organic compounds
[Oxalylbis(azanediyl)]bis{[amino(2-pyridyl)methylene]ammonium}
aSchool of Chemistry and Chemical Engineering, Anhui University, Hefei 230039, People's Republic of China, and bDepartment of Chemistry and Chemical Engineering, Hefei Teachers College, Hefei 230061, People's Republic of China
*Correspondence e-mail: dapdong@163.com
The title compound, C14H16N8O22+·2ClO4−, was prepared by reaction of bis[amino(2-pyridyl)methylene]oxalohydrazide with perchloric acid. The molecular symmetry is Ci and thus the comprises one half-molecule. The dihedral angle between the aromatic ring and the plane of the oxamide group is 70.8 (3)°. The perchlorate anions and the cations are connected by intermolecular N—H⋯O hydrogen bonds.
Related literature
For background to the design and synthesis of polynuclear molecule-based magnetic materials, see: Niel et al. (2008); Zhao et al. (2004); Xu et al. (2001, 2003).
Experimental
Crystal data
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Refinement
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Data collection: SMART (Bruker, 2000); cell SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.
Supporting information
10.1107/S1600536809009015/kp2209sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536809009015/kp2209Isup2.hkl
All solvents and chemicals were of analytical grade and were used without further purification. Ligand was prepared by similar procedure reported in the literature (Zhao et al., 2004). For the synthesis of title compoud, a solution of ligand (0.1 mmol), HClO4(0.1 mmol) in 20 ml methanol was refluxed for 1 h, and then cooled to room temperature and filtered. Single crystals suitable for X-ray analysis were grown from the methanol solution by slow evaporation at room temperature in air. Anal. Calcd. for C14H16N8O10Cl2: C, 31.89; H, 3.06; N, 21.25. Found: C, 32.15; H, 3.18; N, 21.20.
All hydrogen atoms were geomemetrically positioned (C—H 0.93–0.97 Å, N–H 0.86 Å) and refined as riding, with Uiso(H)=1.2 Ueq of the parent atom.
Data collection: SMART (Bruker, 2000); cell
SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C14H16N8O22+·2ClO4− | F(000) = 540 |
Mr = 527.25 | Dx = 1.677 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2046 reflections |
a = 5.0751 (11) Å | θ = 2.7–26.2° |
b = 13.725 (3) Å | µ = 0.39 mm−1 |
c = 15.162 (3) Å | T = 273 K |
β = 98.605 (3)° | Block, colourless |
V = 1044.2 (4) Å3 | 0.31 × 0.25 × 0.22 mm |
Z = 2 |
Bruker SMART CCD area-detector diffractometer | 1824 independent reflections |
Radiation source: fine-focus sealed tube | 1455 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.078 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −6→5 |
Tmin = 0.882, Tmax = 0.914 | k = −13→16 |
5016 measured reflections | l = −15→18 |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.128 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.076P)2] where P = (Fo2 + 2Fc2)/3 |
1824 reflections | (Δ/σ)max = 0.001 |
154 parameters | Δρmax = 0.33 e Å−3 |
0 restraints | Δρmin = −0.47 e Å−3 |
C14H16N8O22+·2ClO4− | V = 1044.2 (4) Å3 |
Mr = 527.25 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 5.0751 (11) Å | µ = 0.39 mm−1 |
b = 13.725 (3) Å | T = 273 K |
c = 15.162 (3) Å | 0.31 × 0.25 × 0.22 mm |
β = 98.605 (3)° |
Bruker SMART CCD area-detector diffractometer | 1824 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 1455 reflections with I > 2σ(I) |
Tmin = 0.882, Tmax = 0.914 | Rint = 0.078 |
5016 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.128 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.33 e Å−3 |
1824 reflections | Δρmin = −0.47 e Å−3 |
154 parameters |
Experimental. The structure was solved by direct methods (Bruker, 2000) and successive difference Fourier syntheses. |
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 | ||
C1 | 0.7001 (5) | 0.85329 (16) | 0.62706 (14) | 0.0356 (5) | |
C2 | 0.8640 (5) | 0.90729 (18) | 0.68880 (16) | 0.0487 (6) | |
H2 | 1.0229 | 0.8819 | 0.7183 | 0.058* | |
C3 | 0.7835 (7) | 1.0013 (2) | 0.70546 (19) | 0.0654 (8) | |
H3 | 0.8887 | 1.0402 | 0.7469 | 0.078* | |
C4 | 0.5517 (8) | 1.03584 (19) | 0.6612 (2) | 0.0679 (9) | |
H4 | 0.4953 | 1.0987 | 0.6719 | 0.081* | |
C5 | 0.4000 (6) | 0.97677 (19) | 0.6001 (2) | 0.0604 (8) | |
H5 | 0.2409 | 1.0013 | 0.5698 | 0.073* | |
C6 | 0.7662 (4) | 0.75221 (14) | 0.60311 (13) | 0.0326 (5) | |
C7 | 0.4737 (4) | 0.54717 (15) | 0.52444 (14) | 0.0352 (5) | |
Cl1 | 0.54991 (12) | 0.77141 (5) | 0.85280 (3) | 0.0450 (3) | |
N1 | 0.5942 (4) | 0.71127 (13) | 0.53978 (12) | 0.0370 (5) | |
H1A | 0.4530 | 0.7425 | 0.5175 | 0.044* | |
N2 | 0.6387 (4) | 0.61898 (12) | 0.50903 (11) | 0.0380 (5) | |
H2A | 0.7700 | 0.6079 | 0.4805 | 0.046* | |
N3 | 0.4704 (4) | 0.88577 (14) | 0.58226 (14) | 0.0486 (5) | |
N4 | 0.9765 (4) | 0.70721 (15) | 0.64025 (12) | 0.0445 (5) | |
H4A | 1.0082 | 0.6489 | 0.6240 | 0.053* | |
H4B | 1.0852 | 0.7355 | 0.6813 | 0.053* | |
O1 | 0.3033 (4) | 0.55207 (11) | 0.57270 (12) | 0.0506 (5) | |
O2 | 0.4275 (4) | 0.72826 (16) | 0.77218 (13) | 0.0710 (6) | |
O3 | 0.4490 (5) | 0.86811 (15) | 0.85821 (15) | 0.0793 (7) | |
O4 | 0.8287 (4) | 0.77292 (16) | 0.85160 (15) | 0.0730 (7) | |
O5 | 0.4956 (6) | 0.71688 (18) | 0.92652 (16) | 0.0973 (9) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0392 (13) | 0.0310 (11) | 0.0376 (11) | −0.0040 (9) | 0.0085 (10) | −0.0016 (9) |
C2 | 0.0529 (16) | 0.0435 (14) | 0.0490 (14) | −0.0095 (11) | 0.0050 (11) | −0.0077 (11) |
C3 | 0.085 (2) | 0.0450 (16) | 0.0675 (18) | −0.0155 (16) | 0.0163 (17) | −0.0204 (14) |
C4 | 0.096 (3) | 0.0315 (15) | 0.083 (2) | −0.0006 (15) | 0.0361 (19) | −0.0080 (13) |
C5 | 0.0628 (19) | 0.0409 (15) | 0.080 (2) | 0.0110 (13) | 0.0182 (15) | 0.0084 (13) |
C6 | 0.0362 (13) | 0.0330 (11) | 0.0287 (12) | −0.0032 (9) | 0.0049 (9) | −0.0007 (9) |
C7 | 0.0380 (13) | 0.0308 (12) | 0.0348 (12) | 0.0014 (9) | −0.0012 (9) | −0.0029 (8) |
Cl1 | 0.0409 (4) | 0.0542 (4) | 0.0375 (4) | 0.0076 (3) | −0.0019 (3) | −0.0028 (2) |
N1 | 0.0371 (11) | 0.0292 (10) | 0.0422 (10) | 0.0005 (7) | −0.0027 (8) | −0.0062 (7) |
N2 | 0.0419 (11) | 0.0300 (10) | 0.0419 (10) | −0.0024 (8) | 0.0058 (8) | −0.0090 (8) |
N3 | 0.0509 (13) | 0.0354 (11) | 0.0576 (12) | 0.0061 (9) | 0.0020 (10) | −0.0010 (9) |
N4 | 0.0430 (12) | 0.0399 (12) | 0.0466 (12) | 0.0047 (9) | −0.0069 (9) | −0.0093 (8) |
O1 | 0.0580 (12) | 0.0374 (9) | 0.0614 (11) | −0.0018 (8) | 0.0246 (9) | −0.0084 (8) |
O2 | 0.0610 (14) | 0.0874 (16) | 0.0572 (12) | −0.0057 (10) | −0.0150 (9) | −0.0154 (10) |
O3 | 0.0885 (16) | 0.0567 (14) | 0.0966 (15) | 0.0244 (12) | 0.0262 (13) | −0.0043 (11) |
O4 | 0.0374 (12) | 0.0868 (16) | 0.0894 (16) | 0.0060 (10) | −0.0079 (10) | −0.0147 (11) |
O5 | 0.130 (2) | 0.106 (2) | 0.0648 (14) | 0.0451 (16) | 0.0439 (15) | 0.0363 (13) |
C1—N3 | 1.335 (3) | C7—O1 | 1.215 (3) |
C1—C2 | 1.373 (3) | C7—N2 | 1.336 (3) |
C1—C6 | 1.485 (3) | C7—C7i | 1.535 (4) |
C2—C3 | 1.387 (4) | Cl1—O5 | 1.406 (2) |
C2—H2 | 0.9300 | Cl1—O2 | 1.415 (2) |
C3—C4 | 1.351 (5) | Cl1—O4 | 1.418 (2) |
C3—H3 | 0.9300 | Cl1—O3 | 1.429 (2) |
C4—C5 | 1.377 (5) | N1—N2 | 1.380 (2) |
C4—H4 | 0.9300 | N1—H1A | 0.8600 |
C5—N3 | 1.338 (3) | N2—H2A | 0.8600 |
C5—H5 | 0.9300 | N4—H4A | 0.8600 |
C6—N4 | 1.287 (3) | N4—H4B | 0.8600 |
C6—N1 | 1.322 (3) | ||
N3—C1—C2 | 124.1 (2) | O1—C7—C7i | 121.9 (2) |
N3—C1—C6 | 113.56 (19) | N2—C7—C7i | 112.3 (2) |
C2—C1—C6 | 122.3 (2) | O5—Cl1—O2 | 110.53 (18) |
C1—C2—C3 | 117.5 (3) | O5—Cl1—O4 | 109.43 (16) |
C1—C2—H2 | 121.3 | O2—Cl1—O4 | 107.75 (14) |
C3—C2—H2 | 121.3 | O5—Cl1—O3 | 109.51 (14) |
C4—C3—C2 | 119.6 (3) | O2—Cl1—O3 | 108.86 (13) |
C4—C3—H3 | 120.2 | O4—Cl1—O3 | 110.74 (13) |
C2—C3—H3 | 120.2 | C6—N1—N2 | 120.78 (19) |
C3—C4—C5 | 119.0 (3) | C6—N1—H1A | 119.6 |
C3—C4—H4 | 120.5 | N2—N1—H1A | 119.6 |
C5—C4—H4 | 120.5 | C7—N2—N1 | 118.65 (18) |
N3—C5—C4 | 123.1 (3) | C7—N2—H2A | 120.7 |
N3—C5—H5 | 118.4 | N1—N2—H2A | 120.7 |
C4—C5—H5 | 118.4 | C1—N3—C5 | 116.6 (2) |
N4—C6—N1 | 121.8 (2) | C6—N4—H4A | 120.0 |
N4—C6—C1 | 123.0 (2) | C6—N4—H4B | 120.0 |
N1—C6—C1 | 115.2 (2) | H4A—N4—H4B | 120.0 |
O1—C7—N2 | 125.83 (19) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O4ii | 0.86 | 2.51 | 2.975 (3) | 115 |
N1—H1A···O5ii | 0.86 | 2.58 | 3.404 (4) | 162 |
N2—H2A···O3iii | 0.86 | 2.21 | 2.970 (3) | 147 |
N4—H4A···O1iv | 0.86 | 2.23 | 2.974 (3) | 145 |
N4—H4B···O2iv | 0.86 | 2.05 | 2.820 (3) | 148 |
Symmetry codes: (ii) x−1/2, −y+3/2, z−1/2; (iii) x+1/2, −y+3/2, z−1/2; (iv) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C14H16N8O22+·2ClO4− |
Mr | 527.25 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 273 |
a, b, c (Å) | 5.0751 (11), 13.725 (3), 15.162 (3) |
β (°) | 98.605 (3) |
V (Å3) | 1044.2 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.39 |
Crystal size (mm) | 0.31 × 0.25 × 0.22 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.882, 0.914 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5016, 1824, 1455 |
Rint | 0.078 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.128, 1.09 |
No. of reflections | 1824 |
No. of parameters | 154 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.33, −0.47 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O4i | 0.86 | 2.509 | 2.975 (3) | 115.0 |
N1—H1A···O5i | 0.86 | 2.578 | 3.404 (4) | 162.0 |
N2—H2A···O3ii | 0.86 | 2.209 | 2.970 (3) | 147.0 |
N4—H4A···O1iii | 0.86 | 2.228 | 2.974 (3) | 145.0 |
N4—H4B···O2iii | 0.86 | 2.052 | 2.820 (3) | 148.0 |
Symmetry codes: (i) x−1/2, −y+3/2, z−1/2; (ii) x+1/2, −y+3/2, z−1/2; (iii) x+1, y, z. |
Acknowledgements
The authors are indebted to Anhui Provincial Natural Science Research Project (KJ2009B240Z) and the National Natural Science Foundation of China (No. 20871039) for financial support.
References
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In recent years, researchers showed considerable interest in design and synthesis of polynuclear molecule-based magnetic materials, which were prepared by reactions of special organic molecules with transitional metals. (Niel et al., 2008; Xu et al., 2001; Xu et al., 2003); Zhao et al., 2004). Here we report a new compound, [(C14H16N8O2)(ClO4)2].
The asymmetric unit of the title compound comprises a half of the molecule (Fig. 1). In the structure of title compound, the dihedral angle between the aromatic ring and the plane of oxamide group is 70.8 °. Perchlorate anions and cations are connected by intermolecular N—H···O hydrogen bonds (Fig. 2, Table 1).