Tetra­methyl­ammonium hemi(terephthalate) dihydrate

Yang, Y.; Shi, L.

doi:10.1107/S1600536811023312

organic compounds

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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Page o1767

doi:10.1107/S1600536811023312

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Tetramethylammonium hemi(terephthalate) dihydrate

Yunxia Yang ^a ^* and Laipeng Shi ^a

^aKey Laboratory of Polymer Materials of Gansu Province, Ministry of Education, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070, Gansu, People's Republic of China
^*Correspondence e-mail: yangyx80@nwnu.edu.cn

(Received 3 June 2011; accepted 15 June 2011; online 22 June 2011)

In the title compound, (CH₃)₄N⁺·0.5C₈H₄O₄²⁻·2H₂O, the complete terephthalate dianion is completed by twofold symmetry and has a dihedral angle of 23.5 (2)° between the carboxylate group and its parent ring. Two independent water molecules serve as both donors and acceptor in the construction of undulating hydrogen-bonded host layers with various O—H⋯O contacts ocurring between the anion and two water molecules. At the same time, the tetramethylammonium cations, as the sphere-like guest species, are arranged in two rows between neighboring host layers, with an approximate interlayer distance of 7.36 Å, forming a sandwich-like crystal structure.

Related literature

Biphenyl-4,4′-dicarboxylic acid can be used as a host molecule in the construction of different host–guest crystal structures with various cations such as tetraethylammonium and choline ions, see: Furey et al. (1996 ); Xu et al. (2002 ).

Experimental

Crystal data

C₄H₁₂N⁺·0.5C₈H₄O₄²⁻·2H₂O
M_r = 192.23
Monoclinic, C 2/c
a = 22.0950 (4) Å
b = 11.2922 (2) Å
c = 9.1101 (1) Å
β = 109.613 (1)°
V = 2141.10 (6) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.23 × 0.16 × 0.10 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.979, T_max = 0.991
6025 measured reflections
2227 independent reflections
1771 reflections with I > 2σ(I)
R_int = 0.015

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.140
S = 1.03
2227 reflections
118 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯O2	0.87	1.87	2.7262 (17)	168
O1W—H1WB⋯O1Wⁱ	0.84	2.41	2.812 (2)	110
O2W—H2WA⋯O1ⁱⁱ	0.86	1.89	2.7291 (15)	164
O2W—H2WB⋯O1ⁱⁱⁱ	0.86	1.96	2.7999 (18)	165
Symmetry codes: (i) -x, -y+1, -z; (ii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ ; (iii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811023312/hg5050sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811023312/hg5050Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811023312/hg5050Isup3.cml

checkCIF report

Comment top

Biphenyl-4,4'-dicarboxylic acid can be used as host molecule to construct different host–guest crystal structures with various cations such as tetraethylammonium and choline ions (Furey et al., 1996; Xu et al., 2002). In this structure, there is half a terephthalate anion disposed at the twofold axis, two water molecules, and one tetramethylammonium cation at general positions in the asymmetric unit. From the packing diagram (Fig. 2), it can be observed that terephthalate anion and two water molecules form hydrogen-bonded host layers along the b axis with the help of four various O—H···O hydrogen bonds between the anion and these two water molecules. The guest cations are doubly contained between the layers with an interlayer distance of a/3≈7.36 Å. Obviously, two independent water molecules, as the complementary host molecules, play a significant linking role in constructing the hydrogen-bonded host layer by generating four O—H···O hydrogen bonds (Fig. 3).

Related literature top

Biphenyl-4,4'-dicarboxylic acid can be used as a host molecule in the construction

of different host–guest crystal structures with various cations such as

tetraethylammonium and choline ions, see: Furey et al. (1996); Xu et al. (2002).

Experimental top

Biphenyl-4,4'-dicarboxylic acid (0.042 g, 0.25 mmol) was dissolved in a water-ethanol (1:2 v/v) mixture and tetramethylammonium hydroxide was added to neutralize the acid. Colorless block crystals formed after several days.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. Thermal ellipsoid plot of the title compound at the 30% probability level; hydrogen atoms are drawn as spheres of arbitrary radius [Symmetry code: (i) -x, y, -z + 1/2.].
	Fig. 2. Packing diagram of the title compound; all hydrogen atoms are omitted for clarity and the cations are represented with the hatched spheres.
	Fig. 3. Hydrogen bond pattern in the host layer of the title compound; all hydrogen atoms are omitted for clarity.

Tetramethylammonium hemi(terephthalate) dihydrate top

Crystal data top

C₄H₁₂N⁺·0.5C₈H₄O₄²⁻·2H₂O	F(000) = 840
M_r = 192.23	D_x = 1.193 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2337 reflections
a = 22.0950 (4) Å	θ = 2.9–26.4°
b = 11.2922 (2) Å	µ = 0.09 mm⁻¹
c = 9.1101 (1) Å	T = 296 K
β = 109.613 (1)°	Block, colorless
V = 2141.10 (6) Å³	0.23 × 0.16 × 0.10 mm
Z = 8

Data collection top

Bruker APEXII CCD area-detector diffractometer	2227 independent reflections
Radiation source: fine-focus sealed tube	1771 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.015
ϕ and ω scans	θ_max = 26.6°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −15→27
T_min = 0.979, T_max = 0.991	k = −12→14
6025 measured reflections	l = −11→11

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.140	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0762P)² + 0.7137P] where P = (F_o² + 2F_c²)/3
2227 reflections	(Δ/σ)_max < 0.001
118 parameters	Δρ_max = 0.19 e Å⁻³
2 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₄H₁₂N⁺·0.5C₈H₄O₄²⁻·2H₂O	V = 2141.10 (6) Å³
M_r = 192.23	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 22.0950 (4) Å	µ = 0.09 mm⁻¹
b = 11.2922 (2) Å	T = 296 K
c = 9.1101 (1) Å	0.23 × 0.16 × 0.10 mm
β = 109.613 (1)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	2227 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	1771 reflections with I > 2σ(I)
T_min = 0.979, T_max = 0.991	R_int = 0.015
6025 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	2 restraints
wR(F²) = 0.140	H-atom parameters constrained
S = 1.03	Δρ_max = 0.19 e Å⁻³
2227 reflections	Δρ_min = −0.24 e Å⁻³
118 parameters

Special details top

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
O1	0.13625 (6)	0.07836 (11)	0.13458 (15)	0.0647 (4)
C1	0.10126 (7)	0.16860 (14)	0.11158 (17)	0.0484 (4)
N1	0.16707 (5)	0.69678 (10)	0.18126 (13)	0.0424 (3)
O1W	0.03390 (7)	0.44906 (11)	−0.09000 (15)	0.0711 (4)
H1WA	0.0527	0.3822	−0.0561	0.107*
H1WB	−0.0051	0.4402	−0.1035	0.107*
O2	0.10772 (6)	0.25714 (12)	0.03731 (16)	0.0753 (4)
C2	0.04837 (6)	0.16903 (12)	0.18277 (15)	0.0414 (3)
O2W	0.30308 (6)	0.52166 (12)	0.05088 (15)	0.0716 (4)
H2WA	0.3259	0.4825	0.0078	0.107*
H2WB	0.3274	0.5319	0.1455	0.107*
C3	0.02429 (8)	0.06406 (14)	0.2185 (2)	0.0593 (4)
H3A	0.0411	−0.0076	0.1997	0.071*
C4	0.02375 (7)	0.27422 (12)	0.21607 (15)	0.0399 (3)
H4A	0.0392	0.3458	0.1927	0.048*
C5	0.16656 (11)	0.58985 (19)	0.2752 (3)	0.0846 (6)
H5A	0.2052	0.5452	0.2905	0.127*
H5B	0.1299	0.5419	0.2214	0.127*
H5C	0.1642	0.6132	0.3745	0.127*
C6	0.17003 (10)	0.66356 (19)	0.0258 (2)	0.0727 (6)
H6A	0.2087	0.6198	0.0389	0.109*
H6B	0.1698	0.7339	−0.0335	0.109*
H6C	0.1335	0.6155	−0.0283	0.109*
C7	0.22409 (10)	0.7706 (2)	0.2642 (3)	0.0810 (6)
H7A	0.2626	0.7260	0.2777	0.121*
H7B	0.2223	0.7932	0.3642	0.121*
H7C	0.2242	0.8404	0.2040	0.121*
C8	0.10738 (8)	0.76601 (17)	0.1586 (2)	0.0628 (5)
H8A	0.1051	0.7884	0.2583	0.094*
H8B	0.0707	0.7185	0.1041	0.094*
H8C	0.1078	0.8358	0.0989	0.094*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0632 (7)	0.0710 (8)	0.0713 (8)	0.0227 (6)	0.0374 (6)	0.0106 (6)
C1	0.0430 (8)	0.0600 (9)	0.0446 (8)	0.0082 (7)	0.0177 (6)	0.0054 (7)
N1	0.0390 (6)	0.0414 (6)	0.0456 (6)	0.0048 (5)	0.0126 (5)	0.0025 (5)
O1W	0.0854 (9)	0.0637 (8)	0.0681 (8)	0.0174 (7)	0.0311 (7)	0.0150 (6)
O2	0.0725 (8)	0.0844 (9)	0.0881 (9)	0.0251 (7)	0.0522 (7)	0.0361 (7)
C2	0.0374 (7)	0.0464 (8)	0.0395 (7)	0.0025 (6)	0.0118 (6)	0.0016 (6)
O2W	0.0567 (7)	0.0910 (9)	0.0671 (8)	0.0201 (7)	0.0206 (6)	−0.0087 (7)
C3	0.0581 (9)	0.0401 (8)	0.0893 (12)	0.0052 (7)	0.0375 (9)	−0.0021 (8)
C4	0.0432 (7)	0.0410 (7)	0.0355 (6)	−0.0016 (5)	0.0134 (6)	0.0027 (5)
C5	0.0846 (14)	0.0652 (12)	0.1042 (16)	0.0117 (10)	0.0319 (12)	0.0371 (11)
C6	0.0670 (11)	0.0936 (14)	0.0606 (10)	0.0172 (10)	0.0255 (9)	−0.0115 (10)
C7	0.0596 (11)	0.0790 (13)	0.0844 (14)	−0.0132 (10)	−0.0021 (10)	−0.0082 (11)
C8	0.0541 (10)	0.0708 (11)	0.0661 (10)	0.0205 (8)	0.0235 (8)	0.0041 (8)

Geometric parameters (Å, º) top

O1—C1	1.2534 (18)	C4—C4ⁱ	1.385 (3)
C1—O2	1.2420 (19)	C4—H4A	0.9300
C1—C2	1.5151 (19)	C5—H5A	0.9600
N1—C5	1.482 (2)	C5—H5B	0.9600
N1—C8	1.4867 (18)	C5—H5C	0.9600
N1—C6	1.487 (2)	C6—H6A	0.9600
N1—C7	1.488 (2)	C6—H6B	0.9600
O1W—H1WA	0.8668	C6—H6C	0.9600
O1W—H1WB	0.8351	C7—H7A	0.9600
C2—C4	1.3818 (19)	C7—H7B	0.9600
C2—C3	1.382 (2)	C7—H7C	0.9600
O2W—H2WA	0.8580	C8—H8A	0.9600
O2W—H2WB	0.8570	C8—H8B	0.9600
C3—C3ⁱ	1.377 (3)	C8—H8C	0.9600
C3—H3A	0.9300

O2—C1—O1	124.64 (14)	H5A—C5—H5B	109.5
O2—C1—C2	118.47 (13)	N1—C5—H5C	109.5
O1—C1—C2	116.88 (13)	H5A—C5—H5C	109.5
C5—N1—C8	109.28 (14)	H5B—C5—H5C	109.5
C5—N1—C6	110.81 (16)	N1—C6—H6A	109.5
C8—N1—C6	108.73 (13)	N1—C6—H6B	109.5
C5—N1—C7	109.44 (15)	H6A—C6—H6B	109.5
C8—N1—C7	109.64 (14)	N1—C6—H6C	109.5
C6—N1—C7	108.92 (15)	H6A—C6—H6C	109.5
H1WA—O1W—H1WB	107.2	H6B—C6—H6C	109.5
C4—C2—C3	118.33 (13)	N1—C7—H7A	109.5
C4—C2—C1	120.92 (12)	N1—C7—H7B	109.5
C3—C2—C1	120.75 (13)	H7A—C7—H7B	109.5
H2WA—O2W—H2WB	105.3	N1—C7—H7C	109.5
C3ⁱ—C3—C2	120.92 (8)	H7A—C7—H7C	109.5
C3ⁱ—C3—H3A	119.5	H7B—C7—H7C	109.5
C2—C3—H3A	119.5	N1—C8—H8A	109.5
C2—C4—C4ⁱ	120.73 (8)	N1—C8—H8B	109.5
C2—C4—H4A	119.6	H8A—C8—H8B	109.5
C4ⁱ—C4—H4A	119.6	N1—C8—H8C	109.5
N1—C5—H5A	109.5	H8A—C8—H8C	109.5
N1—C5—H5B	109.5	H8B—C8—H8C	109.5

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O2	0.87	1.87	2.7262 (17)	168
O1W—H1WB···O1Wⁱⁱ	0.84	2.41	2.812 (2)	110
O2W—H2WA···O1ⁱⁱⁱ	0.86	1.89	2.7291 (15)	164
O2W—H2WB···O1^iv	0.86	1.96	2.7999 (18)	165

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

Experimental details

Crystal data
Chemical formula	C₄H₁₂N⁺·0.5C₈H₄O₄²⁻·2H₂O
M_r	192.23
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	22.0950 (4), 11.2922 (2), 9.1101 (1)
β (°)	109.613 (1)
V (Å³)	2141.10 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.23 × 0.16 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.979, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	6025, 2227, 1771
R_int	0.015
(sin θ/λ)_max (Å⁻¹)	0.630

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.140, 1.03
No. of reflections	2227
No. of parameters	118
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.24

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O2	0.87	1.87	2.7262 (17)	168
O1W—H1WB···O1Wⁱ	0.84	2.41	2.812 (2)	110
O2W—H2WA···O1ⁱⁱ	0.86	1.89	2.7291 (15)	164
O2W—H2WB···O1ⁱⁱⁱ	0.86	1.96	2.7999 (18)	165

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

Acknowledgements

The authors thank the Key Laboratory of Eco-environment-related Polymer Materials of Northwest Normal University for supporting this work.

References

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