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In the title compound, 2C10H15O5·C2H10N2·2H2O, the asymmetric unit is one anion, half a cation and one water molecule. The hydrogen cineolate anion has virtually the same conformation as in racemic cineolic acid. The ethyl­enedi­ammonium cation has a gauche conformation and possesses twofold crystallographic rotation symmetry. The anions form hydrogen-bonded layers parallel to the bc plane. Extensive hydrogen bonding to cations and water mol­ecules connects pairs of these layers to form double layers half a unit cell thick.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803007669/cm6039sup1.cif
Contains datablocks II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803007669/cm6039IIsup2.hkl
Contains datablock II

CCDC reference: 214644

Key indicators

  • Single-crystal X-ray study
  • T = 150 K
  • Mean [sigma](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


Yellow Alert 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

Comment top

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.

Experimental top

Crystals were grown by slow evaporation of an aqueous mixture of 1,2-diaminoethane and racemic cineolic acid (1:1).

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The components of (II), showing ellipsoids at the 50% probability level. The anion is shown in a similar orientation to the free acid (Barnes & Weakley, 2003, Fig.1)
[Figure 2] Fig. 2. View down b, edge on to the hydrogen-bonded double layers which are parallel to the bc plane.
Ethylenediammonium bis(tetrahydro-2,6,6-trimethyl-1,4-pyran-2-carboxylate- 5-carboxylic acid) dihydrate top
Crystal data top
2C10H15O5+·C2H10N22·2H2OF(000) = 1144
Mr = 528.60Dx = 1.329 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 26.5948 (14) ÅCell parameters from 5796 reflections
b = 7.9327 (4) Åθ = 2.9–27.5°
c = 12.8480 (9) ŵ = 0.11 mm1
β = 102.938 (2)°T = 150 K
V = 2641.7 (3) Å3Lath, colourless
Z = 40.30 × 0.15 × 0.06 mm
Data collection top
Enraf–Nonius KappaCCD area-detector
diffractometer
2939 independent reflections
Radiation source: Enraf–Nonius FR591 rotating anode1936 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.070
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.1°
ϕ and ω scans to fill Ewald sphereh = 3433
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)
k = 89
Tmin = 0.848, Tmax = 0.997l = 1616
7946 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050Hydrogen site location: mixed
wR(F2) = 0.114H 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 parametersΔρmax = 0.32 e Å3
0 restraintsΔρmin = 0.32 e Å3
Crystal data top
2C10H15O5+·C2H10N22·2H2OV = 2641.7 (3) Å3
Mr = 528.60Z = 4
Monoclinic, C2/cMo Kα radiation
a = 26.5948 (14) ŵ = 0.11 mm1
b = 7.9327 (4) ÅT = 150 K
c = 12.8480 (9) Å0.30 × 0.15 × 0.06 mm
β = 102.938 (2)°
Data collection top
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 = 0.997Rint = 0.070
7946 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0500 restraints
wR(F2) = 0.114H atoms treated by a mixture of independent and constrained refinement
S = 0.98Δρmax = 0.32 e Å3
2939 reflectionsΔρmin = 0.32 e Å3
190 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)

are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.17776 (4)0.19113 (13)0.05254 (9)0.0179 (3)
C20.17173 (7)0.3687 (2)0.06971 (14)0.0166 (4)
C30.17861 (7)0.4075 (2)0.18810 (14)0.0206 (4)
H3A0.21580.40100.22280.027*
H3B0.16700.52440.19620.027*
C40.14897 (7)0.2884 (2)0.24528 (14)0.0207 (4)
H4A0.11150.30820.22000.027*
H4B0.15840.31060.32310.027*
C50.16153 (7)0.1057 (2)0.22367 (13)0.0180 (4)
H50.19930.08760.25200.023*
C60.14901 (7)0.0713 (2)0.10161 (13)0.0174 (4)
C70.21489 (7)0.4519 (2)0.02614 (15)0.0227 (4)
H7A0.24840.41040.06590.030*
H7B0.21330.57450.03440.030*
H7C0.21050.42400.04970.030*
C80.12075 (7)0.4329 (2)0.00223 (14)0.0157 (4)
O90.09373 (4)0.53977 (14)0.03381 (9)0.0209 (3)
O100.11020 (5)0.38281 (14)0.09797 (9)0.0205 (3)
C110.13248 (7)0.0136 (2)0.28120 (13)0.0202 (4)
O120.09053 (5)0.01903 (15)0.30031 (10)0.0249 (3)
O130.15719 (5)0.15752 (15)0.30868 (10)0.0247 (3)
H13A0.1402 (10)0.232 (3)0.358 (2)0.070 (8)*
C140.17137 (8)0.0966 (2)0.07655 (15)0.0251 (4)
H14A0.16720.10790.00090.033*
H14B0.15320.18890.10320.033*
H14C0.20810.10120.11120.033*
C150.09124 (7)0.0769 (2)0.05274 (14)0.0222 (4)
H15A0.07660.18070.07500.029*
H15B0.07450.02090.07710.029*
H15C0.08550.07450.02530.029*
N160.04617 (6)0.44813 (19)0.20454 (14)0.0203 (4)
H16A0.0671 (8)0.457 (2)0.2744 (18)0.035 (6)*
H16B0.0249 (8)0.556 (3)0.1902 (17)0.047 (6)*
H16C0.0642 (9)0.442 (3)0.1527 (19)0.046 (7)*
C170.01222 (7)0.2973 (2)0.20257 (15)0.0228 (4)
H17A0.01510.29790.13600.030*
H17B0.03290.19340.20320.030*
O180.02658 (5)0.29550 (19)0.37143 (12)0.0295 (4)
H18A0.0525 (11)0.352 (3)0.435 (2)0.072 (8)*
H18B0.0399 (12)0.217 (4)0.348 (2)0.091 (12)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0211 (7)0.0133 (6)0.0219 (7)0.0000 (5)0.0102 (6)0.0012 (5)
C20.0175 (9)0.0122 (8)0.0209 (10)0.0008 (7)0.0061 (8)0.0002 (7)
C30.0214 (10)0.0190 (9)0.0204 (10)0.0005 (7)0.0024 (8)0.0001 (7)
C40.0269 (11)0.0185 (9)0.0176 (10)0.0010 (8)0.0068 (8)0.0006 (7)
C50.0173 (10)0.0158 (9)0.0210 (10)0.0001 (7)0.0045 (8)0.0018 (7)
C60.0212 (10)0.0148 (9)0.0182 (10)0.0013 (7)0.0088 (8)0.0023 (7)
C70.0191 (10)0.0197 (10)0.0311 (11)0.0023 (7)0.0093 (8)0.0025 (8)
C80.0178 (9)0.0137 (8)0.0182 (10)0.0043 (7)0.0093 (8)0.0000 (7)
O90.0220 (7)0.0219 (6)0.0214 (7)0.0043 (5)0.0104 (6)0.0000 (5)
O100.0224 (7)0.0216 (6)0.0179 (7)0.0033 (5)0.0055 (5)0.0011 (5)
C110.0272 (11)0.0195 (9)0.0136 (10)0.0023 (8)0.0038 (8)0.0018 (7)
O120.0243 (8)0.0271 (7)0.0263 (8)0.0012 (6)0.0119 (6)0.0027 (5)
O130.0285 (8)0.0209 (7)0.0278 (8)0.0042 (5)0.0129 (6)0.0086 (5)
C140.0350 (12)0.0172 (9)0.0259 (11)0.0017 (8)0.0128 (9)0.0012 (8)
C150.0236 (11)0.0246 (10)0.0188 (10)0.0056 (8)0.0055 (8)0.0003 (8)
N160.0193 (9)0.0253 (9)0.0177 (9)0.0013 (7)0.0072 (8)0.0003 (7)
C170.0193 (10)0.0215 (10)0.0289 (11)0.0006 (8)0.0080 (8)0.0042 (8)
O180.0271 (8)0.0280 (8)0.0307 (9)0.0017 (6)0.0008 (7)0.0012 (6)
Geometric parameters (Å, º) top
O1—C21.4400 (19)C8—O91.265 (2)
O1—C61.4498 (19)C11—O121.223 (2)
C2—C31.522 (2)C11—O131.325 (2)
C2—C71.535 (2)O13—H13A1.04 (3)
C2—C81.546 (2)C14—H14A0.9800
C3—C41.521 (2)C14—H14B0.9800
C3—H3A0.9900C14—H14C0.9800
C3—H3B0.9900C15—H15A0.9800
C4—C51.527 (2)C15—H15B0.9800
C4—H4A0.9900C15—H15C0.9800
C4—H4B0.9900N16—C171.496 (2)
C5—C111.515 (2)N16—H16A0.95 (2)
C5—C61.553 (2)N16—H16B1.02 (2)
C5—H51.0000N16—H16C0.91 (2)
C6—C141.522 (2)C17—C17i1.504 (3)
C6—C151.525 (2)C17—H17A0.9900
C7—H7A0.9800C17—H17B0.9900
C7—H7B0.9800O18—H18A1.05 (3)
C7—H7C0.9800O18—H18B0.80 (3)
C8—O101.263 (2)
C2—O1—C6119.16 (12)H7A—C7—H7C109.5
O1—C2—C3110.99 (13)H7B—C7—H7C109.5
O1—C2—C7104.30 (13)O10—C8—O9123.15 (16)
C3—C2—C7110.18 (14)O10—C8—C2116.91 (14)
O1—C2—C8110.09 (13)O9—C8—C2119.75 (15)
C3—C2—C8115.08 (14)O12—C11—O13123.33 (16)
C7—C2—C8105.52 (14)O12—C11—C5123.60 (16)
C4—C3—C2113.43 (14)O13—C11—C5113.07 (15)
C4—C3—H3A108.9C11—O13—H13A113.3 (14)
C2—C3—H3A108.9C6—C14—H14A109.5
C4—C3—H3B108.9C6—C14—H14B109.5
C2—C3—H3B108.9H14A—C14—H14B109.5
H3A—C3—H3B107.7C6—C14—H14C109.5
C3—C4—C5110.09 (14)H14A—C14—H14C109.5
C3—C4—H4A109.6H14B—C14—H14C109.5
C5—C4—H4A109.6C6—C15—H15A109.5
C3—C4—H4B109.6C6—C15—H15B109.5
C5—C4—H4B109.6H15A—C15—H15B109.5
H4A—C4—H4B108.2C6—C15—H15C109.5
C11—C5—C4110.38 (14)H15A—C15—H15C109.5
C11—C5—C6111.42 (14)H15B—C15—H15C109.5
C4—C5—C6110.17 (13)C17—N16—H16A107.6 (12)
C11—C5—H5108.3C17—N16—H16B111.0 (12)
C4—C5—H5108.3H16A—N16—H16B107.0 (17)
C6—C5—H5108.3C17—N16—H16C111.1 (14)
O1—C6—C14102.30 (13)H16A—N16—H16C114.0 (19)
O1—C6—C15112.49 (13)H16B—N16—H16C106.2 (18)
C14—C6—C15110.12 (15)N16—C17—C17i110.79 (13)
O1—C6—C5107.99 (13)N16—C17—H17A109.5
C14—C6—C5111.23 (14)C17i—C17—H17A109.5
C15—C6—C5112.28 (14)N16—C17—H17B109.5
C2—C7—H7A109.5C17i—C17—H17B109.5
C2—C7—H7B109.5H17A—C17—H17B108.1
H7A—C7—H7B109.5H18A—O18—H18B111 (3)
C2—C7—H7C109.5
O9—C8—C2—O1140.97 (14)O1—C6—C5—C11179.43 (13)
C8—C2—O1—C678.14 (17)C6—C5—C11—O1387.03 (18)
C2—O1—C6—C555.42 (18)N16—C17—C17i—N16i62.3 (3)
Symmetry code: (i) x, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O13—H13A···O10ii1.04 (3)1.61 (3)2.6202 (17)163 (2)
N16—H16A···O10ii0.95 (2)1.87 (2)2.770 (2)156.8 (17)
N16—H16B···O18iii1.02 (2)1.85 (2)2.826 (2)160.6 (18)
N16—H16C···O9iv0.91 (2)1.87 (2)2.768 (2)170 (2)
O18—H18A···O9v1.05 (3)1.71 (3)2.7533 (19)175 (2)
O18—H18B···O120.80 (3)2.25 (3)3.039 (2)170 (3)
Symmetry codes: (ii) x, y, z+1/2; (iii) x, y1, z+1/2; (iv) x, y1, z; (v) x, y+1, z+1/2.

Experimental details

Crystal data
Chemical formula2C10H15O5+·C2H10N22·2H2O
Mr528.60
Crystal system, space groupMonoclinic, C2/c
Temperature (K)150
a, b, c (Å)26.5948 (14), 7.9327 (4), 12.8480 (9)
β (°) 102.938 (2)
V3)2641.7 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.11
Crystal size (mm)0.30 × 0.15 × 0.06
Data collection
DiffractometerEnraf–Nonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(SORTAV; Blessing, 1995)
Tmin, Tmax0.848, 0.997
No. of measured, independent and
observed [I > 2σ(I)] reflections
7946, 2939, 1936
Rint0.070
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.050, 0.114, 0.98
No. of reflections2939
No. of parameters190
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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.

Selected geometric parameters (Å, º) top
C8—O101.263 (2)C11—O121.223 (2)
C8—O91.265 (2)C11—O131.325 (2)
O10—C8—O9123.15 (16)O12—C11—O13123.33 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O13—H13A···O10i1.04 (3)1.61 (3)2.6202 (17)163 (2)
N16—H16A···O10i0.95 (2)1.87 (2)2.770 (2)156.8 (17)
N16—H16B···O18ii1.02 (2)1.85 (2)2.826 (2)160.6 (18)
N16—H16C···O9iii0.91 (2)1.87 (2)2.768 (2)170 (2)
O18—H18A···O9iv1.05 (3)1.71 (3)2.7533 (19)175 (2)
O18—H18B···O120.80 (3)2.25 (3)3.039 (2)170 (3)
Symmetry codes: (i) x, y, z+1/2; (ii) x, y1, z+1/2; (iii) x, y1, z; (iv) x, y+1, z+1/2.
 

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