Dimethyl­ammonium 4-nitro­phenolate–4-nitro­phenol (1/1)

Xiao, J.-M.

doi:10.1107/S1600536810008317

organic compounds

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Volume 66| Part 4| April 2010| Page o791

doi:10.1107/S1600536810008317

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Dimethylammonium 4-nitrophenolate–4-nitrophenol (1/1)

Jing-Mei Xiao ^a ^*

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: xjm_cool@163.com

(Received 23 August 2009; accepted 4 March 2010; online 10 March 2010)

The title compound, C₂H₈N⁺·C₆H₄NO₃⁻·C₆H₅NO₃, was synthesized from dimethylamine and 4-nitrophenol in an overall yield of 85%. The dihdral angles between the nphenyl rings and their attached nitro groups are 5.7 (6) and 2.5 (7)°. In the crystal, there are strong hydrogen bonds between the ammonium group and the nitrophenol and nitrophenolate O atoms, and between the nitrophenol and nitrophenolate O atoms, forming a chain along the b-axis direction.

Related literature

For background to dialectric behaviour, see: Horiuchi et al. (2007 ); Kumai et al. (2006 ).

Experimental

Crystal data

C₂H₈N⁺·C₆H₄NO₃⁻·C₆H₅NO₃
M_r = 323.31
Monoclinic, P 2₁ /n
a = 6.3185 (10) Å
b = 16.8867 (10) Å
c = 15.1015 (14) Å
β = 101.928 (10)°
V = 1576.5 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 K
0.40 × 0.30 × 0.20 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.960, T_max = 0.977
15857 measured reflections
3617 independent reflections
1474 reflections with I > 2σ(I)
R_int = 0.134

Refinement

R[F² > 2σ(F²)] = 0.076
wR(F²) = 0.212
S = 1.00
3617 reflections
214 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3B⋯O4ⁱ	0.90	2.11	3.000 (4)	170
N3—H3C⋯O1	0.90	1.82	2.704 (4)	165
O2—H1⋯O1ⁱⁱ	0.91 (4)	1.64 (4)	2.548 (3)	175 (4)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810008317/ez2184sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810008317/ez2184Isup2.hkl

checkCIF report

Comment top

Studying dielectric behavior is the basic method of characterization for potential ferroelectrics in which there is a dielectric anomaly at the transition temperature (Kumai et al., 2006; Horiuchi et al. 2007). In our case, unfortunately, the title compound has no dielectric disuniformity between 80 K to 350 K (m.p. 381–365 K), however its structure is reported here.

In this report we have established unambiguously the structure of dimethylammonium 4-nitrophenolate-4-nitrophenol (1/1) in the solid state by X-ray diffraction analysis, as shown in Fig. 1. Intermolecular N—H···O, N—H···N and O—H···O hydrogen bonds are found between the dimethylammonium cation and 4-nitrophenolate anion and the 4-nitrophenolate cation and 4-nitrophenol molecule, forming a chain along the b-axis.

Related literature top

For background to dialectric behaviour, see: Horiuchi et al. (2007); Kumai et al. (2006).

Experimental top

The title complex was obtained by mixing dimethylamine water solution (33%, 0.68 g) and 4-nitrophenol (5 mmol, 0.695 g) in 15 ml ethanol, in the stoichiometric ratio 1:1. After a few weeks, yellow crystals were obtained by slow evaporation.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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).

Figures top

	Fig. 1. The molecular structure of the title compound, showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A view of the packing of the title compound, stacking along the a axis. Dashed lines indicate hydrogen bonds.

Dimethylammonium 4-nitrophenolate–4-nitrophenol (1/1) top

Crystal data top

C₂H₈N⁺·C₆H₄NO₃⁻·C₆H₅NO₃	F(000) = 680
M_r = 323.31	D_x = 1.362 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 0 reflections
a = 6.3185 (10) Å	θ = 2.7–27.3°
b = 16.8867 (10) Å	µ = 0.11 mm⁻¹
c = 15.1015 (14) Å	T = 293 K
β = 101.928 (10)°	Prism, yellow
V = 1576.5 (3) Å³	0.40 × 0.30 × 0.20 mm
Z = 4

Data collection top

Rigaku Mercury2 diffractometer	3617 independent reflections
Radiation source: fine-focus sealed tube	1474 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.134
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
CCD_Profile_fitting scans	h = −8→8
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −21→21
T_min = 0.960, T_max = 0.977	l = −19→19
15857 measured reflections

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)] = 0.076	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.212	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.0781P)²] where P = (F_o² + 2F_c²)/3
3617 reflections	(Δ/σ)_max < 0.001
214 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₂H₈N⁺·C₆H₄NO₃⁻·C₆H₅NO₃	V = 1576.5 (3) Å³
M_r = 323.31	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.3185 (10) Å	µ = 0.11 mm⁻¹
b = 16.8867 (10) Å	T = 293 K
c = 15.1015 (14) Å	0.40 × 0.30 × 0.20 mm
β = 101.928 (10)°

Data collection top

Rigaku Mercury2 diffractometer	3617 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1474 reflections with I > 2σ(I)
T_min = 0.960, T_max = 0.977	R_int = 0.134
15857 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.076	0 restraints
wR(F²) = 0.212	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.19 e Å⁻³
3617 reflections	Δρ_min = −0.19 e Å⁻³
214 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	0.1166 (5)	0.16858 (18)	0.2568 (2)	0.0476 (8)
C2	−0.0163 (5)	0.13397 (19)	0.3106 (2)	0.0551 (9)
H2	−0.1503	0.1564	0.3115	0.066*
C3	0.0485 (6)	0.0682 (2)	0.3612 (2)	0.0622 (10)
H3A	−0.0433	0.0451	0.3946	0.075*
C4	0.2496 (6)	0.03589 (19)	0.3631 (2)	0.0541 (9)
C5	0.3856 (6)	0.06954 (19)	0.3122 (2)	0.0566 (9)
H5	0.5208	0.0474	0.3131	0.068*
C6	0.3216 (5)	0.13475 (19)	0.2612 (2)	0.0530 (9)
H6	0.4154	0.1575	0.2284	0.064*
C7	0.1727 (5)	0.15350 (19)	0.7572 (2)	0.0492 (9)
C8	−0.0224 (5)	0.1312 (2)	0.7775 (2)	0.0563 (9)
H8	−0.1464	0.1606	0.7553	0.068*
C9	−0.0337 (6)	0.0659 (2)	0.8302 (2)	0.0575 (9)
H9	−0.1655	0.0506	0.8431	0.069*
C10	0.1485 (6)	0.02359 (19)	0.8637 (2)	0.0499 (9)
C11	0.3448 (6)	0.0449 (2)	0.8463 (3)	0.0668 (11)
H11	0.4683	0.0156	0.8696	0.080*
C12	0.3560 (6)	0.1109 (2)	0.7933 (3)	0.0642 (11)
H12	0.4888	0.1267	0.7819	0.077*
C13	−0.0771 (7)	0.2605 (2)	−0.0167 (3)	0.0913 (14)
H13A	−0.0713	0.2802	−0.0758	0.137*
H13B	−0.1768	0.2918	0.0085	0.137*
H13C	−0.1244	0.2064	−0.0214	0.137*
C14	0.3086 (7)	0.2208 (2)	0.0111 (3)	0.0861 (13)
H14A	0.2750	0.1653	0.0100	0.129*
H14B	0.4451	0.2299	0.0514	0.129*
H14C	0.3168	0.2379	−0.0488	0.129*
N1	0.3125 (7)	−0.03649 (18)	0.4114 (2)	0.0694 (9)
N2	0.1366 (7)	−0.04734 (19)	0.9189 (2)	0.0692 (9)
N3	0.1396 (5)	0.26538 (15)	0.0422 (2)	0.0671 (9)
H3B	0.1793	0.3166	0.0478	0.081*
H3C	0.1310	0.2477	0.0976	0.081*
O1	0.0540 (4)	0.23037 (12)	0.20599 (14)	0.0553 (7)
O2	0.1749 (4)	0.21762 (15)	0.70479 (17)	0.0650 (8)
O3	0.4907 (5)	−0.06544 (16)	0.4107 (2)	0.0896 (10)
O4	0.1846 (5)	−0.06924 (15)	0.45180 (19)	0.0896 (10)
O5	0.3015 (6)	−0.08400 (18)	0.9483 (2)	0.1126 (12)
O6	−0.0419 (5)	−0.06671 (15)	0.93146 (17)	0.0791 (9)
H1	0.313 (7)	0.233 (2)	0.704 (3)	0.104 (16)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.057 (2)	0.0400 (19)	0.045 (2)	−0.0029 (17)	0.0077 (17)	−0.0043 (16)
C2	0.061 (2)	0.048 (2)	0.060 (2)	0.0018 (18)	0.0225 (19)	−0.0010 (18)
C3	0.074 (3)	0.051 (2)	0.067 (3)	−0.007 (2)	0.028 (2)	0.0028 (19)
C4	0.069 (2)	0.0402 (19)	0.053 (2)	0.0022 (18)	0.011 (2)	0.0003 (17)
C5	0.060 (2)	0.046 (2)	0.064 (2)	0.0070 (18)	0.012 (2)	−0.0058 (19)
C6	0.053 (2)	0.045 (2)	0.063 (2)	−0.0023 (17)	0.0166 (19)	0.0012 (18)
C7	0.052 (2)	0.0426 (19)	0.055 (2)	−0.0042 (17)	0.0154 (18)	−0.0032 (17)
C8	0.046 (2)	0.053 (2)	0.067 (2)	0.0017 (17)	0.0077 (19)	0.0025 (19)
C9	0.051 (2)	0.058 (2)	0.065 (2)	−0.0081 (19)	0.014 (2)	−0.002 (2)
C10	0.057 (2)	0.046 (2)	0.048 (2)	−0.0057 (18)	0.0156 (18)	0.0008 (16)
C11	0.055 (2)	0.061 (2)	0.087 (3)	0.0125 (19)	0.020 (2)	0.011 (2)
C12	0.054 (2)	0.057 (2)	0.086 (3)	0.0044 (19)	0.024 (2)	0.014 (2)
C13	0.099 (4)	0.077 (3)	0.088 (3)	−0.004 (2)	−0.004 (3)	0.014 (2)
C14	0.098 (3)	0.087 (3)	0.083 (3)	−0.012 (3)	0.041 (3)	−0.013 (2)
N1	0.102 (3)	0.046 (2)	0.059 (2)	0.003 (2)	0.013 (2)	0.0026 (16)
N2	0.089 (3)	0.055 (2)	0.065 (2)	−0.014 (2)	0.018 (2)	−0.0048 (17)
N3	0.102 (3)	0.0431 (17)	0.0586 (19)	−0.0083 (17)	0.022 (2)	0.0005 (15)
O1	0.0664 (16)	0.0450 (13)	0.0580 (15)	0.0080 (12)	0.0205 (12)	0.0035 (12)
O2	0.0596 (18)	0.0565 (16)	0.0798 (18)	−0.0041 (13)	0.0167 (15)	0.0149 (13)
O3	0.095 (2)	0.0640 (18)	0.110 (2)	0.0230 (17)	0.022 (2)	0.0174 (16)
O4	0.132 (3)	0.0583 (17)	0.087 (2)	0.0032 (17)	0.044 (2)	0.0174 (15)
O5	0.102 (3)	0.084 (2)	0.148 (3)	0.0146 (19)	0.018 (2)	0.054 (2)
O6	0.098 (2)	0.0679 (18)	0.078 (2)	−0.0276 (16)	0.0314 (17)	0.0043 (14)

Geometric parameters (Å, º) top

C1—O1	1.307 (3)	C10—N2	1.471 (4)
C1—C6	1.405 (4)	C11—C12	1.382 (4)
C1—C2	1.410 (4)	C11—H11	0.9300
C2—C3	1.362 (4)	C12—H12	0.9300
C2—H2	0.9300	C13—N3	1.473 (5)
C3—C4	1.378 (5)	C13—H13A	0.9600
C3—H3A	0.9300	C13—H13B	0.9600
C4—C5	1.387 (4)	C13—H13C	0.9600
C4—N1	1.436 (4)	C14—N3	1.462 (4)
C5—C6	1.357 (4)	C14—H14A	0.9600
C5—H5	0.9300	C14—H14B	0.9600
C6—H6	0.9300	C14—H14C	0.9600
C7—O2	1.343 (4)	N1—O3	1.229 (4)
C7—C12	1.376 (4)	N1—O4	1.239 (4)
C7—C8	1.382 (4)	N2—O5	1.214 (4)
C8—C9	1.371 (4)	N2—O6	1.226 (4)
C8—H8	0.9300	N3—H3B	0.9000
C9—C10	1.360 (4)	N3—H3C	0.9000
C9—H9	0.9300	O2—H1	0.91 (4)
C10—C11	1.368 (4)

O1—C1—C6	121.1 (3)	C10—C11—H11	120.6
O1—C1—C2	121.7 (3)	C12—C11—H11	120.6
C6—C1—C2	117.2 (3)	C7—C12—C11	120.7 (3)
C3—C2—C1	121.0 (3)	C7—C12—H12	119.7
C3—C2—H2	119.5	C11—C12—H12	119.7
C1—C2—H2	119.5	N3—C13—H13A	109.5
C2—C3—C4	120.2 (3)	N3—C13—H13B	109.5
C2—C3—H3A	119.9	H13A—C13—H13B	109.5
C4—C3—H3A	119.9	N3—C13—H13C	109.5
C3—C4—C5	120.0 (3)	H13A—C13—H13C	109.5
C3—C4—N1	120.3 (3)	H13B—C13—H13C	109.5
C5—C4—N1	119.4 (3)	N3—C14—H14A	109.5
C6—C5—C4	120.1 (3)	N3—C14—H14B	109.5
C6—C5—H5	120.0	H14A—C14—H14B	109.5
C4—C5—H5	120.0	N3—C14—H14C	109.5
C5—C6—C1	121.3 (3)	H14A—C14—H14C	109.5
C5—C6—H6	119.3	H14B—C14—H14C	109.5
C1—C6—H6	119.3	O3—N1—O4	121.2 (3)
O2—C7—C12	122.9 (3)	O3—N1—C4	119.5 (4)
O2—C7—C8	117.9 (3)	O4—N1—C4	119.3 (4)
C12—C7—C8	119.1 (3)	O5—N2—O6	123.7 (3)
C9—C8—C7	120.2 (3)	O5—N2—C10	118.8 (4)
C9—C8—H8	119.9	O6—N2—C10	117.5 (4)
C7—C8—H8	119.9	C14—N3—C13	115.2 (3)
C10—C9—C8	119.8 (3)	C14—N3—H3B	108.5
C10—C9—H9	120.1	C13—N3—H3B	108.5
C8—C9—H9	120.1	C14—N3—H3C	108.5
C9—C10—C11	121.4 (3)	C13—N3—H3C	108.5
C9—C10—N2	120.0 (3)	H3B—N3—H3C	107.5
C11—C10—N2	118.6 (3)	C7—O2—H1	111 (3)
C10—C11—C12	118.7 (3)

O1—C1—C2—C3	178.1 (3)	C8—C9—C10—N2	−178.9 (3)
C6—C1—C2—C3	−3.0 (5)	C9—C10—C11—C12	−0.2 (5)
C1—C2—C3—C4	2.3 (5)	N2—C10—C11—C12	179.1 (3)
C2—C3—C4—C5	−1.0 (5)	O2—C7—C12—C11	−179.5 (3)
C2—C3—C4—N1	−175.7 (3)	C8—C7—C12—C11	2.4 (5)
C3—C4—C5—C6	0.6 (5)	C10—C11—C12—C7	−1.2 (5)
N1—C4—C5—C6	175.3 (3)	C3—C4—N1—O3	178.4 (3)
C4—C5—C6—C1	−1.4 (5)	C5—C4—N1—O3	3.7 (5)
O1—C1—C6—C5	−178.5 (3)	C3—C4—N1—O4	−0.5 (5)
C2—C1—C6—C5	2.6 (5)	C5—C4—N1—O4	−175.2 (3)
O2—C7—C8—C9	179.5 (3)	C9—C10—N2—O5	−179.8 (4)
C12—C7—C8—C9	−2.3 (5)	C11—C10—N2—O5	1.0 (5)
C7—C8—C9—C10	0.9 (5)	C9—C10—N2—O6	1.4 (5)
C8—C9—C10—C11	0.3 (5)	C11—C10—N2—O6	−177.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···O4ⁱ	0.90	2.11	3.000 (4)	170
N3—H3C···O1	0.90	1.82	2.704 (4)	165
O2—H1···O1ⁱⁱ	0.91 (4)	1.64 (4)	2.548 (3)	175 (4)

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

Experimental details

Crystal data
Chemical formula	C₂H₈N⁺·C₆H₄NO₃⁻·C₆H₅NO₃
M_r	323.31
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	6.3185 (10), 16.8867 (10), 15.1015 (14)
β (°)	101.928 (10)
V (Å³)	1576.5 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.40 × 0.30 × 0.20

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.960, 0.977
No. of measured, independent and observed [I > 2σ(I)] reflections	15857, 3617, 1474
R_int	0.134
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.076, 0.212, 1.00
No. of reflections	3617
No. of parameters	214
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.19

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···O4ⁱ	0.90	2.11	3.000 (4)	169.7
N3—H3C···O1	0.90	1.82	2.704 (4)	164.8
O2—H1···O1ⁱⁱ	0.91 (4)	1.64 (4)	2.548 (3)	175 (4)

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

Acknowledgements

This work was supported by a start-up grant from Southeast University.

References

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