Tetra­butyl­ammonium 4-hy­droxy­benzoate dihydrate

Yang, Y.; Yang, Y.

doi:10.1107/S1600536811022823

organic compounds

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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Page o1703

doi:10.1107/S1600536811022823

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Tetrabutylammonium 4-hydroxybenzoate dihydrate

Yuan Yang ^a and Yunxia Yang ^b ^*

^aCollege of Chemistry and Material Science, Guizhou Normal University, Guiyang 550001, People's Republic of China, and ^bKey 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 9 June 2011; accepted 13 June 2011; online 18 June 2011)

In the title compound, (n-C₄H₉)₄N⁺·C₇H₅O₃⁻·2H₂O, the carboxylate group is twisted slightly out of the plane of the attached benzene ring, the two C—C—C—O torsion angles being −8.9 (2) and −10.7 (2)°. The anion interacts with two water molecules through several O—H⋯O hydrogen bonds, forming wide ribbons along the a axis constructed from two anion–water chains. These ribbons are contained between unclosed diamond-like (16.2 × 15.0 Å) channels constructed by four rows of tetrabutylammonium cations, which are arranged along the [011] and [01 $[\overline{1}]$ ] directions.

Related literature

For related structures of the p-hydroxybenzoate anion with different cations, see: Marsh & Spek (2001 ); Yang et al. (2010 ).

Experimental

Crystal data

C₁₆H₃₆N⁺·C₇H₅O₃⁻·2H₂O
M_r = 415.60
Monoclinic, P 2₁ /c
a = 10.3679 (1) Å
b = 14.9648 (2) Å
c = 16.1851 (2) Å
β = 93.128 (1)°
V = 2507.43 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 296 K
0.49 × 0.43 × 0.20 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.964, T_max = 0.985
20944 measured reflections
5869 independent reflections
4619 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.143
S = 1.03
5869 reflections
265 parameters
7 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.54 e Å⁻³
Δρ_min = −0.52 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2Wⁱ	0.87 (1)	1.75 (1)	2.6125 (17)	174 (2)
O1W—H1WA⋯O2ⁱⁱ	0.86	1.92	2.7660 (18)	168
O1W—H1WB⋯O2Wⁱⁱ	0.85	2.22	2.987 (2)	150
O2W—H2WB⋯O3	0.85	1.80	2.6431 (16)	171
O2W—H2WA⋯O2ⁱⁱ	0.85	1.88	2.7195 (19)	173
Symmetry codes: (i) x-1, y, z; (ii) -x+1, -y+1, -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: 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/S1600536811022823/fj2432sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811022823/fj2432Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811022823/fj2432Isup3.cml

checkCIF report

Comment top

p-Hydroxybenzoic acid, which can be regarded as a planar aromatic molecule that can form various hydrogen bonds through its different functional groups, has been found to interact with varied cations, such as decyl(trimethyl)ammonium and hexamethonium, to form different crystal structures (Marsh et al., 2001; Yang et al., 2010). Herein we report the crystal structure of tetrabutylammonium p-hydroxybenzoate dihydrate, (n-C₄H₉)₄N⁺.C₇H₅O₃^-.2H₂O, in which the carboxyl group of p-hydroxybenzoate anion retorts a small angle of 10.01 (8)° with respect to the phenyl ring and two C—O bonds of the carboxyl group tend to be average (1.264 (2) Å and 1.2553 (18) Å) for the elimination of the proton. The anion makes full use of two independent water molecules to form various O—H···O hydrogen bonds to generate the wide hydrogen-bonded ribbon along the a axis (Fig. 2). In addition, four neighboring tetrabutylammonium cations construct un-closed diamond-like channels to contain the hydrogen-bonded ribbons to generate the final stable structure (Fig. 3). Obviously, water molecules, as a kind of linking unit, play an important role in constructing this structure.

Related literature top

For related structures of p-hydroxybenzoic acid and different cations, see: Marsh & Spek (2001); Yang et al. (2010).

Experimental top

p-Hydroxybenzoic acid (0.25 mmol, 0.035 g) was dissolved in a water-ethanol (50:100 v/v) mixture and a 25% aqueous solution of tetrabutylammonium hydroxide was added according to the molar ratio of 1:3 of acid to base. Colorless block crystals separated after several weeks.

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: 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.
	Fig. 2. Hydrogen-bonded linking pattern of the wide hydrogen-bonded ribbon in the crystal structure of the title compound.
	Fig. 3. Packing diagram of the title compound; all hydrogen atoms bonded to carbon are omitted for clarity and the cations are represented with the open bonds.

Tetrabutylammonium 4-hydroxybenzoate dihydrate top

Crystal data top

C₁₆H₃₆N⁺·C₇H₅O₃⁻·2H₂O	F(000) = 920
M_r = 415.60	D_x = 1.101 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7508 reflections
a = 10.3679 (1) Å	θ = 2.4–27.6°
b = 14.9648 (2) Å	µ = 0.08 mm⁻¹
c = 16.1851 (2) Å	T = 296 K
β = 93.128 (1)°	Block, colorless
V = 2507.43 (5) Å³	0.49 × 0.43 × 0.20 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	5869 independent reflections
Radiation source: fine-focus sealed tube	4619 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
ϕ and ω scans	θ_max = 27.7°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→13
T_min = 0.964, T_max = 0.985	k = −19→19
20944 measured reflections	l = −21→21

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.143	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.062P)² + 0.9941P] where P = (F_o² + 2F_c²)/3
5869 reflections	(Δ/σ)_max = 0.001
265 parameters	Δρ_max = 0.54 e Å⁻³
7 restraints	Δρ_min = −0.52 e Å⁻³

Crystal data top

C₁₆H₃₆N⁺·C₇H₅O₃⁻·2H₂O	V = 2507.43 (5) Å³
M_r = 415.60	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.3679 (1) Å	µ = 0.08 mm⁻¹
b = 14.9648 (2) Å	T = 296 K
c = 16.1851 (2) Å	0.49 × 0.43 × 0.20 mm
β = 93.128 (1)°

Data collection top

Bruker SMART APEX diffractometer	5869 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	4619 reflections with I > 2σ(I)
T_min = 0.964, T_max = 0.985	R_int = 0.018
20944 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	7 restraints
wR(F²) = 0.143	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.54 e Å⁻³
5869 reflections	Δρ_min = −0.52 e Å⁻³
265 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
C1	−0.05049 (13)	0.44078 (9)	0.19491 (9)	0.0322 (3)
O1	−0.16859 (10)	0.44921 (8)	0.22660 (7)	0.0423 (3)
H1	−0.2234 (17)	0.4650 (14)	0.1867 (10)	0.063*
O1W	0.41847 (13)	0.65365 (10)	0.00965 (8)	0.0612 (4)
H1WA	0.4976	0.6424	−0.0004	0.092*
H1WB	0.3751	0.6104	−0.0121	0.092*
N1	0.64105 (11)	0.22051 (7)	0.24724 (7)	0.0305 (3)
C2	−0.03481 (13)	0.43166 (10)	0.11073 (9)	0.0352 (3)
H2A	−0.1067	0.4295	0.0738	0.042*
O2	0.34027 (11)	0.40824 (11)	0.02796 (8)	0.0614 (4)
O2W	0.65516 (11)	0.49064 (11)	0.11146 (10)	0.0759 (5)
H2WB	0.5771	0.4792	0.1219	0.114*
H2WA	0.6579	0.5261	0.0708	0.114*
C3	0.08817 (14)	0.42582 (10)	0.08181 (9)	0.0351 (3)
H3A	0.0981	0.4199	0.0253	0.042*
O3	0.42311 (10)	0.44241 (8)	0.15484 (7)	0.0457 (3)
C4	0.19687 (13)	0.42867 (9)	0.13567 (9)	0.0309 (3)
C5	0.17951 (13)	0.43526 (10)	0.22016 (9)	0.0335 (3)
H5A	0.2513	0.4359	0.2572	0.040*
C6	0.05727 (14)	0.44095 (10)	0.24987 (9)	0.0357 (3)
H6A	0.0472	0.4449	0.3065	0.043*
C7	0.33068 (14)	0.42652 (11)	0.10361 (9)	0.0381 (3)
C8	0.59979 (14)	0.31219 (9)	0.27669 (8)	0.0310 (3)
H8A	0.6767	0.3471	0.2907	0.037*
H8B	0.5527	0.3421	0.2312	0.037*
C9	0.51640 (16)	0.31144 (10)	0.35062 (9)	0.0383 (3)
H9A	0.5581	0.2761	0.3947	0.046*
H9B	0.4337	0.2841	0.3352	0.046*
C10	0.49506 (16)	0.40589 (11)	0.38123 (10)	0.0412 (4)
H10A	0.5767	0.4306	0.4026	0.049*
H10B	0.4633	0.4429	0.3353	0.049*
C11	0.3990 (2)	0.40765 (15)	0.44849 (12)	0.0632 (5)
H11A	0.3879	0.4680	0.4668	0.095*
H11B	0.4308	0.3716	0.4942	0.095*
H11C	0.3176	0.3845	0.4271	0.095*
C12	0.52590 (15)	0.15764 (10)	0.24022 (10)	0.0379 (3)
H12A	0.5545	0.1005	0.2197	0.045*
H12B	0.4956	0.1478	0.2952	0.045*
C13	0.41328 (16)	0.18998 (12)	0.18441 (10)	0.0457 (4)
H13A	0.3893	0.2499	0.2005	0.055*
H13B	0.4386	0.1921	0.1276	0.055*
C14	0.29857 (18)	0.12804 (13)	0.19044 (16)	0.0640 (6)
H14A	0.3222	0.0690	0.1717	0.077*
H14B	0.2777	0.1232	0.2480	0.077*
C15	0.1799 (2)	0.15924 (18)	0.13996 (17)	0.0785 (7)
H15A	0.1104	0.1180	0.1467	0.118*
H15B	0.1988	0.1621	0.0826	0.118*
H15C	0.1552	0.2174	0.1585	0.118*
C16	0.74005 (15)	0.17943 (9)	0.30893 (9)	0.0350 (3)
H16A	0.7040	0.1788	0.3630	0.042*
H16B	0.7542	0.1178	0.2931	0.042*
C17	0.86989 (15)	0.22653 (11)	0.31640 (10)	0.0418 (4)
H17A	0.9062	0.2290	0.2625	0.050*
H17B	0.8579	0.2874	0.3352	0.050*
C18	0.96302 (17)	0.17843 (12)	0.37662 (11)	0.0466 (4)
H18A	0.9263	0.1761	0.4304	0.056*
H18B	0.9740	0.1175	0.3578	0.056*
C19	1.09404 (19)	0.22334 (15)	0.38535 (13)	0.0622 (5)
H19A	1.1492	0.1905	0.4240	0.093*
H19B	1.0841	0.2833	0.4050	0.093*
H19C	1.1318	0.2246	0.3325	0.093*
C20	0.69736 (14)	0.23417 (10)	0.16349 (8)	0.0327 (3)
H20A	0.6308	0.2593	0.1259	0.039*
H20B	0.7665	0.2777	0.1697	0.039*
C21	0.74994 (17)	0.15052 (11)	0.12424 (10)	0.0427 (4)
H21A	0.8106	0.1213	0.1632	0.051*
H21B	0.6796	0.1093	0.1109	0.051*
C22	0.81703 (17)	0.17376 (12)	0.04617 (10)	0.0464 (4)
H22A	0.8877	0.2145	0.0600	0.056*
H22B	0.7564	0.2043	0.0081	0.056*
C23	0.86954 (18)	0.09191 (13)	0.00355 (11)	0.0525 (4)
H23A	0.9106	0.1100	−0.0455	0.079*
H23B	0.7998	0.0518	−0.0112	0.079*
H23C	0.9314	0.0623	0.0404	0.079*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0260 (6)	0.0262 (6)	0.0448 (8)	−0.0008 (5)	0.0035 (6)	0.0035 (6)
O1	0.0271 (5)	0.0484 (6)	0.0519 (7)	0.0028 (5)	0.0067 (5)	0.0059 (5)
O1W	0.0562 (8)	0.0728 (9)	0.0544 (8)	0.0186 (7)	0.0025 (6)	−0.0214 (7)
N1	0.0372 (6)	0.0251 (5)	0.0295 (6)	−0.0007 (5)	0.0055 (5)	0.0017 (4)
C2	0.0258 (7)	0.0369 (7)	0.0420 (8)	−0.0021 (6)	−0.0061 (6)	−0.0032 (6)
O2	0.0365 (6)	0.1066 (11)	0.0417 (7)	0.0004 (7)	0.0071 (5)	0.0015 (7)
O2W	0.0272 (6)	0.1053 (12)	0.0944 (11)	−0.0056 (7)	−0.0034 (6)	0.0513 (10)
C3	0.0313 (7)	0.0401 (8)	0.0335 (7)	0.0001 (6)	−0.0022 (6)	−0.0035 (6)
O3	0.0247 (5)	0.0664 (8)	0.0455 (6)	−0.0036 (5)	−0.0009 (4)	0.0116 (6)
C4	0.0265 (6)	0.0298 (7)	0.0363 (7)	−0.0008 (5)	−0.0001 (5)	0.0042 (5)
C5	0.0283 (7)	0.0371 (7)	0.0346 (7)	−0.0025 (6)	−0.0042 (5)	0.0075 (6)
C6	0.0346 (7)	0.0393 (8)	0.0334 (7)	−0.0011 (6)	0.0030 (6)	0.0056 (6)
C7	0.0281 (7)	0.0473 (9)	0.0391 (8)	−0.0002 (6)	0.0026 (6)	0.0107 (7)
C8	0.0357 (7)	0.0235 (6)	0.0338 (7)	0.0011 (5)	0.0005 (6)	0.0020 (5)
C9	0.0479 (9)	0.0317 (7)	0.0358 (7)	0.0064 (6)	0.0075 (6)	0.0020 (6)
C10	0.0426 (8)	0.0376 (8)	0.0427 (8)	0.0069 (6)	−0.0049 (7)	−0.0084 (6)
C11	0.0745 (13)	0.0632 (12)	0.0530 (11)	0.0182 (10)	0.0151 (10)	−0.0129 (9)
C12	0.0439 (8)	0.0278 (7)	0.0432 (8)	−0.0078 (6)	0.0129 (7)	−0.0030 (6)
C13	0.0452 (9)	0.0481 (9)	0.0438 (9)	−0.0147 (7)	0.0028 (7)	−0.0034 (7)
C14	0.0422 (10)	0.0452 (10)	0.1057 (17)	−0.0099 (8)	0.0135 (10)	−0.0108 (10)
C15	0.0451 (11)	0.0915 (17)	0.0984 (18)	−0.0205 (11)	−0.0005 (11)	−0.0156 (14)
C16	0.0474 (8)	0.0274 (7)	0.0306 (7)	0.0083 (6)	0.0058 (6)	0.0055 (5)
C17	0.0452 (9)	0.0380 (8)	0.0417 (8)	0.0061 (7)	−0.0028 (7)	0.0078 (6)
C18	0.0521 (10)	0.0433 (9)	0.0439 (9)	0.0139 (7)	−0.0024 (7)	0.0067 (7)
C19	0.0495 (10)	0.0715 (13)	0.0642 (12)	0.0145 (9)	−0.0086 (9)	0.0150 (10)
C20	0.0362 (7)	0.0347 (7)	0.0274 (6)	−0.0032 (6)	0.0038 (5)	0.0036 (5)
C21	0.0531 (9)	0.0382 (8)	0.0381 (8)	−0.0055 (7)	0.0131 (7)	−0.0046 (6)
C22	0.0455 (9)	0.0558 (10)	0.0389 (8)	0.0082 (7)	0.0121 (7)	0.0055 (7)
C23	0.0493 (10)	0.0648 (11)	0.0448 (9)	0.0015 (8)	0.0155 (8)	−0.0085 (8)

Geometric parameters (Å, º) top

C1—O1	1.3589 (16)	C12—H12A	0.9700
C1—C2	1.388 (2)	C12—H12B	0.9700
C1—C6	1.390 (2)	C13—C14	1.515 (2)
O1—H1	0.869 (9)	C13—H13A	0.9700
O1W—H1WA	0.8613	C13—H13B	0.9700
O1W—H1WB	0.8528	C14—C15	1.513 (3)
N1—C20	1.5186 (17)	C14—H14A	0.9700
N1—C12	1.5194 (18)	C14—H14B	0.9700
N1—C8	1.5215 (17)	C15—H15A	0.9600
N1—C16	1.5221 (18)	C15—H15B	0.9600
C2—C3	1.385 (2)	C15—H15C	0.9600
C2—H2A	0.9300	C16—C17	1.518 (2)
O2—C7	1.264 (2)	C16—H16A	0.9700
O2W—H2WB	0.8527	C16—H16B	0.9700
O2W—H2WA	0.8463	C17—C18	1.516 (2)
C3—C4	1.3874 (19)	C17—H17A	0.9700
C3—H3A	0.9300	C17—H17B	0.9700
O3—C7	1.2553 (18)	C18—C19	1.515 (3)
C4—C5	1.392 (2)	C18—H18A	0.9700
C4—C7	1.5078 (19)	C18—H18B	0.9700
C5—C6	1.383 (2)	C19—H19A	0.9600
C5—H5A	0.9300	C19—H19B	0.9600
C6—H6A	0.9300	C19—H19C	0.9600
C8—C9	1.5141 (19)	C20—C21	1.518 (2)
C8—H8A	0.9700	C20—H20A	0.9700
C8—H8B	0.9700	C20—H20B	0.9700
C9—C10	1.518 (2)	C21—C22	1.516 (2)
C9—H9A	0.9700	C21—H21A	0.9700
C9—H9B	0.9700	C21—H21B	0.9700
C10—C11	1.515 (2)	C22—C23	1.521 (2)
C10—H10A	0.9700	C22—H22A	0.9700
C10—H10B	0.9700	C22—H22B	0.9700
C11—H11A	0.9600	C23—H23A	0.9600
C11—H11B	0.9600	C23—H23B	0.9600
C11—H11C	0.9600	C23—H23C	0.9600
C12—C13	1.516 (2)

O1—C1—C2	122.41 (13)	C14—C13—H13B	109.6
O1—C1—C6	117.89 (13)	C12—C13—H13B	109.6
C2—C1—C6	119.70 (13)	H13A—C13—H13B	108.1
C1—O1—H1	108.1 (14)	C15—C14—C13	113.23 (18)
H1WA—O1W—H1WB	105.1	C15—C14—H14A	108.9
C20—N1—C12	110.82 (11)	C13—C14—H14A	108.9
C20—N1—C8	106.65 (10)	C15—C14—H14B	108.9
C12—N1—C8	110.40 (11)	C13—C14—H14B	108.9
C20—N1—C16	111.20 (11)	H14A—C14—H14B	107.7
C12—N1—C16	107.33 (11)	C14—C15—H15A	109.5
C8—N1—C16	110.47 (10)	C14—C15—H15B	109.5
C3—C2—C1	119.84 (13)	H15A—C15—H15B	109.5
C3—C2—H2A	120.1	C14—C15—H15C	109.5
C1—C2—H2A	120.1	H15A—C15—H15C	109.5
H2WB—O2W—H2WA	110.6	H15B—C15—H15C	109.5
C2—C3—C4	121.13 (14)	C17—C16—N1	115.34 (11)
C2—C3—H3A	119.4	C17—C16—H16A	108.4
C4—C3—H3A	119.4	N1—C16—H16A	108.4
C3—C4—C5	118.37 (13)	C17—C16—H16B	108.4
C3—C4—C7	120.95 (13)	N1—C16—H16B	108.4
C5—C4—C7	120.67 (12)	H16A—C16—H16B	107.5
C6—C5—C4	121.07 (13)	C18—C17—C16	111.20 (13)
C6—C5—H5A	119.5	C18—C17—H17A	109.4
C4—C5—H5A	119.5	C16—C17—H17A	109.4
C5—C6—C1	119.83 (13)	C18—C17—H17B	109.4
C5—C6—H6A	120.1	C16—C17—H17B	109.4
C1—C6—H6A	120.1	H17A—C17—H17B	108.0
O3—C7—O2	125.68 (14)	C19—C18—C17	112.69 (15)
O3—C7—C4	116.89 (13)	C19—C18—H18A	109.1
O2—C7—C4	117.42 (13)	C17—C18—H18A	109.1
C9—C8—N1	115.04 (11)	C19—C18—H18B	109.1
C9—C8—H8A	108.5	C17—C18—H18B	109.1
N1—C8—H8A	108.5	H18A—C18—H18B	107.8
C9—C8—H8B	108.5	C18—C19—H19A	109.5
N1—C8—H8B	108.5	C18—C19—H19B	109.5
H8A—C8—H8B	107.5	H19A—C19—H19B	109.5
C8—C9—C10	110.53 (12)	C18—C19—H19C	109.5
C8—C9—H9A	109.5	H19A—C19—H19C	109.5
C10—C9—H9A	109.5	H19B—C19—H19C	109.5
C8—C9—H9B	109.5	C21—C20—N1	115.26 (11)
C10—C9—H9B	109.5	C21—C20—H20A	108.5
H9A—C9—H9B	108.1	N1—C20—H20A	108.5
C11—C10—C9	111.34 (15)	C21—C20—H20B	108.5
C11—C10—H10A	109.4	N1—C20—H20B	108.5
C9—C10—H10A	109.4	H20A—C20—H20B	107.5
C11—C10—H10B	109.4	C22—C21—C20	110.57 (13)
C9—C10—H10B	109.4	C22—C21—H21A	109.5
H10A—C10—H10B	108.0	C20—C21—H21A	109.5
C10—C11—H11A	109.5	C22—C21—H21B	109.5
C10—C11—H11B	109.5	C20—C21—H21B	109.5
H11A—C11—H11B	109.5	H21A—C21—H21B	108.1
C10—C11—H11C	109.5	C21—C22—C23	112.66 (15)
H11A—C11—H11C	109.5	C21—C22—H22A	109.1
H11B—C11—H11C	109.5	C23—C22—H22A	109.1
C13—C12—N1	115.04 (12)	C21—C22—H22B	109.1
C13—C12—H12A	108.5	C23—C22—H22B	109.1
N1—C12—H12A	108.5	H22A—C22—H22B	107.8
C13—C12—H12B	108.5	C22—C23—H23A	109.5
N1—C12—H12B	108.5	C22—C23—H23B	109.5
H12A—C12—H12B	107.5	H23A—C23—H23B	109.5
C14—C13—C12	110.37 (15)	C22—C23—H23C	109.5
C14—C13—H13A	109.6	H23A—C23—H23C	109.5
C12—C13—H13A	109.6	H23B—C23—H23C	109.5

O1—C1—C2—C3	178.21 (13)	N1—C8—C9—C10	172.91 (12)
C6—C1—C2—C3	−2.2 (2)	C8—C9—C10—C11	173.19 (14)
C1—C2—C3—C4	0.2 (2)	C20—N1—C12—C13	−61.49 (16)
C2—C3—C4—C5	1.6 (2)	C8—N1—C12—C13	56.45 (16)
C2—C3—C4—C7	−177.18 (14)	C16—N1—C12—C13	176.91 (12)
C3—C4—C5—C6	−1.5 (2)	N1—C12—C13—C14	−172.98 (14)
C7—C4—C5—C6	177.33 (14)	C12—C13—C14—C15	176.70 (17)
C4—C5—C6—C1	−0.5 (2)	C20—N1—C16—C17	51.15 (16)
O1—C1—C6—C5	−178.05 (13)	C12—N1—C16—C17	172.52 (12)
C2—C1—C6—C5	2.3 (2)	C8—N1—C16—C17	−67.07 (15)
C3—C4—C7—O3	169.88 (14)	N1—C16—C17—C18	−177.71 (12)
C5—C4—C7—O3	−8.9 (2)	C16—C17—C18—C19	179.72 (15)
C3—C4—C7—O2	−10.7 (2)	C12—N1—C20—C21	−62.15 (16)
C5—C4—C7—O2	170.54 (15)	C8—N1—C20—C21	177.65 (13)
C20—N1—C8—C9	168.00 (12)	C16—N1—C20—C21	57.15 (16)
C12—N1—C8—C9	47.53 (16)	N1—C20—C21—C22	−173.52 (13)
C16—N1—C8—C9	−71.03 (15)	C20—C21—C22—C23	−179.01 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2Wⁱ	0.87 (1)	1.75 (1)	2.6125 (17)	174 (2)
O1W—H1WA···O2ⁱⁱ	0.86	1.92	2.7660 (18)	168
O1W—H1WB···O2Wⁱⁱ	0.85	2.22	2.987 (2)	150
O2W—H2WB···O3	0.85	1.80	2.6431 (16)	171
O2W—H2WA···O2ⁱⁱ	0.85	1.88	2.7195 (19)	173

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

Experimental details

Crystal data
Chemical formula	C₁₆H₃₆N⁺·C₇H₅O₃⁻·2H₂O
M_r	415.60
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	10.3679 (1), 14.9648 (2), 16.1851 (2)
β (°)	93.128 (1)
V (Å³)	2507.43 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.49 × 0.43 × 0.20

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.964, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	20944, 5869, 4619
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.654

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.143, 1.03
No. of reflections	5869
No. of parameters	265
No. of restraints	7
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.54, −0.52

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), 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
O1—H1···O2Wⁱ	0.869 (9)	1.746 (10)	2.6125 (17)	174 (2)
O1W—H1WA···O2ⁱⁱ	0.86	1.92	2.7660 (18)	168
O1W—H1WB···O2Wⁱⁱ	0.85	2.22	2.987 (2)	150
O2W—H2WB···O3	0.85	1.80	2.6431 (16)	171
O2W—H2WA···O2ⁱⁱ	0.85	1.88	2.7195 (19)	173

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

Acknowledgements

We thank the Science Technology Foundation of Guizhou (No. [2009] 2266) and the Doctoral Foundation of Guizhou Normal University for supporting this study.

References

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