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Acta Cryst. (2007). E63, o3809    [ doi:10.1107/S1600536807039426 ]

N,N'-Bis(3,4-methenedioxybenzyl)ethane-1,2-diammonium dinitrate: hydrogen-bonded chains of rings

S.-P. Yang, D.-Q. Wang, L.-J. Han and H.-T. Xia

Abstract top

In the title compound, C18H22N2O42+·2NO3-, the cation is centrosymmetric. The asymmetric unit consists of one half-cation and one anion. The molecules are linked by N-H...O and C-H...O hydrogen bonds and by dipolar O-C...O-C interactions, forming a chain of edge-fused R44(18) rings and a chain of R22(4) rings.

Comment top

The crystal of the compound (I), was obtained unexpectedly in the prepartion of a lanthanum complex with N,N'-bis (3,4-methenedioxybenzyl)ethane-1,2-diamine. Here, we report the crystal structure and supramolecular arrangement of (I), (Fig.1).

In the supramolecular arrangement of (I), the reference molecule is selected to lie across a center of inversion (1/2, 0, 0) in monoclinic space group C2/c, the asymmetric unit contains of one half–cation and one anion, cation and anion are linked by N—H···O [H1···O3 = 1.89 (4) Å, N1—H1A···O3 =175 °] hydrogen bonds (Table1).

In the crystal structure of (I), the molecules are linked by N—H···O [H1b···O4ii = 1.98 Å, N1—H1b···O4ii = 173°, symmetry codes: (ii) x, −1 + y, z] hydrogen bonds, the amino N1 atoms at (x, y, z) and (1 − x, −y, −z) in the molecules centred at (1/2, 0, 0) act as hydrogen-bond donors, via H1b, to the nitrate O4 atoms at (x, −1 + y, z) and (1 − x, 1 − y, −z), respectively, which themselves are parts of the molecules centred at (1/2, −1, 0) and (1/2, 1, 0), respectively (Fig. 2). Propagation by translation of this two hydrogen bonds along [010] direction then generates a chain of edge-fused R44(18) rings (Bernstein et al., 1995) running along (1/2,y,0) axis (Fig. 2).

The molecules are linked by dipolar O—C···O—C [C9—O2i = 3.101 (5) Å, O2—C9···O2i = 77.5 (2)°; symmetry codes: (i) 1/2 − x, 3/2 − y, −z] interactions (Bondi, 1964) into a chain of R22(4) rings, the atom C9 at (x, y, z) in the cation centred at (1/2, 0, 0) act as donor to O2 at (1/2 − x, 3/2 − y, −z) in the cation centred at (0, 3/2, 0), generating a chain of R22(4) rings along [1 3 0] (Fig. 3). The combination of the [0 1 0] chain and the [1 3 0] chain generates a [0 0 1] sheet. Adjacent sheets were linked by the further N—H···O and C—H···O hydrogen bonds and the crystal sturecture was stabilized (Table. 1).

Related literature top

For related literature, see: Bernstein et al. (1995); Bondi (1964).

Experimental top

To a solution containing N,N'-bis(4-chlorobenzyl)ethane-1,2-diamine (1.71 g, 5 mmol) and ethanol 30 ml, a solution of lanthanum nitrate (1.08 g, 5 mmol) and methanol (10 ml) was added with stirring for 3 h at 333 K, and then the white solid obtained was filtered off, washed with ethanol in proper order and dried at room temperture. Colourless crystal of (I) suitatble for X-ray structure analysis were obtained by slow evaporation from the solution of DMF-EtOH(1:3) over a period of one month (m.p. 501 − 503 K).

Refinement top

All H atoms were positioned geometrically and refined as riding on their parent atoms, with N—H = 0.90 Å, C—H = 0.93 − 0.97Å and Uiso(H) = 1.2Ueq(C, N) for all H atoms.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecule of compound (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry position: (*) 1 − x, −y, −z].
[Figure 2] Fig. 2. A view of part of the crystal structure of (I), showing the formation of a chain of edge-fused R44(18) rings along [010]. For the sake of clarity, H atoms not involved in the motif shown have been omitted·[Symmetry position: (*) 1 − x, −y, −z; (#) 1 − x, 1 − y, −z; ($) 1 − x, −1 − y, −z; (&) x, −1 + y, z; (@) z, 1 + y, z].
[Figure 3] Fig. 3. A stereoview of part of the crystal structure of (I), showing the formation of a chain R22(4) rings along [1 3 0] by dipolar O—C···O—C interactions. For the sake of clarity, H atoms and nitrate not involved in the motif shown have been omitted.
N,N'-Bis(3,4-methenedioxybenzyl)ethane-1,2-diammonium dinitrate top
Crystal data top
C18H22N2O42+·2NO3–F000 = 952
Mr = 454.40Dx = 1.454 Mg m−3
Monoclinic, C2/cMelting point: 501 K
Hall symbol: -C 2ycMo Kα radiation
λ = 0.71073 Å
a = 33.590 (3) ÅCell parameters from 1077 reflections
b = 5.6421 (8) Åθ = 2.5–21.3º
c = 11.4747 (15) ŵ = 0.12 mm−1
β = 107.326 (2)ºT = 298 (2) K
V = 2076.0 (4) Å3Needle, colourless
Z = 40.35 × 0.18 × 0.09 mm
Data collection top
Siemens SMART 1000 CCD area-detector
diffractometer		1822 independent reflections
Radiation source: fine-focus sealed tube1018 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.046
T = 298(2) Kθmax = 25.0º
φ and ω scansθmin = 2.5º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −39→38
Tmin = 0.959, Tmax = 0.989k = −6→5
4705 measured reflectionsl = −10→13
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.053  w = 1/[σ2(Fo2) + (0.0539P)2 + 2.9489P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.165(Δ/σ)max < 0.001
S = 1.07Δρmax = 0.23 e Å−3
1822 reflectionsΔρmin = −0.21 e Å−3
146 parametersExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0061 (10)
Secondary atom site location: difference Fourier map
Crystal data top
C18H22N2O42+·2NO3–V = 2076.0 (4) Å3
Mr = 454.40Z = 4
Monoclinic, C2/cMo Kα
a = 33.590 (3) ŵ = 0.12 mm−1
b = 5.6421 (8) ÅT = 298 (2) K
c = 11.4747 (15) Å0.35 × 0.18 × 0.09 mm
β = 107.326 (2)º
Data collection top
Siemens SMART 1000 CCD area-detector
diffractometer		1822 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1018 reflections with I > 2σ(I)
Tmin = 0.959, Tmax = 0.989Rint = 0.046
4705 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.053146 parameters
wR(F2) = 0.165H-atom parameters constrained
S = 1.07Δρmax = 0.23 e Å−3
1822 reflectionsΔρmin = −0.21 e Å−3
Special details top

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

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(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
N10.44318 (7)0.0350 (5)−0.0179 (2)0.0396 (7)
H1A0.44390.18900.00310.048*
H1B0.4436−0.05120.04850.048*
O10.29689 (9)0.6277 (5)−0.1979 (3)0.0838 (10)
O20.27695 (9)0.5442 (6)−0.0269 (3)0.0860 (10)
C10.48103 (9)−0.0207 (6)−0.0538 (3)0.0411 (8)
H1C0.48220.0796−0.12140.049*
H1D0.4802−0.1846−0.07990.049*
C20.40307 (10)−0.0125 (6)−0.1155 (3)0.0484 (9)
H2A0.3969−0.1807−0.11830.058*
H2B0.40570.0339−0.19430.058*
C30.36803 (10)0.1246 (6)−0.0901 (3)0.0452 (9)
C40.35020 (11)0.3134 (6)−0.1661 (3)0.0512 (9)
H40.35880.3530−0.23360.061*
C50.31951 (11)0.4381 (7)−0.1368 (3)0.0539 (10)
C60.30722 (11)0.3863 (8)−0.0360 (4)0.0582 (10)
C70.32454 (13)0.2067 (8)0.0397 (4)0.0753 (13)
H70.31630.17310.10850.090*
C80.35531 (12)0.0730 (8)0.0106 (4)0.0667 (12)
H80.3675−0.05360.06040.080*
C90.26771 (15)0.6847 (10)−0.1333 (4)0.0871 (15)
H9A0.26980.8514−0.11170.105*
H9B0.23950.6532−0.18430.105*
N20.44342 (9)0.5341 (5)0.1477 (3)0.0540 (8)
O40.43900 (10)0.7387 (5)0.1821 (2)0.0763 (9)
O30.45031 (9)0.5127 (4)0.0471 (2)0.0678 (8)
O50.44070 (12)0.3594 (6)0.2065 (3)0.0978 (12)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0423 (15)0.0344 (15)0.0444 (15)0.0047 (12)0.0163 (12)−0.0011 (12)
O10.096 (2)0.084 (2)0.080 (2)0.0439 (18)0.0395 (17)0.0151 (17)
O20.0779 (19)0.104 (2)0.088 (2)0.0396 (19)0.0425 (17)0.0074 (19)
C10.0415 (17)0.0417 (19)0.0437 (19)0.0037 (15)0.0182 (14)−0.0014 (16)
C20.0429 (19)0.052 (2)0.049 (2)0.0025 (17)0.0108 (16)−0.0046 (17)
C30.0398 (18)0.053 (2)0.0442 (19)0.0016 (17)0.0147 (15)−0.0011 (17)
C40.055 (2)0.052 (2)0.051 (2)0.0077 (19)0.0211 (17)0.0013 (18)
C50.050 (2)0.054 (2)0.054 (2)0.0115 (19)0.0100 (18)0.0003 (19)
C60.045 (2)0.074 (3)0.061 (2)0.014 (2)0.0248 (18)0.000 (2)
C70.069 (3)0.095 (3)0.075 (3)0.022 (3)0.042 (2)0.021 (3)
C80.062 (2)0.083 (3)0.063 (3)0.020 (2)0.030 (2)0.023 (2)
C90.082 (3)0.101 (4)0.083 (3)0.039 (3)0.032 (3)0.002 (3)
N20.068 (2)0.0422 (19)0.0523 (19)−0.0006 (16)0.0184 (16)0.0017 (16)
O40.122 (2)0.0514 (18)0.0619 (17)0.0111 (17)0.0375 (17)−0.0130 (14)
O30.109 (2)0.0419 (15)0.0667 (17)−0.0004 (15)0.0480 (16)−0.0029 (13)
O50.164 (3)0.060 (2)0.074 (2)−0.010 (2)0.043 (2)0.0233 (16)
Geometric parameters (Å, °) top
N1—C11.483 (4)C3—C41.394 (5)
N1—C21.498 (4)C4—C51.370 (5)
N1—H1A0.9000C4—H40.9300
N1—H1B0.9000C5—C61.371 (5)
O1—C51.377 (4)C6—C71.348 (5)
O1—C91.430 (5)C7—C81.398 (5)
O2—C61.379 (4)C7—H70.9300
O2—C91.411 (5)C8—H80.9300
C1—C1i1.506 (6)C9—O2ii3.101 (5)
C1—H1C0.9700C9—H9A0.9700
C1—H1D0.9700C9—H9B0.9700
C2—C31.508 (4)N2—O51.213 (4)
C2—H2A0.9700N2—O41.243 (4)
C2—H2B0.9700N2—O31.250 (3)
C3—C81.377 (5)
C1—N1—C2114.1 (2)C4—C5—C6122.4 (4)
C1—N1—H1A108.7C4—C5—O1128.0 (3)
C2—N1—H1A108.7C6—C5—O1109.6 (3)
C1—N1—H1B108.7C7—C6—C5121.5 (3)
C2—N1—H1B108.7C7—C6—O2128.6 (4)
H1A—N1—H1B107.6C5—C6—O2109.9 (4)
C5—O1—C9105.7 (3)C6—C7—C8117.4 (4)
C6—O2—C9106.0 (3)C6—C7—H7121.3
N1—C1—C1i109.0 (3)C8—C7—H7121.3
N1—C1—H1C109.9C3—C8—C7121.5 (4)
C1i—C1—H1C109.9C3—C8—H8119.3
N1—C1—H1D109.9C7—C8—H8119.3
C1i—C1—H1D109.9O2—C9—O1108.3 (3)
H1C—C1—H1D108.3O2—C9—O2ii77.5 (2)
N1—C2—C3110.1 (3)O1—C9—O2ii161.0 (4)
N1—C2—H2A109.6O2—C9—H9A110.0
C3—C2—H2A109.6O1—C9—H9A110.0
N1—C2—H2B109.6O2ii—C9—H9A51.7
C3—C2—H2B109.6O2—C9—H9B110.0
H2A—C2—H2B108.2O1—C9—H9B110.0
C8—C3—C4120.3 (3)O2ii—C9—H9B83.7
C8—C3—C2120.6 (3)H9A—C9—H9B108.4
C4—C3—C2119.0 (3)O5—N2—O4122.9 (3)
C5—C4—C3116.9 (3)O5—N2—O3120.0 (3)
C5—C4—H4121.5O4—N2—O3117.1 (3)
C3—C4—H4121.5
C2—N1—C1—C1i−176.7 (3)O1—C5—C6—O2−1.4 (5)
C1—N1—C2—C3−160.1 (3)C9—O2—C6—C7−175.8 (5)
N1—C2—C3—C8−65.9 (4)C9—O2—C6—C55.5 (5)
N1—C2—C3—C4110.5 (3)C5—C6—C7—C8−0.7 (6)
C8—C3—C4—C5−1.3 (5)O2—C6—C7—C8−179.2 (4)
C2—C3—C4—C5−177.7 (3)C4—C3—C8—C7−0.1 (6)
C3—C4—C5—C61.7 (5)C2—C3—C8—C7176.3 (4)
C3—C4—C5—O1−179.0 (4)C6—C7—C8—C31.1 (6)
C9—O1—C5—C4177.3 (4)C6—O2—C9—O1−7.5 (5)
C9—O1—C5—C6−3.3 (4)C6—O2—C9—O2ii−168.7 (3)
C4—C5—C6—C7−0.7 (6)C5—O1—C9—O26.6 (5)
O1—C5—C6—C7179.8 (4)C5—O1—C9—O2ii111.8 (9)
C4—C5—C6—O2178.0 (3)
Symmetry codes: (i) −x+1, −y, −z; (ii) −x+1/2, −y+3/2, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1a···O30.901.892.787 (3)175.1
N1—H1b···O4iii0.901.982.876 (4)173.3
N1—H1a···O50.902.563.180 (4)127.1
C1—H1d···O5iv0.972.613.291 (4)127.6
N1—H1b···O3iii0.902.473.032 (4)120.8
C1—H1d···O3iii0.972.633.170 (4)115.4
C2—H2b···O4v0.972.423.302 (4)151.2
C1—H1c···O4v0.972.513.340 (4)143.8
Symmetry codes: (iii) x, y−1, z; (iv) x, −y, z−1/2; (v) x, −y+1, z−1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1a···O30.901.892.787 (3)175.1
N1—H1b···O4i0.901.982.876 (4)173.3
N1—H1a···O50.902.563.180 (4)127.1
C1—H1d···O5ii0.972.613.291 (4)127.6
N1—H1b···O3i0.902.473.032 (4)120.8
C1—H1d···O3i0.972.633.170 (4)115.4
C2—H2b···O4iii0.972.423.302 (4)151.2
C1—H1c···O4iii0.972.513.340 (4)143.8
Symmetry codes: (i) x, y−1, z; (ii) x, −y, z−1/2; (iii) x, −y+1, z−1/2.
Acknowledgements top

We acknowledge the financial support of the Huaihai Institute of Technology Science Foundation.

references
References top

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.

Bondi, A. (1964). J. Phys. Chem. 68, 441–451.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997a). SHELXL97 and SHELXS97. University of Göttingen,Germany.

Sheldrick, G. M. (1997b). SHELXTL. Version 5.10. Bruker AXS Inc., Madison, Wisconsin, USA.

Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.