Literature DB >> 21577526

4-Chloro-anilinium 2-carb-oxy-4,5-dichloro-benzoate.

Graham Smith, Urs D Wermuth, Jonathan M White.   

Abstract

The structure of the 1:1 proton-transfer compound of 4-chloro-aniline with 4,5-dichloro-phthalic acid (DCPA), viz. C(6)H(7)ClN(+)·C(8)H(3)Cl(2)O(4) (-), has been determined at 130 K. The non-planar hydrogen phthalate anions and the 4-chloro-anilinium cations form two-dimensional O-H⋯O and N-H⋯O hydrogen-bonded substructures which have no peripheral extension. Between the sheets there are weak π-π associations between alternating cation-anion aromatic ring systems [shortest centroid-centroid separation = 3.735 (4) Å].

Entities:  

Year:  2009        PMID： 21577526      PMCID： PMC2970019          DOI： 10.1107/S160053680903044X

Source DB:  PubMed          Journal:  Acta Crystallogr Sect E Struct Rep Online        ISSN： 1600-5368


Related literature

For the structures of other hydrogen DCPA salts with aromatic Lewis bases showing similar two-dimensional substructures, see: Smith et al. (2008. This contrasts with the majority of the compounds in which the DCPA anion is planar with a short intra­molecular carboxylic acid hydrogen bond, see: Smith et al. (2007 ▶, 2008a ▶, 2009 ▶).

Experimental

Crystal data

C6H7ClN+·C8H3Cl2O4 − M = 362.58 Monoclinic, a = 12.8171 (8) Å b = 7.5954 (3) Å c = 16.0909 (6) Å β = 109.815 (5)° V = 1473.72 (13) Å3 Z = 4 Cu Kα radiation μ = 5.80 mm−1 T = 130 K 0.34 × 0.27 × 0.05 mm

Data collection

Oxford Diffraction Gemini Ultra CCD-detector diffractometer Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.201, T max = 0.748 3680 measured reflections 2288 independent reflections 1879 reflections with I > 2σ(I) R int = 0.061

Refinement

R[F 2 > 2σ(F 2)] = 0.062 wR(F 2) = 0.175 S = 1.00 2288 reflections 215 parameters 1 restraint H atoms treated by a mixture of independent and constrained refinement Δρmax = 0.64 e Å−3 Δρmin = −0.56 e Å−3 Absolute structure: Flack (1983 ▶), 723 Friedel pairs Flack parameter: 0.04 (3) Data collection: CrysAlis CCD (Oxford Diffraction, 2007 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2007 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON. Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680903044X/at2844sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S160053680903044X/at2844Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report
C6H7ClN+·C8H3Cl2O4−F(000) = 736
Mr = 362.58Dx = 1.634 Mg m−3
Monoclinic, C2Melting point: 492 K
Hall symbol: C 2yCu Kα radiation, λ = 1.54184 Å
a = 12.8171 (8) ÅCell parameters from 1721 reflections
b = 7.5954 (3) Åθ = 2.9–71.8°
c = 16.0909 (6) ŵ = 5.80 mm−1
β = 109.815 (5)°T = 130 K
V = 1473.72 (13) Å3Plate, colourless
Z = 40.34 × 0.27 × 0.05 mm
Oxford Diffraction Gemini Ultra CCD-detector diffractometer2288 independent reflections
Radiation source: Enhance Ultra (Cu) X-ray source1879 reflections with I > 2σ(I)
mirrorRint = 0.061
ω scansθmax = 72.1°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −15→14
Tmin = 0.201, Tmax = 0.748k = −9→8
3680 measured reflectionsl = −15→19
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.062H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.175w = 1/[σ2(Fo2) + (0.135P)2] where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
2288 reflectionsΔρmax = 0.64 e Å−3
215 parametersΔρmin = −0.56 e Å−3
1 restraintAbsolute structure: Flack (1983), 723 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.04 (3)
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles
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.
xyzUiso*/Ueq
Cl40.39571 (14)0.8094 (3)0.55613 (9)0.0377 (5)
Cl50.37318 (14)0.3980 (3)0.58289 (9)0.0418 (5)
O110.5642 (4)0.3295 (7)0.9286 (3)0.0348 (14)
O120.6750 (3)0.5632 (6)0.9688 (2)0.0282 (11)
O210.7198 (3)0.9010 (6)0.8943 (2)0.0243 (10)
O220.5704 (3)0.9285 (6)0.9364 (2)0.0272 (13)
C10.5441 (5)0.5652 (8)0.8257 (4)0.0244 (16)
C20.5583 (5)0.7457 (8)0.8141 (3)0.0222 (16)
C30.5118 (5)0.8181 (9)0.7299 (4)0.0257 (16)
C40.4522 (5)0.7126 (9)0.6581 (4)0.0289 (18)
C50.4402 (5)0.5333 (9)0.6707 (4)0.0311 (18)
C60.4861 (5)0.4599 (9)0.7537 (4)0.0276 (17)
C110.5956 (5)0.4739 (9)0.9139 (4)0.0244 (17)
C210.6212 (4)0.8673 (7)0.8897 (3)0.0237 (16)
Cl4A0.13666 (14)0.6564 (2)0.60330 (9)0.0387 (5)
N1A0.3688 (4)1.1240 (7)0.9059 (3)0.0234 (14)
C1A0.3149 (5)1.0096 (8)0.8304 (3)0.0233 (16)
C2A0.2717 (5)1.0813 (9)0.7460 (4)0.0292 (17)
C3A0.2162 (5)0.9729 (9)0.6753 (4)0.0300 (18)
C4A0.2064 (5)0.7965 (9)0.6903 (4)0.0286 (17)
C5A0.2510 (5)0.7210 (9)0.7743 (4)0.0283 (17)
C6A0.3054 (5)0.8316 (9)0.8443 (3)0.0263 (18)
H30.520500.937600.721400.0310*
H60.478300.340000.761700.0340*
H120.700 (3)0.509 (4)1.015 (2)0.042 (11)*
H2A0.279901.200800.737100.0340*
H3A0.186101.019000.618600.0360*
H5A0.244500.601000.782900.0340*
H6A0.335600.785600.901000.0320*
H11A0.425 (3)1.179 (4)0.897 (3)0.035 (10)*
H12A0.393 (4)1.059 (3)0.954 (2)0.041 (11)*
H13A0.320 (4)1.202 (4)0.910 (3)0.038 (11)*
U11U22U33U12U13U23
Cl40.0444 (9)0.0546 (10)0.0141 (6)−0.0005 (8)0.0035 (5)0.0056 (6)
Cl50.0482 (10)0.0479 (10)0.0206 (6)−0.0014 (8)0.0002 (6)−0.0120 (6)
O110.038 (2)0.035 (3)0.026 (2)−0.011 (2)0.0037 (17)0.0002 (19)
O120.031 (2)0.034 (2)0.0147 (17)0.0000 (18)0.0015 (15)0.0039 (16)
O210.0266 (18)0.031 (2)0.0155 (15)−0.0022 (18)0.0075 (14)−0.0015 (15)
O220.026 (2)0.033 (3)0.0203 (17)0.0019 (17)0.0050 (15)−0.0038 (16)
C10.028 (3)0.027 (3)0.017 (2)0.001 (2)0.006 (2)−0.004 (2)
C20.023 (3)0.029 (3)0.015 (2)−0.001 (2)0.007 (2)−0.001 (2)
C30.028 (3)0.029 (3)0.020 (2)0.001 (3)0.008 (2)−0.001 (2)
C40.029 (3)0.043 (4)0.011 (2)0.002 (3)0.002 (2)0.000 (2)
C50.030 (3)0.041 (4)0.017 (2)−0.005 (3)0.001 (2)−0.006 (3)
C60.030 (3)0.031 (3)0.024 (3)−0.003 (3)0.012 (2)−0.002 (2)
C110.022 (3)0.033 (3)0.019 (3)−0.003 (2)0.008 (2)−0.001 (2)
C210.023 (3)0.030 (3)0.018 (2)−0.002 (2)0.007 (2)−0.001 (2)
Cl4A0.0489 (9)0.0436 (10)0.0201 (6)−0.0072 (8)0.0073 (6)−0.0054 (6)
N1A0.023 (2)0.030 (3)0.016 (2)0.001 (2)0.0050 (16)0.0040 (19)
C1A0.024 (3)0.029 (3)0.017 (2)−0.004 (2)0.007 (2)−0.003 (2)
C2A0.036 (3)0.029 (3)0.020 (3)0.005 (3)0.006 (2)0.001 (2)
C3A0.034 (3)0.039 (4)0.016 (2)0.000 (3)0.007 (2)0.001 (2)
C4A0.035 (3)0.029 (3)0.022 (3)0.003 (3)0.010 (2)0.000 (2)
C5A0.032 (3)0.031 (3)0.021 (3)−0.002 (3)0.008 (2)0.002 (2)
C6A0.029 (3)0.032 (4)0.018 (2)0.000 (3)0.008 (2)0.002 (2)
Cl4—C41.718 (6)C2—C31.395 (8)
Cl5—C51.723 (7)C3—C41.401 (9)
Cl4A—C4A1.744 (7)C4—C51.393 (10)
O11—C111.219 (9)C5—C61.381 (9)
O12—C111.291 (8)C3—H30.9300
O21—C211.267 (7)C6—H60.9300
O22—C211.240 (6)C1A—C6A1.383 (9)
O12—H120.81 (3)C1A—C2A1.392 (8)
N1A—C1A1.463 (7)C2A—C3A1.389 (9)
N1A—H13A0.89 (4)C3A—C4A1.375 (10)
N1A—H12A0.88 (3)C4A—C5A1.400 (9)
N1A—H11A0.88 (4)C5A—C6A1.389 (8)
C1—C21.404 (9)C2A—H2A0.9300
C1—C111.515 (9)C3A—H3A0.9300
C1—C61.397 (9)C5A—H5A0.9300
C2—C211.523 (7)C6A—H6A0.9300
C11—O12—H12110 (2)O22—C21—C2117.9 (5)
H11A—N1A—H12A110 (4)O21—C21—C2114.6 (5)
H11A—N1A—H13A109 (4)C2—C3—H3120.00
C1A—N1A—H13A108 (3)C4—C3—H3120.00
C1A—N1A—H11A109 (3)C5—C6—H6120.00
H12A—N1A—H13A111 (4)C1—C6—H6120.00
C6—C1—C11117.1 (6)C2A—C1A—C6A120.9 (5)
C2—C1—C11122.5 (5)N1A—C1A—C6A119.3 (4)
C2—C1—C6120.4 (5)N1A—C1A—C2A119.8 (5)
C1—C2—C3118.8 (5)C1A—C2A—C3A119.4 (6)
C3—C2—C21118.2 (5)C2A—C3A—C4A119.1 (6)
C1—C2—C21122.9 (5)Cl4A—C4A—C3A120.4 (5)
C2—C3—C4120.6 (6)Cl4A—C4A—C5A117.1 (5)
C3—C4—C5119.7 (6)C3A—C4A—C5A122.5 (6)
Cl4—C4—C5121.7 (5)C4A—C5A—C6A117.6 (6)
Cl4—C4—C3118.6 (5)C1A—C6A—C5A120.5 (5)
Cl5—C5—C6118.9 (5)C1A—C2A—H2A120.00
C4—C5—C6120.2 (6)C3A—C2A—H2A120.00
Cl5—C5—C4120.9 (5)C2A—C3A—H3A120.00
C1—C6—C5120.2 (6)C4A—C3A—H3A120.00
O11—C11—C1121.7 (6)C4A—C5A—H5A121.00
O11—C11—O12125.1 (6)C6A—C5A—H5A121.00
O12—C11—C1113.1 (6)C1A—C6A—H6A120.00
O21—C21—O22127.4 (5)C5A—C6A—H6A120.00
C6—C1—C2—C31.2 (10)C2—C3—C4—C5−0.7 (10)
C6—C1—C2—C21−179.6 (6)Cl4—C4—C5—Cl53.1 (9)
C11—C1—C2—C3177.4 (6)Cl4—C4—C5—C6−179.6 (5)
C11—C1—C2—C21−3.4 (10)C3—C4—C5—Cl5−176.9 (5)
C2—C1—C6—C5−1.4 (10)C3—C4—C5—C60.5 (10)
C11—C1—C6—C5−177.8 (6)Cl5—C5—C6—C1177.9 (5)
C2—C1—C11—O11163.7 (7)C4—C5—C6—C10.5 (10)
C2—C1—C11—O12−17.4 (9)N1A—C1A—C2A—C3A−177.1 (6)
C6—C1—C11—O11−20.0 (10)C6A—C1A—C2A—C3A1.5 (10)
C6—C1—C11—O12159.0 (6)N1A—C1A—C6A—C5A177.6 (6)
C1—C2—C3—C4−0.2 (10)C2A—C1A—C6A—C5A−0.9 (10)
C21—C2—C3—C4−179.4 (6)C1A—C2A—C3A—C4A−0.8 (10)
C1—C2—C21—O21100.2 (7)C2A—C3A—C4A—Cl4A179.7 (5)
C1—C2—C21—O22−83.3 (8)C2A—C3A—C4A—C5A−0.5 (10)
C3—C2—C21—O21−80.6 (7)Cl4A—C4A—C5A—C6A−179.1 (5)
C3—C2—C21—O2295.9 (7)C3A—C4A—C5A—C6A1.0 (10)
C2—C3—C4—Cl4179.4 (5)C4A—C5A—C6A—C1A−0.3 (10)
D—H···AD—HH···AD···AD—H···A
O12—H12···O21i0.81 (3)1.69 (3)2.485 (5)166 (4)
N1A—H11A···O11ii0.89 (4)2.03 (4)2.867 (8)157 (4)
N1A—H11A···O220.89 (4)2.59 (4)2.875 (7)100 (2)
N1A—H12A···O220.88 (3)2.58 (5)2.875 (7)100 (3)
N1A—H12A···O22iii0.88 (3)1.94 (3)2.813 (6)172 (5)
N1A—H13A···O12iv0.88 (4)2.58 (5)3.019 (7)112 (3)
N1A—H13A···O21iv0.88 (4)1.94 (4)2.805 (7)166 (4)
C5A—H5A···O21v0.932.453.212 (8)139
Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯AD—HH⋯AD⋯AD—H⋯A
O12—H12⋯O21i0.81 (3)1.69 (3)2.485 (5)166 (4)
N1A—H11A⋯O11ii0.89 (4)2.03 (4)2.867 (8)157 (4)
N1A—H11A⋯O220.89 (4)2.59 (4)2.875 (7)100 (2)
N1A—H12A⋯O220.88 (3)2.58 (5)2.875 (7)100 (3)
N1A—H12A⋯O22iii0.88 (3)1.94 (3)2.813 (6)172 (5)
N1A—H13A⋯O12iv0.88 (4)2.58 (5)3.019 (7)112 (3)
N1A—H13A⋯O21iv0.88 (4)1.94 (4)2.805 (7)166 (4)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .

  5 in total

1.  A short history of SHELX.

Authors:  George M Sheldrick
Journal:  Acta Crystallogr A       Date:  2007-12-21       Impact factor: 2.290

2.  Zero-, one- and two-dimensional hydrogen-bonded structures in the 1:1 proton-transfer compounds of 4,5-dichlorophthalic acid with the monocyclic heteroaromatic Lewis bases 2-aminopyrimidine, nicotinamide and isonicotinamide.

Authors:  Graham Smith; Urs D Wermuth; Jonathan M White
Journal:  Acta Crystallogr C       Date:  2009-02-21       Impact factor: 1.172

3.  Two- and three-dimensional hydrogen-bonded structures in the 1:1 proton-transfer compounds of 4,5-dichlorophthalic acid with the isomeric monoaminobenzoic acids.

Authors:  Graham Smith; Urs D Wermuth; Jonathan M White
Journal:  Acta Crystallogr C       Date:  2008-08-29       Impact factor: 1.172

4.  One-dimensional hydrogen-bonded structures in the 1:1 proton-transfer compounds of 4,5-dichlorophthalic acid with 8-hydroxyquinoline, 8-aminoquinoline and quinoline-2-carboxylic acid (quinaldic acid).

Authors:  Graham Smith; Urs D Wermuth; Jonathan M White
Journal:  Acta Crystallogr C       Date:  2008-02-23       Impact factor: 1.172

5.  Structure validation in chemical crystallography.

Authors:  Anthony L Spek
Journal:  Acta Crystallogr D Biol Crystallogr       Date:  2009-01-20
  5 in total
  6 in total

1.  4-Methyl-pyridinium 2-carb-oxy-4,5-dichloro-benzoate monohydrate.

Authors:  Graham Smith; Urs D Wermuth
Journal:  Acta Crystallogr Sect E Struct Rep Online       Date:  2010-05-08

2.  Isopropyl-aminium 2-carb-oxy-4,5-di-chloro-benzoate.

Authors:  Graham Smith; Urs D Wermuth
Journal:  Acta Crystallogr Sect E Struct Rep Online       Date:  2009-12-12

3.  1,10-Phenanthrolin-1-ium 2-carb-oxy-4,5-dichloro-benzoate.

Authors:  Graham Smith; Urs D Wermuth; Jonathan M White
Journal:  Acta Crystallogr Sect E Struct Rep Online       Date:  2009-09-05

4.  4-Chloro-anilinium 4-methyl-benzene-sulfonate.

Authors:  Jerry P Jasinski; James A Golen; A S Praveen; H S Yathirajan; B Narayana
Journal:  Acta Crystallogr Sect E Struct Rep Online       Date:  2011-11-12

5.  4-Chloro-anilinium 3-carb-oxy-prop-2-enoate.

Authors:  R Anitha; S Athimoolam; S Asath Bahadur; M Gunasekaran
Journal:  Acta Crystallogr Sect E Struct Rep Online       Date:  2012-03-03

6.  4-Meth-oxy-anilinium 2-carb-oxy-4,5-di-chloro-benzoate.

Authors:  Graham Smith; Urs D Wermuth
Journal:  Acta Crystallogr Sect E Struct Rep Online       Date:  2013-09-18
  6 in total

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