Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807039736/gg3117sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807039736/gg3117Isup2.hkl |
CCDC reference: 635370
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.009 Å
- R factor = 0.072
- wR factor = 0.215
- Data-to-parameter ratio = 14.2
checkCIF/PLATON results
No syntax errors found
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
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).
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).
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).
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).
C16H22N22+·2NO3− | F(000) = 388 |
Mr = 366.38 | Dx = 1.265 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 995 reflections |
a = 5.7889 (15) Å | θ = 2.7–22.8° |
b = 5.5654 (14) Å | µ = 0.10 mm−1 |
c = 29.858 (3) Å | T = 293 K |
β = 91.638 (3)° | Block, colourless |
V = 961.5 (4) Å3 | 0.58 × 0.23 × 0.09 mm |
Z = 2 |
Siemens SMART 1000 CCD area-detector diffractometer | 1676 independent reflections |
Radiation source: fine-focus sealed tube | 942 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.060 |
φ and ω scans | θmax = 25.0°, θmin = 1.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −6→6 |
Tmin = 0.945, Tmax = 0.991 | k = −6→6 |
4707 measured reflections | l = −31→35 |
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)] = 0.072 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.215 | H-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 parameters | Δρmax = 0.37 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
C16H22N22+·2NO3− | V = 961.5 (4) Å3 |
Mr = 366.38 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 5.7889 (15) Å | µ = 0.10 mm−1 |
b = 5.5654 (14) Å | T = 293 K |
c = 29.858 (3) Å | 0.58 × 0.23 × 0.09 mm |
β = 91.638 (3)° |
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 = 0.991 | Rint = 0.060 |
4707 measured reflections |
R[F2 > 2σ(F2)] = 0.072 | 0 restraints |
wR(F2) = 0.215 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.37 e Å−3 |
1676 reflections | Δρmin = −0.21 e Å−3 |
118 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 | ||
N1 | 0.4744 (4) | 0.9458 (4) | 0.06168 (7) | 0.0488 (7) | |
H1A | 0.3281 | 0.8909 | 0.0607 | 0.059* | |
H1B | 0.5690 | 0.8174 | 0.0626 | 0.059* | |
N2 | 0.9771 (5) | 0.6263 (5) | 0.05954 (9) | 0.0599 (8) | |
O1 | 0.9957 (4) | 0.8469 (4) | 0.05704 (9) | 0.0742 (8) | |
O2 | 0.7799 (5) | 0.5400 (4) | 0.06156 (10) | 0.0882 (9) | |
O3 | 1.1532 (5) | 0.5046 (4) | 0.05864 (12) | 0.1054 (11) | |
C1 | 0.5158 (5) | 1.0821 (5) | 0.01998 (9) | 0.0478 (8) | |
H1C | 0.6714 | 1.1468 | 0.0209 | 0.057* | |
H1D | 0.4081 | 1.2154 | 0.0174 | 0.057* | |
C2 | 0.5114 (6) | 1.0864 (5) | 0.10331 (11) | 0.0617 (9) | |
H2A | 0.4219 | 1.2336 | 0.1014 | 0.074* | |
H2B | 0.6733 | 1.1295 | 0.1066 | 0.074* | |
C3 | 0.4409 (7) | 0.9453 (7) | 0.14330 (12) | 0.0719 (10) | |
C4 | 0.2417 (10) | 0.9825 (12) | 0.16382 (17) | 0.132 (2) | |
H4 | 0.1406 | 1.1026 | 0.1540 | 0.158* | |
C5 | 0.1848 (15) | 0.827 (2) | 0.2029 (2) | 0.161 (3) | |
H5 | 0.0499 | 0.8447 | 0.2187 | 0.194* | |
C6 | 0.347 (2) | 0.656 (2) | 0.2133 (3) | 0.159 (3) | |
H6 | 0.3149 | 0.5565 | 0.2374 | 0.191* | |
C7 | 0.5403 (19) | 0.6153 (13) | 0.1939 (2) | 0.152 (3) | |
H7 | 0.6420 | 0.4952 | 0.2034 | 0.182* | |
C8 | 0.5840 (11) | 0.7599 (9) | 0.15861 (14) | 0.1118 (17) | |
H8 | 0.7199 | 0.7332 | 0.1435 | 0.134* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0431 (14) | 0.0402 (12) | 0.0633 (16) | −0.0065 (10) | 0.0058 (11) | 0.0016 (12) |
N2 | 0.0537 (18) | 0.0480 (16) | 0.0781 (19) | −0.0011 (14) | 0.0037 (13) | −0.0052 (14) |
O1 | 0.0509 (15) | 0.0458 (13) | 0.126 (2) | −0.0046 (10) | 0.0056 (13) | 0.0070 (13) |
O2 | 0.0651 (17) | 0.0567 (14) | 0.143 (2) | −0.0189 (13) | 0.0094 (15) | 0.0008 (15) |
O3 | 0.0756 (19) | 0.0674 (16) | 0.174 (3) | 0.0276 (14) | 0.0076 (18) | −0.0031 (17) |
C1 | 0.0504 (17) | 0.0350 (14) | 0.0584 (18) | −0.0032 (13) | 0.0059 (14) | 0.0043 (13) |
C2 | 0.075 (2) | 0.0476 (17) | 0.063 (2) | −0.0073 (16) | 0.0040 (16) | −0.0075 (16) |
C3 | 0.074 (3) | 0.082 (3) | 0.060 (2) | −0.023 (2) | 0.0055 (19) | −0.009 (2) |
C4 | 0.109 (4) | 0.205 (6) | 0.082 (3) | −0.028 (4) | 0.033 (3) | −0.033 (4) |
C5 | 0.123 (6) | 0.261 (10) | 0.102 (5) | −0.062 (6) | 0.040 (4) | −0.034 (6) |
C6 | 0.177 (8) | 0.191 (8) | 0.112 (5) | −0.077 (7) | 0.036 (6) | −0.005 (5) |
C7 | 0.238 (9) | 0.132 (5) | 0.085 (4) | −0.005 (6) | 0.004 (5) | 0.021 (4) |
C8 | 0.176 (5) | 0.095 (3) | 0.064 (3) | −0.009 (3) | 0.003 (3) | 0.015 (3) |
N1—C2 | 1.479 (4) | C2—H2B | 0.9700 |
N1—C1 | 1.484 (3) | C3—C4 | 1.337 (6) |
N1—H1A | 0.9000 | C3—C8 | 1.392 (6) |
N1—H1B | 0.9000 | C4—C5 | 1.498 (10) |
N2—O3 | 1.225 (3) | C4—H4 | 0.9300 |
N2—O1 | 1.235 (3) | C5—C6 | 1.367 (11) |
N2—O2 | 1.241 (3) | C5—H5 | 0.9300 |
C1—C1i | 1.510 (6) | C6—C7 | 1.294 (11) |
C1—H1C | 0.9700 | C6—H6 | 0.9300 |
C1—H1D | 0.9700 | C7—C8 | 1.355 (8) |
C2—C3 | 1.496 (5) | C7—H7 | 0.9300 |
C2—H2A | 0.9700 | C8—H8 | 0.9300 |
C2—N1—C1 | 114.3 (2) | H2A—C2—H2B | 108.0 |
C2—N1—H1A | 108.7 | C4—C3—C8 | 118.5 (5) |
C1—N1—H1A | 108.7 | C4—C3—C2 | 122.9 (5) |
C2—N1—H1B | 108.7 | C8—C3—C2 | 118.6 (4) |
C1—N1—H1B | 108.7 | C3—C4—C5 | 118.6 (7) |
H1A—N1—H1B | 107.6 | C3—C4—H4 | 120.7 |
O3—N2—O1 | 118.4 (3) | C5—C4—H4 | 120.7 |
O3—N2—O2 | 123.6 (3) | C6—C5—C4 | 114.5 (7) |
O1—N2—O2 | 118.0 (3) | C6—C5—H5 | 122.7 |
N1—C1—C1i | 109.5 (3) | C4—C5—H5 | 122.7 |
N1—C1—H1C | 109.8 | C7—C6—C5 | 128.0 (8) |
C1i—C1—H1C | 109.8 | C7—C6—H6 | 116.0 |
N1—C1—H1D | 109.8 | C5—C6—H6 | 116.0 |
C1i—C1—H1D | 109.8 | C6—C7—C8 | 115.4 (8) |
H1C—C1—H1D | 108.2 | C6—C7—H7 | 122.3 |
N1—C2—C3 | 110.9 (2) | C8—C7—H7 | 122.3 |
N1—C2—H2A | 109.5 | C7—C8—C3 | 124.9 (6) |
C3—C2—H2A | 109.5 | C7—C8—H8 | 117.5 |
N1—C2—H2B | 109.5 | C3—C8—H8 | 117.5 |
C3—C2—H2B | 109.5 | ||
C2—N1—C1—C1i | 177.3 (3) | C3—C4—C5—C6 | −0.7 (9) |
C1—N1—C2—C3 | 173.6 (3) | C4—C5—C6—C7 | 0.3 (12) |
N1—C2—C3—C4 | −102.3 (4) | C5—C6—C7—C8 | −0.6 (12) |
N1—C2—C3—C8 | 74.7 (4) | C6—C7—C8—C3 | 1.3 (9) |
C8—C3—C4—C5 | 1.4 (7) | C4—C3—C8—C7 | −1.8 (7) |
C2—C3—C4—C5 | 178.4 (4) | C2—C3—C8—C7 | −178.9 (5) |
Symmetry code: (i) −x+1, −y+2, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1ii | 0.90 | 1.94 | 2.825 (3) | 168 |
N1—H1A···O3ii | 0.90 | 2.39 | 3.080 (3) | 135 |
N1—H1B···O1 | 0.90 | 2.49 | 3.075 (3) | 124 |
N1—H1B···O2 | 0.90 | 1.96 | 2.869 (3) | 177 |
C1—H1C···O2iii | 0.97 | 2.58 | 3.204 (4) | 123 |
C1—H1D···O3iv | 0.97 | 2.53 | 3.377 (4) | 147 |
C2—H2A···O3iv | 0.97 | 2.49 | 3.367 (4) | 150 |
Symmetry codes: (ii) x−1, y, z; (iii) x, y+1, z; (iv) x−1, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | C16H22N22+·2NO3− |
Mr | 366.38 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 5.7889 (15), 5.5654 (14), 29.858 (3) |
β (°) | 91.638 (3) |
V (Å3) | 961.5 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.58 × 0.23 × 0.09 |
Data collection | |
Diffractometer | Siemens SMART 1000 CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.945, 0.991 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4707, 1676, 942 |
Rint | 0.060 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.072, 0.215, 1.02 |
No. of reflections | 1676 |
No. of parameters | 118 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.37, −0.21 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1i | 0.90 | 1.94 | 2.825 (3) | 167.7 |
N1—H1A···O3i | 0.90 | 2.39 | 3.080 (3) | 135.3 |
N1—H1B···O1 | 0.90 | 2.49 | 3.075 (3) | 123.6 |
N1—H1B···O2 | 0.90 | 1.96 | 2.869 (3) | 177.1 |
C1—H1C···O2ii | 0.97 | 2.58 | 3.204 (4) | 122.8 |
C1—H1D···O3iii | 0.97 | 2.53 | 3.377 (4) | 146.5 |
C2—H2A···O3iii | 0.97 | 2.49 | 3.367 (4) | 150.0 |
Symmetry codes: (i) x−1, y, z; (ii) x, y+1, z; (iii) x−1, y+1, z. |
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.