.7221	0.031*
C6	0.13877 (7)	0.7572 (2)	0.6114 (3)	0.0241 (5)
H6	0.1208	0.8306	0.6493	0.029*
C7	0.07329 (7)	0.6516 (2)	0.4662 (3)	0.0235 (5)
O1	0.06027 (5)	0.56982 (14)	0.34560 (18)	0.0263 (3)
O2	0.04919 (5)	0.73454 (15)	0.5467 (2)	0.0332 (4)
I1	0.274626 (5)	0.652799 (16)	0.66287 (2)	0.03283 (6)
C8	0.05737 (7)	0.8095 (2)	−0.0226 (3)	0.0257 (5)
H8	0.0536	0.8472	−0.146	0.031*
C9	0.05800 (8)	0.9120 (2)	0.1242 (3)	0.0353 (6)
H9A	0.0452	0.8852	0.2405	0.042*
H9B	0.0542	1.0096	0.0918	0.042*
C10	0.09938 (8)	0.8420 (2)	0.0668 (3)	0.0383 (6)
H10A	0.1209	0.8967	−0.0008	0.046*
H10B	0.1119	0.7723	0.1479	0.046*
N1	0.03677 (6)	0.67743 (18)	0.0111 (3)	0.0227 (4)
H1A	0.0424 (9)	0.650 (2)	0.118 (4)	0.042 (8)*
H1B	0.0454 (7)	0.607 (2)	−0.068 (3)	0.034 (7)*
H1C	0.0101 (8)	0.686 (2)	−0.001 (3)	0.032 (7)*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0246 (10)	0.0218 (10)	0.0174 (10)	−0.0011 (9)	−0.0012 (9)	0.0029 (9)
C2	0.0308 (12)	0.0221 (11)	0.0214 (11)	−0.0006 (9)	−0.0023 (9)	−0.0045 (9)
C3	0.0282 (11)	0.0266 (11)	0.0255 (11)	0.0046 (9)	0.0017 (10)	−0.0037 (10)
C4	0.0212 (10)	0.0273 (11)	0.0190 (10)	−0.0010 (9)	−0.0001 (9)	0.0021 (10)
C5	0.0287 (11)	0.0240 (11)	0.0258 (12)	−0.0040 (9)	−0.0015 (10)	−0.0028 (10)
C6	0.0265 (11)	0.0207 (11)	0.0249 (11)	0.0018 (9)	−0.0003 (9)	−0.0036 (9)
C7	0.0287 (11)	0.0199 (10)	0.0220 (11)	−0.0018 (9)	−0.0040 (9)	0.0065 (10)
O1	0.0329 (8)	0.0222 (8)	0.0238 (8)	−0.0030 (6)	−0.0087 (7)	0.0008 (7)
O2	0.0240 (8)	0.0341 (9)	0.0416 (10)	0.0048 (7)	−0.0064 (7)	−0.0119 (8)
I1	0.02229 (8)	0.04054 (10)	0.03566 (10)	−0.00054 (6)	−0.00137 (7)	−0.00002 (8)
C8	0.0310 (12)	0.0249 (11)	0.0212 (11)	−0.0076 (9)	0.0002 (10)	0.0037 (9)
C9	0.0491 (16)	0.0231 (12)	0.0337 (14)	−0.0057 (11)	0.0002 (12)	−0.0024 (11)
C10	0.0373 (14)	0.0449 (15)	0.0327 (14)	−0.0172 (12)	−0.0037 (11)	0.0041 (12)
N1	0.0240 (10)	0.0213 (10)	0.0229 (11)	0.0007 (8)	−0.0038 (9)	−0.0004 (8)

Geometric parameters (Å, º)

C1—C2	1.384 (3)	C7—O1	1.269 (2)
C1—C6	1.391 (3)	C8—N1	1.459 (3)
C1—C7	1.506 (3)	C8—C9	1.485 (3)
C2—C3	1.384 (3)	C8—C10	1.490 (3)
C2—H2	0.95	C8—H8	1
C3—C4	1.382 (3)	C9—C10	1.508 (3)
C3—H3	0.95	C9—H9A	0.99
C4—C5	1.383 (3)	C9—H9B	0.99
C4—I1	2.101 (2)	C10—H10A	0.99
C5—C6	1.380 (3)	C10—H10B	0.99
C5—H5	0.95	N1—H1A	0.86 (3)
C6—H6	0.95	N1—H1B	0.95 (2)
C7—O2	1.253 (2)	N1—H1C	0.83 (3)
C2—C1—C6	119.13 (19)	C9—C8—C10	60.91 (15)
C2—C1—C7	120.76 (18)	N1—C8—H8	115.8
C6—C1—C7	120.11 (18)	C9—C8—H8	115.8
C3—C2—C1	120.59 (19)	C10—C8—H8	115.8
C3—C2—H2	119.7	C8—C9—C10	59.71 (14)
C1—C2—H2	119.7	C8—C9—H9A	117.8
C4—C3—C2	119.3 (2)	C10—C9—H9A	117.8
C4—C3—H3	120.4	C8—C9—H9B	117.8
C2—C3—H3	120.4	C10—C9—H9B	117.8
C3—C4—C5	121.2 (2)	H9A—C9—H9B	114.9
C3—C4—I1	119.99 (15)	C8—C10—C9	59.38 (15)
C5—C4—I1	118.84 (15)	C8—C10—H10A	117.8
C6—C5—C4	118.9 (2)	C9—C10—H10A	117.8
C6—C5—H5	120.5	C8—C10—H10B	117.8
C4—C5—H5	120.5	C9—C10—H10B	117.8
C5—C6—C1	120.91 (19)	H10A—C10—H10B	115
C5—C6—H6	119.5	C8—N1—H1A	110.5 (16)
C1—C6—H6	119.5	C8—N1—H1B	114.5 (14)
O2—C7—O1	124.1 (2)	H1A—N1—H1B	107 (2)
O2—C7—C1	118.10 (19)	C8—N1—H1C	108.7 (16)
O1—C7—C1	117.78 (19)	H1A—N1—H1C	109 (2)
N1—C8—C9	118.27 (19)	H1B—N1—H1C	107 (2)
N1—C8—C10	119.23 (19)
C6—C1—C2—C3	0.7 (3)	C2—C1—C6—C5	0.2 (3)
C7—C1—C2—C3	−178.98 (19)	C7—C1—C6—C5	179.90 (19)
C1—C2—C3—C4	−1.4 (3)	C2—C1—C7—O2	166.03 (19)
C2—C3—C4—C5	1.1 (3)	C6—C1—C7—O2	−13.6 (3)
C2—C3—C4—I1	−177.88 (16)	C2—C1—C7—O1	−15.2 (3)
C3—C4—C5—C6	−0.2 (3)	C6—C1—C7—O1	165.19 (18)
I1—C4—C5—C6	178.79 (15)	N1—C8—C9—C10	109.6 (2)
C4—C5—C6—C1	−0.5 (3)	N1—C8—C10—C9	−108.0 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.86 (3)	1.95 (3)	2.807 (3)	173 (2)
N1—H1B···O1i	0.95 (2)	1.90 (2)	2.807 (2)	161 (2)
N1—H1C···O2ii	0.83 (3)	1.92 (3)	2.739 (2)	171 (2)

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