Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807039426/at2368sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807039426/at2368Isup2.hkl |
CCDC reference: 654270
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.005 Å
- R factor = 0.053
- wR factor = 0.165
- Data-to-parameter ratio = 12.5
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for N2 PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 6 PLAT480_ALERT_4_C Long H...A H-Bond Reported H1D .. O5 .. 2.61 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H1D .. O3 .. 2.63 Ang.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 3 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
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).
All H atoms were positioned geometrically and refined as riding on their parent atoms, with N—H = 0.90 Å, C—H = 0.93 - 0.97 Å and Uiso(H) = 1.2Ueq(C, N) for all H atoms.
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).
For related literature, see: Bernstein et al. (1995); Bondi (1964).
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.
C18H22N2O42+·2NO3− | F(000) = 952 |
Mr = 454.40 | Dx = 1.454 Mg m−3 |
Monoclinic, C2/c | Melting point: 501 K |
Hall symbol: -C 2yc | Mo Kα radiation, λ = 0.71073 Å |
a = 33.590 (3) Å | Cell parameters from 1077 reflections |
b = 5.6421 (8) Å | θ = 2.5–21.3° |
c = 11.4747 (15) Å | µ = 0.12 mm−1 |
β = 107.326 (2)° | T = 298 K |
V = 2076.0 (4) Å3 | Needle, colourless |
Z = 4 | 0.35 × 0.18 × 0.09 mm |
Siemens SMART 1000 CCD area-detector diffractometer | 1822 independent reflections |
Radiation source: fine-focus sealed tube | 1018 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.046 |
φ and ω scans | θmax = 25.0°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −39→38 |
Tmin = 0.959, Tmax = 0.989 | k = −6→5 |
4705 measured reflections | l = −10→13 |
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)] = 0.053 | H-atom parameters constrained |
wR(F2) = 0.165 | w = 1/[σ2(Fo2) + (0.0539P)2 + 2.9489P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
1822 reflections | Δρmax = 0.23 e Å−3 |
146 parameters | Δρmin = −0.21 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0061 (10) |
C18H22N2O42+·2NO3− | V = 2076.0 (4) Å3 |
Mr = 454.40 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 33.590 (3) Å | µ = 0.12 mm−1 |
b = 5.6421 (8) Å | T = 298 K |
c = 11.4747 (15) Å | 0.35 × 0.18 × 0.09 mm |
β = 107.326 (2)° |
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 = 0.989 | Rint = 0.046 |
4705 measured reflections |
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.165 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.23 e Å−3 |
1822 reflections | Δρmin = −0.21 e Å−3 |
146 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 | 0.44318 (7) | 0.0350 (5) | −0.0179 (2) | 0.0396 (7) | |
H1A | 0.4439 | 0.1890 | 0.0031 | 0.048* | |
H1B | 0.4436 | −0.0512 | 0.0485 | 0.048* | |
O1 | 0.29689 (9) | 0.6277 (5) | −0.1979 (3) | 0.0838 (10) | |
O2 | 0.27695 (9) | 0.5442 (6) | −0.0269 (3) | 0.0860 (10) | |
C1 | 0.48103 (9) | −0.0207 (6) | −0.0538 (3) | 0.0411 (8) | |
H1C | 0.4822 | 0.0796 | −0.1214 | 0.049* | |
H1D | 0.4802 | −0.1846 | −0.0799 | 0.049* | |
C2 | 0.40307 (10) | −0.0125 (6) | −0.1155 (3) | 0.0484 (9) | |
H2A | 0.3969 | −0.1807 | −0.1183 | 0.058* | |
H2B | 0.4057 | 0.0339 | −0.1943 | 0.058* | |
C3 | 0.36803 (10) | 0.1246 (6) | −0.0901 (3) | 0.0452 (9) | |
C4 | 0.35020 (11) | 0.3134 (6) | −0.1661 (3) | 0.0512 (9) | |
H4 | 0.3588 | 0.3530 | −0.2336 | 0.061* | |
C5 | 0.31951 (11) | 0.4381 (7) | −0.1368 (3) | 0.0539 (10) | |
C6 | 0.30722 (11) | 0.3863 (8) | −0.0360 (4) | 0.0582 (10) | |
C7 | 0.32454 (13) | 0.2067 (8) | 0.0397 (4) | 0.0753 (13) | |
H7 | 0.3163 | 0.1731 | 0.1085 | 0.090* | |
C8 | 0.35531 (12) | 0.0730 (8) | 0.0106 (4) | 0.0667 (12) | |
H8 | 0.3675 | −0.0536 | 0.0604 | 0.080* | |
C9 | 0.26771 (15) | 0.6847 (10) | −0.1333 (4) | 0.0871 (15) | |
H9A | 0.2698 | 0.8514 | −0.1117 | 0.105* | |
H9B | 0.2395 | 0.6532 | −0.1843 | 0.105* | |
N2 | 0.44342 (9) | 0.5341 (5) | 0.1477 (3) | 0.0540 (8) | |
O4 | 0.43900 (10) | 0.7387 (5) | 0.1821 (2) | 0.0763 (9) | |
O3 | 0.45031 (9) | 0.5127 (4) | 0.0471 (2) | 0.0678 (8) | |
O5 | 0.44070 (12) | 0.3594 (6) | 0.2065 (3) | 0.0978 (12) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0423 (15) | 0.0344 (15) | 0.0444 (15) | 0.0047 (12) | 0.0163 (12) | −0.0011 (12) |
O1 | 0.096 (2) | 0.084 (2) | 0.080 (2) | 0.0439 (18) | 0.0395 (17) | 0.0151 (17) |
O2 | 0.0779 (19) | 0.104 (2) | 0.088 (2) | 0.0396 (19) | 0.0425 (17) | 0.0074 (19) |
C1 | 0.0415 (17) | 0.0417 (19) | 0.0437 (19) | 0.0037 (15) | 0.0182 (14) | −0.0014 (16) |
C2 | 0.0429 (19) | 0.052 (2) | 0.049 (2) | 0.0025 (17) | 0.0108 (16) | −0.0046 (17) |
C3 | 0.0398 (18) | 0.053 (2) | 0.0442 (19) | 0.0016 (17) | 0.0147 (15) | −0.0011 (17) |
C4 | 0.055 (2) | 0.052 (2) | 0.051 (2) | 0.0077 (19) | 0.0211 (17) | 0.0013 (18) |
C5 | 0.050 (2) | 0.054 (2) | 0.054 (2) | 0.0115 (19) | 0.0100 (18) | 0.0003 (19) |
C6 | 0.045 (2) | 0.074 (3) | 0.061 (2) | 0.014 (2) | 0.0248 (18) | 0.000 (2) |
C7 | 0.069 (3) | 0.095 (3) | 0.075 (3) | 0.022 (3) | 0.042 (2) | 0.021 (3) |
C8 | 0.062 (2) | 0.083 (3) | 0.063 (3) | 0.020 (2) | 0.030 (2) | 0.023 (2) |
C9 | 0.082 (3) | 0.101 (4) | 0.083 (3) | 0.039 (3) | 0.032 (3) | 0.002 (3) |
N2 | 0.068 (2) | 0.0422 (19) | 0.0523 (19) | −0.0006 (16) | 0.0184 (16) | 0.0017 (16) |
O4 | 0.122 (2) | 0.0514 (18) | 0.0619 (17) | 0.0111 (17) | 0.0375 (17) | −0.0130 (14) |
O3 | 0.109 (2) | 0.0419 (15) | 0.0667 (17) | −0.0004 (15) | 0.0480 (16) | −0.0029 (13) |
O5 | 0.164 (3) | 0.060 (2) | 0.074 (2) | −0.010 (2) | 0.043 (2) | 0.0233 (16) |
N1—C1 | 1.483 (4) | C3—C4 | 1.394 (5) |
N1—C2 | 1.498 (4) | C4—C5 | 1.370 (5) |
N1—H1A | 0.9000 | C4—H4 | 0.9300 |
N1—H1B | 0.9000 | C5—C6 | 1.371 (5) |
O1—C5 | 1.377 (4) | C6—C7 | 1.348 (5) |
O1—C9 | 1.430 (5) | C7—C8 | 1.398 (5) |
O2—C6 | 1.379 (4) | C7—H7 | 0.9300 |
O2—C9 | 1.411 (5) | C8—H8 | 0.9300 |
C1—C1i | 1.506 (6) | C9—O2ii | 3.101 (5) |
C1—H1C | 0.9700 | C9—H9A | 0.9700 |
C1—H1D | 0.9700 | C9—H9B | 0.9700 |
C2—C3 | 1.508 (4) | N2—O5 | 1.213 (4) |
C2—H2A | 0.9700 | N2—O4 | 1.243 (4) |
C2—H2B | 0.9700 | N2—O3 | 1.250 (3) |
C3—C8 | 1.377 (5) | ||
C1—N1—C2 | 114.1 (2) | C4—C5—C6 | 122.4 (4) |
C1—N1—H1A | 108.7 | C4—C5—O1 | 128.0 (3) |
C2—N1—H1A | 108.7 | C6—C5—O1 | 109.6 (3) |
C1—N1—H1B | 108.7 | C7—C6—C5 | 121.5 (3) |
C2—N1—H1B | 108.7 | C7—C6—O2 | 128.6 (4) |
H1A—N1—H1B | 107.6 | C5—C6—O2 | 109.9 (4) |
C5—O1—C9 | 105.7 (3) | C6—C7—C8 | 117.4 (4) |
C6—O2—C9 | 106.0 (3) | C6—C7—H7 | 121.3 |
N1—C1—C1i | 109.0 (3) | C8—C7—H7 | 121.3 |
N1—C1—H1C | 109.9 | C3—C8—C7 | 121.5 (4) |
C1i—C1—H1C | 109.9 | C3—C8—H8 | 119.3 |
N1—C1—H1D | 109.9 | C7—C8—H8 | 119.3 |
C1i—C1—H1D | 109.9 | O2—C9—O1 | 108.3 (3) |
H1C—C1—H1D | 108.3 | O2—C9—O2ii | 77.5 (2) |
N1—C2—C3 | 110.1 (3) | O1—C9—O2ii | 161.0 (4) |
N1—C2—H2A | 109.6 | O2—C9—H9A | 110.0 |
C3—C2—H2A | 109.6 | O1—C9—H9A | 110.0 |
N1—C2—H2B | 109.6 | O2ii—C9—H9A | 51.7 |
C3—C2—H2B | 109.6 | O2—C9—H9B | 110.0 |
H2A—C2—H2B | 108.2 | O1—C9—H9B | 110.0 |
C8—C3—C4 | 120.3 (3) | O2ii—C9—H9B | 83.7 |
C8—C3—C2 | 120.6 (3) | H9A—C9—H9B | 108.4 |
C4—C3—C2 | 119.0 (3) | O5—N2—O4 | 122.9 (3) |
C5—C4—C3 | 116.9 (3) | O5—N2—O3 | 120.0 (3) |
C5—C4—H4 | 121.5 | O4—N2—O3 | 117.1 (3) |
C3—C4—H4 | 121.5 | ||
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—C5 | 5.5 (5) |
N1—C2—C3—C4 | 110.5 (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—C6 | 1.7 (5) | C2—C3—C8—C7 | 176.3 (4) |
C3—C4—C5—O1 | −179.0 (4) | C6—C7—C8—C3 | 1.1 (6) |
C9—O1—C5—C4 | 177.3 (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—O2 | 6.6 (5) |
O1—C5—C6—C7 | 179.8 (4) | C5—O1—C9—O2ii | 111.8 (9) |
C4—C5—C6—O2 | 178.0 (3) |
Symmetry codes: (i) −x+1, −y, −z; (ii) −x+1/2, −y+3/2, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1a···O3 | 0.90 | 1.89 | 2.787 (3) | 175 |
N1—H1b···O4iii | 0.90 | 1.98 | 2.876 (4) | 173 |
N1—H1a···O5 | 0.90 | 2.56 | 3.180 (4) | 127 |
C1—H1d···O5iv | 0.97 | 2.61 | 3.291 (4) | 128 |
N1—H1b···O3iii | 0.90 | 2.47 | 3.032 (4) | 121 |
C1—H1d···O3iii | 0.97 | 2.63 | 3.170 (4) | 115 |
C2—H2b···O4v | 0.97 | 2.42 | 3.302 (4) | 151 |
C1—H1c···O4v | 0.97 | 2.51 | 3.340 (4) | 144 |
Symmetry codes: (iii) x, y−1, z; (iv) x, −y, z−1/2; (v) x, −y+1, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C18H22N2O42+·2NO3− |
Mr | 454.40 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 298 |
a, b, c (Å) | 33.590 (3), 5.6421 (8), 11.4747 (15) |
β (°) | 107.326 (2) |
V (Å3) | 2076.0 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.12 |
Crystal size (mm) | 0.35 × 0.18 × 0.09 |
Data collection | |
Diffractometer | Siemens SMART 1000 CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.959, 0.989 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4705, 1822, 1018 |
Rint | 0.046 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.165, 1.07 |
No. of reflections | 1822 |
No. of parameters | 146 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.23, −0.21 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1a···O3 | 0.90 | 1.89 | 2.787 (3) | 175.1 |
N1—H1b···O4i | 0.90 | 1.98 | 2.876 (4) | 173.3 |
N1—H1a···O5 | 0.90 | 2.56 | 3.180 (4) | 127.1 |
C1—H1d···O5ii | 0.97 | 2.61 | 3.291 (4) | 127.6 |
N1—H1b···O3i | 0.90 | 2.47 | 3.032 (4) | 120.8 |
C1—H1d···O3i | 0.97 | 2.63 | 3.170 (4) | 115.4 |
C2—H2b···O4iii | 0.97 | 2.42 | 3.302 (4) | 151.2 |
C1—H1c···O4iii | 0.97 | 2.51 | 3.340 (4) | 143.8 |
Symmetry codes: (i) x, y−1, z; (ii) x, −y, z−1/2; (iii) x, −y+1, z−1/2. |
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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).