catena-Poly[[bis­(dimethyl­formamide-κO)cadmium(II)]-di-μ2-dicyanamido-κ4N1:N5]

Zhang, J.

doi:10.1107/S1600536809046364

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page m1550

doi:10.1107/S1600536809046364

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catena-Poly[[bis(dimethylformamide-κO)cadmium(II)]-di-μ₂-dicyanamido-κ⁴N¹:N⁵]

Jinfang Zhang ^a ^*

^aMolecular Materials Research Center, Scientific Research Academy, School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, People's Republic of China
^*Correspondence e-mail: zjf260@ujs.edu.cn

(Received 22 October 2009; accepted 4 November 2009; online 11 November 2009)

In the title compound, [Cd(C₂N₃)₂(C₃H₇NO)₂], the Cd²⁺ ion lies on an inversion center and adopts an octahedral coordination geometry, in which four N atoms from four different dicyanamide ligands lie in the equatorial plane and two dimethylformamide O atoms occupy the axial positions. The Cd atoms are connected by two dicyanamide ligands, resulting in a neutral chain propagating parallel to [010].

Related literature

For architectures and topologies of metal-organic compounds, see: Eddaoudi et al. (2001 ); Zhang et al. (2008 ). For their potential applications, see: Banerjee et al. (2008 ); Zhang et al. (2007 ). For metal-organic compounds including dicyanamide ligands, see: Jensen et al. (1999 ); Zhang (2009 ).

Experimental

Crystal data

[Cd(C₂N₃)₂(C₃H₇NO)₂]
M_r = 390.70
Triclinic, $[P \overline 1]$
a = 6.5325 (13) Å
b = 7.6003 (15) Å
c = 8.6051 (17) Å
α = 104.28 (3)°
β = 106.90 (3)°
γ = 97.05 (3)°
V = 387.35 (17) Å³
Z = 1
Mo Kα radiation
μ = 1.43 mm⁻¹
T = 293 K
0.20 × 0.16 × 0.12 mm

Data collection

Rigaku Saturn724+ diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.239, T_max = 0.480
3505 measured reflections
1410 independent reflections
1408 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.022
wR(F²) = 0.058
S = 1.10
1410 reflections
97 parameters
H-atom parameters constrained
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Data collection: CrystalClear (Rigaku, 2008 ); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXT07 (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/S1600536809046364/pv2226sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809046364/pv2226Isup2.hkl

checkCIF report

Comment top

The designed syntheses of metal-organic compounds have attracted great attention in recent years because of not only their intriguing variety of architectures and topologies (Eddaoudi et al., 2001; Zhang et al., 2008) but also their potential applications (Banerjee et al., 2008; Zhang et al., 2007). Dicyanamide acting as flexible bridging ligands can construct metal-organic compounds with various structures (Jensen et al., 1999; Zhang, 2009). The one-dimensional neutral compounds {Cd[N(CN)₂]₂(dmf)₂}_n are constructed by this bridging ligands through diffusion reactions. In this paper, the crystal structure of the title compound, (I), is presented.

As illustrated in Fig. 1, Cd²⁺ which lies on an inversion center, adopts an octahedral coordination geometry, where four N atoms from four different dicyanamide ligands lies in equatorial plane and two O atoms from dmf occupy the axial positions. Every two neighboring Cd atoms connected by two dicyanamide ligands, gives rise to a one-dimensional neutral chain.

Related literature top

For architectures and topologies of metal-organic compounds, see: Eddaoudi et al. (2001); Zhang et al. (2008). For their potential applications, see: Banerjee et al. (2008); Zhang et al. (2007). For metal-organic compounds including dicyanamide ligands, see: Jensen et al. (1999); Zhang (2009).

Experimental top

Cd(NO₃)₂.4 H₂O (123.2 mg, 0.4 mmol) was added into 2 ml dmf with thorough stirring for 5 minutes. After filtration, the filtrate was carefully laid on the surface with the solution of NaN(CN)₂ (89.1 mg, 1 mmol) in 1 ml dmf and 6 ml CH₃CN. colorless block crystals were obtained after eight days. Yield: 199.3 mg in pure form, 51.0% based on Cd.

Computing details top

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXT07 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound, with atom labels and 30% probability displacement ellipsoids, all H atoms have been omitted (i -x + 1,-y + 1,-z; ii -x + 1,-y,-z).

catena-Poly[[bis(dimethylformamide-κO)cadmium(II)]- di-µ₂-dicyanamido-κ⁴N¹:N⁵] top

Crystal data top

[Cd(C₂N₃)₂(C₃H₇NO)₂]	Z = 1
M_r = 390.70	F(000) = 194
Triclinic, P1	D_x = 1.675 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.5325 (13) Å	Cell parameters from 1884 reflections
b = 7.6003 (15) Å	θ = 3.3–28.4°
c = 8.6051 (17) Å	µ = 1.43 mm⁻¹
α = 104.28 (3)°	T = 293 K
β = 106.90 (3)°	Block, colorless
γ = 97.05 (3)°	0.2 × 0.16 × 0.12 mm
V = 387.35 (17) Å³

Data collection top

Rigaku Saturn724+ diffractometer	1410 independent reflections
Radiation source: fine-focus sealed tube	1408 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
dtprofit.ref scans	θ_max = 25.5°, θ_min = 3.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
T_min = 0.239, T_max = 0.480	k = −7→9
3505 measured reflections	l = −9→10

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)] = 0.022	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.058	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.039P)² + 0.0503P] where P = (F_o² + 2F_c²)/3
1410 reflections	(Δ/σ)_max < 0.001
97 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.36 e Å⁻³

Crystal data top

[Cd(C₂N₃)₂(C₃H₇NO)₂]	γ = 97.05 (3)°
M_r = 390.70	V = 387.35 (17) Å³
Triclinic, P1	Z = 1
a = 6.5325 (13) Å	Mo Kα radiation
b = 7.6003 (15) Å	µ = 1.43 mm⁻¹
c = 8.6051 (17) Å	T = 293 K
α = 104.28 (3)°	0.2 × 0.16 × 0.12 mm
β = 106.90 (3)°

Data collection top

Rigaku Saturn724+ diffractometer	1410 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1408 reflections with I > 2σ(I)
T_min = 0.239, T_max = 0.480	R_int = 0.025
3505 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.022	0 restraints
wR(F²) = 0.058	H-atom parameters constrained
S = 1.10	Δρ_max = 0.44 e Å⁻³
1410 reflections	Δρ_min = −0.36 e Å⁻³
97 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	0.0000	0.04117 (11)
O1	0.7512 (3)	0.6362 (3)	0.2708 (2)	0.0572 (5)
N1	0.2979 (4)	0.3110 (3)	0.0987 (3)	0.0570 (6)
N2	0.2301 (6)	0.0218 (4)	0.1653 (4)	0.0781 (9)
N4	1.1012 (4)	0.7109 (3)	0.4447 (3)	0.0500 (5)
N3	0.6991 (4)	0.2758 (3)	−0.0440 (3)	0.0598 (6)
C1	0.2690 (4)	0.1705 (3)	0.1214 (3)	0.0449 (5)
C5	1.3277 (5)	0.6980 (6)	0.4658 (4)	0.0755 (9)
H5A	1.3381	0.6327	0.3586	0.113*
H5B	1.3766	0.6322	0.5470	0.113*
H5C	1.4177	0.8205	0.5059	0.113*
C4	1.0524 (7)	0.8062 (5)	0.5930 (4)	0.0728 (9)
H4A	0.8984	0.8039	0.5624	0.109*
H4B	1.1323	0.9326	0.6357	0.109*
H4C	1.0943	0.7454	0.6792	0.109*
C2	0.9476 (4)	0.6352 (4)	0.2975 (3)	0.0468 (6)
H2A	0.9885	0.5765	0.2063	0.056*
C3	0.7261 (4)	0.1317 (3)	−0.0954 (3)	0.0427 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.04194 (16)	0.03209 (15)	0.04955 (17)	0.01065 (10)	0.01353 (11)	0.01291 (10)
O1	0.0480 (11)	0.0673 (13)	0.0488 (9)	0.0118 (9)	0.0137 (8)	0.0076 (9)
N1	0.0607 (14)	0.0420 (12)	0.0744 (15)	0.0081 (10)	0.0296 (12)	0.0209 (11)
N2	0.136 (3)	0.0421 (13)	0.0862 (18)	0.0263 (15)	0.077 (2)	0.0210 (13)
N4	0.0533 (12)	0.0530 (12)	0.0389 (10)	0.0105 (10)	0.0105 (9)	0.0115 (9)
N3	0.0660 (15)	0.0466 (13)	0.0771 (15)	0.0271 (11)	0.0296 (12)	0.0221 (11)
C1	0.0469 (13)	0.0378 (13)	0.0505 (13)	0.0082 (10)	0.0217 (10)	0.0080 (10)
C5	0.0518 (17)	0.100 (3)	0.0616 (18)	0.0162 (17)	0.0065 (14)	0.0165 (17)
C4	0.093 (2)	0.076 (2)	0.0426 (14)	0.0225 (18)	0.0204 (15)	0.0069 (14)
C2	0.0495 (14)	0.0473 (14)	0.0397 (12)	0.0070 (11)	0.0134 (10)	0.0096 (10)
C3	0.0457 (13)	0.0391 (13)	0.0461 (12)	0.0110 (10)	0.0167 (10)	0.0150 (10)

Geometric parameters (Å, º) top

Cd1—N3ⁱ	2.291 (2)	N4—C4	1.446 (4)
Cd1—N3	2.291 (2)	N4—C5	1.456 (4)
Cd1—N1	2.306 (2)	N3—C3	1.132 (3)
Cd1—N1ⁱ	2.306 (2)	C5—H5A	0.9600
Cd1—O1	2.316 (2)	C5—H5B	0.9600
Cd1—O1ⁱ	2.316 (2)	C5—H5C	0.9600
O1—C2	1.237 (3)	C4—H4A	0.9600
N1—C1	1.136 (3)	C4—H4B	0.9600
N2—C3ⁱⁱ	1.281 (4)	C4—H4C	0.9600
N2—C1	1.296 (4)	C2—H2A	0.9300
N4—C2	1.305 (3)	C3—N2ⁱⁱ	1.281 (4)

N3ⁱ—Cd1—N3	180.0	C4—N4—C5	117.7 (3)
N3ⁱ—Cd1—N1	91.27 (9)	C3—N3—Cd1	156.3 (2)
N3—Cd1—N1	88.73 (9)	N1—C1—N2	172.2 (3)
N3ⁱ—Cd1—N1ⁱ	88.73 (9)	N4—C5—H5A	109.5
N3—Cd1—N1ⁱ	91.27 (9)	N4—C5—H5B	109.5
N1—Cd1—N1ⁱ	180.00 (11)	H5A—C5—H5B	109.5
N3ⁱ—Cd1—O1	90.45 (9)	N4—C5—H5C	109.5
N3—Cd1—O1	89.55 (9)	H5A—C5—H5C	109.5
N1—Cd1—O1	91.26 (9)	H5B—C5—H5C	109.5
N1ⁱ—Cd1—O1	88.74 (9)	N4—C4—H4A	109.5
N3ⁱ—Cd1—O1ⁱ	89.55 (9)	N4—C4—H4B	109.5
N3—Cd1—O1ⁱ	90.45 (9)	H4A—C4—H4B	109.5
N1—Cd1—O1ⁱ	88.74 (9)	N4—C4—H4C	109.5
N1ⁱ—Cd1—O1ⁱ	91.26 (9)	H4A—C4—H4C	109.5
O1—Cd1—O1ⁱ	180.00 (11)	H4B—C4—H4C	109.5
C2—O1—Cd1	120.12 (16)	O1—C2—N4	124.5 (2)
C1—N1—Cd1	145.5 (2)	O1—C2—H2A	117.7
C3ⁱⁱ—N2—C1	122.3 (2)	N4—C2—H2A	117.7
C2—N4—C4	121.4 (3)	N3—C3—N2ⁱⁱ	172.2 (3)
C2—N4—C5	120.8 (2)

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

Experimental details

Crystal data
Chemical formula	[Cd(C₂N₃)₂(C₃H₇NO)₂]
M_r	390.70
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	6.5325 (13), 7.6003 (15), 8.6051 (17)
α, β, γ (°)	104.28 (3), 106.90 (3), 97.05 (3)
V (Å³)	387.35 (17)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.43
Crystal size (mm)	0.2 × 0.16 × 0.12

Data collection
Diffractometer	Rigaku Saturn724+ diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.239, 0.480
No. of measured, independent and observed [I > 2σ(I)] reflections	3505, 1410, 1408
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.058, 1.10
No. of reflections	1410
No. of parameters	97
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.36

Computer programs: CrystalClear (Rigaku, 2008), SHELXS97 (Sheldrick, 2008), SHELXT07 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

This work was supported by the Foundation of Jiangsu University (08JDG036).

References

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