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Acta Crystallogr Sect E Struct Rep Online. 2010 April 1; 66(Pt 4): o791.
Published online 2010 March 10. doi:  10.1107/S1600536810008317
PMCID: PMC2984031

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

Abstract

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 [triangle]); Kumai et al. (2006 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0o791-scheme1.jpg

Experimental

Crystal data

  • C2H8N+·C6H4NO3 ·C6H5NO3
  • M r = 323.31
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0o791-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.076
  • wR(F 2) = 0.212
  • S = 1.00
  • 3617 reflections
  • 214 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.19 e Å−3
  • Δρmin = −0.19 e Å−3

Data collection: CrystalClear (Rigaku, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

All H-atoms were located from difference maps and those on N and C were positioned geometrically and refined using a riding model with (N—H = 0.90, C—H = 0.93 and 0.96 Å for aromatic, methyl H respectively) and constrained to ride on their parent atoms with Uiso(H) = xUeq(C), where x = 1.5 for methyl H and x = 1.2 for all other H atoms. Atom H1 on atom O2 was refined isotropically.

Figures

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.

Crystal data

C2H8N+·C6H4NO3·C6H5NO3F(000) = 680
Mr = 323.31Dx = 1.362 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 0 reflections
a = 6.3185 (10) Åθ = 2.7–27.3°
b = 16.8867 (10) ŵ = 0.11 mm1
c = 15.1015 (14) ÅT = 293 K
β = 101.928 (10)°Prism, yellow
V = 1576.5 (3) Å30.40 × 0.30 × 0.20 mm
Z = 4

Data collection

Rigaku Mercury2 diffractometer3617 independent reflections
Radiation source: fine-focus sealed tube1474 reflections with I > 2σ(I)
graphiteRint = 0.134
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.0°
CCD_Profile_fitting scansh = −8→8
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)k = −21→21
Tmin = 0.960, Tmax = 0.977l = −19→19
15857 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.076Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.212H atoms treated by a mixture of independent and constrained refinement
S = 1.00w = 1/[σ2(Fo2) + (0.0781P)2] where P = (Fo2 + 2Fc2)/3
3617 reflections(Δ/σ)max < 0.001
214 parametersΔρmax = 0.19 e Å3
0 restraintsΔρmin = −0.18 e Å3

Special details

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)

xyzUiso*/Ueq
C10.1166 (5)0.16858 (18)0.2568 (2)0.0476 (8)
C2−0.0163 (5)0.13397 (19)0.3106 (2)0.0551 (9)
H2−0.15030.15640.31150.066*
C30.0485 (6)0.0682 (2)0.3612 (2)0.0622 (10)
H3A−0.04330.04510.39460.075*
C40.2496 (6)0.03589 (19)0.3631 (2)0.0541 (9)
C50.3856 (6)0.06954 (19)0.3122 (2)0.0566 (9)
H50.52080.04740.31310.068*
C60.3216 (5)0.13475 (19)0.2612 (2)0.0530 (9)
H60.41540.15750.22840.064*
C70.1727 (5)0.15350 (19)0.7572 (2)0.0492 (9)
C8−0.0224 (5)0.1312 (2)0.7775 (2)0.0563 (9)
H8−0.14640.16060.75530.068*
C9−0.0337 (6)0.0659 (2)0.8302 (2)0.0575 (9)
H9−0.16550.05060.84310.069*
C100.1485 (6)0.02359 (19)0.8637 (2)0.0499 (9)
C110.3448 (6)0.0449 (2)0.8463 (3)0.0668 (11)
H110.46830.01560.86960.080*
C120.3560 (6)0.1109 (2)0.7933 (3)0.0642 (11)
H120.48880.12670.78190.077*
C13−0.0771 (7)0.2605 (2)−0.0167 (3)0.0913 (14)
H13A−0.07130.2802−0.07580.137*
H13B−0.17680.29180.00850.137*
H13C−0.12440.2064−0.02140.137*
C140.3086 (7)0.2208 (2)0.0111 (3)0.0861 (13)
H14A0.27500.16530.01000.129*
H14B0.44510.22990.05140.129*
H14C0.31680.2379−0.04880.129*
N10.3125 (7)−0.03649 (18)0.4114 (2)0.0694 (9)
N20.1366 (7)−0.04734 (19)0.9189 (2)0.0692 (9)
N30.1396 (5)0.26538 (15)0.0422 (2)0.0671 (9)
H3B0.17930.31660.04780.081*
H3C0.13100.24770.09760.081*
O10.0540 (4)0.23037 (12)0.20599 (14)0.0553 (7)
O20.1749 (4)0.21762 (15)0.70479 (17)0.0650 (8)
O30.4907 (5)−0.06544 (16)0.4107 (2)0.0896 (10)
O40.1846 (5)−0.06924 (15)0.45180 (19)0.0896 (10)
O50.3015 (6)−0.08400 (18)0.9483 (2)0.1126 (12)
O6−0.0419 (5)−0.06671 (15)0.93146 (17)0.0791 (9)
H10.313 (7)0.233 (2)0.704 (3)0.104 (16)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.057 (2)0.0400 (19)0.045 (2)−0.0029 (17)0.0077 (17)−0.0043 (16)
C20.061 (2)0.048 (2)0.060 (2)0.0018 (18)0.0225 (19)−0.0010 (18)
C30.074 (3)0.051 (2)0.067 (3)−0.007 (2)0.028 (2)0.0028 (19)
C40.069 (2)0.0402 (19)0.053 (2)0.0022 (18)0.011 (2)0.0003 (17)
C50.060 (2)0.046 (2)0.064 (2)0.0070 (18)0.012 (2)−0.0058 (19)
C60.053 (2)0.045 (2)0.063 (2)−0.0023 (17)0.0166 (19)0.0012 (18)
C70.052 (2)0.0426 (19)0.055 (2)−0.0042 (17)0.0154 (18)−0.0032 (17)
C80.046 (2)0.053 (2)0.067 (2)0.0017 (17)0.0077 (19)0.0025 (19)
C90.051 (2)0.058 (2)0.065 (2)−0.0081 (19)0.014 (2)−0.002 (2)
C100.057 (2)0.046 (2)0.048 (2)−0.0057 (18)0.0156 (18)0.0008 (16)
C110.055 (2)0.061 (2)0.087 (3)0.0125 (19)0.020 (2)0.011 (2)
C120.054 (2)0.057 (2)0.086 (3)0.0044 (19)0.024 (2)0.014 (2)
C130.099 (4)0.077 (3)0.088 (3)−0.004 (2)−0.004 (3)0.014 (2)
C140.098 (3)0.087 (3)0.083 (3)−0.012 (3)0.041 (3)−0.013 (2)
N10.102 (3)0.046 (2)0.059 (2)0.003 (2)0.013 (2)0.0026 (16)
N20.089 (3)0.055 (2)0.065 (2)−0.014 (2)0.018 (2)−0.0048 (17)
N30.102 (3)0.0431 (17)0.0586 (19)−0.0083 (17)0.022 (2)0.0005 (15)
O10.0664 (16)0.0450 (13)0.0580 (15)0.0080 (12)0.0205 (12)0.0035 (12)
O20.0596 (18)0.0565 (16)0.0798 (18)−0.0041 (13)0.0167 (15)0.0149 (13)
O30.095 (2)0.0640 (18)0.110 (2)0.0230 (17)0.022 (2)0.0174 (16)
O40.132 (3)0.0583 (17)0.087 (2)0.0032 (17)0.044 (2)0.0174 (15)
O50.102 (3)0.084 (2)0.148 (3)0.0146 (19)0.018 (2)0.054 (2)
O60.098 (2)0.0679 (18)0.078 (2)−0.0276 (16)0.0314 (17)0.0043 (14)

Geometric parameters (Å, °)

C1—O11.307 (3)C10—N21.471 (4)
C1—C61.405 (4)C11—C121.382 (4)
C1—C21.410 (4)C11—H110.9300
C2—C31.362 (4)C12—H120.9300
C2—H20.9300C13—N31.473 (5)
C3—C41.378 (5)C13—H13A0.9600
C3—H3A0.9300C13—H13B0.9600
C4—C51.387 (4)C13—H13C0.9600
C4—N11.436 (4)C14—N31.462 (4)
C5—C61.357 (4)C14—H14A0.9600
C5—H50.9300C14—H14B0.9600
C6—H60.9300C14—H14C0.9600
C7—O21.343 (4)N1—O31.229 (4)
C7—C121.376 (4)N1—O41.239 (4)
C7—C81.382 (4)N2—O51.214 (4)
C8—C91.371 (4)N2—O61.226 (4)
C8—H80.9300N3—H3B0.9000
C9—C101.360 (4)N3—H3C0.9000
C9—H90.9300O2—H10.91 (4)
C10—C111.368 (4)
O1—C1—C6121.1 (3)C10—C11—H11120.6
O1—C1—C2121.7 (3)C12—C11—H11120.6
C6—C1—C2117.2 (3)C7—C12—C11120.7 (3)
C3—C2—C1121.0 (3)C7—C12—H12119.7
C3—C2—H2119.5C11—C12—H12119.7
C1—C2—H2119.5N3—C13—H13A109.5
C2—C3—C4120.2 (3)N3—C13—H13B109.5
C2—C3—H3A119.9H13A—C13—H13B109.5
C4—C3—H3A119.9N3—C13—H13C109.5
C3—C4—C5120.0 (3)H13A—C13—H13C109.5
C3—C4—N1120.3 (3)H13B—C13—H13C109.5
C5—C4—N1119.4 (3)N3—C14—H14A109.5
C6—C5—C4120.1 (3)N3—C14—H14B109.5
C6—C5—H5120.0H14A—C14—H14B109.5
C4—C5—H5120.0N3—C14—H14C109.5
C5—C6—C1121.3 (3)H14A—C14—H14C109.5
C5—C6—H6119.3H14B—C14—H14C109.5
C1—C6—H6119.3O3—N1—O4121.2 (3)
O2—C7—C12122.9 (3)O3—N1—C4119.5 (4)
O2—C7—C8117.9 (3)O4—N1—C4119.3 (4)
C12—C7—C8119.1 (3)O5—N2—O6123.7 (3)
C9—C8—C7120.2 (3)O5—N2—C10118.8 (4)
C9—C8—H8119.9O6—N2—C10117.5 (4)
C7—C8—H8119.9C14—N3—C13115.2 (3)
C10—C9—C8119.8 (3)C14—N3—H3B108.5
C10—C9—H9120.1C13—N3—H3B108.5
C8—C9—H9120.1C14—N3—H3C108.5
C9—C10—C11121.4 (3)C13—N3—H3C108.5
C9—C10—N2120.0 (3)H3B—N3—H3C107.5
C11—C10—N2118.6 (3)C7—O2—H1111 (3)
C10—C11—C12118.7 (3)
O1—C1—C2—C3178.1 (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—C42.3 (5)N2—C10—C11—C12179.1 (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—C112.4 (5)
C3—C4—C5—C60.6 (5)C10—C11—C12—C7−1.2 (5)
N1—C4—C5—C6175.3 (3)C3—C4—N1—O3178.4 (3)
C4—C5—C6—C1−1.4 (5)C5—C4—N1—O33.7 (5)
O1—C1—C6—C5−178.5 (3)C3—C4—N1—O4−0.5 (5)
C2—C1—C6—C52.6 (5)C5—C4—N1—O4−175.2 (3)
O2—C7—C8—C9179.5 (3)C9—C10—N2—O5−179.8 (4)
C12—C7—C8—C9−2.3 (5)C11—C10—N2—O51.0 (5)
C7—C8—C9—C100.9 (5)C9—C10—N2—O61.4 (5)
C8—C9—C10—C110.3 (5)C11—C10—N2—O6−177.9 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N3—H3B···O4i0.902.113.000 (4)170
N3—H3C···O10.901.822.704 (4)165
O2—H1···O1ii0.91 (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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: EZ2184).

References

  • Horiuchi, S., Kumai, R. & Tokura, Y. (2007). Angew. Chem. Int. Ed.46, 3497–3501. [PubMed]
  • Kumai, R., Horiuchi, S., Okimoto, Y. & Tokura, Y. (2006). J. Chem. Phys.125, 084715. [PubMed]
  • Rigaku (2005). CrystalClear Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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