Rerefinement of catena-poly­[[bis(2-pyrrolidone-κO)­cobalt(II)]-di-μ-1,5-dicyan­amido-κ⁴N¹:N⁵] in the centrosymmetric space ­group C2/m

The structure of the title compound, [Co(C₂N₃)₂(C₄H₇NO)₂]_n, which was reported in space group Cm [Sun et al. (2001). Inorg. Chem. Commun. 4, 72–75], was rerefined in the centrosymmetric space group C2/m to reveal a close analogy with the structure of the Co–dicyan­amide complex with N,N-di­methyl­form­amide. The Co atom and the dicyan­amide bridging ligand occupy special positions of symmetry 2/m and m, respectively.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.030
• wR factor = 0.082
• Data-to-parameter ratio = 14.0

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



PLAT_710  Alert C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         18
                   CO1 -N2  -C5  -N3   -135.00  2.00   1.555   1.555   1.555   1.555


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

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S1. Comment

The structure of the title compound, (I), which was reported in the Cm space group (Sun et al., 2001), was rerefined in the centrosymmetric C2/m space group to reveal a close analogy with the structure of the Co–dicyanamide complex with N,N-dimethylformamide (Tong et al., 2003). A pair of L-shaped dicyanamido anions link the bis(2-pyrrolidone)cobalt(II) units into a linear chain running along the b axis of the crystal (Fig. 1) The Co atom and the dicyanamide bridging ligand occupy special positions of symmetry 2/m and m, respectively. Adjacent chains are linked by an N—H···N hydrogen bond [3.072 (3) Å], giving rise to layers parallel to the ab plane of the crystal (Fig. 2). The same paper by Sun et al. (2001) also mentions (but does not provide full structural details for) the isostructural Mn complex. It is likely that this complex should also be rerefined in the C2/m space group.

S2. Experimental

PLEASE PROVIDE SOME PREPARATION DETAILS OR A REFERENCE TO THE SYNTHESIS

S3. Refinement

The diffraction measurements were those used in the original refinement (Sun et al., 2001). The aliphatic H atoms were generated geometrically (C—H = 0.97 Å) and were allowed to ride on their parent C atoms in the riding-model approximation; their displacement parameters were set to 1.2 times those of the C atoms. The amide H atom was located and refined [N1—H1 = 0.83 (3) Å].

Computing details

Data collection: KappaCCD Software (Nonius, 1998); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. ORTEPII (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) x, 1 − y, z; (iii) 1 − x, y, 1 − z.]
	Fig. 2. ORTEPII (Johnson, 1976) plot of the hydrogen-bonded layer structure.

catena-poly[[bis(2-pyrrolidone-κO)cobalt(II)]-di-µ-1,5-dicyanamido- κ⁴N¹:N⁵]

Crystal data

[Co(C2N3)2(C4H7NO)2]	F(000) = 370
Mr = 361.24	Dx = 1.684 Mg m^−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
a = 15.420 (3) Å	Cell parameters from 6994 reflections
b = 7.220 (1) Å	θ = 4.1–28.5°
c = 6.950 (1) Å	µ = 1.23 mm^−1
β = 112.94 (3)°	T = 298 K
V = 712.6 (2) Å^3	Block, pink
Z = 2	0.25 × 0.23 × 0.23 mm

Data collection

Nonius KappaCCD diffractometer	949 independent reflections
Radiation source: fine-focus sealed tube	903 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
Detector resolution: 0.76 pixels mm^-1	θmax = 28.5°, θmin = 4.1°
ϕ scans	h = −20→20
Absorption correction: multi-scan (Blessing, 1995)	k = −9→9
Tmin = 0.712, Tmax = 0.754	l = −9→9
6996 measured reflections

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.082	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0546P)^2 + 0.4762P] where P = (Fo^2 + 2Fc^2)/3
949 reflections	(Δ/σ)max = 0.001
68 parameters	Δρmax = 0.43 e Å^−3
0 restraints	Δρmin = −0.41 e Å^−3

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Co1	0.5000	0.5000	0.5000	0.0242 (2)
O1	0.6426 (1)	0.5000	0.6958 (3)	0.034 (1)
N1	0.7781 (1)	0.5000	0.9799 (3)	0.035 (1)
N2	0.5315 (1)	0.2911 (2)	0.3290 (2)	0.033 (1)
N3	0.5844 (2)	0.0000	0.2424 (4)	0.035 (1)
C1	0.6859 (2)	0.5000	0.8873 (4)	0.029 (1)
C2	0.6462 (2)	0.5000	1.0505 (4)	0.045 (1)
C3	0.7281 (2)	0.5000	1.2534 (5)	0.075 (1)
C4	0.8145 (2)	0.5000	1.2060 (4)	0.039 (1)
C5	0.5545 (1)	0.1516 (2)	0.2916 (2)	0.026 (1)
H1	0.812 (2)	0.5000	0.912 (5)	0.033 (7)*
H2a	0.6077	0.6092	1.0378	0.054*	0.50
H2b	0.6077	0.3908	1.0378	0.054*	0.50
H3a	0.7268	0.3909	1.3338	0.090*	0.50
H3b	0.7268	0.6091	1.3338	0.090*	0.50
H4a	0.8524	0.6094	1.2627	0.047*	0.50
H4b	0.8524	0.3906	1.2627	0.047*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0282 (2)	0.0182 (2)	0.0287 (2)	0.000	0.0138 (2)	0.000
O1	0.030 (1)	0.043 (1)	0.030 (1)	0.000	0.012 (1)	0.000
N1	0.026 (1)	0.045 (1)	0.036 (1)	0.000	0.016 (1)	0.000
N2	0.042 (1)	0.025 (1)	0.039 (1)	0.000 (1)	0.023 (1)	−0.002 (1)
N3	0.047 (1)	0.023 (1)	0.049 (1)	0.000	0.034 (1)	0.000
C1	0.028 (1)	0.027 (1)	0.033 (1)	0.000	0.014 (1)	0.000
C2	0.031 (1)	0.077 (2)	0.032 (1)	0.000	0.017 (1)	0.000
C3	0.036 (2)	0.156 (4)	0.033 (1)	0.000	0.015 (1)	0.000
C4	0.031 (1)	0.046 (1)	0.035 (1)	0.000	0.008 (1)	0.000
C5	0.029 (1)	0.025 (1)	0.027 (1)	−0.003 (1)	0.015 (1)	0.002 (1)

Geometric parameters (Å, º)

Co1—O1	2.087 (2)	N3—C5^iv	1.284 (2)
Co1—O1^i	2.087 (2)	C1—C2	1.484 (3)
Co1—N2	2.091 (1)	C2—C3	1.482 (4)
Co1—N2^ii	2.091 (1)	C3—C4	1.493 (4)
Co1—N2^i	2.091 (1)	N1—H1	0.83 (3)
Co1—N2^iii	2.091 (1)	C2—H2a	0.97
O1—C1	1.235 (3)	C2—H2b	0.97
N1—C1	1.312 (3)	C3—H3a	0.97
N1—C4	1.448 (3)	C3—H3b	0.97
N2—C5	1.131 (2)	C4—H4a	0.97
N3—C5	1.284 (2)	C4—H4b	0.97
O1—Co1—O1^i	180.0	C3—C2—C1	105.9 (2)
O1—Co1—N2	87.2 (1)	C2—C3—C4	107.0 (2)
O1—Co1—N2^ii	87.2 (1)	N1—C4—C3	103.8 (2)
O1—Co1—N2^i	92.8 (1)	N2—C5—N3	175.5 (2)
O1—Co1—N2^iii	92.8 (1)	C1—N1—H1	122 (2)
O1^i—Co1—N2	92.8 (1)	C4—N1—H1	123 (2)
O1^i—Co1—N2^ii	92.8 (1)	C3—C2—H2a	110.5
O1^i—Co1—N2^i	87.2 (1)	C1—C2—H2a	110.5
O1^i—Co1—N2^iii	87.2 (1)	C3—C2—H2b	110.5
N2—Co1—N2^ii	92.3 (1)	C1—C2—H2b	110.5
N2—Co1—N2^i	180.0	H2a—C2—H2b	108.7
N2—Co1—N2^iii	87.7 (1)	C2—C3—H3a	110.3
N2^ii—Co1—N2^i	87.7 (1)	C4—C3—H3a	110.3
N2^ii—Co1—N2^iii	180.0 (1)	C2—C3—H3b	110.3
N2^i—Co1—N2^iii	92.3 (1)	C4—C3—H3b	110.3
C1—O1—Co1	133.9 (2)	H3a—C3—H3b	108.6
C1—N1—C4	114.8 (2)	N1—C4—H4a	111.0
C5—N2—Co1	159.4 (1)	C3—C4—H4a	111.0
C5^iv—N3—C5	116.9 (2)	N1—C4—H4b	111.0
O1—C1—N1	123.8 (2)	C3—C4—H4b	111.0
O1—C1—C2	127.8 (2)	H4a—C4—H4b	109.0
N1—C1—C2	108.5 (2)
N2^i—Co1—O1—C1	46.2 (1)	Co1—O1—C1—C2	0.0
N2—Co1—O1—C1	−133.8 (1)	C4—N1—C1—O1	180.0
N2^ii—Co1—O1—C1	133.8 (1)	C4—N1—C1—C2	0.0
N2^iii—Co1—O1—C1	−46.2 (1)	O1—C1—C2—C3	180.0
O1^i—Co1—N2—C5	−115.1 (4)	N1—C1—C2—C3	0.0
O1—Co1—N2—C5	64.9 (4)	C1—C2—C3—C4	0.0
N2^ii—Co1—N2—C5	152.0 (3)	C1—N1—C4—C3	0.0
N2^iii—Co1—N2—C5	−28.0 (3)	C2—C3—C4—N1	0.0
Co1—O1—C1—N1	180.0	Co1—N2—C5—N3	−135 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N3^v	0.83 (3)	2.24 (3)	3.072 (3)	175 (3)

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