Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109021490/sk3318sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109021490/sk3318Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109021490/sk3318IIsup3.hkl |
CCDC references: 742249; 742250
Suitable crystals of (I) and (II) were obtained by slow evaporation of a solution of 2-amino-5-chloropyridine or 2-methyl-5-nitroaniline in 5% trichloroacetic acid. An SHG (second harmonic generation) experiment was carried out using the Kutz–Perry powder technique (Kutz & Perry, 1968). Samples of 2-amino-5-chloropyridinium trichloroacetate were irradiated at 1064 nm by an Nd:YAG laser and the second harmonic beam power diffused by the sample at 532 nm was measured as a function of the fundamental beam power. The SHG efficiency in relation to potassium dihydrogen phosphate KDP is equal to 0.77 [deff = 0.77deff(KDP)].
H atoms involved in hydrogen bonding were located in difference Fourier maps and their positions refined. C-bound H atoms were introduced at calculated positions and refined as riding on their carrier atoms. Uiso(H) values were constrained as 1.5 or 1.2 times Ueq of the carrier atoms.
For both compounds, data collection: CrysAlis CCD (Oxford Diffraction Poland, 2008); cell refinement: CrysAlis RED (Oxford Diffraction Poland, 2008); data reduction: CrysAlis RED (Oxford Diffraction Poland, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Diamond (Brandenburg & Putz, 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
C5H6ClN2+·C2Cl3O2− | F(000) = 584 |
Mr = 291.94 | Dx = 1.738 Mg m−3 Dm = 1.73 Mg m−3 Dm measured by flotation |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C -2yc | Cell parameters from 1217 reflections |
a = 5.6426 (11) Å | θ = 2.9–29.5° |
b = 17.512 (3) Å | µ = 1.04 mm−1 |
c = 11.323 (2) Å | T = 295 K |
β = 94.36 (1)° | Paralellepiped, colourless |
V = 1115.6 (4) Å3 | 0.32 × 0.24 × 0.16 mm |
Z = 4 |
KUMA KM-4 diffractometer with CCD area detector | 2699 independent reflections |
Radiation source: fine-focus sealed tube | 1817 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
Detector resolution: 1024x1024 with blocks 2x2 pixels mm-1 | θmax = 29.5°, θmin = 2.9° |
ω–scan | h = −7→7 |
Absorption correction: numerical (CrysAlis RED; Oxford Diffraction Poland, 2008) | k = −23→23 |
Tmin = 0.732, Tmax = 0.851 | l = −15→15 |
7423 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.029 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.047 | w = 1/[σ2(Fo2) + (0.018P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max < 0.001 |
2699 reflections | Δρmax = 0.35 e Å−3 |
145 parameters | Δρmin = −0.20 e Å−3 |
2 restraints | Absolute structure: Flack (1983) , 1226 Friedel-pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.10 (5) |
C5H6ClN2+·C2Cl3O2− | V = 1115.6 (4) Å3 |
Mr = 291.94 | Z = 4 |
Monoclinic, Cc | Mo Kα radiation |
a = 5.6426 (11) Å | µ = 1.04 mm−1 |
b = 17.512 (3) Å | T = 295 K |
c = 11.323 (2) Å | 0.32 × 0.24 × 0.16 mm |
β = 94.36 (1)° |
KUMA KM-4 diffractometer with CCD area detector | 2699 independent reflections |
Absorption correction: numerical (CrysAlis RED; Oxford Diffraction Poland, 2008) | 1817 reflections with I > 2σ(I) |
Tmin = 0.732, Tmax = 0.851 | Rint = 0.023 |
7423 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.047 | Δρmax = 0.35 e Å−3 |
S = 1.00 | Δρmin = −0.20 e Å−3 |
2699 reflections | Absolute structure: Flack (1983) , 1226 Friedel-pairs |
145 parameters | Absolute structure parameter: 0.10 (5) |
2 restraints |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.8197 (3) | 0.20645 (8) | 0.43104 (13) | 0.0379 (3) | |
O2 | 0.8956 (3) | 0.19674 (9) | 0.24250 (14) | 0.0538 (4) | |
C1 | 0.9029 (3) | 0.17544 (12) | 0.3453 (2) | 0.0331 (5) | |
C2 | 1.0399 (3) | 0.09901 (11) | 0.37160 (19) | 0.0332 (5) | |
Cl1 | 0.92493 (11) | 0.04745 (4) | 0.48701 (6) | 0.06049 (19) | |
Cl2 | 1.03526 (11) | 0.03988 (4) | 0.24724 (6) | 0.0648 (2) | |
Cl3 | 1.33706 (11) | 0.12339 (4) | 0.41361 (7) | 0.0659 (2) | |
Cl4 | −0.03208 (11) | 0.40766 (4) | 0.55293 (6) | 0.0687 (2) | |
C3 | 0.3297 (4) | 0.33705 (12) | 0.46320 (19) | 0.0407 (6) | |
H3 | 0.3868 | 0.3284 | 0.5413 | 0.049* | |
N1 | 0.4502 (3) | 0.31029 (10) | 0.37330 (17) | 0.0369 (4) | |
H1 | 0.564 (5) | 0.2805 (14) | 0.386 (2) | 0.055* | |
C4 | 0.3780 (4) | 0.31981 (12) | 0.25802 (19) | 0.0376 (5) | |
C5 | 0.1671 (4) | 0.36193 (14) | 0.2344 (2) | 0.0453 (6) | |
H5 | 0.1108 | 0.3713 | 0.1564 | 0.054* | |
C6 | 0.0477 (4) | 0.38837 (14) | 0.3227 (2) | 0.0481 (6) | |
H6 | −0.0921 | 0.4157 | 0.3056 | 0.058* | |
C7 | 0.1287 (4) | 0.37587 (13) | 0.4395 (2) | 0.0414 (6) | |
N2 | 0.5010 (4) | 0.29059 (13) | 0.17702 (18) | 0.0526 (5) | |
H21 | 0.440 (4) | 0.2925 (15) | 0.1043 (9) | 0.063* | |
H22 | 0.620 (3) | 0.2601 (11) | 0.193 (2) | 0.063* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0441 (8) | 0.0385 (8) | 0.0302 (8) | 0.0071 (7) | −0.0030 (7) | −0.0036 (7) |
O2 | 0.0758 (10) | 0.0521 (11) | 0.0332 (10) | 0.0147 (9) | 0.0033 (8) | 0.0078 (8) |
C1 | 0.0285 (12) | 0.0388 (13) | 0.0310 (13) | −0.0031 (10) | −0.0041 (10) | −0.0007 (11) |
C2 | 0.0298 (12) | 0.0371 (12) | 0.0323 (11) | −0.0037 (9) | 0.0009 (9) | −0.0018 (10) |
Cl1 | 0.0725 (4) | 0.0495 (4) | 0.0617 (4) | 0.0052 (3) | 0.0196 (3) | 0.0202 (3) |
Cl2 | 0.0858 (5) | 0.0555 (4) | 0.0517 (4) | 0.0141 (4) | −0.0038 (3) | −0.0169 (3) |
Cl3 | 0.0343 (3) | 0.0683 (5) | 0.0923 (5) | −0.0045 (3) | −0.0133 (3) | 0.0067 (4) |
Cl4 | 0.0605 (4) | 0.0788 (5) | 0.0696 (5) | 0.0130 (4) | 0.0221 (4) | −0.0065 (4) |
C3 | 0.0520 (15) | 0.0392 (13) | 0.0313 (13) | −0.0043 (12) | 0.0045 (11) | 0.0008 (10) |
N1 | 0.0429 (12) | 0.0377 (11) | 0.0292 (9) | 0.0070 (9) | −0.0025 (9) | 0.0031 (9) |
C4 | 0.0462 (14) | 0.0342 (13) | 0.0306 (13) | −0.0039 (11) | −0.0076 (11) | 0.0038 (10) |
C5 | 0.0440 (14) | 0.0477 (14) | 0.0417 (13) | −0.0012 (11) | −0.0120 (12) | 0.0056 (11) |
C6 | 0.0337 (14) | 0.0486 (14) | 0.0608 (17) | 0.0041 (12) | −0.0035 (12) | 0.0092 (13) |
C7 | 0.0388 (13) | 0.0384 (13) | 0.0471 (15) | −0.0024 (12) | 0.0042 (11) | 0.0032 (12) |
N2 | 0.0636 (15) | 0.0665 (15) | 0.0269 (11) | 0.0182 (12) | −0.0024 (11) | 0.0028 (11) |
O1—C1 | 1.236 (2) | N1—C4 | 1.348 (3) |
O2—C1 | 1.220 (2) | N1—H1 | 0.83 (3) |
C1—C2 | 1.563 (3) | C4—N2 | 1.297 (3) |
C2—Cl2 | 1.746 (2) | C4—C5 | 1.409 (3) |
C2—Cl1 | 1.753 (2) | C5—C6 | 1.330 (3) |
C2—Cl3 | 1.761 (2) | C5—H5 | 0.9300 |
Cl4—C7 | 1.720 (2) | C6—C7 | 1.383 (3) |
C3—C7 | 1.332 (3) | C6—H6 | 0.9300 |
C3—N1 | 1.350 (3) | N2—H21 | 0.87 (2) |
C3—H3 | 0.9300 | N2—H22 | 0.87 (2) |
O2—C1—O1 | 128.9 (2) | N2—C4—N1 | 119.8 (2) |
O2—C1—C2 | 115.1 (2) | N2—C4—C5 | 124.2 (2) |
O1—C1—C2 | 116.0 (2) | N1—C4—C5 | 115.9 (2) |
C1—C2—Cl2 | 112.15 (15) | C6—C5—C4 | 120.6 (2) |
C1—C2—Cl1 | 112.20 (15) | C6—C5—H5 | 119.7 |
Cl2—C2—Cl1 | 108.18 (11) | C4—C5—H5 | 119.7 |
C1—C2—Cl3 | 106.91 (14) | C5—C6—C7 | 120.9 (2) |
Cl2—C2—Cl3 | 108.49 (12) | C5—C6—H6 | 119.5 |
Cl1—C2—Cl3 | 108.80 (12) | C7—C6—H6 | 119.5 |
C7—C3—N1 | 119.7 (2) | C3—C7—C6 | 119.2 (2) |
C7—C3—H3 | 120.2 | C3—C7—Cl4 | 120.25 (18) |
N1—C3—H3 | 120.2 | C6—C7—Cl4 | 120.54 (18) |
C4—N1—C3 | 123.7 (2) | C4—N2—H21 | 117.4 (19) |
C4—N1—H1 | 114.7 (18) | C4—N2—H22 | 122.8 (16) |
C3—N1—H1 | 120.9 (18) | H21—N2—H22 | 118 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1 | 0.83 (2) | 1.98 (2) | 2.806 (3) | 174 (2) |
N2—H21···O1i | 0.87 (2) | 2.03 (1) | 2.893 (3) | 176 (3) |
N2—H22···O2 | 0.87 (2) | 1.96 (2) | 2.821 (3) | 175 (2) |
Symmetry code: (i) x−1/2, −y+1/2, z−1/2. |
C7H9N2O2+·C2Cl3O2−·H2O | Z = 2 |
Mr = 333.55 | F(000) = 340 |
Triclinic, P1 | Dx = 1.606 Mg m−3 Dm = 1.60 Mg m−3 Dm measured by flotation |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.9810 (14) Å | Cell parameters from 2229 reflections |
b = 8.3611 (17) Å | θ = 3.3–28.0° |
c = 12.229 (2) Å | µ = 0.68 mm−1 |
α = 103.74 (1)° | T = 295 K |
β = 92.29 (1)° | Paralellepiped, colourless |
γ = 94.77 (1)° | 0.34 × 0.30 × 0.16 mm |
V = 689.6 (2) Å3 |
KUMA KM-4 diffractometer with CCD area detector | 3305 independent reflections |
Radiation source: fine-focus sealed tube | 2306 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.020 |
Detector resolution: 1024x1024 with blocks 2x2 pixels mm-1 | θmax = 28.0°, θmin = 3.3° |
ω–scan | h = −9→6 |
Absorption correction: numerical (CrysAlis RED; Oxford Diffraction Poland, 2008) | k = −10→11 |
Tmin = 0.811, Tmax = 0.908 | l = −15→16 |
7531 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.058 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.131 | w = 1/[σ2(Fo2) + (0.036P)2 + 1.180P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max < 0.001 |
3305 reflections | Δρmax = 0.42 e Å−3 |
189 parameters | Δρmin = −0.46 e Å−3 |
2 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.368 (12) |
C7H9N2O2+·C2Cl3O2−·H2O | γ = 94.77 (1)° |
Mr = 333.55 | V = 689.6 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.9810 (14) Å | Mo Kα radiation |
b = 8.3611 (17) Å | µ = 0.68 mm−1 |
c = 12.229 (2) Å | T = 295 K |
α = 103.74 (1)° | 0.34 × 0.30 × 0.16 mm |
β = 92.29 (1)° |
KUMA KM-4 diffractometer with CCD area detector | 3305 independent reflections |
Absorption correction: numerical (CrysAlis RED; Oxford Diffraction Poland, 2008) | 2306 reflections with I > 2σ(I) |
Tmin = 0.811, Tmax = 0.908 | Rint = 0.020 |
7531 measured reflections |
R[F2 > 2σ(F2)] = 0.058 | 2 restraints |
wR(F2) = 0.131 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.42 e Å−3 |
3305 reflections | Δρmin = −0.46 e Å−3 |
189 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cl1 | 0.09763 (12) | 0.49673 (11) | 0.72041 (7) | 0.0545 (3) | |
Cl2 | −0.14642 (12) | 0.67926 (12) | 0.61423 (8) | 0.0597 (3) | |
Cl3 | 0.13394 (16) | 0.85225 (13) | 0.79153 (8) | 0.0725 (3) | |
C8 | 0.0874 (4) | 0.6815 (4) | 0.6751 (3) | 0.0443 (7) | |
C9 | 0.2460 (4) | 0.6981 (3) | 0.5892 (2) | 0.0409 (6) | |
O1 | 0.2077 (3) | 0.7828 (3) | 0.52093 (19) | 0.0516 (6) | |
O2 | 0.3938 (3) | 0.6314 (3) | 0.59792 (19) | 0.0507 (5) | |
C1 | 0.5921 (4) | 0.3670 (4) | 0.7533 (2) | 0.0411 (6) | |
C2 | 0.6526 (5) | 0.2370 (4) | 0.7937 (3) | 0.0496 (7) | |
C3 | 0.7331 (5) | 0.2737 (5) | 0.9034 (3) | 0.0600 (9) | |
H3 | 0.7725 | 0.1884 | 0.9332 | 0.072* | |
C4 | 0.7561 (5) | 0.4325 (5) | 0.9692 (3) | 0.0625 (10) | |
H4 | 0.8114 | 0.4554 | 1.0423 | 0.075* | |
C5 | 0.6957 (5) | 0.5566 (4) | 0.9244 (3) | 0.0523 (8) | |
C6 | 0.6115 (4) | 0.5270 (4) | 0.8161 (3) | 0.0455 (7) | |
H6 | 0.5699 | 0.6124 | 0.7872 | 0.055* | |
N1 | 0.5078 (4) | 0.3350 (4) | 0.6382 (2) | 0.0452 (6) | |
H11 | 0.471 (6) | 0.428 (5) | 0.625 (3) | 0.068* | |
H12 | 0.406 (6) | 0.260 (5) | 0.629 (3) | 0.068* | |
H13 | 0.595 (6) | 0.296 (5) | 0.590 (4) | 0.068* | |
C7 | 0.6315 (6) | 0.0630 (5) | 0.7225 (4) | 0.0721 (11) | |
H71 | 0.4974 | 0.0275 | 0.7036 | 0.108* | |
H72 | 0.6860 | −0.0084 | 0.7637 | 0.108* | |
H73 | 0.6975 | 0.0587 | 0.6546 | 0.108* | |
N2 | 0.7213 (5) | 0.7267 (5) | 0.9930 (3) | 0.0680 (9) | |
O3 | 0.6749 (6) | 0.8364 (4) | 0.9505 (3) | 0.0991 (11) | |
O4 | 0.7880 (5) | 0.7511 (4) | 1.0915 (3) | 0.0983 (11) | |
O5 | 0.1684 (4) | 0.1276 (3) | 0.5972 (3) | 0.0748 (8) | |
H51 | 0.062 (5) | 0.156 (5) | 0.562 (4) | 0.112* | |
H52 | 0.158 (7) | 0.0142 (13) | 0.576 (4) | 0.112* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0525 (5) | 0.0609 (5) | 0.0601 (5) | 0.0046 (4) | 0.0063 (4) | 0.0342 (4) |
Cl2 | 0.0452 (4) | 0.0767 (6) | 0.0653 (6) | 0.0053 (4) | −0.0033 (4) | 0.0344 (5) |
Cl3 | 0.0869 (7) | 0.0688 (6) | 0.0479 (5) | −0.0117 (5) | 0.0117 (4) | −0.0080 (4) |
C8 | 0.0428 (15) | 0.0491 (16) | 0.0424 (16) | 0.0020 (12) | −0.0025 (12) | 0.0156 (13) |
C9 | 0.0473 (16) | 0.0383 (14) | 0.0348 (14) | −0.0072 (12) | −0.0046 (12) | 0.0093 (11) |
O1 | 0.0624 (14) | 0.0485 (12) | 0.0517 (13) | 0.0043 (10) | 0.0074 (10) | 0.0272 (10) |
O2 | 0.0463 (12) | 0.0578 (13) | 0.0528 (13) | 0.0013 (10) | 0.0032 (10) | 0.0240 (11) |
C1 | 0.0376 (14) | 0.0490 (16) | 0.0394 (15) | −0.0009 (12) | 0.0046 (11) | 0.0171 (12) |
C2 | 0.0447 (16) | 0.0583 (19) | 0.0511 (18) | 0.0012 (14) | 0.0004 (13) | 0.0254 (15) |
C3 | 0.058 (2) | 0.072 (2) | 0.058 (2) | 0.0040 (17) | −0.0054 (16) | 0.0353 (19) |
C4 | 0.0459 (18) | 0.096 (3) | 0.0493 (19) | 0.0014 (18) | −0.0048 (15) | 0.029 (2) |
C5 | 0.0452 (17) | 0.064 (2) | 0.0449 (17) | −0.0050 (14) | 0.0029 (13) | 0.0108 (15) |
C6 | 0.0417 (15) | 0.0523 (17) | 0.0447 (16) | −0.0006 (13) | 0.0068 (12) | 0.0170 (13) |
N1 | 0.0500 (15) | 0.0469 (15) | 0.0414 (14) | 0.0005 (12) | 0.0049 (11) | 0.0171 (12) |
C7 | 0.081 (3) | 0.059 (2) | 0.083 (3) | 0.0110 (19) | 0.002 (2) | 0.030 (2) |
N2 | 0.0630 (19) | 0.073 (2) | 0.0567 (19) | −0.0048 (16) | 0.0093 (15) | −0.0035 (16) |
O3 | 0.142 (3) | 0.0557 (18) | 0.089 (2) | −0.0053 (19) | 0.005 (2) | 0.0024 (16) |
O4 | 0.097 (2) | 0.111 (3) | 0.0638 (19) | 0.0080 (19) | −0.0163 (17) | −0.0201 (18) |
O5 | 0.0735 (18) | 0.0490 (14) | 0.099 (2) | −0.0083 (12) | −0.0243 (16) | 0.0224 (14) |
Cl1—C8 | 1.766 (3) | C4—H4 | 0.9300 |
Cl2—C8 | 1.763 (3) | C5—C6 | 1.386 (4) |
Cl3—C8 | 1.759 (3) | C5—N2 | 1.462 (5) |
C8—C9 | 1.576 (4) | C6—H6 | 0.9300 |
C9—O2 | 1.226 (4) | N1—H11 | 0.86 (4) |
C9—O1 | 1.251 (3) | N1—H12 | 0.88 (4) |
C1—C6 | 1.368 (4) | N1—H13 | 0.86 (4) |
C1—C2 | 1.385 (4) | C7—H71 | 0.9600 |
C1—N1 | 1.458 (4) | C7—H72 | 0.9600 |
C2—C3 | 1.387 (5) | C7—H73 | 0.9600 |
C2—C7 | 1.499 (5) | N2—O3 | 1.216 (5) |
C3—C4 | 1.372 (6) | N2—O4 | 1.238 (4) |
C3—H3 | 0.9300 | O5—H51 | 0.92 (4) |
C4—C5 | 1.370 (5) | O5—H52 | 0.92 (4) |
C9—C8—Cl3 | 107.0 (2) | C4—C5—N2 | 119.0 (3) |
C9—C8—Cl2 | 111.6 (2) | C6—C5—N2 | 118.6 (3) |
Cl3—C8—Cl2 | 110.00 (17) | C1—C6—C5 | 117.3 (3) |
C9—C8—Cl1 | 111.1 (2) | C1—C6—H6 | 121.4 |
Cl3—C8—Cl1 | 109.49 (16) | C5—C6—H6 | 121.4 |
Cl2—C8—Cl1 | 107.61 (16) | C1—N1—H11 | 110 (2) |
O2—C9—O1 | 127.2 (3) | C1—N1—H12 | 110 (2) |
O2—C9—C8 | 117.4 (2) | H11—N1—H12 | 110 (4) |
O1—C9—C8 | 115.4 (3) | C1—N1—H13 | 110 (3) |
C6—C1—C2 | 122.8 (3) | H11—N1—H13 | 110 (4) |
C6—C1—N1 | 117.7 (3) | H12—N1—H13 | 109 (4) |
C2—C1—N1 | 119.5 (3) | C2—C7—H71 | 109.5 |
C1—C2—C3 | 117.3 (3) | C2—C7—H72 | 109.5 |
C1—C2—C7 | 121.6 (3) | H71—C7—H72 | 109.5 |
C3—C2—C7 | 121.0 (3) | C2—C7—H73 | 109.5 |
C4—C3—C2 | 121.8 (3) | H71—C7—H73 | 109.5 |
C4—C3—H3 | 119.1 | H72—C7—H73 | 109.5 |
C2—C3—H3 | 119.1 | O3—N2—O4 | 123.5 (4) |
C5—C4—C3 | 118.4 (3) | O3—N2—C5 | 118.3 (3) |
C5—C4—H4 | 120.8 | O4—N2—C5 | 118.2 (4) |
C3—C4—H4 | 120.8 | H51—O5—H52 | 104 (2) |
C4—C5—C6 | 122.4 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H11···O2 | 0.86 (4) | 1.95 (4) | 2.810 (4) | 179 (6) |
N1—H12···O5 | 0.88 (4) | 1.90 (4) | 2.772 (4) | 169 (4) |
N1—H13···O1i | 0.86 (4) | 2.04 (4) | 2.903 (4) | 177 (4) |
N1—H13···O2i | 0.86 (4) | 2.52 (4) | 3.066 (3) | 122 (3) |
O5—H51···O1ii | 0.92 (4) | 2.26 (4) | 3.175 (4) | 178 (4) |
O5—H52···O1iii | 0.92 (4) | 1.96 (4) | 2.851 (4) | 165 (5) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z+1; (iii) x, y−1, z. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C5H6ClN2+·C2Cl3O2− | C7H9N2O2+·C2Cl3O2−·H2O |
Mr | 291.94 | 333.55 |
Crystal system, space group | Monoclinic, Cc | Triclinic, P1 |
Temperature (K) | 295 | 295 |
a, b, c (Å) | 5.6426 (11), 17.512 (3), 11.323 (2) | 6.9810 (14), 8.3611 (17), 12.229 (2) |
α, β, γ (°) | 90, 94.36 (1), 90 | 103.74 (1), 92.29 (1), 94.77 (1) |
V (Å3) | 1115.6 (4) | 689.6 (2) |
Z | 4 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.04 | 0.68 |
Crystal size (mm) | 0.32 × 0.24 × 0.16 | 0.34 × 0.30 × 0.16 |
Data collection | ||
Diffractometer | KUMA KM-4 diffractometer with CCD area detector | KUMA KM-4 diffractometer with CCD area detector |
Absorption correction | Numerical (CrysAlis RED; Oxford Diffraction Poland, 2008) | Numerical (CrysAlis RED; Oxford Diffraction Poland, 2008) |
Tmin, Tmax | 0.732, 0.851 | 0.811, 0.908 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7423, 2699, 1817 | 7531, 3305, 2306 |
Rint | 0.023 | 0.020 |
(sin θ/λ)max (Å−1) | 0.692 | 0.661 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.047, 1.00 | 0.058, 0.131, 1.01 |
No. of reflections | 2699 | 3305 |
No. of parameters | 145 | 189 |
No. of restraints | 2 | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.35, −0.20 | 0.42, −0.46 |
Absolute structure | Flack (1983) , 1226 Friedel-pairs | ? |
Absolute structure parameter | 0.10 (5) | ? |
Computer programs: CrysAlis CCD (Oxford Diffraction Poland, 2008), CrysAlis RED (Oxford Diffraction Poland, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Diamond (Brandenburg & Putz, 2006).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1 | 0.83 (2) | 1.98 (2) | 2.806 (3) | 174 (2) |
N2—H21···O1i | 0.87 (2) | 2.03 (1) | 2.893 (3) | 176 (3) |
N2—H22···O2 | 0.87 (2) | 1.96 (2) | 2.821 (3) | 175 (2) |
Symmetry code: (i) x−1/2, −y+1/2, z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H11···O2 | 0.86 (4) | 1.95 (4) | 2.810 (4) | 179 (6) |
N1—H12···O5 | 0.88 (4) | 1.90 (4) | 2.772 (4) | 169 (4) |
N1—H13···O1i | 0.86 (4) | 2.04 (4) | 2.903 (4) | 177 (4) |
N1—H13···O2i | 0.86 (4) | 2.52 (4) | 3.066 (3) | 122 (3) |
O5—H51···O1ii | 0.92 (4) | 2.26 (4) | 3.175 (4) | 178 (4) |
O5—H52···O1iii | 0.92 (4) | 1.96 (4) | 2.851 (4) | 165 (5) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z+1; (iii) x, y−1, z. |
The hybrid crystals of base–acid interactions are potentially good materials for exhibiting nonlinear optical properties (Chemla & Zyss, 1987; Marchewka et al. 2003). In these materials, the anion is responsible for favourable chemical and mechanical properties as a result of directional and relatively strong hydrogen-bond interactions, while the organic base, owing to its relatively high hyperpolarizability, is mainly responsible for the nonlinear optical properties (Bhattacharya et al. 1994; Blagden & Seddon, 1999; Głowiak et al. 2001). Continuing our studies on characterization of the acid–base hybrid crystals exhibiting nonlinear properties as well as hydrogen-bond interactions and molecular recognition in the solid-state (Janczak & Perpétuo, 2007; Perpétuo & Janczak, 2007), in the present work we investigate the solid-state structures of two crystals, 2-amino-5-chloropyridinium trichloroacetate, (I), and 2-methyl-5-nitroanilinium trichloroacetate monohydrate, (II).
The asymmetric unit of (I) consists of a 2-amino-5-chloropyridinium cation protonated at the ring N atom and a trichloroacetate anion joined together by two almost linear N—H···O hydrogen bonds (Fig. 1). Oppositely charged hydrogen-bonded C5H6ClN2+ and C2Cl3O2- units related by a c-glide plane interact with one another via an additional pair of symmetry-equivalent N—H···O hydrogen bonds (Table 1) between the amine group of the 2-amino-5-chloropyridinium cation and an O atom of the trichloroacetate anion [N2—H21···O1i; symmetry code: (i) x - 1/2, -y + 1/2, z - 1/2] forming a one-dimensional chain in the [101] direction. The hydrogen-bonded chains related by a translation along the a axis form sheets located parallel to the (010) crystallographic plane at b = 1/2 and 3/4 (Fig. 2). No hydrogen bonds are present between the sheets; they interact only through van der Waals forces. The C—O bond lengths of the COO- group of the trichloroacetate anion are slightly different [C1—O1 = 1.236 (2) Å and C1—O2 = 1.220 (2) Å] and correlate well with the number and the strength of the hydrogen bonds in which they are involved as acceptors. The O atom with the longer C—O bond is involved in two hydrogen bonds and that with the shorter C—O bond in only one hydrogen bond.
The asymmetric unit of (II) consists of a 2-methyl-5-nitroanilinium cation, a trichloroacetate anion and a water molecule joined together via N—H···O hydrogen bonds (Fig. 3). All H atoms of the protonated amine group are involved in N—H···O hydrogen bonds, with the neighbouring trichloroacetate anions and with the water molecule as acceptors. The water molecule, besides the N—H···O(water) hydrogen bond in which it acts as an acceptor, acts also as a donor in two O—H···O hydrogen bonds linking two trichloroacetate anions (Table 2). Hydrogen-bonded aggregates related by an inversion center form a stacking structure along the a axis. The aromatic rings of the 2-methyl-5-nitroanilinium cations are slipped and separated by a distance of 3.408 (3) Å, pointing to a π–π interactions between the rings, since the value is comparable to the sum of the van der Waals radii of the C atoms of the interacting ring systems (Pauling, 1960; Janiak, 2000; Hunter et al. 2001). The oppositely charged 2-methyl-5-nitroanilinium and trichloroacetate units are interconnected via N—H···O hydrogen bonds, together with much weaker C4—H41···Cl1iv [symmetry code: (i) -x + 1, -y + 1, -z + 2] hydrogen bonds, form double chains that are interconnected via hydrogen bonds with water molecules into a three-dimensional network (Fig. 4).
This study illustrates the utility of trichloroacetic acid in crystal engineering for developing supramolecular structures in solids. One of the investigated crystals exhibits nonlinear optical properties. The structures illustrate that weak π–π aromatic interactions between slipped rings modulated by stronger hydrogen bonds play a significant role in assembling of the components of the supramolecular systems. In (I), the components interact via an R22(8) hydrogen-bond motif between the COO- group and the 2-amino-5-chloropyridinium cation, whereas in (II), the O atoms of COO- are involved as acceptors with two 2-methyl-5-nitroanilinium cations. Thus the different topology of the hydrogen-bonding interractions between the components reflects in the dimensionality of the formed hydrogen-bonding networks.