A triclinic polymorph of hexa­nedioic acid

Fun, H.-K.; Chantrapromma, S.

doi:10.1107/S1600536809006448

organic compounds

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Volume 65| Part 3| March 2009| Page o624

doi:10.1107/S1600536809006448

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A triclinic polymorph of hexanedioic acid

Hoong-Kun Fun ^a ^* and Suchada Chantrapromma ^b ‡

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^bCrystal Materials Research Unit, Department of Chemistry, Faculty of Science, Prince of Songkla University, Hat-Yai, Songkhla 90112, Thailand
^*Correspondence e-mail: hkfun@usm.my

(Received 20 February 2009; accepted 22 February 2009; online 28 February 2009)

Hexanedioic acid (or adipic acid), C₆H₁₀O₄, crystallizes with two crystallographically independent half-molecules in the asymmetric unit of the triclinic unit cell, space group P $[\overline{1}]$ , as each molecule lies across a crystallographic inversion centre. A monoclinic polymorph has been reported previously, most recently by Ranganathan, Kulkarni & Rao [J. Phys. Chem. A, (2003), 107, 6073–6081]. The molecules adopt the expected zigzag structure and are linked via centrosymmetric pairs of O—H⋯O hydrogen bonds, forming infinite one-dimensional chains along [011]. These chains are stacked along the a axis. The crystal is further stabilized by weak C—H⋯O interactions.

Related literature

For bond-length data, see Allen et al. (1987 ). For related structures, see, for example: Ranganathan et al. (2003 ); Srinivasa Gopalan et al. (1999 , 2000 ). For general background to the influence of hydrogen bonding on phase transitions, see, for example: Chantrapromma et al. (2006 ); Dunitz (1991 ); Fun et al. (2003 , 2006 ); How et al. (2005 ). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

C₆H₁₀O₄
M_r = 146.14
Triclinic, $[P \overline 1]$
a = 6.7666 (5) Å
b = 6.9992 (5) Å
c = 7.7180 (5) Å
α = 93.794 (4)°
β = 104.321 (4)°
γ = 102.689 (4)°
V = 342.70 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 100 K
0.55 × 0.11 × 0.06 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.847, T_max = 0.993
7773 measured reflections
1553 independent reflections
1419 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.094
S = 1.09
1553 reflections
91 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2A—H2OA⋯O1Aⁱ	0.82	1.82	2.6397 (13)	172
O2B—H2OB⋯O1Bⁱⁱ	0.82	1.82	2.6421 (13)	174
C2A—H2AB⋯O2Aⁱⁱⁱ	0.97	2.58	3.5415 (16)	171
Symmetry codes: (i) -x, -y, -z; (ii) -x+1, -y+1, -z; (iii) -x, -y+1, -z.

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809006448/sj2583sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809006448/sj2583Isup2.hkl

checkCIF report

Comment top

Structural investigation of crystalline solids undergoing phase transition has been an interesting area of research. Molecular solids are more interesting in that they often crystallize in different structural forms and exhibit polymorphic transformations (Dunitz, 1991). We have previously reported reversible phase transitions due to hydrogen bonds in some organic compounds (Chantrapromma et al., 2006; Fun et al., 2003; 2006); How et al., 2005). Aliphatic dicarboxylic acids form an interesting class of organic compounds for hydrogen bonding and phase transition studies. In the course of our research on the influence of hydrogen bonding on phase transitions, we have found that adipic acid exists in both monoclinic and triclinic polymorphs. The triclinic form does not undergo a phase transition in sharp contrast to the behaviour of the monoclinic form (Srinivasa Gopalan et al., (1999). We report herein the crystal structure of the triclinic polymorph of adipic acid (I).

The crystal structure of the hexanedioic acid or adipic acid was previously reported by Ranganathan et al., (2003) and Srinivasa Gopalan et al., (1999, 2000) in the monoclinic space group P21/c. It was found that adipic acid exhibits a phase transition at around 136 K (Srinivasa Gopalan et al., 1999) and does not exhibit polymorphism (Srinivasa Gopalan et al., 2000). However, in the present work, we have found that adipic acid actually does exhibit polymorphisim in which the compound crystallized out in the triclinic space group P -1.

In the structure of (I), Fig. 1, each of the two unique adipic acid molecules, C₆H₁₀O₄, lies across a different crystallographic inversion centre. There are two crystallographically independent half molecules in the asymmetric unit, A and B, with slightly different bond lengths and bond angles. The molecules exist in an zigzag form. Atoms O1A, O2A, C1A, C2A and C3 lie on the same plane in one molecule with a maximum deviation of 0.006 (1) Å for C1A while atoms O1B, O2B, C1B and C2B in the other molecule are also coplanar with a maximum deviation -0.005 (1) Å for atom C1B. The interplanar angle between these two planes is 61.14 (7)°. Bond lengths and angles in the title compound are within normal ranges (Allen et al., 1987) and comparable to those in related structures (Ranganathan et al., 2003; Srinivasa Gopalan et al., 1999; 2000).

In the crystal packing (Fig. 2), the molecules are linked by centrosymmetric pairs of O—H···O hydrogen bonds forming infinite one-dimensional chains along the [0 1 1] directions and these molecular chains are stacked along the a axis. The crystal is stablized by O—H···O hydrogen bonds and weak C—H···O interactions (Table 1). It is interesting to note that this triclinic polymorph has fewer O—H···O hydrogen bonds and weak C—H···O interactions in comparison to the monoclinic form (Srinivasa Gopalan et al., 1999; 2000).

Related literature top

For bond-length data, see Allen et al. (1987). For related structures, see, for example: Ranganathan et al. (2003); Srinivasa Gopalan et al. (1999, 2000). For general background to the influence of hydrogen bonding on phase transitions, see, for example: Chantrapromma et al. (2006); Dunitz (1991); Fun et al. (2003, 2006); How et al. (2005). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986).

Experimental top

Adipic acid was obtained commercially (Fluka, Germany). Single crystals of adipic acid were grown by slow evaporation of ethyl acetate solution at room temperature.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, showing 50% probability displacement ellipsoids and the atomic numbering. [Symmetry code: (AA) -x, -y+1, -z+1 and (BA) -x+1, -y+2, -z+1].
	Fig. 2. The crystal packing of the title compound, viewed down the a axis showing one-dimensional chains along the [0 1 1] direction. Hydrogen bonds are shown as dashed lines.

hexanedioic acid top

Crystal data top

C₆H₁₀O₄	Z = 2
M_r = 146.14	F(000) = 156
Triclinic, P1	D_x = 1.416 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.7666 (5) Å	Cell parameters from 1553 reflections
b = 6.9992 (5) Å	θ = 2.8–27.5°
c = 7.7180 (5) Å	µ = 0.12 mm⁻¹
α = 93.794 (4)°	T = 100 K
β = 104.321 (4)°	Needle, colorless
γ = 102.689 (4)°	0.55 × 0.11 × 0.06 mm
V = 342.70 (4) Å³

Data collection top

Bruker APEXII CCD area-detector diffractometer	1553 independent reflections
Radiation source: sealed tube	1419 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ϕ and ω scans	θ_max = 27.5°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −8→8
T_min = 0.847, T_max = 0.993	k = −9→9
7773 measured reflections	l = −10→10

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.094	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0402P)² + 0.1411P] where P = (F_o² + 2F_c²)/3
1553 reflections	(Δ/σ)_max = 0.001
91 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₆H₁₀O₄	γ = 102.689 (4)°
M_r = 146.14	V = 342.70 (4) Å³
Triclinic, P1	Z = 2
a = 6.7666 (5) Å	Mo Kα radiation
b = 6.9992 (5) Å	µ = 0.12 mm⁻¹
c = 7.7180 (5) Å	T = 100 K
α = 93.794 (4)°	0.55 × 0.11 × 0.06 mm
β = 104.321 (4)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	1553 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1419 reflections with I > 2σ(I)
T_min = 0.847, T_max = 0.993	R_int = 0.027
7773 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.094	H-atom parameters constrained
S = 1.09	Δρ_max = 0.32 e Å⁻³
1553 reflections	Δρ_min = −0.20 e Å⁻³
91 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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 (Å²) top

	x	y	z	U_iso*/U_eq
O1A	0.07345 (14)	0.10624 (13)	0.21778 (12)	0.0182 (2)
O2A	−0.11534 (14)	0.20271 (13)	−0.02751 (12)	0.0198 (2)
H2OA	−0.0961	0.1042	−0.0779	0.030*
C1A	−0.02548 (19)	0.22010 (17)	0.14771 (16)	0.0156 (3)
C2A	−0.0623 (2)	0.39330 (18)	0.24950 (16)	0.0174 (3)
H2AA	−0.2127	0.3787	0.2269	0.021*
H2AB	−0.0057	0.5124	0.2026	0.021*
C3A	0.03484 (19)	0.41932 (17)	0.45233 (16)	0.0167 (3)
H3AA	0.1794	0.4448	0.4777	0.020*
H3AB	−0.0108	0.3012	0.4996	0.020*
O1B	0.45905 (14)	0.56597 (12)	0.19844 (12)	0.0189 (2)
O2B	0.61849 (14)	0.75868 (13)	0.02759 (12)	0.0204 (2)
H2OB	0.5906	0.6539	−0.0380	0.031*
C1B	0.54652 (19)	0.72852 (18)	0.17064 (16)	0.0159 (3)
C2B	0.5885 (2)	0.91565 (18)	0.29479 (16)	0.0173 (3)
H2BA	0.5457	1.0160	0.2236	0.021*
H2BB	0.7389	0.9603	0.3491	0.021*
C3B	0.47841 (19)	0.89970 (17)	0.44459 (16)	0.0161 (3)
H3BA	0.5266	0.8106	0.5238	0.019*
H3BB	0.3356	0.8519	0.3947	0.019*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1A	0.0225 (5)	0.0180 (4)	0.0144 (4)	0.0084 (4)	0.0033 (3)	−0.0012 (3)
O2A	0.0287 (5)	0.0185 (4)	0.0129 (4)	0.0113 (4)	0.0033 (4)	−0.0023 (3)
C1A	0.0165 (6)	0.0157 (6)	0.0135 (6)	0.0019 (4)	0.0049 (4)	−0.0014 (4)
C2A	0.0218 (6)	0.0156 (6)	0.0151 (6)	0.0066 (5)	0.0044 (5)	−0.0013 (5)
C3A	0.0192 (6)	0.0155 (6)	0.0149 (6)	0.0050 (5)	0.0039 (5)	−0.0021 (5)
O1B	0.0248 (5)	0.0160 (4)	0.0166 (4)	0.0050 (4)	0.0078 (4)	−0.0008 (3)
O2B	0.0278 (5)	0.0164 (4)	0.0173 (5)	0.0022 (4)	0.0111 (4)	−0.0034 (3)
C1B	0.0157 (6)	0.0177 (6)	0.0140 (6)	0.0056 (5)	0.0028 (4)	−0.0009 (5)
C2B	0.0204 (6)	0.0149 (6)	0.0156 (6)	0.0029 (5)	0.0055 (5)	−0.0028 (5)
C3B	0.0185 (6)	0.0150 (6)	0.0138 (6)	0.0034 (5)	0.0039 (5)	−0.0019 (5)

Geometric parameters (Å, º) top

O1A—C1A	1.2199 (15)	O1B—C1B	1.2207 (15)
O2A—C1A	1.3237 (14)	O2B—C1B	1.3238 (15)
O2A—H2OA	0.8200	O2B—H2OB	0.8200
C1A—C2A	1.5007 (16)	C1B—C2B	1.5001 (16)
C2A—C3A	1.5220 (16)	C2B—C3B	1.5201 (17)
C2A—H2AA	0.9700	C2B—H2BA	0.9700
C2A—H2AB	0.9700	C2B—H2BB	0.9700
C3A—C3Aⁱ	1.528 (2)	C3B—C3Bⁱⁱ	1.525 (2)
C3A—H3AA	0.9222	C3B—H3BA	0.9537
C3A—H3AB	0.9462	C3B—H3BB	0.9224

C1A—O2A—H2OA	109.5	C1B—O2B—H2OB	109.5
O1A—C1A—O2A	123.52 (11)	O1B—C1B—O2B	123.41 (11)
O1A—C1A—C2A	124.18 (11)	O1B—C1B—C2B	124.33 (11)
O2A—C1A—C2A	112.29 (10)	O2B—C1B—C2B	112.25 (10)
C1A—C2A—C3A	114.73 (10)	C1B—C2B—C3B	115.27 (10)
C1A—C2A—H2AA	108.6	C1B—C2B—H2BA	108.5
C3A—C2A—H2AA	108.6	C3B—C2B—H2BA	108.5
C1A—C2A—H2AB	108.6	C1B—C2B—H2BB	108.5
C3A—C2A—H2AB	108.6	C3B—C2B—H2BB	108.5
H2AA—C2A—H2AB	107.6	H2BA—C2B—H2BB	107.5
C2A—C3A—C3Aⁱ	111.19 (13)	C2B—C3B—C3Bⁱⁱ	110.83 (12)
C2A—C3A—H3AA	110.2	C2B—C3B—H3BA	110.6
C3Aⁱ—C3A—H3AA	111.6	C3Bⁱⁱ—C3B—H3BA	108.1
C2A—C3A—H3AB	109.9	C2B—C3B—H3BB	109.3
C3Aⁱ—C3A—H3AB	106.7	C3Bⁱⁱ—C3B—H3BB	109.7
H3AA—C3A—H3AB	107.0	H3BA—C3B—H3BB	108.3

O1A—C1A—C2A—C3A	0.07 (17)	O1B—C1B—C2B—C3B	−11.15 (18)
O2A—C1A—C2A—C3A	179.19 (10)	O2B—C1B—C2B—C3B	169.89 (10)
C1A—C2A—C3A—C3Aⁱ	−172.28 (12)	C1B—C2B—C3B—C3Bⁱⁱ	−176.67 (13)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2A—H2OA···O1Aⁱⁱⁱ	0.82	1.82	2.6397 (13)	172
O2B—H2OB···O1B^iv	0.82	1.82	2.6421 (13)	174
C2A—H2AB···O2A^v	0.97	2.58	3.5415 (16)	171

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

Experimental details

Crystal data
Chemical formula	C₆H₁₀O₄
M_r	146.14
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	6.7666 (5), 6.9992 (5), 7.7180 (5)
α, β, γ (°)	93.794 (4), 104.321 (4), 102.689 (4)
V (Å³)	342.70 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.55 × 0.11 × 0.06

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.847, 0.993
No. of measured, independent and observed [I > 2σ(I)] reflections	7773, 1553, 1419
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.094, 1.09
No. of reflections	1553
No. of parameters	91
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.20

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2A—H2OA···O1Aⁱ	0.82	1.82	2.6397 (13)	172
O2B—H2OB···O1Bⁱⁱ	0.82	1.82	2.6421 (13)	174
C2A—H2AB···O2Aⁱⁱⁱ	0.97	2.58	3.5415 (16)	171

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

Footnotes

‡Additional correspondence author, e-mail: suchada.c@psu.ac.th.

Acknowledgements

SC thanks Prince of Songkla University for financial support through the Crystal Materials Research Unit. The authors also thank Universiti Sains Malaysia for the Research University Golden Goose Grant No. 1001/PFIZIK/811012.

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