Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270111048165/fg3233sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111048165/fg3233Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111048165/fg3233IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111048165/fg3233IIIsup4.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111048165/fg3233IVsup5.hkl | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270111048165/fg3233Isup6.cml | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270111048165/fg3233IIsup7.cml | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270111048165/fg3233IIIsup8.cml | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270111048165/fg3233IVsup9.cml | |
Portable Document Format (PDF) file https://doi.org/10.1107/S0108270111048165/fg3233sup10.pdf |
CCDC references: 862239; 862240; 862241; 862242
Single crystals of the 1:1 compounds (I) and (III) were obtained by slow evaporation from acetonitrile solutions [120 and 200 ml for (I) and (III), respectively] of chloranilic acid with pyrrolidin-2-one or piperidin-2-one in a 1:1 molar ratio [0.475 g of chloranilic acid and 0.194 g of pyrrolidin-2-one for (I), and 1.03 g of chloranilic acid and 0.49 g of piperidin-2-one for (III)] at room temperature. Single crystals of the 1:2 compounds (II) and (IV) were obtained by slow evaporation from acetonitrile solutions [200 and 125 ml for (II) and (IV), respectively] of chloranilic acid with pyrrolidin-2-one or piperidin-2-one in a 1:2.2 molar ratio [0.452 g of chloranilic acid and 0.405 g of pyrrolidin-2-one for (II), and 0.367 g of chloranilic acid and 0.383 g of piperidin-2-one for (IV)] at room temperature. About 10% excess pyrrolidin-2-one or piperidin-2-one was used to avoid contamination of the 1:1 compound.
H atoms attached to O and N atoms were found in difference Fourier maps and refined isotropically (refined O—H and N—H distances are given in Tables 1–4). For compound (IV), the O-bound H atom, which is involved in the O···H···O hydrogen bond, was found to be disordered over two positions in a difference Fourier map. Since the site-occupancy factors and isotropic displacement parameters were strongly correlated, the positional parameters and occupancy factors were refined, with Uiso(H) = 1.5Ueq(O). The positional parameters were refined with bond restraints of O—H = 0.84 (2) Å. Other H atoms were treated as riding, with C—H = 0.99 Å and Uiso(H) = 1.2Ueq(C).
For all compounds, data collection: PROCESS-AUTO (Rigaku/MSC, 2004); cell refinement: PROCESS-AUTO (Rigaku/MSC, 2004); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008). Molecular graphics: ORTEP-3 (Farrugia, 1997) for (I), (II), (III); ORTEP-3 (Farrugia, 1997) and WinGX (Farrugia, 1999) for (IV). For all compounds, software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2004) and PLATON (Spek, 2009).
C4H7NO·C6H2Cl2O4 | F(000) = 1200.00 |
Mr = 294.09 | Dx = 1.716 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71075 Å |
Hall symbol: -P 2ybc | Cell parameters from 36720 reflections |
a = 7.7256 (4) Å | θ = 3.0–30.2° |
b = 19.3792 (11) Å | µ = 0.58 mm−1 |
c = 15.2486 (8) Å | T = 180 K |
β = 94.404 (2)° | Block, brown |
V = 2276.2 (2) Å3 | 0.35 × 0.20 × 0.15 mm |
Z = 8 |
Rigaku R-AXIS RAPID II diffractometer | 5477 reflections with I > 2σ(I) |
Detector resolution: 10.00 pixels mm-1 | Rint = 0.022 |
ω scans | θmax = 30.0° |
Absorption correction: numerical (NUMABS; Higashi, 1999) | h = −10→10 |
Tmin = 0.858, Tmax = 0.916 | k = −27→27 |
47031 measured reflections | l = −21→21 |
6636 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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.108 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0744P)2 + 0.1003P] where P = (Fo2 + 2Fc2)/3 |
6636 reflections | (Δ/σ)max = 0.002 |
349 parameters | Δρmax = 1.05 e Å−3 |
0 restraints | Δρmin = −0.30 e Å−3 |
C4H7NO·C6H2Cl2O4 | V = 2276.2 (2) Å3 |
Mr = 294.09 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.7256 (4) Å | µ = 0.58 mm−1 |
b = 19.3792 (11) Å | T = 180 K |
c = 15.2486 (8) Å | 0.35 × 0.20 × 0.15 mm |
β = 94.404 (2)° |
Rigaku R-AXIS RAPID II diffractometer | 6636 independent reflections |
Absorption correction: numerical (NUMABS; Higashi, 1999) | 5477 reflections with I > 2σ(I) |
Tmin = 0.858, Tmax = 0.916 | Rint = 0.022 |
47031 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.108 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 1.05 e Å−3 |
6636 reflections | Δρmin = −0.30 e Å−3 |
349 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Cl1 | 0.47142 (4) | 0.074726 (14) | 0.338731 (17) | 0.02434 (8) | |
Cl2 | 0.03903 (3) | 0.115359 (14) | 0.669443 (17) | 0.02511 (8) | |
Cl3 | 0.03936 (4) | 0.737210 (15) | 0.663182 (19) | 0.03042 (9) | |
Cl4 | 0.43434 (4) | 0.696135 (15) | 0.320246 (19) | 0.02849 (9) | |
O1 | 0.31761 (11) | −0.03179 (4) | 0.44873 (5) | 0.02405 (17) | |
O2 | 0.38228 (11) | 0.20697 (4) | 0.41873 (5) | 0.02328 (17) | |
O3 | 0.19289 (11) | 0.22175 (4) | 0.56024 (6) | 0.02743 (19) | |
O4 | 0.12838 (11) | −0.01809 (4) | 0.58734 (6) | 0.02334 (17) | |
O5 | 0.17091 (11) | 0.84382 (4) | 0.54524 (6) | 0.02559 (18) | |
O6 | 0.12580 (12) | 0.60462 (4) | 0.58253 (5) | 0.02783 (19) | |
O7 | 0.29328 (12) | 0.59007 (4) | 0.43419 (6) | 0.02925 (19) | |
O8 | 0.35646 (11) | 0.82973 (4) | 0.40553 (6) | 0.02527 (18) | |
O9 | 0.33325 (12) | 0.32916 (4) | 0.45643 (5) | 0.02627 (18) | |
O10 | 0.19689 (11) | 0.48186 (4) | 0.55062 (5) | 0.02815 (19) | |
N1 | 0.36175 (14) | 0.43510 (5) | 0.39621 (6) | 0.0243 (2) | |
N2 | 0.15944 (13) | 0.37558 (5) | 0.60968 (6) | 0.02284 (19) | |
C1 | 0.29092 (13) | 0.02762 (5) | 0.47153 (7) | 0.01785 (19) | |
C2 | 0.35319 (13) | 0.08757 (5) | 0.42792 (7) | 0.01731 (19) | |
C3 | 0.32313 (13) | 0.15273 (5) | 0.45676 (6) | 0.01677 (19) | |
C4 | 0.21969 (13) | 0.16321 (5) | 0.53620 (7) | 0.01796 (19) | |
C5 | 0.15645 (13) | 0.10223 (5) | 0.58002 (7) | 0.01801 (19) | |
C6 | 0.18762 (13) | 0.03833 (5) | 0.55030 (7) | 0.01796 (19) | |
C7 | 0.20045 (13) | 0.78418 (5) | 0.52370 (7) | 0.0198 (2) | |
C8 | 0.14501 (14) | 0.72414 (5) | 0.56984 (7) | 0.0200 (2) | |
C9 | 0.17536 (14) | 0.65934 (5) | 0.54141 (7) | 0.0198 (2) | |
C10 | 0.26969 (14) | 0.64856 (5) | 0.45899 (7) | 0.0201 (2) | |
C11 | 0.32711 (13) | 0.70957 (5) | 0.41302 (7) | 0.0200 (2) | |
C12 | 0.29929 (13) | 0.77344 (5) | 0.44357 (7) | 0.0196 (2) | |
C13 | 0.37277 (14) | 0.36749 (5) | 0.39448 (7) | 0.0205 (2) | |
C14 | 0.43783 (15) | 0.34400 (6) | 0.30898 (7) | 0.0231 (2) | |
H14A | 0.3433 | 0.3229 | 0.2705 | 0.028* | |
H14B | 0.5332 | 0.3101 | 0.3192 | 0.028* | |
C15 | 0.50285 (16) | 0.41064 (6) | 0.26846 (8) | 0.0262 (2) | |
H15A | 0.6308 | 0.4141 | 0.2775 | 0.031* | |
H15B | 0.4684 | 0.4126 | 0.2046 | 0.031* | |
C16 | 0.41537 (15) | 0.46817 (6) | 0.31736 (7) | 0.0248 (2) | |
H16A | 0.4978 | 0.5062 | 0.3324 | 0.030* | |
H16B | 0.3139 | 0.4868 | 0.2813 | 0.030* | |
C17 | 0.14719 (14) | 0.44354 (5) | 0.61008 (7) | 0.0205 (2) | |
C18 | 0.06943 (15) | 0.46823 (6) | 0.69205 (7) | 0.0242 (2) | |
H18A | −0.0308 | 0.4990 | 0.6774 | 0.029* | |
H18B | 0.1565 | 0.4932 | 0.7312 | 0.029* | |
C19 | 0.01142 (15) | 0.40086 (6) | 0.73566 (7) | 0.0243 (2) | |
H19A | 0.0465 | 0.4010 | 0.7995 | 0.029* | |
H19B | −0.1162 | 0.3953 | 0.7272 | 0.029* | |
C20 | 0.10378 (15) | 0.34266 (5) | 0.68915 (7) | 0.0234 (2) | |
H20A | 0.2047 | 0.3252 | 0.7266 | 0.028* | |
H20B | 0.0234 | 0.3039 | 0.6741 | 0.028* | |
H1 | 0.3189 (19) | 0.4563 (8) | 0.4399 (10) | 0.035 (4)* | |
H2B | 0.2074 (19) | 0.3547 (8) | 0.5699 (10) | 0.034 (4)* | |
H2A | 0.350 (3) | 0.2562 (11) | 0.4403 (15) | 0.082 (7)* | |
H4 | 0.172 (2) | −0.0543 (9) | 0.5668 (12) | 0.045 (5)* | |
H6 | 0.161 (3) | 0.5596 (11) | 0.5596 (13) | 0.069 (6)* | |
H8 | 0.311 (2) | 0.8651 (9) | 0.4274 (11) | 0.043 (4)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.03294 (15) | 0.01817 (14) | 0.02329 (14) | 0.00229 (9) | 0.01115 (11) | −0.00179 (9) |
Cl2 | 0.02980 (15) | 0.02248 (15) | 0.02446 (14) | 0.00148 (10) | 0.01112 (11) | −0.00045 (9) |
Cl3 | 0.04477 (18) | 0.02118 (14) | 0.02749 (15) | −0.00090 (11) | 0.01685 (12) | −0.00437 (10) |
Cl4 | 0.03442 (15) | 0.02384 (15) | 0.02919 (15) | 0.00121 (10) | 0.01530 (11) | 0.00017 (10) |
O1 | 0.0322 (4) | 0.0103 (3) | 0.0302 (4) | 0.0006 (3) | 0.0066 (3) | −0.0018 (3) |
O2 | 0.0346 (4) | 0.0098 (3) | 0.0267 (4) | −0.0003 (3) | 0.0110 (3) | 0.0017 (3) |
O3 | 0.0395 (5) | 0.0121 (3) | 0.0324 (4) | 0.0008 (3) | 0.0137 (4) | −0.0038 (3) |
O4 | 0.0290 (4) | 0.0118 (3) | 0.0304 (4) | −0.0010 (3) | 0.0096 (3) | 0.0029 (3) |
O5 | 0.0331 (4) | 0.0133 (3) | 0.0312 (4) | 0.0002 (3) | 0.0077 (3) | −0.0018 (3) |
O6 | 0.0463 (5) | 0.0114 (3) | 0.0273 (4) | −0.0012 (3) | 0.0127 (4) | 0.0019 (3) |
O7 | 0.0457 (5) | 0.0129 (3) | 0.0304 (4) | 0.0018 (3) | 0.0110 (4) | −0.0022 (3) |
O8 | 0.0300 (4) | 0.0141 (4) | 0.0329 (4) | 0.0000 (3) | 0.0106 (3) | 0.0047 (3) |
O9 | 0.0423 (5) | 0.0139 (3) | 0.0239 (4) | 0.0008 (3) | 0.0107 (3) | 0.0024 (3) |
O10 | 0.0429 (5) | 0.0143 (3) | 0.0289 (4) | 0.0010 (3) | 0.0136 (4) | 0.0028 (3) |
N1 | 0.0378 (5) | 0.0134 (4) | 0.0230 (4) | 0.0014 (4) | 0.0119 (4) | 0.0014 (3) |
N2 | 0.0325 (5) | 0.0152 (4) | 0.0223 (4) | 0.0030 (4) | 0.0119 (4) | 0.0023 (3) |
C1 | 0.0201 (5) | 0.0129 (4) | 0.0205 (5) | 0.0001 (3) | 0.0011 (4) | 0.0001 (4) |
C2 | 0.0220 (5) | 0.0124 (4) | 0.0180 (4) | 0.0015 (3) | 0.0046 (4) | −0.0004 (3) |
C3 | 0.0205 (4) | 0.0118 (4) | 0.0182 (4) | 0.0007 (3) | 0.0023 (4) | 0.0007 (3) |
C4 | 0.0215 (5) | 0.0131 (4) | 0.0195 (4) | 0.0004 (4) | 0.0031 (4) | −0.0006 (4) |
C5 | 0.0210 (5) | 0.0149 (4) | 0.0187 (4) | 0.0010 (4) | 0.0046 (4) | 0.0006 (4) |
C6 | 0.0197 (5) | 0.0132 (4) | 0.0211 (5) | −0.0002 (3) | 0.0019 (4) | 0.0023 (4) |
C7 | 0.0216 (5) | 0.0138 (4) | 0.0240 (5) | 0.0001 (4) | 0.0019 (4) | −0.0003 (4) |
C8 | 0.0257 (5) | 0.0144 (4) | 0.0205 (5) | 0.0007 (4) | 0.0055 (4) | −0.0005 (4) |
C9 | 0.0263 (5) | 0.0136 (4) | 0.0198 (5) | −0.0005 (4) | 0.0038 (4) | 0.0009 (4) |
C10 | 0.0247 (5) | 0.0151 (4) | 0.0208 (5) | 0.0006 (4) | 0.0037 (4) | 0.0003 (4) |
C11 | 0.0215 (5) | 0.0164 (5) | 0.0226 (5) | 0.0009 (4) | 0.0045 (4) | 0.0008 (4) |
C12 | 0.0206 (5) | 0.0147 (4) | 0.0238 (5) | −0.0006 (4) | 0.0028 (4) | 0.0025 (4) |
C13 | 0.0245 (5) | 0.0150 (4) | 0.0224 (5) | 0.0011 (4) | 0.0042 (4) | 0.0009 (4) |
C14 | 0.0304 (5) | 0.0160 (5) | 0.0234 (5) | 0.0030 (4) | 0.0057 (4) | −0.0017 (4) |
C15 | 0.0313 (6) | 0.0238 (5) | 0.0248 (5) | 0.0007 (4) | 0.0106 (4) | 0.0016 (4) |
C16 | 0.0334 (6) | 0.0187 (5) | 0.0239 (5) | −0.0041 (4) | 0.0122 (4) | −0.0005 (4) |
C17 | 0.0238 (5) | 0.0158 (4) | 0.0226 (5) | 0.0007 (4) | 0.0050 (4) | 0.0003 (4) |
C18 | 0.0267 (5) | 0.0238 (5) | 0.0234 (5) | −0.0008 (4) | 0.0098 (4) | −0.0068 (4) |
C19 | 0.0297 (5) | 0.0217 (5) | 0.0224 (5) | −0.0009 (4) | 0.0085 (4) | −0.0002 (4) |
C20 | 0.0308 (5) | 0.0161 (5) | 0.0242 (5) | 0.0004 (4) | 0.0083 (4) | 0.0031 (4) |
Cl1—C2 | 1.7137 (10) | C3—C4 | 1.5151 (13) |
Cl2—C5 | 1.7138 (10) | C4—C5 | 1.4601 (14) |
Cl3—C8 | 1.7130 (11) | C5—C6 | 1.3466 (14) |
Cl4—C11 | 1.7133 (11) | C7—C8 | 1.4418 (14) |
O1—C1 | 1.2247 (12) | C7—C12 | 1.5042 (14) |
O2—C3 | 1.3002 (11) | C8—C9 | 1.3548 (14) |
O2—H2A | 1.05 (2) | C9—C10 | 1.5149 (14) |
O3—C4 | 1.2148 (12) | C10—C11 | 1.4606 (14) |
O4—C6 | 1.3281 (12) | C11—C12 | 1.3457 (14) |
O4—H4 | 0.848 (18) | C13—C14 | 1.5035 (14) |
O5—C7 | 1.2277 (12) | C14—C15 | 1.5327 (15) |
O6—C9 | 1.3043 (12) | C14—H14A | 0.9900 |
O6—H6 | 0.99 (2) | C14—H14B | 0.9900 |
O7—C10 | 1.2131 (12) | C15—C16 | 1.5274 (15) |
O8—C12 | 1.3269 (12) | C15—H15A | 0.9900 |
O8—H8 | 0.851 (17) | C15—H15B | 0.9900 |
O9—C13 | 1.2576 (12) | C16—H16A | 0.9900 |
O10—C17 | 1.2548 (13) | C16—H16B | 0.9900 |
N1—C13 | 1.3133 (13) | C17—C18 | 1.5058 (14) |
N1—C16 | 1.4507 (13) | C18—C19 | 1.5471 (16) |
N1—H1 | 0.869 (16) | C18—H18A | 0.9900 |
N2—C17 | 1.3204 (13) | C18—H18B | 0.9900 |
N2—C20 | 1.4631 (13) | C19—C20 | 1.5368 (15) |
N2—H2B | 0.838 (15) | C19—H19A | 0.9900 |
C1—C2 | 1.4397 (13) | C19—H19B | 0.9900 |
C1—C6 | 1.5066 (14) | C20—H20A | 0.9900 |
C2—C3 | 1.3630 (13) | C20—H20B | 0.9900 |
C3—O2—H2A | 119.7 (12) | O8—C12—C7 | 116.62 (9) |
C6—O4—H4 | 111.4 (12) | C11—C12—C7 | 120.87 (9) |
C9—O6—H6 | 116.7 (12) | O9—C13—N1 | 123.66 (10) |
C12—O8—H8 | 109.1 (11) | O9—C13—C14 | 126.09 (9) |
C13—O9—H2A | 114.9 (9) | N1—C13—C14 | 110.25 (9) |
C13—N1—C16 | 113.63 (9) | C13—C14—C15 | 103.66 (9) |
C13—N1—H1 | 121.1 (10) | C13—C14—H14A | 111.0 |
C16—N1—H1 | 125.1 (10) | C15—C14—H14A | 111.0 |
C17—N2—C20 | 113.91 (9) | C13—C14—H14B | 111.0 |
C17—N2—H2B | 121.3 (10) | C15—C14—H14B | 111.0 |
C20—N2—H2B | 124.3 (10) | H14A—C14—H14B | 109.0 |
O1—C1—C2 | 123.92 (9) | C16—C15—C14 | 104.32 (8) |
O1—C1—C6 | 117.83 (9) | C16—C15—H15A | 110.9 |
C2—C1—C6 | 118.24 (9) | C14—C15—H15A | 110.9 |
C3—C2—C1 | 121.83 (9) | C16—C15—H15B | 110.9 |
C3—C2—Cl1 | 120.34 (8) | C14—C15—H15B | 110.9 |
C1—C2—Cl1 | 117.82 (7) | H15A—C15—H15B | 108.9 |
O2—C3—C2 | 122.04 (9) | N1—C16—C15 | 104.32 (9) |
O2—C3—C4 | 118.25 (8) | N1—C16—H16A | 110.9 |
C2—C3—C4 | 119.70 (9) | C15—C16—H16A | 110.9 |
O3—C4—C5 | 123.16 (9) | N1—C16—H16B | 110.9 |
O3—C4—C3 | 118.62 (9) | C15—C16—H16B | 110.9 |
C5—C4—C3 | 118.23 (8) | H16A—C16—H16B | 108.9 |
C6—C5—C4 | 121.03 (9) | O10—C17—N2 | 124.12 (10) |
C6—C5—Cl2 | 121.57 (8) | O10—C17—C18 | 125.13 (10) |
C4—C5—Cl2 | 117.40 (8) | N2—C17—C18 | 110.74 (9) |
O4—C6—C5 | 122.52 (10) | C17—C18—C19 | 103.64 (9) |
O4—C6—C1 | 116.52 (9) | C17—C18—H18A | 111.0 |
C5—C6—C1 | 120.96 (9) | C19—C18—H18A | 111.0 |
O5—C7—C8 | 124.12 (10) | C17—C18—H18B | 111.0 |
O5—C7—C12 | 117.65 (9) | C19—C18—H18B | 111.0 |
C8—C7—C12 | 118.24 (9) | H18A—C18—H18B | 109.0 |
C9—C8—C7 | 121.78 (9) | C20—C19—C18 | 105.12 (8) |
C9—C8—Cl3 | 120.54 (8) | C20—C19—H19A | 110.7 |
C7—C8—Cl3 | 117.68 (8) | C18—C19—H19A | 110.7 |
O6—C9—C8 | 122.37 (9) | C20—C19—H19B | 110.7 |
O6—C9—C10 | 117.67 (9) | C18—C19—H19B | 110.7 |
C8—C9—C10 | 119.96 (9) | H19A—C19—H19B | 108.8 |
O7—C10—C11 | 123.25 (10) | N2—C20—C19 | 103.81 (8) |
O7—C10—C9 | 118.74 (9) | N2—C20—H20A | 111.0 |
C11—C10—C9 | 118.01 (9) | C19—C20—H20A | 111.0 |
C12—C11—C10 | 121.06 (9) | N2—C20—H20B | 111.0 |
C12—C11—Cl4 | 121.72 (8) | C19—C20—H20B | 111.0 |
C10—C11—Cl4 | 117.21 (8) | H20A—C20—H20B | 109.0 |
O8—C12—C11 | 122.51 (10) | ||
O1—C1—C2—C3 | −178.68 (10) | Cl3—C8—C9—C10 | −179.71 (8) |
C6—C1—C2—C3 | 0.93 (16) | O6—C9—C10—O7 | 0.87 (16) |
O1—C1—C2—Cl1 | 0.09 (15) | C8—C9—C10—O7 | −179.02 (11) |
C6—C1—C2—Cl1 | 179.69 (7) | O6—C9—C10—C11 | −179.42 (10) |
C1—C2—C3—O2 | 178.49 (10) | C8—C9—C10—C11 | 0.69 (16) |
Cl1—C2—C3—O2 | −0.24 (15) | O7—C10—C11—C12 | −179.39 (11) |
C1—C2—C3—C4 | −0.73 (16) | C9—C10—C11—C12 | 0.91 (16) |
Cl1—C2—C3—C4 | −179.47 (7) | O7—C10—C11—Cl4 | −0.58 (15) |
O2—C3—C4—O3 | 1.49 (15) | C9—C10—C11—Cl4 | 179.73 (7) |
C2—C3—C4—O3 | −179.25 (10) | C10—C11—C12—O8 | 176.98 (10) |
O2—C3—C4—C5 | −178.71 (9) | Cl4—C11—C12—O8 | −1.78 (16) |
C2—C3—C4—C5 | 0.54 (15) | C10—C11—C12—C7 | −2.98 (16) |
O3—C4—C5—C6 | 179.17 (11) | Cl4—C11—C12—C7 | 178.26 (7) |
C3—C4—C5—C6 | −0.61 (15) | O5—C7—C12—O8 | 4.11 (15) |
O3—C4—C5—Cl2 | 0.04 (15) | C8—C7—C12—O8 | −176.45 (9) |
C3—C4—C5—Cl2 | −179.74 (7) | O5—C7—C12—C11 | −175.92 (10) |
C4—C5—C6—O4 | −178.33 (9) | C8—C7—C12—C11 | 3.51 (15) |
Cl2—C5—C6—O4 | 0.77 (15) | C16—N1—C13—O9 | 179.68 (11) |
C4—C5—C6—C1 | 0.84 (16) | C16—N1—C13—C14 | −0.46 (14) |
Cl2—C5—C6—C1 | 179.93 (8) | O9—C13—C14—C15 | −167.72 (11) |
O1—C1—C6—O4 | −2.14 (15) | N1—C13—C14—C15 | 12.42 (12) |
C2—C1—C6—O4 | 178.23 (9) | C13—C14—C15—C16 | −18.55 (12) |
O1—C1—C6—C5 | 178.65 (10) | C13—N1—C16—C15 | −11.78 (14) |
C2—C1—C6—C5 | −0.98 (16) | C14—C15—C16—N1 | 18.43 (12) |
O5—C7—C8—C9 | 177.48 (11) | C20—N2—C17—O10 | 175.97 (11) |
C12—C7—C8—C9 | −1.92 (16) | C20—N2—C17—C18 | −2.85 (13) |
O5—C7—C8—Cl3 | −2.87 (15) | O10—C17—C18—C19 | 173.19 (11) |
C12—C7—C8—Cl3 | 177.73 (7) | N2—C17—C18—C19 | −7.99 (13) |
C7—C8—C9—O6 | −179.96 (10) | C17—C18—C19—C20 | 14.86 (12) |
Cl3—C8—C9—O6 | 0.40 (16) | C17—N2—C20—C19 | 12.47 (13) |
C7—C8—C9—C10 | −0.07 (16) | C18—C19—C20—N2 | −16.35 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O10 | 0.870 (15) | 2.056 (15) | 2.9065 (13) | 165.5 (14) |
O2—H2A···O9 | 1.05 (2) | 1.44 (2) | 2.4728 (11) | 167 (2) |
N2—H2B···O9 | 0.839 (15) | 2.108 (15) | 2.9249 (13) | 164.6 (15) |
O4—H4···O5i | 0.849 (17) | 2.002 (17) | 2.7774 (11) | 151.6 (15) |
O6—H6···O10 | 0.99 (2) | 1.54 (2) | 2.4978 (11) | 163 (2) |
O8—H8···O1ii | 0.850 (17) | 2.025 (17) | 2.7850 (11) | 148.5 (15) |
Symmetry codes: (i) x, y−1, z; (ii) x, y+1, z. |
C6H2Cl2O4·2C4H7NO | Z = 1 |
Mr = 379.20 | F(000) = 196.00 |
Triclinic, P1 | Dx = 1.588 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71075 Å |
a = 4.9665 (3) Å | Cell parameters from 8795 reflections |
b = 7.4767 (4) Å | θ = 3.0–30.1° |
c = 11.8445 (6) Å | µ = 0.44 mm−1 |
α = 106.7904 (19)° | T = 180 K |
β = 90.299 (2)° | Block, brown |
γ = 108.734 (2)° | 0.38 × 0.32 × 0.25 mm |
V = 396.42 (4) Å3 |
Rigaku R-AXIS RAPID II diffractometer | 2156 reflections with I > 2σ(I) |
Detector resolution: 10.00 pixels mm-1 | Rint = 0.024 |
ω scans | θmax = 30.0°, θmin = 3.0° |
Absorption correction: numerical (NUMABS; Higashi, 1999) | h = −6→6 |
Tmin = 0.853, Tmax = 0.895 | k = −10→10 |
9315 measured reflections | l = −16→15 |
2296 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)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.081 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.11 | w = 1/[σ2(Fo2) + (0.0452P)2 + 0.0921P] where P = (Fo2 + 2Fc2)/3 |
2296 reflections | (Δ/σ)max = 0.001 |
117 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.39 e Å−3 |
C6H2Cl2O4·2C4H7NO | γ = 108.734 (2)° |
Mr = 379.20 | V = 396.42 (4) Å3 |
Triclinic, P1 | Z = 1 |
a = 4.9665 (3) Å | Mo Kα radiation |
b = 7.4767 (4) Å | µ = 0.44 mm−1 |
c = 11.8445 (6) Å | T = 180 K |
α = 106.7904 (19)° | 0.38 × 0.32 × 0.25 mm |
β = 90.299 (2)° |
Rigaku R-AXIS RAPID II diffractometer | 2296 independent reflections |
Absorption correction: numerical (NUMABS; Higashi, 1999) | 2156 reflections with I > 2σ(I) |
Tmin = 0.853, Tmax = 0.895 | Rint = 0.024 |
9315 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.081 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.11 | Δρmax = 0.31 e Å−3 |
2296 reflections | Δρmin = −0.39 e Å−3 |
117 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Cl1 | 1.08647 (5) | 0.76633 (4) | 0.94308 (2) | 0.02797 (9) | |
O1 | 0.85407 (19) | 0.79167 (13) | 1.17509 (7) | 0.0369 (2) | |
O2 | 0.63936 (17) | 0.43116 (13) | 0.76924 (6) | 0.02898 (17) | |
O3 | 0.29637 (16) | 0.17553 (12) | 0.58756 (6) | 0.02901 (17) | |
N1 | 0.26260 (19) | 0.08485 (14) | 0.38446 (7) | 0.02405 (18) | |
C1 | 0.6975 (2) | 0.65861 (15) | 1.09265 (8) | 0.02316 (19) | |
C2 | 0.7647 (2) | 0.61826 (14) | 0.96995 (8) | 0.02138 (18) | |
C3 | 0.5824 (2) | 0.47035 (14) | 0.88085 (8) | 0.02189 (18) | |
C4 | 0.39885 (19) | 0.18575 (14) | 0.49228 (8) | 0.02097 (18) | |
C5 | 0.6955 (2) | 0.31323 (15) | 0.48221 (9) | 0.02438 (19) | |
H5A | 0.8407 | 0.2657 | 0.5096 | 0.029* | |
H5B | 0.7331 | 0.4531 | 0.5299 | 0.029* | |
C6 | 0.7007 (2) | 0.29287 (18) | 0.34969 (9) | 0.0303 (2) | |
H6A | 0.6949 | 0.4153 | 0.3348 | 0.036* | |
H6B | 0.8761 | 0.2677 | 0.3211 | 0.036* | |
C7 | 0.4338 (2) | 0.11639 (17) | 0.28707 (9) | 0.0289 (2) | |
H7A | 0.3300 | 0.1484 | 0.2283 | 0.035* | |
H7B | 0.4845 | −0.0023 | 0.2466 | 0.035* | |
H1 | 0.118 (4) | 0.014 (3) | 0.3762 (16) | 0.045 (5)* | |
H2 | 0.512 (4) | 0.338 (3) | 0.7191 (18) | 0.058 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.02311 (13) | 0.03086 (14) | 0.02313 (13) | 0.00043 (9) | 0.00508 (9) | 0.00788 (10) |
O1 | 0.0312 (4) | 0.0403 (5) | 0.0188 (4) | −0.0069 (3) | 0.0021 (3) | 0.0001 (3) |
O2 | 0.0265 (4) | 0.0340 (4) | 0.0150 (3) | −0.0008 (3) | 0.0037 (3) | 0.0030 (3) |
O3 | 0.0237 (3) | 0.0348 (4) | 0.0171 (3) | −0.0024 (3) | 0.0042 (3) | 0.0048 (3) |
N1 | 0.0189 (4) | 0.0273 (4) | 0.0173 (4) | −0.0010 (3) | 0.0019 (3) | 0.0039 (3) |
C1 | 0.0220 (4) | 0.0259 (4) | 0.0173 (4) | 0.0038 (3) | 0.0023 (3) | 0.0053 (3) |
C2 | 0.0192 (4) | 0.0245 (4) | 0.0175 (4) | 0.0035 (3) | 0.0032 (3) | 0.0064 (3) |
C3 | 0.0216 (4) | 0.0252 (4) | 0.0162 (4) | 0.0050 (3) | 0.0030 (3) | 0.0056 (3) |
C4 | 0.0181 (4) | 0.0218 (4) | 0.0182 (4) | 0.0019 (3) | 0.0024 (3) | 0.0046 (3) |
C5 | 0.0186 (4) | 0.0273 (4) | 0.0201 (4) | −0.0005 (3) | 0.0030 (3) | 0.0059 (3) |
C6 | 0.0245 (5) | 0.0377 (6) | 0.0219 (5) | −0.0005 (4) | 0.0047 (4) | 0.0113 (4) |
C7 | 0.0284 (5) | 0.0325 (5) | 0.0179 (4) | 0.0019 (4) | 0.0053 (4) | 0.0054 (4) |
Cl1—C2 | 1.7186 (10) | C3—C1i | 1.5095 (13) |
O1—C1 | 1.2173 (12) | C4—C5 | 1.5031 (12) |
O2—C3 | 1.3217 (11) | C5—C6 | 1.5338 (14) |
O2—H2 | 0.84 (2) | C5—H5A | 0.9900 |
O3—C4 | 1.2528 (11) | C5—H5B | 0.9900 |
N1—C4 | 1.3283 (12) | C6—C7 | 1.5328 (15) |
N1—C7 | 1.4654 (13) | C6—H6A | 0.9900 |
N1—H1 | 0.731 (19) | C6—H6B | 0.9900 |
C1—C2 | 1.4598 (13) | C7—H7A | 0.9900 |
C1—C3i | 1.5095 (13) | C7—H7B | 0.9900 |
C2—C3 | 1.3524 (13) | ||
C3—O2—H2 | 116.2 (14) | C4—C5—H5A | 110.8 |
C4—N1—C7 | 114.73 (8) | C6—C5—H5A | 110.8 |
C4—N1—H1 | 121.1 (14) | C4—C5—H5B | 110.8 |
C7—N1—H1 | 124.0 (14) | C6—C5—H5B | 110.8 |
O1—C1—C2 | 123.62 (9) | H5A—C5—H5B | 108.9 |
O1—C1—C3i | 117.95 (8) | C7—C6—C5 | 105.67 (8) |
C2—C1—C3i | 118.43 (8) | C7—C6—H6A | 110.6 |
C3—C2—C1 | 121.62 (8) | C5—C6—H6A | 110.6 |
C3—C2—Cl1 | 121.16 (7) | C7—C6—H6B | 110.6 |
C1—C2—Cl1 | 117.22 (7) | C5—C6—H6B | 110.6 |
O2—C3—C2 | 122.56 (9) | H6A—C6—H6B | 108.7 |
O2—C3—C1i | 117.48 (8) | N1—C7—C6 | 103.28 (8) |
C2—C3—C1i | 119.95 (8) | N1—C7—H7A | 111.1 |
O3—C4—N1 | 125.27 (9) | C6—C7—H7A | 111.1 |
O3—C4—C5 | 125.29 (8) | N1—C7—H7B | 111.1 |
N1—C4—C5 | 109.45 (8) | C6—C7—H7B | 111.1 |
C4—C5—C6 | 104.66 (8) | H7A—C7—H7B | 109.1 |
O1—C1—C2—C3 | −179.09 (11) | C7—N1—C4—O3 | −177.42 (10) |
C3i—C1—C2—C3 | 0.41 (16) | C7—N1—C4—C5 | 2.27 (13) |
O1—C1—C2—Cl1 | 1.09 (15) | O3—C4—C5—C6 | −172.89 (10) |
C3i—C1—C2—Cl1 | −179.40 (7) | N1—C4—C5—C6 | 7.42 (12) |
C1—C2—C3—O2 | −179.87 (9) | C4—C5—C6—C7 | −13.55 (12) |
Cl1—C2—C3—O2 | −0.07 (15) | C4—N1—C7—C6 | −10.88 (13) |
C1—C2—C3—C1i | −0.42 (16) | C5—C6—C7—N1 | 14.51 (12) |
Cl1—C2—C3—C1i | 179.38 (7) |
Symmetry code: (i) −x+1, −y+1, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1ii | 0.73 (2) | 2.537 (19) | 3.0036 (12) | 123.8 (17) |
N1—H1···O3iii | 0.73 (2) | 2.22 (2) | 2.9185 (13) | 162.0 (19) |
O2—H2···O3 | 0.84 (2) | 1.76 (2) | 2.5845 (11) | 164 (2) |
Symmetry codes: (ii) x−1, y−1, z−1; (iii) −x, −y, −z+1. |
C6H2Cl2O4·C5H9NO | F(000) = 632.00 |
Mr = 308.12 | Dx = 1.644 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71075 Å |
Hall symbol: -P 2ybc | Cell parameters from 20671 reflections |
a = 9.41079 (17) Å | θ = 3.1–30.1° |
b = 8.0690 (4) Å | µ = 0.54 mm−1 |
c = 18.1026 (3) Å | T = 180 K |
β = 115.1397 (7)° | Block, brown |
V = 1244.42 (7) Å3 | 0.43 × 0.36 × 0.26 mm |
Z = 4 |
Rigaku R-AXIS RAPID II diffractometer | 3461 reflections with I > 2σ(I) |
Detector resolution: 10.00 pixels mm-1 | Rint = 0.018 |
ω scans | θmax = 30.0° |
Absorption correction: numerical (NUMABS; Higashi, 1999) | h = −13→13 |
Tmin = 0.793, Tmax = 0.870 | k = −11→11 |
22572 measured reflections | l = −25→23 |
3626 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)] = 0.029 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.083 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0504P)2 + 0.3081P] where P = (Fo2 + 2Fc2)/3 |
3626 reflections | (Δ/σ)max = 0.001 |
184 parameters | Δρmax = 0.48 e Å−3 |
0 restraints | Δρmin = −0.30 e Å−3 |
C6H2Cl2O4·C5H9NO | V = 1244.42 (7) Å3 |
Mr = 308.12 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.41079 (17) Å | µ = 0.54 mm−1 |
b = 8.0690 (4) Å | T = 180 K |
c = 18.1026 (3) Å | 0.43 × 0.36 × 0.26 mm |
β = 115.1397 (7)° |
Rigaku R-AXIS RAPID II diffractometer | 3626 independent reflections |
Absorption correction: numerical (NUMABS; Higashi, 1999) | 3461 reflections with I > 2σ(I) |
Tmin = 0.793, Tmax = 0.870 | Rint = 0.018 |
22572 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.083 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.48 e Å−3 |
3626 reflections | Δρmin = −0.30 e Å−3 |
184 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Cl1 | −0.30305 (3) | −0.02569 (4) | 0.031690 (16) | 0.03449 (9) | |
Cl2 | 0.80710 (3) | 0.06618 (3) | 0.475761 (15) | 0.02900 (8) | |
O1 | −0.24763 (9) | −0.16354 (12) | −0.10548 (5) | 0.03547 (19) | |
O2 | −0.00427 (9) | 0.14039 (10) | 0.13842 (4) | 0.02759 (16) | |
O3 | 0.77697 (8) | −0.06244 (10) | 0.62203 (4) | 0.02892 (16) | |
O4 | 0.48019 (8) | 0.14740 (9) | 0.35802 (4) | 0.02517 (15) | |
O5 | 0.23199 (8) | 0.29476 (9) | 0.25294 (4) | 0.02459 (14) | |
N1 | 0.11471 (9) | 0.53820 (10) | 0.20403 (5) | 0.02419 (16) | |
C1 | −0.13645 (10) | −0.08690 (11) | −0.05607 (5) | 0.02177 (17) | |
C2 | −0.13551 (10) | −0.00962 (12) | 0.01693 (6) | 0.02176 (17) | |
C3 | −0.00826 (10) | 0.07172 (11) | 0.07132 (5) | 0.02066 (17) | |
C4 | 0.65172 (10) | −0.03715 (11) | 0.56359 (5) | 0.01989 (16) | |
C5 | 0.63718 (10) | 0.03365 (11) | 0.48650 (6) | 0.01996 (16) | |
C6 | 0.49578 (10) | 0.07663 (11) | 0.42678 (5) | 0.01946 (16) | |
C7 | 0.24018 (10) | 0.45058 (11) | 0.24947 (5) | 0.01901 (16) | |
C8 | 0.39309 (10) | 0.53859 (12) | 0.29494 (6) | 0.02279 (17) | |
H8A | 0.4586 | 0.5255 | 0.2646 | 0.027* | |
H8B | 0.4493 | 0.4855 | 0.3490 | 0.027* | |
C9 | 0.37450 (12) | 0.72260 (12) | 0.30730 (6) | 0.0292 (2) | |
H9A | 0.4780 | 0.7781 | 0.3277 | 0.035* | |
H9B | 0.3318 | 0.7378 | 0.3483 | 0.035* | |
C10 | 0.26314 (11) | 0.79935 (12) | 0.22612 (6) | 0.02631 (19) | |
H10A | 0.2539 | 0.9200 | 0.2331 | 0.032* | |
H10B | 0.3055 | 0.7830 | 0.1851 | 0.032* | |
C11 | 0.10335 (11) | 0.71930 (12) | 0.19677 (7) | 0.0285 (2) | |
H11A | 0.0490 | 0.7620 | 0.2292 | 0.034* | |
H11B | 0.0398 | 0.7497 | 0.1390 | 0.034* | |
H1 | 0.0264 (19) | 0.486 (2) | 0.1784 (10) | 0.045 (4)* | |
H2 | 0.088 (2) | 0.189 (2) | 0.1716 (11) | 0.053 (5)* | |
H4 | 0.391 (2) | 0.186 (2) | 0.3278 (11) | 0.046 (4)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.02054 (13) | 0.05097 (18) | 0.03451 (14) | −0.00548 (9) | 0.01415 (10) | −0.00441 (11) |
Cl2 | 0.01766 (12) | 0.03618 (14) | 0.03463 (14) | −0.00054 (8) | 0.01251 (10) | 0.00429 (9) |
O1 | 0.0231 (3) | 0.0473 (5) | 0.0324 (4) | −0.0127 (3) | 0.0083 (3) | −0.0133 (3) |
O2 | 0.0240 (3) | 0.0343 (4) | 0.0231 (3) | −0.0020 (3) | 0.0087 (3) | −0.0063 (3) |
O3 | 0.0164 (3) | 0.0365 (4) | 0.0276 (3) | 0.0018 (3) | 0.0033 (3) | 0.0079 (3) |
O4 | 0.0210 (3) | 0.0300 (3) | 0.0232 (3) | 0.0028 (3) | 0.0081 (3) | 0.0068 (3) |
O5 | 0.0250 (3) | 0.0202 (3) | 0.0219 (3) | −0.0004 (2) | 0.0035 (3) | 0.0009 (2) |
N1 | 0.0155 (3) | 0.0235 (4) | 0.0280 (4) | −0.0005 (3) | 0.0039 (3) | 0.0044 (3) |
C1 | 0.0172 (4) | 0.0234 (4) | 0.0213 (4) | −0.0012 (3) | 0.0049 (3) | 0.0004 (3) |
C2 | 0.0153 (4) | 0.0261 (4) | 0.0229 (4) | −0.0004 (3) | 0.0071 (3) | 0.0014 (3) |
C3 | 0.0186 (4) | 0.0215 (4) | 0.0197 (4) | 0.0010 (3) | 0.0060 (3) | 0.0012 (3) |
C4 | 0.0154 (4) | 0.0187 (4) | 0.0231 (4) | 0.0006 (3) | 0.0057 (3) | 0.0001 (3) |
C5 | 0.0143 (4) | 0.0213 (4) | 0.0237 (4) | −0.0005 (3) | 0.0075 (3) | 0.0003 (3) |
C6 | 0.0174 (4) | 0.0186 (4) | 0.0213 (4) | 0.0003 (3) | 0.0072 (3) | −0.0004 (3) |
C7 | 0.0178 (4) | 0.0215 (4) | 0.0169 (4) | 0.0006 (3) | 0.0067 (3) | 0.0005 (3) |
C8 | 0.0159 (4) | 0.0213 (4) | 0.0268 (4) | 0.0011 (3) | 0.0049 (3) | −0.0005 (3) |
C9 | 0.0246 (4) | 0.0213 (4) | 0.0321 (5) | 0.0010 (3) | 0.0030 (4) | −0.0036 (4) |
C10 | 0.0232 (4) | 0.0208 (4) | 0.0328 (5) | 0.0003 (3) | 0.0098 (4) | 0.0029 (3) |
C11 | 0.0200 (4) | 0.0238 (4) | 0.0376 (5) | 0.0045 (3) | 0.0084 (4) | 0.0081 (4) |
Cl1—C2 | 1.7124 (9) | C4—C5 | 1.4596 (13) |
Cl2—C5 | 1.7111 (9) | C4—C6ii | 1.5047 (12) |
O1—C1 | 1.2174 (11) | C5—C6 | 1.3556 (12) |
O2—C3 | 1.3211 (11) | C7—C8 | 1.4987 (12) |
O2—H2 | 0.913 (19) | C8—C9 | 1.5226 (13) |
O3—C4 | 1.2209 (11) | C8—H8A | 0.9900 |
O4—C6 | 1.3197 (11) | C8—H8B | 0.9900 |
O4—H4 | 0.845 (18) | C9—C10 | 1.5273 (14) |
O5—C7 | 1.2629 (11) | C9—H9A | 0.9900 |
N1—C7 | 1.3211 (11) | C9—H9B | 0.9900 |
N1—C11 | 1.4671 (13) | C10—C11 | 1.5106 (13) |
N1—H1 | 0.870 (17) | C10—H10A | 0.9900 |
C1—C2 | 1.4578 (13) | C10—H10B | 0.9900 |
C1—C3i | 1.5051 (12) | C11—H11A | 0.9900 |
C2—C3 | 1.3537 (12) | C11—H11B | 0.9900 |
C3—O2—H2 | 115.6 (12) | N1—C7—C8 | 118.95 (8) |
C6—O4—H4 | 116.8 (12) | C7—C8—C9 | 113.54 (8) |
C7—N1—C11 | 126.92 (8) | C7—C8—H8A | 108.9 |
C7—N1—H1 | 118.0 (12) | C9—C8—H8A | 108.9 |
C11—N1—H1 | 114.8 (12) | C7—C8—H8B | 108.9 |
O1—C1—C2 | 123.76 (9) | C9—C8—H8B | 108.9 |
O1—C1—C3i | 117.95 (9) | H8A—C8—H8B | 107.7 |
C2—C1—C3i | 118.29 (7) | C8—C9—C10 | 109.19 (8) |
C3—C2—C1 | 121.97 (8) | C8—C9—H9A | 109.8 |
C3—C2—Cl1 | 120.79 (7) | C10—C9—H9A | 109.8 |
C1—C2—Cl1 | 117.23 (7) | C8—C9—H9B | 109.8 |
O2—C3—C2 | 122.88 (8) | C10—C9—H9B | 109.8 |
O2—C3—C1i | 117.39 (8) | H9A—C9—H9B | 108.3 |
C2—C3—C1i | 119.73 (8) | C11—C10—C9 | 109.80 (8) |
O3—C4—C5 | 123.89 (8) | C11—C10—H10A | 109.7 |
O3—C4—C6ii | 117.57 (8) | C9—C10—H10A | 109.7 |
C5—C4—C6ii | 118.51 (7) | C11—C10—H10B | 109.7 |
C6—C5—C4 | 121.62 (8) | C9—C10—H10B | 109.7 |
C6—C5—Cl2 | 121.21 (7) | H10A—C10—H10B | 108.2 |
C4—C5—Cl2 | 117.14 (6) | N1—C11—C10 | 111.75 (8) |
O4—C6—C5 | 122.75 (8) | N1—C11—H11A | 109.3 |
O4—C6—C4ii | 117.55 (7) | C10—C11—H11A | 109.3 |
C5—C6—C4ii | 119.65 (8) | N1—C11—H11B | 109.3 |
O5—C7—N1 | 120.43 (8) | C10—C11—H11B | 109.3 |
O5—C7—C8 | 120.60 (8) | H11A—C11—H11B | 107.9 |
O1—C1—C2—C3 | 178.61 (10) | C4—C5—C6—O4 | 176.99 (8) |
C3i—C1—C2—C3 | −1.23 (14) | Cl2—C5—C6—O4 | −0.99 (13) |
O1—C1—C2—Cl1 | −1.33 (13) | C4—C5—C6—C4ii | −5.53 (14) |
C3i—C1—C2—Cl1 | 178.83 (7) | Cl2—C5—C6—C4ii | 176.49 (6) |
C1—C2—C3—O2 | −178.95 (9) | C11—N1—C7—O5 | 176.79 (10) |
Cl1—C2—C3—O2 | 0.99 (13) | C11—N1—C7—C8 | −4.85 (14) |
C1—C2—C3—C1i | 1.25 (15) | O5—C7—C8—C9 | −161.19 (9) |
Cl1—C2—C3—C1i | −178.82 (7) | N1—C7—C8—C9 | 20.45 (12) |
O3—C4—C5—C6 | −172.46 (9) | C7—C8—C9—C10 | −48.49 (12) |
C6ii—C4—C5—C6 | 5.47 (14) | C8—C9—C10—C11 | 61.75 (11) |
O3—C4—C5—Cl2 | 5.60 (13) | C7—N1—C11—C10 | 18.13 (15) |
C6ii—C4—C5—Cl2 | −176.48 (6) | C9—C10—C11—N1 | −45.75 (12) |
Symmetry codes: (i) −x, −y, −z; (ii) −x+1, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O3iii | 0.869 (18) | 2.213 (19) | 2.8871 (12) | 134.2 (14) |
O2—H2···O5 | 0.909 (19) | 1.743 (18) | 2.6223 (11) | 162.1 (18) |
O4—H4···O5 | 0.843 (19) | 1.767 (18) | 2.5909 (10) | 165.1 (19) |
Symmetry code: (iii) x−1, −y+1/2, z−1/2. |
C6H0.88Cl2O4·2C5H9.56NO | F(000) = 848.00 |
Mr = 407.25 | Dx = 1.562 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71075 Å |
Hall symbol: -C 2yc | Cell parameters from 16592 reflections |
a = 17.8438 (5) Å | θ = 3.1–30.1° |
b = 5.4253 (3) Å | µ = 0.41 mm−1 |
c = 19.5958 (5) Å | T = 180 K |
β = 114.0658 (7)° | Block, brown |
V = 1732.12 (12) Å3 | 0.45 × 0.40 × 0.15 mm |
Z = 4 |
Rigaku R-AXIS RAPID II diffractometer | 2382 reflections with I > 2σ(I) |
Detector resolution: 10.00 pixels mm-1 | Rint = 0.024 |
ω scans | θmax = 30.0° |
Absorption correction: numerical (NUMABS; Higashi, 1999) | h = −24→23 |
Tmin = 0.835, Tmax = 0.940 | k = −7→7 |
17611 measured reflections | l = −27→27 |
2524 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)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.083 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0457P)2 + 1.3417P] where P = (Fo2 + 2Fc2)/3 |
2524 reflections | (Δ/σ)max < 0.001 |
129 parameters | Δρmax = 0.51 e Å−3 |
2 restraints | Δρmin = −0.24 e Å−3 |
C6H0.88Cl2O4·2C5H9.56NO | V = 1732.12 (12) Å3 |
Mr = 407.25 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 17.8438 (5) Å | µ = 0.41 mm−1 |
b = 5.4253 (3) Å | T = 180 K |
c = 19.5958 (5) Å | 0.45 × 0.40 × 0.15 mm |
β = 114.0658 (7)° |
Rigaku R-AXIS RAPID II diffractometer | 2524 independent reflections |
Absorption correction: numerical (NUMABS; Higashi, 1999) | 2382 reflections with I > 2σ(I) |
Tmin = 0.835, Tmax = 0.940 | Rint = 0.024 |
17611 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | 2 restraints |
wR(F2) = 0.083 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.51 e Å−3 |
2524 reflections | Δρmin = −0.24 e Å−3 |
129 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Cl1 | 0.465981 (16) | 0.09806 (5) | 0.374641 (14) | 0.02668 (9) | |
O1 | 0.61956 (5) | 0.19341 (17) | 0.50597 (4) | 0.02586 (18) | |
O2 | 0.34615 (4) | 0.48559 (15) | 0.38457 (4) | 0.02051 (16) | |
H2 | 0.337 (2) | 0.409 (6) | 0.3457 (15) | 0.031* | 0.44 (3) |
O3 | 0.29272 (5) | 0.32019 (14) | 0.25730 (4) | 0.02089 (16) | |
H3 | 0.3147 (18) | 0.373 (5) | 0.3016 (11) | 0.031* | 0.56 (3) |
N1 | 0.26990 (5) | 0.41843 (16) | 0.14037 (5) | 0.01920 (17) | |
C1 | 0.56330 (6) | 0.33049 (18) | 0.50198 (5) | 0.01697 (18) | |
C2 | 0.48207 (6) | 0.32122 (18) | 0.44190 (5) | 0.01725 (18) | |
C3 | 0.41991 (6) | 0.47818 (18) | 0.43657 (5) | 0.01609 (17) | |
C4 | 0.31035 (6) | 0.45331 (18) | 0.21213 (5) | 0.01705 (18) | |
C5 | 0.37794 (6) | 0.6410 (2) | 0.24154 (6) | 0.0223 (2) | |
H5A | 0.4314 | 0.5542 | 0.2631 | 0.027* | |
H5B | 0.3719 | 0.7351 | 0.2823 | 0.027* | |
C6 | 0.37856 (7) | 0.8198 (2) | 0.18228 (6) | 0.0261 (2) | |
H6A | 0.3337 | 0.9413 | 0.1710 | 0.031* | |
H6B | 0.4313 | 0.9104 | 0.2008 | 0.031* | |
C7 | 0.36730 (7) | 0.6781 (2) | 0.11206 (6) | 0.0270 (2) | |
H7A | 0.4112 | 0.5529 | 0.1237 | 0.032* | |
H7B | 0.3710 | 0.7922 | 0.0741 | 0.032* | |
C8 | 0.28386 (7) | 0.5527 (2) | 0.08166 (6) | 0.0241 (2) | |
H8A | 0.2404 | 0.6784 | 0.0596 | 0.029* | |
H8B | 0.2804 | 0.4364 | 0.0415 | 0.029* | |
H1 | 0.2306 (10) | 0.317 (3) | 0.1275 (9) | 0.030 (4)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.02541 (14) | 0.02710 (15) | 0.02114 (13) | 0.00458 (9) | 0.00296 (10) | −0.01027 (9) |
O1 | 0.0203 (3) | 0.0312 (4) | 0.0216 (4) | 0.0097 (3) | 0.0039 (3) | −0.0047 (3) |
O2 | 0.0149 (3) | 0.0273 (4) | 0.0153 (3) | 0.0020 (3) | 0.0020 (3) | −0.0029 (3) |
O3 | 0.0226 (3) | 0.0209 (3) | 0.0163 (3) | −0.0045 (3) | 0.0051 (3) | −0.0014 (3) |
N1 | 0.0174 (4) | 0.0213 (4) | 0.0157 (4) | −0.0048 (3) | 0.0035 (3) | −0.0021 (3) |
C1 | 0.0162 (4) | 0.0193 (4) | 0.0141 (4) | 0.0016 (3) | 0.0049 (3) | −0.0002 (3) |
C2 | 0.0172 (4) | 0.0189 (4) | 0.0134 (4) | 0.0011 (3) | 0.0040 (3) | −0.0037 (3) |
C3 | 0.0154 (4) | 0.0190 (4) | 0.0131 (4) | −0.0002 (3) | 0.0049 (3) | 0.0001 (3) |
C4 | 0.0148 (4) | 0.0167 (4) | 0.0176 (4) | −0.0002 (3) | 0.0045 (3) | −0.0024 (3) |
C5 | 0.0202 (4) | 0.0252 (5) | 0.0188 (4) | −0.0086 (4) | 0.0053 (4) | −0.0047 (4) |
C6 | 0.0269 (5) | 0.0245 (5) | 0.0258 (5) | −0.0091 (4) | 0.0096 (4) | −0.0026 (4) |
C7 | 0.0234 (5) | 0.0366 (6) | 0.0216 (5) | −0.0080 (4) | 0.0097 (4) | −0.0017 (4) |
C8 | 0.0220 (5) | 0.0322 (5) | 0.0159 (4) | −0.0059 (4) | 0.0055 (4) | −0.0001 (4) |
Cl1—C2 | 1.7254 (9) | C4—C5 | 1.5020 (13) |
O1—C1 | 1.2259 (12) | C5—C6 | 1.5169 (15) |
O2—C3 | 1.2956 (11) | C5—H5A | 0.9900 |
O2—H2 | 0.824 (19) | C5—H5B | 0.9900 |
O3—C4 | 1.2773 (12) | C6—C7 | 1.5166 (16) |
O3—H3 | 0.844 (18) | C6—H6A | 0.9900 |
N1—C4 | 1.3063 (12) | C6—H6B | 0.9900 |
N1—C8 | 1.4662 (13) | C7—C8 | 1.5201 (15) |
N1—H1 | 0.845 (18) | C7—H7A | 0.9900 |
C1—C2 | 1.4483 (13) | C7—H7B | 0.9900 |
C1—C3i | 1.5241 (13) | C8—H8A | 0.9900 |
C2—C3 | 1.3681 (13) | C8—H8B | 0.9900 |
C3—O2—H2 | 118 (3) | C6—C5—H5B | 108.9 |
C4—O3—H3 | 112 (2) | H5A—C5—H5B | 107.7 |
C4—N1—C8 | 125.21 (9) | C7—C6—C5 | 109.30 (9) |
C4—N1—H1 | 116.3 (11) | C7—C6—H6A | 109.8 |
C8—N1—H1 | 118.4 (11) | C5—C6—H6A | 109.8 |
O1—C1—C2 | 123.56 (9) | C7—C6—H6B | 109.8 |
O1—C1—C3i | 118.08 (8) | C5—C6—H6B | 109.8 |
C2—C1—C3i | 118.36 (8) | H6A—C6—H6B | 108.3 |
C3—C2—C1 | 123.50 (8) | C6—C7—C8 | 109.18 (9) |
C3—C2—Cl1 | 120.08 (7) | C6—C7—H7A | 109.8 |
C1—C2—Cl1 | 116.42 (7) | C8—C7—H7A | 109.8 |
O2—C3—C2 | 127.68 (9) | C6—C7—H7B | 109.8 |
O2—C3—C1i | 114.18 (8) | C8—C7—H7B | 109.8 |
C2—C3—C1i | 118.14 (8) | H7A—C7—H7B | 108.3 |
O3—C4—N1 | 118.69 (9) | N1—C8—C7 | 111.56 (8) |
O3—C4—C5 | 120.22 (9) | N1—C8—H8A | 109.3 |
N1—C4—C5 | 121.07 (9) | C7—C8—H8A | 109.3 |
C4—C5—C6 | 113.28 (9) | N1—C8—H8B | 109.3 |
C4—C5—H5A | 108.9 | C7—C8—H8B | 109.3 |
C6—C5—H5A | 108.9 | H8A—C8—H8B | 108.0 |
C4—C5—H5B | 108.9 | ||
O1—C1—C2—C3 | −178.38 (10) | C8—N1—C4—O3 | −178.86 (10) |
C3i—C1—C2—C3 | 1.26 (16) | C8—N1—C4—C5 | −0.52 (16) |
O1—C1—C2—Cl1 | 1.34 (14) | O3—C4—C5—C6 | −167.26 (9) |
C3i—C1—C2—Cl1 | −179.02 (7) | N1—C4—C5—C6 | 14.43 (14) |
C1—C2—C3—O2 | 178.93 (9) | C4—C5—C6—C7 | −45.18 (12) |
Cl1—C2—C3—O2 | −0.78 (15) | C5—C6—C7—C8 | 62.86 (12) |
C1—C2—C3—C1i | −1.25 (16) | C4—N1—C8—C7 | 18.30 (15) |
Cl1—C2—C3—C1i | 179.03 (7) | C6—C7—C8—N1 | −48.79 (13) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1ii | 0.845 (18) | 2.398 (17) | 2.9561 (12) | 124.1 (14) |
N1—H1···O2iii | 0.845 (18) | 2.214 (17) | 3.0358 (12) | 164.3 (15) |
O3—H3···O2 | 0.84 (2) | 1.61 (2) | 2.4484 (10) | 173 (3) |
O2—H2···O3 | 0.82 (3) | 1.66 (3) | 2.4484 (10) | 161 (4) |
Symmetry codes: (ii) x−1/2, −y+1/2, z−1/2; (iii) −x+1/2, y−1/2, −z+1/2. |
Experimental details
(I) | (II) | (III) | (IV) | |
Crystal data | ||||
Chemical formula | C4H7NO·C6H2Cl2O4 | C6H2Cl2O4·2C4H7NO | C6H2Cl2O4·C5H9NO | C6H0.88Cl2O4·2C5H9.56NO |
Mr | 294.09 | 379.20 | 308.12 | 407.25 |
Crystal system, space group | Monoclinic, P21/c | Triclinic, P1 | Monoclinic, P21/c | Monoclinic, C2/c |
Temperature (K) | 180 | 180 | 180 | 180 |
a, b, c (Å) | 7.7256 (4), 19.3792 (11), 15.2486 (8) | 4.9665 (3), 7.4767 (4), 11.8445 (6) | 9.41079 (17), 8.0690 (4), 18.1026 (3) | 17.8438 (5), 5.4253 (3), 19.5958 (5) |
α, β, γ (°) | 90, 94.404 (2), 90 | 106.7904 (19), 90.299 (2), 108.734 (2) | 90, 115.1397 (7), 90 | 90, 114.0658 (7), 90 |
V (Å3) | 2276.2 (2) | 396.42 (4) | 1244.42 (7) | 1732.12 (12) |
Z | 8 | 1 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.58 | 0.44 | 0.54 | 0.41 |
Crystal size (mm) | 0.35 × 0.20 × 0.15 | 0.38 × 0.32 × 0.25 | 0.43 × 0.36 × 0.26 | 0.45 × 0.40 × 0.15 |
Data collection | ||||
Diffractometer | Rigaku R-AXIS RAPID II diffractometer | Rigaku R-AXIS RAPID II diffractometer | Rigaku R-AXIS RAPID II diffractometer | Rigaku R-AXIS RAPID II diffractometer |
Absorption correction | Numerical (NUMABS; Higashi, 1999) | Numerical (NUMABS; Higashi, 1999) | Numerical (NUMABS; Higashi, 1999) | Numerical (NUMABS; Higashi, 1999) |
Tmin, Tmax | 0.858, 0.916 | 0.853, 0.895 | 0.793, 0.870 | 0.835, 0.940 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 47031, 6636, 5477 | 9315, 2296, 2156 | 22572, 3626, 3461 | 17611, 2524, 2382 |
Rint | 0.022 | 0.024 | 0.018 | 0.024 |
(sin θ/λ)max (Å−1) | 0.704 | 0.703 | 0.704 | 0.704 |
Refinement | ||||
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.108, 1.06 | 0.030, 0.081, 1.11 | 0.029, 0.083, 1.06 | 0.031, 0.083, 1.07 |
No. of reflections | 6636 | 2296 | 3626 | 2524 |
No. of parameters | 349 | 117 | 184 | 129 |
No. of restraints | 0 | 0 | 0 | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.05, −0.30 | 0.31, −0.39 | 0.48, −0.30 | 0.51, −0.24 |
Computer programs: PROCESS-AUTO (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and WinGX (Farrugia, 1999), CrystalStructure (Rigaku/MSC, 2004) and PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O10 | 0.870 (15) | 2.056 (15) | 2.9065 (13) | 165.5 (14) |
O2—H2A···O9 | 1.05 (2) | 1.44 (2) | 2.4728 (11) | 167 (2) |
N2—H2B···O9 | 0.839 (15) | 2.108 (15) | 2.9249 (13) | 164.6 (15) |
O4—H4···O5i | 0.849 (17) | 2.002 (17) | 2.7774 (11) | 151.6 (15) |
O6—H6···O10 | 0.99 (2) | 1.54 (2) | 2.4978 (11) | 163 (2) |
O8—H8···O1ii | 0.850 (17) | 2.025 (17) | 2.7850 (11) | 148.5 (15) |
Symmetry codes: (i) x, y−1, z; (ii) x, y+1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.73 (2) | 2.537 (19) | 3.0036 (12) | 123.8 (17) |
N1—H1···O3ii | 0.73 (2) | 2.22 (2) | 2.9185 (13) | 162.0 (19) |
O2—H2···O3 | 0.84 (2) | 1.76 (2) | 2.5845 (11) | 164 (2) |
Symmetry codes: (i) x−1, y−1, z−1; (ii) −x, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O3i | 0.869 (18) | 2.213 (19) | 2.8871 (12) | 134.2 (14) |
O2—H2···O5 | 0.909 (19) | 1.743 (18) | 2.6223 (11) | 162.1 (18) |
O4—H4···O5 | 0.843 (19) | 1.767 (18) | 2.5909 (10) | 165.1 (19) |
Symmetry code: (i) x−1, −y+1/2, z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.845 (18) | 2.398 (17) | 2.9561 (12) | 124.1 (14) |
N1—H1···O2ii | 0.845 (18) | 2.214 (17) | 3.0358 (12) | 164.3 (15) |
O3—H3···O2 | 0.84 (2) | 1.61 (2) | 2.4484 (10) | 173 (3) |
O2—H2···O3 | 0.82 (3) | 1.66 (3) | 2.4484 (10) | 161 (4) |
Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) −x+1/2, y−1/2, −z+1/2. |
Chloranilic acid (2,5-dichloro-3,6-dihydroxycyclohexa-2,5-diene-1,4-dione), a strong dibasic acid with both hydrogen-bond donor and acceptor groups, appears particularly attractive as a template for generating tightly bound self-assemblies with various organic bases (Ishida & Kashino, 1999a,b, 2002; Zaman et al., 1999, 2004; Gotoh, Maruyama & Ishida, 2010), and also as a model compound for investigating hydrogen-transfer mechanisms in O—H···N and N—H···O hydrogen-bond systems (Ikeda et al., 2005; Suzuki et al., 2007; Gotoh et al., 2008; Gotoh, Asaji & Ishida, 2010; Seliger et al., 2009, 2011; Asaji, Hoshino et al., 2010; Asaji, Seliger et al., 2010). Furthermore, salts and co-crystals of chloranilic acid with pyridine derivatives have recently attracted much interest with respect to organic ferroelectrics (Horiuchi, Ishii et al., 2005; Horiuchi, Kumai & Tokura, 2005; Asaji et al., 2007; Gotoh et al., 2007; Horiuchi & Tokura, 2008; Horiuchi et al., 2010).
In the present study, we have prepared four compounds of chloranilic acid with pyrrolidin-2-one and piperidin-2-one, namely, chloranilic acid–pyrrolidin-2-one (1/1), (I), chloranilic acid–pyrrolidin-2-one (1/2), (II), chloranilic acid–piperidin-2-one (1/1), (III), and chloranilic acid–piperidin-2-one (1/2), (IV), and determined their crystal structures at 180 K in order to extend our study of D—H···A hydrogen bonding (D = N, O or C; A = N, O or Cl) in chloranilic acid–organic base systems (Gotoh et al., 2009; Gotoh & Ishida, 2009).
The molecular structures of (I), (II), (III) and (IV) are shown in Figs. 1, 2, 3 and 4, respectively. The chloranilic acid molecules in all four compounds show a characteristic structure with two long and two short C—C bonds, as described by Andersen (1967). The pyrrolidin-2-one molecules in (I) and (II) adopt an approximate envelope conformation, while the piperidin-2-one molecules in (III) and (IV) have half-chair conformations.
The asymmetric unit of (I) contains two crystallographically independent pyrrolidin-2-one molecules and two chloranilic acid molecules (Fig. 1). The acid and base are held together by short O—H···O hydrogen bonds (O2—H2A···O9 and O6—H6···O10; Table 1), and the two bases are further connected to each other by a pair of N—H···O hydrogen bonds (N1—H1···O10 and N2—H2B···O9; Table 1), thus forming a quasi-centrosymmetric 2+2 aggregate. These 2+2 aggregates are linked through a pair of O—H···O hydrogen bonds between the chloranilic acid molecules (O4—H4···O5i and O8—H8···O1ii; details and symmetry codes in Table 1), forming an approximately flat tape structure along the b axis (Fig. 5). The hydrogen-bonded pyrrolidin-2-one dimers are thus linked by hydrogen bonding across the hydrogen-bonded chloranilic acid dimer, forming a tape. In this tape, the dihedral angle between the acid C1–C6 and C7–C12 rings is 2.67 (5)°, and those between the least-squares plane of atoms N1/C13–C16/O9/N2/C17–C20/O10 of the hydrogen-bonded pyrrolidin-2-one dimer and the acid C1–C6 and C7–C12 rings are 9.23 (4) and 6.92 (4)°, respectively. The tapes, related to each other by an inversion centre, are stacked alternately along the a axis, forming a layer parallel to the ab plane.
In compound (II), the acid molecule is located on an inversion centre, so that the asymmetric unit contains one pyrrolidin-2-one molecule and one half-molecule of chloranilic acid (Fig. 2). The acid and the base are connected by a short O—H···O hydrogen bond (O2—H2···O3; Table 2) and the two components are further connected by an N—H···(O,O) bifurcated hydrogen bond (N1—H1···O1i/O3ii; details and symmetry codes in Table 2), forming a centrosymmetric 2+2 aggregate similar to (I). The 2+2 units are further connected by hydrogen bonds such that the hydrogen-bonded pyrrolidin-2-one dimer and the chloranilic acid are arranged alternately into an essentially planar molecular tape along the [111] direction (Fig. 6). In this tape, the dihedral angle between the acid ring and the least-squares plane of atoms N1/C4–C7/O3 of the pyrrolidin-2-one is 8.81 (12)°. The tapes are stacked along the a axis and form a layer parallel to the (011) plane.
In the asymmetric unit of (III), there are one piperidin-2-one molecule and two crystallographically independent half-molecules of chloranilic acid, with each of the acid molecules lying about an inversion centre (Fig. 3). No formation of dimers of piperidin-2-one molecules is observed, while the piperidin-2-one O atom participates in two O—H···O hydrogen bonds as an acceptor for two chloranilic acid O—H groups (O2—H2···O5 and O4—H4···O5; Table 3), forming a zigzag chain along the [101] direction in which the two components are arranged alternately (Fig. 7). The N—H···O hydrogen bond (N1—H1···O3i; symmetry code in Table 3) formed between the piperidin-2-one and chloranilic acid molecules connects the chains into a three-dimensional network (Fig. 8).
The asymmetric unit of (IV) contains one piperidin-2-one molecule and one half-molecule of chloranilic acid, which is located on an inversion centre (Fig. 4). A short O—H···O hydrogen bond with an O···O distance of 2.4484 (10) Å connects the two components. The H atom in the hydrogen bond is disordered over two positions with refined occupancies of 0.44 (3) and 0.56 (3) at the O2 and O3 sites, respectively. This disordered feature is confirmed in a difference Fourier map (see supplementary figure). The acid and base are further connected by an N—H···(O,O) bifurcated hydrogen bond [N1—H1···(O1i,O2ii); details and symmetry codes in Table 4], forming a layer parallel to the (101) plane (Fig. 9).
We have shown that in all compounds the primary intermolecular interactions are O—H···O hydrogen bonds formed between the acid and the base. The secondary interactions are N—H···O hydrogen bonds, which connect the pyrrolidin-2-one molecules into a dimer in (I) and (II), and link the acid and base into three- and two-dimensional hydrogen-bonded networks, respectively, in (III) and (IV). Furthermore, in (IV) it is noteworthy that (a) the orientation of the O—H group of the acid is different from that in (I), (II) and (III), in that the O—H group in (IV) points to the Cl atom due to the N—H···(O,O) hydrogen bond; and (b) the O atom of the base acts as a single acceptor only for the O—H group. These may cause the disorder of the H atom in the O···H···O hydrogen bond.