Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100000664/bm1360sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100000664/bm1360Isup2.hkl |
CCDC reference: 144647
Crystals of (I) were obtained from a 1:1 solution of DMAN and 1,4,5,6,7,7-hexachlorobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid (Aldrich) in a mixture of acetonitrile and water.
The carboxylic H atom was located in a difference Fourier synthesis and subsequently included as part of a rigid rotating group. The water H atoms were placed in hydrogen-bond-forming positions and their coordinates were refined freely. The amino H atoms were introduced at calculated positions and during refinement idealized tetrahedral geometry at the N carrier atom was enforced, with the N—H bond distance and the H atom occupancies allowed to refine. All other H atoms were introduced at calculated positions and refined riding on their carrier atoms.
Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: HELENA (Spek, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1998); software used to prepare material for publication: SHELXL97 and PLATON.
C14H19N2+C9H3Cl6O4−·H2O | Z = 2 |
Mr = 621.17 | F(000) = 636 |
Triclinic, P1 | Dx = 1.508 Mg m−3 |
a = 8.7122 (5) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 12.8097 (11) Å | Cell parameters from 25 reflections |
c = 13.7023 (12) Å | θ = 12.7–19.3° |
α = 113.200 (7)° | µ = 0.67 mm−1 |
β = 91.680 (6)° | T = 295 K |
γ = 101.350 (6)° | Block, colourless |
V = 1368.32 (19) Å3 | 0.6 × 0.6 × 0.3 mm |
Enraf-Nonius CAD4 diffractometer | 4286 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.036 |
β-filter monochromator | θmax = 27.5°, θmin = 1.6° |
ω/2θ scans | h = −11→11 |
Absorption correction: ψ-scan (PLATON; Spek, 1998) | k = −16→16 |
Tmin = 0.745, Tmax = 0.819 | l = −17→17 |
13079 measured reflections | 3 standard reflections every 60 min |
6272 independent reflections | intensity decay: none |
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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.107 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0421P)2 + 0.5928P] where P = (Fo2 + 2Fc2)/3 |
6272 reflections | (Δ/σ)max = 0.001 |
335 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.40 e Å−3 |
C14H19N2+C9H3Cl6O4−·H2O | γ = 101.350 (6)° |
Mr = 621.17 | V = 1368.32 (19) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.7122 (5) Å | Mo Kα radiation |
b = 12.8097 (11) Å | µ = 0.67 mm−1 |
c = 13.7023 (12) Å | T = 295 K |
α = 113.200 (7)° | 0.6 × 0.6 × 0.3 mm |
β = 91.680 (6)° |
Enraf-Nonius CAD4 diffractometer | 4286 reflections with I > 2σ(I) |
Absorption correction: ψ-scan (PLATON; Spek, 1998) | Rint = 0.036 |
Tmin = 0.745, Tmax = 0.819 | 3 standard reflections every 60 min |
13079 measured reflections | intensity decay: none |
6272 independent reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.107 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.32 e Å−3 |
6272 reflections | Δρmin = −0.40 e Å−3 |
335 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) | |
N1 | 0.4274 (2) | 0.79225 (16) | 0.10208 (15) | 0.0416 (6) | |
N2 | 0.3389 (2) | 0.69069 (19) | 0.22781 (15) | 0.0489 (6) | |
C1 | 0.2808 (2) | 0.58622 (19) | 0.03054 (17) | 0.0410 (7) | |
C2 | 0.3558 (3) | 0.68381 (19) | 0.01113 (17) | 0.0418 (7) | |
C3 | 0.3622 (3) | 0.6769 (2) | −0.0903 (2) | 0.0600 (9) | |
C4 | 0.2930 (4) | 0.5742 (3) | −0.1786 (2) | 0.0745 (11) | |
C5 | 0.2194 (4) | 0.4800 (3) | −0.1635 (2) | 0.0692 (10) | |
C6 | 0.2108 (3) | 0.4811 (2) | −0.0604 (2) | 0.0531 (8) | |
C7 | 0.1352 (3) | 0.3826 (2) | −0.0453 (3) | 0.0706 (10) | |
C8 | 0.1277 (4) | 0.3843 (3) | 0.0536 (4) | 0.0848 (13) | |
C9 | 0.1965 (4) | 0.4860 (3) | 0.1432 (3) | 0.0735 (11) | |
C10 | 0.2704 (3) | 0.5844 (2) | 0.1335 (2) | 0.0483 (8) | |
C11 | 0.4641 (4) | 0.6764 (3) | 0.2937 (3) | 0.0916 (16) | |
C12 | 0.2168 (4) | 0.7392 (3) | 0.2927 (2) | 0.0748 (11) | |
C13 | 0.6013 (3) | 0.8224 (3) | 0.1056 (2) | 0.0725 (10) | |
C14 | 0.3562 (4) | 0.8902 (2) | 0.1097 (2) | 0.0670 (10) | |
Cl1 | −0.23133 (10) | 0.63941 (6) | 0.45831 (6) | 0.0730 (3) | |
Cl4 | 0.18774 (9) | 0.87102 (6) | 0.82435 (5) | 0.0661 (2) | |
Cl5 | −0.16978 (11) | 0.88067 (7) | 0.88994 (5) | 0.0780 (3) | |
Cl6 | −0.42978 (9) | 0.73966 (9) | 0.66334 (9) | 0.0940 (4) | |
Cl7A | 0.16982 (8) | 0.71621 (6) | 0.55167 (5) | 0.0561 (2) | |
Cl7B | −0.03243 (9) | 0.60440 (5) | 0.65705 (6) | 0.0644 (2) | |
O28A | −0.2680 (2) | 0.96606 (18) | 0.62968 (14) | 0.0661 (7) | |
O28B | −0.20688 (19) | 0.94016 (16) | 0.46864 (13) | 0.0551 (6) | |
O29A | 0.0090 (2) | 1.08385 (14) | 0.83283 (13) | 0.0542 (6) | |
O29B | 0.0780 (2) | 1.13227 (13) | 0.70034 (13) | 0.0494 (5) | |
C21 | −0.1357 (2) | 0.75166 (18) | 0.57849 (16) | 0.0399 (6) | |
C22 | −0.0629 (2) | 0.86740 (17) | 0.56825 (15) | 0.0343 (6) | |
C23 | 0.0568 (2) | 0.93294 (17) | 0.67242 (15) | 0.0327 (5) | |
C24 | 0.0337 (2) | 0.84618 (18) | 0.72709 (15) | 0.0373 (6) | |
C25 | −0.1304 (3) | 0.8324 (2) | 0.76085 (17) | 0.0452 (7) | |
C26 | −0.2303 (3) | 0.7774 (2) | 0.6737 (2) | 0.0480 (8) | |
C27 | 0.0094 (3) | 0.72899 (18) | 0.62807 (16) | 0.0392 (6) | |
C28 | −0.1906 (2) | 0.93008 (18) | 0.55544 (17) | 0.0390 (6) | |
C29 | 0.0429 (2) | 1.05569 (18) | 0.74321 (17) | 0.0396 (6) | |
O30 | −0.5503 (3) | 1.0333 (3) | 0.64988 (18) | 0.0855 (9) | |
H1N | 0.4097 (13) | 0.7805 (8) | 0.156 (4) | 0.0500* | 0.60 (5) |
H3 | 0.41350 | 0.74180 | −0.10100 | 0.0720* | |
H4 | 0.29770 | 0.57090 | −0.24750 | 0.0890* | |
H5 | 0.17290 | 0.41220 | −0.22270 | 0.0830* | |
H7 | 0.08920 | 0.31460 | −0.10450 | 0.0850* | |
H8 | 0.07690 | 0.31790 | 0.06210 | 0.1020* | |
H9 | 0.19150 | 0.48610 | 0.21090 | 0.0880* | |
H11A | 0.50520 | 0.74890 | 0.35400 | 0.1380* | |
H11B | 0.54740 | 0.65350 | 0.25140 | 0.1380* | |
H11C | 0.42100 | 0.61740 | 0.31830 | 0.1380* | |
H12A | 0.26610 | 0.80910 | 0.35360 | 0.1120* | |
H12B | 0.16020 | 0.68310 | 0.31650 | 0.1120* | |
H12C | 0.14500 | 0.75690 | 0.25020 | 0.1120* | |
H13A | 0.64400 | 0.89410 | 0.16650 | 0.1090* | |
H13B | 0.62810 | 0.83150 | 0.04140 | 0.1090* | |
H13C | 0.64440 | 0.76120 | 0.11100 | 0.1090* | |
H14A | 0.40750 | 0.95880 | 0.17120 | 0.1000* | |
H14B | 0.24600 | 0.87100 | 0.11650 | 0.1000* | |
H14C | 0.36880 | 0.90460 | 0.04640 | 0.1000* | |
H2N | 0.388 (5) | 0.748 (6) | 0.202 (2) | 0.0590* | 0.40 (5) |
H22 | −0.00440 | 0.85010 | 0.50580 | 0.0410* | |
H23 | 0.16320 | 0.93840 | 0.65060 | 0.0390* | |
H29B | 0.11700 | 1.10320 | 0.64500 | 0.0740* | |
H30A | −0.477 (5) | 0.999 (4) | 0.626 (3) | 0.1280* | |
H30B | −0.598 (5) | 1.031 (4) | 0.591 (4) | 0.1280* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0384 (10) | 0.0447 (10) | 0.0412 (9) | 0.0095 (8) | 0.0068 (8) | 0.0168 (8) |
N2 | 0.0506 (11) | 0.0613 (12) | 0.0426 (10) | 0.0206 (10) | 0.0084 (9) | 0.0253 (10) |
C1 | 0.0339 (11) | 0.0434 (12) | 0.0472 (12) | 0.0174 (9) | 0.0074 (9) | 0.0158 (10) |
C2 | 0.0390 (11) | 0.0473 (12) | 0.0393 (11) | 0.0150 (10) | 0.0058 (9) | 0.0154 (10) |
C3 | 0.0714 (17) | 0.0641 (16) | 0.0456 (13) | 0.0140 (14) | 0.0058 (12) | 0.0241 (13) |
C4 | 0.086 (2) | 0.086 (2) | 0.0417 (14) | 0.0208 (18) | 0.0025 (14) | 0.0155 (15) |
C5 | 0.0657 (18) | 0.0665 (18) | 0.0501 (15) | 0.0193 (15) | −0.0038 (13) | −0.0037 (14) |
C6 | 0.0428 (13) | 0.0450 (13) | 0.0615 (15) | 0.0166 (11) | 0.0035 (11) | 0.0085 (11) |
C7 | 0.0598 (17) | 0.0410 (14) | 0.098 (2) | 0.0143 (12) | 0.0067 (16) | 0.0136 (15) |
C8 | 0.078 (2) | 0.0501 (18) | 0.135 (3) | 0.0122 (15) | 0.024 (2) | 0.047 (2) |
C9 | 0.084 (2) | 0.0682 (19) | 0.088 (2) | 0.0211 (16) | 0.0251 (17) | 0.0496 (18) |
C10 | 0.0456 (13) | 0.0502 (13) | 0.0579 (14) | 0.0200 (11) | 0.0129 (11) | 0.0263 (12) |
C11 | 0.095 (3) | 0.101 (3) | 0.091 (2) | 0.035 (2) | −0.022 (2) | 0.048 (2) |
C12 | 0.0742 (19) | 0.084 (2) | 0.0627 (17) | 0.0235 (16) | 0.0329 (15) | 0.0220 (16) |
C13 | 0.0395 (14) | 0.088 (2) | 0.0662 (17) | −0.0021 (13) | 0.0091 (12) | 0.0144 (16) |
C14 | 0.090 (2) | 0.0577 (16) | 0.0616 (16) | 0.0334 (15) | 0.0111 (15) | 0.0250 (14) |
Cl1 | 0.0857 (5) | 0.0499 (4) | 0.0569 (4) | 0.0013 (3) | −0.0256 (3) | 0.0033 (3) |
Cl4 | 0.0760 (5) | 0.0680 (4) | 0.0531 (3) | 0.0212 (3) | −0.0222 (3) | 0.0232 (3) |
Cl5 | 0.1221 (7) | 0.0764 (5) | 0.0537 (4) | 0.0381 (5) | 0.0487 (4) | 0.0356 (4) |
Cl6 | 0.0401 (4) | 0.1072 (7) | 0.1358 (8) | 0.0010 (4) | 0.0211 (4) | 0.0574 (6) |
Cl7A | 0.0608 (4) | 0.0610 (4) | 0.0588 (4) | 0.0347 (3) | 0.0239 (3) | 0.0264 (3) |
Cl7B | 0.0899 (5) | 0.0448 (3) | 0.0716 (4) | 0.0205 (3) | 0.0135 (4) | 0.0345 (3) |
O28A | 0.0642 (11) | 0.0968 (14) | 0.0612 (11) | 0.0514 (11) | 0.0229 (9) | 0.0404 (11) |
O28B | 0.0498 (9) | 0.0812 (12) | 0.0546 (10) | 0.0269 (9) | 0.0064 (8) | 0.0430 (9) |
O29A | 0.0626 (11) | 0.0440 (9) | 0.0473 (9) | 0.0108 (8) | 0.0140 (8) | 0.0096 (7) |
O29B | 0.0538 (10) | 0.0364 (8) | 0.0601 (10) | 0.0128 (7) | 0.0106 (8) | 0.0204 (8) |
C21 | 0.0412 (11) | 0.0362 (11) | 0.0373 (10) | 0.0049 (9) | −0.0034 (9) | 0.0123 (9) |
C22 | 0.0365 (10) | 0.0402 (11) | 0.0294 (9) | 0.0128 (9) | 0.0043 (8) | 0.0156 (8) |
C23 | 0.0295 (9) | 0.0362 (10) | 0.0343 (9) | 0.0097 (8) | 0.0036 (8) | 0.0154 (8) |
C24 | 0.0419 (11) | 0.0399 (11) | 0.0322 (10) | 0.0130 (9) | −0.0007 (8) | 0.0156 (9) |
C25 | 0.0581 (14) | 0.0481 (12) | 0.0409 (11) | 0.0199 (11) | 0.0209 (10) | 0.0255 (10) |
C26 | 0.0391 (12) | 0.0495 (13) | 0.0618 (14) | 0.0080 (10) | 0.0137 (11) | 0.0299 (12) |
C27 | 0.0482 (12) | 0.0366 (11) | 0.0380 (10) | 0.0149 (9) | 0.0087 (9) | 0.0180 (9) |
C28 | 0.0332 (10) | 0.0424 (11) | 0.0442 (11) | 0.0091 (9) | 0.0011 (9) | 0.0204 (10) |
C29 | 0.0336 (10) | 0.0372 (11) | 0.0443 (12) | 0.0064 (9) | 0.0009 (9) | 0.0138 (9) |
O30 | 0.0640 (13) | 0.140 (2) | 0.0626 (12) | 0.0559 (14) | 0.0090 (10) | 0.0364 (14) |
Cl1—C21 | 1.748 (2) | C6—C7 | 1.398 (4) |
Cl4—C24 | 1.753 (2) | C7—C8 | 1.350 (6) |
Cl5—C25 | 1.699 (2) | C7—H7 | 0.93 |
Cl6—C26 | 1.696 (3) | C8—H8 | 0.93 |
Cl7A—C27 | 1.765 (2) | C9—C8 | 1.398 (6) |
Cl7B—C27 | 1.765 (2) | C9—H9 | 0.93 |
O28A—C28 | 1.223 (3) | C10—C9 | 1.356 (5) |
O28B—C28 | 1.253 (2) | C11—H11A | 0.96 |
O29A—C29 | 1.200 (3) | C11—H11B | 0.96 |
O29B—C29 | 1.322 (3) | C11—H11C | 0.96 |
O29B—H29B | 0.82 | C12—H12A | 0.96 |
O30—H30A | 0.85 (5) | C12—H12B | 0.96 |
O30—H30B | 0.88 (5) | C12—H12C | 0.96 |
N1—C2 | 1.456 (3) | C13—H13A | 0.96 |
N1—C13 | 1.482 (3) | C13—H13B | 0.96 |
N1—C14 | 1.475 (4) | C13—H13C | 0.96 |
N1—H1N | 0.82 (4) | C14—H14A | 0.96 |
N2—C10 | 1.459 (3) | C14—H14B | 0.96 |
N2—C12 | 1.479 (4) | C14—H14C | 0.96 |
N2—C11 | 1.480 (4) | C21—C26 | 1.523 (3) |
N2—H2N | 0.97 (7) | C21—C27 | 1.547 (3) |
C1—C2 | 1.418 (4) | C22—C21 | 1.555 (3) |
C1—C6 | 1.431 (3) | C22—C23 | 1.566 (3) |
C1—C10 | 1.425 (3) | C22—C28 | 1.538 (3) |
C2—C3 | 1.361 (3) | C22—H22 | 0.98 |
C3—C4 | 1.396 (4) | C23—C29 | 1.519 (3) |
C3—H3 | 0.93 | C23—H23 | 0.98 |
C4—H4 | 0.93 | C24—C23 | 1.554 (3) |
C5—C4 | 1.345 (5) | C24—C25 | 1.514 (3) |
C5—H5 | 0.93 | C24—C27 | 1.547 (3) |
C6—C5 | 1.412 (4) | C25—C26 | 1.309 (3) |
C29—O29B—H29B | 109.5 | H12B—C12—H12C | 109.5 |
H30A—O30—H30B | 102 (4) | N1—C13—H13A | 109.5 |
C2—N1—C13 | 112.0 (2) | N1—C13—H13B | 109.5 |
C2—N1—C14 | 113.28 (19) | N1—C13—H13C | 109.5 |
C14—N1—C13 | 112.0 (2) | H13A—C13—H13B | 109.5 |
C2—N1—H1N | 106.3 | H13A—C13—H13C | 109.5 |
C13—N1—H1N | 106.3 | H13B—C13—H13C | 109.5 |
C14—N1—H1N | 106.3 | N1—C14—H14A | 109.5 |
C10—N2—C11 | 113.2 (2) | N1—C14—H14B | 109.5 |
C10—N2—C12 | 111.9 (2) | N1—C14—H14C | 109.5 |
C11—N2—C12 | 111.4 (2) | H14A—C14—H14B | 109.5 |
C10—N2—H2N | 106.6 | H14A—C14—H14C | 109.5 |
C11—N2—H2N | 106.6 | H14B—C14—H14C | 109.5 |
C12—N2—H2N | 106.6 | Cl1—C21—C22 | 113.80 (14) |
C2—C1—C6 | 117.4 (2) | Cl1—C21—C27 | 115.64 (16) |
C2—C1—C10 | 125.1 (2) | Cl1—C21—C26 | 116.06 (16) |
C6—C1—C10 | 117.4 (2) | C22—C21—C26 | 109.45 (18) |
N1—C2—C1 | 118.75 (19) | C22—C21—C27 | 101.43 (16) |
N1—C2—C3 | 120.2 (2) | C26—C21—C27 | 98.57 (17) |
C1—C2—C3 | 121.0 (2) | C21—C22—C23 | 101.54 (16) |
C2—C3—C4 | 121.2 (3) | C21—C22—C28 | 111.57 (16) |
C2—C3—H3 | 119.4 | C23—C22—C28 | 116.09 (17) |
C4—C3—H3 | 119.4 | C21—C22—H22 | 109.1 |
C3—C4—C5 | 119.6 (3) | C23—C22—H22 | 109.1 |
C3—C4—H4 | 120.2 | C28—C22—H22 | 109.1 |
C5—C4—H4 | 120.2 | C22—C23—C24 | 103.07 (17) |
C4—C5—C6 | 121.9 (3) | C22—C23—C29 | 116.08 (16) |
C4—C5—H5 | 119.0 | C24—C23—C29 | 114.84 (16) |
C6—C5—H5 | 119.0 | Cl4—C23—C24 | 114.96 (14) |
C7—C6—C5 | 121.7 (3) | C22—C23—H23 | 107.5 |
C7—C6—C1 | 119.6 (3) | C24—C23—H23 | 107.5 |
C5—C6—C1 | 118.8 (3) | C29—C23—H23 | 107.5 |
C8—C7—C6 | 121.3 (3) | C23—C24—C27 | 100.42 (16) |
C8—C7—H7 | 119.4 | C22—C24—C25 | 109.87 (17) |
C6—C7—H7 | 119.4 | C25—C24—C27 | 98.95 (18) |
C7—C8—C9 | 119.9 (4) | Cl4—C24—C25 | 115.68 (15) |
C7—C8—H8 | 120.1 | Cl4—C24—C27 | 114.88 (16) |
C9—C8—H8 | 120.1 | Cl5—C25—C24 | 124.33 (17) |
C8—C9—C10 | 121.5 (4) | Cl5—C25—C26 | 128.2 (2) |
C8—C9—H9 | 119.3 | C24—C25—C26 | 107.5 (2) |
C10—C9—H9 | 119.3 | C21—C26—C25 | 107.8 (2) |
N2—C10—C1 | 118.7 (2) | Cl6—C26—C21 | 124.20 (18) |
N2—C10—C9 | 120.9 (3) | Cl6—C26—C25 | 128.0 (2) |
C9—C10—C1 | 120.4 (3) | C21—C27—C24 | 92.18 (17) |
N2—C11—H11A | 109.5 | Cl7A—C27—Cl7B | 106.72 (14) |
N2—C11—H11B | 109.5 | Cl7A—C27—C21 | 115.10 (15) |
N2—C11—H11C | 109.5 | Cl7A—C27—C24 | 114.19 (17) |
H11A—C11—H11B | 109.5 | Cl7B—C27—C21 | 114.07 (17) |
H11A—C11—H11C | 109.5 | Cl7B—C27—C24 | 114.44 (15) |
H11B—C11—H11C | 109.5 | O28A—C28—O28B | 125.1 (2) |
N2—C12—H12A | 109.5 | O28A—C28—C22 | 118.2 (2) |
N2—C12—H12B | 109.5 | O28B—C28—C22 | 116.73 (18) |
N2—C12—H12C | 109.5 | O29A—C29—O29B | 121.5 (2) |
H12A—C12—H12B | 109.5 | O29A—C29—C23 | 123.6 (2) |
H12A—C12—H12C | 109.5 | O29B—C29—C23 | 114.81 (18) |
C14—N1—C2—C3 | 62.0 (3) | C22—C21—C27—Cl7A | −58.82 (19) |
C14—N1—C2—C1 | −118.4 (2) | C22—C21—C27—Cl7B | 177.32 (14) |
C13—N1—C2—C3 | −65.9 (3) | C22—C21—C27—C24 | 59.25 (17) |
C13—N1—C2—C1 | 113.7 (3) | C26—C21—C27—Cl7A | −170.79 (17) |
C11—N2—C10—C9 | 60.8 (4) | C26—C21—C27—Cl7B | 65.4 (2) |
C12—N2—C10—C9 | −66.1 (4) | C26—C21—C27—C24 | −52.7 (2) |
C12—N2—C10—C1 | 113.1 (3) | C27—C21—C26—C25 | 35.1 (3) |
C11—N2—C10—C1 | −120.0 (3) | C27—C21—C26—Cl6 | −145.1 (2) |
C2—C1—C6—C7 | −179.9 (2) | C21—C22—C23—C29 | −127.00 (18) |
C2—C1—C6—C5 | −0.2 (4) | C28—C22—C23—C24 | 120.61 (18) |
C10—C1—C2—C3 | 178.9 (2) | C21—C22—C28—O28A | 64.6 (3) |
C6—C1—C10—C9 | 0.0 (4) | C21—C22—C28—O28B | −115.4 (2) |
C6—C1—C2—C3 | −0.7 (4) | C28—C22—C23—C29 | −5.8 (3) |
C6—C1—C2—N1 | 179.7 (2) | C21—C22—C23—C24 | −0.57 (17) |
C6—C1—C10—N2 | −179.2 (2) | C23—C22—C28—O28B | 128.9 (2) |
C10—C1—C2—N1 | −0.7 (4) | C23—C22—C28—O28A | −51.1 (3) |
C10—C1—C6—C7 | 0.5 (3) | C22—C23—C24—C25 | −65.63 (19) |
C2—C1—C10—N2 | 1.1 (3) | C22—C23—C24—C27 | 37.95 (18) |
C10—C1—C6—C5 | −179.9 (3) | C29—C23—C24—C25 | 61.6 (2) |
C2—C1—C10—C9 | −179.7 (3) | C29—C23—C24—C27 | 165.16 (17) |
C1—C2—C3—C4 | 1.1 (4) | C29—C23—C24—Cl4 | −70.97 (18) |
N1—C2—C3—C4 | −179.3 (3) | C22—C23—C24—Cl4 | 161.82 (13) |
C2—C3—C4—C5 | −0.4 (5) | C24—C23—C29—O29A | −3.6 (3) |
C3—C4—C5—C6 | −0.6 (5) | C24—C23—C29—O29B | 173.55 (16) |
C4—C5—C6—C1 | 0.9 (5) | C22—C23—C29—O29A | 116.7 (2) |
C4—C5—C6—C7 | −179.5 (3) | C22—C23—C29—O29B | −66.2 (2) |
C5—C6—C7—C8 | 179.9 (5) | C23—C24—C25—Cl5 | −111.8 (2) |
C1—C6—C7—C8 | −0.4 (4) | Cl4—C24—C25—Cl5 | 20.4 (3) |
C6—C7—C8—C9 | 0.0 (5) | Cl4—C24—C25—C26 | −159.2 (2) |
C7—C8—C9—C10 | 0.5 (5) | C27—C24—C25—C26 | −35.9 (3) |
C8—C9—C10—C1 | −0.5 (5) | Cl4—C24—C27—Cl7A | −64.0 (2) |
C8—C9—C10—N2 | 178.7 (3) | Cl4—C24—C27—Cl7B | 59.4 (2) |
C26—C21—C22—C23 | 66.35 (19) | Cl4—C24—C27—C21 | 177.12 (15) |
Cl1—C21—C22—C23 | −161.98 (13) | C23—C24—C27—Cl7A | 59.89 (18) |
Cl1—C21—C22—C28 | 73.74 (18) | C23—C24—C27—Cl7B | −176.71 (15) |
C27—C21—C22—C28 | −161.40 (16) | C23—C24—C27—C21 | −58.96 (17) |
Cl1—C21—C26—Cl6 | −21.0 (3) | C25—C24—C27—Cl7A | 172.15 (16) |
Cl1—C21—C26—C25 | 159.2 (2) | C25—C24—C27—Cl7B | −64.4 (2) |
C22—C21—C26—Cl6 | 109.5 (2) | C25—C24—C27—C21 | 53.30 (19) |
C22—C21—C26—C25 | −70.3 (3) | C23—C24—C25—C26 | 68.6 (3) |
C26—C21—C22—C28 | −57.9 (2) | C27—C24—C25—Cl5 | 143.7 (2) |
C27—C21—C22—C23 | −37.11 (17) | Cl5—C25—C26—Cl6 | 1.1 (4) |
Cl1—C21—C27—Cl7A | 64.8 (2) | C24—C25—C26—C21 | 0.5 (3) |
Cl1—C21—C27—Cl7B | −59.06 (19) | Cl5—C25—C26—C21 | −179.1 (2) |
Cl1—C21—C27—C24 | −177.13 (15) | C24—C25—C26—Cl6 | −179.3 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···N2 | 0.82 (4) | 1.82 (3) | 2.589 (3) | 154 (4) |
N2—H2N···N1 | 0.97 (7) | 1.70 (5) | 2.589 (3) | 152 (4) |
O29B—H29B···O28Bi | 0.82 | 1.70 | 2.520 (2) | 173 |
O30—H30B···O28Bii | 0.89 (5) | 2.02 (5) | 2.783 (3) | 143 (4) |
O30—H30A···O28A | 0.85 (5) | 1.95 (5) | 2.749 (3) | 156 (4) |
C9—H9···Cl7Biii | 0.93 | 2.78 | 3.599 (4) | 148 |
C12—H12C···O29Bi | 0.96 | 2.58 | 3.297 (4) | 132 |
C13—H13A···O30i | 0.96 | 2.54 | 3.220 (3) | 128 |
C14—H14B···O29Ai | 0.96 | 2.46 | 3.348 (4) | 155 |
C23—H23···Cl7A | 0.98 | 2.64 | 2.994 (2) | 102 |
C23—H23···O30iv | 0.98 | 2.55 | 3.480 (4) | 157 |
Symmetry codes: (i) −x, −y+2, −z+1; (ii) −x−1, −y+2, −z+1; (iii) −x, −y+1, −z+1; (iv) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C14H19N2+C9H3Cl6O4−·H2O |
Mr | 621.17 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 295 |
a, b, c (Å) | 8.7122 (5), 12.8097 (11), 13.7023 (12) |
α, β, γ (°) | 113.200 (7), 91.680 (6), 101.350 (6) |
V (Å3) | 1368.32 (19) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.67 |
Crystal size (mm) | 0.6 × 0.6 × 0.3 |
Data collection | |
Diffractometer | Enraf-Nonius CAD4 diffractometer |
Absorption correction | ψ-scan (PLATON; Spek, 1998) |
Tmin, Tmax | 0.745, 0.819 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13079, 6272, 4286 |
Rint | 0.036 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.107, 1.00 |
No. of reflections | 6272 |
No. of parameters | 335 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.32, −0.40 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, HELENA (Spek, 1997), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 1998), SHELXL97 and PLATON.
O28A—C28 | 1.223 (3) | N1—C13 | 1.482 (3) |
O28B—C28 | 1.253 (2) | N1—C14 | 1.475 (4) |
O29A—C29 | 1.200 (3) | N2—C10 | 1.459 (3) |
O29B—C29 | 1.322 (3) | N2—C12 | 1.479 (4) |
N1—C2 | 1.456 (3) | N2—C11 | 1.480 (4) |
H30A—O30—H30B | 102 (4) | N2—C10—C1 | 118.7 (2) |
C2—N1—C13 | 112.0 (2) | N2—C10—C9 | 120.9 (3) |
C2—N1—C14 | 113.28 (19) | O28A—C28—O28B | 125.1 (2) |
C14—N1—C13 | 112.0 (2) | O28A—C28—C22 | 118.2 (2) |
C10—N2—C11 | 113.2 (2) | O28B—C28—C22 | 116.73 (18) |
C10—N2—C12 | 111.9 (2) | O29A—C29—O29B | 121.5 (2) |
C11—N2—C12 | 111.4 (2) | O29A—C29—C23 | 123.6 (2) |
N1—C2—C1 | 118.75 (19) | O29B—C29—C23 | 114.81 (18) |
N1—C2—C3 | 120.2 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···N2 | 0.82 (4) | 1.82 (3) | 2.589 (3) | 154 (4) |
N2—H2N···N1 | 0.97 (7) | 1.70 (5) | 2.589 (3) | 152 (4) |
O29B—H29B···O28Bi | 0.82 | 1.70 | 2.520 (2) | 173 |
O30—H30B···O28Bii | 0.89 (5) | 2.02 (5) | 2.783 (3) | 143 (4) |
O30—H30A···O28A | 0.85 (5) | 1.95 (5) | 2.749 (3) | 156 (4) |
C9—H9···Cl7Biii | 0.93 | 2.78 | 3.599 (4) | 148 |
C12—H12C···O29Bi | 0.96 | 2.58 | 3.297 (4) | 132 |
C13—H13A···O30i | 0.96 | 2.54 | 3.220 (3) | 128 |
C14—H14B···O29Ai | 0.96 | 2.46 | 3.348 (4) | 155 |
C23—H23···Cl7A | 0.98 | 2.64 | 2.994 (2) | 102 |
C23—H23···O30iv | 0.98 | 2.55 | 3.480 (4) | 157 |
Symmetry codes: (i) −x, −y+2, −z+1; (ii) −x−1, −y+2, −z+1; (iii) −x, −y+1, −z+1; (iv) x+1, y, z. |
The term `proton sponges' describes a class of compounds which combine an unusually high basicity with a low nucleophilic character. Most of these compounds are diamines (Llamas-Saiz et al., 1994). The [N—H···N]+ hydrogen bonds play an important role in these proton sponges. In a complex of 1,8-bis(dimethylamino)naphthalene (DMAN) with a (slightly) acidic compound, DMAN will absorb a proton from the acidic compound and an intramolecular hydrogen bond will be formed. These hydrogen bonds can be symmetric or asymmetric. When the bridge is asymmetric this will be reflected in the other bond distances of the DMAN·H+ cation (Kanters, Schouten, Duisenberg et al., 1991). It is remarkable that the N—H distance in proton sponges is found to be well out of the range usually observed for N—H···N hydrogen bonds in other molecules (Kanters, Schouten, Kroon & Grech, 1991). For protonated proton sponges the N···N distances are in the range 2.553–2.654 Å (Llamas-Saiz et al., 1994; Kanters, Schouten, Duisenberg et al., 1991). The H atom seems to be located on a rather flat potential energy surface, the nature of which is influenced by the crystal field environment (Jeffrey, 1997). The subject of the present study, (I), is the monohydrated complex of DMAN with 1,4,5,6,7,7-hexachloro-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid (1:1), in which DMAN accepts one proton from the carboxylic acid molecule. \scheme
The asymmetric unit of (I) (Fig. 1, Table 1) consists of one DMAN·H+ cation, one singly deprotonated (3-carboxy-1,4,5,6,7,7-hexachlorobicyclo[2.2.1]hept-5-ene-2-carboxylate)- anion and one water molecule.
The DMAN ring system in (I) is planar (σplane 0.007 Å) and N1 and N2 lie within 0.020 and 0.022 Å, respectively, of the least squares mean plane of the ring system. The disordered H atoms (H1N and H2N) are also in the plane of the ring system, being displaced by only 0.040 and -0.038 Å, respectively. The DMAN residues are ordered in π-stacked colums along the a axis and the perpendicular distances between two DMAN molecules alternate between 4.261 and 4.711 Å.
Among the three different residues several types of hydrogen bonds were observed. In the DMAN molecule there is a strong, somewhat bent, intramolecular [N—H···N]+ hydrogen bond with an N···N distance of 2.589 (3) Å. The hydrogen is disordered over two positions whose occupancies refined to 0.60 (5) for H1N and 0.40 (5) for H2N. The resulting difference in occupancy of 0.20 (10) suggests a possible asymmetric hydrogen bond, although the evidence is not conclusive.
The deprotonated acid moiety accepts a hydrogen bond from the still-protonated acid moiety of a symmetry-related molecule, thereby forming a dimer [unitary graph set R22(14)] over the inversion centre at (0,0,1/2) (Fig. 2). Protonated and deprotonated acid moieties can easily be distinguished on the basis of their C—O bond lengths (Table 1). Intermolecular O···O distances clearly indicate that the water molecules link these rings into infinite chains along [100] by donating hydrogen bonds to both carboxylate O atoms. The water links also form hydrogen-bonded ring systems with the anions [unitary graph set DD, binary graph set R44(12)]. There are also weak intermolecular C—H···A interactions present (Table 2).