[Oxalylbis(aza­nedi­yl)]bis­{[amino­(2-pyrid­yl)methyl­ene]ammonium}

Bi, W.-T.; Hu, N.-L.; Bi, J.-H.

doi:10.1107/S1600536809009015

organic compounds

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ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page o782

doi:10.1107/S1600536809009015

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[Oxalylbis(azanediyl)]bis{[amino(2-pyridyl)methylene]ammonium}

Wen-Tao Bi,^a Nai-Liang Hu ^a ^* and Jian-Hong Bi ^b

^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

(Received 6 March 2009; accepted 11 March 2009; online 19 March 2009)

The title compound, C₁₄H₁₆N₈O₂²⁺·2ClO₄⁻, was prepared by reaction of bis[amino(2-pyridyl)methylene]oxalohydrazide with perchloric acid. The molecular symmetry is C_i and thus the asymmetric unit 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

C₁₄H₁₆N₈O₂²⁺·2ClO₄⁻
M_r = 527.25
Monoclinic, P 2₁ /n
a = 5.0751 (11) Å
b = 13.725 (3) Å
c = 15.162 (3) Å
β = 98.605 (3)°
V = 1044.2 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.39 mm⁻¹
T = 273 K
0.31 × 0.25 × 0.22 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.882, T_max = 0.914
5016 measured reflections
1824 independent reflections
1455 reflections with I > 2σ(I)
R_int = 0.078

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.128
S = 1.09
1824 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O4ⁱ	0.86	2.51	2.975 (3)	115
N1—H1A⋯O5ⁱ	0.86	2.58	3.404 (4)	162
N2—H2A⋯O3ⁱⁱ	0.86	2.21	2.970 (3)	147
N4—H4A⋯O1ⁱⁱⁱ	0.86	2.23	2.974 (3)	145
N4—H4B⋯O2ⁱⁱⁱ	0.86	2.05	2.820 (3)	148
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iii) x+1, y, z.

Data collection: SMART (Bruker, 2000); cell refinement: 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

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809009015/kp2209sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809009015/kp2209Isup2.hkl

checkCIF report

Comment top

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).

Related literature top

For backgroud 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 top

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.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: 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).

Figures top

	Fig. 1. Molecular structure of the title compound, showing the 30% probability displacement ellipsoids and the atom-numbering [symmetry code: 1 - x,1 - y,1 - z].
	Fig. 2. The crystal packing of the title compound generated by intermolecular hydrogen bonds.

[Oxalylbis(azanediyl)]bis{[amino(2-pyridyl)methylene]ammonium} top

Crystal data top

C₁₄H₁₆N₈O₂²⁺·2ClO₄⁻	F(000) = 540
M_r = 527.25	D_x = 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

Data collection top

Bruker SMART CCD area-detector diffractometer	1824 independent reflections
Radiation source: fine-focus sealed tube	1455 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.078
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −6→5
T_min = 0.882, T_max = 0.914	k = −13→16
5016 measured reflections	l = −15→18

Refinement top

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(F_o²) + (0.076P)²] where P = (F_o² + 2F_c²)/3
1824 reflections	(Δ/σ)_max = 0.001
154 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.47 e Å⁻³

Crystal data top

C₁₄H₁₆N₈O₂²⁺·2ClO₄⁻	V = 1044.2 (4) Å³
M_r = 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)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1824 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1455 reflections with I > 2σ(I)
T_min = 0.882, T_max = 0.914	R_int = 0.078
5016 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.128	H-atom parameters constrained
S = 1.09	Δρ_max = 0.33 e Å⁻³
1824 reflections	Δρ_min = −0.47 e Å⁻³
154 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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.

Hydrogen-bond geometry (Å, º) top

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···O1^iv	0.86	2.23	2.974 (3)	145
N4—H4B···O2^iv	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⁻
M_r	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)
T_min, T_max	0.882, 0.914
No. of measured, independent and observed [I > 2σ(I)] reflections	5016, 1824, 1455
R_int	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
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.47

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

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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