Cyclo­propylammonium 4-iodo­benzoate

Lemmerer, A.

doi:10.1107/S160053681202449X

organic compounds

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Volume 68| Part 7| July 2012| Page o2096

https://doi.org/10.1107/S160053681202449X

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Cyclopropylammonium 4-iodobenzoate

Andreas Lemmerer ^a ^*

^aCentre for Supramolecular Chemistry Research, Department of Chemistry, University of Cape Town, Rondebosch 7701, South Africa
^*Correspondence e-mail: andreas.lemmerer@wits.ac.za

(Received 28 May 2012; accepted 29 May 2012; online 13 June 2012)

In the title molecular salt, C₃H₈N⁺·C₇H₄IO₂⁻, the cyclopropanaminium cation forms three hydrogen bonds to the 4-iodobenzoate anion, forming two unique repeating R₄⁴(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, P b c n
a = 30.7877 (6) Å
b = 9.7608 (2) Å
c = 7.4757 (2) Å
V = 2246.54 (9) Å³
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[F² > 2σ(F²)] = 0.023
wR(F²) = 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

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) $[x, -y+1, z-{\script{1\over 2}}]$ ; (ii) $[-x, y, -z+{\script{1\over 2}}]$ .

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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S160053681202449X/bt5937sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681202449X/bt5937Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S160053681202449X/bt5937Isup3.mol

Supporting information file. DOI: https://doi.org/10.1107/S160053681202449X/bt5937Isup4.cml

checkCIF report

Comment top

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).

Related literature top

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 top

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.

Structure description top

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).

Computing details top

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).

Figures top

	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.

Cyclopropylammonium 4-iodobenzoate top

Crystal data top

C₃H₈N⁺·C₇H₄IO₂⁻	F(000) = 1184
M_r = 305.11	D_x = 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 top

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

Refinement top

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(F_o²) + (0.0206P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.047	(Δ/σ)_max = 0.001
S = 0.97	Δρ_max = 0.42 e Å⁻³
2705 reflections	Δρ_min = −0.79 e Å⁻³
139 parameters

Crystal data top

C₃H₈N⁺·C₇H₄IO₂⁻	V = 2246.54 (9) Å³
M_r = 305.11	Z = 8
Orthorhombic, Pbcn	Mo Kα radiation
a = 30.7877 (6) Å	µ = 2.83 mm⁻¹
b = 9.7608 (2) Å	T = 173 K
c = 7.4757 (2) Å	0.5 × 0.15 × 0.11 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	2705 independent reflections
Absorption correction: integration (XPREP; Bruker, 2004)	2103 reflections with I > 2σ(I)
T_min = 0.332, T_max = 0.746	R_int = 0.037
11693 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	0 restraints
wR(F²) = 0.047	H atoms treated by a mixture of independent and constrained refinement
S = 0.97	Δρ_max = 0.42 e Å⁻³
2705 reflections	Δρ_min = −0.79 e Å⁻³
139 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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) top

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) top

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.

Experimental details

Crystal data
Chemical formula	C₃H₈N⁺·C₇H₄IO₂⁻
M_r	305.11
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	173
a, b, c (Å)	30.7877 (6), 9.7608 (2), 7.4757 (2)
V (Å³)	2246.54 (9)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	2.83
Crystal size (mm)	0.5 × 0.15 × 0.11

Data collection
Diffractometer	Bruker APEXII CCD area-detector
Absorption correction	Integration (XPREP; Bruker, 2004)
T_min, T_max	0.332, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	11693, 2705, 2103
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.047, 0.97
No. of reflections	2705
No. of parameters	139
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.79

Computer programs: APEX2 (Bruker, 2005), SAINT-Plus (Bruker, 2004), SAINT-Plus and XPREP (Bruker 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 1999), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

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.

Acknowledgements

The University of Cape Town is thanked for providing the infrastructure required to do this work and the National Research Fund (SFP2006061500015) for the award of a postdoctoral fellowship.

References

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