catena-Poly[[bis­(3-methyl-4-nitro­pyridine N-oxide-κO)cadmium(II)]-di-μ-dicyanamido-κ4N1:N5]

Wei, R.-M.

doi:10.1107/S1600536808044000

metal-organic compounds

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Volume 65| Part 2| February 2009| Page m154

doi:10.1107/S1600536808044000

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catena-Poly[[bis(3-methyl-4-nitropyridine N-oxide-κO)cadmium(II)]-di-μ-dicyanamido-κ⁴N¹:N⁵]

Rong-Min Wei ^a ^*

^aDepartment of Chemistry, Dezhou University, Dezhou Shandong 253023, People's Republic of China
^*Correspondence e-mail: wrm0505@126.com

(Received 15 December 2008; accepted 26 December 2008; online 8 January 2009)

In the title compound, [Cd(C₂N₃)₂(C₆H₆N₂O₃)₂]_n, the Cd^II ion (site symmetry $[\overline{1}]$ ) adopts a distorted trans-CdO₂N₄ octahedral environment, being coordinated by two O-bonded 3-methyl-4-nitropyridine N-oxide ligands and four dicyanamide (dca) anions. The bridging dca anions lead to a polymeric chain propagating in [100].

Related literature

For related structures, see: Ghoshal et al. (2004 ); Wu et al. (2004 ); Schlueter et al. (2005 ).

Experimental

Crystal data

[Cd(C₂N₃)₂(C₆H₆N₂O₃)₂]
M_r = 552.76
Triclinic, $[P \overline 1]$
a = 7.5472 (8) Å
b = 7.5606 (8) Å
c = 9.8352 (10) Å
α = 83.680 (1)°
β = 68.528 (1)°
γ = 79.639 (1)°
V = 513.14 (9) Å³
Z = 1
Mo Kα radiation
μ = 1.12 mm⁻¹
T = 293 (2) K
0.32 × 0.22 × 0.18 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.692, T_max = 0.817
2770 measured reflections
1780 independent reflections
1764 reflections with I > 2σ(I)
R_int = 0.015

Refinement

R[F² > 2σ(F²)] = 0.020
wR(F²) = 0.053
S = 1.00
1780 reflections
152 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Cd1—N3ⁱ	2.288 (2)
Cd1—N1	2.309 (2)
Cd1—O3	2.3110 (19)
Symmetry code: (i) x+1, y, z.

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1998); 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 global, I. DOI: 10.1107/S1600536808044000/hb2881sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808044000/hb2881Isup2.hkl

checkCIF report

Comment top

The pseudohalide ligand dicyanamide (dca) has been used widely due to its polydentate character and bridging ability, yielding a variety of structures and interesting magnetic properties (Ghoshal et al., 2004; Wu et al., 2004; Schlueter et al., 2005). As a further study of such complexes, the title Cd^II complex, (I), is reported in this paper (Fig. 1).

Each Cd^II atom exhibits a slightly distorted octahedral environment with four nitrogen atoms from dicyanamide groups in the equatorial plane, and two oxygen atoms from two N-oxide (pom) ligands at the axial positions (Table 1). Each Cd^II atom is coordinated to each other by the double bridging –NC—N—CN– ligands to form a one-dimensional chain structure, the Cd···Cd separation being equal to the value of the a-axis.

Related literature top

For related structures, see: Ghoshal et al. (2004); Wu et al. (2004); Schlueter et al. (2005).

Experimental top

5 ml of a methanol solution of cadmium(II) chloride tetrahydrate (0.5 mmol, 128 mg) and 5 ml of a methanol sulution of dicyanamide (1 mmol, 170 mg) were aded to 10 ml of a methanol solution of POM (1 mmol, 154 mg). The mixture was stirred for 2 h and filtered. The filtrate was slowly evaporated at room temperture and red blocks of (I) were obtained after three weeks.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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. Fagment of the infinite chain structure in (I) showing 50% displacement ellipsoids for the non-hydrogen atoms. Symmetry codes: (i) 1–x, 1–y, 1–z; (ii) –x, 1–y, 1–z; (iii) x–1, y, z; (iv) 1+x, y, z.

catena-Poly[[bis(3-methyl-4-nitropyridine N-oxide-κO)cadmium(II)]-di-µ-dicyanamido- κ⁴N¹:N⁵] top

Crystal data top

[Cd(C₂N₃)₂(C₆H₆N₂O₃)₂]	Z = 1
M_r = 552.76	F(000) = 274
Triclinic, P1	D_x = 1.789 Mg m⁻³ D_m = 1.789 Mg m⁻³ D_m measured by not measured
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.5472 (8) Å	Cell parameters from 2499 reflections
b = 7.5606 (8) Å	θ = 2.7–27.9°
c = 9.8352 (10) Å	µ = 1.12 mm⁻¹
α = 83.680 (1)°	T = 293 K
β = 68.528 (1)°	Block, red
γ = 79.639 (1)°	0.32 × 0.22 × 0.18 mm
V = 513.14 (9) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	1780 independent reflections
Radiation source: fine-focus sealed tube	1764 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.015
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→5
T_min = 0.692, T_max = 0.817	k = −8→8
2770 measured reflections	l = −11→11

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)] = 0.020	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.053	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0283P)² + 0.2723P] where P = (F_o² + 2F_c²)/3
1780 reflections	(Δ/σ)_max = 0.001
152 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.38 e Å⁻³

Crystal data top

[Cd(C₂N₃)₂(C₆H₆N₂O₃)₂]	γ = 79.639 (1)°
M_r = 552.76	V = 513.14 (9) Å³
Triclinic, P1	Z = 1
a = 7.5472 (8) Å	Mo Kα radiation
b = 7.5606 (8) Å	µ = 1.12 mm⁻¹
c = 9.8352 (10) Å	T = 293 K
α = 83.680 (1)°	0.32 × 0.22 × 0.18 mm
β = 68.528 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1780 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1764 reflections with I > 2σ(I)
T_min = 0.692, T_max = 0.817	R_int = 0.015
2770 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.020	0 restraints
wR(F²) = 0.053	H-atom parameters constrained
S = 1.00	Δρ_max = 0.34 e Å⁻³
1780 reflections	Δρ_min = −0.38 e Å⁻³
152 parameters

Special details top

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
Cd1	0.5000	0.5000	0.5000	0.04339 (10)
O1	−0.1329 (4)	−0.2147 (3)	0.8956 (2)	0.0773 (6)
O2	−0.3397 (3)	−0.0003 (3)	0.8532 (3)	0.0777 (6)
O3	0.3605 (3)	0.3892 (3)	0.7372 (2)	0.0664 (5)
N1	0.4059 (3)	0.2818 (3)	0.4054 (3)	0.0602 (5)
N2	0.1066 (3)	0.1677 (3)	0.4552 (3)	0.0601 (6)
N3	−0.2102 (3)	0.3289 (3)	0.4816 (3)	0.0697 (7)
N4	−0.1834 (3)	−0.0583 (3)	0.8629 (2)	0.0528 (5)
N5	0.2298 (3)	0.2829 (3)	0.7670 (2)	0.0474 (4)
C1	0.2592 (3)	0.2383 (3)	0.4278 (2)	0.0417 (5)
C2	−0.0590 (3)	0.2619 (3)	0.4680 (2)	0.0424 (5)
C3	−0.3067 (4)	0.3407 (4)	0.9163 (4)	0.0644 (7)
H3A	−0.3083	0.4579	0.9460	0.097*
H3B	−0.3774	0.2705	0.9994	0.097*
H3C	−0.3652	0.3524	0.8433	0.097*
C4	−0.1028 (3)	0.2488 (3)	0.8542 (2)	0.0416 (5)
C5	−0.0425 (3)	0.0661 (3)	0.8317 (2)	0.0404 (5)
C6	0.1501 (4)	−0.0059 (3)	0.7798 (2)	0.0481 (5)
H6	0.1871	−0.1290	0.7677	0.058*
C7	0.2853 (4)	0.1047 (4)	0.7467 (3)	0.0529 (6)
H7	0.4155	0.0579	0.7101	0.063*
C8	0.0426 (3)	0.3523 (3)	0.8193 (3)	0.0466 (5)
H8	0.0092	0.4754	0.8326	0.056*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.02232 (12)	0.04541 (15)	0.06540 (16)	−0.00754 (9)	−0.01648 (10)	−0.00752 (10)
O1	0.1114 (18)	0.0440 (10)	0.0825 (14)	−0.0268 (11)	−0.0370 (13)	0.0064 (9)
O2	0.0531 (12)	0.0775 (14)	0.1087 (17)	−0.0215 (10)	−0.0273 (11)	−0.0157 (12)
O3	0.0540 (11)	0.0882 (14)	0.0684 (11)	−0.0361 (10)	−0.0250 (9)	0.0028 (10)
N1	0.0430 (12)	0.0582 (12)	0.0873 (16)	−0.0097 (10)	−0.0270 (11)	−0.0188 (11)
N2	0.0338 (11)	0.0471 (11)	0.1011 (17)	−0.0055 (9)	−0.0260 (11)	−0.0039 (11)
N3	0.0386 (13)	0.0663 (14)	0.109 (2)	0.0053 (11)	−0.0341 (12)	−0.0165 (13)
N4	0.0665 (15)	0.0482 (12)	0.0449 (10)	−0.0183 (10)	−0.0151 (9)	−0.0078 (8)
N5	0.0407 (11)	0.0577 (12)	0.0483 (10)	−0.0143 (9)	−0.0189 (8)	0.0006 (8)
C1	0.0333 (12)	0.0389 (11)	0.0559 (12)	−0.0019 (9)	−0.0185 (9)	−0.0114 (9)
C2	0.0361 (13)	0.0462 (11)	0.0487 (12)	−0.0063 (9)	−0.0181 (9)	−0.0071 (9)
C3	0.0403 (14)	0.0534 (14)	0.094 (2)	0.0019 (11)	−0.0176 (13)	−0.0192 (13)
C4	0.0370 (11)	0.0405 (11)	0.0470 (11)	−0.0040 (9)	−0.0147 (9)	−0.0043 (9)
C5	0.0450 (12)	0.0398 (11)	0.0375 (10)	−0.0078 (9)	−0.0152 (9)	−0.0018 (8)
C6	0.0527 (14)	0.0429 (12)	0.0475 (12)	0.0049 (10)	−0.0206 (10)	−0.0075 (9)
C7	0.0383 (12)	0.0652 (15)	0.0529 (13)	0.0042 (11)	−0.0174 (10)	−0.0087 (11)
C8	0.0446 (13)	0.0395 (11)	0.0573 (13)	−0.0061 (9)	−0.0201 (10)	−0.0028 (9)

Geometric parameters (Å, º) top

Cd1—N3ⁱ	2.288 (2)	N4—C5	1.472 (3)
Cd1—N3ⁱⁱ	2.288 (2)	N5—C8	1.341 (3)
Cd1—N1	2.309 (2)	N5—C7	1.351 (3)
Cd1—N1ⁱⁱⁱ	2.309 (2)	C3—C4	1.498 (3)
Cd1—O3ⁱⁱⁱ	2.3110 (19)	C3—H3A	0.9600
Cd1—O3	2.3110 (19)	C3—H3B	0.9600
O1—N4	1.221 (3)	C3—H3C	0.9600
O2—N4	1.216 (3)	C4—C8	1.381 (3)
O3—N5	1.314 (3)	C4—C5	1.390 (3)
N1—C1	1.149 (3)	C5—C6	1.379 (3)
N2—C1	1.283 (3)	C6—C7	1.360 (4)
N2—C2	1.292 (3)	C6—H6	0.9300
N3—C2	1.128 (3)	C7—H7	0.9300
N3—Cd1^iv	2.288 (2)	C8—H8	0.9300

N3ⁱ—Cd1—N3ⁱⁱ	180.0	C8—N5—C7	120.7 (2)
N3ⁱ—Cd1—N1	87.09 (8)	N1—C1—N2	172.1 (2)
N3ⁱⁱ—Cd1—N1	92.91 (8)	N3—C2—N2	173.4 (3)
N3ⁱ—Cd1—N1ⁱⁱⁱ	92.91 (8)	C4—C3—H3A	109.5
N3ⁱⁱ—Cd1—N1ⁱⁱⁱ	87.09 (8)	C4—C3—H3B	109.5
N1—Cd1—N1ⁱⁱⁱ	180.0	H3A—C3—H3B	109.5
N3ⁱ—Cd1—O3ⁱⁱⁱ	91.11 (9)	C4—C3—H3C	109.5
N3ⁱⁱ—Cd1—O3ⁱⁱⁱ	88.89 (9)	H3A—C3—H3C	109.5
N1—Cd1—O3ⁱⁱⁱ	87.78 (8)	H3B—C3—H3C	109.5
N1ⁱⁱⁱ—Cd1—O3ⁱⁱⁱ	92.22 (8)	C8—C4—C5	115.5 (2)
N3ⁱ—Cd1—O3	88.89 (9)	C8—C4—C3	117.9 (2)
N3ⁱⁱ—Cd1—O3	91.11 (9)	C5—C4—C3	126.5 (2)
N1—Cd1—O3	92.22 (8)	C6—C5—C4	121.8 (2)
N1ⁱⁱⁱ—Cd1—O3	87.78 (8)	C6—C5—N4	117.4 (2)
O3ⁱⁱⁱ—Cd1—O3	180.0	C4—C5—N4	120.8 (2)
N5—O3—Cd1	119.76 (14)	C7—C6—C5	119.4 (2)
C1—N1—Cd1	132.98 (19)	C7—C6—H6	120.3
C1—N2—C2	123.0 (2)	C5—C6—H6	120.3
C2—N3—Cd1^iv	172.3 (2)	N5—C7—C6	119.8 (2)
O2—N4—O1	124.5 (2)	N5—C7—H7	120.1
O2—N4—C5	118.6 (2)	C6—C7—H7	120.1
O1—N4—C5	116.8 (2)	N5—C8—C4	122.8 (2)
O3—N5—C8	119.5 (2)	N5—C8—H8	118.6
O3—N5—C7	119.7 (2)	C4—C8—H8	118.6

N3ⁱ—Cd1—O3—N5	68.54 (19)	C3—C4—C5—C6	−177.0 (2)
N3ⁱⁱ—Cd1—O3—N5	−111.46 (19)	C8—C4—C5—N4	−179.23 (19)
N1—Cd1—O3—N5	−18.51 (19)	C3—C4—C5—N4	2.9 (4)
N1ⁱⁱⁱ—Cd1—O3—N5	161.49 (19)	O2—N4—C5—C6	−151.9 (2)
O3ⁱⁱⁱ—Cd1—O3—N5	−103 (100)	O1—N4—C5—C6	27.3 (3)
N3ⁱ—Cd1—N1—C1	−34.0 (3)	O2—N4—C5—C4	28.2 (3)
N3ⁱⁱ—Cd1—N1—C1	146.0 (3)	O1—N4—C5—C4	−152.6 (2)
N1ⁱⁱⁱ—Cd1—N1—C1	139 (100)	C4—C5—C6—C7	−1.5 (3)
O3ⁱⁱⁱ—Cd1—N1—C1	−125.2 (3)	N4—C5—C6—C7	178.7 (2)
O3—Cd1—N1—C1	54.8 (3)	O3—N5—C7—C6	178.9 (2)
Cd1—O3—N5—C8	−97.0 (2)	C8—N5—C7—C6	−0.2 (3)
Cd1—O3—N5—C7	84.0 (2)	C5—C6—C7—N5	1.1 (3)
Cd1—N1—C1—N2	−128.5 (19)	O3—N5—C8—C4	−179.4 (2)
C2—N2—C1—N1	174.7 (18)	C7—N5—C8—C4	−0.4 (3)
Cd1^iv—N3—C2—N2	−173.9 (15)	C5—C4—C8—N5	0.1 (3)
C1—N2—C2—N3	−180 (100)	C3—C4—C8—N5	178.1 (2)
C8—C4—C5—C6	0.9 (3)

Symmetry codes: (i) −x, −y+1, −z+1; (ii) x+1, y, z; (iii) −x+1, −y+1, −z+1; (iv) x−1, y, z.

Experimental details

Crystal data
Chemical formula	[Cd(C₂N₃)₂(C₆H₆N₂O₃)₂]
M_r	552.76
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.5472 (8), 7.5606 (8), 9.8352 (10)
α, β, γ (°)	83.680 (1), 68.528 (1), 79.639 (1)
V (Å³)	513.14 (9)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.12
Crystal size (mm)	0.32 × 0.22 × 0.18

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.692, 0.817
No. of measured, independent and observed [I > 2σ(I)] reflections	2770, 1780, 1764
R_int	0.015
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.020, 0.053, 1.00
No. of reflections	1780
No. of parameters	152
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.38

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Cd1—N3ⁱ	2.288 (2)	Cd1—O3	2.3110 (19)
Cd1—N1	2.309 (2)

N3ⁱⁱ—Cd1—N3ⁱ	180.0	N1—Cd1—O3ⁱⁱⁱ	87.78 (8)
N3ⁱⁱ—Cd1—N1	87.09 (8)	N1ⁱⁱⁱ—Cd1—O3ⁱⁱⁱ	92.22 (8)
N3ⁱ—Cd1—N1	92.91 (8)	N3ⁱⁱ—Cd1—O3	88.89 (9)
N3ⁱⁱ—Cd1—N1ⁱⁱⁱ	92.91 (8)	N3ⁱ—Cd1—O3	91.11 (9)
N3ⁱ—Cd1—N1ⁱⁱⁱ	87.09 (8)	N1—Cd1—O3	92.22 (8)
N1—Cd1—N1ⁱⁱⁱ	180.0	N1ⁱⁱⁱ—Cd1—O3	87.78 (8)
N3ⁱⁱ—Cd1—O3ⁱⁱⁱ	91.11 (9)	O3ⁱⁱⁱ—Cd1—O3	180.0
N3ⁱ—Cd1—O3ⁱⁱⁱ	88.89 (9)	C1—N2—C2	123.0 (2)

Symmetry codes: (i) x+1, y, z; (ii) −x, −y+1, −z+1; (iii) −x+1, −y+1, −z+1.

Acknowledgements

This work was supported by the Department of Chemistry of Dezhou University.

References

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