Tetra-n-propyl­ammonium acetate–boric acid (1/1)

Yang, Y.-X.; Li, Q.; Ng, S.W.

doi:10.1107/S1600536809044225

organic compounds

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Volume 65| Part 11| November 2009| Page o2958

https://doi.org/10.1107/S1600536809044225

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Tetra-n-propylammonium acetate–boric acid (1/1)

Yun-Xia Yang,^a Qi Li ^a and Seik Weng Ng ^b ^*

^aCollege of Chemistry, Beijing Normal University, Beijing 100875, People's Republic of China, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 20 October 2009; accepted 23 October 2009; online 31 October 2009)

In the crystal structure of the ammonium carboxylate–boric acid cocrystal, (C₃H₇)₄N⁺·CH₃CO₂⁻·H₃BO₃, the boric acid forms two O—H⋯O hydrogen bonds to the acetate anion. The acetate–boric acid species is hydrogen bonded to another acetate–boric acid species through the third OH unit of the boric acid about a twofold rotation axis.

Related literature

For the crystal structure of tetra-n-propyl pentaborate–boric acid co-crystal, see: Freyhardt et al. (1994 ).

Experimental

Crystal data

C₁₂H₂₈N⁺·C₂H₃O₂⁻·BH₃O₃
M_r = 307.23
Orthorhombic, P c c n
a = 16.4594 (3) Å
b = 16.7680 (3) Å
c = 14.4526 (3) Å
V = 3988.79 (13) Å³
Z = 8
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 293 K
0.24 × 0.24 × 0.22 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: none
19907 measured reflections
4581 independent reflections
2803 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.183
S = 1.02
4581 reflections
204 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O4	0.86 (1)	1.75 (1)	2.600 (2)	175 (2)
O2—H2⋯O5	0.85 (1)	1.79 (1)	2.638 (2)	172 (3)
O3—H3⋯O1ⁱ	0.85 (1)	1.88 (1)	2.729 (2)	174 (2)
Symmetry code: (i) $[-x+{\script{3\over 2}}, -y+{\script{1\over 2}}, z]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536809044225/xu2651sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809044225/xu2651Isup2.hkl

checkCIF report

Related literature top

For the crystal structure of tetra-n-propyl pentaborate–boric acid co-crystal, see: Freyhardt et al. (1994).

Experimental top

1,3,5-Tris(4-carboxyphenyl)benzene (0.055 g, 0.125 mmol) and boric acid (0.25 mmol, 0.015 g) were dissolved in a water-ethanol (50/100 v/v) mixture. An aqueous solution of 30% tetra-n-propylammonium hydroxide was added in an acid:base ratio of 1.3. Several drops of acetic acid were added and the clear solution set aside for the formation of crystals after several weeks.

Structure description top

For the crystal structure of tetra-n-propyl pentaborate–boric acid co-crystal, see: Freyhardt et al. (1994).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of [N(C₃H₇)₄] [CH₃CO₂]^.H₃BO₃ at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

Tetra-n-propylammonium acetate–boric acid (1/1) top

Crystal data top

C₁₂H₂₈N⁺·C₂H₃O₂⁻·BH₃O₃	F(000) = 1360
M_r = 307.23	D_x = 1.023 Mg m⁻³
Orthorhombic, Pccn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ab 2ac	Cell parameters from 5166 reflections
a = 16.4594 (3) Å	θ = 2.2–25.7°
b = 16.7680 (3) Å	µ = 0.07 mm⁻¹
c = 14.4526 (3) Å	T = 293 K
V = 3988.79 (13) Å³	Block, colorless
Z = 8	0.24 × 0.24 × 0.22 mm

Data collection top

Bruker APEXII diffractometer	2803 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.022
Graphite monochromator	θ_max = 27.5°, θ_min = 2.2°
ω and ω scans	h = −20→21
19907 measured reflections	k = −21→21
4581 independent reflections	l = −18→17

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.051	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.183	w = 1/[σ²(F_o²) + (0.0888P)² + 0.6196P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
4581 reflections	Δρ_max = 0.23 e Å⁻³
204 parameters	Δρ_min = −0.13 e Å⁻³
3 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0029 (8)

Crystal data top

C₁₂H₂₈N⁺·C₂H₃O₂⁻·BH₃O₃	V = 3988.79 (13) Å³
M_r = 307.23	Z = 8
Orthorhombic, Pccn	Mo Kα radiation
a = 16.4594 (3) Å	µ = 0.07 mm⁻¹
b = 16.7680 (3) Å	T = 293 K
c = 14.4526 (3) Å	0.24 × 0.24 × 0.22 mm

Data collection top

Bruker APEXII diffractometer	2803 reflections with I > 2σ(I)
19907 measured reflections	R_int = 0.022
4581 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	3 restraints
wR(F²) = 0.183	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.23 e Å⁻³
4581 reflections	Δρ_min = −0.13 e Å⁻³
204 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.65031 (7)	0.26154 (7)	0.38659 (8)	0.0628 (3)
H1	0.5997 (7)	0.2504 (13)	0.3918 (13)	0.083 (6)*
O2	0.60919 (9)	0.39766 (8)	0.38631 (11)	0.0822 (4)
H2	0.5628 (10)	0.3765 (17)	0.396 (2)	0.131 (11)*
O3	0.74569 (8)	0.36496 (8)	0.37814 (10)	0.0783 (4)
H3	0.7800 (12)	0.3273 (10)	0.3834 (16)	0.104 (8)*
O4	0.49799 (8)	0.22127 (8)	0.39542 (12)	0.0942 (5)
O5	0.46002 (8)	0.34620 (9)	0.41629 (12)	0.0923 (5)
N1	0.57206 (9)	0.42369 (8)	0.68832 (9)	0.0628 (4)
C1	0.48754 (11)	0.42868 (11)	0.64651 (13)	0.0732 (5)
H1A	0.4724	0.4845	0.6421	0.088*
H1B	0.4898	0.4076	0.5840	0.088*
C2	0.42181 (13)	0.38518 (18)	0.69837 (19)	0.1086 (8)
H2A	0.4354	0.3290	0.7024	0.130*
H2B	0.4179	0.4061	0.7608	0.130*
C3	0.34159 (15)	0.39487 (19)	0.6499 (2)	0.1243 (10)
H3A	0.3001	0.3675	0.6841	0.186*
H3B	0.3452	0.3728	0.5888	0.186*
H3C	0.3283	0.4505	0.6459	0.186*
C4	0.57384 (13)	0.45737 (12)	0.78584 (12)	0.0750 (5)
H4A	0.5387	0.4250	0.8245	0.090*
H4B	0.6287	0.4522	0.8097	0.090*
C5	0.54799 (17)	0.54338 (15)	0.79533 (16)	0.1045 (8)
H5A	0.5782	0.5761	0.7520	0.125*
H5B	0.4907	0.5484	0.7809	0.125*
C6	0.5634 (2)	0.5719 (2)	0.8927 (2)	0.1579 (16)
H6A	0.5471	0.6266	0.8982	0.237*
H6B	0.6203	0.5672	0.9066	0.237*
H6C	0.5327	0.5399	0.9353	0.237*
C7	0.62782 (12)	0.46947 (10)	0.62404 (12)	0.0693 (5)
H7A	0.6252	0.4450	0.5633	0.083*
H7B	0.6072	0.5234	0.6182	0.083*
C8	0.71601 (13)	0.47402 (14)	0.65287 (17)	0.0922 (6)
H8A	0.7204	0.5036	0.7103	0.111*
H8B	0.7367	0.4206	0.6635	0.111*
C9	0.76609 (17)	0.51429 (15)	0.5795 (2)	0.1162 (9)
H9A	0.8216	0.5173	0.5995	0.174*
H9B	0.7456	0.5671	0.5690	0.174*
H9C	0.7630	0.4842	0.5231	0.174*
C10	0.59924 (11)	0.33770 (10)	0.69796 (12)	0.0647 (4)
H10A	0.6521	0.3372	0.7276	0.078*
H10B	0.5616	0.3106	0.7390	0.078*
C11	0.60502 (16)	0.29084 (12)	0.61010 (14)	0.0875 (7)
H11A	0.6441	0.3158	0.5691	0.105*
H11B	0.5527	0.2907	0.5793	0.105*
C12	0.63080 (17)	0.20624 (12)	0.62980 (17)	0.0967 (7)
H12A	0.6343	0.1771	0.5727	0.145*
H12B	0.5916	0.1813	0.6696	0.145*
H12C	0.6829	0.2064	0.6596	0.145*
C13	0.44575 (11)	0.27397 (13)	0.40662 (15)	0.0781 (5)
C14	0.35937 (14)	0.24694 (18)	0.4140 (3)	0.1411 (12)
H14A	0.3351	0.2698	0.4682	0.212*
H14B	0.3577	0.1898	0.4183	0.212*
H14C	0.3299	0.2639	0.3601	0.212*
B1	0.66733 (12)	0.34081 (11)	0.38298 (13)	0.0591 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0555 (7)	0.0561 (7)	0.0769 (8)	0.0019 (5)	0.0024 (5)	−0.0096 (5)
O2	0.0748 (9)	0.0586 (7)	0.1131 (12)	0.0115 (6)	0.0009 (8)	0.0088 (7)
O3	0.0670 (8)	0.0588 (7)	0.1091 (11)	−0.0027 (6)	0.0061 (7)	0.0111 (7)
O4	0.0616 (8)	0.0783 (9)	0.1426 (14)	−0.0003 (6)	0.0061 (8)	−0.0330 (8)
O5	0.0673 (8)	0.0771 (9)	0.1325 (13)	0.0137 (7)	0.0019 (8)	−0.0022 (8)
N1	0.0729 (8)	0.0629 (8)	0.0527 (8)	0.0194 (6)	−0.0066 (6)	0.0040 (6)
C1	0.0755 (12)	0.0766 (12)	0.0675 (11)	0.0210 (9)	−0.0140 (9)	0.0027 (9)
C2	0.0780 (14)	0.137 (2)	0.1105 (19)	0.0113 (14)	−0.0109 (13)	0.0199 (16)
C3	0.0839 (16)	0.134 (2)	0.155 (3)	0.0127 (15)	−0.0238 (16)	−0.0001 (19)
C4	0.0852 (12)	0.0848 (12)	0.0548 (10)	0.0224 (10)	−0.0081 (9)	−0.0031 (9)
C5	0.133 (2)	0.0994 (16)	0.0814 (14)	0.0463 (15)	−0.0204 (13)	−0.0260 (12)
C6	0.199 (4)	0.165 (3)	0.109 (2)	0.071 (3)	−0.046 (2)	−0.063 (2)
C7	0.0914 (12)	0.0551 (9)	0.0613 (10)	0.0137 (9)	−0.0014 (9)	0.0079 (7)
C8	0.0873 (14)	0.0955 (15)	0.0937 (15)	0.0014 (11)	−0.0033 (11)	0.0164 (12)
C9	0.114 (2)	0.1079 (18)	0.127 (2)	−0.0218 (15)	0.0101 (16)	0.0175 (16)
C10	0.0757 (11)	0.0598 (9)	0.0584 (10)	0.0148 (8)	−0.0033 (8)	0.0128 (7)
C11	0.1289 (19)	0.0639 (11)	0.0698 (12)	0.0226 (11)	−0.0088 (12)	0.0032 (9)
C12	0.1239 (18)	0.0607 (11)	0.1054 (17)	0.0151 (11)	−0.0040 (14)	−0.0001 (11)
C13	0.0555 (10)	0.0852 (14)	0.0936 (14)	0.0044 (9)	−0.0024 (9)	−0.0198 (11)
C14	0.0603 (13)	0.125 (2)	0.238 (4)	−0.0056 (14)	0.0121 (17)	−0.054 (2)
B1	0.0658 (11)	0.0570 (10)	0.0545 (10)	0.0053 (8)	0.0001 (8)	0.0027 (8)

Geometric parameters (Å, º) top

O1—B1	1.359 (2)	C5—H5B	0.9700
O1—H1	0.856 (9)	C6—H6A	0.9600
O2—B1	1.352 (2)	C6—H6B	0.9600
O2—H2	0.853 (10)	C6—H6C	0.9600
O3—B1	1.354 (2)	C7—C8	1.512 (3)
O3—H3	0.851 (9)	C7—H7A	0.9700
O4—C13	1.244 (2)	C7—H7B	0.9700
O5—C13	1.242 (2)	C8—C9	1.503 (3)
N1—C7	1.515 (2)	C8—H8A	0.9700
N1—C10	1.516 (2)	C8—H8B	0.9700
N1—C4	1.519 (2)	C9—H9A	0.9600
N1—C1	1.519 (2)	C9—H9B	0.9600
C1—C2	1.505 (3)	C9—H9C	0.9600
C1—H1A	0.9700	C10—C11	1.496 (3)
C1—H1B	0.9700	C10—H10A	0.9700
C2—C3	1.503 (3)	C10—H10B	0.9700
C2—H2A	0.9700	C11—C12	1.508 (3)
C2—H2B	0.9700	C11—H11A	0.9700
C3—H3A	0.9600	C11—H11B	0.9700
C3—H3B	0.9600	C12—H12A	0.9600
C3—H3C	0.9600	C12—H12B	0.9600
C4—C5	1.510 (3)	C12—H12C	0.9600
C4—H4A	0.9700	C13—C14	1.496 (3)
C4—H4B	0.9700	C14—H14A	0.9600
C5—C6	1.508 (3)	C14—H14B	0.9600
C5—H5A	0.9700	C14—H14C	0.9600

B1—O1—H1	114.6 (15)	N1—C7—H7A	108.3
B1—O2—H2	110 (2)	C8—C7—H7B	108.3
B1—O3—H3	113.9 (16)	N1—C7—H7B	108.3
C7—N1—C10	111.08 (13)	H7A—C7—H7B	107.4
C7—N1—C4	111.66 (15)	C9—C8—C7	110.8 (2)
C10—N1—C4	105.23 (12)	C9—C8—H8A	109.5
C7—N1—C1	106.44 (13)	C7—C8—H8A	109.5
C10—N1—C1	111.05 (14)	C9—C8—H8B	109.5
C4—N1—C1	111.49 (13)	C7—C8—H8B	109.5
C2—C1—N1	115.70 (16)	H8A—C8—H8B	108.1
C2—C1—H1A	108.4	C8—C9—H9A	109.5
N1—C1—H1A	108.4	C8—C9—H9B	109.5
C2—C1—H1B	108.4	H9A—C9—H9B	109.5
N1—C1—H1B	108.4	C8—C9—H9C	109.5
H1A—C1—H1B	107.4	H9A—C9—H9C	109.5
C3—C2—C1	110.3 (2)	H9B—C9—H9C	109.5
C3—C2—H2A	109.6	C11—C10—N1	116.12 (13)
C1—C2—H2A	109.6	C11—C10—H10A	108.3
C3—C2—H2B	109.6	N1—C10—H10A	108.3
C1—C2—H2B	109.6	C11—C10—H10B	108.3
H2A—C2—H2B	108.1	N1—C10—H10B	108.3
C2—C3—H3A	109.5	H10A—C10—H10B	107.4
C2—C3—H3B	109.5	C10—C11—C12	110.60 (16)
H3A—C3—H3B	109.5	C10—C11—H11A	109.5
C2—C3—H3C	109.5	C12—C11—H11A	109.5
H3A—C3—H3C	109.5	C10—C11—H11B	109.5
H3B—C3—H3C	109.5	C12—C11—H11B	109.5
C5—C4—N1	115.72 (15)	H11A—C11—H11B	108.1
C5—C4—H4A	108.4	C11—C12—H12A	109.5
N1—C4—H4A	108.4	C11—C12—H12B	109.5
C5—C4—H4B	108.4	H12A—C12—H12B	109.5
N1—C4—H4B	108.4	C11—C12—H12C	109.5
H4A—C4—H4B	107.4	H12A—C12—H12C	109.5
C6—C5—C4	109.9 (2)	H12B—C12—H12C	109.5
C6—C5—H5A	109.7	O5—C13—O4	125.24 (18)
C4—C5—H5A	109.7	O5—C13—C14	117.86 (19)
C6—C5—H5B	109.7	O4—C13—C14	116.8 (2)
C4—C5—H5B	109.7	C13—C14—H14A	109.5
H5A—C5—H5B	108.2	C13—C14—H14B	109.5
C5—C6—H6A	109.5	H14A—C14—H14B	109.5
C5—C6—H6B	109.5	C13—C14—H14C	109.5
H6A—C6—H6B	109.5	H14A—C14—H14C	109.5
C5—C6—H6C	109.5	H14B—C14—H14C	109.5
H6A—C6—H6C	109.5	O2—B1—O3	117.74 (16)
H6B—C6—H6C	109.5	O2—B1—O1	122.85 (17)
C8—C7—N1	115.99 (15)	O3—B1—O1	119.39 (15)
C8—C7—H7A	108.3

C7—N1—C1—C2	178.63 (18)	C10—N1—C7—C8	−60.1 (2)
C10—N1—C1—C2	57.6 (2)	C4—N1—C7—C8	57.0 (2)
C4—N1—C1—C2	−59.4 (2)	C1—N1—C7—C8	178.90 (16)
N1—C1—C2—C3	180.0 (2)	N1—C7—C8—C9	174.83 (18)
C7—N1—C4—C5	60.1 (2)	C7—N1—C10—C11	−57.4 (2)
C10—N1—C4—C5	−179.33 (19)	C4—N1—C10—C11	−178.41 (18)
C1—N1—C4—C5	−58.9 (2)	C1—N1—C10—C11	60.8 (2)
N1—C4—C5—C6	−172.4 (2)	N1—C10—C11—C12	−178.76 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O4	0.86 (1)	1.75 (1)	2.600 (2)	175 (2)
O2—H2···O5	0.85 (1)	1.79 (1)	2.638 (2)	172 (3)
O3—H3···O1ⁱ	0.85 (1)	1.88 (1)	2.729 (2)	174 (2)

Symmetry code: (i) −x+3/2, −y+1/2, z.

Experimental details

Crystal data
Chemical formula	C₁₂H₂₈N⁺·C₂H₃O₂⁻·BH₃O₃
M_r	307.23
Crystal system, space group	Orthorhombic, Pccn
Temperature (K)	293
a, b, c (Å)	16.4594 (3), 16.7680 (3), 14.4526 (3)
V (Å³)	3988.79 (13)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.24 × 0.24 × 0.22

Data collection
Diffractometer	Bruker APEXII
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	19907, 4581, 2803
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.183, 1.02
No. of reflections	4581
No. of parameters	204
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.13

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O4	0.86 (1)	1.75 (1)	2.600 (2)	175 (2)
O2—H2···O5	0.85 (1)	1.79 (1)	2.638 (2)	172 (3)
O3—H3···O1ⁱ	0.85 (1)	1.88 (1)	2.729 (2)	174 (2)

Symmetry code: (i) −x+3/2, −y+1/2, z.

Acknowledgements

We thank Beijing Normal University and the University of Malaya for supporting this study.

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