catena-Poly­[[bis(N,N-di­methyl­form­amide)­cobalt(II)]-di-μ-1,5-dicyan­amido]

A pair of L-shaped dicyan­amide anions link the bis(N,N-di­methyl­form­amide)­cobalt(II) units into a linear chain running along the b axis of the monoclinic crystal of (C₂N₃)₂(DMF)₂Co. The Co atom and the dicyan­amido bridging ligand occupy special positions of symmetry 2/m and m, respectively. The coordination polyhedron of the Co atom is close to a regular octahedron.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](N-C) = 0.005 Å
• R factor = 0.029
• wR factor = 0.087
• Data-to-parameter ratio = 11.6

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



ABSTM_02  Alert C The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
          Tmin and Tmax reported:      0.528     0.721
          Tmin' and Tmax expected:      0.605     0.705
          RR' =      0.853
          Please check that your absorption correction is appropriate.

PLAT_702  Alert C Angle   Calc    88.44(5), Rep   88.50(10), Dev..       1.20 Sigma
                     O1   -CO1  -N1      1.555   1.555   2.656

PLAT_702  Alert C Angle   Calc    88.44(5), Rep   88.50(10), Dev..       1.20 Sigma
                     O1   -CO1  -N1      1.555   1.555   5.666

PLAT_702  Alert C Angle   Calc    88.44(5), Rep   88.50(10), Dev..       1.20 Sigma
                     O1   -CO1  -N1      5.666   1.555   1.555

PLAT_702  Alert C Angle   Calc    88.44(5), Rep   88.50(10), Dev..       1.20 Sigma
                     O1   -CO1  -N1      5.666   1.555   6.565

PLAT_731  Alert C Bond    Calc     0.94(3), Rep   0.940(10) ......       3.00 su-Rat
                     C2   -H2      1.555   1.555

PLAT_731  Alert C Bond    Calc     0.94(3), Rep   0.940(10) ......       3.00 su-Rat
                     C3   -H3A     1.555   1.555

PLAT_731  Alert C Bond    Calc     0.95(3), Rep   0.950(10) ......       3.00 su-Rat
                     C3   -H3B     1.555   1.555

PLAT_731  Alert C Bond    Calc     0.93(4), Rep   0.940(10) ......       4.00 su-Rat
                     C4   -H4A     1.555   1.555

PLAT_733  Alert C Torsion Calc   -46.02(4), Rep  -46.00(10) ......       2.50 su-Rat
                     N1  -CO1 -O1  -C2     1.555   1.555   1.555   1.555

PLAT_733  Alert C Torsion Calc   133.98(4), Rep  134.00(10) ......       2.50 su-Rat
                     N1  -CO1 -O1  -C2     5.666   1.555   1.555   1.555

PLAT_733  Alert C Torsion Calc    46.02(4), Rep   46.00(10) ......       2.50 su-Rat
                     N1  -CO1 -O1  -C2     6.565   1.555   1.555   1.555

PLAT_733  Alert C Torsion Calc  -133.98(4), Rep -134.00(10) ......       2.50 su-Rat
                     N1  -CO1 -O1  -C2     2.656   1.555   1.555   1.555

PLAT_735  Alert C D-H     Calc     0.94(3), Rep   0.940(10) ......       3.00 su-Rat
                     C2   -H2      1.555   1.555

PLAT_736  Alert C H...A   Calc     2.54(3), Rep   2.530(10) ......       3.00 su-Rat
                     H2   -N2      1.555   7.666


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 15 Alert Level C = Please check

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S1. Comment

Owing to its capacity for binding to metal atoms in different modes, the dicyanamido anion, [N(CN)₂]⁻ (dca), is an excellent building block for the synthesis of a wide range of metal complexes. Polymeric dicyanamido complexes possess interesting magnetic properties and unusual coordination architectures (Miller & Manson, 2001). A number of one-, two- and three-dimensional coordination polymers featuring various structural motifs have been reported. The one-dimensional [M(dca)₂L] chains (L = neutral terminal or chelating ligand) (Manson et al., 1999; Vangdal et al., 2002), two-dimensional β-M(dca)₂ sheets and three-dimensional rutile-like α-M(dca)₂ networks (Miller & Manson, 2001), along with other motifs (Gao et al., 2002; Shi et al., 2002; Yeung et al., 2002) may be mentioned as a few examples. The recently published structures of benzyltrialkylammonium tris(dicyanamido)metalates, [C₆H₅CH₂NR₃][M(dca)₃] (R = n-C₄H₉, M = Mn, Co; R = C₂H₅, M = Mn, Fe) (Tong et al., 2003), exhibit a three-dimensional architecture based on a cubic network of [MN₆] coordination octahedra, following the motif of the α-Po-like type, and bridged by the dca ligand.

In the title compound, (I), the bis-DMF adduct of Co(dca)₂, forms one-dimensional chains in the crystal (Fig. 1). The Co atom lies at the 2c Wyckoff position (1/2,1/2,1/2) of site symmetry 2/m. The dca occupies a special position across the mirror plane (Wyckoff 4i). The Co atom has an octahedral environment, formed by four N atoms belonging to four different dca groups [Co1—N1 2.123 (2) Å] and two O atoms of two DMF ligands [Co1—O1 2.096 (2) Å]; the DMF ligands, in compliance with symmetry requirements, are trans to each other. Adjacent chains are held together by a weak C—H···N hydrogen bond, forming layers parallel to the ab plane (Fig. 2; Table 2).

S2. Experimental

Cobalt(II) chloride (0.12 g, 0.5 mmol) and sodium dicyanamide (0.09 g, 1.0 mmol) were placed in a 10:1 v/v methanol/DMF mixture and the solution was heated until the reagents dissolved. Polyhedral crystals separated from the solution in about 80% yield after 10 d.

S3. Refinement

The diffraction data were of sufficiently high quality to allow for the refinement of the H atoms. These were refined subject to bond constraints of C—H = 0.95 (1) Å for the methyl groups, the H···H distance was restrained to 1.50 (1) Å.

Computing details

Data collection: CrystalClear (Rigaku, 2002); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-II (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. ORTEP (Johnson, 1976) plot depicting a fragment of the structure. Displacement ellipsoids are plotted at the 50% probability level; H atoms are shown as small spheres of arbitrary radii. [Symmetry codes: (i) 1 − x, 1 − y, 1 − z; (ii) 1 − x, y, 1 − z; (iii) x, 1 − y, z.]
	Fig. 2. ORTEP (Johnson, 1976) plot of the hydrogen-bonded layer structure.

catena-poly[bis(µ-1,5-dicyanamido)-bis(N,N-dimethylformamide)cobalt(II)]

Crystal data

C10H14CoN8O2	F(000) = 346
Mr = 337.22	Dx = 1.499 Mg m^−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
a = 13.525 (4) Å	Cell parameters from 282 reflections
b = 7.383 (2) Å	θ = 3.3–27.5°
c = 8.094 (3) Å	µ = 1.17 mm^−1
β = 112.399 (5)°	T = 293 K
V = 747.3 (4) Å^3	Block, pink
Z = 2	0.42 × 0.36 × 0.30 mm

Data collection

Rigaku Mercury CCD diffractometer	878 independent reflections
Radiation source: rotating-anode generator	847 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
ω scan	θmax = 27.5°, θmin = 3.3°
Absorption correction: multi-scan CrystalClear (Rigaku, 2002)	h = −17→12
Tmin = 0.528, Tmax = 0.721	k = −9→9
2432 measured reflections	l = −9→10

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.087	All H-atom parameters refined
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0676P)^2 + 0.0203P] where P = (Fo^2 + 2Fc^2)/3
878 reflections	(Δ/σ)max = 0.001
76 parameters	Δρmax = 0.36 e Å^−3
5 restraints	Δρmin = −0.36 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Co1	0.5000	0.5000	0.5000	0.0247 (2)
O1	0.5839 (1)	0.5000	0.7776 (2)	0.036 (1)
N1	0.5997 (1)	0.7068 (2)	0.4662 (2)	0.036 (1)
N2	0.6333 (2)	1.0000	0.3560 (3)	0.041 (1)
N3	0.7372 (2)	0.5000	1.0206 (3)	0.039 (1)
C1	0.6142 (1)	0.8476 (2)	0.4199 (2)	0.028 (1)
C2	0.6826 (2)	0.5000	0.8466 (3)	0.033 (1)
C3	0.6836 (3)	0.5000	1.1447 (4)	0.080 (1)
C4	0.8536 (2)	0.5000	1.0963 (4)	0.050 (1)
H2	0.726 (2)	0.5000	0.780 (4)	0.04 (1)*
H3a	0.738 (3)	0.5000	1.259 (4)	0.12 (2)*
H3b	0.646 (3)	0.389 (3)	1.131 (6)	0.16 (2)*
H4a	0.879 (3)	0.5000	1.004 (4)	0.06 (1)*
H4b	0.886 (2)	0.401 (2)	1.171 (3)	0.08 (1)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0297 (3)	0.0196 (3)	0.0242 (3)	0.000	0.0097 (2)	0.000
O1	0.035 (1)	0.048 (1)	0.024 (1)	0.000	0.009 (1)	0.000
N1	0.043 (1)	0.026 (1)	0.044 (1)	−0.004 (1)	0.023 (1)	−0.002 (1)
N2	0.062 (1)	0.026 (1)	0.052 (1)	0.000	0.042 (1)	0.000
N3	0.036 (1)	0.050 (1)	0.027 (1)	0.000	0.008 (1)	0.000
C1	0.027 (1)	0.028 (1)	0.031 (1)	0.000 (1)	0.015 (1)	−0.005 (1)
C2	0.038 (1)	0.035 (1)	0.027 (1)	0.000	0.013 (1)	0.000
C3	0.057 (2)	0.157 (5)	0.029 (1)	0.000	0.021 (1)	0.000
C4	0.036 (1)	0.061 (2)	0.043 (1)	0.000	0.004 (1)	0.000

Geometric parameters (Å, º)

Co1—O1	2.096 (2)	N2—C1	1.305 (2)
Co1—O1^i	2.096 (2)	N3—C2	1.318 (3)
Co1—N1	2.123 (2)	N3—C3	1.446 (4)
Co1—N1^ii	2.123 (2)	N3—C4	1.455 (4)
Co1—N1^i	2.123 (2)	C2—H2	0.94 (1)
Co1—N1^iii	2.123 (2)	C3—H3a	0.94 (1)
O1—C2	1.235 (3)	C3—H3b	0.95 (1)
N1—C1	1.147 (2)	C4—H4a	0.94 (1)
N2—C1^iv	1.305 (2)	C4—H4b	0.94 (1)
O1—Co1—O1^i	180	C1—N1—Co1	152.9 (1)
O1—Co1—N1	91.6 (1)	C1^iv—N2—C1	119.2 (2)
O1—Co1—N1^ii	88.5 (1)	C2—N3—C3	121.1 (2)
O1—Co1—N1^i	88.5 (1)	C2—N3—C4	121.7 (2)
O1—Co1—N1^iii	91.6 (1)	C3—N3—C4	117.1 (2)
O1^i—Co1—N1	88.5 (1)	N1—C1—N2	174.6 (2)
O1^i—Co1—N1^ii	91.6 (1)	O1—C2—N3	123.5 (2)
O1^i—Co1—N1^i	91.6 (1)	O1—C2—H2	123 (2)
O1^i—Co1—N1^iii	88.5 (1)	N3—C2—H2	113 (2)
N1—Co1—N1^ii	88.0 (1)	N3—C3—H3a	105 (4)
N1—Co1—N1^i	180.0 (1)	N3—C3—H3b	108 (3)
N1—Co1—N1^iii	92.0 (1)	H3a—C3—H3b	108 (3)
N1^i—Co1—N1^ii	92.0 (1)	N3—C4—H4a	110 (2)
N1^i—Co1—N1^iii	88.0 (1)	N3—C4—H4b	116 (2)
N1^ii—Co1—N1^iii	180.0 (1)	H4b—C4—H4b	107 (2)
C2—O1—Co1	122.3 (2)
N1—Co1—O1—C2	−46.0 (1)	N1^iii—Co1—N1—C1	147.2 (3)
N1^i—Co1—O1—C2	134.0 (1)	N1^ii—Co1—N1—C1	−32.8 (3)
N1^iii—Co1—O1—C2	46.0 (1)	Co1—O1—C2—N3	180.0
N1^ii—Co1—O1—C2	−134.0 (1)	C3—N3—C2—O1	0.0
O1^i—Co1—N1—C1	58.8 (3)	C4—N3—C2—O1	180.0
O1—Co1—N1—C1	−121.2 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···N2^v	0.94 (1)	2.53 (1)	3.464 (3)	172 (3)

Symmetry code: (v) −x+3/2, −y+3/2, −z+1.