Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807040949/xu2312sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807040949/xu2312Isup2.hkl |
CCDC reference: 652292
To a methanol solution (30 ml) of N,N'-bis(4-chlorobenzyl)ethane-1,2-diamine (3.42 g, 10 mmol) a methanol solution (10 ml) of lanthanum nitrate (2.16 g, 10 mmol) was added, and the mixture was stirred for 3 h at 333 k. The white solid was filtered off, washed with ethanol and dried at room temperature. Colourless crystals of the title compound suitaible for X-ray structure analysis were obtained by slow evaporation of a DMF solution containing the crude solid product over a period of two months.
H atoms were placed in calculated positions with C—H = 0.93 Å (aromatic), 0.97 Å (methylene) and N—H = 0.90 Å, and refined in riding mode with Uiso(H) = 1.2Ueq(C,N).
We intended to prepare a lanthanum(III) complex with N,N'-bis(4-chlorobenzyl)ethane-1,2-diamine. However, we obtained the crystal of the title compound. Here we report its structure (Fig. 1).
In the crystal, the cation is located across on an inversion center, the asymmetric unit contains one half-cation and one anion, the cation and the anion are linked by N—H···O hydrogen bonding (Table 1 and Fig. 1).
In the crystal structure, the molecules are linked by two N—H···O hydrogen bonds, the atoms N1(amine) at (x,y,z) and (1 - x,1 - y,1 - z) in the molecule centred at (1/2,1/2,1/2) act as hydrogen-bond donors to the atom O3 (nitrate) at (x,y,-1 + z) in the molecule centred at(1/2,1/2,-1/2) and the atom O3 (nitrate) at (1 - x,1 - y,2 - z) in the molecule centred at(1/2,1/2, 3/2), respectively. Propagation by translation of the two hydrogen bonds generates a chain of R44(18) rings (Bernstein et al., 1995) (Table 1 and Fig. 2).
The molecules are linked by two C—H···O and two N—H···O hydrogen bonds, so forming a [1 0 0] chain of R44(20) ring, the atoms C2 at (x,y,z) and (1 - x,1 - y,1 - z) in the molecule centred at (1/2,1/2,1/2) act as hydrogen-bond donors, via H2b, to the atom O2 (nitrate)at (1 + x,y,z) in the molecule centred at(3/2,1/2,1/2) and the atom O2 (nitrate)at (-x,1 - y,1 - z) in the molecule centred at(-1/2,1/2, 1/2), respectively, and the atoms N1(amino) at (x,y,z) and (1 - x,1 - y,1 - z) in the molecule centred at (1/2,1/2,1/2) act as hydrogen-bond donors, via H1a, to the atom O1 (nitrate) at (x,y,z) in the molecule centred at(1/2,1/2,1/2) and the atom O1 (nitrate) at (1 - x,1 - y,1 - z) in the molecule centred at(3/2,1/2,1/2), respectively. Propagation by translation of the two pairs of hydrogen bonds generates a chain of R44(20) rings along [1 0 0]direction (Table 1 and Fig. 3).
The combination of the [0 0 1] chain and the [1 0 0] chain generates a [0 1 0] stack, the stack lies in a domain of 0.260 < y < 0.740. Neighbouring stacks are linked by the intermolecular Cl···C weak interactions [Cl1···C6i = 3.441 (3) Å, symmetry codes: (i)1/2 + x,3/2 - y,-1/2 + z], resulting in a three-dimensional structure.
For related literature, see: Bernstein et al. (1995).
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (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).
C16H20Cl2N22+·2NO3− | F(000) = 452 |
Mr = 435.26 | Dx = 1.442 Mg m−3 |
Monoclinic, P21/n | Melting point = 523–525 K |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 5.6168 (7) Å | Cell parameters from 2811 reflections |
b = 31.132 (3) Å | θ = 2.5–27.9° |
c = 5.7361 (8) Å | µ = 0.36 mm−1 |
β = 91.533 (2)° | T = 298 K |
V = 1002.7 (2) Å3 | Block, colourless |
Z = 2 | 0.56 × 0.49 × 0.45 mm |
Bruker SMART CCD area-detector diffractometer | 1768 independent reflections |
Radiation source: fine-focus sealed tube | 1486 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.034 |
φ and ω scans | θmax = 25.0°, θmin = 1.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −6→6 |
Tmin = 0.822, Tmax = 0.853 | k = −37→19 |
5098 measured reflections | l = −6→6 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.056 | H-atom parameters constrained |
wR(F2) = 0.169 | w = 1/[σ2(Fo2) + (0.0938P)2 + 1.0094P] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max < 0.001 |
1768 reflections | Δρmax = 0.22 e Å−3 |
128 parameters | Δρmin = −0.26 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997a), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.40 (3) |
C16H20Cl2N22+·2NO3− | V = 1002.7 (2) Å3 |
Mr = 435.26 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 5.6168 (7) Å | µ = 0.36 mm−1 |
b = 31.132 (3) Å | T = 298 K |
c = 5.7361 (8) Å | 0.56 × 0.49 × 0.45 mm |
β = 91.533 (2)° |
Bruker SMART CCD area-detector diffractometer | 1768 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1486 reflections with I > 2σ(I) |
Tmin = 0.822, Tmax = 0.853 | Rint = 0.034 |
5098 measured reflections |
R[F2 > 2σ(F2)] = 0.056 | 0 restraints |
wR(F2) = 0.169 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.22 e Å−3 |
1768 reflections | Δρmin = −0.26 e Å−3 |
128 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 | ||
Cl1 | 0.0520 (2) | 0.73850 (3) | 1.0413 (2) | 0.0699 (5) | |
N1 | 0.4390 (4) | 0.55809 (7) | 0.5597 (4) | 0.0316 (6) | |
H1A | 0.3978 | 0.5555 | 0.7096 | 0.038* | |
H1B | 0.3039 | 0.5588 | 0.4718 | 0.038* | |
N2 | 0.1099 (5) | 0.55806 (9) | 1.0499 (4) | 0.0411 (7) | |
O1 | 0.3261 (4) | 0.55003 (9) | 1.0333 (4) | 0.0567 (8) | |
O3 | 0.0322 (4) | 0.56523 (10) | 1.2485 (4) | 0.0619 (8) | |
O2 | −0.0175 (5) | 0.55903 (12) | 0.8745 (5) | 0.0843 (11) | |
C1 | 0.5788 (5) | 0.51959 (9) | 0.4944 (5) | 0.0325 (7) | |
H1C | 0.7148 | 0.5163 | 0.6006 | 0.039* | |
H1D | 0.6371 | 0.5230 | 0.3378 | 0.039* | |
C2 | 0.5679 (5) | 0.59956 (10) | 0.5305 (5) | 0.0395 (8) | |
H2A | 0.5778 | 0.6062 | 0.3659 | 0.047* | |
H2B | 0.7288 | 0.5969 | 0.5947 | 0.047* | |
C3 | 0.4409 (5) | 0.63547 (9) | 0.6525 (5) | 0.0357 (7) | |
C4 | 0.2310 (6) | 0.65296 (10) | 0.5608 (6) | 0.0424 (8) | |
H4 | 0.1703 | 0.6433 | 0.4178 | 0.051* | |
C5 | 0.1111 (6) | 0.68469 (10) | 0.6801 (6) | 0.0461 (8) | |
H5 | −0.0299 | 0.6962 | 0.6189 | 0.055* | |
C6 | 0.2042 (6) | 0.69886 (10) | 0.8906 (6) | 0.0437 (8) | |
C7 | 0.4130 (6) | 0.68286 (11) | 0.9844 (6) | 0.0481 (9) | |
H7 | 0.4747 | 0.6934 | 1.1253 | 0.058* | |
C8 | 0.5312 (6) | 0.65058 (10) | 0.8650 (6) | 0.0442 (8) | |
H8 | 0.6715 | 0.6391 | 0.9280 | 0.053* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0765 (8) | 0.0546 (7) | 0.0796 (8) | 0.0153 (5) | 0.0193 (5) | −0.0206 (5) |
N1 | 0.0344 (13) | 0.0332 (13) | 0.0274 (12) | 0.0030 (10) | 0.0051 (9) | −0.0039 (9) |
N2 | 0.0415 (15) | 0.0510 (16) | 0.0309 (14) | −0.0042 (12) | −0.0003 (11) | −0.0007 (11) |
O1 | 0.0449 (14) | 0.093 (2) | 0.0330 (12) | 0.0156 (13) | 0.0078 (10) | 0.0070 (12) |
O3 | 0.0445 (14) | 0.097 (2) | 0.0453 (14) | 0.0002 (13) | 0.0147 (11) | −0.0157 (13) |
O2 | 0.0629 (18) | 0.138 (3) | 0.0511 (17) | −0.0002 (18) | −0.0231 (14) | −0.0028 (18) |
C1 | 0.0302 (14) | 0.0373 (16) | 0.0303 (15) | 0.0041 (12) | 0.0031 (11) | −0.0023 (11) |
C2 | 0.0383 (16) | 0.0395 (17) | 0.0411 (17) | −0.0016 (13) | 0.0099 (13) | −0.0036 (13) |
C3 | 0.0379 (16) | 0.0282 (15) | 0.0412 (16) | −0.0001 (12) | 0.0079 (12) | 0.0008 (12) |
C4 | 0.0434 (18) | 0.0396 (17) | 0.0440 (18) | 0.0002 (13) | −0.0017 (14) | −0.0048 (13) |
C5 | 0.0437 (18) | 0.0382 (18) | 0.056 (2) | 0.0070 (14) | 0.0019 (15) | 0.0008 (14) |
C6 | 0.0523 (19) | 0.0291 (16) | 0.0503 (19) | 0.0004 (13) | 0.0156 (15) | −0.0047 (13) |
C7 | 0.057 (2) | 0.049 (2) | 0.0389 (18) | −0.0035 (16) | 0.0033 (15) | −0.0092 (14) |
C8 | 0.0450 (18) | 0.0441 (18) | 0.0437 (18) | 0.0034 (14) | 0.0030 (14) | 0.0012 (14) |
Cl1—C6 | 1.744 (3) | C2—H2A | 0.9700 |
Cl1—C6i | 3.441 (3) | C2—H2B | 0.9700 |
N1—C1 | 1.486 (3) | C3—C4 | 1.389 (4) |
N1—C2 | 1.492 (4) | C3—C8 | 1.389 (5) |
N1—H1A | 0.9000 | C4—C5 | 1.387 (4) |
N1—H1B | 0.9000 | C4—H4 | 0.9300 |
N2—O2 | 1.219 (3) | C5—C6 | 1.375 (5) |
N2—O1 | 1.246 (3) | C5—H5 | 0.9300 |
N2—O3 | 1.251 (3) | C6—C7 | 1.371 (5) |
C1—C1ii | 1.509 (6) | C7—C8 | 1.394 (4) |
C1—H1C | 0.9700 | C7—H7 | 0.9300 |
C1—H1D | 0.9700 | C8—H8 | 0.9300 |
C2—C3 | 1.508 (4) | ||
C6—Cl1—C6i | 169.47 (12) | C3—C2—H2B | 109.5 |
C1—N1—C2 | 114.1 (2) | H2A—C2—H2B | 108.1 |
C1—N1—H1A | 108.7 | C4—C3—C8 | 119.1 (3) |
C2—N1—H1A | 108.7 | C4—C3—C2 | 121.5 (3) |
C1—N1—H1B | 108.7 | C8—C3—C2 | 119.5 (3) |
C2—N1—H1B | 108.7 | C5—C4—C3 | 120.7 (3) |
H1A—N1—H1B | 107.6 | C5—C4—H4 | 119.6 |
O2—N2—O1 | 119.6 (3) | C3—C4—H4 | 119.6 |
O2—N2—O3 | 122.4 (3) | C6—C5—C4 | 118.9 (3) |
O1—N2—O3 | 118.0 (2) | C6—C5—H5 | 120.5 |
N1—C1—C1ii | 109.1 (3) | C4—C5—H5 | 120.5 |
N1—C1—H1C | 109.9 | C7—C6—C5 | 121.9 (3) |
C1ii—C1—H1C | 109.9 | C7—C6—Cl1 | 119.2 (3) |
N1—C1—H1D | 109.9 | C5—C6—Cl1 | 118.8 (3) |
C1ii—C1—H1D | 109.9 | C6—C7—C8 | 118.9 (3) |
H1C—C1—H1D | 108.3 | C6—C7—H7 | 120.6 |
N1—C2—C3 | 110.6 (2) | C8—C7—H7 | 120.6 |
N1—C2—H2A | 109.5 | C3—C8—C7 | 120.5 (3) |
C3—C2—H2A | 109.5 | C3—C8—H8 | 119.8 |
N1—C2—H2B | 109.5 | C7—C8—H8 | 119.8 |
C2—N1—C1—C1ii | −173.8 (3) | C4—C5—C6—Cl1 | −179.5 (2) |
C1—N1—C2—C3 | −166.4 (2) | C6i—Cl1—C6—C7 | −86.6 (11) |
N1—C2—C3—C4 | −74.6 (4) | C6i—Cl1—C6—C5 | 93.6 (10) |
N1—C2—C3—C8 | 103.4 (3) | C5—C6—C7—C8 | −1.5 (5) |
C8—C3—C4—C5 | −0.8 (5) | Cl1—C6—C7—C8 | 178.8 (2) |
C2—C3—C4—C5 | 177.2 (3) | C4—C3—C8—C7 | 0.0 (5) |
C3—C4—C5—C6 | 0.5 (5) | C2—C3—C8—C7 | −178.1 (3) |
C4—C5—C6—C7 | 0.7 (5) | C6—C7—C8—C3 | 1.1 (5) |
Symmetry codes: (i) x−1/2, −y+3/2, z+1/2; (ii) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1 | 0.90 | 1.92 | 2.818 (3) | 177 |
N1—H1B···O3iii | 0.90 | 1.98 | 2.870 (3) | 172 |
C2—H2B···O2iv | 0.97 | 2.42 | 3.265 (4) | 145 |
Symmetry codes: (iii) x, y, z−1; (iv) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C16H20Cl2N22+·2NO3− |
Mr | 435.26 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 298 |
a, b, c (Å) | 5.6168 (7), 31.132 (3), 5.7361 (8) |
β (°) | 91.533 (2) |
V (Å3) | 1002.7 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.36 |
Crystal size (mm) | 0.56 × 0.49 × 0.45 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.822, 0.853 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5098, 1768, 1486 |
Rint | 0.034 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.056, 0.169, 1.00 |
No. of reflections | 1768 |
No. of parameters | 128 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.22, −0.26 |
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···O1 | 0.90 | 1.92 | 2.818 (3) | 177 |
N1—H1B···O3i | 0.90 | 1.98 | 2.870 (3) | 172 |
C2—H2B···O2ii | 0.97 | 2.42 | 3.265 (4) | 145 |
Symmetry codes: (i) x, y, z−1; (ii) x+1, y, z. |
We intended to prepare a lanthanum(III) complex with N,N'-bis(4-chlorobenzyl)ethane-1,2-diamine. However, we obtained the crystal of the title compound. Here we report its structure (Fig. 1).
In the crystal, the cation is located across on an inversion center, the asymmetric unit contains one half-cation and one anion, the cation and the anion are linked by N—H···O hydrogen bonding (Table 1 and Fig. 1).
In the crystal structure, the molecules are linked by two N—H···O hydrogen bonds, the atoms N1(amine) at (x,y,z) and (1 - x,1 - y,1 - z) in the molecule centred at (1/2,1/2,1/2) act as hydrogen-bond donors to the atom O3 (nitrate) at (x,y,-1 + z) in the molecule centred at(1/2,1/2,-1/2) and the atom O3 (nitrate) at (1 - x,1 - y,2 - z) in the molecule centred at(1/2,1/2, 3/2), respectively. Propagation by translation of the two hydrogen bonds generates a chain of R44(18) rings (Bernstein et al., 1995) (Table 1 and Fig. 2).
The molecules are linked by two C—H···O and two N—H···O hydrogen bonds, so forming a [1 0 0] chain of R44(20) ring, the atoms C2 at (x,y,z) and (1 - x,1 - y,1 - z) in the molecule centred at (1/2,1/2,1/2) act as hydrogen-bond donors, via H2b, to the atom O2 (nitrate)at (1 + x,y,z) in the molecule centred at(3/2,1/2,1/2) and the atom O2 (nitrate)at (-x,1 - y,1 - z) in the molecule centred at(-1/2,1/2, 1/2), respectively, and the atoms N1(amino) at (x,y,z) and (1 - x,1 - y,1 - z) in the molecule centred at (1/2,1/2,1/2) act as hydrogen-bond donors, via H1a, to the atom O1 (nitrate) at (x,y,z) in the molecule centred at(1/2,1/2,1/2) and the atom O1 (nitrate) at (1 - x,1 - y,1 - z) in the molecule centred at(3/2,1/2,1/2), respectively. Propagation by translation of the two pairs of hydrogen bonds generates a chain of R44(20) rings along [1 0 0]direction (Table 1 and Fig. 3).
The combination of the [0 0 1] chain and the [1 0 0] chain generates a [0 1 0] stack, the stack lies in a domain of 0.260 < y < 0.740. Neighbouring stacks are linked by the intermolecular Cl···C weak interactions [Cl1···C6i = 3.441 (3) Å, symmetry codes: (i)1/2 + x,3/2 - y,-1/2 + z], resulting in a three-dimensional structure.