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The cation of the title compound, C16H22N22+·2NO3, resides on a crystallographic inversion centre (at the mid-point of the central C—C bond), with the nitrate anion on a general position. The ions are linked into chains by N—H...O hydrogen bonds and adjacent chains are further linked into sheets in the ab plane.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807039736/gg3117sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807039736/gg3117Isup2.hkl
Contains datablock I

CCDC reference: 635370

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.009 Å
  • R factor = 0.072
  • wR factor = 0.215
  • Data-to-parameter ratio = 14.2

checkCIF/PLATON results

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Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 3.36 Ratio PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.40 Ratio PLAT230_ALERT_2_C Hirshfeld Test Diff for C6 - C7 .. 5.20 su PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C5 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C7 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C3 PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for N2 PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.01 PLAT332_ALERT_2_C Large Phenyl C-C Range C3 -C8 0.20 Ang. PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 9
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 11 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 7 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

We have recently reported crystal structures of diamine derivatives, for example, N,N'-bis(2-hydroxy-3-methoxybenzyl) ethane-1,2-diamine (Xia et al., 2006), N,N'-bis(2-hydroxy-3-methoxybenzyl) propane-1,2-diamine (Xia et al., 2007). We have now continued our studied in this area with the title compound, (I). We compare the supramolecular aggregation in (I) with that in the analogous compound (II), a o-vanillin ethylenediamine nitrate (Liu et al., 2007). In (II), the asymmetric unit consists of one cation, two half-cations and four anions in the space group P1, and the cations are linked into two chains by C—H···O hydrogen bonds: the nitrate anions linking two chains into a sheet parallel to the [001] plane.

In (I), the asymmetric unit consists of one half-cation and one anion. The cation has a inversion centre of at the mid-point of the central C—C bond (Fig. 1). The bond lengths and angles are normal (Allen et al., 1987). The molecules are linked into a complex three-dimensional framework by a combination of N—H···O, C—H···O and C—H···π hydrogen bonds (Table 2). However, the formation of the structure of (I) can be analysed in terms of two one-dimensional and one two-dimensional substructures.

In the first substructure, atoms N1 in the molecule at (x, y, z) and (1 + x, y, z) act as hydrogen-bond donors to nitrate atoms O1, O2 and O3 in the molecule at (x, y, z), respectively, and propagation by inversion and translation of these three hydrogen bonds generates a chain of rings parallel to the a axis direction, with R44(18) rings (Bernstein et al., 1995) surrounds an R42(14) ring centred at (n, 1, 0) (n = zero or integer) (Fig. 2).

In the second substructure, atoms C1 and C2 in the molecule at (x,-1 + y,z) act as hydrogen-bond donors, respectively, to nitro atoms O2 in the molecule at (x, y, z) and O3 in the molecule at (-1 + x, y, z), at the same time, atom N1 at (x, y, z) acts as a hydrogen-bond donor to nitro atom O1 in the molecule at (-1 + x, y, z), so generating by a inversion centrosymmetric R44 (20) motif centred at (1/2, 1/2, 0). Propagation by inversion and translation of these three hydrogen bonds generates a chain parallel to the b axis direction containing R44 (20) ring centred at (1/2, 1/2 + n, 0) (n = zero or integer) (Fig. 3). The combination of the a and b chains generates a sheet runing parallel to [001] plane.

The action of the two-dimensional substructure is to link adjacent cations into [100] sheets. Atom C6 in the molecule at (x, y, z) acts as a hydrogen-bond donor to Cg (aryl ring C3—C8) in the molecule at (1 - x, -1/2 + y, 1/2 - z), so forming a sheet running parallel to the [100] plane, and geneated by the 21 screw axis along (1/2, y, 1/4) and by the n-glide plane at y = 1/2 (Fig. 4). The combination of the [001] and [100] sheets suffices to generate the three-dimensional framework structure. Hence it can be seen that the direction specific intermolecular interactions in compounds (I) and (II) are different, leading to markedly different supramolecular structures.

Related literature top

For related literature, see: Allen et al. (1987); Bernstein et al. (1995); Liu et al. (2007); Xia et al. (2006, 2007).

Experimental top

To a solution of N,N'-dibenzylethane-1,2-diamine (2 mmol) in methanol (20 ml) was added a solution of zinc(II) nitrate (1 mmol) in methanol (10 ml). The mixed solution was stirred for 4 h and then filtered. The solution was allowed to stand, slowly producing crystals of (I).

Refinement top

The space group was uniquely assigned from the systematic absences. All H atoms were located in difference Fourier maps. H atoms bonded to C and N atoms were treated as riding atoms, with C—H distances of 0.93 Å (aryl), 0.97 Å (methylene), N—H distances of 0.90 Å (amine), and with Uiso(H) = 1.2Ueq(C,N) (aryl, methylene, amine).

Structure description top

We have recently reported crystal structures of diamine derivatives, for example, N,N'-bis(2-hydroxy-3-methoxybenzyl) ethane-1,2-diamine (Xia et al., 2006), N,N'-bis(2-hydroxy-3-methoxybenzyl) propane-1,2-diamine (Xia et al., 2007). We have now continued our studied in this area with the title compound, (I). We compare the supramolecular aggregation in (I) with that in the analogous compound (II), a o-vanillin ethylenediamine nitrate (Liu et al., 2007). In (II), the asymmetric unit consists of one cation, two half-cations and four anions in the space group P1, and the cations are linked into two chains by C—H···O hydrogen bonds: the nitrate anions linking two chains into a sheet parallel to the [001] plane.

In (I), the asymmetric unit consists of one half-cation and one anion. The cation has a inversion centre of at the mid-point of the central C—C bond (Fig. 1). The bond lengths and angles are normal (Allen et al., 1987). The molecules are linked into a complex three-dimensional framework by a combination of N—H···O, C—H···O and C—H···π hydrogen bonds (Table 2). However, the formation of the structure of (I) can be analysed in terms of two one-dimensional and one two-dimensional substructures.

In the first substructure, atoms N1 in the molecule at (x, y, z) and (1 + x, y, z) act as hydrogen-bond donors to nitrate atoms O1, O2 and O3 in the molecule at (x, y, z), respectively, and propagation by inversion and translation of these three hydrogen bonds generates a chain of rings parallel to the a axis direction, with R44(18) rings (Bernstein et al., 1995) surrounds an R42(14) ring centred at (n, 1, 0) (n = zero or integer) (Fig. 2).

In the second substructure, atoms C1 and C2 in the molecule at (x,-1 + y,z) act as hydrogen-bond donors, respectively, to nitro atoms O2 in the molecule at (x, y, z) and O3 in the molecule at (-1 + x, y, z), at the same time, atom N1 at (x, y, z) acts as a hydrogen-bond donor to nitro atom O1 in the molecule at (-1 + x, y, z), so generating by a inversion centrosymmetric R44 (20) motif centred at (1/2, 1/2, 0). Propagation by inversion and translation of these three hydrogen bonds generates a chain parallel to the b axis direction containing R44 (20) ring centred at (1/2, 1/2 + n, 0) (n = zero or integer) (Fig. 3). The combination of the a and b chains generates a sheet runing parallel to [001] plane.

The action of the two-dimensional substructure is to link adjacent cations into [100] sheets. Atom C6 in the molecule at (x, y, z) acts as a hydrogen-bond donor to Cg (aryl ring C3—C8) in the molecule at (1 - x, -1/2 + y, 1/2 - z), so forming a sheet running parallel to the [100] plane, and geneated by the 21 screw axis along (1/2, y, 1/4) and by the n-glide plane at y = 1/2 (Fig. 4). The combination of the [001] and [100] sheets suffices to generate the three-dimensional framework structure. Hence it can be seen that the direction specific intermolecular interactions in compounds (I) and (II) are different, leading to markedly different supramolecular structures.

For related literature, see: Allen et al. (1987); Bernstein et al. (1995); Liu et al. (2007); Xia et al. (2006, 2007).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SMART (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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 (Sheldrick, 1997b).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with the atom-labelling scheme. Displacement ellipsoids are at the 30% probability level. Unlabelled atoms in the N1 cation are related to labelled atoms by (1 - x,2 - y,-z).
[Figure 2] Fig. 2. A large part of the crystal structure of (I), showing the formation of a hydrogen-bonded chain built from N—H···O. For clarity, H atomes not involved in the hydrogen bonding have been omitted. Dashed lines indicate hydrogen bonds: [symmetry code: (A) 1 + x, y, z].
[Figure 3] Fig. 3. A large part of the crystal structure of (I), showing the formation of a hydrogen-bonded chain built from N—H···O and C—H···O. For clarity, H atomes not involved in the hydrogen bonding have been omitted. Dashed lines indicate hydrogen bonds. [symmetry code: (B) x,-1 + y,z, (C) -1 + x,y,z].
[Figure 4] Fig. 4. The crystal structure of (I). Neighboring chains are connected by C—H···π hydrogen bonds. For clarty, H atomes not involved in the hydrogen bonding have been omitted. Dashed lines indicate hydrogen bonds. [symmetry code: (D) 1 - x,-1/2 + y,1/2 - z].
N,N'-Dibenzylethane-1,2-diammonium dinitrate top
Crystal data top
C16H22N22+·2NO3F(000) = 388
Mr = 366.38Dx = 1.265 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 995 reflections
a = 5.7889 (15) Åθ = 2.7–22.8°
b = 5.5654 (14) ŵ = 0.10 mm1
c = 29.858 (3) ÅT = 293 K
β = 91.638 (3)°Block, colourless
V = 961.5 (4) Å30.58 × 0.23 × 0.09 mm
Z = 2
Data collection top
Siemens SMART 1000 CCD area-detector
diffractometer
1676 independent reflections
Radiation source: fine-focus sealed tube942 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.060
φ and ω scansθmax = 25.0°, θmin = 1.4°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 66
Tmin = 0.945, Tmax = 0.991k = 66
4707 measured reflectionsl = 3135
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)] = 0.072Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.215H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.1189P)2]
where P = (Fo2 + 2Fc2)/3
1676 reflections(Δ/σ)max < 0.001
118 parametersΔρmax = 0.37 e Å3
0 restraintsΔρmin = 0.21 e Å3
Crystal data top
C16H22N22+·2NO3V = 961.5 (4) Å3
Mr = 366.38Z = 2
Monoclinic, P21/cMo Kα radiation
a = 5.7889 (15) ŵ = 0.10 mm1
b = 5.5654 (14) ÅT = 293 K
c = 29.858 (3) Å0.58 × 0.23 × 0.09 mm
β = 91.638 (3)°
Data collection top
Siemens SMART 1000 CCD area-detector
diffractometer
1676 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
942 reflections with I > 2σ(I)
Tmin = 0.945, Tmax = 0.991Rint = 0.060
4707 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0720 restraints
wR(F2) = 0.215H-atom parameters constrained
S = 1.02Δρmax = 0.37 e Å3
1676 reflectionsΔρmin = 0.21 e Å3
118 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. 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
N10.4744 (4)0.9458 (4)0.06168 (7)0.0488 (7)
H1A0.32810.89090.06070.059*
H1B0.56900.81740.06260.059*
N20.9771 (5)0.6263 (5)0.05954 (9)0.0599 (8)
O10.9957 (4)0.8469 (4)0.05704 (9)0.0742 (8)
O20.7799 (5)0.5400 (4)0.06156 (10)0.0882 (9)
O31.1532 (5)0.5046 (4)0.05864 (12)0.1054 (11)
C10.5158 (5)1.0821 (5)0.01998 (9)0.0478 (8)
H1C0.67141.14680.02090.057*
H1D0.40811.21540.01740.057*
C20.5114 (6)1.0864 (5)0.10331 (11)0.0617 (9)
H2A0.42191.23360.10140.074*
H2B0.67331.12950.10660.074*
C30.4409 (7)0.9453 (7)0.14330 (12)0.0719 (10)
C40.2417 (10)0.9825 (12)0.16382 (17)0.132 (2)
H40.14061.10260.15400.158*
C50.1848 (15)0.827 (2)0.2029 (2)0.161 (3)
H50.04990.84470.21870.194*
C60.347 (2)0.656 (2)0.2133 (3)0.159 (3)
H60.31490.55650.23740.191*
C70.5403 (19)0.6153 (13)0.1939 (2)0.152 (3)
H70.64200.49520.20340.182*
C80.5840 (11)0.7599 (9)0.15861 (14)0.1118 (17)
H80.71990.73320.14350.134*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0431 (14)0.0402 (12)0.0633 (16)0.0065 (10)0.0058 (11)0.0016 (12)
N20.0537 (18)0.0480 (16)0.0781 (19)0.0011 (14)0.0037 (13)0.0052 (14)
O10.0509 (15)0.0458 (13)0.126 (2)0.0046 (10)0.0056 (13)0.0070 (13)
O20.0651 (17)0.0567 (14)0.143 (2)0.0189 (13)0.0094 (15)0.0008 (15)
O30.0756 (19)0.0674 (16)0.174 (3)0.0276 (14)0.0076 (18)0.0031 (17)
C10.0504 (17)0.0350 (14)0.0584 (18)0.0032 (13)0.0059 (14)0.0043 (13)
C20.075 (2)0.0476 (17)0.063 (2)0.0073 (16)0.0040 (16)0.0075 (16)
C30.074 (3)0.082 (3)0.060 (2)0.023 (2)0.0055 (19)0.009 (2)
C40.109 (4)0.205 (6)0.082 (3)0.028 (4)0.033 (3)0.033 (4)
C50.123 (6)0.261 (10)0.102 (5)0.062 (6)0.040 (4)0.034 (6)
C60.177 (8)0.191 (8)0.112 (5)0.077 (7)0.036 (6)0.005 (5)
C70.238 (9)0.132 (5)0.085 (4)0.005 (6)0.004 (5)0.021 (4)
C80.176 (5)0.095 (3)0.064 (3)0.009 (3)0.003 (3)0.015 (3)
Geometric parameters (Å, º) top
N1—C21.479 (4)C2—H2B0.9700
N1—C11.484 (3)C3—C41.337 (6)
N1—H1A0.9000C3—C81.392 (6)
N1—H1B0.9000C4—C51.498 (10)
N2—O31.225 (3)C4—H40.9300
N2—O11.235 (3)C5—C61.367 (11)
N2—O21.241 (3)C5—H50.9300
C1—C1i1.510 (6)C6—C71.294 (11)
C1—H1C0.9700C6—H60.9300
C1—H1D0.9700C7—C81.355 (8)
C2—C31.496 (5)C7—H70.9300
C2—H2A0.9700C8—H80.9300
C2—N1—C1114.3 (2)H2A—C2—H2B108.0
C2—N1—H1A108.7C4—C3—C8118.5 (5)
C1—N1—H1A108.7C4—C3—C2122.9 (5)
C2—N1—H1B108.7C8—C3—C2118.6 (4)
C1—N1—H1B108.7C3—C4—C5118.6 (7)
H1A—N1—H1B107.6C3—C4—H4120.7
O3—N2—O1118.4 (3)C5—C4—H4120.7
O3—N2—O2123.6 (3)C6—C5—C4114.5 (7)
O1—N2—O2118.0 (3)C6—C5—H5122.7
N1—C1—C1i109.5 (3)C4—C5—H5122.7
N1—C1—H1C109.8C7—C6—C5128.0 (8)
C1i—C1—H1C109.8C7—C6—H6116.0
N1—C1—H1D109.8C5—C6—H6116.0
C1i—C1—H1D109.8C6—C7—C8115.4 (8)
H1C—C1—H1D108.2C6—C7—H7122.3
N1—C2—C3110.9 (2)C8—C7—H7122.3
N1—C2—H2A109.5C7—C8—C3124.9 (6)
C3—C2—H2A109.5C7—C8—H8117.5
N1—C2—H2B109.5C3—C8—H8117.5
C3—C2—H2B109.5
C2—N1—C1—C1i177.3 (3)C3—C4—C5—C60.7 (9)
C1—N1—C2—C3173.6 (3)C4—C5—C6—C70.3 (12)
N1—C2—C3—C4102.3 (4)C5—C6—C7—C80.6 (12)
N1—C2—C3—C874.7 (4)C6—C7—C8—C31.3 (9)
C8—C3—C4—C51.4 (7)C4—C3—C8—C71.8 (7)
C2—C3—C4—C5178.4 (4)C2—C3—C8—C7178.9 (5)
Symmetry code: (i) x+1, y+2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O1ii0.901.942.825 (3)168
N1—H1A···O3ii0.902.393.080 (3)135
N1—H1B···O10.902.493.075 (3)124
N1—H1B···O20.901.962.869 (3)177
C1—H1C···O2iii0.972.583.204 (4)123
C1—H1D···O3iv0.972.533.377 (4)147
C2—H2A···O3iv0.972.493.367 (4)150
Symmetry codes: (ii) x1, y, z; (iii) x, y+1, z; (iv) x1, y+1, z.

Experimental details

Crystal data
Chemical formulaC16H22N22+·2NO3
Mr366.38
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)5.7889 (15), 5.5654 (14), 29.858 (3)
β (°) 91.638 (3)
V3)961.5 (4)
Z2
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.58 × 0.23 × 0.09
Data collection
DiffractometerSiemens SMART 1000 CCD area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.945, 0.991
No. of measured, independent and
observed [I > 2σ(I)] reflections
4707, 1676, 942
Rint0.060
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.072, 0.215, 1.02
No. of reflections1676
No. of parameters118
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.37, 0.21

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O1i0.901.942.825 (3)167.7
N1—H1A···O3i0.902.393.080 (3)135.3
N1—H1B···O10.902.493.075 (3)123.6
N1—H1B···O20.901.962.869 (3)177.1
C1—H1C···O2ii0.972.583.204 (4)122.8
C1—H1D···O3iii0.972.533.377 (4)146.5
C2—H2A···O3iii0.972.493.367 (4)150.0
Symmetry codes: (i) x1, y, z; (ii) x, y+1, z; (iii) x1, y+1, z.
 

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