A triclinic polymorph of catena-poly[[bis­(N,N-dimethyl­formamide-κO)cobalt(II)]-di-μ-1,5-dicyanamido-κ4N1:N5]

Meng, S.C.

doi:10.1107/S1600536812043310

metal-organic compounds

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Volume 68| Part 11| November 2012| Page m1404

doi:10.1107/S1600536812043310

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A triclinic polymorph of catena-poly[[bis(N,N-dimethylformamide-κO)cobalt(II)]-di-μ-1,5-dicyanamido-κ⁴N¹:N⁵]

S. C. Meng ^a ^*

^aSchool of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, People's Republic of China
^*Correspondence e-mail: mengsc@ujs.edu.cn

(Received 10 October 2012; accepted 18 October 2012; online 24 October 2012)

The title compound, [Co(C₂N₃)₂(C₃H₇NO)₂]_n, is a triclinic polymorph of the previously reported monoclinic structure [Tong et al. (2003 ). Acta Cryst. E59, m405–m407]. The Co^II ion lies on an inversion centre and adopts an almost regular octahedral N₄O₂ coordination geometry. Adjacent Co^II atoms are connected by two bridging dicyanamide ligands, resulting in the formation of neutral chains parallel to the b axis. The title complex is isotypic with the Mn^II analogue but not with the Ni^II analogue.

Related literature

For the design and synthesis of metal-organic compounds, see: Long & Yaghi (2009 ). For the structures of the Mn^II and Ni^II analogues, see: Batten et al. (1999 ); Shen & Yuan (2005 ). For the structure of the monoclinic polymorph, see: Tong et al. (2003).

Experimental

Crystal data

[Co(C₂N₃)₂(C₃H₇NO)₂]
M_r = 337.22
Triclinic, $[P \overline 1]$
a = 6.4315 (13) Å
b = 7.3879 (15) Å
c = 8.6210 (17) Å
α = 105.69 (3)°
β = 107.94 (3)°
γ = 96.19 (3)°
V = 366.93 (17) Å³
Z = 1
Mo Kα radiation
μ = 1.19 mm⁻¹
T = 150 K
0.22 × 0.18 × 0.15 mm

Data collection

Rigaku Saturn724+ diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008 ) T_min = 0.845, T_max = 1.000
2514 measured reflections
1319 independent reflections
1242 reflections with I > 2σ(I)
R_int = 0.015

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.061
S = 1.04
1319 reflections
97 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.24 e Å⁻³

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

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812043310/rz5015sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812043310/rz5015Isup2.hkl

checkCIF report

Comment top

The design and synthesis of metal-organic compounds have attracted great attention in recent years (Long & Yaghi, 2009), in particular focusing on the properties of flexible bridging ligands able to construct metal-organic compounds with various structures. The title compound is constructed by the flexible dicyanamide bridging ligand through diffusion reaction.

As illustrated in Fig. 1, the cobalt(II) ion lies on an inversion centre and adopts an octahedral coordination geometry. Metal atoms are connected by two dicyanamide bridging ligands, resulting in the formation of neutral chains parallel the b axis. The title complex is isotypic with the Mn analogue (Batten et al., 1999) but not with the Ni analogue (Shen & Yuan, 2005). A monoclinic polymorph of the title compound was previously reported (Tong et al., 2003).

Related literature top

For the design and synthesis of metal-organic compounds, see: Long & Yaghi (2009). For the structures of the Mn and Ni analogues, see: Batten et al. (1999); Shen & Yuan (2005). For the structure of the monoclinic polymorph, see: Tong et al. (2003).

Experimental top

Co(NO₃)₂.6H₂O (116.6 mg, 0.4 mmol) was added into 1 ml dmf with thorough stir for 5 minutes. After filtration, the purple filtrate was carefully laid on the surface with a solution of NaN(CN)₂ (89.1 mg, 1 mmol) in 1 ml dmf and 4 ml i-PrOH. Purple block crystals were obtained after five days.

Computing details top

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

Figures top

Fig. 1. The polymeric structure of the title compound, with atom labels and 30% probability displacement ellipsoids. All H atoms have been omitted. Symmetry code: (i) 1 - x, -y, 1 - z.

catena-poly[[bis(N,N-dimethylformamide- κO)cobalt(II)]-di-µ-1,5-dicyanamido-κ⁴N¹:N⁵] top

Crystal data top

[Co(C₂N₃)₂(C₃H₇NO)₂]	Z = 1
M_r = 337.22	F(000) = 173
Triclinic, P1	D_x = 1.526 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.4315 (13) Å	Cell parameters from 1585 reflections
b = 7.3879 (15) Å	θ = 4.5–29.1°
c = 8.6210 (17) Å	µ = 1.19 mm⁻¹
α = 105.69 (3)°	T = 150 K
β = 107.94 (3)°	Block, purple
γ = 96.19 (3)°	0.22 × 0.18 × 0.15 mm
V = 366.93 (17) Å³

Data collection top

Rigaku Saturn724+ diffractometer	1319 independent reflections
Radiation source: fine-focus sealed tube	1242 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.015
ω scans	θ_max = 25.3°, θ_min = 4.0°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008)	h = −7→7
T_min = 0.845, T_max = 1.000	k = −8→7
2514 measured reflections	l = −10→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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.061	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0266P)² + 0.119P] where P = (F_o² + 2F_c²)/3
1319 reflections	(Δ/σ)_max < 0.001
97 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

[Co(C₂N₃)₂(C₃H₇NO)₂]	γ = 96.19 (3)°
M_r = 337.22	V = 366.93 (17) Å³
Triclinic, P1	Z = 1
a = 6.4315 (13) Å	Mo Kα radiation
b = 7.3879 (15) Å	µ = 1.19 mm⁻¹
c = 8.6210 (17) Å	T = 150 K
α = 105.69 (3)°	0.22 × 0.18 × 0.15 mm
β = 107.94 (3)°

Data collection top

Rigaku Saturn724+ diffractometer	1319 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008)	1242 reflections with I > 2σ(I)
T_min = 0.845, T_max = 1.000	R_int = 0.015
2514 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	0 restraints
wR(F²) = 0.061	H-atom parameters constrained
S = 1.04	Δρ_max = 0.22 e Å⁻³
1319 reflections	Δρ_min = −0.24 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
Co1	0.5000	0.0000	0.5000	0.03475 (14)
O1	0.7337 (2)	0.1252 (2)	0.75360 (17)	0.0458 (3)
N1	0.3153 (3)	−0.1843 (2)	0.5846 (2)	0.0450 (4)
N2	0.3184 (3)	0.2157 (2)	0.5512 (2)	0.0461 (4)
N3	0.2307 (3)	−0.4729 (2)	0.6597 (2)	0.0540 (5)
N4	1.0908 (3)	0.2096 (2)	0.9389 (2)	0.0429 (4)
C1	0.2790 (3)	−0.3244 (3)	0.6133 (2)	0.0361 (4)
C2	0.2822 (3)	0.3654 (3)	0.5966 (2)	0.0335 (4)
C3	0.9359 (3)	0.1312 (3)	0.7855 (2)	0.0397 (4)
H3C	0.9817	0.0763	0.6944	0.048*
C4	1.0358 (5)	0.3018 (4)	1.0885 (3)	0.0620 (6)
H4A	0.8777	0.2958	1.0544	0.093*
H4B	1.1137	0.4337	1.1379	0.093*
H4C	1.0796	0.2367	1.1720	0.093*
C5	1.3232 (4)	0.2040 (4)	0.9659 (3)	0.0666 (7)
H5A	1.3381	0.1399	0.8582	0.100*
H5B	1.3753	0.1357	1.0456	0.100*
H5C	1.4105	0.3329	1.0117	0.100*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0364 (2)	0.02626 (19)	0.0418 (2)	0.00779 (14)	0.01291 (16)	0.01186 (15)
O1	0.0401 (8)	0.0490 (8)	0.0434 (8)	0.0089 (6)	0.0120 (7)	0.0100 (7)
N1	0.0503 (10)	0.0333 (9)	0.0546 (11)	0.0081 (7)	0.0214 (9)	0.0163 (8)
N2	0.0510 (10)	0.0356 (9)	0.0582 (11)	0.0160 (8)	0.0235 (9)	0.0177 (8)
N3	0.0846 (14)	0.0345 (9)	0.0629 (12)	0.0196 (9)	0.0489 (11)	0.0178 (9)
N4	0.0446 (10)	0.0461 (9)	0.0336 (9)	0.0087 (8)	0.0104 (8)	0.0102 (7)
C1	0.0374 (10)	0.0322 (10)	0.0381 (10)	0.0096 (8)	0.0155 (9)	0.0070 (8)
C2	0.0331 (9)	0.0331 (10)	0.0348 (10)	0.0050 (8)	0.0114 (8)	0.0127 (8)
C3	0.0451 (12)	0.0366 (10)	0.0370 (11)	0.0083 (9)	0.0145 (9)	0.0110 (8)
C4	0.0828 (18)	0.0611 (14)	0.0381 (12)	0.0177 (13)	0.0210 (12)	0.0087 (11)
C5	0.0450 (13)	0.0853 (18)	0.0556 (15)	0.0097 (12)	0.0047 (11)	0.0174 (13)

Geometric parameters (Å, º) top

Co1—N2ⁱ	2.1061 (17)	N4—C3	1.313 (3)
Co1—N2	2.1061 (17)	N4—C5	1.448 (3)
Co1—O1	2.1157 (17)	N4—C4	1.452 (3)
Co1—O1ⁱ	2.1157 (17)	C2—N3ⁱⁱⁱ	1.295 (2)
Co1—N1	2.1254 (17)	C3—H3C	0.9300
Co1—N1ⁱ	2.1254 (17)	C4—H4A	0.9600
O1—C3	1.237 (2)	C4—H4B	0.9600
N1—C1	1.145 (2)	C4—H4C	0.9600
N2—C2	1.144 (2)	C5—H5A	0.9600
N3—C2ⁱⁱ	1.295 (2)	C5—H5B	0.9600
N3—C1	1.304 (2)	C5—H5C	0.9600

N2ⁱ—Co1—N2	180.00 (11)	C3—N4—C4	121.59 (19)
N2ⁱ—Co1—O1	90.92 (7)	C5—N4—C4	117.31 (19)
N2—Co1—O1	89.08 (7)	N1—C1—N3	173.5 (2)
N2ⁱ—Co1—O1ⁱ	89.08 (7)	N2—C2—N3ⁱⁱⁱ	173.04 (19)
N2—Co1—O1ⁱ	90.92 (7)	O1—C3—N4	124.73 (18)
O1—Co1—O1ⁱ	180.0	O1—C3—H3C	117.6
N2ⁱ—Co1—N1	88.01 (7)	N4—C3—H3C	117.6
N2—Co1—N1	91.99 (7)	N4—C4—H4A	109.5
O1—Co1—N1	90.34 (7)	N4—C4—H4B	109.5
O1ⁱ—Co1—N1	89.66 (7)	H4A—C4—H4B	109.5
N2ⁱ—Co1—N1ⁱ	91.99 (7)	N4—C4—H4C	109.5
N2—Co1—N1ⁱ	88.01 (7)	H4A—C4—H4C	109.5
O1—Co1—N1ⁱ	89.66 (7)	H4B—C4—H4C	109.5
O1ⁱ—Co1—N1ⁱ	90.34 (7)	N4—C5—H5A	109.5
N1—Co1—N1ⁱ	180.00 (8)	N4—C5—H5B	109.5
C3—O1—Co1	121.36 (13)	H5A—C5—H5B	109.5
C1—N1—Co1	151.54 (16)	N4—C5—H5C	109.5
C2—N2—Co1	159.60 (16)	H5A—C5—H5C	109.5
C2ⁱⁱ—N3—C1	120.72 (16)	H5B—C5—H5C	109.5
C3—N4—C5	121.09 (18)

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

Experimental details

Crystal data
Chemical formula	[Co(C₂N₃)₂(C₃H₇NO)₂]
M_r	337.22
Crystal system, space group	Triclinic, P1
Temperature (K)	150
a, b, c (Å)	6.4315 (13), 7.3879 (15), 8.6210 (17)
α, β, γ (°)	105.69 (3), 107.94 (3), 96.19 (3)
V (Å³)	366.93 (17)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.19
Crystal size (mm)	0.22 × 0.18 × 0.15

Data collection
Diffractometer	Rigaku Saturn724+ diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2008)
T_min, T_max	0.845, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	2514, 1319, 1242
R_int	0.015
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.061, 1.04
No. of reflections	1319
No. of parameters	97
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.24

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

Acknowledgements

This work was supported by the Foundation of Jiangsu University (08JDG037).

References

Batten, S. R., Jensen, P., Kepert, C. J., Kurmoo, M., Moubaraki, B., Murray, K. S. & Price, D. J. (1999). J. Chem. Soc. Dalton Trans. pp. 2987–2997 CrossRef Google Scholar
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