catena-Poly[[bis­[4-(dimethyl­amino)­pyridine-κN1]cobalt(II)]-di-μ-azido-κ4N1:N3]

Guenifa, F.; Zeghouan, O.; Hadjadj, N.; Bendjeddou, L.; Merazig, H.

doi:10.1107/S1600536813005205

metal-organic compounds

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doi:10.1107/S1600536813005205

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catena-Poly[[bis[4-(dimethylamino)pyridine-κN¹]cobalt(II)]-di-μ-azido-κ⁴N¹:N³]

Fatiha Guenifa,^a Ouahida Zeghouan,^a Nasreddine Hadjadj,^a Lamia Bendjeddou ^a ^* and Hocine Merazig ^a

^aUnité de Recherche de Chimie de l'Environnement et Moléculaire Structurale (CHEMS), Faculté des Sciences Exactes, Campus Chaabet Ersas, Université Constantine I, 25000 Constantine, Algeria
^*Correspondence e-mail: Lamiabendjeddou@yahoo.fr

(Received 10 February 2013; accepted 22 February 2013; online 28 February 2013)

The title layered polymer, [Co(N₃)₂(C₇H₁₀N₂)₂]_n, contains Co^II, azide and 4-(dimethylamino)pyridine (4-DMAP) species with site symmetries m2m, 2 and m, respectively. The Co²⁺ ion adopts an octahedral coordination geometry in which four N atoms from azide ligands lie in the equatorial plane and two 4-DMAP N atoms occupy the axial positions. The Co^II atoms are connected by two bridging azide ligands, resulting in a chain parallel to the c axis.

Related literature

For applications of coordination polymers, see: Fujita et al. (1994 ); Hagrman et al. (1999 ); Hoskins & Robson (1990 ); Yaghi & Li (1995 ). For a related Cu complex, see: Dalai et al. (2002 ).

Experimental

Crystal data

[Co(N₃)₂(C₇H₁₀N₂)₂]
M_r = 387.33
Orthorhombic, C m c m
a = 9.622 (5) Å
b = 18.404 (5) Å
c = 9.734 (5) Å
V = 1723.7 (13) Å³
Z = 4
Mo Kα radiation
μ = 1.02 mm⁻¹
T = 293 K
0.1 × 0.09 × 0.08 mm

Data collection

Bruker APEXII diffractometer
5192 measured reflections
1393 independent reflections
1099 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.086
S = 1.07
1393 reflections
79 parameters
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Table 1
Selected bond lengths (Å)

Co—N1	2.1764 (19)
Co—N1A	2.110 (3)
Co—N1B	2.135 (3)

Data collection: APEX2 (Bruker, 2006 ); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: SIR2002 (Burla et al., 2003 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: WinGX (Farrugia, 2012), Mercury (Macrae et al., 2006 ) and POVRay (Persistence of Vision Team, 2004 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813005205/vm2189sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813005205/vm2189Isup2.hkl

checkCIF report

Comment top

The chemistry of coordination polymers has evolved rapidly in recent years and a variety of topologies has been constructed through ligand design and the use of different transition metal geometries. These polymers may have interesting properties and applications, e.g. adsorption, ion exchange, non-linear optical and magnetic materials (Hoskins et al., 1990; Fujita et al., 1994; Yaghi & Li, 1995; Hagrman et al., 1999).

Pseudohalide anions are excellent ligands for obtaining discrete, one-dimensional, two-dimensional or three-dimensional systems. Among these, the azido ligand is the most versatile in linking divalent metal ions. When the azide group acts as bridging ligand there are two typical coordination modes: end-to-end (EE or µ-1,3) in which the resulting complexes usually shows ferromagnetic behavior, and end-on (EO or µ-1,1) which results in antiferromagnetic behavior.

In the course of our investigation of functional coordination complexes and polymers, a new azide-bridged coordination polymer with 4-dimethylaminopyridine has been prepared and structurally characterized.

Part of the structure of (I) with the atom numbering scheme is shown in Figure 1. The structure consists of layers of cobalt atoms linked by double end-to-end (EE) azido bridges, placed along the [001] direction at b = 0 and b = 1/2, forming a one-dimensional polymeric chain with each cobalt(II) ion in an octahedral environment (Fig. 2). In the crystal, parallel one-dimensional polymers form a three-dimensional network. The minimum interdinuclear Co···Co distance bridged by the EE-azido ligands is 5.097 (2) Å. In this structure, the ligand L displays monodentate binding to Co^II.

The octahedral coordination around the cobalt(II) atoms (Fig. 3, Table 1) consists of two L ligands coordinated via the pyridine nitrogen atom which occupy the axial positions (Co—N1A = 2.110 (3) Å and Co—N1B = 2.135 (3) Å) and four azide bridges in the equatorial plane (Co—N1 = 2.1764 (19) Å) which act as symmetrical end-to-end (µ-1,3) double bridges betwee two neighboring cobalt atoms.

This structure can be compared with that observed for [Cu(L)2(N3)2]n (L: 4-dimethylaminopyridine (Dalai et al., 2002), which shows also double end-to-end (EE) azido bridges. Here each copper is bonded to two nitrogen atoms of the pyridine ligands (1.999 (7) Å, 2.014 (7) Å) and two nitrogen atoms of the azide (2.029 (5) Å). There are also two weak attachments to two nitrogen atoms of the azide (2.611 (6) Å) in axial positions to create a doubl EE-bridged one-dimensional polymer with each copper(II) ion in a pseudo-octahedral environment. The distance between two neighboring copper ions is 5.20 (1) Å.

Related literature top

For applications of coordination polymers, see: Fujita et al. (1994); Hagrman et al. (1999); Hoskins & Robson (1990); Yaghi & Li (1995). For a related Cu complex, see: Dalai et al. (2002).

Experimental top

A mixture of NaN₃ and CoCl₂.6H₂O in methanol was stirred for half an hour, then 4-dimethylaminopyridine was added to the solution and the reaction continued to stir for one hour. After filtration, the pink filtrate was allowed to stand at room temperature. Pink crystals were obtained by slow evaporation.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012), Mercury (Macrae et al., 2006) and POVRay (Persistence of Vision Team, 2004).

Figures top

	Fig. 1. View of the structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are represented as spheres of arbitrary radii [symmetry codes: (i) x + 1, y, -z + 1/2; (ii) x, y, -z + 1/2; (iii) x + 1, y, z; (v) x + 1, -y + 1, -z; (vii) x + 1, -y + 1, z + 1/2; (viii) x + 1, -y + 1, z - 1/2; (ix) x, -y + 1, z - 1/2; (x) x, -y + 1, -z; (xvii) x, -y + 1, z + 1/2; (xviii) x, -y + 1, -z + 1; (xix) x + 1, -y + 1, -z + 1].
	Fig. 2. View of part of the crystal structure of (I), showing layers along the [001] direction. Hydrogen atoms are omitted for clarity.
	Fig. 3. Part of the crystal structure, showing the octahedral coordination around the cobalt(II) atoms. Hydrogen atoms are omitted for clarity [symmetry codes: (i): -x + 1,y,-z + 1/2; (ii): x,y,-z + 1/2; (iii): -x + 1,y,z].

catena-Poly[[bis[4-(dimethylamino)pyridine-κN¹]cobalt(II)]-di-µ-azido-κ⁴N¹,N³] top

Crystal data top

[Co(N₃)₂(C₇H₁₀N₂)₂]	F(000) = 804
M_r = 387.33	D_x = 1.493 Mg m⁻³
Orthorhombic, Cmcm	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2c 2	Cell parameters from 1393 reflections
a = 9.622 (5) Å	θ = 3.1–30.0°
b = 18.404 (5) Å	µ = 1.02 mm⁻¹
c = 9.734 (5) Å	T = 293 K
V = 1723.7 (13) Å³	Needle, pink
Z = 4	0.1 × 0.09 × 0.08 mm

Data collection top

Bruker APEXII diffractometer	1099 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.031
Graphite monochromator	θ_max = 30.0°, θ_min = 3.1°
ϕ scans	h = −11→13
5192 measured reflections	k = −25→25
1393 independent reflections	l = −9→13

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.032	w = 1/[σ²(F_o²) + (0.0383P)² + 1.0521P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.086	(Δ/σ)_max < 0.001
S = 1.07	Δρ_max = 0.43 e Å⁻³
1393 reflections	Δρ_min = −0.37 e Å⁻³
79 parameters

Crystal data top

[Co(N₃)₂(C₇H₁₀N₂)₂]	V = 1723.7 (13) Å³
M_r = 387.33	Z = 4
Orthorhombic, Cmcm	Mo Kα radiation
a = 9.622 (5) Å	µ = 1.02 mm⁻¹
b = 18.404 (5) Å	T = 293 K
c = 9.734 (5) Å	0.1 × 0.09 × 0.08 mm

Data collection top

Bruker APEXII diffractometer	1099 reflections with I > 2σ(I)
5192 measured reflections	R_int = 0.031
1393 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.086	H-atom parameters constrained
S = 1.07	Δρ_max = 0.43 e Å⁻³
1393 reflections	Δρ_min = −0.37 e Å⁻³
79 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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	Occ. (<1)
Co	0.50000	0.45887 (2)	0.25000	0.0257 (1)
N1	0.33908 (16)	0.45953 (7)	0.09288 (16)	0.0355 (4)
N1A	0.50000	0.34420 (13)	0.25000	0.0267 (8)
N1B	0.50000	0.57488 (14)	0.25000	0.0279 (8)
N2	0.34145 (19)	0.50000	0.00000	0.0263 (5)
N2A	0.50000	0.11621 (15)	0.25000	0.0383 (10)
N2B	0.50000	0.80246 (14)	0.25000	0.0358 (9)
C1A	0.50000	0.07558 (14)	0.1240 (3)	0.0536 (10)
C1B	0.6285 (3)	0.84282 (14)	0.25000	0.0514 (9)
C2A	0.50000	0.19006 (16)	0.25000	0.0280 (9)
C2B	0.50000	0.72899 (16)	0.25000	0.0264 (9)
C3A	0.50000	0.23072 (12)	0.1278 (3)	0.0315 (7)
C3B	0.6237 (2)	0.68797 (12)	0.25000	0.0318 (7)
C4A	0.50000	0.30567 (12)	0.1330 (3)	0.0311 (7)
C4B	0.6178 (2)	0.61381 (12)	0.25000	0.0313 (7)
H1B1	0.60862	0.89393	0.25000	0.0769*
H1B2	0.68126	0.83069	0.16947	0.0769*	0.500
H1B3	0.68126	0.83069	0.33053	0.0769*	0.500
H3A	0.50000	0.20711	0.04332	0.0377*
H3B	0.70933	0.71138	0.25000	0.0382*
H1A1	0.50000	0.02454	0.14436	0.0805*
H4A	0.50000	0.33101	0.05031	0.0373*
H4B	0.70142	0.58851	0.25000	0.0376*
H1A2	0.58146	0.08752	0.07175	0.0805*	0.500
H1A3	0.41854	0.08752	0.07175	0.0805*	0.500

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co	0.0356 (3)	0.0196 (2)	0.0218 (2)	0.0000	0.0000	0.0000
N1	0.0437 (8)	0.0333 (7)	0.0296 (8)	−0.0070 (6)	−0.0062 (7)	0.0078 (6)
N1A	0.0357 (15)	0.0223 (11)	0.0222 (14)	0.0000	0.0000	0.0000
N1B	0.0291 (14)	0.0221 (12)	0.0324 (16)	0.0000	0.0000	0.0000
N2	0.0259 (9)	0.0259 (8)	0.0270 (10)	0.0000	0.0000	−0.0017 (8)
N2A	0.0530 (19)	0.0234 (13)	0.0385 (18)	0.0000	0.0000	0.0000
N2B	0.0355 (15)	0.0209 (12)	0.051 (2)	0.0000	0.0000	0.0000
C1A	0.074 (2)	0.0299 (13)	0.057 (2)	0.0000	0.0000	−0.0100 (13)
C1B	0.0459 (16)	0.0292 (12)	0.079 (2)	−0.0094 (11)	0.0000	0.0000
C2A	0.0265 (15)	0.0234 (13)	0.0341 (19)	0.0000	0.0000	0.0000
C2B	0.0277 (15)	0.0242 (13)	0.0272 (17)	0.0000	0.0000	0.0000
C3A	0.0422 (13)	0.0266 (10)	0.0256 (12)	0.0000	0.0000	−0.0049 (9)
C3B	0.0227 (10)	0.0283 (10)	0.0445 (15)	−0.0022 (8)	0.0000	0.0000
C4A	0.0450 (13)	0.0274 (10)	0.0209 (12)	0.0000	0.0000	0.0016 (9)
C4B	0.0242 (11)	0.0287 (10)	0.0411 (14)	0.0036 (8)	0.0000	0.0000

Geometric parameters (Å, º) top

Co—N1	2.1764 (19)	C2A—C3A	1.405 (3)
Co—N1A	2.110 (3)	C2A—C3Aⁱ	1.405 (3)
Co—N1B	2.135 (3)	C2B—C3B	1.410 (3)
Co—N1ⁱ	2.1764 (19)	C2B—C3Bⁱ	1.410 (3)
Co—N1ⁱⁱ	2.1764 (19)	C3A—C4A	1.380 (3)
Co—N1ⁱⁱⁱ	2.1764 (19)	C3B—C4B	1.366 (3)
N1—N2	1.1716 (16)	C1A—H1A1	0.9600
N1A—C4A	1.342 (3)	C1A—H1A2	0.9600
N1A—C4Aⁱ	1.342 (3)	C1A—H1A3	0.9600
N1B—C4B	1.341 (3)	C1B—H1B1	0.9600
N1B—C4Bⁱ	1.340 (3)	C1B—H1B2	0.9600
N2A—C1A	1.437 (3)	C1B—H1B3	0.9600
N2A—C2A	1.359 (4)	C3A—H3A	0.9300
N2A—C1Aⁱ	1.437 (3)	C3B—H3B	0.9300
N2B—C1B	1.442 (3)	C4A—H4A	0.9300
N2B—C2B	1.352 (4)	C4B—H4B	0.9300
N2B—C1Bⁱ	1.442 (3)

N1—Co—N1A	90.32 (4)	N2A—C2A—C3Aⁱ	122.17 (14)
N1—Co—N1B	89.68 (4)	C3A—C2A—C3Aⁱ	115.7 (2)
N1—Co—N1ⁱ	179.36 (5)	N2B—C2B—C3B	122.39 (13)
N1—Co—N1ⁱⁱ	89.29 (6)	N2B—C2B—C3Bⁱ	122.39 (13)
N1—Co—N1ⁱⁱⁱ	90.70 (6)	C3B—C2B—C3Bⁱ	115.2 (2)
N1A—Co—N1B	180.00	C2A—C3A—C4A	120.1 (3)
N1ⁱ—Co—N1A	90.32 (4)	C2B—C3B—C4B	120.00 (19)
N1ⁱⁱ—Co—N1A	90.32 (4)	N1A—C4A—C3A	124.0 (3)
N1ⁱⁱⁱ—Co—N1A	90.32 (4)	N1B—C4B—C3B	124.68 (19)
N1ⁱ—Co—N1B	89.68 (4)	N2A—C1A—H1A1	109.00
N1ⁱⁱ—Co—N1B	89.68 (4)	N2A—C1A—H1A2	109.00
N1ⁱⁱⁱ—Co—N1B	89.68 (4)	N2A—C1A—H1A3	109.00
N1ⁱ—Co—N1ⁱⁱ	90.70 (6)	H1A1—C1A—H1A2	109.00
N1ⁱ—Co—N1ⁱⁱⁱ	89.29 (6)	H1A1—C1A—H1A3	109.00
N1ⁱⁱ—Co—N1ⁱⁱⁱ	179.36 (5)	H1A2—C1A—H1A3	109.00
Co—N1—N2	122.14 (12)	N2B—C1B—H1B1	110.00
Co—N1A—C4A	121.91 (14)	N2B—C1B—H1B2	109.00
Co—N1A—C4Aⁱ	121.91 (14)	N2B—C1B—H1B3	109.00
C4A—N1A—C4Aⁱ	116.2 (2)	H1B1—C1B—H1B2	109.00
Co—N1B—C4B	122.30 (13)	H1B1—C1B—H1B3	109.00
Co—N1B—C4Bⁱ	122.32 (13)	H1B2—C1B—H1B3	109.00
C4B—N1B—C4Bⁱ	115.4 (2)	C2A—C3A—H3A	120.00
N1—N2—N1^iv	177.8 (2)	C4A—C3A—H3A	120.00
C1A—N2A—C2A	121.37 (14)	C2B—C3B—H3B	120.00
C1A—N2A—C1Aⁱ	117.3 (2)	C4B—C3B—H3B	120.00
C1Aⁱ—N2A—C2A	121.37 (14)	N1A—C4A—H4A	118.00
C1B—N2B—C2B	121.00 (14)	C3A—C4A—H4A	118.00
C1B—N2B—C1Bⁱ	118.0 (2)	N1B—C4B—H4B	118.00
C1Bⁱ—N2B—C2B	121.00 (14)	C3B—C4B—H4B	118.00
N2A—C2A—C3A	122.17 (14)

Symmetry codes: (i) −x+1, y, −z+1/2; (ii) x, y, −z+1/2; (iii) −x+1, y, z; (iv) x, −y+1, −z.

Experimental details

Crystal data
Chemical formula	[Co(N₃)₂(C₇H₁₀N₂)₂]
M_r	387.33
Crystal system, space group	Orthorhombic, Cmcm
Temperature (K)	293
a, b, c (Å)	9.622 (5), 18.404 (5), 9.734 (5)
V (Å³)	1723.7 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.02
Crystal size (mm)	0.1 × 0.09 × 0.08

Data collection
Diffractometer	Bruker APEXII diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	5192, 1393, 1099
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.704

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.086, 1.07
No. of reflections	1393
No. of parameters	79
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.37

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SIR2002 (Burla et al., 2003), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), WinGX (Farrugia, 2012), Mercury (Macrae et al., 2006) and POVRay (Persistence of Vision Team, 2004).

Selected bond lengths (Å) top

Co—N1	2.1764 (19)	Co—N1B	2.135 (3)
Co—N1A	2.110 (3)

Acknowledgements

This work was supported by the Unité de Recherche de Chimie de l'Environnement et Moléculaire Structurale (CHEMS), Université de Constantine 1, Algeria. Thanks are also due to MESRS and ATRST (Ministère de l'Enseignement Supérieur et de la Recherche Scientifique et l'Agence Thématique de Recherche en Sciences et Technologie, Algérie) via the PNR program for financial support.

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