Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803007669/cm6039sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803007669/cm6039IIsup2.hkl |
CCDC reference: 214644
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (C-C) = 0.002 Å
- R factor = 0.049
- wR factor = 0.113
- Data-to-parameter ratio = 15.5
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
ABSTM_02 Alert C The ratio of expected to reported Tmax/Tmin(RR') is < 0.90 Tmin and Tmax reported: 0.848 0.997 Tmin' and Tmax expected: 0.968 0.994 RR' = 0.873 Please check that your absorption correction is appropriate. PLAT_353 Alert C Long N-H Bond (0.87A) N(16) - H(16B) = 1.02 Ang.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
2 Alert Level C = Please check
Crystals were grown by slow evaporation of an aqueous mixture of 1,2-diaminoethane and racemic cineolic acid (1:1).
Data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1999); software used to prepare material for publication: SHELXL97.
2C10H15O5+·C2H10N22−·2H2O | F(000) = 1144 |
Mr = 528.60 | Dx = 1.329 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 26.5948 (14) Å | Cell parameters from 5796 reflections |
b = 7.9327 (4) Å | θ = 2.9–27.5° |
c = 12.8480 (9) Å | µ = 0.11 mm−1 |
β = 102.938 (2)° | T = 150 K |
V = 2641.7 (3) Å3 | Lath, colourless |
Z = 4 | 0.30 × 0.15 × 0.06 mm |
Enraf–Nonius KappaCCD area-detector diffractometer | 2939 independent reflections |
Radiation source: Enraf–Nonius FR591 rotating anode | 1936 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.070 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
ϕ and ω scans to fill Ewald sphere | h = −34→33 |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | k = −8→9 |
Tmin = 0.848, Tmax = 0.997 | l = −16→16 |
7946 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.050 | Hydrogen site location: mixed |
wR(F2) = 0.114 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.98 | w = 1/[σ2(Fo2) + (0.0487P)2] where P = (Fo2 + 2Fc2)/3 |
2939 reflections | (Δ/σ)max < 0.001 |
190 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.32 e Å−3 |
2C10H15O5+·C2H10N22−·2H2O | V = 2641.7 (3) Å3 |
Mr = 528.60 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 26.5948 (14) Å | µ = 0.11 mm−1 |
b = 7.9327 (4) Å | T = 150 K |
c = 12.8480 (9) Å | 0.30 × 0.15 × 0.06 mm |
β = 102.938 (2)° |
Enraf–Nonius KappaCCD area-detector diffractometer | 2939 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 1936 reflections with I > 2σ(I) |
Tmin = 0.848, Tmax = 0.997 | Rint = 0.070 |
7946 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.114 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.98 | Δρmax = 0.32 e Å−3 |
2939 reflections | Δρmin = −0.32 e Å−3 |
190 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. H atoms attached to C atoms were placed in calculated positions and allowed to ride during the refinement. Isotropic displacement parameters were constrained to be 1.3Ueq of the parent C atom. H atoms attached to O or N atoms were located on a difference synthesis. The positional and isotropic displacement parameters of these H atoms were allowed to refine. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.17776 (4) | 0.19113 (13) | 0.05254 (9) | 0.0179 (3) | |
C2 | 0.17173 (7) | 0.3687 (2) | 0.06971 (14) | 0.0166 (4) | |
C3 | 0.17861 (7) | 0.4075 (2) | 0.18810 (14) | 0.0206 (4) | |
H3A | 0.2158 | 0.4010 | 0.2228 | 0.027* | |
H3B | 0.1670 | 0.5244 | 0.1962 | 0.027* | |
C4 | 0.14897 (7) | 0.2884 (2) | 0.24528 (14) | 0.0207 (4) | |
H4A | 0.1115 | 0.3082 | 0.2200 | 0.027* | |
H4B | 0.1584 | 0.3106 | 0.3231 | 0.027* | |
C5 | 0.16153 (7) | 0.1057 (2) | 0.22367 (13) | 0.0180 (4) | |
H5 | 0.1993 | 0.0876 | 0.2520 | 0.023* | |
C6 | 0.14901 (7) | 0.0713 (2) | 0.10161 (13) | 0.0174 (4) | |
C7 | 0.21489 (7) | 0.4519 (2) | 0.02614 (15) | 0.0227 (4) | |
H7A | 0.2484 | 0.4104 | 0.0659 | 0.030* | |
H7B | 0.2133 | 0.5745 | 0.0344 | 0.030* | |
H7C | 0.2105 | 0.4240 | −0.0497 | 0.030* | |
C8 | 0.12075 (7) | 0.4329 (2) | −0.00223 (14) | 0.0157 (4) | |
O9 | 0.09373 (4) | 0.53977 (14) | 0.03381 (9) | 0.0209 (3) | |
O10 | 0.11020 (5) | 0.38281 (14) | −0.09797 (9) | 0.0205 (3) | |
C11 | 0.13248 (7) | −0.0136 (2) | 0.28120 (13) | 0.0202 (4) | |
O12 | 0.09053 (5) | 0.01903 (15) | 0.30031 (10) | 0.0249 (3) | |
O13 | 0.15719 (5) | −0.15752 (15) | 0.30868 (10) | 0.0247 (3) | |
H13A | 0.1402 (10) | −0.232 (3) | 0.358 (2) | 0.070 (8)* | |
C14 | 0.17137 (8) | −0.0966 (2) | 0.07655 (15) | 0.0251 (4) | |
H14A | 0.1672 | −0.1079 | −0.0009 | 0.033* | |
H14B | 0.1532 | −0.1889 | 0.1032 | 0.033* | |
H14C | 0.2081 | −0.1012 | 0.1112 | 0.033* | |
C15 | 0.09124 (7) | 0.0769 (2) | 0.05274 (14) | 0.0222 (4) | |
H15A | 0.0766 | 0.1807 | 0.0750 | 0.029* | |
H15B | 0.0745 | −0.0209 | 0.0771 | 0.029* | |
H15C | 0.0855 | 0.0745 | −0.0253 | 0.029* | |
N16 | 0.04617 (6) | −0.44813 (19) | 0.20454 (14) | 0.0203 (4) | |
H16A | 0.0671 (8) | −0.457 (2) | 0.2744 (18) | 0.035 (6)* | |
H16B | 0.0249 (8) | −0.556 (3) | 0.1902 (17) | 0.047 (6)* | |
H16C | 0.0642 (9) | −0.442 (3) | 0.1527 (19) | 0.046 (7)* | |
C17 | 0.01222 (7) | −0.2973 (2) | 0.20257 (15) | 0.0228 (4) | |
H17A | −0.0151 | −0.2979 | 0.1360 | 0.030* | |
H17B | 0.0329 | −0.1934 | 0.2032 | 0.030* | |
O18 | 0.02658 (5) | 0.29550 (19) | 0.37143 (12) | 0.0295 (4) | |
H18A | 0.0525 (11) | 0.352 (3) | 0.435 (2) | 0.072 (8)* | |
H18B | 0.0399 (12) | 0.217 (4) | 0.348 (2) | 0.091 (12)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0211 (7) | 0.0133 (6) | 0.0219 (7) | 0.0000 (5) | 0.0102 (6) | 0.0012 (5) |
C2 | 0.0175 (9) | 0.0122 (8) | 0.0209 (10) | −0.0008 (7) | 0.0061 (8) | −0.0002 (7) |
C3 | 0.0214 (10) | 0.0190 (9) | 0.0204 (10) | −0.0005 (7) | 0.0024 (8) | 0.0001 (7) |
C4 | 0.0269 (11) | 0.0185 (9) | 0.0176 (10) | 0.0010 (8) | 0.0068 (8) | −0.0006 (7) |
C5 | 0.0173 (10) | 0.0158 (9) | 0.0210 (10) | 0.0001 (7) | 0.0045 (8) | 0.0018 (7) |
C6 | 0.0212 (10) | 0.0148 (9) | 0.0182 (10) | −0.0013 (7) | 0.0088 (8) | 0.0023 (7) |
C7 | 0.0191 (10) | 0.0197 (10) | 0.0311 (11) | −0.0023 (7) | 0.0093 (8) | 0.0025 (8) |
C8 | 0.0178 (9) | 0.0137 (8) | 0.0182 (10) | −0.0043 (7) | 0.0093 (8) | 0.0000 (7) |
O9 | 0.0220 (7) | 0.0219 (6) | 0.0214 (7) | 0.0043 (5) | 0.0104 (6) | 0.0000 (5) |
O10 | 0.0224 (7) | 0.0216 (6) | 0.0179 (7) | 0.0033 (5) | 0.0055 (5) | −0.0011 (5) |
C11 | 0.0272 (11) | 0.0195 (9) | 0.0136 (10) | −0.0023 (8) | 0.0038 (8) | −0.0018 (7) |
O12 | 0.0243 (8) | 0.0271 (7) | 0.0263 (8) | 0.0012 (6) | 0.0119 (6) | 0.0027 (5) |
O13 | 0.0285 (8) | 0.0209 (7) | 0.0278 (8) | 0.0042 (5) | 0.0129 (6) | 0.0086 (5) |
C14 | 0.0350 (12) | 0.0172 (9) | 0.0259 (11) | 0.0017 (8) | 0.0128 (9) | 0.0012 (8) |
C15 | 0.0236 (11) | 0.0246 (10) | 0.0188 (10) | −0.0056 (8) | 0.0055 (8) | 0.0003 (8) |
N16 | 0.0193 (9) | 0.0253 (9) | 0.0177 (9) | 0.0013 (7) | 0.0072 (8) | 0.0003 (7) |
C17 | 0.0193 (10) | 0.0215 (10) | 0.0289 (11) | 0.0006 (8) | 0.0080 (8) | 0.0042 (8) |
O18 | 0.0271 (8) | 0.0280 (8) | 0.0307 (9) | 0.0017 (6) | 0.0008 (7) | −0.0012 (6) |
O1—C2 | 1.4400 (19) | C8—O9 | 1.265 (2) |
O1—C6 | 1.4498 (19) | C11—O12 | 1.223 (2) |
C2—C3 | 1.522 (2) | C11—O13 | 1.325 (2) |
C2—C7 | 1.535 (2) | O13—H13A | 1.04 (3) |
C2—C8 | 1.546 (2) | C14—H14A | 0.9800 |
C3—C4 | 1.521 (2) | C14—H14B | 0.9800 |
C3—H3A | 0.9900 | C14—H14C | 0.9800 |
C3—H3B | 0.9900 | C15—H15A | 0.9800 |
C4—C5 | 1.527 (2) | C15—H15B | 0.9800 |
C4—H4A | 0.9900 | C15—H15C | 0.9800 |
C4—H4B | 0.9900 | N16—C17 | 1.496 (2) |
C5—C11 | 1.515 (2) | N16—H16A | 0.95 (2) |
C5—C6 | 1.553 (2) | N16—H16B | 1.02 (2) |
C5—H5 | 1.0000 | N16—H16C | 0.91 (2) |
C6—C14 | 1.522 (2) | C17—C17i | 1.504 (3) |
C6—C15 | 1.525 (2) | C17—H17A | 0.9900 |
C7—H7A | 0.9800 | C17—H17B | 0.9900 |
C7—H7B | 0.9800 | O18—H18A | 1.05 (3) |
C7—H7C | 0.9800 | O18—H18B | 0.80 (3) |
C8—O10 | 1.263 (2) | ||
C2—O1—C6 | 119.16 (12) | H7A—C7—H7C | 109.5 |
O1—C2—C3 | 110.99 (13) | H7B—C7—H7C | 109.5 |
O1—C2—C7 | 104.30 (13) | O10—C8—O9 | 123.15 (16) |
C3—C2—C7 | 110.18 (14) | O10—C8—C2 | 116.91 (14) |
O1—C2—C8 | 110.09 (13) | O9—C8—C2 | 119.75 (15) |
C3—C2—C8 | 115.08 (14) | O12—C11—O13 | 123.33 (16) |
C7—C2—C8 | 105.52 (14) | O12—C11—C5 | 123.60 (16) |
C4—C3—C2 | 113.43 (14) | O13—C11—C5 | 113.07 (15) |
C4—C3—H3A | 108.9 | C11—O13—H13A | 113.3 (14) |
C2—C3—H3A | 108.9 | C6—C14—H14A | 109.5 |
C4—C3—H3B | 108.9 | C6—C14—H14B | 109.5 |
C2—C3—H3B | 108.9 | H14A—C14—H14B | 109.5 |
H3A—C3—H3B | 107.7 | C6—C14—H14C | 109.5 |
C3—C4—C5 | 110.09 (14) | H14A—C14—H14C | 109.5 |
C3—C4—H4A | 109.6 | H14B—C14—H14C | 109.5 |
C5—C4—H4A | 109.6 | C6—C15—H15A | 109.5 |
C3—C4—H4B | 109.6 | C6—C15—H15B | 109.5 |
C5—C4—H4B | 109.6 | H15A—C15—H15B | 109.5 |
H4A—C4—H4B | 108.2 | C6—C15—H15C | 109.5 |
C11—C5—C4 | 110.38 (14) | H15A—C15—H15C | 109.5 |
C11—C5—C6 | 111.42 (14) | H15B—C15—H15C | 109.5 |
C4—C5—C6 | 110.17 (13) | C17—N16—H16A | 107.6 (12) |
C11—C5—H5 | 108.3 | C17—N16—H16B | 111.0 (12) |
C4—C5—H5 | 108.3 | H16A—N16—H16B | 107.0 (17) |
C6—C5—H5 | 108.3 | C17—N16—H16C | 111.1 (14) |
O1—C6—C14 | 102.30 (13) | H16A—N16—H16C | 114.0 (19) |
O1—C6—C15 | 112.49 (13) | H16B—N16—H16C | 106.2 (18) |
C14—C6—C15 | 110.12 (15) | N16—C17—C17i | 110.79 (13) |
O1—C6—C5 | 107.99 (13) | N16—C17—H17A | 109.5 |
C14—C6—C5 | 111.23 (14) | C17i—C17—H17A | 109.5 |
C15—C6—C5 | 112.28 (14) | N16—C17—H17B | 109.5 |
C2—C7—H7A | 109.5 | C17i—C17—H17B | 109.5 |
C2—C7—H7B | 109.5 | H17A—C17—H17B | 108.1 |
H7A—C7—H7B | 109.5 | H18A—O18—H18B | 111 (3) |
C2—C7—H7C | 109.5 | ||
O9—C8—C2—O1 | 140.97 (14) | O1—C6—C5—C11 | 179.43 (13) |
C8—C2—O1—C6 | −78.14 (17) | C6—C5—C11—O13 | 87.03 (18) |
C2—O1—C6—C5 | −55.42 (18) | N16—C17—C17i—N16i | −62.3 (3) |
Symmetry code: (i) −x, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O13—H13A···O10ii | 1.04 (3) | 1.61 (3) | 2.6202 (17) | 163 (2) |
N16—H16A···O10ii | 0.95 (2) | 1.87 (2) | 2.770 (2) | 156.8 (17) |
N16—H16B···O18iii | 1.02 (2) | 1.85 (2) | 2.826 (2) | 160.6 (18) |
N16—H16C···O9iv | 0.91 (2) | 1.87 (2) | 2.768 (2) | 170 (2) |
O18—H18A···O9v | 1.05 (3) | 1.71 (3) | 2.7533 (19) | 175 (2) |
O18—H18B···O12 | 0.80 (3) | 2.25 (3) | 3.039 (2) | 170 (3) |
Symmetry codes: (ii) x, −y, z+1/2; (iii) −x, y−1, −z+1/2; (iv) x, y−1, z; (v) x, −y+1, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | 2C10H15O5+·C2H10N22−·2H2O |
Mr | 528.60 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 150 |
a, b, c (Å) | 26.5948 (14), 7.9327 (4), 12.8480 (9) |
β (°) | 102.938 (2) |
V (Å3) | 2641.7 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.30 × 0.15 × 0.06 |
Data collection | |
Diffractometer | Enraf–Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.848, 0.997 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7946, 2939, 1936 |
Rint | 0.070 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.114, 0.98 |
No. of reflections | 2939 |
No. of parameters | 190 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.32, −0.32 |
Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), DENZO and COLLECT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 1999), SHELXL97.
C8—O10 | 1.263 (2) | C11—O12 | 1.223 (2) |
C8—O9 | 1.265 (2) | C11—O13 | 1.325 (2) |
O10—C8—O9 | 123.15 (16) | O12—C11—O13 | 123.33 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
O13—H13A···O10i | 1.04 (3) | 1.61 (3) | 2.6202 (17) | 163 (2) |
N16—H16A···O10i | 0.95 (2) | 1.87 (2) | 2.770 (2) | 156.8 (17) |
N16—H16B···O18ii | 1.02 (2) | 1.85 (2) | 2.826 (2) | 160.6 (18) |
N16—H16C···O9iii | 0.91 (2) | 1.87 (2) | 2.768 (2) | 170 (2) |
O18—H18A···O9iv | 1.05 (3) | 1.71 (3) | 2.7533 (19) | 175 (2) |
O18—H18B···O12 | 0.80 (3) | 2.25 (3) | 3.039 (2) | 170 (3) |
Symmetry codes: (i) x, −y, z+1/2; (ii) −x, y−1, −z+1/2; (iii) x, y−1, z; (iv) x, −y+1, z+1/2. |
Salts of polycarboxylic acids with protonated cations, such as the ammonium and ethylenediammonium, (NH3CH3)22+, ions, often contain extended hydrogen-bonded arrays. The importance of these arrays has been reviewed by Jeffrey & Saenger (1994). Examples from this laboratory include di-, tri- and tetracarboxylates in which the groups linking the acid functions may be rigid (Barnes et al., 1991, 1997) or rotationally unrestricted (Barnes et al., 1996, 1998, 2000).
The structure of cineolic acid, (I), was reported in the previous paper (Barnes & Weakley, 2003). Reaction of (I) with 1,2-diaminoethane in various proportions gave only one product, (II), in which the asymmetric unit is one anion, one water molecule and half a cation. The formation of the acid salt rather than full neutralization is typical of reactions of this type. Frequently, only one of the range of likely salts can be obtained as a solid product regardless of the proportions of components in the solution (Barnes et al., 1996, 1997, 1998, 2000).
Fig. 1 shows that the conformation of the anion in (II) is very similar to the free acid, (I). The deprotonated carboxylate group on C2 is axial, whereas the group on C5 is equatorial with the hydrogen on O13 in (II), whereas (I) has this H atom on O12. The torsion angles O9—C8—C2—O1 and C6—C5—C11—O13 are 141.0 (1) and 87.0 (2)° in (II) compared with 142.26 (7) and 82.90 (7)° in (I). This similarity between acid and anion is unusual. It suggests that the carboxylate groups are not free to rotate about the bonds to C2 and C5 because of intramolecular crowding by the methyl groups. More often, the relative orientation of carboxylate groups is controlled by optimization of the intermolecular hydrogen bonding for each structure. Relatively free rotation in the cation allows the gauche conformation in (II) [N16—C15—C15'-N16' −62.3 (3)°], rather than the staggered conformation seen in, for example, ethyenediammonium bis(hydrogenmalonate) (Barnes et al., 2000). The structure shows no unusual interatomic distances or angles.
The extensive intermolecular hydrogen bonding is shown in Fig. 2. Two layers of anions lying parallel to the bc-plane are crosslinked by cations and water molecules to form a double layer half a unit cell thick in the a direction. Network analysis of this hydrogen bonding by the techniques of Etter (1990) as extended by Bernstein et al. (1995) are unprofitable since the double layer contains many linked pathways including a 32-membered ring. There are only van der Waals' contacts between these double layers.