Pyridinium-3-carboxylic acid perchlorate was synthesized and separated as crystals. Differential scanning calorimetry (DSC) measurements show that this compound undergoes a reversible phase transition at ∼ 135 K with a wide hysteresis of 15 K. Dielectric measurements confirm the transition at ∼ 127 K. Measurement of the unit-cell parameters versus temperature shows that the values of the c axis and β angle change abruptly and remarkably at 129 (2) K, indicating that the system undergoes a first-order transition at Tc = 129 K. The crystal structures determined at 103 and 298 K are all monoclinic in P21/c, showing that the phase transition is isosymmetric. The crystal contains one-dimensional hydrogen-bonded chains of the pyridinium-3-carboxylic acid cations, which are further linked to perchlorate anions by hydrogen bonds to form well separated infinite planar layers. The most distinct differences between the structures of the higher-temperature phase and the lower-temperature phase are the change of the distance between the adjacent pyridinium ring planes within the hydrogen-bonded chains and the relative displacement between the hydrogen-bonded layers. Structural analysis shows that the driving force of the transition is the reorientation of the pyridinium-3-carboxylic acid cations. The degree of order of the perchlorate anions may be a secondary order parameter.
Supporting information
CCDC references: 782732; 782733; 782734
For all structures, data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); diamond (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
Crystal data top
| C6H6NO2·ClO4 | F(000) = 456 |
| Mr = 223.57 | Dx = 1.627 Mg m−3 |
| Monoclinic, p21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 2128 reflections |
| a = 7.400 (7) Å | θ = 3.7–27.5° |
| b = 16.996 (13) Å | µ = 0.42 mm−1 |
| c = 7.865 (7) Å | T = 298 K |
| β = 112.717 (12)° | Block, colorless |
| V = 912.4 (13) Å3 | 0.45 × 0.40 × 0.40 mm |
| Z = 4 | |
Data collection top
Saturn724+ (4x4 bin mode)
diffractometer | 2075 independent reflections |
| Radiation source: Rotating anode target | 1803 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.033 |
| Detector resolution: 28.5714 pixels mm-1 | θmax = 27.5°, θmin = 3.7° |
| CCD_Profile_fitting scans | h = −9→9 |
Absorption correction: multi-scan
crystalclear (Rigaku, 2005) | k = −21→22 |
| Tmin = 0.867, Tmax = 1.000 | l = −10→10 |
| 9560 measured reflections | |
Refinement top
| 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)] = 0.077 | Hydrogen site location: difference Fourier map |
| wR(F2) = 0.216 | H-atom parameters constrained |
| S = 1.06 | w = 1/[σ2(Fo2) + (0.1194P)2 + 0.9244P]
where P = (Fo2 + 2Fc2)/3 |
| 2075 reflections | (Δ/σ)max = 0.001 |
| 141 parameters | Δρmax = 0.64 e Å−3 |
| 0 restraints | Δρmin = −0.48 e Å−3 |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top| | x | y | z | Uiso*/Ueq | Occ. (<1) |
| Cl1 | −0.07890 (12) | 0.36492 (5) | 0.31739 (12) | 0.0493 (3) | 0.809 (3) |
| O3 | −0.2091 (11) | 0.3625 (3) | 0.4044 (10) | 0.115 (2) | 0.809 (3) |
| O4 | 0.1273 (7) | 0.3717 (3) | 0.4272 (8) | 0.1095 (18) | 0.809 (3) |
| O5 | −0.0904 (7) | 0.29102 (19) | 0.2180 (7) | 0.0772 (12) | 0.809 (3) |
| O6 | −0.1273 (6) | 0.4266 (2) | 0.1851 (5) | 0.0665 (9) | 0.809 (3) |
| Cl1' | −0.07890 (12) | 0.36492 (5) | 0.31739 (12) | 0.0493 (3) | 0.191 (3) |
| O3' | −0.287 (5) | 0.3608 (12) | 0.265 (4) | 0.115 (2) | 0.191 (3) |
| O4' | 0.007 (3) | 0.4248 (15) | 0.476 (3) | 0.1095 (18) | 0.191 (3) |
| O5' | 0.010 (3) | 0.2974 (8) | 0.419 (3) | 0.0772 (12) | 0.191 (3) |
| O6' | −0.014 (3) | 0.3885 (9) | 0.181 (2) | 0.0665 (9) | 0.191 (3) |
| O1 | 0.3348 (5) | 0.24826 (18) | 0.3296 (7) | 0.0954 (13) | |
| H1 | 0.2401 | 0.2697 | 0.3396 | 0.143* | |
| O2 | 0.1894 (4) | 0.13874 (17) | 0.3663 (5) | 0.0659 (8) | |
| N1 | 0.7823 (4) | 0.12861 (16) | 0.2836 (4) | 0.0462 (7) | |
| H1A | 0.8828 | 0.1541 | 0.2837 | 0.055* | |
| C1 | 0.7783 (5) | 0.0514 (2) | 0.2604 (5) | 0.0549 (9) | |
| H1B | 0.8827 | 0.0260 | 0.2459 | 0.066* | |
| C2 | 0.6198 (6) | 0.0092 (2) | 0.2579 (6) | 0.0578 (9) | |
| H2A | 0.6142 | −0.0450 | 0.2398 | 0.069* | |
| C3 | 0.4684 (5) | 0.0483 (2) | 0.2828 (5) | 0.0504 (8) | |
| H3A | 0.3602 | 0.0206 | 0.2830 | 0.060* | |
| C4 | 0.4783 (4) | 0.12927 (18) | 0.3074 (4) | 0.0393 (7) | |
| C5 | 0.6393 (4) | 0.16891 (19) | 0.3068 (4) | 0.0413 (7) | |
| H5A | 0.6485 | 0.2232 | 0.3223 | 0.050* | |
| C6 | 0.3171 (5) | 0.1718 (2) | 0.3367 (6) | 0.0536 (9) | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| Cl1 | 0.0475 (5) | 0.0411 (5) | 0.0588 (5) | 0.0017 (3) | 0.0199 (4) | 0.0053 (3) |
| O3 | 0.185 (6) | 0.081 (3) | 0.147 (5) | −0.008 (3) | 0.140 (6) | −0.009 (3) |
| O4 | 0.070 (3) | 0.123 (4) | 0.099 (3) | −0.001 (3) | −0.007 (3) | −0.001 (3) |
| O5 | 0.095 (3) | 0.0398 (17) | 0.117 (3) | 0.0044 (17) | 0.063 (3) | −0.0044 (18) |
| O6 | 0.080 (2) | 0.0473 (18) | 0.070 (2) | 0.0047 (15) | 0.0264 (19) | 0.0086 (15) |
| Cl1' | 0.0475 (5) | 0.0411 (5) | 0.0588 (5) | 0.0017 (3) | 0.0199 (4) | 0.0053 (3) |
| O3' | 0.185 (6) | 0.081 (3) | 0.147 (5) | −0.008 (3) | 0.140 (6) | −0.009 (3) |
| O4' | 0.070 (3) | 0.123 (4) | 0.099 (3) | −0.001 (3) | −0.007 (3) | −0.001 (3) |
| O5' | 0.095 (3) | 0.0398 (17) | 0.117 (3) | 0.0044 (17) | 0.063 (3) | −0.0044 (18) |
| O6' | 0.080 (2) | 0.0473 (18) | 0.070 (2) | 0.0047 (15) | 0.0264 (19) | 0.0086 (15) |
| O1 | 0.075 (2) | 0.0540 (18) | 0.186 (4) | 0.0194 (15) | 0.083 (3) | 0.012 (2) |
| O2 | 0.0399 (13) | 0.0783 (19) | 0.091 (2) | 0.0059 (12) | 0.0379 (14) | 0.0127 (15) |
| N1 | 0.0327 (12) | 0.0521 (16) | 0.0604 (16) | −0.0012 (10) | 0.0252 (12) | 0.0024 (12) |
| C1 | 0.0459 (17) | 0.059 (2) | 0.067 (2) | 0.0127 (15) | 0.0299 (16) | 0.0007 (17) |
| C2 | 0.062 (2) | 0.0388 (17) | 0.078 (2) | 0.0003 (15) | 0.034 (2) | −0.0045 (17) |
| C3 | 0.0424 (16) | 0.0457 (18) | 0.064 (2) | −0.0100 (13) | 0.0221 (15) | −0.0021 (15) |
| C4 | 0.0282 (13) | 0.0424 (16) | 0.0478 (15) | 0.0004 (11) | 0.0150 (11) | 0.0028 (12) |
| C5 | 0.0340 (14) | 0.0415 (16) | 0.0511 (16) | −0.0009 (11) | 0.0195 (12) | 0.0036 (13) |
| C6 | 0.0344 (16) | 0.057 (2) | 0.075 (2) | 0.0090 (14) | 0.0271 (16) | 0.0074 (17) |
Geometric parameters (Å, º) top
| Cl1—O3 | 1.381 (5) | C1—C2 | 1.369 (5) |
| Cl1—O6 | 1.422 (4) | C1—H1B | 0.9300 |
| Cl1—O4 | 1.438 (5) | C2—C3 | 1.380 (5) |
| Cl1—O5 | 1.464 (4) | C2—H2A | 0.9300 |
| O1—C6 | 1.309 (5) | C3—C4 | 1.387 (5) |
| O1—H1 | 0.8200 | C3—H3A | 0.9300 |
| O2—C6 | 1.197 (4) | C4—C5 | 1.371 (4) |
| N1—C1 | 1.324 (5) | C4—C6 | 1.487 (4) |
| N1—C5 | 1.331 (4) | C5—H5A | 0.9300 |
| N1—H1A | 0.8600 | | |
| | | |
| O3—Cl1—O6 | 111.0 (3) | C1—C2—H2A | 120.6 |
| O3—Cl1—O4 | 119.1 (4) | C3—C2—H2A | 120.6 |
| O6—Cl1—O4 | 106.8 (3) | C2—C3—C4 | 119.8 (3) |
| O3—Cl1—O5 | 109.3 (3) | C2—C3—H3A | 120.1 |
| O6—Cl1—O5 | 107.2 (2) | C4—C3—H3A | 120.1 |
| O4—Cl1—O5 | 102.6 (3) | C5—C4—C3 | 119.1 (3) |
| C6—O1—H1 | 109.5 | C5—C4—C6 | 120.8 (3) |
| C1—N1—C5 | 123.5 (3) | C3—C4—C6 | 120.1 (3) |
| C1—N1—H1A | 118.2 | N1—C5—C4 | 119.1 (3) |
| C5—N1—H1A | 118.2 | N1—C5—H5A | 120.5 |
| N1—C1—C2 | 119.7 (3) | C4—C5—H5A | 120.5 |
| N1—C1—H1B | 120.1 | O2—C6—O1 | 125.0 (3) |
| C2—C1—H1B | 120.1 | O2—C6—C4 | 122.8 (4) |
| C1—C2—C3 | 118.9 (3) | O1—C6—C4 | 112.1 (3) |
Hydrogen-bond geometry (Å, º) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1···O4 | 0.82 | 2.15 | 2.874 (7) | 147 |
| O1—H1···O5 | 0.82 | 2.28 | 3.011 (6) | 148 |
| N1—H1A···O2i | 0.86 | 2.12 | 2.831 (4) | 140 |
| N1—H1A···O5i | 0.86 | 2.41 | 3.024 (5) | 129 |
| C1—H1B···O6ii | 0.93 | 2.38 | 3.240 (5) | 154 |
| C3—H3A···O6iii | 0.93 | 2.43 | 3.349 (5) | 168 |
| C5—H5A···O3i | 0.93 | 2.57 | 3.465 (6) | 162 |
| Symmetry codes: (i) x+1, y, z; (ii) −x+1, y−1/2, −z+1/2; (iii) −x, y−1/2, −z+1/2. |
Crystal data top
| C6H6NO2·ClO4 | F(000) = 456 |
| Mr = 223.57 | Dx = 1.672 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 1607 reflections |
| a = 7.404 (6) Å | θ = 3.1–27.5° |
| b = 16.793 (11) Å | µ = 0.44 mm−1 |
| c = 7.751 (6) Å | T = 148 K |
| β = 112.817 (10)° | Block, colorless |
| V = 888.3 (11) Å3 | 0.45 × 0.40 × 0.40 mm |
| Z = 4 | |
Data collection top
Saturn724+ (4x4 bin mode)
diffractometer | 2013 independent reflections |
| Radiation source: Rotating anode target | 1823 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.028 |
| Detector resolution: 28.5714 pixels mm-1 | θmax = 27.5°, θmin = 3.5° |
| CCD_Profile_fitting scans | h = −9→9 |
Absorption correction: multi-scan
crystalclear | k = −21→21 |
| Tmin = 0.877, Tmax = 1.000 | l = −10→10 |
| 9255 measured reflections | |
Refinement top
| 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)] = 0.059 | Hydrogen site location: difference Fourier map |
| wR(F2) = 0.147 | H-atom parameters constrained |
| S = 1.09 | w = 1/[σ2(Fo2) + (0.0673P)2 + 1.3927P]
where P = (Fo2 + 2Fc2)/3 |
| 2013 reflections | (Δ/σ)max < 0.001 |
| 141 parameters | Δρmax = 0.82 e Å−3 |
| 6 restraints | Δρmin = −0.57 e Å−3 |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top| | x | y | z | Uiso*/Ueq | Occ. (<1) |
| Cl1 | −0.07996 (9) | 0.36420 (4) | 0.31165 (9) | 0.0267 (2) | 0.832 (4) |
| O3 | −0.2010 (6) | 0.36234 (17) | 0.4119 (5) | 0.0479 (9) | 0.832 (4) |
| O4 | 0.1281 (4) | 0.36979 (19) | 0.4308 (4) | 0.0500 (8) | 0.832 (4) |
| O5 | −0.1014 (5) | 0.29018 (16) | 0.2027 (4) | 0.0355 (7) | 0.832 (4) |
| O6 | −0.1309 (6) | 0.4297 (2) | 0.1827 (5) | 0.0293 (7) | 0.832 (4) |
| Cl1' | −0.07996 (9) | 0.36420 (4) | 0.31165 (9) | 0.0267 (2) | 0.168 (4) |
| O3' | −0.282 (2) | 0.3616 (10) | 0.311 (3) | 0.0479 (9) | 0.168 (4) |
| O4' | 0.038 (2) | 0.3953 (10) | 0.4951 (18) | 0.0500 (8) | 0.168 (4) |
| O5' | −0.053 (3) | 0.2858 (8) | 0.277 (2) | 0.0355 (7) | 0.168 (4) |
| O6' | −0.092 (4) | 0.4184 (12) | 0.171 (3) | 0.0293 (7) | 0.168 (4) |
| O1 | 0.3404 (4) | 0.25126 (14) | 0.3384 (5) | 0.0627 (9) | |
| H1 | 0.2400 | 0.2740 | 0.3400 | 0.094* | |
| O2 | 0.1877 (3) | 0.13967 (14) | 0.3688 (3) | 0.0413 (6) | |
| N1 | 0.7809 (3) | 0.12926 (13) | 0.2821 (3) | 0.0239 (5) | |
| H1A | 0.8832 | 0.1555 | 0.2809 | 0.029* | |
| C1 | 0.7754 (4) | 0.05039 (16) | 0.2583 (4) | 0.0284 (6) | |
| H1B | 0.8813 | 0.0238 | 0.2425 | 0.034* | |
| C2 | 0.6165 (4) | 0.00770 (16) | 0.2568 (4) | 0.0308 (6) | |
| H2A | 0.6101 | −0.0483 | 0.2377 | 0.037* | |
| C3 | 0.4660 (4) | 0.04749 (16) | 0.2834 (4) | 0.0268 (5) | |
| H3A | 0.3553 | 0.0190 | 0.2838 | 0.032* | |
| C4 | 0.4779 (3) | 0.12953 (15) | 0.3098 (3) | 0.0226 (5) | |
| C5 | 0.6387 (3) | 0.17005 (15) | 0.3077 (3) | 0.0227 (5) | |
| H5A | 0.6482 | 0.2262 | 0.3242 | 0.027* | |
| C6 | 0.3180 (4) | 0.17335 (18) | 0.3414 (4) | 0.0331 (6) | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| Cl1 | 0.0250 (3) | 0.0220 (3) | 0.0301 (4) | 0.0004 (2) | 0.0076 (3) | 0.0043 (2) |
| O3 | 0.076 (2) | 0.0384 (14) | 0.052 (2) | −0.0052 (15) | 0.050 (2) | −0.0047 (15) |
| O4 | 0.0280 (14) | 0.064 (2) | 0.0438 (16) | 0.0028 (12) | −0.0023 (11) | −0.0011 (14) |
| O5 | 0.0487 (19) | 0.0216 (11) | 0.0420 (18) | 0.0048 (11) | 0.0238 (16) | 0.0037 (13) |
| O6 | 0.033 (2) | 0.0220 (15) | 0.0358 (12) | 0.0056 (10) | 0.0163 (11) | 0.0021 (11) |
| Cl1' | 0.0250 (3) | 0.0220 (3) | 0.0301 (4) | 0.0004 (2) | 0.0076 (3) | 0.0043 (2) |
| O3' | 0.076 (2) | 0.0384 (14) | 0.052 (2) | −0.0052 (15) | 0.050 (2) | −0.0047 (15) |
| O4' | 0.0280 (14) | 0.064 (2) | 0.0438 (16) | 0.0028 (12) | −0.0023 (11) | −0.0011 (14) |
| O5' | 0.0487 (19) | 0.0216 (11) | 0.0420 (18) | 0.0048 (11) | 0.0238 (16) | 0.0037 (13) |
| O6' | 0.033 (2) | 0.0220 (15) | 0.0358 (12) | 0.0056 (10) | 0.0163 (11) | 0.0021 (11) |
| O1 | 0.0571 (16) | 0.0334 (13) | 0.125 (3) | 0.0217 (11) | 0.0659 (18) | 0.0207 (14) |
| O2 | 0.0232 (10) | 0.0509 (14) | 0.0582 (14) | 0.0076 (9) | 0.0248 (10) | 0.0174 (11) |
| N1 | 0.0177 (9) | 0.0275 (11) | 0.0299 (11) | −0.0008 (8) | 0.0128 (8) | 0.0013 (8) |
| C1 | 0.0285 (13) | 0.0299 (13) | 0.0293 (13) | 0.0087 (10) | 0.0139 (11) | 0.0010 (10) |
| C2 | 0.0380 (15) | 0.0212 (12) | 0.0340 (14) | −0.0004 (11) | 0.0150 (12) | −0.0023 (11) |
| C3 | 0.0227 (11) | 0.0272 (13) | 0.0291 (13) | −0.0059 (10) | 0.0086 (10) | 0.0007 (10) |
| C4 | 0.0165 (11) | 0.0247 (12) | 0.0268 (12) | 0.0028 (9) | 0.0085 (9) | 0.0045 (9) |
| C5 | 0.0203 (11) | 0.0225 (12) | 0.0267 (12) | 0.0004 (9) | 0.0108 (9) | 0.0021 (9) |
| C6 | 0.0227 (12) | 0.0350 (15) | 0.0465 (16) | 0.0087 (11) | 0.0188 (12) | 0.0106 (12) |
Geometric parameters (Å, º) top
| Cl1—O3 | 1.396 (3) | C1—C2 | 1.374 (4) |
| Cl1—O6 | 1.434 (3) | C1—H1B | 0.9500 |
| Cl1—O4 | 1.460 (3) | C2—C3 | 1.381 (4) |
| Cl1—O5 | 1.476 (3) | C2—H2A | 0.9500 |
| O1—C6 | 1.320 (4) | C3—C4 | 1.391 (4) |
| O1—H1 | 0.8400 | C3—H3A | 0.9500 |
| O2—C6 | 1.207 (3) | C4—C5 | 1.377 (3) |
| N1—C5 | 1.334 (3) | C4—C6 | 1.493 (3) |
| N1—C1 | 1.336 (4) | C5—H5A | 0.9500 |
| N1—H1A | 0.8800 | | |
| | | |
| O3—Cl1—O6 | 110.69 (18) | C1—C2—H2A | 120.5 |
| O3—Cl1—O4 | 113.4 (2) | C3—C2—H2A | 120.5 |
| O6—Cl1—O4 | 108.6 (2) | C2—C3—C4 | 119.5 (2) |
| O3—Cl1—O5 | 110.47 (19) | C2—C3—H3A | 120.2 |
| O6—Cl1—O5 | 107.8 (2) | C4—C3—H3A | 120.2 |
| O4—Cl1—O5 | 105.61 (18) | C5—C4—C3 | 119.6 (2) |
| C6—O1—H1 | 109.5 | C5—C4—C6 | 120.2 (2) |
| C5—N1—C1 | 123.1 (2) | C3—C4—C6 | 120.2 (2) |
| C5—N1—H1A | 118.4 | N1—C5—C4 | 118.9 (2) |
| C1—N1—H1A | 118.4 | N1—C5—H5A | 120.5 |
| N1—C1—C2 | 119.9 (2) | C4—C5—H5A | 120.5 |
| N1—C1—H1B | 120.1 | O2—C6—O1 | 125.6 (3) |
| C2—C1—H1B | 120.1 | O2—C6—C4 | 122.5 (3) |
| C1—C2—C3 | 118.9 (3) | O1—C6—C4 | 111.9 (2) |
Hydrogen-bond geometry (Å, º) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1···O4 | 0.84 | 2.05 | 2.796 (4) | 147 |
| O1—H1···O5 | 0.84 | 2.35 | 3.092 (5) | 148 |
| N1—H1A···O2i | 0.88 | 2.10 | 2.825 (4) | 139 |
| N1—H1A···O5i | 0.88 | 2.35 | 2.976 (4) | 128 |
| C1—H1B···O6ii | 0.95 | 2.33 | 3.211 (5) | 154 |
| C3—H3A···O6iii | 0.95 | 2.33 | 3.263 (4) | 168 |
| C5—H5A···O3i | 0.95 | 2.52 | 3.427 (4) | 160 |
| Symmetry codes: (i) x+1, y, z; (ii) −x+1, y−1/2, −z+1/2; (iii) −x, y−1/2, −z+1/2. |
Crystal data top
| C6H6ClNO6 | F(000) = 456 |
| Mr = 223.57 | Dx = 1.718 Mg m−3 |
| Monoclinic, p21/c | Mo Kα radiation, λ = 0.71073 Å |
| a = 7.4564 (10) Å | Cell parameters from 1607 reflections |
| b = 16.5261 (18) Å | θ = 3.1–27.5° |
| c = 7.1282 (8) Å | µ = 0.45 mm−1 |
| β = 79.754 (4)° | T = 103 K |
| V = 864.37 (18) Å3 | Block, colorless |
| Z = 4 | 0.45 × 0.40 × 0.40 mm |
Data collection top
Saturn724+ (4x4 bin mode)
diffractometer | 1971 independent reflections |
| Radiation source: Rotating anode target | 1772 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.039 |
| Detector resolution: 28.5714 pixels mm-1 | θmax = 27.5°, θmin = 3.0° |
| CCD_Profile_fitting scans | h = −9→9 |
Absorption correction: multi-scan
crystalclear | k = −21→21 |
| Tmin = 0.877, Tmax = 1.000 | l = −9→8 |
| 8182 measured reflections | |
Refinement top
| 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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.098 | H-atom parameters constrained |
| S = 1.07 | w = 1/[σ2(Fo2) + (0.0495P)2 + 0.5586P]
where P = (Fo2 + 2Fc2)/3 |
| 1971 reflections | (Δ/σ)max < 0.001 |
| 128 parameters | Δρmax = 0.44 e Å−3 |
| 0 restraints | Δρmin = −0.55 e Å−3 |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top| | x | y | z | Uiso*/Ueq | |
| N1 | 0.77145 (19) | 0.12629 (9) | 0.2783 (2) | 0.0168 (3) | |
| H1A | 0.8727 | 0.1522 | 0.2869 | 0.020* | |
| C1 | 0.7809 (2) | 0.04626 (10) | 0.2428 (2) | 0.0188 (3) | |
| H1B | 0.8948 | 0.0190 | 0.2281 | 0.023* | |
| C2 | 0.6245 (2) | 0.00393 (10) | 0.2277 (2) | 0.0197 (4) | |
| H2A | 0.6292 | −0.0527 | 0.2041 | 0.024* | |
| C3 | 0.4599 (2) | 0.04545 (10) | 0.2477 (2) | 0.0183 (3) | |
| H3A | 0.3512 | 0.0175 | 0.2355 | 0.022* | |
| C4 | 0.4552 (2) | 0.12833 (10) | 0.2857 (2) | 0.0154 (3) | |
| C5 | 0.6156 (2) | 0.16836 (10) | 0.3013 (2) | 0.0162 (3) | |
| H5A | 0.6148 | 0.2247 | 0.3279 | 0.019* | |
| C6 | 0.2792 (2) | 0.17379 (10) | 0.3011 (2) | 0.0163 (3) | |
| O1 | 0.28957 (16) | 0.24839 (7) | 0.3676 (2) | 0.0228 (3) | |
| H1 | 0.1884 | 0.2715 | 0.3741 | 0.034* | |
| O2 | 0.14506 (16) | 0.14334 (7) | 0.25567 (18) | 0.0198 (3) | |
| Cl1 | −0.11551 (5) | 0.36159 (2) | 0.24658 (5) | 0.01479 (14) | |
| O4 | 0.01840 (17) | 0.36194 (7) | 0.37277 (18) | 0.0207 (3) | |
| O6 | −0.09096 (17) | 0.43332 (7) | 0.12920 (17) | 0.0205 (3) | |
| O3 | −0.29683 (16) | 0.36138 (7) | 0.36047 (18) | 0.0204 (3) | |
| O5 | −0.09061 (16) | 0.28962 (7) | 0.12870 (17) | 0.0205 (3) | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| N1 | 0.0098 (6) | 0.0202 (7) | 0.0216 (7) | −0.0016 (5) | −0.0058 (5) | 0.0004 (6) |
| C1 | 0.0143 (7) | 0.0196 (8) | 0.0232 (8) | 0.0046 (6) | −0.0051 (6) | 0.0012 (7) |
| C2 | 0.0182 (8) | 0.0152 (8) | 0.0263 (9) | −0.0003 (6) | −0.0060 (7) | 0.0005 (6) |
| C3 | 0.0139 (8) | 0.0187 (8) | 0.0233 (8) | −0.0027 (6) | −0.0055 (6) | 0.0003 (7) |
| C4 | 0.0091 (7) | 0.0183 (8) | 0.0195 (7) | −0.0005 (6) | −0.0044 (6) | 0.0013 (6) |
| C5 | 0.0114 (7) | 0.0174 (8) | 0.0204 (8) | −0.0002 (6) | −0.0041 (6) | 0.0000 (6) |
| C6 | 0.0107 (7) | 0.0196 (8) | 0.0190 (8) | −0.0009 (6) | −0.0035 (6) | 0.0014 (6) |
| O1 | 0.0108 (6) | 0.0213 (6) | 0.0375 (7) | 0.0038 (5) | −0.0076 (5) | −0.0068 (5) |
| O2 | 0.0105 (5) | 0.0238 (7) | 0.0264 (7) | −0.0012 (4) | −0.0066 (5) | −0.0003 (5) |
| Cl1 | 0.0111 (2) | 0.0137 (2) | 0.0202 (2) | 0.00028 (12) | −0.00447 (15) | −0.00003 (13) |
| O4 | 0.0157 (6) | 0.0229 (6) | 0.0260 (6) | 0.0025 (5) | −0.0102 (5) | 0.0004 (5) |
| O6 | 0.0225 (6) | 0.0152 (6) | 0.0254 (6) | −0.0010 (5) | −0.0084 (5) | 0.0027 (5) |
| O3 | 0.0124 (6) | 0.0218 (6) | 0.0262 (6) | 0.0007 (4) | −0.0010 (5) | −0.0027 (5) |
| O5 | 0.0193 (6) | 0.0156 (6) | 0.0262 (6) | −0.0011 (5) | −0.0030 (5) | −0.0025 (5) |
Geometric parameters (Å, º) top
| N1—C5 | 1.339 (2) | C4—C6 | 1.499 (2) |
| N1—C1 | 1.346 (2) | C5—H5A | 0.9500 |
| N1—H1A | 0.8800 | C6—O2 | 1.214 (2) |
| C1—C2 | 1.380 (2) | C6—O1 | 1.328 (2) |
| C1—H1B | 0.9500 | O1—H1 | 0.8400 |
| C2—C3 | 1.391 (2) | Cl1—O6 | 1.4437 (12) |
| C2—H2A | 0.9500 | Cl1—O3 | 1.4479 (12) |
| C3—C4 | 1.395 (2) | Cl1—O5 | 1.4489 (12) |
| C3—H3A | 0.9500 | Cl1—O4 | 1.4579 (13) |
| C4—C5 | 1.389 (2) | | |
| | | |
| C5—N1—C1 | 123.28 (15) | C3—C4—C6 | 119.86 (14) |
| C5—N1—H1A | 118.4 | N1—C5—C4 | 118.94 (16) |
| C1—N1—H1A | 118.4 | N1—C5—H5A | 120.5 |
| N1—C1—C2 | 119.72 (15) | C4—C5—H5A | 120.5 |
| N1—C1—H1B | 120.1 | O2—C6—O1 | 125.69 (15) |
| C2—C1—H1B | 120.1 | O2—C6—C4 | 121.63 (15) |
| C1—C2—C3 | 118.96 (16) | O1—C6—C4 | 112.68 (14) |
| C1—C2—H2A | 120.5 | C6—O1—H1 | 109.5 |
| C3—C2—H2A | 120.5 | O6—Cl1—O3 | 109.65 (7) |
| C2—C3—C4 | 119.70 (15) | O6—Cl1—O5 | 110.36 (8) |
| C2—C3—H3A | 120.1 | O3—Cl1—O5 | 109.50 (7) |
| C4—C3—H3A | 120.1 | O6—Cl1—O4 | 108.92 (7) |
| C5—C4—C3 | 119.38 (15) | O3—Cl1—O4 | 109.13 (8) |
| C5—C4—C6 | 120.71 (15) | O5—Cl1—O4 | 109.26 (7) |
Hydrogen-bond geometry (Å, º) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1···O4 | 0.84 | 1.96 | 2.7540 (17) | 157 |
| N1—H1A···O2i | 0.88 | 2.01 | 2.7760 (19) | 145 |
| N1—H1A···O5i | 0.88 | 2.53 | 3.0151 (19) | 116 |
| C1—H1B···O6ii | 0.95 | 2.39 | 3.227 (2) | 147 |
| C3—H3A···O6iii | 0.95 | 2.44 | 3.304 (2) | 151 |
| C5—H5A···O3i | 0.95 | 2.38 | 3.298 (2) | 164 |
| Symmetry codes: (i) x+1, y, z; (ii) −x+1, y−1/2, −z+1/2; (iii) −x, y−1/2, −z+1/2. |
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