catena-Poly[[bis­(dimethyl­formamide-κO)cadmium(II)]-di-μ₂-dicyanamido-κ⁴ N ¹:N ⁵]

Abstract

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,

• 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) ų

• 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[F ² > 2σ(F ²)] = 0.022

• wR(F ²) = 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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

H atoms were positioned geometrically and refined with riding model, with U_iso = 1.5 and 1.2 U_eq for methyl and formyl H atoms, respectively. The C—H bonds are 0.96 Å in methyl and 0.93 Å in formyl.

Figures

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).

Crystal data

[Cd(C2N3)2(C3H7NO)2]	Z = 1
Mr = 390.70	F(000) = 194
Triclinic, P1	Dx = 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

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

Refinement

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(Fo2) + (0.039P)2 + 0.0503P] where P = (Fo2 + 2Fc2)/3
1410 reflections	(Δ/σ)max < 0.001
97 parameters	Δρmax = 0.44 e Å−3
0 restraints	Δρmin = −0.36 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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.