Two cobalt(II) supra­molecular isomers based on N,N′-bis­(pyridin-3-yl)oxalamide induced by the mol­ecular orientation of lattice DMF mol­ecules

Supra­molecular isomerism for coordination networks refers to the existence of different architectures having the same building blocks and identical stoi­chi­om­etries. For a given building block, different arrangements can lead to the formation of a series of supra­molecular isomers. Two one-dimensional Co^II coordination polymers based on N,N′-bis­(pyridin-3-yl)oxalamide (BPO), both catena-poly[[[di­chlorido­cobalt(II)]-bis­[μ-N,N′-bis­(pyridin-3-yl)oxalamide-κ²N:N′]] di­methyl­formamide disolvate], {[CoCl₂(C₁₂H₁₀N₄O₂)₂]·2C₃H₇NO}_n, have been assembled by the solvothermal method. Single-crystal X-ray diffraction analyses reveal that the two compounds are supra­molecular isomers, the isomerism being induced by the orientation of the di­methyl­formamide (DMF) mol­e­cules in the crystal lattice.

S1. Introduction

Recently, increasing attention have been focused on supra­molecular isomerism in the field of molecular architectures (Chen et al., 2015; Jiang et al., 2005; Zhang et al., 2009). Supra­molecular isomerism for coordination networks refers to the existence of different architectures with the same building blocks and identical stoichiometry (Moulton & Zaworotko, 2001). For a given building block, different arrangements can lead to the formation of a series of supra­molecular isomers. The architectures of supra­molecular isomers are sensitive to temperature, reaction time, template molecules, solvents and so on (Chen et al., 2005; Ghosh et al., 2013; Haldar et al., 2014; Ma et al., 2007; Panda et al., 2011). Normally, flexible ligands can engender conformational changes to generate different coordination supra­molecular isomer networks. We report here two coordination supra­molecular isomers based on the rigid N,N'-bis­(pyridin-3-yl)oxalamide (BPO) ligand. It is inter­esting to find that the isomerism originates from the different orientation of the lattice DMF molecules.

S2. Experimental

S2.1. Synthesis and crystallization

A mixture of CoCl₂.6H₂O (0.2 mmol, 0.0476 g), BPO (0.2 mmol, 0.0480 g) and DMF (5 ml) was heated in an oven at 373 K for 48 h. After the oven had been cooled over a period of 16 h at a rate of 5 K h^-1, the mixture was filtered. Deep-red needle-shaped crystals of (1a) were collected by hand. The resulting clear light-red solution was allowed to evaporate slowly at room temperature. After one month, light-red block-shaped crystals of (1b) were isolated, collected and dried in air. The yields were 0.009 (12%) and 0.013 g (17%), based on BPO, for (1a) and (1b), respectively.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms attached to C and N atoms were placed geometrically and refined isotropically as riding atoms.

S3. Results and discussion

In isomer (1a) (Fig. 1a), which crystallizes in the triclinic P1 space group, the central Co^II atom coordinates with four N atoms from four individual BPO ligands and two Cl^- anions, generating a distorted o­cta­hedral geometry (Table 2). Through the connection of the BPO ligands, Co^II ions are bridged together to form a one-dimensional CoCl₂–BPO chain (Fig. 2a). These one-dimensional chains are further linked together by π–π inter­actions to generate a three-dimensional supra­molecular structure (Fig. 3a). There is a strong hydrogen bond between the BPO ligand and the lattice DMF molecule. The imino group (N3) of the BPO ligand donates an H atom to DMF atom O3 to form a strong N3—H···O3 hydrogen bond [2.801 (6) Å; Table 3]. As a result of these hydrogen-bond inter­actions, the lattice DMF molecules are strongly bound with the BPO ligands and anchored to the CoCl₂—BPO chain along the direction of the chain growth (Fig. 2a). It should be noted that the molecular plane of the DMF molecule is nearly parallel with the plane of the bis­amide (C₂O₂N₂), with a dihedral angle of only 4.0°.

Isomer (1b) (Fig. 1b), which also crystallizes in the triclinic P1 space group, has the same formula as that for (1a), which means that (1a) and (1b) are supra­molecular isomers. Furthermore, the structure of (1b) is very similar to that of (1a). As shown in Fig. 1(b), in isomer (1b), the central Co^II atom has the same coordination environment and the BPO ligand employs the same coordination mode as those in isomer (1a) (Table 4). The binding inter­action between lattice DMF molecules and BPO ligands in (1b) also depends on N—H···O hydrogen bonding [2.856 (4) Å; Table 5]. The only differences between (1a) and (1b) are the orientations of the lattice DMF molecules (Fig. 2b). In (1b), the molecular plane of the DMF molecule is not parallel with the plane of the bis­amide (C2O2N2). The dihedral angel is 67.6°, which is markedly different from that in (1a), where the molecular plane of the DMF is nearly parallel with the plane of the bi-amide (C₂O₂N₂; dihedral amgle = 4.0°). Due to the different orientations of the DMF molecules in (1a) and (1b), the cell parameters of (1b) are slightly different from those of (1a) (Table 1), further indicating that (1a) and (1b) are supra­molecular isomers. To the best of our knowledge, although numerous supra­molecular isomers have been reported to date, isomerism induced by the orientation of the lattice guest molecule has not been documented. The formation of supra­molecular isomers indiced by the orientation of the lattice guest molecules is quite novel and inter­esting.

Structure description

Recently, increasing attention have been focused on supra­molecular isomerism in the field of molecular architectures (Chen et al., 2015; Jiang et al., 2005; Zhang et al., 2009). Supra­molecular isomerism for coordination networks refers to the existence of different architectures with the same building blocks and identical stoichiometry (Moulton & Zaworotko, 2001). For a given building block, different arrangements can lead to the formation of a series of supra­molecular isomers. The architectures of supra­molecular isomers are sensitive to temperature, reaction time, template molecules, solvents and so on (Chen et al., 2005; Ghosh et al., 2013; Haldar et al., 2014; Ma et al., 2007; Panda et al., 2011). Normally, flexible ligands can engender conformational changes to generate different coordination supra­molecular isomer networks. We report here two coordination supra­molecular isomers based on the rigid N,N'-bis­(pyridin-3-yl)oxalamide (BPO) ligand. It is inter­esting to find that the isomerism originates from the different orientation of the lattice DMF molecules.

In isomer (1a) (Fig. 1a), which crystallizes in the triclinic P1 space group, the central Co^II atom coordinates with four N atoms from four individual BPO ligands and two Cl^- anions, generating a distorted o­cta­hedral geometry (Table 2). Through the connection of the BPO ligands, Co^II ions are bridged together to form a one-dimensional CoCl₂–BPO chain (Fig. 2a). These one-dimensional chains are further linked together by π–π inter­actions to generate a three-dimensional supra­molecular structure (Fig. 3a). There is a strong hydrogen bond between the BPO ligand and the lattice DMF molecule. The imino group (N3) of the BPO ligand donates an H atom to DMF atom O3 to form a strong N3—H···O3 hydrogen bond [2.801 (6) Å; Table 3]. As a result of these hydrogen-bond inter­actions, the lattice DMF molecules are strongly bound with the BPO ligands and anchored to the CoCl₂—BPO chain along the direction of the chain growth (Fig. 2a). It should be noted that the molecular plane of the DMF molecule is nearly parallel with the plane of the bis­amide (C₂O₂N₂), with a dihedral angle of only 4.0°.

Isomer (1b) (Fig. 1b), which also crystallizes in the triclinic P1 space group, has the same formula as that for (1a), which means that (1a) and (1b) are supra­molecular isomers. Furthermore, the structure of (1b) is very similar to that of (1a). As shown in Fig. 1(b), in isomer (1b), the central Co^II atom has the same coordination environment and the BPO ligand employs the same coordination mode as those in isomer (1a) (Table 4). The binding inter­action between lattice DMF molecules and BPO ligands in (1b) also depends on N—H···O hydrogen bonding [2.856 (4) Å; Table 5]. The only differences between (1a) and (1b) are the orientations of the lattice DMF molecules (Fig. 2b). In (1b), the molecular plane of the DMF molecule is not parallel with the plane of the bis­amide (C2O2N2). The dihedral angel is 67.6°, which is markedly different from that in (1a), where the molecular plane of the DMF is nearly parallel with the plane of the bi-amide (C₂O₂N₂; dihedral amgle = 4.0°). Due to the different orientations of the DMF molecules in (1a) and (1b), the cell parameters of (1b) are slightly different from those of (1a) (Table 1), further indicating that (1a) and (1b) are supra­molecular isomers. To the best of our knowledge, although numerous supra­molecular isomers have been reported to date, isomerism induced by the orientation of the lattice guest molecule has not been documented. The formation of supra­molecular isomers indiced by the orientation of the lattice guest molecules is quite novel and inter­esting.

Synthesis and crystallization

A mixture of CoCl₂.6H₂O (0.2 mmol, 0.0476 g), BPO (0.2 mmol, 0.0480 g) and DMF (5 ml) was heated in an oven at 373 K for 48 h. After the oven had been cooled over a period of 16 h at a rate of 5 K h^-1, the mixture was filtered. Deep-red needle-shaped crystals of (1a) were collected by hand. The resulting clear light-red solution was allowed to evaporate slowly at room temperature. After one month, light-red block-shaped crystals of (1b) were isolated, collected and dried in air. The yields were 0.009 (12%) and 0.013 g (17%), based on BPO, for (1a) and (1b), respectively.

Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms attached to C and N atoms were placed geometrically and refined isotropically as riding atoms.

Computing details

For both compounds, data collection: SMART (Bruker, 1998); cell refinement: SMART (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structures of (1a) and (1b), with displacement ellipsoids drawn at tyhe 50% probability level. [Symmetry codes: for (1a), (A) -x+3, -y+2, -z; (B) -x+2, -y+2, -z+1; for (1a), (A) -x, -y+1, -z+1; (B) -x+1, -y+1, ???.].
	Fig. 2. The orientation of the DMF molecules observed in (1a) and (1b).
	Fig. 3. The three-dimensional supramolecular structures of (1a) and (1b).

(1a) catena-Poly[[[dichloridocobalt(II)]-bis[µ-N,N'-bis(pyridin-3-yl)oxalamide-κ²N:N']] dimethylformamide disolvate]

Crystal data

[CoCl2(C12H10N4O2)2]·2C3H7NO	Z = 1
Mr = 760.50	F(000) = 393
Triclinic, P1	Dx = 1.492 Mg m^−3
a = 8.5194 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.0059 (3) Å	Cell parameters from 1206 reflections
c = 10.2685 (3) Å	θ = 2.0–26.3°
α = 82.304 (3)°	µ = 0.72 mm^−1
β = 84.182 (2)°	T = 296 K
γ = 78.163 (2)°	Needle, deep-red
V = 846.53 (5) Å^3	0.22 × 0.18 × 0.12 mm

Data collection

Bruker SMART CCD area-detector diffractometer	2951 independent reflections
Radiation source: fine-focus sealed tube	1836 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.060
phi and ω scans	θmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −10→10
Tmin = 0.857, Tmax = 0.918	k = −11→11
6964 measured reflections	l = −12→12

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)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.128	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0524P)^2] where P = (Fo^2 + 2Fc^2)/3
2951 reflections	(Δ/σ)max < 0.001
225 parameters	Δρmax = 0.40 e Å^−3
0 restraints	Δρmin = −0.67 e Å^−3

Special details

Experimental. Single-crystal data for (1a) and (1b) were collected on a Bruker Smart 1000 CCD diffractometer with graphitemonochromated Mo Kα radiation (λ=0.71073 Å) at 296 (2) K. All empirical absorption corrections were applied using the SADABS program. Both structures were solved using direct methods, which yielded the positions of all non-hydrogen atoms. These were refined first isotropically and then anisotropically.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 (Ų)

	x	y	z	Uiso*/Ueq
Co1	1.5000	1.0000	0.0000	0.0328 (3)
N1	1.2823 (4)	0.9109 (4)	0.0488 (3)	0.0345 (9)
N4	0.6240 (4)	0.8015 (4)	0.9290 (3)	0.0371 (9)
N5	0.6688 (5)	0.3055 (5)	0.4517 (4)	0.0512 (11)
Cl1	1.41423 (12)	1.08488 (12)	−0.21949 (10)	0.0395 (3)
O1	0.9210 (4)	0.6483 (4)	0.3669 (3)	0.0542 (10)
O2	0.9081 (4)	0.8854 (4)	0.5915 (3)	0.0539 (10)
O3	0.6733 (5)	0.4633 (5)	0.5903 (4)	0.0814 (13)
C1	1.2107 (5)	0.8656 (5)	−0.0421 (4)	0.0418 (12)
H1	1.2567	0.8700	−0.1282	0.050*
C2	1.0726 (5)	0.8128 (5)	−0.0144 (4)	0.0414 (12)
H2	1.0284	0.7816	−0.0810	0.050*
C3	0.9998 (5)	0.8062 (5)	0.1111 (4)	0.0388 (12)
H3	0.9056	0.7719	0.1313	0.047*
C4	1.0716 (5)	0.8522 (4)	0.2061 (4)	0.0322 (11)
C5	1.2121 (5)	0.9012 (5)	0.1720 (4)	0.0358 (11)
H5	1.2609	0.9290	0.2380	0.043*
N2	1.0073 (4)	0.8531 (4)	0.3392 (3)	0.0380 (10)
H6	1.0120	0.9226	0.3787	0.046*
C7	0.9394 (5)	0.7521 (5)	0.4078 (4)	0.0402 (12)
C8	0.8873 (5)	0.7808 (5)	0.5501 (4)	0.0392 (12)
N3	0.8237 (4)	0.6801 (4)	0.6208 (3)	0.0431 (10)
H2A	0.8165	0.6114	0.5811	0.052*
C10	0.7670 (5)	0.6767 (5)	0.7558 (4)	0.0371 (12)
C11	0.7884 (6)	0.5565 (6)	0.8376 (5)	0.0583 (15)
H11	0.8434	0.4747	0.8077	0.070*
C12	0.7250 (7)	0.5608 (6)	0.9670 (5)	0.0656 (17)
H12	0.7367	0.4808	1.0258	0.079*
C13	0.6454 (6)	0.6825 (6)	1.0083 (5)	0.0528 (14)
H13	0.6042	0.6829	1.0957	0.063*
C14	0.6822 (5)	0.7973 (5)	0.8036 (4)	0.0352 (11)
H14	0.6656	0.8779	0.7458	0.042*
C15	0.6402 (6)	0.3559 (6)	0.5663 (5)	0.0569 (15)
H15	0.5904	0.3054	0.6350	0.068*
C16	0.7287 (7)	0.3858 (7)	0.3359 (5)	0.084 (2)
H16A	0.7611	0.4641	0.3619	0.126*
H16B	0.6453	0.4162	0.2764	0.126*
H16C	0.8192	0.3300	0.2930	0.126*
C17	0.6224 (7)	0.1795 (6)	0.4351 (6)	0.0771 (19)
H17A	0.5855	0.1374	0.5191	0.116*
H17B	0.7131	0.1184	0.3985	0.116*
H17C	0.5374	0.1982	0.3767	0.116*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0368 (5)	0.0329 (6)	0.0266 (5)	−0.0072 (4)	0.0138 (4)	−0.0073 (4)
N1	0.039 (2)	0.033 (3)	0.0303 (19)	−0.0074 (17)	0.0109 (16)	−0.0075 (18)
N4	0.048 (2)	0.031 (3)	0.032 (2)	−0.0139 (18)	0.0155 (17)	−0.0062 (19)
N5	0.063 (3)	0.051 (3)	0.041 (2)	−0.015 (2)	0.001 (2)	−0.008 (2)
Cl1	0.0408 (7)	0.0437 (8)	0.0309 (6)	−0.0063 (5)	0.0090 (5)	−0.0054 (5)
O1	0.081 (2)	0.042 (2)	0.0436 (19)	−0.0255 (19)	0.0232 (17)	−0.0176 (18)
O2	0.078 (2)	0.043 (3)	0.0453 (19)	−0.0297 (18)	0.0285 (17)	−0.0204 (18)
O3	0.113 (3)	0.072 (3)	0.072 (3)	−0.043 (3)	−0.002 (2)	−0.019 (3)
C1	0.047 (3)	0.042 (3)	0.034 (3)	−0.006 (2)	0.012 (2)	−0.012 (2)
C2	0.044 (3)	0.047 (4)	0.034 (2)	−0.009 (2)	0.003 (2)	−0.011 (2)
C3	0.035 (3)	0.039 (3)	0.041 (3)	−0.008 (2)	0.006 (2)	−0.007 (2)
C4	0.040 (3)	0.025 (3)	0.030 (2)	−0.007 (2)	0.0114 (19)	−0.007 (2)
C5	0.036 (3)	0.040 (3)	0.030 (2)	−0.009 (2)	0.0110 (19)	−0.010 (2)
N2	0.044 (2)	0.037 (3)	0.032 (2)	−0.0123 (18)	0.0181 (17)	−0.0098 (19)
C7	0.049 (3)	0.033 (3)	0.037 (3)	−0.013 (2)	0.018 (2)	−0.009 (2)
C8	0.044 (3)	0.037 (3)	0.033 (2)	−0.007 (2)	0.018 (2)	−0.006 (2)
N3	0.060 (3)	0.033 (3)	0.034 (2)	−0.012 (2)	0.0235 (18)	−0.0135 (19)
C10	0.043 (3)	0.039 (3)	0.028 (2)	−0.009 (2)	0.014 (2)	−0.008 (2)
C11	0.094 (4)	0.031 (4)	0.040 (3)	0.001 (3)	0.019 (3)	−0.006 (3)
C12	0.126 (5)	0.029 (4)	0.031 (3)	−0.004 (3)	0.016 (3)	0.002 (2)
C13	0.080 (4)	0.039 (4)	0.037 (3)	−0.014 (3)	0.020 (3)	−0.007 (3)
C14	0.037 (2)	0.034 (3)	0.031 (2)	−0.004 (2)	0.0128 (19)	−0.006 (2)
C15	0.065 (4)	0.056 (4)	0.049 (3)	−0.015 (3)	0.000 (3)	−0.002 (3)
C16	0.099 (5)	0.098 (6)	0.056 (4)	−0.035 (4)	0.020 (3)	−0.007 (4)
C17	0.102 (5)	0.055 (5)	0.080 (4)	−0.024 (4)	−0.008 (4)	−0.019 (4)

Geometric parameters (Å, º)

Co1—N1	2.204 (3)	C4—N2	1.420 (5)
Co1—N1^i	2.204 (3)	C5—H5	0.9300
Co1—N4^ii	2.228 (3)	N2—C7	1.348 (6)
Co1—N4^iii	2.228 (3)	N2—H6	0.8600
Co1—Cl1	2.4293 (11)	C7—C8	1.531 (5)
Co1—Cl1^i	2.4293 (11)	C8—N3	1.336 (6)
N1—C1	1.338 (5)	N3—C10	1.420 (5)
N1—C5	1.343 (5)	N3—H2A	0.8600
N4—C14	1.335 (5)	C10—C11	1.362 (6)
N4—C13	1.340 (6)	C10—C14	1.395 (6)
N4—Co1^iv	2.228 (3)	C11—C12	1.386 (6)
N5—C15	1.322 (6)	C11—H11	0.9300
N5—C17	1.433 (6)	C12—C13	1.365 (6)
N5—C16	1.452 (6)	C12—H12	0.9300
O1—C7	1.215 (5)	C13—H13	0.9300
O2—C8	1.232 (5)	C14—H14	0.9300
O3—C15	1.227 (6)	C15—H15	0.9300
C1—C2	1.375 (6)	C16—H16A	0.9600
C1—H1	0.9300	C16—H16B	0.9600
C2—C3	1.373 (5)	C16—H16C	0.9600
C2—H2	0.9300	C17—H17A	0.9600
C3—C4	1.377 (5)	C17—H17B	0.9600
C3—H3	0.9300	C17—H17C	0.9600
C4—C5	1.380 (6)
N1—Co1—N1^i	180.0	C4—N2—H6	117.8
N1—Co1—N4^ii	91.79 (12)	O1—C7—N2	126.4 (4)
N1^i—Co1—N4^ii	88.21 (12)	O1—C7—C8	121.8 (4)
N1—Co1—N4^iii	88.21 (12)	N2—C7—C8	111.7 (4)
N1^i—Co1—N4^iii	91.79 (12)	O2—C8—N3	125.7 (4)
N4^ii—Co1—N4^iii	180.0	O2—C8—C7	121.5 (4)
N1—Co1—Cl1	90.10 (9)	N3—C8—C7	112.7 (4)
N1^i—Co1—Cl1	89.90 (9)	C8—N3—C10	125.6 (4)
N4^ii—Co1—Cl1	89.97 (10)	C8—N3—H2A	117.2
N4^iii—Co1—Cl1	90.03 (10)	C10—N3—H2A	117.2
N1—Co1—Cl1^i	89.90 (9)	C11—C10—C14	119.8 (4)
N1^i—Co1—Cl1^i	90.10 (9)	C11—C10—N3	120.8 (4)
N4^ii—Co1—Cl1^i	90.03 (10)	C14—C10—N3	119.3 (4)
N4^iii—Co1—Cl1^i	89.97 (10)	C10—C11—C12	117.4 (4)
Cl1—Co1—Cl1^i	180.0	C10—C11—H11	121.3
C1—N1—C5	116.1 (4)	C12—C11—H11	121.3
C1—N1—Co1	122.3 (3)	C13—C12—C11	120.0 (5)
C5—N1—Co1	121.6 (3)	C13—C12—H12	120.0
C14—N4—C13	117.0 (4)	C11—C12—H12	120.0
C14—N4—Co1^iv	120.4 (3)	N4—C13—C12	123.1 (4)
C13—N4—Co1^iv	122.5 (3)	N4—C13—H13	118.4
C15—N5—C17	120.9 (5)	C12—C13—H13	118.4
C15—N5—C16	120.3 (5)	N4—C14—C10	122.6 (4)
C17—N5—C16	118.3 (4)	N4—C14—H14	118.7
N1—C1—C2	123.3 (4)	C10—C14—H14	118.7
N1—C1—H1	118.4	O3—C15—N5	126.0 (5)
C2—C1—H1	118.4	O3—C15—H15	117.0
C3—C2—C1	120.2 (4)	N5—C15—H15	117.0
C3—C2—H2	119.9	N5—C16—H16A	109.5
C1—C2—H2	119.9	N5—C16—H16B	109.5
C2—C3—C4	117.4 (4)	H16A—C16—H16B	109.5
C2—C3—H3	121.3	N5—C16—H16C	109.5
C4—C3—H3	121.3	H16A—C16—H16C	109.5
C3—C4—C5	119.3 (4)	H16B—C16—H16C	109.5
C3—C4—N2	123.1 (4)	N5—C17—H17A	109.5
C5—C4—N2	117.6 (4)	N5—C17—H17B	109.5
N1—C5—C4	123.7 (4)	H17A—C17—H17B	109.5
N1—C5—H5	118.2	N5—C17—H17C	109.5
C4—C5—H5	118.2	H17A—C17—H17C	109.5
C7—N2—C4	124.3 (4)	H17B—C17—H17C	109.5
C7—N2—H6	117.8

Symmetry codes: (i) −x+3, −y+2, −z; (ii) −x+2, −y+2, −z+1; (iii) x+1, y, z−1; (iv) x−1, y, z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H2A···O3	0.86	2.09	2.801 (6)	140
N2—H6···O2^ii	0.86	2.23	3.041 (5)	157

Symmetry code: (ii) −x+2, −y+2, −z+1.

(1b) catena-Poly[[[dichloridocobalt(II)]-bis(µ-N,N'-bis(pyridin-3-yl)oxalamide-κ²N:N'] dimethylformamide disolvate]

Crystal data

[CoCl2(C6H10N4O2)2]·2C3H7NO	Z = 1
Mr = 760.50	F(000) = 393
Triclinic, P1	Dx = 1.501 Mg m^−3
a = 9.2991 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.3832 (6) Å	Cell parameters from 897 reflections
c = 10.7003 (6) Å	θ = 2.1–27.3°
α = 66.316 (4)°	µ = 0.73 mm^−1
β = 79.647 (4)°	T = 296 K
γ = 85.347 (4)°	Block, light red
V = 841.06 (8) Å^3	0.18 × 0.16 × 0.12 mm

Data collection

Bruker SMART CCD area-detector diffractometer	2960 independent reflections
Radiation source: fine-focus sealed tube	2247 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
phi and ω scans	θmax = 25.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −11→11
Tmin = 0.880, Tmax = 0.918	k = −8→11
7588 measured reflections	l = −11→12

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.132	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0689P)^2 + 0.4777P] where P = (Fo^2 + 2Fc^2)/3
2960 reflections	(Δ/σ)max < 0.001
225 parameters	Δρmax = 0.97 e Å^−3
0 restraints	Δρmin = −0.38 e Å^−3

Special details

Experimental. Single-crystal data for (1a) and (1b) were collected on a Bruker Smart 1000 CCD diffractometer with graphitemonochromated Mo Kα radiation (λ=0.71073 Å) at 296 (2) K. All empirical absorption corrections were applied using the SADABS program. Both structures were solved using direct methods, which yielded the positions of all non-hydrogen atoms. These were refined first isotropically and then anisotropically.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 (Ų)

	x	y	z	Uiso*/Ueq
Co1	0.0000	0.5000	0.5000	0.0356 (2)
C1	0.1105 (5)	0.1692 (4)	0.5239 (4)	0.0505 (10)
H1	0.0537	0.1419	0.6109	0.061*
C2	0.1880 (5)	0.0543 (4)	0.4908 (4)	0.0612 (12)
H2	0.1828	−0.0482	0.5552	0.073*
C3	0.2728 (5)	0.0903 (4)	0.3637 (4)	0.0552 (11)
H3	0.3271	0.0140	0.3408	0.066*
C4	0.2753 (4)	0.2430 (4)	0.2707 (3)	0.0365 (8)
C5	0.1947 (4)	0.3520 (4)	0.3115 (4)	0.0382 (8)
H5	0.1972	0.4551	0.2484	0.046*
C6	0.3752 (4)	0.2085 (4)	0.0568 (4)	0.0382 (8)
C7	0.4696 (4)	0.2939 (4)	−0.0836 (4)	0.0390 (8)
C8	0.7028 (4)	0.3216 (4)	−0.3287 (4)	0.0377 (8)
H8	0.7462	0.3135	−0.2542	0.045*
C9	0.5605 (4)	0.2721 (4)	−0.3024 (4)	0.0374 (8)
C10	0.4980 (4)	0.2748 (4)	−0.4110 (4)	0.0490 (9)
H10	0.4028	0.2410	−0.3964	0.059*
C11	0.5795 (5)	0.3286 (5)	−0.5409 (4)	0.0554 (10)
H11	0.5414	0.3284	−0.6155	0.067*
C12	0.7178 (4)	0.3828 (4)	−0.5596 (4)	0.0477 (9)
H12	0.7701	0.4232	−0.6489	0.057*
C13	0.7662 (6)	0.0557 (6)	0.1423 (5)	0.0784 (14)
H13	0.8111	−0.0388	0.1490	0.094*
C14	1.0066 (6)	0.1429 (9)	0.1123 (6)	0.121 (3)
H14A	1.0411	0.1624	0.1833	0.181*
H14B	1.0559	0.2101	0.0234	0.181*
H14C	1.0261	0.0364	0.1250	0.181*
C15	0.7981 (8)	0.3224 (8)	0.0964 (7)	0.114 (2)
H15A	0.7785	0.3718	0.0033	0.170*
H15B	0.8691	0.3815	0.1097	0.170*
H15C	0.7093	0.3173	0.1598	0.170*
Cl1	0.03678 (10)	0.34894 (10)	0.73576 (9)	0.0457 (3)
N1	0.1136 (3)	0.3181 (3)	0.4360 (3)	0.0381 (7)
N2	0.3557 (3)	0.2930 (3)	0.1358 (3)	0.0406 (7)
H2A	0.3950	0.3834	0.1012	0.049*
N3	0.4815 (3)	0.2170 (3)	−0.1667 (3)	0.0385 (7)
H3A	0.4385	0.1288	−0.1355	0.046*
N4	0.7816 (3)	0.3805 (3)	−0.4556 (3)	0.0396 (7)
N5	0.8519 (4)	0.1727 (5)	0.1203 (4)	0.0620 (10)
O1	0.3252 (3)	0.0813 (3)	0.0879 (3)	0.0473 (6)
O2	0.5226 (3)	0.4213 (3)	−0.1152 (3)	0.0555 (7)
O3	0.6336 (3)	0.0623 (4)	0.1545 (4)	0.0758 (10)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0385 (4)	0.0378 (4)	0.0277 (4)	0.0073 (3)	0.0015 (3)	−0.0142 (3)
C1	0.065 (3)	0.044 (2)	0.037 (2)	−0.0012 (18)	0.0073 (18)	−0.0167 (18)
C2	0.097 (3)	0.036 (2)	0.041 (2)	0.009 (2)	0.000 (2)	−0.0110 (18)
C3	0.075 (3)	0.040 (2)	0.048 (2)	0.0158 (19)	0.000 (2)	−0.0220 (19)
C4	0.0386 (19)	0.0375 (18)	0.0345 (19)	0.0024 (15)	0.0013 (15)	−0.0189 (16)
C5	0.0421 (19)	0.0356 (18)	0.0361 (19)	0.0036 (15)	0.0010 (15)	−0.0170 (16)
C6	0.0342 (18)	0.0379 (19)	0.043 (2)	0.0034 (15)	0.0030 (15)	−0.0210 (16)
C7	0.0353 (18)	0.039 (2)	0.045 (2)	0.0018 (15)	0.0022 (15)	−0.0230 (17)
C8	0.0390 (19)	0.0425 (19)	0.0359 (19)	0.0065 (15)	−0.0024 (15)	−0.0227 (16)
C9	0.0407 (19)	0.0353 (18)	0.039 (2)	0.0042 (15)	−0.0021 (15)	−0.0204 (16)
C10	0.048 (2)	0.051 (2)	0.053 (2)	−0.0024 (17)	−0.0078 (18)	−0.0260 (19)
C11	0.069 (3)	0.063 (3)	0.039 (2)	−0.009 (2)	−0.0107 (19)	−0.022 (2)
C12	0.057 (2)	0.053 (2)	0.036 (2)	−0.0046 (18)	−0.0022 (17)	−0.0221 (18)
C13	0.082 (4)	0.075 (3)	0.075 (3)	0.006 (3)	−0.018 (3)	−0.024 (3)
C14	0.067 (4)	0.180 (7)	0.081 (4)	0.005 (4)	−0.014 (3)	−0.017 (4)
C15	0.137 (6)	0.108 (5)	0.111 (5)	−0.014 (4)	−0.019 (4)	−0.056 (4)
Cl1	0.0513 (6)	0.0487 (5)	0.0321 (5)	0.0085 (4)	−0.0050 (4)	−0.0131 (4)
N1	0.0402 (16)	0.0388 (16)	0.0324 (16)	0.0041 (12)	0.0022 (12)	−0.0154 (13)
N2	0.0437 (17)	0.0343 (15)	0.0435 (17)	−0.0039 (12)	0.0095 (13)	−0.0214 (14)
N3	0.0410 (16)	0.0357 (15)	0.0408 (17)	−0.0025 (12)	0.0014 (13)	−0.0202 (13)
N4	0.0406 (16)	0.0428 (17)	0.0354 (17)	0.0030 (13)	0.0017 (13)	−0.0194 (14)
N5	0.045 (2)	0.082 (3)	0.052 (2)	−0.0200 (19)	−0.0099 (16)	−0.0149 (19)
O1	0.0488 (15)	0.0420 (14)	0.0516 (16)	−0.0107 (11)	0.0076 (12)	−0.0236 (12)
O2	0.0737 (19)	0.0431 (15)	0.0523 (17)	−0.0184 (13)	0.0164 (14)	−0.0294 (13)
O3	0.0409 (17)	0.069 (2)	0.124 (3)	−0.0009 (14)	−0.0169 (17)	−0.043 (2)

Geometric parameters (Å, º)

Co1—N1^i	2.210 (3)	C8—H8	0.9300
Co1—N1	2.210 (3)	C9—C10	1.380 (5)
Co1—N4^ii	2.281 (3)	C9—N3	1.411 (4)
Co1—N4^iii	2.281 (3)	C10—C11	1.372 (5)
Co1—Cl1	2.4185 (8)	C10—H10	0.9300
Co1—Cl1^i	2.4185 (8)	C11—C12	1.373 (5)
C1—N1	1.333 (4)	C11—H11	0.9300
C1—C2	1.377 (5)	C12—N4	1.344 (5)
C1—H1	0.9300	C12—H12	0.9300
C2—C3	1.370 (5)	C13—O3	1.215 (6)
C2—H2	0.9300	C13—N5	1.328 (6)
C3—C4	1.377 (5)	C13—H13	0.9300
C3—H3	0.9300	C14—N5	1.437 (6)
C4—C5	1.384 (4)	C14—H14A	0.9600
C4—N2	1.410 (4)	C14—H14B	0.9600
C5—N1	1.335 (4)	C14—H14C	0.9600
C5—H5	0.9300	C15—N5	1.390 (7)
C6—O1	1.211 (4)	C15—H15A	0.9600
C6—N2	1.355 (4)	C15—H15B	0.9600
C6—C7	1.531 (5)	C15—H15C	0.9600
C7—O2	1.224 (4)	N2—H2A	0.8600
C7—N3	1.338 (4)	N3—H3A	0.8600
C8—N4	1.339 (4)	N4—Co1^iv	2.281 (3)
C8—C9	1.381 (5)
N1^i—Co1—N1	180.0	C8—C9—N3	120.6 (3)
N1^i—Co1—N4^ii	90.55 (10)	C11—C10—C9	118.5 (4)
N1—Co1—N4^ii	89.45 (10)	C11—C10—H10	120.8
N1^i—Co1—N4^iii	89.45 (10)	C9—C10—H10	120.8
N1—Co1—N4^iii	90.55 (10)	C10—C11—C12	119.3 (4)
N4^ii—Co1—N4^iii	180.0	C10—C11—H11	120.4
N1^i—Co1—Cl1	89.79 (8)	C12—C11—H11	120.4
N1—Co1—Cl1	90.21 (8)	N4—C12—C11	123.4 (3)
N4^ii—Co1—Cl1	89.97 (8)	N4—C12—H12	118.3
N4^iii—Co1—Cl1	90.03 (8)	C11—C12—H12	118.3
N1^i—Co1—Cl1^i	90.21 (8)	O3—C13—N5	125.1 (5)
N1—Co1—Cl1^i	89.79 (8)	O3—C13—H13	117.4
N4^ii—Co1—Cl1^i	90.03 (8)	N5—C13—H13	117.4
N4^iii—Co1—Cl1^i	89.97 (8)	N5—C14—H14A	109.5
Cl1—Co1—Cl1^i	180.0	N5—C14—H14B	109.5
N1—C1—C2	122.6 (3)	H14A—C14—H14B	109.5
N1—C1—H1	118.7	N5—C14—H14C	109.5
C2—C1—H1	118.7	H14A—C14—H14C	109.5
C3—C2—C1	120.3 (4)	H14B—C14—H14C	109.5
C3—C2—H2	119.9	N5—C15—H15A	109.5
C1—C2—H2	119.9	N5—C15—H15B	109.5
C2—C3—C4	117.9 (3)	H15A—C15—H15B	109.5
C2—C3—H3	121.0	N5—C15—H15C	109.5
C4—C3—H3	121.0	H15A—C15—H15C	109.5
C3—C4—C5	118.4 (3)	H15B—C15—H15C	109.5
C3—C4—N2	122.9 (3)	C1—N1—C5	116.8 (3)
C5—C4—N2	118.6 (3)	C1—N1—Co1	120.9 (2)
N1—C5—C4	123.9 (3)	C5—N1—Co1	122.1 (2)
N1—C5—H5	118.0	C6—N2—C4	124.5 (3)
C4—C5—H5	118.0	C6—N2—H2A	117.7
O1—C6—N2	126.4 (3)	C4—N2—H2A	117.7
O1—C6—C7	121.7 (3)	C7—N3—C9	123.8 (3)
N2—C6—C7	111.9 (3)	C7—N3—H3A	118.1
O2—C7—N3	125.1 (3)	C9—N3—H3A	118.1
O2—C7—C6	122.2 (3)	C8—N4—C12	116.5 (3)
N3—C7—C6	112.7 (3)	C8—N4—Co1^iv	122.4 (2)
N4—C8—C9	123.5 (3)	C12—N4—Co1^iv	120.7 (2)
N4—C8—H8	118.3	C13—N5—C15	122.4 (5)
C9—C8—H8	118.3	C13—N5—C14	117.7 (5)
C10—C9—C8	118.8 (3)	C15—N5—C14	119.8 (5)
C10—C9—N3	120.6 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O2^ii	0.86	2.11	2.906 (4)	153
N3—H3A···O3^v	0.86	2.06	2.856 (4)	154

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