Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109036476/mx3019sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109036476/mx3019Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109036476/mx3019IIasup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109036476/mx3019IIbsup4.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109036476/mx3019IIcsup5.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109036476/mx3019IIdsup6.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109036476/mx3019IRTsup7.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109036476/mx3019IIdRTsup8.hkl |
CCDC references: 755988; 755989; 755990; 755991; 755992; 755993; 755994
The synthesis of (I) has been described previously (Behrman, 2008). Crystals suitable for X-ray diffraction analysis of each of the solvates were prepared as follows. For (IIa), from CHCl3: the crude material (200 mg) was dissolved in hot CHCl3 (9 ml). For (IIb), from CCl4: CHCl3-containing crystals (25 mg) were dissolved in boiling CCl4 (25 ml). For (IIc), from CH2ClCH2Cl: CHCl3-containing crystals (200 mg) were dissolved in boiling CH2ClCH2Cl (10 ml). For (IId), rom CHCl2CHCl2: CHCl3-containing crystals (50 mg) were dissolved in hot (not boiling) CHCl2CHCl2 (2.5 ml). In each case, crystals grew on cooling as pale-yellow needles. Small crystals of (I) formed on sublimation of the solvate crystals at 378 K and 0.5 mm Hg (1mm Hg = 133.322 Pa).
Crystals formed from all four solvents melt at 424–425 K (decomposition), as does the sublimate. This implies that solvent loss below the melting point occurs for all forms of (II), which then transforms to (I), thereby yielding a single melting point. All solvate crystals give identical IR spectra as mulls in Nujol: 1668, 1605, 1491, 1325, 1283, 1240, 1208, 1182, 1085, 912, 811, 691 cm-1. When these crystals are sublimed in vacuo, different IR spectra result: 1591, 1503, 1337, 1246, 1195, 1183, 1168, 1081, 910, 810, 693 cm-1. UV [1 × 10-4M aqueous HCl, λmax (nm), ε (M-1 cm-1)]: 301, 4900; 222, 5100; 330–340 (sh). The sublimate gives 301, 5700; 222, 5550, 330–340 (sh). Crystallization from chlorobenzene gives material with the same IR spectrum as the sublimate. The 1H NMR spectrum of the sublimate no longer shows evidence of solvent but is otherwise identical to that reported previously (Behrman, 2008). 1H NMR spectra of crystals grown from either acetone or propan-2-ol suggested stoichiometry similar to (IIa), (IIb), (IIc) and (IId) but the crystals were too small for X-ray analysis. Estimates of guest:host molecule ratios were made either by 600 MHz 1H NMR [(IIa), (IIc) and (IId)], or by 800 MHz 13C NMR with inverse gated 1H decoupling and a delay time of 8 s under the following conditions: 18 mg crystals, 15 mg Cr(acac)3, 0.6 ml CDCl3, 0.3 ml DMSO-d6 (Berger & Braun, 2004), as well as by disorder model refinement [(IIa) and (IIb)] and by a count of the number of electrons present within the channels of (IIa), (IIb), (IIc) and (IId) using SQUEEZE in PLATON (Spek, 2009).
H atoms in each of the structures were found in difference Fourier maps and subsequently placed in idealized positions, with C—H = 0.95 (CArH) or 1.00 Å [in the CHCl3 of (IIa)], N—H = 0.88 Å and O—H = 0.84 Å, and with Uiso(H) = 1.2Ueq(C,N) or 1.5Ueq(O).
In (IIa) and (IIb), the solvent molecules are disordered on sites of 4 point symmetry. They required restraints on interatomic distances (SADI in SHELXL97; Sheldrick, 2008) to maintain a chemically sensible geometry, and on displacement parameters (SIMU in SHELXL97) to counteract distortion of the resulting ellipsoids caused by the symmetry of the solvent site. In (IIb), the CCl4 was split over two sites, each with occupancy 0.125. The corresponding atoms in each fragment were close enough to warrant use of the EADP constraint in addition to SIMU. In (IIc) and (IId), molecules of solvent were also disordered on sites of 4 symmetry, but suitable disorder models could not be found. In order to obtain a better quality refinement of the host-molecule framework, the SQUEEZE routine in PLATON (Spek, 2009) was used to remove the contribution from the disordered solvent.
Data collection: COLLECT (Nonius, 1998) for (I), (IIa), (IIc), IRT, IIdRT; APEX2 (Bruker, 2006) for (IIb), (IId). Cell refinement: SCALEPACK (Otwinowski & Minor, 1997) for (I), (IIa), (IIc), IRT, IIdRT; APEX2 (Bruker, 2006) for (IIb), (IId). Data reduction: DENZO-SMN (Otwinowski & Minor, 1997) for (I), (IIa), (IIc), IRT, IIdRT; APEX2 (Bruker, 2006) for (IIb), (IId). For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008). Software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and local procedures for (I), (IIa), (IIb), (IIc), (IId), IRT; SHELXL97 (Sheldrick, 2008) and local procedures. for IIdRT.
C5H4ClNO2 | F(000) = 296 |
Mr = 145.54 | Dx = 1.670 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 1401 reflections |
a = 4.1960 (1) Å | θ = 1.0–27.5° |
b = 10.6058 (3) Å | µ = 0.57 mm−1 |
c = 13.0059 (4) Å | T = 90 K |
β = 90.8559 (12)° | Block, colourless |
V = 578.72 (3) Å3 | 0.15 × 0.15 × 0.12 mm |
Z = 4 |
Nonius KappaCCD area-detector diffractometer | 1124 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.037 |
Graphite monochromator | θmax = 27.5°, θmin = 2.5° |
Detector resolution: 9.1 pixels mm-1 | h = −5→5 |
ω scans at fixed χ = 55° | k = −11→13 |
7956 measured reflections | l = −16→16 |
1329 independent reflections |
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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.081 | H-atom parameters constrained |
S = 1.12 | w = 1/[σ2(Fo2) + (0.0256P)2 + 0.4865P] where P = (Fo2 + 2Fc2)/3 |
1329 reflections | (Δ/σ)max = 0.001 |
83 parameters | Δρmax = 0.28 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
C5H4ClNO2 | V = 578.72 (3) Å3 |
Mr = 145.54 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 4.1960 (1) Å | µ = 0.57 mm−1 |
b = 10.6058 (3) Å | T = 90 K |
c = 13.0059 (4) Å | 0.15 × 0.15 × 0.12 mm |
β = 90.8559 (12)° |
Nonius KappaCCD area-detector diffractometer | 1124 reflections with I > 2σ(I) |
7956 measured reflections | Rint = 0.037 |
1329 independent reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.081 | H-atom parameters constrained |
S = 1.12 | Δρmax = 0.28 e Å−3 |
1329 reflections | Δρmin = −0.26 e Å−3 |
83 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 > 2σ(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 | ||
N1 | 0.7527 (3) | 0.39466 (14) | 0.42347 (10) | 0.0135 (3) | |
H1 | 0.8152 | 0.4063 | 0.4877 | 0.016* | |
C2 | 0.8634 (4) | 0.47507 (16) | 0.35071 (13) | 0.0144 (4) | |
C3 | 0.7474 (4) | 0.45377 (17) | 0.24818 (13) | 0.0154 (3) | |
H3 | 0.8150 | 0.5071 | 0.1940 | 0.019* | |
C4 | 0.5417 (4) | 0.35810 (17) | 0.22780 (13) | 0.0168 (4) | |
H4 | 0.4658 | 0.3464 | 0.1593 | 0.020* | |
C5 | 0.4369 (4) | 0.27523 (16) | 0.30544 (13) | 0.0148 (4) | |
C6 | 0.5503 (4) | 0.29713 (16) | 0.40244 (13) | 0.0142 (3) | |
O1 | 1.0593 (3) | 0.56173 (12) | 0.37709 (9) | 0.0170 (3) | |
O2 | 0.2272 (3) | 0.18022 (12) | 0.28759 (10) | 0.0188 (3) | |
H2 | 0.2661 | 0.1465 | 0.2307 | 0.028* | |
Cl1 | 0.44759 (11) | 0.20514 (4) | 0.50532 (3) | 0.02215 (15) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0152 (7) | 0.0155 (7) | 0.0098 (6) | 0.0000 (6) | −0.0016 (5) | −0.0013 (6) |
C2 | 0.0162 (8) | 0.0128 (8) | 0.0142 (8) | 0.0030 (6) | 0.0009 (6) | −0.0002 (6) |
C3 | 0.0186 (8) | 0.0162 (9) | 0.0115 (8) | 0.0025 (7) | 0.0010 (6) | 0.0021 (7) |
C4 | 0.0177 (8) | 0.0207 (9) | 0.0120 (8) | 0.0046 (7) | −0.0003 (6) | −0.0031 (7) |
C5 | 0.0125 (8) | 0.0154 (9) | 0.0164 (8) | 0.0021 (6) | 0.0005 (6) | −0.0044 (7) |
C6 | 0.0153 (8) | 0.0134 (8) | 0.0139 (8) | 0.0016 (7) | 0.0015 (6) | 0.0011 (7) |
O1 | 0.0207 (6) | 0.0155 (6) | 0.0148 (6) | −0.0024 (5) | −0.0013 (5) | 0.0007 (5) |
O2 | 0.0183 (6) | 0.0204 (7) | 0.0178 (6) | −0.0047 (5) | 0.0010 (5) | −0.0057 (5) |
Cl1 | 0.0246 (3) | 0.0252 (3) | 0.0167 (2) | −0.00672 (18) | −0.00072 (17) | 0.00559 (18) |
N1—C2 | 1.361 (2) | C4—C5 | 1.414 (2) |
N1—C6 | 1.363 (2) | C4—H4 | 0.9500 |
N1—H1 | 0.8800 | C5—O2 | 1.356 (2) |
C2—O1 | 1.277 (2) | C5—C6 | 1.362 (2) |
C2—C3 | 1.431 (2) | C6—Cl1 | 1.7162 (17) |
C3—C4 | 1.356 (2) | O2—H2 | 0.8400 |
C3—H3 | 0.9500 | ||
C2—N1—C6 | 123.64 (14) | C3—C4—H4 | 119.0 |
C2—N1—H1 | 118.2 | C5—C4—H4 | 119.0 |
C6—N1—H1 | 118.2 | O2—C5—C6 | 120.16 (16) |
O1—C2—N1 | 119.31 (15) | O2—C5—C4 | 123.23 (15) |
O1—C2—C3 | 124.95 (15) | C6—C5—C4 | 116.59 (16) |
N1—C2—C3 | 115.74 (15) | C5—C6—N1 | 121.55 (16) |
C4—C3—C2 | 120.48 (16) | C5—C6—Cl1 | 122.48 (14) |
C4—C3—H3 | 119.8 | N1—C6—Cl1 | 115.97 (12) |
C2—C3—H3 | 119.8 | C5—O2—H2 | 109.5 |
C3—C4—C5 | 121.98 (16) | ||
C6—N1—C2—O1 | −178.08 (15) | O2—C5—C6—N1 | −177.66 (15) |
C6—N1—C2—C3 | 1.6 (2) | C4—C5—C6—N1 | 0.5 (2) |
O1—C2—C3—C4 | 179.30 (16) | O2—C5—C6—Cl1 | 2.1 (2) |
N1—C2—C3—C4 | −0.3 (2) | C4—C5—C6—Cl1 | −179.81 (12) |
C2—C3—C4—C5 | −0.8 (3) | C2—N1—C6—C5 | −1.7 (3) |
C3—C4—C5—O2 | 178.80 (16) | C2—N1—C6—Cl1 | 178.57 (13) |
C3—C4—C5—C6 | 0.7 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.88 | 1.86 | 2.7393 (18) | 177 |
O2—H2···O1ii | 0.84 | 1.83 | 2.6507 (17) | 166 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+3/2, y−1/2, −z+1/2. |
C5H4ClNO2·0.125CHCl3 | Dx = 1.667 Mg m−3 |
Mr = 160.46 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, I41/a | Cell parameters from 3119 reflections |
Hall symbol: -I 4ad | θ = 1.0–27.5° |
a = 27.1736 (10) Å | µ = 0.68 mm−1 |
c = 6.9253 (2) Å | T = 90 K |
V = 5113.7 (3) Å3 | Block cut from needle, pale yellow |
Z = 32 | 0.20 × 0.18 × 0.18 mm |
F(000) = 2600 |
Nonius KappaCCD area-detector diffractometer | 2924 independent reflections |
Radiation source: fine-focus sealed tube | 1731 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.069 |
Detector resolution: 9.1 pixels mm-1 | θmax = 27.5°, θmin = 1.5° |
ω scans at fixed χ = 55° | h = −35→35 |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | k = −24→24 |
Tmin = 0.877, Tmax = 0.888 | l = −5→8 |
12800 measured reflections |
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)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.146 | H-atom parameters constrained |
S = 0.99 | w = 1/[σ2(Fo2) + (0.0769P)2] where P = (Fo2 + 2Fc2)/3 |
2924 reflections | (Δ/σ)max = 0.001 |
198 parameters | Δρmax = 0.53 e Å−3 |
12 restraints | Δρmin = −0.44 e Å−3 |
C5H4ClNO2·0.125CHCl3 | Z = 32 |
Mr = 160.46 | Mo Kα radiation |
Tetragonal, I41/a | µ = 0.68 mm−1 |
a = 27.1736 (10) Å | T = 90 K |
c = 6.9253 (2) Å | 0.20 × 0.18 × 0.18 mm |
V = 5113.7 (3) Å3 |
Nonius KappaCCD area-detector diffractometer | 2924 independent reflections |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | 1731 reflections with I > 2σ(I) |
Tmin = 0.877, Tmax = 0.888 | Rint = 0.069 |
12800 measured reflections |
R[F2 > 2σ(F2)] = 0.052 | 12 restraints |
wR(F2) = 0.146 | H-atom parameters constrained |
S = 0.99 | Δρmax = 0.53 e Å−3 |
2924 reflections | Δρmin = −0.44 e Å−3 |
198 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 > 2σ(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. The chloroform solvent is disordered on a 4, and as such required restraints on interatomic distances (SADI in SHELXL97) to maintain a chemically sensible geometry, and on displacement parameters (SIMU in SHELXL97) to counteract the influence of the disorder. Quantitative 1H NMR spectroscopy indicated a ratio of pyridine:solvent of about 8:1, which was is good agreement with the amount required by full occupancy of the 4 sites within the channels of this crystal structure. A count of electrons (59.5 e) within the channels by the SQUEEZE routine in PLATON (Spek, 2003) also indicated full occupancy for the solvent sites. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
N1A | 0.42002 (9) | 0.46883 (9) | 0.4204 (3) | 0.0177 (6) | |
C2A | 0.44769 (11) | 0.47793 (11) | 0.2654 (4) | 0.0195 (7) | |
C3A | 0.42923 (11) | 0.50030 (11) | 0.1000 (4) | 0.0191 (7) | |
H3A | 0.4500 | 0.5072 | −0.0070 | 0.023* | |
C4A | 0.38012 (12) | 0.51209 (11) | 0.0957 (4) | 0.0206 (7) | |
H4A | 0.3664 | 0.5272 | −0.0157 | 0.025* | |
C5A | 0.35031 (11) | 0.50183 (11) | 0.2551 (4) | 0.0175 (7) | |
C6A | 0.37214 (11) | 0.48039 (11) | 0.4116 (4) | 0.0182 (7) | |
O1A | 0.49568 (8) | 0.46619 (9) | 0.2699 (3) | 0.0278 (6) | |
H1A | 0.5021 | 0.4518 | 0.3742 | 0.042* | |
O2A | 0.30080 (7) | 0.51153 (8) | 0.2389 (3) | 0.0230 (5) | |
H2A | 0.2898 | 0.5210 | 0.3461 | 0.035* | |
Cl1A | 0.33779 (3) | 0.46810 (3) | 0.61766 (11) | 0.0208 (2) | |
N1B | 0.52399 (9) | 0.41149 (9) | 0.5796 (4) | 0.0197 (6) | |
C2B | 0.49708 (11) | 0.40275 (11) | 0.7368 (4) | 0.0206 (7) | |
C3B | 0.51585 (12) | 0.37849 (12) | 0.8973 (4) | 0.0240 (8) | |
H3B | 0.4958 | 0.3726 | 1.0074 | 0.029* | |
C4B | 0.56389 (12) | 0.36319 (11) | 0.8936 (4) | 0.0232 (7) | |
H4B | 0.5775 | 0.3466 | 1.0021 | 0.028* | |
C5B | 0.59301 (11) | 0.37184 (11) | 0.7306 (4) | 0.0194 (7) | |
C6B | 0.57061 (11) | 0.39608 (11) | 0.5798 (4) | 0.0193 (7) | |
O1B | 0.44964 (8) | 0.41806 (8) | 0.7360 (3) | 0.0251 (6) | |
H1B | 0.4440 | 0.4337 | 0.6338 | 0.038* | |
O2B | 0.64090 (8) | 0.35919 (9) | 0.7141 (3) | 0.0298 (6) | |
H2B | 0.6495 | 0.3430 | 0.8119 | 0.045* | |
Cl1B | 0.60408 (3) | 0.40782 (3) | 0.37067 (11) | 0.0230 (2) | |
C1S | 0.5269 (5) | 0.2395 (4) | 0.267 (2) | 0.033 (4)* | 0.25 |
H1S | 0.5518 | 0.2320 | 0.1642 | 0.039* | 0.25 |
Cl1S | 0.5185 (3) | 0.1854 (2) | 0.3863 (10) | 0.0471 (18) | 0.25 |
Cl2S | 0.47528 (19) | 0.25883 (18) | 0.1432 (10) | 0.0811 (19) | 0.25 |
Cl3S | 0.5522 (3) | 0.2856 (3) | 0.3983 (13) | 0.073 (3) | 0.25 |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1A | 0.0188 (14) | 0.0167 (14) | 0.0176 (14) | −0.0007 (10) | 0.0028 (11) | 0.0031 (11) |
C2A | 0.0221 (18) | 0.0202 (17) | 0.0161 (17) | −0.0012 (13) | 0.0023 (14) | 0.0011 (13) |
C3A | 0.0224 (18) | 0.0195 (17) | 0.0155 (17) | −0.0028 (13) | 0.0014 (13) | 0.0006 (13) |
C4A | 0.0275 (19) | 0.0177 (16) | 0.0166 (17) | 0.0003 (13) | 0.0002 (14) | 0.0024 (13) |
C5A | 0.0164 (17) | 0.0166 (16) | 0.0196 (16) | 0.0002 (12) | 0.0005 (13) | −0.0024 (13) |
C6A | 0.0221 (17) | 0.0154 (16) | 0.0171 (17) | −0.0051 (12) | 0.0024 (14) | −0.0005 (13) |
O1A | 0.0196 (13) | 0.0403 (15) | 0.0235 (13) | 0.0076 (10) | 0.0033 (10) | 0.0109 (11) |
O2A | 0.0176 (12) | 0.0300 (13) | 0.0214 (13) | 0.0024 (9) | −0.0016 (10) | −0.0025 (10) |
Cl1A | 0.0216 (4) | 0.0231 (4) | 0.0177 (4) | −0.0013 (3) | 0.0038 (3) | 0.0023 (3) |
N1B | 0.0182 (14) | 0.0185 (14) | 0.0226 (14) | 0.0002 (11) | 0.0027 (12) | 0.0034 (12) |
C2B | 0.0215 (18) | 0.0206 (18) | 0.0196 (17) | −0.0014 (13) | −0.0017 (14) | 0.0007 (14) |
C3B | 0.0241 (18) | 0.0305 (19) | 0.0172 (17) | −0.0009 (14) | 0.0053 (15) | 0.0045 (15) |
C4B | 0.0302 (19) | 0.0206 (17) | 0.0187 (17) | −0.0025 (14) | −0.0034 (15) | 0.0051 (14) |
C5B | 0.0200 (17) | 0.0198 (17) | 0.0184 (17) | −0.0011 (13) | −0.0004 (13) | −0.0020 (14) |
C6B | 0.0222 (17) | 0.0172 (16) | 0.0184 (16) | −0.0033 (13) | 0.0029 (13) | −0.0023 (14) |
O1B | 0.0226 (13) | 0.0294 (13) | 0.0232 (13) | 0.0036 (9) | 0.0059 (10) | 0.0124 (10) |
O2B | 0.0255 (13) | 0.0375 (15) | 0.0264 (13) | 0.0060 (10) | −0.0005 (11) | 0.0096 (11) |
Cl1B | 0.0211 (4) | 0.0297 (5) | 0.0182 (4) | 0.0019 (3) | 0.0042 (3) | 0.0045 (3) |
Cl1S | 0.073 (5) | 0.037 (3) | 0.031 (3) | −0.006 (3) | −0.010 (3) | 0.008 (2) |
Cl2S | 0.060 (3) | 0.051 (3) | 0.133 (6) | −0.009 (2) | −0.062 (3) | 0.029 (3) |
Cl3S | 0.090 (7) | 0.042 (4) | 0.087 (6) | −0.023 (4) | −0.025 (5) | −0.004 (4) |
N1A—C2A | 1.333 (4) | C2B—O1B | 1.355 (4) |
N1A—C6A | 1.340 (4) | C2B—C3B | 1.390 (4) |
C2A—O1A | 1.343 (3) | C3B—C4B | 1.370 (4) |
C2A—C3A | 1.391 (4) | C3B—H3B | 0.9500 |
C3A—C4A | 1.373 (4) | C4B—C5B | 1.399 (4) |
C3A—H3A | 0.9500 | C4B—H4B | 0.9500 |
C4A—C5A | 1.397 (4) | C5B—O2B | 1.351 (4) |
C4A—H4A | 0.9500 | C5B—C6B | 1.376 (4) |
C5A—C6A | 1.366 (4) | C6B—Cl1B | 1.740 (3) |
C5A—O2A | 1.375 (3) | O1B—H1B | 0.8400 |
C6A—Cl1A | 1.738 (3) | O2B—H2B | 0.8400 |
O1A—H1A | 0.8400 | C1S—Cl3S | 1.696 (11) |
O2A—H2A | 0.8400 | C1S—Cl1S | 1.703 (11) |
N1B—C2B | 1.333 (4) | C1S—Cl2S | 1.726 (11) |
N1B—C6B | 1.334 (4) | C1S—H1S | 1.0000 |
C2A—N1A—C6A | 117.9 (3) | O1B—C2B—C3B | 119.9 (3) |
N1A—C2A—O1A | 119.0 (3) | C4B—C3B—C2B | 118.6 (3) |
N1A—C2A—C3A | 122.7 (3) | C4B—C3B—H3B | 120.7 |
O1A—C2A—C3A | 118.2 (3) | C2B—C3B—H3B | 120.7 |
C4A—C3A—C2A | 118.1 (3) | C3B—C4B—C5B | 120.2 (3) |
C4A—C3A—H3A | 121.0 | C3B—C4B—H4B | 119.9 |
C2A—C3A—H3A | 121.0 | C5B—C4B—H4B | 119.9 |
C3A—C4A—C5A | 120.0 (3) | O2B—C5B—C6B | 118.9 (3) |
C3A—C4A—H4A | 120.0 | O2B—C5B—C4B | 124.8 (3) |
C5A—C4A—H4A | 120.0 | C6B—C5B—C4B | 116.3 (3) |
C6A—C5A—O2A | 124.8 (3) | N1B—C6B—C5B | 124.8 (3) |
C6A—C5A—C4A | 117.4 (3) | N1B—C6B—Cl1B | 116.0 (2) |
O2A—C5A—C4A | 117.7 (3) | C5B—C6B—Cl1B | 119.2 (2) |
N1A—C6A—C5A | 123.9 (3) | C2B—O1B—H1B | 109.5 |
N1A—C6A—Cl1A | 116.1 (2) | C5B—O2B—H2B | 109.5 |
C5A—C6A—Cl1A | 120.0 (2) | Cl3S—C1S—Cl1S | 115.5 (8) |
C2A—O1A—H1A | 109.5 | Cl3S—C1S—Cl2S | 111.8 (7) |
C5A—O2A—H2A | 109.5 | Cl1S—C1S—Cl2S | 113.3 (7) |
C2B—N1B—C6B | 117.7 (3) | Cl3S—C1S—H1S | 105.0 |
N1B—C2B—O1B | 117.7 (3) | Cl1S—C1S—H1S | 105.0 |
N1B—C2B—C3B | 122.5 (3) | Cl2S—C1S—H1S | 105.0 |
C6A—N1A—C2A—O1A | −179.3 (3) | C6B—N1B—C2B—O1B | −179.5 (3) |
C6A—N1A—C2A—C3A | 2.4 (4) | C6B—N1B—C2B—C3B | −0.1 (4) |
N1A—C2A—C3A—C4A | −1.9 (5) | N1B—C2B—C3B—C4B | 0.2 (5) |
O1A—C2A—C3A—C4A | 179.8 (3) | O1B—C2B—C3B—C4B | 179.7 (3) |
C2A—C3A—C4A—C5A | 0.4 (4) | C2B—C3B—C4B—C5B | −0.2 (5) |
C3A—C4A—C5A—C6A | 0.5 (4) | C3B—C4B—C5B—O2B | 178.6 (3) |
C3A—C4A—C5A—O2A | −176.0 (3) | C3B—C4B—C5B—C6B | 0.1 (5) |
C2A—N1A—C6A—C5A | −1.4 (4) | C2B—N1B—C6B—C5B | −0.1 (4) |
C2A—N1A—C6A—Cl1A | −179.7 (2) | C2B—N1B—C6B—Cl1B | 179.4 (2) |
O2A—C5A—C6A—N1A | 176.3 (3) | O2B—C5B—C6B—N1B | −178.5 (3) |
C4A—C5A—C6A—N1A | 0.0 (4) | C4B—C5B—C6B—N1B | 0.1 (5) |
O2A—C5A—C6A—Cl1A | −5.6 (4) | O2B—C5B—C6B—Cl1B | 2.0 (4) |
C4A—C5A—C6A—Cl1A | 178.2 (2) | C4B—C5B—C6B—Cl1B | −179.4 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1A—H1A···N1B | 0.84 | 1.89 | 2.721 (3) | 169 |
O2A—H2A···O2Ai | 0.84 | 1.89 | 2.647 (2) | 149 |
O1B—H1B···N1A | 0.84 | 1.88 | 2.707 (3) | 170 |
O2B—H2B···O1Bii | 0.84 | 1.89 | 2.723 (3) | 174 |
Symmetry codes: (i) −y+3/4, x+1/4, z+1/4; (ii) y+1/4, −x+3/4, −z+7/4. |
C5H4ClNO2·0.125CCl4 | Dx = 1.707 Mg m−3 |
Mr = 164.77 | Cu Kα radiation, λ = 1.54178 Å |
Tetragonal, I41/a | Cell parameters from 9933 reflections |
Hall symbol: -I 4ad | θ = 3.3–68.3° |
a = 27.1708 (4) Å | µ = 6.62 mm−1 |
c = 6.9458 (1) Å | T = 90 K |
V = 5127.75 (13) Å3 | Needle, colourless |
Z = 32 | 0.12 × 0.02 × 0.01 mm |
F(000) = 2664 |
Bruker X8 Proteum diffractometer | 2344 independent reflections |
Radiation source: fine-focus rotating anode | 2237 reflections with I > 2σ(I) |
Graded multilayer optics monochromator | Rint = 0.042 |
Detector resolution: 5.6 pixels mm-1 | θmax = 68.0°, θmin = 3.3° |
ϕ and ω scans | h = −32→32 |
Absorption correction: multi-scan (SADABS in APEX2; Bruker, 2006) | k = −32→32 |
Tmin = 0.672, Tmax = 0.937 | l = −7→8 |
37025 measured reflections |
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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.092 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0491P)2 + 12.1459P] where P = (Fo2 + 2Fc2)/3 |
2344 reflections | (Δ/σ)max < 0.001 |
223 parameters | Δρmax = 0.55 e Å−3 |
63 restraints | Δρmin = −0.81 e Å−3 |
C5H4ClNO2·0.125CCl4 | Z = 32 |
Mr = 164.77 | Cu Kα radiation |
Tetragonal, I41/a | µ = 6.62 mm−1 |
a = 27.1708 (4) Å | T = 90 K |
c = 6.9458 (1) Å | 0.12 × 0.02 × 0.01 mm |
V = 5127.75 (13) Å3 |
Bruker X8 Proteum diffractometer | 2344 independent reflections |
Absorption correction: multi-scan (SADABS in APEX2; Bruker, 2006) | 2237 reflections with I > 2σ(I) |
Tmin = 0.672, Tmax = 0.937 | Rint = 0.042 |
37025 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 63 restraints |
wR(F2) = 0.092 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0491P)2 + 12.1459P] where P = (Fo2 + 2Fc2)/3 |
2344 reflections | Δρmax = 0.55 e Å−3 |
223 parameters | Δρmin = −0.81 e Å−3 |
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 > 2σ(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. The carbon tetrachloride solvent is disordered on a 4, and as such required restraints on interatomic distances (SADI in SHELXL97) to maintain a chemically sensible geometry and on displacement parameters (SIMU in SHELXL97) to counteract the influence of the disorder. The CCl4 was split over two sites, each with occupancy 0.125. The corresponding atoms in each fragment were close enough to warrant use of the EADP constraint in addition to SIMU. Quantitative 13C NMR spectroscopy indicated a ratio of pyridine:solvent of about 7:1, which is in good agreement with the amount required by full occupancy of the 4 sites within the channels of this crystal structure. A count of electrons (74.7 e) within the channels by the SQUEEZE routine in PLATON (Spek, 2003) also indicated full occupancy for the solvent sites. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
N1A | 0.42009 (6) | 0.46889 (6) | 0.4207 (3) | 0.0164 (4) | |
C2A | 0.44786 (7) | 0.47826 (7) | 0.2661 (3) | 0.0176 (4) | |
C3A | 0.42893 (8) | 0.50055 (7) | 0.1005 (3) | 0.0177 (4) | |
H3A | 0.4496 | 0.5075 | −0.0065 | 0.021* | |
C4A | 0.38005 (8) | 0.51206 (7) | 0.0963 (3) | 0.0180 (4) | |
H4A | 0.3663 | 0.5270 | −0.0150 | 0.022* | |
C5A | 0.35011 (7) | 0.50192 (7) | 0.2548 (3) | 0.0170 (4) | |
C6A | 0.37236 (8) | 0.48054 (7) | 0.4121 (3) | 0.0163 (4) | |
O1A | 0.49565 (5) | 0.46650 (6) | 0.2699 (2) | 0.0242 (4) | |
H1A | 0.5018 | 0.4503 | 0.3701 | 0.036* | |
O2A | 0.30080 (5) | 0.51133 (6) | 0.2398 (2) | 0.0205 (3) | |
H2A | 0.2897 | 0.5198 | 0.3478 | 0.031* | |
Cl1A | 0.337915 (18) | 0.468164 (18) | 0.61718 (7) | 0.01895 (16) | |
N1B | 0.52401 (6) | 0.41179 (6) | 0.5796 (3) | 0.0170 (4) | |
C2B | 0.49704 (7) | 0.40343 (8) | 0.7367 (3) | 0.0183 (4) | |
C3B | 0.51594 (8) | 0.37910 (8) | 0.8967 (3) | 0.0211 (5) | |
H3B | 0.4960 | 0.3735 | 1.0070 | 0.025* | |
C4B | 0.56412 (8) | 0.36336 (8) | 0.8918 (3) | 0.0212 (5) | |
H4B | 0.5777 | 0.3467 | 0.9996 | 0.025* | |
C5B | 0.59303 (8) | 0.37185 (8) | 0.7288 (3) | 0.0186 (4) | |
C6B | 0.57058 (8) | 0.39612 (7) | 0.5778 (3) | 0.0171 (4) | |
O1B | 0.44977 (5) | 0.41855 (6) | 0.7365 (2) | 0.0231 (3) | |
H1B | 0.4438 | 0.4335 | 0.6333 | 0.035* | |
O2B | 0.64073 (6) | 0.35852 (6) | 0.7108 (2) | 0.0257 (4) | |
H2B | 0.6501 | 0.3446 | 0.8125 | 0.039* | |
Cl1B | 0.603645 (18) | 0.407700 (19) | 0.36973 (7) | 0.02072 (16) | |
C1S | 0.5022 (7) | 0.2620 (5) | 0.3477 (18) | 0.059 (3)* | 0.125 |
Cl1S | 0.4941 (8) | 0.2449 (5) | 0.1066 (13) | 0.079 (2) | 0.125 |
Cl2S | 0.4858 (6) | 0.2183 (6) | 0.5193 (17) | 0.098 (3) | 0.125 |
Cl3S | 0.5651 (9) | 0.2778 (14) | 0.378 (3) | 0.048 (3) | 0.125 |
Cl4S | 0.4668 (15) | 0.3161 (6) | 0.385 (3) | 0.0433 (18) | 0.125 |
C2S | 0.5025 (9) | 0.2552 (7) | 0.391 (2) | 0.059 (3)* | 0.125 |
Cl5S | 0.4862 (4) | 0.2234 (3) | 0.1840 (17) | 0.079 (2) | 0.125 |
Cl6S | 0.4941 (8) | 0.2273 (7) | 0.6125 (19) | 0.098 (3) | 0.125 |
Cl7S | 0.5653 (9) | 0.2709 (14) | 0.358 (3) | 0.048 (3) | 0.125 |
Cl8S | 0.4680 (16) | 0.3107 (7) | 0.381 (3) | 0.0433 (18) | 0.125 |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1A | 0.0173 (8) | 0.0169 (8) | 0.0151 (8) | −0.0014 (6) | 0.0017 (7) | 0.0016 (7) |
C2A | 0.0181 (10) | 0.0183 (10) | 0.0164 (10) | −0.0011 (8) | 0.0023 (8) | 0.0014 (8) |
C3A | 0.0220 (10) | 0.0169 (10) | 0.0141 (10) | −0.0017 (8) | 0.0027 (8) | 0.0014 (8) |
C4A | 0.0242 (11) | 0.0160 (10) | 0.0137 (10) | −0.0008 (8) | −0.0011 (8) | 0.0013 (8) |
C5A | 0.0175 (10) | 0.0152 (9) | 0.0182 (10) | −0.0008 (7) | −0.0012 (8) | −0.0024 (8) |
C6A | 0.0185 (10) | 0.0156 (9) | 0.0148 (10) | −0.0036 (8) | 0.0013 (8) | −0.0003 (8) |
O1A | 0.0169 (7) | 0.0363 (9) | 0.0195 (8) | 0.0047 (6) | 0.0032 (6) | 0.0111 (7) |
O2A | 0.0177 (7) | 0.0267 (8) | 0.0172 (7) | 0.0025 (6) | −0.0003 (6) | −0.0025 (6) |
Cl1A | 0.0193 (3) | 0.0221 (3) | 0.0154 (3) | −0.00207 (17) | 0.00419 (18) | 0.00127 (18) |
N1B | 0.0178 (8) | 0.0181 (8) | 0.0150 (8) | −0.0004 (7) | 0.0013 (7) | 0.0027 (7) |
C2B | 0.0189 (10) | 0.0184 (10) | 0.0176 (10) | −0.0012 (8) | 0.0025 (8) | 0.0020 (8) |
C3B | 0.0256 (11) | 0.0223 (11) | 0.0155 (10) | −0.0012 (8) | 0.0036 (8) | 0.0044 (8) |
C4B | 0.0273 (11) | 0.0202 (10) | 0.0161 (10) | −0.0001 (8) | −0.0023 (9) | 0.0041 (8) |
C5B | 0.0192 (10) | 0.0179 (10) | 0.0188 (10) | 0.0000 (8) | −0.0019 (8) | 0.0008 (8) |
C6B | 0.0189 (10) | 0.0177 (10) | 0.0149 (10) | −0.0017 (8) | 0.0015 (8) | 0.0003 (8) |
O1B | 0.0205 (8) | 0.0299 (8) | 0.0188 (8) | 0.0037 (6) | 0.0052 (6) | 0.0106 (6) |
O2B | 0.0213 (8) | 0.0334 (9) | 0.0224 (8) | 0.0064 (6) | −0.0007 (6) | 0.0091 (7) |
Cl1B | 0.0191 (3) | 0.0274 (3) | 0.0157 (3) | 0.00228 (19) | 0.00335 (18) | 0.00476 (19) |
Cl1S | 0.092 (4) | 0.048 (4) | 0.098 (5) | 0.001 (4) | −0.039 (4) | −0.040 (4) |
Cl2S | 0.095 (5) | 0.094 (5) | 0.106 (6) | 0.006 (4) | 0.032 (6) | 0.075 (5) |
Cl3S | 0.019 (2) | 0.084 (8) | 0.041 (4) | 0.024 (3) | 0.012 (3) | 0.008 (4) |
Cl4S | 0.028 (2) | 0.064 (4) | 0.038 (3) | 0.026 (3) | −0.0047 (16) | 0.002 (3) |
Cl5S | 0.092 (4) | 0.048 (4) | 0.098 (5) | 0.001 (4) | −0.039 (4) | −0.040 (4) |
Cl6S | 0.095 (5) | 0.094 (5) | 0.106 (6) | 0.006 (4) | 0.032 (6) | 0.075 (5) |
Cl7S | 0.019 (2) | 0.084 (8) | 0.041 (4) | 0.024 (3) | 0.012 (3) | 0.008 (4) |
Cl8S | 0.028 (2) | 0.064 (4) | 0.038 (3) | 0.026 (3) | −0.0047 (16) | 0.002 (3) |
N1A—C6A | 1.336 (3) | N1B—C2B | 1.334 (3) |
N1A—C2A | 1.337 (3) | N1B—C6B | 1.335 (3) |
C2A—O1A | 1.338 (2) | C2B—O1B | 1.348 (3) |
C2A—C3A | 1.398 (3) | C2B—C3B | 1.392 (3) |
C3A—C4A | 1.365 (3) | C3B—C4B | 1.377 (3) |
C3A—H3A | 0.9500 | C3B—H3B | 0.9500 |
C4A—C5A | 1.397 (3) | C4B—C5B | 1.397 (3) |
C4A—H4A | 0.9500 | C4B—H4B | 0.9500 |
C5A—O2A | 1.368 (2) | C5B—O2B | 1.351 (3) |
C5A—C6A | 1.377 (3) | C5B—C6B | 1.381 (3) |
C6A—Cl1A | 1.737 (2) | C6B—Cl1B | 1.731 (2) |
O1A—H1A | 0.8400 | O1B—H1B | 0.8400 |
O2A—H2A | 0.8400 | O2B—H2B | 0.8400 |
C6A—N1A—C2A | 117.82 (18) | C2B—N1B—C6B | 118.29 (18) |
N1A—C2A—O1A | 119.13 (18) | N1B—C2B—O1B | 118.08 (18) |
N1A—C2A—C3A | 122.41 (19) | N1B—C2B—C3B | 122.12 (19) |
O1A—C2A—C3A | 118.46 (18) | O1B—C2B—C3B | 119.79 (19) |
C4A—C3A—C2A | 118.35 (19) | C4B—C3B—C2B | 118.6 (2) |
C4A—C3A—H3A | 120.8 | C4B—C3B—H3B | 120.7 |
C2A—C3A—H3A | 120.8 | C2B—C3B—H3B | 120.7 |
C3A—C4A—C5A | 120.31 (19) | C3B—C4B—C5B | 120.2 (2) |
C3A—C4A—H4A | 119.8 | C3B—C4B—H4B | 119.9 |
C5A—C4A—H4A | 119.8 | C5B—C4B—H4B | 119.9 |
O2A—C5A—C6A | 124.69 (19) | O2B—C5B—C6B | 118.79 (19) |
O2A—C5A—C4A | 118.26 (18) | O2B—C5B—C4B | 124.73 (19) |
C6A—C5A—C4A | 116.95 (19) | C6B—C5B—C4B | 116.47 (19) |
N1A—C6A—C5A | 124.16 (19) | N1B—C6B—C5B | 124.33 (19) |
N1A—C6A—Cl1A | 116.13 (15) | N1B—C6B—Cl1B | 116.22 (16) |
C5A—C6A—Cl1A | 119.71 (16) | C5B—C6B—Cl1B | 119.45 (16) |
C2A—O1A—H1A | 109.5 | C2B—O1B—H1B | 109.5 |
C5A—O2A—H2A | 109.5 | C5B—O2B—H2B | 109.5 |
C6A—N1A—C2A—O1A | −179.29 (18) | C6B—N1B—C2B—O1B | −178.86 (18) |
C6A—N1A—C2A—C3A | 1.5 (3) | C6B—N1B—C2B—C3B | 0.0 (3) |
N1A—C2A—C3A—C4A | −1.4 (3) | N1B—C2B—C3B—C4B | 0.1 (3) |
O1A—C2A—C3A—C4A | 179.36 (19) | O1B—C2B—C3B—C4B | 179.0 (2) |
C2A—C3A—C4A—C5A | 0.4 (3) | C2B—C3B—C4B—C5B | 0.0 (3) |
C3A—C4A—C5A—O2A | −176.08 (18) | C3B—C4B—C5B—O2B | 179.0 (2) |
C3A—C4A—C5A—C6A | 0.5 (3) | C3B—C4B—C5B—C6B | −0.3 (3) |
C2A—N1A—C6A—C5A | −0.5 (3) | C2B—N1B—C6B—C5B | −0.3 (3) |
C2A—N1A—C6A—Cl1A | −179.46 (15) | C2B—N1B—C6B—Cl1B | 179.65 (15) |
O2A—C5A—C6A—N1A | 175.89 (18) | O2B—C5B—C6B—N1B | −178.92 (19) |
C4A—C5A—C6A—N1A | −0.4 (3) | C4B—C5B—C6B—N1B | 0.4 (3) |
O2A—C5A—C6A—Cl1A | −5.2 (3) | O2B—C5B—C6B—Cl1B | 1.2 (3) |
C4A—C5A—C6A—Cl1A | 178.44 (15) | C4B—C5B—C6B—Cl1B | −179.51 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1A—H1A···N1B | 0.84 | 1.89 | 2.726 (2) | 172 |
O2A—H2A···O2Ai | 0.84 | 1.90 | 2.6487 (15) | 148 |
O1B—H1B···N1A | 0.84 | 1.88 | 2.708 (2) | 171 |
O2B—H2B···O1Bii | 0.84 | 1.91 | 2.738 (2) | 168 |
Symmetry codes: (i) −y+3/4, x+1/4, z+1/4; (ii) y+1/4, −x+3/4, −z+7/4. |
C5H4ClNO2 | Dx = 1.639 Mg m−3 |
Mr = 157.91 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, I41/a | Cell parameters from 6336 reflections |
Hall symbol: -I 4ad | θ = 1.0–27.5° |
a = 27.1149 (10) Å | µ = 0.62 mm−1 |
c = 6.9618 (2) Å | T = 90 K |
V = 5118.4 (3) Å3 | Rod cut from needle, pale yellow |
Z = 32 | 0.35 × 0.13 × 0.12 mm |
F(000) = 2568 |
Nonius KappaCCD area-detector diffractometer | 2927 independent reflections |
Radiation source: fine-focus sealed tube | 1964 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.087 |
Detector resolution: 9.1 pixels mm-1 | θmax = 27.5°, θmin = 1.5° |
ω scans at fixed χ = 55° | h = −34→34 |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | k = −34→34 |
Tmin = 0.841, Tmax = 0.941 | l = −9→9 |
52191 measured reflections |
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)] = 0.051 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.133 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0797P)2] where P = (Fo2 + 2Fc2)/3 |
2927 reflections | (Δ/σ)max = 0.001 |
167 parameters | Δρmax = 0.82 e Å−3 |
0 restraints | Δρmin = −0.36 e Å−3 |
C5H4ClNO2 | Z = 32 |
Mr = 157.91 | Mo Kα radiation |
Tetragonal, I41/a | µ = 0.62 mm−1 |
a = 27.1149 (10) Å | T = 90 K |
c = 6.9618 (2) Å | 0.35 × 0.13 × 0.12 mm |
V = 5118.4 (3) Å3 |
Nonius KappaCCD area-detector diffractometer | 2927 independent reflections |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | 1964 reflections with I > 2σ(I) |
Tmin = 0.841, Tmax = 0.941 | Rint = 0.087 |
52191 measured reflections |
R[F2 > 2σ(F2)] = 0.051 | 0 restraints |
wR(F2) = 0.133 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.82 e Å−3 |
2927 reflections | Δρmin = −0.36 e Å−3 |
167 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 > 2σ(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. Molecules of 1,2-dichloroethane were disordered on a site of 4 symmetry and were too badly disordered to decipher. Eventually it was decided to use SQUEEZE in PLATON (Spek, 2003) to remove the contribution from this disordered solvent. Quantitative 1H NMR spectroscopy indicated a ratio of pyridine:solvent of about 12:1, but this was (of necessity) obtained from a bulk sample rather than the single-crystal used for data collection. The SQUEEZE procedure indicated that 48.9 electrons were removed, which corresponds to essentially full solvent occupancy. |
x | y | z | Uiso*/Ueq | ||
N1A | 0.42000 (7) | 0.46910 (7) | 0.4194 (3) | 0.0214 (5) | |
C2A | 0.44795 (9) | 0.47827 (9) | 0.2657 (4) | 0.0222 (6) | |
C3A | 0.42918 (9) | 0.50034 (9) | 0.0997 (4) | 0.0226 (6) | |
H3A | 0.4499 | 0.5069 | −0.0073 | 0.027* | |
C4A | 0.38012 (9) | 0.51223 (9) | 0.0957 (3) | 0.0215 (5) | |
H4A | 0.3664 | 0.5274 | −0.0152 | 0.026* | |
C5A | 0.35022 (8) | 0.50212 (8) | 0.2541 (3) | 0.0191 (5) | |
C6A | 0.37221 (8) | 0.48087 (8) | 0.4103 (3) | 0.0208 (5) | |
O1A | 0.49575 (6) | 0.46627 (7) | 0.2695 (3) | 0.0312 (5) | |
H1A | 0.5025 | 0.4530 | 0.3752 | 0.047* | |
O2A | 0.30059 (6) | 0.51174 (6) | 0.2376 (2) | 0.0237 (4) | |
H2A | 0.2900 | 0.5232 | 0.3417 | 0.036* | |
Cl1A | 0.33764 (2) | 0.46858 (2) | 0.61573 (9) | 0.02273 (19) | |
N1B | 0.52363 (7) | 0.41110 (7) | 0.5785 (3) | 0.0230 (5) | |
C2B | 0.49665 (9) | 0.40300 (9) | 0.7348 (4) | 0.0239 (6) | |
C3B | 0.51547 (9) | 0.37917 (9) | 0.8957 (4) | 0.0274 (6) | |
H3B | 0.4954 | 0.3736 | 1.0054 | 0.033* | |
C4B | 0.56381 (9) | 0.36379 (9) | 0.8927 (4) | 0.0263 (6) | |
H4B | 0.5774 | 0.3475 | 1.0013 | 0.032* | |
C5B | 0.59299 (8) | 0.37199 (9) | 0.7309 (4) | 0.0235 (6) | |
C6B | 0.57025 (9) | 0.39555 (8) | 0.5787 (4) | 0.0231 (6) | |
O1B | 0.44919 (6) | 0.41809 (7) | 0.7342 (3) | 0.0298 (5) | |
H1B | 0.4430 | 0.4325 | 0.6302 | 0.045* | |
O2B | 0.64076 (6) | 0.35911 (7) | 0.7147 (3) | 0.0319 (5) | |
H2B | 0.6500 | 0.3451 | 0.8160 | 0.048* | |
Cl1B | 0.60376 (2) | 0.40687 (2) | 0.37057 (9) | 0.0276 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1A | 0.0211 (11) | 0.0192 (10) | 0.0240 (12) | −0.0015 (8) | 0.0035 (9) | 0.0038 (9) |
C2A | 0.0208 (12) | 0.0234 (13) | 0.0223 (14) | −0.0012 (10) | 0.0018 (10) | 0.0036 (10) |
C3A | 0.0251 (13) | 0.0231 (13) | 0.0196 (14) | −0.0018 (10) | 0.0027 (10) | 0.0013 (10) |
C4A | 0.0226 (13) | 0.0203 (12) | 0.0217 (14) | 0.0001 (10) | −0.0029 (10) | 0.0021 (10) |
C5A | 0.0190 (12) | 0.0179 (12) | 0.0206 (13) | −0.0022 (9) | 0.0000 (10) | −0.0026 (10) |
C6A | 0.0194 (12) | 0.0217 (12) | 0.0212 (14) | −0.0052 (10) | 0.0026 (10) | 0.0024 (10) |
O1A | 0.0211 (9) | 0.0432 (12) | 0.0294 (11) | 0.0053 (8) | 0.0020 (8) | 0.0146 (9) |
O2A | 0.0201 (9) | 0.0284 (10) | 0.0225 (10) | 0.0018 (7) | −0.0006 (7) | −0.0024 (8) |
Cl1A | 0.0217 (3) | 0.0246 (3) | 0.0219 (4) | −0.0019 (2) | 0.0040 (2) | 0.0026 (2) |
N1B | 0.0197 (11) | 0.0226 (10) | 0.0266 (12) | −0.0004 (8) | 0.0010 (9) | 0.0039 (9) |
C2B | 0.0220 (13) | 0.0249 (14) | 0.0249 (15) | −0.0018 (10) | −0.0004 (11) | 0.0065 (11) |
C3B | 0.0273 (14) | 0.0306 (14) | 0.0243 (15) | −0.0019 (11) | 0.0031 (11) | 0.0099 (11) |
C4B | 0.0280 (14) | 0.0266 (14) | 0.0244 (15) | 0.0018 (11) | −0.0037 (11) | 0.0053 (11) |
C5B | 0.0197 (13) | 0.0238 (13) | 0.0269 (15) | 0.0011 (10) | −0.0023 (11) | 0.0003 (11) |
C6B | 0.0229 (13) | 0.0219 (12) | 0.0245 (14) | −0.0014 (10) | 0.0017 (11) | 0.0012 (11) |
O1B | 0.0223 (9) | 0.0371 (11) | 0.0298 (12) | 0.0048 (7) | 0.0068 (8) | 0.0173 (9) |
O2B | 0.0271 (10) | 0.0408 (12) | 0.0278 (11) | 0.0072 (8) | −0.0023 (8) | 0.0104 (9) |
Cl1B | 0.0231 (3) | 0.0365 (4) | 0.0233 (4) | 0.0045 (3) | 0.0033 (3) | 0.0049 (3) |
N1A—C2A | 1.335 (3) | N1B—C2B | 1.330 (3) |
N1A—C6A | 1.336 (3) | N1B—C6B | 1.332 (3) |
C2A—O1A | 1.336 (3) | C2B—O1B | 1.350 (3) |
C2A—C3A | 1.397 (3) | C2B—C3B | 1.390 (3) |
C3A—C4A | 1.369 (3) | C3B—C4B | 1.375 (3) |
C3A—H3A | 0.9500 | C3B—H3B | 0.9500 |
C4A—C5A | 1.396 (3) | C4B—C5B | 1.395 (3) |
C4A—H4A | 0.9500 | C4B—H4B | 0.9500 |
C5A—C6A | 1.367 (3) | C5B—O2B | 1.346 (3) |
C5A—O2A | 1.376 (3) | C5B—C6B | 1.382 (3) |
C6A—Cl1A | 1.742 (2) | C6B—Cl1B | 1.738 (3) |
O1A—H1A | 0.8400 | O1B—H1B | 0.8400 |
O2A—H2A | 0.8400 | O2B—H2B | 0.8400 |
C2A—N1A—C6A | 117.9 (2) | C2B—N1B—C6B | 117.9 (2) |
N1A—C2A—O1A | 119.3 (2) | N1B—C2B—O1B | 118.1 (2) |
N1A—C2A—C3A | 122.4 (2) | N1B—C2B—C3B | 122.3 (2) |
O1A—C2A—C3A | 118.3 (2) | O1B—C2B—C3B | 119.6 (2) |
C4A—C3A—C2A | 118.2 (2) | C4B—C3B—C2B | 118.6 (2) |
C4A—C3A—H3A | 120.9 | C4B—C3B—H3B | 120.7 |
C2A—C3A—H3A | 120.9 | C2B—C3B—H3B | 120.7 |
C3A—C4A—C5A | 120.1 (2) | C3B—C4B—C5B | 120.3 (2) |
C3A—C4A—H4A | 119.9 | C3B—C4B—H4B | 119.8 |
C5A—C4A—H4A | 119.9 | C5B—C4B—H4B | 119.8 |
C6A—C5A—O2A | 124.9 (2) | O2B—C5B—C6B | 119.0 (2) |
C6A—C5A—C4A | 117.3 (2) | O2B—C5B—C4B | 124.9 (2) |
O2A—C5A—C4A | 117.7 (2) | C6B—C5B—C4B | 116.1 (2) |
N1A—C6A—C5A | 124.1 (2) | N1B—C6B—C5B | 124.8 (2) |
N1A—C6A—Cl1A | 115.92 (18) | N1B—C6B—Cl1B | 116.05 (19) |
C5A—C6A—Cl1A | 119.93 (18) | C5B—C6B—Cl1B | 119.17 (19) |
C2A—O1A—H1A | 109.5 | C2B—O1B—H1B | 109.5 |
C5A—O2A—H2A | 109.5 | C5B—O2B—H2B | 109.5 |
C6A—N1A—C2A—O1A | −179.1 (2) | C6B—N1B—C2B—O1B | −179.1 (2) |
C6A—N1A—C2A—C3A | 1.3 (3) | C6B—N1B—C2B—C3B | 0.0 (4) |
N1A—C2A—C3A—C4A | −0.8 (4) | N1B—C2B—C3B—C4B | 0.4 (4) |
O1A—C2A—C3A—C4A | 179.5 (2) | O1B—C2B—C3B—C4B | 179.5 (2) |
C2A—C3A—C4A—C5A | −0.3 (3) | C2B—C3B—C4B—C5B | −0.1 (4) |
C3A—C4A—C5A—C6A | 0.9 (3) | C3B—C4B—C5B—O2B | 178.9 (2) |
C3A—C4A—C5A—O2A | −175.7 (2) | C3B—C4B—C5B—C6B | −0.5 (4) |
C2A—N1A—C6A—C5A | −0.6 (3) | C2B—N1B—C6B—C5B | −0.8 (4) |
C2A—N1A—C6A—Cl1A | −179.45 (17) | C2B—N1B—C6B—Cl1B | 179.77 (18) |
O2A—C5A—C6A—N1A | 175.8 (2) | O2B—C5B—C6B—N1B | −178.5 (2) |
C4A—C5A—C6A—N1A | −0.5 (4) | C4B—C5B—C6B—N1B | 1.0 (4) |
O2A—C5A—C6A—Cl1A | −5.4 (3) | O2B—C5B—C6B—Cl1B | 1.0 (3) |
C4A—C5A—C6A—Cl1A | 178.36 (18) | C4B—C5B—C6B—Cl1B | −179.55 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1A—H1A···N1B | 0.84 | 1.90 | 2.727 (3) | 167 |
O2A—H2A···O2Ai | 0.84 | 1.88 | 2.6448 (17) | 150 |
O1B—H1B···N1A | 0.84 | 1.88 | 2.710 (3) | 170 |
O2B—H2B···O1Bii | 0.84 | 1.90 | 2.728 (2) | 168 |
Symmetry codes: (i) −y+3/4, x+1/4, z+1/4; (ii) y+1/4, −x+3/4, −z+7/4. |
C5H4ClNO2 | Dx = 1.715 Mg m−3 |
Mr = 166.52 | Cu Kα radiation, λ = 1.54178 Å |
Tetragonal, I41/a | Cell parameters from 9942 reflections |
Hall symbol: -I 4ad | θ = 3.2–68.5° |
a = 27.2426 (10) Å | µ = 6.58 mm−1 |
c = 6.9534 (3) Å | T = 90 K |
V = 5160.5 (3) Å3 | Wedge cut from shard, pale yellow |
Z = 32 | 0.12 × 0.05 × 0.03 mm |
F(000) = 2696 |
Bruker X8 Proteum diffractometer | 2384 independent reflections |
Radiation source: fine-focus rotating anode | 2212 reflections with I > 2σ(I) |
Graded multilayer optics monochromator | Rint = 0.047 |
Detector resolution: 5.6 pixels mm-1 | θmax = 68.5°, θmin = 3.2° |
ϕ and ω scans | h = −32→32 |
Absorption correction: multi-scan (SADABS in APEX2; Bruker, 2006) | k = −32→32 |
Tmin = 0.598, Tmax = 0.874 | l = −8→8 |
36806 measured reflections |
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)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.093 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0394P)2 + 11.959P] where P = (Fo2 + 2Fc2)/3 |
2384 reflections | (Δ/σ)max = 0.001 |
167 parameters | Δρmax = 0.46 e Å−3 |
0 restraints | Δρmin = −0.36 e Å−3 |
C5H4ClNO2 | Z = 32 |
Mr = 166.52 | Cu Kα radiation |
Tetragonal, I41/a | µ = 6.58 mm−1 |
a = 27.2426 (10) Å | T = 90 K |
c = 6.9534 (3) Å | 0.12 × 0.05 × 0.03 mm |
V = 5160.5 (3) Å3 |
Bruker X8 Proteum diffractometer | 2384 independent reflections |
Absorption correction: multi-scan (SADABS in APEX2; Bruker, 2006) | 2212 reflections with I > 2σ(I) |
Tmin = 0.598, Tmax = 0.874 | Rint = 0.047 |
36806 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.093 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0394P)2 + 11.959P] where P = (Fo2 + 2Fc2)/3 |
2384 reflections | Δρmax = 0.46 e Å−3 |
167 parameters | Δρmin = −0.36 e Å−3 |
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 > 2σ(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. Molecules of 1,1,2,2-tetrachloroethane were disordered on a site of 4 symmetry and were too badly disordered to decipher. Eventually it was decided to use SQUEEZE in PLATON (Spek, 2003) to remove the contribution from this disordered solvent. Quantitative 1H NMR spectroscopy gave a ratio of pyridine:solvent of about 10.5:1, but this was (of necessity) from a bulk sample rather than the single-crystal used for data collection. The SQUEEZE procedure indicated that 86.7 electrons were removed, which corresponds to essentially full solvent occupancy. |
x | y | z | Uiso*/Ueq | ||
N1A | 0.41959 (6) | 0.46761 (6) | 0.4167 (2) | 0.0195 (4) | |
C2A | 0.44769 (7) | 0.47697 (7) | 0.2635 (3) | 0.0205 (4) | |
C3A | 0.42906 (8) | 0.49870 (7) | 0.0969 (3) | 0.0203 (4) | |
H3A | 0.4498 | 0.5055 | −0.0096 | 0.024* | |
C4A | 0.38019 (7) | 0.50996 (7) | 0.0910 (3) | 0.0194 (4) | |
H4A | 0.3666 | 0.5247 | −0.0207 | 0.023* | |
C5A | 0.35016 (7) | 0.49983 (7) | 0.2488 (3) | 0.0186 (4) | |
C6A | 0.37187 (7) | 0.47888 (7) | 0.4065 (3) | 0.0182 (4) | |
O1A | 0.49530 (5) | 0.46571 (6) | 0.2698 (2) | 0.0283 (4) | |
H1A | 0.5017 | 0.4520 | 0.3750 | 0.042* | |
O2A | 0.30093 (5) | 0.50920 (5) | 0.2325 (2) | 0.0221 (3) | |
H2A | 0.2897 | 0.5174 | 0.3403 | 0.033* | |
Cl1A | 0.337368 (17) | 0.466564 (17) | 0.61034 (7) | 0.02086 (15) | |
N1B | 0.52409 (6) | 0.41370 (6) | 0.5842 (3) | 0.0219 (4) | |
C2B | 0.49663 (7) | 0.40471 (8) | 0.7391 (3) | 0.0224 (4) | |
C3B | 0.51531 (8) | 0.38083 (8) | 0.8999 (3) | 0.0258 (5) | |
H3B | 0.4952 | 0.3750 | 1.0092 | 0.031* | |
C4B | 0.56349 (9) | 0.36582 (8) | 0.8969 (3) | 0.0263 (5) | |
H4B | 0.5769 | 0.3493 | 1.0051 | 0.032* | |
C5B | 0.59280 (8) | 0.37472 (8) | 0.7363 (3) | 0.0224 (4) | |
C6B | 0.57059 (8) | 0.39877 (8) | 0.5849 (3) | 0.0216 (4) | |
O1B | 0.44928 (5) | 0.41880 (6) | 0.7356 (2) | 0.0272 (3) | |
H1B | 0.4434 | 0.4333 | 0.6316 | 0.041* | |
O2B | 0.64029 (6) | 0.36158 (6) | 0.7201 (2) | 0.0303 (4) | |
H2B | 0.6488 | 0.3458 | 0.8184 | 0.045* | |
Cl1B | 0.604194 (18) | 0.411055 (19) | 0.37925 (7) | 0.02530 (15) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1A | 0.0181 (8) | 0.0216 (8) | 0.0188 (8) | −0.0006 (6) | 0.0030 (7) | 0.0036 (7) |
C2A | 0.0193 (10) | 0.0215 (10) | 0.0209 (10) | −0.0003 (7) | 0.0036 (8) | 0.0030 (8) |
C3A | 0.0225 (10) | 0.0206 (10) | 0.0178 (10) | −0.0015 (8) | 0.0038 (8) | 0.0027 (8) |
C4A | 0.0233 (10) | 0.0184 (9) | 0.0165 (9) | −0.0018 (8) | −0.0009 (8) | 0.0015 (7) |
C5A | 0.0177 (9) | 0.0165 (9) | 0.0216 (10) | −0.0003 (7) | 0.0000 (8) | −0.0018 (8) |
C6A | 0.0192 (9) | 0.0180 (9) | 0.0174 (9) | −0.0039 (7) | 0.0034 (8) | −0.0012 (7) |
O1A | 0.0184 (7) | 0.0418 (9) | 0.0246 (8) | 0.0059 (6) | 0.0045 (6) | 0.0129 (7) |
O2A | 0.0182 (7) | 0.0282 (8) | 0.0200 (7) | 0.0024 (6) | 0.0000 (6) | −0.0020 (6) |
Cl1A | 0.0203 (2) | 0.0236 (3) | 0.0186 (2) | −0.00292 (17) | 0.00502 (17) | 0.00143 (17) |
N1B | 0.0202 (8) | 0.0248 (9) | 0.0207 (9) | 0.0005 (7) | 0.0014 (7) | 0.0054 (7) |
C2B | 0.0218 (10) | 0.0236 (10) | 0.0218 (10) | −0.0003 (8) | 0.0034 (8) | 0.0033 (8) |
C3B | 0.0294 (11) | 0.0275 (11) | 0.0207 (10) | −0.0021 (9) | 0.0042 (9) | 0.0066 (8) |
C4B | 0.0326 (12) | 0.0259 (11) | 0.0205 (10) | −0.0003 (9) | −0.0028 (9) | 0.0058 (8) |
C5B | 0.0227 (10) | 0.0222 (10) | 0.0222 (10) | 0.0002 (8) | −0.0033 (8) | 0.0012 (8) |
C6B | 0.0223 (10) | 0.0225 (10) | 0.0199 (10) | −0.0002 (8) | 0.0018 (8) | 0.0011 (8) |
O1B | 0.0228 (7) | 0.0347 (8) | 0.0242 (8) | 0.0038 (6) | 0.0061 (6) | 0.0117 (6) |
O2B | 0.0243 (8) | 0.0387 (9) | 0.0278 (8) | 0.0071 (6) | −0.0022 (6) | 0.0099 (7) |
Cl1B | 0.0211 (3) | 0.0338 (3) | 0.0210 (3) | 0.00342 (19) | 0.00374 (18) | 0.00595 (19) |
N1A—C2A | 1.337 (3) | N1B—C6B | 1.331 (3) |
N1A—C6A | 1.338 (3) | N1B—C2B | 1.334 (3) |
C2A—O1A | 1.333 (2) | C2B—O1B | 1.346 (3) |
C2A—C3A | 1.396 (3) | C2B—C3B | 1.390 (3) |
C3A—C4A | 1.367 (3) | C3B—C4B | 1.375 (3) |
C3A—H3A | 0.9500 | C3B—H3B | 0.9500 |
C4A—C5A | 1.396 (3) | C4B—C5B | 1.394 (3) |
C4A—H4A | 0.9500 | C4B—H4B | 0.9500 |
C5A—O2A | 1.370 (2) | C5B—O2B | 1.347 (3) |
C5A—C6A | 1.370 (3) | C5B—C6B | 1.380 (3) |
C6A—Cl1A | 1.7336 (19) | C6B—Cl1B | 1.730 (2) |
O1A—H1A | 0.8400 | O1B—H1B | 0.8400 |
O2A—H2A | 0.8400 | O2B—H2B | 0.8400 |
C2A—N1A—C6A | 118.07 (17) | C6B—N1B—C2B | 118.36 (18) |
O1A—C2A—N1A | 119.14 (18) | N1B—C2B—O1B | 118.06 (18) |
O1A—C2A—C3A | 118.59 (18) | N1B—C2B—C3B | 122.01 (19) |
N1A—C2A—C3A | 122.27 (19) | O1B—C2B—C3B | 119.92 (19) |
C4A—C3A—C2A | 118.30 (18) | C4B—C3B—C2B | 118.48 (19) |
C4A—C3A—H3A | 120.9 | C4B—C3B—H3B | 120.8 |
C2A—C3A—H3A | 120.9 | C2B—C3B—H3B | 120.8 |
C3A—C4A—C5A | 120.19 (19) | C3B—C4B—C5B | 120.5 (2) |
C3A—C4A—H4A | 119.9 | C3B—C4B—H4B | 119.8 |
C5A—C4A—H4A | 119.9 | C5B—C4B—H4B | 119.8 |
O2A—C5A—C6A | 124.51 (18) | O2B—C5B—C6B | 118.89 (19) |
O2A—C5A—C4A | 118.14 (18) | O2B—C5B—C4B | 124.82 (19) |
C6A—C5A—C4A | 117.26 (18) | C6B—C5B—C4B | 116.28 (19) |
N1A—C6A—C5A | 123.90 (18) | N1B—C6B—C5B | 124.40 (19) |
N1A—C6A—Cl1A | 116.05 (15) | N1B—C6B—Cl1B | 116.22 (16) |
C5A—C6A—Cl1A | 120.04 (15) | C5B—C6B—Cl1B | 119.37 (16) |
C2A—O1A—H1A | 109.5 | C2B—O1B—H1B | 109.5 |
C5A—O2A—H2A | 109.5 | C5B—O2B—H2B | 109.5 |
C6A—N1A—C2A—O1A | −179.50 (18) | C6B—N1B—C2B—O1B | −178.35 (19) |
C6A—N1A—C2A—C3A | 1.2 (3) | C6B—N1B—C2B—C3B | 0.6 (3) |
O1A—C2A—C3A—C4A | 179.72 (19) | N1B—C2B—C3B—C4B | −0.5 (3) |
N1A—C2A—C3A—C4A | −1.0 (3) | O1B—C2B—C3B—C4B | 178.4 (2) |
C2A—C3A—C4A—C5A | 0.1 (3) | C2B—C3B—C4B—C5B | 0.3 (3) |
C3A—C4A—C5A—O2A | −176.40 (18) | C3B—C4B—C5B—O2B | 179.8 (2) |
C3A—C4A—C5A—C6A | 0.5 (3) | C3B—C4B—C5B—C6B | −0.2 (3) |
C2A—N1A—C6A—C5A | −0.6 (3) | C2B—N1B—C6B—C5B | −0.5 (3) |
C2A—N1A—C6A—Cl1A | −179.30 (15) | C2B—N1B—C6B—Cl1B | 179.50 (16) |
O2A—C5A—C6A—N1A | 176.40 (18) | O2B—C5B—C6B—N1B | −179.7 (2) |
C4A—C5A—C6A—N1A | −0.3 (3) | C4B—C5B—C6B—N1B | 0.3 (3) |
O2A—C5A—C6A—Cl1A | −4.9 (3) | O2B—C5B—C6B—Cl1B | 0.3 (3) |
C4A—C5A—C6A—Cl1A | 178.42 (15) | C4B—C5B—C6B—Cl1B | −179.69 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1A—H1A···N1B | 0.84 | 1.89 | 2.721 (2) | 169 |
O2A—H2A···O2Ai | 0.84 | 1.89 | 2.6453 (15) | 148 |
O1B—H1B···N1A | 0.84 | 1.88 | 2.709 (2) | 170 |
O2B—H2B···O1Bii | 0.84 | 1.91 | 2.746 (2) | 170 |
Symmetry codes: (i) −y+3/4, x+1/4, z+1/4; (ii) y+1/4, −x+3/4, −z+7/4. |
C5H4ClNO2 | F(000) = 296 |
Mr = 145.54 | Dx = 1.631 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 1430 reflections |
a = 4.2481 (1) Å | θ = 1.0–27.5° |
b = 10.7075 (2) Å | µ = 0.56 mm−1 |
c = 13.0362 (3) Å | T = 293 K |
β = 91.2416 (11)° | Block, colourless |
V = 592.83 (2) Å3 | 0.15 × 0.10 × 0.10 mm |
Z = 4 |
Nonius KappaCCD area-detector diffractometer | 930 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.022 |
Graphite monochromator | θmax = 27.5°, θmin = 2.5° |
Detector resolution: 9.1 pixels mm-1 | h = −5→5 |
ω scans at fixed χ = 55° | k = −13→13 |
8239 measured reflections | l = −16→16 |
1356 independent reflections |
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.106 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0427P)2 + 0.2661P] where P = (Fo2 + 2Fc2)/3 |
1356 reflections | (Δ/σ)max < 0.001 |
83 parameters | Δρmax = 0.22 e Å−3 |
0 restraints | Δρmin = −0.34 e Å−3 |
C5H4ClNO2 | V = 592.83 (2) Å3 |
Mr = 145.54 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 4.2481 (1) Å | µ = 0.56 mm−1 |
b = 10.7075 (2) Å | T = 293 K |
c = 13.0362 (3) Å | 0.15 × 0.10 × 0.10 mm |
β = 91.2416 (11)° |
Nonius KappaCCD area-detector diffractometer | 930 reflections with I > 2σ(I) |
8239 measured reflections | Rint = 0.022 |
1356 independent reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.106 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.22 e Å−3 |
1356 reflections | Δρmin = −0.34 e Å−3 |
83 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 > 2σ(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 | ||
N1 | 0.7531 (4) | 0.39519 (16) | 0.42306 (12) | 0.0365 (4) | |
H1 | 0.8126 | 0.4072 | 0.4858 | 0.044* | |
C2 | 0.8612 (5) | 0.47464 (19) | 0.35078 (15) | 0.0377 (5) | |
C3 | 0.7456 (5) | 0.4530 (2) | 0.24871 (15) | 0.0408 (5) | |
H3 | 0.8082 | 0.5049 | 0.1957 | 0.049* | |
C4 | 0.5462 (5) | 0.3578 (2) | 0.22867 (15) | 0.0425 (5) | |
H4 | 0.4734 | 0.3459 | 0.1616 | 0.051* | |
C5 | 0.4442 (5) | 0.2759 (2) | 0.30531 (16) | 0.0392 (5) | |
C6 | 0.5560 (5) | 0.29753 (19) | 0.40232 (15) | 0.0377 (5) | |
O1 | 1.0526 (4) | 0.56135 (14) | 0.37712 (10) | 0.0447 (4) | |
O2 | 0.2389 (4) | 0.18119 (15) | 0.28727 (11) | 0.0516 (4) | |
H2 | 0.2772 | 0.1484 | 0.2321 | 0.077* | |
Cl1 | 0.45728 (16) | 0.20689 (6) | 0.50437 (5) | 0.0636 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0419 (9) | 0.0409 (10) | 0.0266 (8) | −0.0001 (8) | −0.0040 (7) | −0.0014 (7) |
C2 | 0.0429 (11) | 0.0372 (11) | 0.0330 (10) | 0.0054 (9) | −0.0011 (8) | −0.0006 (9) |
C3 | 0.0508 (12) | 0.0447 (12) | 0.0268 (10) | 0.0023 (11) | −0.0005 (8) | 0.0026 (9) |
C4 | 0.0464 (12) | 0.0526 (13) | 0.0285 (10) | 0.0056 (11) | −0.0040 (8) | −0.0057 (9) |
C5 | 0.0358 (11) | 0.0421 (12) | 0.0396 (11) | 0.0039 (9) | 0.0002 (8) | −0.0100 (9) |
C6 | 0.0398 (11) | 0.0398 (11) | 0.0335 (10) | 0.0024 (9) | 0.0014 (8) | 0.0021 (9) |
O1 | 0.0566 (9) | 0.0413 (8) | 0.0361 (8) | −0.0063 (7) | −0.0045 (7) | 0.0017 (7) |
O2 | 0.0509 (9) | 0.0540 (10) | 0.0499 (10) | −0.0094 (8) | 0.0028 (7) | −0.0135 (7) |
Cl1 | 0.0724 (5) | 0.0720 (5) | 0.0461 (3) | −0.0198 (3) | −0.0031 (3) | 0.0156 (3) |
N1—C2 | 1.357 (3) | C4—C5 | 1.405 (3) |
N1—C6 | 1.363 (3) | C4—H4 | 0.9300 |
N1—H1 | 0.8600 | C5—O2 | 1.354 (2) |
C2—O1 | 1.276 (2) | C5—C6 | 1.361 (3) |
C2—C3 | 1.427 (3) | C6—Cl1 | 1.706 (2) |
C3—C4 | 1.347 (3) | O2—H2 | 0.8200 |
C3—H3 | 0.9300 | ||
C2—N1—C6 | 123.99 (16) | C3—C4—H4 | 118.8 |
C2—N1—H1 | 118.0 | C5—C4—H4 | 118.8 |
C6—N1—H1 | 118.0 | O2—C5—C6 | 119.96 (19) |
O1—C2—N1 | 119.51 (17) | O2—C5—C4 | 123.45 (18) |
O1—C2—C3 | 124.99 (18) | C6—C5—C4 | 116.57 (19) |
N1—C2—C3 | 115.50 (18) | C5—C6—N1 | 121.04 (18) |
C4—C3—C2 | 120.41 (19) | C5—C6—Cl1 | 122.72 (17) |
C4—C3—H3 | 119.8 | N1—C6—Cl1 | 116.24 (15) |
C2—C3—H3 | 119.8 | C5—O2—H2 | 109.5 |
C3—C4—C5 | 122.46 (18) | ||
C6—N1—C2—O1 | −177.96 (18) | O2—C5—C6—N1 | −177.40 (18) |
C6—N1—C2—C3 | 2.2 (3) | C4—C5—C6—N1 | 0.9 (3) |
O1—C2—C3—C4 | 179.3 (2) | O2—C5—C6—Cl1 | 1.9 (3) |
N1—C2—C3—C4 | −0.9 (3) | C4—C5—C6—Cl1 | −179.79 (15) |
C2—C3—C4—C5 | −0.3 (3) | C2—N1—C6—C5 | −2.3 (3) |
C3—C4—C5—O2 | 178.6 (2) | C2—N1—C6—Cl1 | 178.35 (16) |
C3—C4—C5—C6 | 0.3 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.86 | 1.90 | 2.755 (2) | 178 |
O2—H2···O1ii | 0.82 | 1.86 | 2.666 (2) | 167 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+3/2, y−1/2, −z+1/2. |
C5H4ClNO2 | Dx = 1.663 Mg m−3 |
Mr = 166.52 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, I41/a | Cell parameters from 3298 reflections |
Hall symbol: -I 4ad | θ = 1.0–27.5° |
a = 27.4722 (2) Å | µ = 0.70 mm−1 |
c = 7.0495 (1) Å | T = 293 K |
V = 5320.41 (9) Å3 | Irregular shard, pale yellow |
Z = 32 | 0.22 × 0.11 × 0.06 mm |
F(000) = 2696 |
Nonius KappaCCD area-detector diffractometer | 3045 independent reflections |
Radiation source: fine-focus sealed tube | 2043 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
Detector resolution: 9.1 pixels mm-1 | θmax = 27.5°, θmin = 1.5° |
ω scans at fixed χ = 55° | h = −24→24 |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | k = −35→35 |
Tmin = 0.899, Tmax = 0.971 | l = −9→9 |
61598 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)] = 0.059 | H-atom parameters constrained |
wR(F2) = 0.196 | w = 1/[σ2(Fo2) + (0.1179P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.15 | (Δ/σ)max = 0.001 |
3045 reflections | Δρmax = 0.63 e Å−3 |
168 parameters | Δρmin = −0.37 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0033 (5) |
C5H4ClNO2 | Z = 32 |
Mr = 166.52 | Mo Kα radiation |
Tetragonal, I41/a | µ = 0.70 mm−1 |
a = 27.4722 (2) Å | T = 293 K |
c = 7.0495 (1) Å | 0.22 × 0.11 × 0.06 mm |
V = 5320.41 (9) Å3 |
Nonius KappaCCD area-detector diffractometer | 3045 independent reflections |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | 2043 reflections with I > 2σ(I) |
Tmin = 0.899, Tmax = 0.971 | Rint = 0.024 |
61598 measured reflections |
R[F2 > 2σ(F2)] = 0.059 | 0 restraints |
wR(F2) = 0.196 | H-atom parameters constrained |
S = 1.15 | Δρmax = 0.63 e Å−3 |
3045 reflections | Δρmin = −0.37 e Å−3 |
168 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 > 2σ(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. Molecules of 1,1,2,2-tetrachloroethane were disordered on a site of 4 symmetry and were too badly disordered to decipher. Eventually it was decided to use SQUEEZE in PLATON (Spek, 2003) to remove the contribution from this disordered solvent. Quantitative 1H NMR spectroscopy gave a ratio of pyridine:solvent of about 10.5:1, but this was (of necessity) from a bulk sample rather than the single-crystal used for data collection. |
x | y | z | Uiso*/Ueq | ||
N1A | 0.41897 (8) | 0.46641 (8) | 0.4137 (3) | 0.0456 (5) | |
C2A | 0.44724 (9) | 0.47554 (9) | 0.2624 (4) | 0.0468 (7) | |
C3A | 0.42865 (11) | 0.49698 (10) | 0.0987 (4) | 0.0491 (7) | |
H3A | 0.4488 | 0.5036 | −0.0042 | 0.059* | |
C4A | 0.38020 (10) | 0.50814 (9) | 0.0922 (4) | 0.0471 (6) | |
H4A | 0.3671 | 0.5221 | −0.0166 | 0.057* | |
C5A | 0.35044 (9) | 0.49870 (9) | 0.2475 (4) | 0.0429 (6) | |
C6A | 0.37192 (9) | 0.47794 (9) | 0.4023 (4) | 0.0429 (6) | |
O1A | 0.49416 (7) | 0.46435 (9) | 0.2697 (3) | 0.0651 (6) | |
H1A | 0.4999 | 0.4499 | 0.3691 | 0.098* | |
O2A | 0.30163 (6) | 0.50815 (8) | 0.2304 (3) | 0.0540 (5) | |
H2A | 0.2910 | 0.5180 | 0.3322 | 0.081* | |
Cl1A | 0.33749 (2) | 0.46581 (3) | 0.60416 (10) | 0.0535 (3) | |
N1B | 0.52308 (8) | 0.41327 (8) | 0.5845 (3) | 0.0462 (5) | |
C2B | 0.49579 (10) | 0.40439 (10) | 0.7387 (4) | 0.0499 (7) | |
C3B | 0.51423 (11) | 0.38194 (12) | 0.8966 (4) | 0.0591 (8) | |
H3B | 0.4946 | 0.3765 | 1.0020 | 0.071* | |
C4B | 0.56188 (12) | 0.36762 (11) | 0.8970 (4) | 0.0608 (8) | |
H4B | 0.5747 | 0.3521 | 1.0031 | 0.073* | |
C5B | 0.59134 (10) | 0.37607 (10) | 0.7396 (4) | 0.0499 (7) | |
C6B | 0.56950 (10) | 0.39890 (9) | 0.5888 (4) | 0.0463 (6) | |
O1B | 0.44867 (7) | 0.41769 (8) | 0.7315 (3) | 0.0626 (6) | |
H1B | 0.4427 | 0.4293 | 0.6270 | 0.094* | |
O2B | 0.63876 (8) | 0.36357 (9) | 0.7273 (3) | 0.0727 (7) | |
H2B | 0.6476 | 0.3515 | 0.8278 | 0.109* | |
Cl1B | 0.60320 (3) | 0.41090 (3) | 0.38634 (11) | 0.0611 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1A | 0.0479 (12) | 0.0468 (12) | 0.0420 (13) | −0.0026 (9) | 0.0050 (10) | 0.0063 (10) |
C2A | 0.0429 (14) | 0.0510 (15) | 0.0465 (16) | −0.0021 (11) | 0.0081 (11) | 0.0070 (12) |
C3A | 0.0548 (16) | 0.0510 (15) | 0.0413 (15) | −0.0024 (12) | 0.0078 (12) | 0.0063 (12) |
C4A | 0.0551 (16) | 0.0479 (14) | 0.0383 (15) | 0.0002 (12) | −0.0013 (12) | 0.0029 (11) |
C5A | 0.0448 (14) | 0.0405 (13) | 0.0434 (15) | −0.0012 (10) | −0.0017 (11) | −0.0022 (11) |
C6A | 0.0452 (14) | 0.0419 (13) | 0.0415 (14) | −0.0054 (10) | 0.0054 (11) | −0.0010 (11) |
O1A | 0.0461 (11) | 0.0916 (16) | 0.0576 (14) | 0.0129 (10) | 0.0094 (9) | 0.0246 (12) |
O2A | 0.0441 (10) | 0.0659 (12) | 0.0518 (12) | 0.0030 (9) | 0.0000 (9) | −0.0091 (10) |
Cl1A | 0.0526 (4) | 0.0605 (5) | 0.0474 (5) | −0.0043 (3) | 0.0126 (3) | 0.0038 (3) |
N1B | 0.0435 (12) | 0.0518 (12) | 0.0432 (12) | 0.0018 (10) | 0.0032 (10) | 0.0107 (10) |
C2B | 0.0498 (15) | 0.0523 (15) | 0.0476 (16) | 0.0019 (12) | 0.0063 (12) | 0.0091 (13) |
C3B | 0.0610 (18) | 0.0707 (19) | 0.0455 (17) | 0.0024 (15) | 0.0096 (14) | 0.0160 (14) |
C4B | 0.072 (2) | 0.0656 (19) | 0.0453 (17) | 0.0016 (15) | −0.0056 (14) | 0.0138 (14) |
C5B | 0.0495 (15) | 0.0485 (15) | 0.0517 (18) | 0.0029 (11) | −0.0021 (12) | 0.0054 (13) |
C6B | 0.0506 (15) | 0.0462 (14) | 0.0421 (14) | −0.0020 (11) | 0.0043 (12) | 0.0019 (11) |
O1B | 0.0537 (12) | 0.0787 (14) | 0.0553 (14) | 0.0083 (9) | 0.0158 (10) | 0.0266 (11) |
O2B | 0.0577 (12) | 0.0887 (16) | 0.0716 (16) | 0.0131 (11) | −0.0056 (11) | 0.0264 (13) |
Cl1B | 0.0518 (5) | 0.0778 (6) | 0.0538 (5) | 0.0066 (3) | 0.0108 (3) | 0.0126 (4) |
N1A—C6A | 1.333 (3) | N1B—C6B | 1.335 (3) |
N1A—C2A | 1.343 (3) | N1B—C2B | 1.343 (3) |
C2A—O1A | 1.326 (3) | C2B—O1B | 1.346 (3) |
C2A—C3A | 1.393 (4) | C2B—C3B | 1.370 (4) |
C3A—C4A | 1.366 (4) | C3B—C4B | 1.367 (4) |
C3A—H3A | 0.9300 | C3B—H3B | 0.9300 |
C4A—C5A | 1.391 (4) | C4B—C5B | 1.393 (4) |
C4A—H4A | 0.9300 | C4B—H4B | 0.9300 |
C5A—C6A | 1.365 (4) | C5B—O2B | 1.350 (3) |
C5A—O2A | 1.371 (3) | C5B—C6B | 1.372 (4) |
C6A—Cl1A | 1.741 (3) | C6B—Cl1B | 1.733 (3) |
O1A—H1A | 0.8200 | O1B—H1B | 0.8200 |
O2A—H2A | 0.8200 | O2B—H2B | 0.8200 |
C6A—N1A—C2A | 118.0 (2) | C6B—N1B—C2B | 117.4 (2) |
O1A—C2A—N1A | 119.2 (2) | N1B—C2B—O1B | 117.2 (2) |
O1A—C2A—C3A | 119.1 (2) | N1B—C2B—C3B | 122.2 (3) |
N1A—C2A—C3A | 121.7 (2) | O1B—C2B—C3B | 120.6 (2) |
C4A—C3A—C2A | 118.7 (2) | C4B—C3B—C2B | 119.0 (3) |
C4A—C3A—H3A | 120.7 | C4B—C3B—H3B | 120.5 |
C2A—C3A—H3A | 120.7 | C2B—C3B—H3B | 120.5 |
C3A—C4A—C5A | 120.3 (2) | C3B—C4B—C5B | 120.5 (3) |
C3A—C4A—H4A | 119.9 | C3B—C4B—H4B | 119.8 |
C5A—C4A—H4A | 119.9 | C5B—C4B—H4B | 119.8 |
C6A—C5A—O2A | 124.9 (2) | O2B—C5B—C6B | 119.2 (2) |
C6A—C5A—C4A | 117.0 (2) | O2B—C5B—C4B | 124.7 (2) |
O2A—C5A—C4A | 118.1 (2) | C6B—C5B—C4B | 116.0 (3) |
N1A—C6A—C5A | 124.5 (2) | N1B—C6B—C5B | 124.8 (2) |
N1A—C6A—Cl1A | 115.63 (19) | N1B—C6B—Cl1B | 115.8 (2) |
C5A—C6A—Cl1A | 119.9 (2) | C5B—C6B—Cl1B | 119.4 (2) |
C2A—O1A—H1A | 109.5 | C2B—O1B—H1B | 109.5 |
C5A—O2A—H2A | 109.5 | C5B—O2B—H2B | 109.5 |
C6A—N1A—C2A—O1A | −179.9 (2) | C6B—N1B—C2B—O1B | −178.1 (2) |
C6A—N1A—C2A—C3A | 0.9 (4) | C6B—N1B—C2B—C3B | 0.6 (4) |
O1A—C2A—C3A—C4A | 179.7 (3) | N1B—C2B—C3B—C4B | −0.7 (5) |
N1A—C2A—C3A—C4A | −1.1 (4) | O1B—C2B—C3B—C4B | 178.1 (3) |
C2A—C3A—C4A—C5A | 0.8 (4) | C2B—C3B—C4B—C5B | 0.5 (5) |
C3A—C4A—C5A—C6A | −0.3 (4) | C3B—C4B—C5B—O2B | 179.6 (3) |
C3A—C4A—C5A—O2A | −176.6 (2) | C3B—C4B—C5B—C6B | −0.3 (4) |
C2A—N1A—C6A—C5A | −0.4 (4) | C2B—N1B—C6B—C5B | −0.5 (4) |
C2A—N1A—C6A—Cl1A | −179.29 (19) | C2B—N1B—C6B—Cl1B | 179.7 (2) |
O2A—C5A—C6A—N1A | 176.1 (2) | O2B—C5B—C6B—N1B | −179.6 (3) |
C4A—C5A—C6A—N1A | 0.1 (4) | C4B—C5B—C6B—N1B | 0.3 (4) |
O2A—C5A—C6A—Cl1A | −5.0 (3) | O2B—C5B—C6B—Cl1B | 0.2 (4) |
C4A—C5A—C6A—Cl1A | 178.98 (19) | C4B—C5B—C6B—Cl1B | −179.9 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1A—H1A···N1B | 0.82 | 1.93 | 2.743 (3) | 171 |
O2A—H2A···O2Ai | 0.82 | 1.94 | 2.6887 (19) | 151 |
O1B—H1B···N1A | 0.82 | 1.93 | 2.734 (3) | 167 |
O2B—H2B···O1Bii | 0.82 | 2.00 | 2.788 (3) | 160 |
Symmetry codes: (i) −y+3/4, x+1/4, z+1/4; (ii) y+1/4, −x+3/4, −z+7/4. |
Experimental details
(I) | (IIa) | (IIb) | (IIc) | |
Crystal data | ||||
Chemical formula | C5H4ClNO2 | C5H4ClNO2·0.125CHCl3 | C5H4ClNO2·0.125CCl4 | C5H4ClNO2 |
Mr | 145.54 | 160.46 | 164.77 | 157.91 |
Crystal system, space group | Monoclinic, P21/n | Tetragonal, I41/a | Tetragonal, I41/a | Tetragonal, I41/a |
Temperature (K) | 90 | 90 | 90 | 90 |
a, b, c (Å) | 4.1960 (1), 10.6058 (3), 13.0059 (4) | 27.1736 (10), 27.1736 (10), 6.9253 (2) | 27.1708 (4), 27.1708 (4), 6.9458 (1) | 27.1149 (10), 27.1149 (10), 6.9618 (2) |
α, β, γ (°) | 90, 90.8559 (12), 90 | 90, 90, 90 | 90, 90, 90 | 90, 90, 90 |
V (Å3) | 578.72 (3) | 5113.7 (3) | 5127.75 (13) | 5118.4 (3) |
Z | 4 | 32 | 32 | 32 |
Radiation type | Mo Kα | Mo Kα | Cu Kα | Mo Kα |
µ (mm−1) | 0.57 | 0.68 | 6.62 | 0.62 |
Crystal size (mm) | 0.15 × 0.15 × 0.12 | 0.20 × 0.18 × 0.18 | 0.12 × 0.02 × 0.01 | 0.35 × 0.13 × 0.12 |
Data collection | ||||
Diffractometer | Nonius KappaCCD area-detector diffractometer | Nonius KappaCCD area-detector diffractometer | Bruker X8 Proteum diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | – | Multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | Multi-scan (SADABS in APEX2; Bruker, 2006) | Multi-scan (SCALEPACK; Otwinowski & Minor, 1997) |
Tmin, Tmax | – | 0.877, 0.888 | 0.672, 0.937 | 0.841, 0.941 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7956, 1329, 1124 | 12800, 2924, 1731 | 37025, 2344, 2237 | 52191, 2927, 1964 |
Rint | 0.037 | 0.069 | 0.042 | 0.087 |
(sin θ/λ)max (Å−1) | 0.649 | 0.649 | 0.601 | 0.649 |
Refinement | ||||
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.081, 1.12 | 0.052, 0.146, 0.99 | 0.034, 0.092, 1.04 | 0.051, 0.133, 1.01 |
No. of reflections | 1329 | 2924 | 2344 | 2927 |
No. of parameters | 83 | 198 | 223 | 167 |
No. of restraints | 0 | 12 | 63 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0256P)2 + 0.4865P] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.0769P)2] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.0491P)2 + 12.1459P] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.0797P)2] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.28, −0.26 | 0.53, −0.44 | 0.55, −0.81 | 0.82, −0.36 |
(IId) | (IRT) | (IIdRT) | |
Crystal data | |||
Chemical formula | C5H4ClNO2 | C5H4ClNO2 | C5H4ClNO2 |
Mr | 166.52 | 145.54 | 166.52 |
Crystal system, space group | Tetragonal, I41/a | Monoclinic, P21/n | Tetragonal, I41/a |
Temperature (K) | 90 | 293 | 293 |
a, b, c (Å) | 27.2426 (10), 27.2426 (10), 6.9534 (3) | 4.2481 (1), 10.7075 (2), 13.0362 (3) | 27.4722 (2), 27.4722 (2), 7.0495 (1) |
α, β, γ (°) | 90, 90, 90 | 90, 91.2416 (11), 90 | 90, 90, 90 |
V (Å3) | 5160.5 (3) | 592.83 (2) | 5320.41 (9) |
Z | 32 | 4 | 32 |
Radiation type | Cu Kα | Mo Kα | Mo Kα |
µ (mm−1) | 6.58 | 0.56 | 0.70 |
Crystal size (mm) | 0.12 × 0.05 × 0.03 | 0.15 × 0.10 × 0.10 | 0.22 × 0.11 × 0.06 |
Data collection | |||
Diffractometer | Bruker X8 Proteum diffractometer | Nonius KappaCCD area-detector diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS in APEX2; Bruker, 2006) | – | Multi-scan (SCALEPACK; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.598, 0.874 | – | 0.899, 0.971 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 36806, 2384, 2212 | 8239, 1356, 930 | 61598, 3045, 2043 |
Rint | 0.047 | 0.022 | 0.024 |
(sin θ/λ)max (Å−1) | 0.603 | 0.649 | 0.649 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.093, 1.09 | 0.040, 0.106, 1.03 | 0.059, 0.196, 1.15 |
No. of reflections | 2384 | 1356 | 3045 |
No. of parameters | 167 | 83 | 168 |
No. of restraints | 0 | 0 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0394P)2 + 11.959P] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.0427P)2 + 0.2661P] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.1179P)2] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.46, −0.36 | 0.22, −0.34 | 0.63, −0.37 |
Computer programs: COLLECT (Nonius, 1998), APEX2 (Bruker, 2006), SCALEPACK (Otwinowski & Minor, 1997), DENZO-SMN (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and local procedures..
N1—C2 | 1.361 (2) | C4—C5 | 1.414 (2) |
N1—C6 | 1.363 (2) | C5—O2 | 1.356 (2) |
C2—O1 | 1.277 (2) | C5—C6 | 1.362 (2) |
C2—C3 | 1.431 (2) | C6—Cl1 | 1.7162 (17) |
C3—C4 | 1.356 (2) | ||
C2—N1—C6 | 123.64 (14) | O2—C5—C6 | 120.16 (16) |
O1—C2—N1 | 119.31 (15) | O2—C5—C4 | 123.23 (15) |
O1—C2—C3 | 124.95 (15) | C6—C5—C4 | 116.59 (16) |
N1—C2—C3 | 115.74 (15) | C5—C6—N1 | 121.55 (16) |
C4—C3—C2 | 120.48 (16) | C5—C6—Cl1 | 122.48 (14) |
C3—C4—C5 | 121.98 (16) | N1—C6—Cl1 | 115.97 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.88 | 1.86 | 2.7393 (18) | 177.4 |
O2—H2···O1ii | 0.84 | 1.83 | 2.6507 (17) | 166.0 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+3/2, y−1/2, −z+1/2. |
N1A—C2A | 1.333 (4) | N1B—C2B | 1.333 (4) |
N1A—C6A | 1.340 (4) | N1B—C6B | 1.334 (4) |
C2A—O1A | 1.343 (3) | C2B—O1B | 1.355 (4) |
C2A—C3A | 1.391 (4) | C2B—C3B | 1.390 (4) |
C3A—C4A | 1.373 (4) | C3B—C4B | 1.370 (4) |
C4A—C5A | 1.397 (4) | C4B—C5B | 1.399 (4) |
C5A—C6A | 1.366 (4) | C5B—O2B | 1.351 (4) |
C5A—O2A | 1.375 (3) | C5B—C6B | 1.376 (4) |
C6A—Cl1A | 1.738 (3) | C6B—Cl1B | 1.740 (3) |
C2A—N1A—C6A | 117.9 (3) | C2B—N1B—C6B | 117.7 (3) |
N1A—C2A—O1A | 119.0 (3) | N1B—C2B—O1B | 117.7 (3) |
N1A—C2A—C3A | 122.7 (3) | N1B—C2B—C3B | 122.5 (3) |
O1A—C2A—C3A | 118.2 (3) | O1B—C2B—C3B | 119.9 (3) |
C4A—C3A—C2A | 118.1 (3) | C4B—C3B—C2B | 118.6 (3) |
C3A—C4A—C5A | 120.0 (3) | C3B—C4B—C5B | 120.2 (3) |
C6A—C5A—O2A | 124.8 (3) | O2B—C5B—C6B | 118.9 (3) |
C6A—C5A—C4A | 117.4 (3) | O2B—C5B—C4B | 124.8 (3) |
O2A—C5A—C4A | 117.7 (3) | C6B—C5B—C4B | 116.3 (3) |
N1A—C6A—C5A | 123.9 (3) | N1B—C6B—C5B | 124.8 (3) |
N1A—C6A—Cl1A | 116.1 (2) | N1B—C6B—Cl1B | 116.0 (2) |
C5A—C6A—Cl1A | 120.0 (2) | C5B—C6B—Cl1B | 119.2 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1A—H1A···N1B | 0.84 | 1.89 | 2.721 (3) | 169.2 |
O2A—H2A···O2Ai | 0.84 | 1.89 | 2.647 (2) | 148.6 |
O1B—H1B···N1A | 0.84 | 1.88 | 2.707 (3) | 170.1 |
O2B—H2B···O1Bii | 0.84 | 1.89 | 2.723 (3) | 173.5 |
Symmetry codes: (i) −y+3/4, x+1/4, z+1/4; (ii) y+1/4, −x+3/4, −z+7/4. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1A—H1A···N1B | 0.84 | 1.89 | 2.726 (2) | 172.0 |
O2A—H2A···O2Ai | 0.84 | 1.90 | 2.6487 (15) | 147.8 |
O1B—H1B···N1A | 0.84 | 1.88 | 2.708 (2) | 170.5 |
O2B—H2B···O1Bii | 0.84 | 1.91 | 2.738 (2) | 167.6 |
Symmetry codes: (i) −y+3/4, x+1/4, z+1/4; (ii) y+1/4, −x+3/4, −z+7/4. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1A—H1A···N1B | 0.84 | 1.90 | 2.727 (3) | 166.8 |
O2A—H2A···O2Ai | 0.84 | 1.88 | 2.6448 (17) | 150.0 |
O1B—H1B···N1A | 0.84 | 1.88 | 2.710 (3) | 170.4 |
O2B—H2B···O1Bii | 0.84 | 1.90 | 2.728 (2) | 167.8 |
Symmetry codes: (i) −y+3/4, x+1/4, z+1/4; (ii) y+1/4, −x+3/4, −z+7/4. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1A—H1A···N1B | 0.84 | 1.89 | 2.721 (2) | 169.4 |
O2A—H2A···O2Ai | 0.84 | 1.89 | 2.6453 (15) | 148.3 |
O1B—H1B···N1A | 0.84 | 1.88 | 2.709 (2) | 170.3 |
O2B—H2B···O1Bii | 0.84 | 1.91 | 2.746 (2) | 170.4 |
Symmetry codes: (i) −y+3/4, x+1/4, z+1/4; (ii) y+1/4, −x+3/4, −z+7/4. |
6-Chloro-5-hydroxy-2-pyridone, (I), was synthesized as part of a study of the Elbs oxidation of 2-pyridones (Behrman, 2008). The crude material contains some of the o-isomer, 6-chloro-2,3-dihydroxypyridine, but that can be removed by recrystallization from CHCl3. Elemental analysis of the crystals and their 1H NMR spectra showed the presence of approximately one CHCl3 guest for every eight of the pyridine host - an unusual ratio. Some small molecules are known to form large-diameter channels via elaborate hydrogen-bonding networks (see, for example, Glidewell et al., 2005; Hao et al., 2005), and this seemed a likely cause of the unusual guest:host ratio. Given the considerable current interest in crystal engineering, the potential applications of large solvent-accessible channels (Sisson et al., 2005; Maly et al., 2007, Comotti et al., 2009; Furukawa & Yaghi, 2009) and the influence of substituents at the 6-position on tautomerism in 2-pyridones (Almlöf et al., 1971; Kvick, 1976; Johnson, 1984), we undertook a study of (I) crystallized from a series of solvents. We report here the structure of the pyridine tautomer, 6-chloro-2,5-dihydroxypyridine, (II), as the chloroform solvate, (IIa), and the carbon tetrachloride solvate, (IIb). Solvate crystals grown from CH2ClCH2Cl, (IIc), and CHCl2CHCl2, (IId), were also obtained. Although the host-molecule framework is ostensibly the same in all four solvates, the disorder of the solvent was too severe in (IIc) and (IId) to be modelled in an acceptable way. Refined models of (IIc) and (IId) in which the solvent contribution was removed using SQUEEZE (PLATON; Spek, 2009) are given in the Supplementary Material. In addition to the low-temperature structures, room temperature structure determinations of (I) and (IId) were also performed. There were no substantive differences between these room-temperature structures and their low-temperature counterparts, other than the expected difference in volume, which was ca 2–3%, as is common for molecular crystals.
Attempts to anneal the disordered solvent or to drive the solvent from the channels at elevated temperatures (above ca 378 K) led to the collapse of the host framework and to sublimation growth of solvent-free crystals of the pyridone tautomer, (I) (Fig. 1). Bond lengths and angles in (I) (Table 1) are within the normal range (Allen et al., 1987). In these sublimed crystals, inversion-related molecules form R22(8) dimers (Bernstein et al., 1995) via pairs of N—H···O hydrogen bonds. Four such dimers are linked by O—H···O hydrogen bonds into R46(28) motifs, which combine to form extensive pleated sheets (Fig. 2) that stack along the a axis. Hydrogen-bond parameters for (I) are given in Table 2.
Crystals of (IIa), (IIb), (IIc) and (IId) are isostructural with regard to the host-molecule framework. The following description is based upon the structure of (IIa), but unless stated otherwise the general features apply to all four solvates. Bond lengths and angles (Table 3) in the two independent molecules (designated A and B in Fig. 3) are normal, and the molecules are largely flat [r.m.s. deviations from planarity are 0.027 (2) and 0.009 (2) Å, respectively, for all non-H atoms of A and B). Indeed, the only significant deviation from planarity is for atom H1A, which is almost syn with respect to the O1A—H1A hydroxyl group para to it, but twisted out of the plane of the ring by about 39°. This is a consequence of intermolecular hydrogen bonding of molecule A in a repeating C(2) chain motif to 41 screw-related equivalents, to form helices that propagate along c (Fig. 4). In molecule B, the corresponding torsion angle is only 4° out of planarity, and so strictly anti with respect to O2B—H2B. The B molecules are linked by O—H···O hydrogen bonds to 4 related equivalents to form large tetrameric R44(28) rings (Fig. 5). The two independent molecules (A helix-forming and B ring-forming) are linked in a pseudo inversion-related manner into planar R22(8) dimers by pairs of hydrogen bonds (O2A—H2A···N1B and O2B—H2B···N1A). These dimers are π–π stacked with inversion-related dimers [mean π–π spacing = 3.351 (3) Å], with concomitant stacking of the R44(28) rings along the c axis to form continuous solvent-accessible channels (Fig. 6). Solvent molecules of appropriate size (e.g. CHCl3, CCl4, CH2ClCH2Cl and CHCl2CHCl2) are able to occupy the channels, but are disordered as a consequence of the 4 symmetry. Crystals grown from either acetone or propan-2-ol were too small for conventional X-ray analysis, but gave 1H NMR spectra that suggested similar stoichiometry to (IIa), (IIb), (IIc) and (IId). Larger solvent molecules, such as chlorobenzene, gave tiny crystals that were far too small for diffraction studies, but that gave IR spectra identical to the sublimate, as distinct from the IR spectra of the solvated crystals.
We anticipated that since CCl4 is tetrahedral it might occupy the channels in an ordered fashion, but this was not the case. Indeed, it is the nature of the solvent within these solvate crystals that causes the most significant (albeit small) differences between them. Channel volumes differ slightly owing to the need to accomodate solvent molecules of different size. Estimates of channel volume per unit cell using PLATON (Spek, 2009), were 186.0, 187.5, 185.9 and 198.6 Å3 for (IIa), (IIb), (IIc) and (IId), respectively, at 90 K. For structures (IIa) and (IIb) it proved possible to model CHCl3 and CCl4 solvent molecules disordered on the 4 of Wyckoff site a in I41/a, such that the site is fully occupied overall. For (IIc) and (IId), although no satisfactory disorder model could be found, an estimate of the occupancy of the solvent channels was made via the electron count of the SQUEEZE routine in PLATON. To within a few percent, the 4 sites in each of (IIa), (IIb), (IIc) and (IId) appear to be fully occupied, giving a solvent:host ratio of 1:8. Alternative estimates based on NMR spectroscopy [600 MHz, 1H NMR, for (IIa), (IIc) and (IId); 800 MHz, 13C NMR for (IIb)] were less clear cut [1:8, 1:7, 1:12, 1:10.5 for (IIa), (IIb), (IIc) and (IId), respectively], but the sample treatment was necessarily very different for the NMR experiments.
Johnson (1984) gives a comprehensive summary of the factors which influence the tautomeric ratio for the 2-pyridone/2-hydroxypyridine system. Whereas the pyridone form predominates in the parent compound, a 6-chloro substituent shifts the equilibrium toward the hydroxyl form, both in solution and in the gas phase. Thus, changes in molecular environment within a crystal structure can easily favour one form or the other. In the present case, differences between the molecular structures of (I) and (IIa) (Tables 1 and 3) are largely as expected for pyridone–pyridine tautomerism. The C2—O1 carbonyl bond in (I) lengthens from 1.277 (2) Å upon hydrogen shift to 1.338 (2) and 1.348 (3) Å, respectively, for the hydroxyl groups of molecules A and B in (IIb). The lack of aromaticity in (I) is clearly evident in the alternation of C—C bond lengths around the ring, while the aromaticity in (II) is well displayed by the similarity in the C—C bond lengths. Although the R22(8) dimers in (I) and in (IIa), (IIb), (IIc) and (IId) are superficially similar in appearance, in (I) the pairs of hydrogen bonds are N—H···O interactions between molecules related by crystallographic inversion, while in (IIa), (IIb), (IIc) and (IId) they are O—H···N interactions and each molecule of the dimer is crystallographically unique. Average donor–acceptor distances within these dimers are slightly shorter for O—H···N at 2.716 (8) Å (for the eight hydrogen bonds of this type in the four pyridine structures), compared with the pyridone N—H···O distance of 2.7393 (18) Å in (I). The O—H···O donor–acceptor distances that link dimers in pyridines (IIa), (IIb), (IIc) and (IId) [average 2.734 (10) Å for four such bonds], where the acceptor is a hydroxyl O atom, are considerably longer than that in (I) [2.6507 (17) Å], where the acceptor is a carbonyl O atom.