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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803012042/ya6166sup1.cif
Contains datablocks I, ya6166

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803012042/ya6166Isup2.hkl
Contains datablock I

CCDC reference: 217352

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


Yellow Alert 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

Comment top

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).

Experimental top

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.

Refinement top

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 top

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 top
[Figure 1] 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.]
[Figure 2] 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)] top
Crystal data top
C10H14CoN8O2F(000) = 346
Mr = 337.22Dx = 1.499 Mg m3
Monoclinic, C2/mMo Kα radiation, λ = 0.71073 Å
a = 13.525 (4) ÅCell parameters from 282 reflections
b = 7.383 (2) Åθ = 3.3–27.5°
c = 8.094 (3) ŵ = 1.17 mm1
β = 112.399 (5)°T = 293 K
V = 747.3 (4) Å3Block, pink
Z = 20.42 × 0.36 × 0.30 mm
Data collection top
Rigaku Mercury CCD
diffractometer
878 independent reflections
Radiation source: rotating-anode generator847 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.019
ω scanθmax = 27.5°, θmin = 3.3°
Absorption correction: multi-scan
CrystalClear (Rigaku, 2002)
h = 1712
Tmin = 0.528, Tmax = 0.721k = 99
2432 measured reflectionsl = 910
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.087All H-atom parameters refined
S = 1.06 w = 1/[σ2(Fo2) + (0.0676P)2 + 0.0203P]
where P = (Fo2 + 2Fc2)/3
878 reflections(Δ/σ)max = 0.001
76 parametersΔρmax = 0.36 e Å3
5 restraintsΔρmin = 0.36 e Å3
Crystal data top
C10H14CoN8O2V = 747.3 (4) Å3
Mr = 337.22Z = 2
Monoclinic, C2/mMo Kα radiation
a = 13.525 (4) ŵ = 1.17 mm1
b = 7.383 (2) ÅT = 293 K
c = 8.094 (3) Å0.42 × 0.36 × 0.30 mm
β = 112.399 (5)°
Data collection top
Rigaku Mercury CCD
diffractometer
878 independent reflections
Absorption correction: multi-scan
CrystalClear (Rigaku, 2002)
847 reflections with I > 2σ(I)
Tmin = 0.528, Tmax = 0.721Rint = 0.019
2432 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0295 restraints
wR(F2) = 0.087All H-atom parameters refined
S = 1.06Δρmax = 0.36 e Å3
878 reflectionsΔρmin = 0.36 e Å3
76 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Co10.50000.50000.50000.0247 (2)
O10.5839 (1)0.50000.7776 (2)0.036 (1)
N10.5997 (1)0.7068 (2)0.4662 (2)0.036 (1)
N20.6333 (2)1.00000.3560 (3)0.041 (1)
N30.7372 (2)0.50001.0206 (3)0.039 (1)
C10.6142 (1)0.8476 (2)0.4199 (2)0.028 (1)
C20.6826 (2)0.50000.8466 (3)0.033 (1)
C30.6836 (3)0.50001.1447 (4)0.080 (1)
C40.8536 (2)0.50001.0963 (4)0.050 (1)
H20.726 (2)0.50000.780 (4)0.04 (1)*
H3a0.738 (3)0.50001.259 (4)0.12 (2)*
H3b0.646 (3)0.389 (3)1.131 (6)0.16 (2)*
H4a0.879 (3)0.50001.004 (4)0.06 (1)*
H4b0.886 (2)0.401 (2)1.171 (3)0.08 (1)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0297 (3)0.0196 (3)0.0242 (3)0.0000.0097 (2)0.000
O10.035 (1)0.048 (1)0.024 (1)0.0000.009 (1)0.000
N10.043 (1)0.026 (1)0.044 (1)0.004 (1)0.023 (1)0.002 (1)
N20.062 (1)0.026 (1)0.052 (1)0.0000.042 (1)0.000
N30.036 (1)0.050 (1)0.027 (1)0.0000.008 (1)0.000
C10.027 (1)0.028 (1)0.031 (1)0.000 (1)0.015 (1)0.005 (1)
C20.038 (1)0.035 (1)0.027 (1)0.0000.013 (1)0.000
C30.057 (2)0.157 (5)0.029 (1)0.0000.021 (1)0.000
C40.036 (1)0.061 (2)0.043 (1)0.0000.004 (1)0.000
Geometric parameters (Å, º) top
Co1—O12.096 (2)N2—C11.305 (2)
Co1—O1i2.096 (2)N3—C21.318 (3)
Co1—N12.123 (2)N3—C31.446 (4)
Co1—N1ii2.123 (2)N3—C41.455 (4)
Co1—N1i2.123 (2)C2—H20.94 (1)
Co1—N1iii2.123 (2)C3—H3a0.94 (1)
O1—C21.235 (3)C3—H3b0.95 (1)
N1—C11.147 (2)C4—H4a0.94 (1)
N2—C1iv1.305 (2)C4—H4b0.94 (1)
O1—Co1—O1i180C1—N1—Co1152.9 (1)
O1—Co1—N191.6 (1)C1iv—N2—C1119.2 (2)
O1—Co1—N1ii88.5 (1)C2—N3—C3121.1 (2)
O1—Co1—N1i88.5 (1)C2—N3—C4121.7 (2)
O1—Co1—N1iii91.6 (1)C3—N3—C4117.1 (2)
O1i—Co1—N188.5 (1)N1—C1—N2174.6 (2)
O1i—Co1—N1ii91.6 (1)O1—C2—N3123.5 (2)
O1i—Co1—N1i91.6 (1)O1—C2—H2123 (2)
O1i—Co1—N1iii88.5 (1)N3—C2—H2113 (2)
N1—Co1—N1ii88.0 (1)N3—C3—H3a105 (4)
N1—Co1—N1i180.0 (1)N3—C3—H3b108 (3)
N1—Co1—N1iii92.0 (1)H3a—C3—H3b108 (3)
N1i—Co1—N1ii92.0 (1)N3—C4—H4a110 (2)
N1i—Co1—N1iii88.0 (1)N3—C4—H4b116 (2)
N1ii—Co1—N1iii180.0 (1)H4b—C4—H4b107 (2)
C2—O1—Co1122.3 (2)
N1—Co1—O1—C246.0 (1)N1iii—Co1—N1—C1147.2 (3)
N1i—Co1—O1—C2134.0 (1)N1ii—Co1—N1—C132.8 (3)
N1iii—Co1—O1—C246.0 (1)Co1—O1—C2—N3180.0
N1ii—Co1—O1—C2134.0 (1)C3—N3—C2—O10.0
O1i—Co1—N1—C158.8 (3)C4—N3—C2—O1180.0
O1—Co1—N1—C1121.2 (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) top
D—H···AD—HH···AD···AD—H···A
C2—H2···N2v0.94 (1)2.53 (1)3.464 (3)172 (3)
Symmetry code: (v) x+3/2, y+3/2, z+1.

Experimental details

Crystal data
Chemical formulaC10H14CoN8O2
Mr337.22
Crystal system, space groupMonoclinic, C2/m
Temperature (K)293
a, b, c (Å)13.525 (4), 7.383 (2), 8.094 (3)
β (°) 112.399 (5)
V3)747.3 (4)
Z2
Radiation typeMo Kα
µ (mm1)1.17
Crystal size (mm)0.42 × 0.36 × 0.30
Data collection
DiffractometerRigaku Mercury CCD
diffractometer
Absorption correctionMulti-scan
CrystalClear (Rigaku, 2002)
Tmin, Tmax0.528, 0.721
No. of measured, independent and
observed [I > 2σ(I)] reflections
2432, 878, 847
Rint0.019
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.087, 1.06
No. of reflections878
No. of parameters76
No. of restraints5
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.36, 0.36

Computer programs: CrystalClear (Rigaku, 2002), CrystalClear, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-II (Johnson, 1976), SHELXL97.

Selected geometric parameters (Å, º) top
Co1—O12.096 (2)N2—C11.305 (2)
Co1—N12.123 (2)N3—C21.318 (3)
O1—C21.235 (3)N3—C31.446 (4)
N1—C11.147 (2)N3—C41.455 (4)
O1—Co1—N191.6 (1)N1—Co1—N1i88.0 (1)
O1—Co1—N1i88.5 (1)
Symmetry code: (i) x+1, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···N2ii0.94 (1)2.53 (1)3.464 (3)172 (3)
Symmetry code: (ii) x+3/2, y+3/2, z+1.
 

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