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In the crystals of two title salts of chloranilic acid (2,5-dichloro-3,6-dihydroxy-
p-benzoquinone), namely ethylammonium chloranilate, C
2H
8N
+·C
6HCl
2O
4-, (I), and diethylammonium chloranilate, C
4H
12N
+·C
6HCl
2O
4-, (II), the chloranilate ions are present as a hydrogen-bonded dimer which has an inversion center. The ethylammonium and diethylammonium ions link the dimers through N-H
O hydrogen bonds, forming a three-dimensional hydrogen-bond network in (I) and a one-dimensional chain in (II).
Supporting information
CCDC references: 145646; 145647
Crystals of the title complexes were prepared by slow evaporation from acetonitrile solutions of chloranilic acid with ethylamine or diethylamine (molar ratio 1:1) at room temperature.
H atoms were found in a difference Fourier map and refined isotropically; C—H = 0.94–1.14, N—H = 0.89–1.06 and O—H = 0.92 Å for (I), and C—H = 0.94–1.05, N—H = 0.93–0.97 and O—H = 0.82 Å for (II).
For both compounds, data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation,1990); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1997). Program(s) used to solve structure: SAPI91 (Fan, 1991) for (I); SIR92 (Altomare, et al. 1993) for (II). For both compounds, program(s) used to refine structure: TEXSAN; software used to prepare material for publication: TEXSAN.
Crystal data top
C2H8N+·C6HO4Cl2− | Z = 2 |
Mr = 254.07 | F(000) = 260 |
Triclinic, P1 | Dx = 1.603 Mg m−3 |
a = 7.201 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.348 (2) Å | Cell parameters from 25 reflections |
c = 7.190 (2) Å | θ = 10.6–11.5° |
α = 95.59 (2)° | µ = 0.61 mm−1 |
β = 92.95 (2)° | T = 303 K |
γ = 98.47 (2)° | Plate, brown |
V = 526.3 (2) Å3 | 0.30 × 0.20 × 0.10 mm |
Data collection top
Rigaku AFC-5R diffractometer | 1402 reflections with I > 2σ(I) |
Radiation source: Rigaku rotating anode | Rint = 0.019 |
Graphite monochromator | θmax = 27.5°, θmin = 2.0° |
ω–2θ scans | h = 0→9 |
Absorption correction: ψ (North et al., 1968) | k = −13→13 |
Tmin = 0.898, Tmax = 0.941 | l = −9→9 |
2620 measured reflections | 3 standard reflections every 97 reflections |
2425 independent reflections | intensity decay: none |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | 0 constraints |
R[F2 > 2σ(F2)] = 0.042 | All H-atom parameters refined |
wR(F2) = 0.050 | Weighting scheme based on measured s.u.'s w = 1/[σ2(Fo) + 0.00002|Fo|2] |
S = 1.29 | (Δ/σ)max = 0.01 |
2424 reflections | Δρmax = 0.50 e Å−3 |
172 parameters | Δρmin = −0.56 e Å−3 |
Crystal data top
C2H8N+·C6HO4Cl2− | γ = 98.47 (2)° |
Mr = 254.07 | V = 526.3 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.201 (2) Å | Mo Kα radiation |
b = 10.348 (2) Å | µ = 0.61 mm−1 |
c = 7.190 (2) Å | T = 303 K |
α = 95.59 (2)° | 0.30 × 0.20 × 0.10 mm |
β = 92.95 (2)° | |
Data collection top
Rigaku AFC-5R diffractometer | 1402 reflections with I > 2σ(I) |
Absorption correction: ψ (North et al., 1968) | Rint = 0.019 |
Tmin = 0.898, Tmax = 0.941 | 3 standard reflections every 97 reflections |
2620 measured reflections | intensity decay: none |
2425 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.050 | All H-atom parameters refined |
S = 1.29 | Δρmax = 0.50 e Å−3 |
2424 reflections | Δρmin = −0.56 e Å−3 |
172 parameters | |
Special details top
Experimental. The scan width was (1.31 + 0.30tanθ)° with an ω scan speed of 6° per minute (up to 2 scans to achieve I/σ(I) > 10). Stationary background counts were recorded at each end of the scan, and the scan time:background time ratio was 2:1. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cl1 | 0.8078 (1) | 0.09592 (6) | 0.53082 (9) | 0.0628 (2) | |
Cl2 | 0.72839 (8) | 0.69762 (5) | 0.52971 (8) | 0.0429 (2) | |
O1 | 0.6727 (2) | 0.2313 (1) | 0.2162 (2) | 0.0485 (5) | |
O2 | 0.9132 (3) | 0.3098 (2) | 0.8409 (2) | 0.0563 (6) | |
O3 | 0.8862 (2) | 0.5590 (1) | 0.8350 (2) | 0.0443 (5) | |
O4 | 0.6260 (2) | 0.4824 (1) | 0.2123 (2) | 0.0439 (5) | |
N | 0.3609 (4) | 0.2878 (2) | −0.0309 (3) | 0.0410 (7) | |
C1 | 0.7179 (3) | 0.3043 (2) | 0.3592 (3) | 0.0329 (7) | |
C2 | 0.7896 (3) | 0.2603 (2) | 0.5310 (3) | 0.0356 (7) | |
C3 | 0.8432 (3) | 0.3460 (2) | 0.6817 (3) | 0.0360 (7) | |
C4 | 0.8293 (3) | 0.4896 (2) | 0.6849 (3) | 0.0322 (7) | |
C5 | 0.7533 (3) | 0.5328 (2) | 0.5239 (3) | 0.0316 (7) | |
C6 | 0.6953 (3) | 0.4500 (2) | 0.3600 (3) | 0.0320 (7) | |
C7 | 0.3071 (5) | 0.1481 (2) | −0.1103 (4) | 0.0542 (9) | |
C8 | 0.2599 (5) | 0.0613 (3) | 0.0410 (5) | 0.065 (1) | |
H1 | 0.931 (4) | 0.385 (2) | 0.923 (3) | 0.10 (1)* | |
H2 | 0.473 (4) | 0.303 (2) | 0.033 (3) | 0.08 (1)* | |
H3 | 0.259 (4) | 0.322 (3) | 0.056 (4) | 0.12 (1)* | |
H4 | 0.380 (4) | 0.347 (3) | −0.124 (3) | 0.09 (1)* | |
H5 | 0.429 (3) | 0.117 (2) | −0.190 (3) | 0.070 (8)* | |
H6 | 0.203 (3) | 0.147 (2) | −0.195 (3) | 0.09 (1)* | |
H7 | 0.377 (4) | 0.063 (2) | 0.124 (3) | 0.09 (1)* | |
H8 | 0.150 (4) | 0.088 (2) | 0.106 (3) | 0.09 (1)* | |
H9 | 0.223 (4) | −0.032 (3) | −0.017 (4) | 0.11 (1)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.0949 (6) | 0.0344 (4) | 0.0577 (5) | 0.0151 (4) | −0.0187 (4) | 0.0022 (3) |
Cl2 | 0.0513 (4) | 0.0357 (4) | 0.0425 (4) | 0.0121 (3) | −0.0018 (3) | 0.0022 (3) |
O1 | 0.061 (1) | 0.046 (1) | 0.0364 (9) | 0.0159 (9) | −0.0127 (8) | −0.0103 (8) |
O2 | 0.089 (1) | 0.046 (1) | 0.035 (1) | 0.023 (1) | −0.021 (1) | 0.0025 (9) |
O3 | 0.054 (1) | 0.045 (1) | 0.0329 (9) | 0.0166 (8) | −0.0126 (8) | −0.0067 (7) |
O4 | 0.059 (1) | 0.041 (1) | 0.0303 (9) | 0.0066 (9) | −0.0115 (8) | 0.0067 (7) |
N | 0.050 (1) | 0.037 (1) | 0.035 (1) | 0.008 (1) | −0.011 (1) | 0.003 (1) |
C1 | 0.030 (1) | 0.037 (1) | 0.031 (1) | 0.006 (1) | −0.000 (1) | 0.000 (1) |
C2 | 0.041 (2) | 0.029 (1) | 0.038 (1) | 0.007 (1) | −0.004 (1) | 0.003 (1) |
C3 | 0.038 (2) | 0.040 (1) | 0.031 (1) | 0.011 (1) | −0.005 (1) | 0.004 (1) |
C4 | 0.028 (1) | 0.036 (1) | 0.031 (1) | 0.006 (1) | −0.003 (1) | −0.001 (1) |
C5 | 0.031 (1) | 0.031 (1) | 0.033 (1) | 0.009 (1) | −0.002 (1) | 0.002 (1) |
C6 | 0.030 (1) | 0.036 (1) | 0.030 (1) | 0.005 (1) | 0.000 (1) | 0.005 (1) |
C7 | 0.082 (2) | 0.036 (1) | 0.042 (2) | 0.014 (1) | −0.013 (2) | −0.006 (1) |
C8 | 0.078 (3) | 0.041 (2) | 0.072 (2) | 0.003 (2) | −0.007 (2) | 0.004 (2) |
Geometric parameters (Å, º) top
CL1—C2 | 1.725 (2) | C5—C6 | 1.394 (3) |
CL2—C5 | 1.737 (2) | N—C7 | 1.490 (3) |
O1—C1 | 1.215 (2) | C7—C8 | 1.497 (4) |
O2—C3 | 1.336 (3) | C7—H5 | 1.14 (2) |
O2—H1 | 0.92 (3) | C7—H6 | 0.94 (3) |
O3—C4 | 1.251 (2) | C8—H7 | 1.01 (3) |
O4—C6 | 1.246 (2) | C8—H8 | 1.00 (3) |
C1—C2 | 1.453 (3) | C8—H9 | 1.01 (3) |
C1—C6 | 1.540 (3) | N—H2 | 0.89 (3) |
C2—C3 | 1.334 (3) | N—H3 | 1.06 (3) |
C3—C4 | 1.502 (3) | N—H4 | 0.96 (3) |
C4—C5 | 1.396 (3) | | |
| | | |
O1···N | 2.953 (3) | O4···Niii | 2.813 (3) |
O2···O3i | 2.797 (2) | O4···N | 2.932 (3) |
O3···Nii | 2.883 (3) | | |
| | | |
C3—O2—H1 | 105 (2) | CL2—C5—C4 | 118.1 (2) |
C7—N—H2 | 113 (2) | CL2—C5—C6 | 118.7 (2) |
C7—N—H3 | 113 (2) | C4—C5—C6 | 123.1 (2) |
C7—N—H4 | 113 (2) | O4—C6—C1 | 116.2 (2) |
H2—N—H3 | 109 (2) | O4—C6—C5 | 126.2 (2) |
H2—N—H4 | 101 (2) | C1—C6—C5 | 117.6 (2) |
H3—N—H4 | 106 (2) | N—C7—C8 | 111.0 (2) |
O1—C1—C2 | 123.2 (2) | N—C7—H5 | 109 (1) |
O1—C1—C6 | 118.6 (2) | N—C7—H6 | 105 (2) |
C2—C1—C6 | 118.3 (2) | C8—C7—H5 | 111 (1) |
CL1—C2—C1 | 117.9 (2) | C8—C7—H6 | 112 (2) |
CL1—C2—C3 | 121.6 (2) | H5—C7—H6 | 109 (2) |
C1—C2—C3 | 120.4 (2) | C7—C8—H7 | 108 (2) |
O2—C3—C2 | 122.2 (2) | C7—C8—H8 | 110 (2) |
O2—C3—C4 | 115.3 (2) | C7—C8—H9 | 109 (2) |
C2—C3—C4 | 122.6 (2) | H7—C8—H8 | 115 (2) |
O3—C4—C3 | 115.9 (2) | H7—C8—H9 | 106 (2) |
O3—C4—C5 | 126.2 (2) | H8—C8—H9 | 108 (2) |
C3—C4—C5 | 117.9 (2) | | |
| | | |
CL1—C2—C1—O1 | −0.9 (3) | O2—C3—C4—O3 | 0.7 (4) |
CL1—C2—C1—C6 | 178.1 (2) | O2—C3—C4—C5 | −178.6 (2) |
CL1—C2—C3—O2 | −0.2 (4) | O3—C4—C3—C2 | −179.4 (2) |
CL1—C2—C3—C4 | 179.8 (2) | O3—C4—C5—C6 | 178.9 (2) |
CL2—C5—C4—O3 | −1.6 (3) | O4—C6—C1—C2 | −177.1 (2) |
CL2—C5—C4—C3 | 177.6 (2) | O4—C6—C5—C4 | 179.7 (2) |
CL2—C5—C6—O4 | 0.3 (4) | C1—C2—C3—C4 | 1.3 (4) |
CL2—C5—C6—C1 | −179.6 (2) | C1—C6—C5—C4 | −0.2 (3) |
O1—C1—C2—C3 | 177.6 (3) | C2—C1—C6—C5 | 2.8 (3) |
O1—C1—C6—O4 | 1.9 (4) | C2—C3—C4—C5 | 1.4 (4) |
O1—C1—C6—C5 | −178.1 (2) | C3—C2—C1—C6 | −3.4 (3) |
O2—C3—C2—C1 | −178.7 (2) | C3—C4—C5—C6 | −1.9 (4) |
Symmetry codes: (i) −x+2, −y+1, −z+2; (ii) −x+1, −y+1, −z+1; (iii) −x+1, −y+1, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H1···O3i | 0.92 (3) | 2.10 (3) | 2.797 (2) | 131 (3) |
O2—H1···O3 | 0.92 (3) | 2.04 (3) | 2.797 (2) | 120 (2) |
N—H2···O1 | 0.89 (3) | 2.16 (3) | 2.953 (3) | 147 (2) |
N—H2···O4 | 0.89 (3) | 2.26 (3) | 2.932 (3) | 132 (2) |
N—H3···O3ii | 1.06 (3) | 1.87 (3) | 2.883 (3) | 158 (2) |
N—H4···O4iii | 0.96 (3) | 1.94 (3) | 2.813 (3) | 152 (3) |
Symmetry codes: (i) −x+2, −y+1, −z+2; (ii) −x+1, −y+1, −z+1; (iii) −x+1, −y+1, −z. |
Crystal data top
C4H12N+·C6HO4Cl2− | Z = 2 |
Mr = 282.12 | F(000) = 292.00 |
Triclinic, P1 | Dx = 1.458 Mg m−3 |
a = 9.159 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.617 (2) Å | Cell parameters from 25 reflections |
c = 8.979 (3) Å | θ = 10.7–12.4° |
α = 108.17 (2)° | µ = 0.51 mm−1 |
β = 111.27 (3)° | T = 302 K |
γ = 103.78 (2)° | Prismatic, dark purple |
V = 642.8 (5) Å3 | 0.40 × 0.30 × 0.30 mm |
Data collection top
Rigaku AFC-5R diffractometer | 1793 reflections with I > 2σ(I) |
Radiation source: Rigaku rotating anode | Rint = 0.016 |
Graphite monochromator | θmax = 27.5°, θmin = 2.4° |
ω–2θ scans | h = 0→11 |
Absorption correction: ψ (North et al., 1968) | k = −12→12 |
Tmin = 0.839, Tmax = 0.859 | l = −11→10 |
3144 measured reflections | 3 standard reflections every 97 reflections |
2958 independent reflections | intensity decay: none |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | 0 constraints |
R[F2 > 2σ(F2)] = 0.053 | All H-atom parameters refined |
wR(F2) = 0.091 | Weighting scheme based on measured s.u.'s w = 1/[σ2(Fo) + 0.00012|Fo|2] |
S = 1.64 | (Δ/σ)max = 0.01 |
2956 reflections | Δρmax = 0.55 e Å−3 |
206 parameters | Δρmin = −0.61 e Å−3 |
Crystal data top
C4H12N+·C6HO4Cl2− | γ = 103.78 (2)° |
Mr = 282.12 | V = 642.8 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.159 (3) Å | Mo Kα radiation |
b = 9.617 (2) Å | µ = 0.51 mm−1 |
c = 8.979 (3) Å | T = 302 K |
α = 108.17 (2)° | 0.40 × 0.30 × 0.30 mm |
β = 111.27 (3)° | |
Data collection top
Rigaku AFC-5R diffractometer | 1793 reflections with I > 2σ(I) |
Absorption correction: ψ (North et al., 1968) | Rint = 0.016 |
Tmin = 0.839, Tmax = 0.859 | 3 standard reflections every 97 reflections |
3144 measured reflections | intensity decay: none |
2958 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.091 | All H-atom parameters refined |
S = 1.64 | Δρmax = 0.55 e Å−3 |
2956 reflections | Δρmin = −0.61 e Å−3 |
206 parameters | |
Special details top
Experimental. The scan width was (1.21 + 0.30tanθ)° with an ω scan speed of 6° per minute (up to 3 scans to achieve I/σ(I) > 10). Stationary background counts were recorded at each end of the scan, and the scan time:background time ratio was 2:1. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cl1 | 0.43126 (7) | −0.21089 (7) | 0.7574 (1) | 0.0984 (2) | |
Cl2 | 0.47197 (6) | 0.40876 (7) | 0.63997 (9) | 0.0813 (2) | |
O1 | 0.7413 (2) | 0.0652 (2) | 0.8661 (2) | 0.0771 (5) | |
O2 | 0.1471 (2) | −0.1291 (2) | 0.5868 (2) | 0.0597 (4) | |
O3 | 0.1659 (1) | 0.1276 (2) | 0.5307 (2) | 0.0632 (4) | |
O4 | 0.7657 (1) | 0.3296 (1) | 0.8233 (2) | 0.0520 (4) | |
N | 1.0613 (2) | 0.3561 (2) | 1.1187 (2) | 0.0437 (5) | |
C1 | 0.6087 (2) | 0.0761 (2) | 0.7867 (3) | 0.0487 (6) | |
C2 | 0.4415 (2) | −0.0449 (2) | 0.7209 (3) | 0.0508 (6) | |
C3 | 0.3001 (2) | −0.0229 (2) | 0.6412 (3) | 0.0436 (5) | |
C4 | 0.3048 (2) | 0.1216 (2) | 0.6086 (3) | 0.0439 (5) | |
C5 | 0.4661 (2) | 0.2397 (2) | 0.6710 (3) | 0.0452 (5) | |
C6 | 0.6183 (2) | 0.2272 (2) | 0.7595 (2) | 0.0403 (5) | |
C7 | 1.0199 (3) | 0.3931 (3) | 1.2683 (3) | 0.0658 (9) | |
C8 | 0.9265 (4) | 0.5006 (3) | 1.2643 (4) | 0.0731 (9) | |
C9 | 1.1389 (3) | 0.2358 (2) | 1.1026 (3) | 0.0549 (7) | |
C10 | 1.1648 (4) | 0.1956 (4) | 0.9427 (4) | 0.078 (1) | |
H1 | 0.069 (3) | −0.104 (3) | 0.540 (3) | 0.094 (8)* | |
H2 | 0.961 (3) | 0.316 (2) | 1.006 (3) | 0.070 (6)* | |
H3 | 1.133 (2) | 0.448 (2) | 1.128 (3) | 0.064 (6)* | |
H4 | 0.957 (3) | 0.289 (3) | 1.256 (3) | 0.078 (7)* | |
H5 | 1.132 (3) | 0.448 (3) | 1.380 (3) | 0.101 (9)* | |
H6 | 0.811 (4) | 0.459 (3) | 1.148 (4) | 0.12 (1)* | |
H7 | 0.987 (3) | 0.608 (3) | 1.272 (3) | 0.112 (9)* | |
H8 | 0.905 (3) | 0.528 (3) | 1.362 (4) | 0.106 (9)* | |
H9 | 1.061 (2) | 0.143 (2) | 1.104 (2) | 0.058 (6)* | |
H10 | 1.245 (2) | 0.276 (2) | 1.209 (3) | 0.054 (5)* | |
H11 | 1.059 (3) | 0.164 (3) | 0.826 (4) | 0.113 (9)* | |
H12 | 1.234 (3) | 0.292 (3) | 0.935 (3) | 0.097 (9)* | |
H13 | 1.205 (3) | 0.111 (3) | 0.927 (3) | 0.100 (8)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.0413 (3) | 0.0561 (3) | 0.1895 (8) | 0.0179 (3) | 0.0306 (4) | 0.0740 (5) |
Cl2 | 0.0412 (3) | 0.0720 (4) | 0.1236 (6) | 0.0104 (3) | 0.0145 (3) | 0.0727 (4) |
O1 | 0.0278 (7) | 0.0560 (9) | 0.129 (1) | 0.0125 (6) | 0.0137 (8) | 0.050 (1) |
O2 | 0.0241 (6) | 0.0460 (8) | 0.096 (1) | 0.0067 (6) | 0.0162 (7) | 0.0366 (8) |
O3 | 0.0250 (6) | 0.0680 (9) | 0.092 (1) | 0.0130 (6) | 0.0137 (7) | 0.0511 (9) |
O4 | 0.0244 (6) | 0.0482 (8) | 0.068 (1) | 0.0020 (5) | 0.0102 (6) | 0.0313 (7) |
N | 0.0318 (8) | 0.0410 (9) | 0.050 (1) | 0.0079 (7) | 0.0129 (8) | 0.0231 (9) |
C1 | 0.0268 (9) | 0.038 (1) | 0.072 (1) | 0.0105 (8) | 0.017 (1) | 0.023 (1) |
C2 | 0.0305 (9) | 0.033 (1) | 0.079 (2) | 0.0088 (8) | 0.018 (1) | 0.026 (1) |
C3 | 0.0256 (9) | 0.0354 (9) | 0.059 (1) | 0.0070 (7) | 0.0157 (9) | 0.017 (1) |
C4 | 0.0279 (9) | 0.047 (1) | 0.051 (1) | 0.0093 (8) | 0.0139 (9) | 0.025 (1) |
C5 | 0.0284 (9) | 0.045 (1) | 0.056 (1) | 0.0072 (8) | 0.0115 (9) | 0.031 (1) |
C6 | 0.0260 (8) | 0.040 (1) | 0.045 (1) | 0.0052 (7) | 0.0118 (8) | 0.0190 (9) |
C7 | 0.063 (2) | 0.081 (2) | 0.063 (2) | 0.024 (1) | 0.034 (1) | 0.042 (2) |
C8 | 0.082 (2) | 0.068 (2) | 0.076 (2) | 0.026 (1) | 0.050 (2) | 0.026 (2) |
C9 | 0.039 (1) | 0.047 (1) | 0.070 (2) | 0.0155 (9) | 0.013 (1) | 0.031 (1) |
C10 | 0.075 (2) | 0.083 (2) | 0.087 (2) | 0.048 (2) | 0.037 (2) | 0.038 (2) |
Geometric parameters (Å, º) top
CL1—C2 | 1.715 (2) | C7—C8 | 1.492 (5) |
CL2—C5 | 1.725 (2) | C9—C10 | 1.487 (5) |
O1—C1 | 1.215 (2) | N—H2 | 0.97 (3) |
O2—C3 | 1.325 (2) | N—H3 | 0.93 (2) |
O2—H1 | 0.82 (3) | C7—H4 | 0.97 (3) |
O3—C4 | 1.235 (2) | C7—H5 | 1.00 (3) |
O4—C6 | 1.255 (2) | C8—H6 | 1.05 (4) |
C1—C2 | 1.454 (3) | C8—H7 | 1.01 (3) |
C1—C6 | 1.534 (3) | C8—H8 | 0.94 (4) |
C2—C3 | 1.336 (3) | C9—H9 | 1.01 (2) |
C3—C4 | 1.501 (3) | C9—H10 | 0.96 (2) |
C4—C5 | 1.411 (3) | C10—H11 | 1.03 (3) |
C5—C6 | 1.387 (3) | C10—H12 | 1.03 (3) |
N—C7 | 1.488 (4) | C10—H13 | 0.97 (3) |
N—C9 | 1.492 (3) | | |
| | | |
O1···N | 2.979 (3) | O4···Nii | 2.838 (3) |
O2···O3i | 2.677 (2) | O4···N | 2.910 (3) |
| | | |
C3—O2—H1 | 113 (2) | N—C7—C8 | 110.9 (3) |
C7—N—C9 | 114.1 (2) | N—C7—H4 | 105 (2) |
C7—N—H2 | 111 (2) | N—C7—H5 | 106 (2) |
C7—N—H3 | 111 (2) | C8—C7—H4 | 115 (2) |
C9—N—H2 | 107 (2) | C8—C7—H5 | 110 (2) |
C9—N—H3 | 109 (2) | H4—C7—H5 | 110 (2) |
H2—N—H3 | 104 (2) | C7—C8—H6 | 117 (2) |
O1—C1—C2 | 123.1 (2) | C7—C8—H7 | 117 (2) |
O1—C1—C6 | 118.3 (2) | C7—C8—H8 | 111 (2) |
C2—C1—C6 | 118.5 (2) | H6—C8—H7 | 100 (3) |
CL1—C2—C1 | 118.4 (2) | H6—C8—H8 | 108 (3) |
CL1—C2—C3 | 121.2 (2) | H7—C8—H8 | 104 (3) |
C1—C2—C3 | 120.3 (2) | N—C9—C10 | 111.2 (2) |
O2—C3—C2 | 121.1 (2) | N—C9—H9 | 105 (1) |
O2—C3—C4 | 116.4 (2) | N—C9—H10 | 110 (1) |
C2—C3—C4 | 122.5 (2) | C10—C9—H9 | 115 (1) |
O3—C4—C3 | 116.8 (2) | C10—C9—H10 | 111 (1) |
O3—C4—C5 | 125.4 (2) | H9—C9—H10 | 105 (2) |
C3—C4—C5 | 117.8 (2) | C9—C10—H11 | 115 (2) |
CL2—C5—C4 | 117.9 (2) | C9—C10—H12 | 115 (2) |
CL2—C5—C6 | 119.3 (2) | C9—C10—H13 | 111 (2) |
C4—C5—C6 | 122.9 (2) | H11—C10—H12 | 93 (2) |
O4—C6—C1 | 115.8 (2) | H11—C10—H13 | 109 (3) |
O4—C6—C5 | 126.2 (2) | H12—C10—H13 | 114 (3) |
C1—C6—C5 | 118.0 (2) | | |
| | | |
CL1—C2—C1—O1 | 0.1 (4) | O2—C3—C4—C5 | 177.7 (2) |
CL1—C2—C1—C6 | −178.1 (2) | O3—C4—C3—C2 | 178.6 (3) |
CL1—C2—C3—O2 | −0.4 (4) | O3—C4—C5—C6 | 179.3 (3) |
CL1—C2—C3—C4 | 179.6 (2) | O4—C6—C1—C2 | 178.1 (2) |
CL2—C5—C4—O3 | 1.1 (4) | O4—C6—C5—C4 | −177.6 (2) |
CL2—C5—C4—C3 | −177.9 (2) | C1—C2—C3—C4 | 2.6 (4) |
CL2—C5—C6—O4 | 0.6 (4) | C1—C6—C5—C4 | 1.2 (4) |
CL2—C5—C6—C1 | 179.3 (2) | C2—C1—C6—C5 | −0.8 (4) |
O1—C1—C2—C3 | 177.1 (3) | C2—C3—C4—C5 | −2.2 (4) |
O1—C1—C6—O4 | −0.2 (4) | C3—C2—C1—C6 | −1.1 (4) |
O1—C1—C6—C5 | −179.1 (3) | C3—C4—C5—C6 | 0.2 (4) |
O2—C3—C2—C1 | −177.3 (2) | C7—N—C9—C10 | 175.7 (3) |
O2—C3—C4—O3 | −1.4 (4) | C8—C7—N—C9 | −174.0 (3) |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x+2, −y+1, −z+2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H1···O3i | 0.82 (3) | 1.94 (3) | 2.677 (2) | 148 (3) |
O2—H1···O3 | 0.82 (3) | 2.23 (3) | 2.649 (2) | 112 (3) |
N—H2···O4 | 0.97 (3) | 2.00 (3) | 2.910 (3) | 155 (2) |
N—H2···O1 | 0.97 (3) | 2.33 (3) | 2.979 (3) | 124 (2) |
N—H3···O4ii | 0.93 (2) | 1.95 (3) | 2.838 (3) | 160 (2) |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x+2, −y+1, −z+2. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C2H8N+·C6HO4Cl2− | C4H12N+·C6HO4Cl2− |
Mr | 254.07 | 282.12 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 303 | 302 |
a, b, c (Å) | 7.201 (2), 10.348 (2), 7.190 (2) | 9.159 (3), 9.617 (2), 8.979 (3) |
α, β, γ (°) | 95.59 (2), 92.95 (2), 98.47 (2) | 108.17 (2), 111.27 (3), 103.78 (2) |
V (Å3) | 526.3 (2) | 642.8 (5) |
Z | 2 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.61 | 0.51 |
Crystal size (mm) | 0.30 × 0.20 × 0.10 | 0.40 × 0.30 × 0.30 |
|
Data collection |
Diffractometer | Rigaku AFC-5R diffractometer | Rigaku AFC-5R diffractometer |
Absorption correction | ψ (North et al., 1968) | ψ (North et al., 1968) |
Tmin, Tmax | 0.898, 0.941 | 0.839, 0.859 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2620, 2425, 1402 | 3144, 2958, 1793 |
Rint | 0.019 | 0.016 |
(sin θ/λ)max (Å−1) | 0.650 | 0.650 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.050, 1.29 | 0.053, 0.091, 1.64 |
No. of reflections | 2424 | 2956 |
No. of parameters | 172 | 206 |
H-atom treatment | All H-atom parameters refined | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.50, −0.56 | 0.55, −0.61 |
Selected geometric parameters (Å, º) for (I) topCL1—C2 | 1.725 (2) | C1—C6 | 1.540 (3) |
CL2—C5 | 1.737 (2) | C2—C3 | 1.334 (3) |
O1—C1 | 1.215 (2) | C3—C4 | 1.502 (3) |
O2—C3 | 1.336 (3) | C4—C5 | 1.396 (3) |
O3—C4 | 1.251 (2) | C5—C6 | 1.394 (3) |
O4—C6 | 1.246 (2) | N—C7 | 1.490 (3) |
C1—C2 | 1.453 (3) | C7—C8 | 1.497 (4) |
| | | |
N—C7—C8 | 111.0 (2) | | |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H1···O3i | 0.92 (3) | 2.10 (3) | 2.797 (2) | 131 (3) |
O2—H1···O3 | 0.92 (3) | 2.04 (3) | 2.797 (2) | 120 (2) |
N—H2···O1 | 0.89 (3) | 2.16 (3) | 2.953 (3) | 147 (2) |
N—H2···O4 | 0.89 (3) | 2.26 (3) | 2.932 (3) | 132 (2) |
N—H3···O3ii | 1.06 (3) | 1.87 (3) | 2.883 (3) | 158 (2) |
N—H4···O4iii | 0.96 (3) | 1.94 (3) | 2.813 (3) | 152 (3) |
Symmetry codes: (i) −x+2, −y+1, −z+2; (ii) −x+1, −y+1, −z+1; (iii) −x+1, −y+1, −z. |
Selected geometric parameters (Å, º) for (II) topCL1—C2 | 1.715 (2) | C2—C3 | 1.336 (3) |
CL2—C5 | 1.725 (2) | C3—C4 | 1.501 (3) |
O1—C1 | 1.215 (2) | C4—C5 | 1.411 (3) |
O2—C3 | 1.325 (2) | C5—C6 | 1.387 (3) |
O3—C4 | 1.235 (2) | N—C7 | 1.488 (4) |
O4—C6 | 1.255 (2) | N—C9 | 1.492 (3) |
C1—C2 | 1.454 (3) | C7—C8 | 1.492 (5) |
C1—C6 | 1.534 (3) | C9—C10 | 1.487 (5) |
| | | |
N—C7—C8 | 110.9 (3) | N—C9—C10 | 111.2 (2) |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H1···O3i | 0.82 (3) | 1.94 (3) | 2.677 (2) | 148 (3) |
O2—H1···O3 | 0.82 (3) | 2.23 (3) | 2.649 (2) | 112 (3) |
N—H2···O4 | 0.97 (3) | 2.00 (3) | 2.910 (3) | 155 (2) |
N—H2···O1 | 0.97 (3) | 2.33 (3) | 2.979 (3) | 124 (2) |
N—H3···O4ii | 0.93 (2) | 1.95 (3) | 2.838 (3) | 160 (2) |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x+2, −y+1, −z+2. |
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Several hydrogen-bonded complexes of chloranilic acid–amine (1/1) in the solid state were studied by IR (Issa et al., 1991; Habeeb et al., 1995). Habeeb et al. analyzed the IR data on the assumption that the complex consists of a pair of chloranilic acid and amine molecules, and reported that the hydrogen bond formed in the pair varies from an N—H···O to an N···H—O type with decreasing pKa values of the amines. Recently, we determined the structures of the chloranilic acid–pyrazine (1/1) complex and morpholinium chloranilate (Ishida & Kashino, 1999) and showed that these complexes are not present as a pair of chloranilic acid and amine. In the pyrazine complex, pyrazine and chloranilic acid are alternately arranged to form an O—H···N hydrogen-bond chain. On the other hand, in the morpholinium salt, a chain of chloranilate ions is formed through O—H···O hydrogen bonds and morpholinium ions link the two chains through N—H···O hydrogen bonds, forming the two-dimensional hydrogen-bond network. The complexes of chloranilic acid–amine are, therefore, expected to be a noticeable system in view of our interest in hydrogen-bond patterns and their nature in the solid state. As part of an investigation on this system, we prepared the 1/1 complexes of chloranilic acid with strong bases, ethylamine (pKa = 10.64) and diethylamine (pKa = 10.94) and determined their crystal structures.
In (I) and (II), an acid–base interaction involving a proton transfer is observed as expected from high basicity of the present amines. The molecules of chloranilate ion form a dimer connected by O2—H1···O3i hydrogen bonds [symmetry code: (i) 2 − x, 1 − y, 2 − z; Tables 2 and 4]. The H1 atom is also involved in an intramolecular hydrogen bond with O3.
In (I), the ethylammonium ion links the three dimers of chloranilic acid through N—H3···O3ii and N—H4···O4iii hydrogen bonds [symmetry codes: (ii) 1 − x, 1 − y, 1 − z; (iii) 1 − x, 1 − y, −z], and a bifurcated hydrogen bond of N—H2···O1 and N—H2···O4, forming a three-dimensional hydrogen-bond network. A weak C—H···O interaction between the methyl group of the cation and the anion is observed [C8—H7 1.01 (3), H7···O1 2.56 (3), C8···O1 3.340 (4) Å, and C8—H7···O1 134 (2)°], which may stabilize the orientation of C8—C7 bond. In (II), the diethylammonium ions related by an inversion center link the two dimers of chloranilic acid through a bifurcated hydrogen bond of N—H2···O1 and N—H2···O4, and an N—H3···O4i hydrogen bond, forming an infinite chain along [211]. The shortest contact between the chains is O2···H4i 2.63 (3) Å [C7—H4 0.97 (3), O2···C7iv 3.483 (4) Å, O2···H4iv—C7iv 146 (2)°; symmetry code: (iv) 1 − x, −y, 2 − z].
The anions form dimers in both salts, but the O2···O3 contact distance between the anions in the dimer in (I), 2.797 (2) Å, is rather longer than in (II), 2.677 (2) Å. The O3 atom in (I) is linked to the cation through a hydrogen bond, while the O3 atom in (II) does not participate in such an additional hydrogen bond. This may cause the difference in the O2···O3 distance between (I) and (II).