An organic-inorganic hybrid compound containing imidazolium cations and a one-dimensional lithium hexa­cyanido­cobaltate-based anionic framework

An organic-inorganic hybrid compound, catena-poly[bis­(3H-imidazol-1-ium) [[tetra­cyanido-[kappa]⁴C-cobalt(III)]-[mu]-cyanido-[kappa]²C:N-[di­aqua­lithium(I)]-[mu]-cyanido-[kappa]²N:C]], {(C₃H₅N₂)₂[CoLi(CN)₆(H₂O)₂]}_n, was synthesized by the reaction of Li₃[Co(CN)₆] with imidazolium chloride in aqueous solution. The compound crystallizes in the monoclinic space group C2/c (data collected at 273 K). In the crystal structure, neighbouring [Co(CN)₆]^3- anionic units are linked by Li⁺ cations through the cyanide groups in a trans mode, forming a one-dimensional zigzag chain structure extending along the c axis. A three-dimensional supra­molecular network is formed through hydrogen-bonding inter­actions and is further stabilized by weak CN...[pi] inter­actions between the cyanide groups and the imidazolium cations.

S1. Introduction

Organic–inorganic hybrids are important materials which have rich magnetic, electrical, optical and porous properties, and they have potential applications in areas as diverse as biology, crystal engineering and materials science (Zhou et al., 2012; Zhang & Xiong, 2012). Cyano­metallates, e.g. [M(CN)₆]^3- (M = Cr, Mn, Fe, Co), are commonly used as building blocks for the assembly of multidimensional organic–inorganic hybrid architectures, varying from clusters through one-dimensional chains and two-dimensional layers to three-dimensional frameworks (Ohba & Okawa, 2000; Cernak et al., 2002). Although there have been numerous compounds synthesized from the combination of [M(CN)₆]^3- and transition metal ions, the number of alkali metal hexa­cyano­metallates is still small (Witzel et al., 1988, 2000; Schwarten et al., 2000; Meske & Babel, 1998; Atanasov et al., 2006; Sima & Zhang, 2011). In this paper, we report the structure of an Li^I-containing hexa­cyano­cobaltate-based inorganic–organic hybrid compound, catena-poly[bis­(3H-imidazol-1-ium) [[tetra­cyanido-κ⁴C-cobalt(III)]-µ-cyanido-κ²C:N-[di­aqua­lithium(I)]-κ²N:C], (I), in which the Li⁺ cations link the hexa­cyano­cobaltate units to form one-dimensional zigzag chains.

S2. Experimental

S2.1. Synthesis and crystallization

The title compound, (I), was synthesized by combining Li₃[Co(CN)₆] (0.236 g, 1 mmol), imidazolium chloride (0.204 g, 3 mmol) and H₂O (10 ml). The resulting solution was evaporated slowly at room temperature over a period of several days, affording pale-yellow crystals of (I). Spectroscopic analysis: IR (KBr pellet, ν, cm^-1): 2999 (w, C—H), 2133 (vs, C≡ N), 1593 (s, C═C and C═N).

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms bonded to C and N atoms were placed in calculated positions, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C), and N—H = 0.86 Å and U_iso(H) = 1.2U_eq(N). H atoms bonded to N atoms were refined freely [Contradicts previous sentence] with isotropic displacement parameters. The water H atoms were located in a difference Fourier synthesis and refined with an O—H distance restraint of 0.82(s.u.?) Å and with U_iso(H) = 1.5U_eq(O).

S3. Results and discussion

Compound (I) crystallizes in the monoclinic space group C2/c (data collected at 273 K). The asymmetric unit contains one half of an [LiCo(CN)₆]^2- anion, one free imidazolium cation and one coordinated water molecule (Fig. 1). Atom Co1 is o­cta­hedrally coordinated by six cyanide groups with Co—C distances in the range 1.8913 (18)–1.8964 (16) Å [Table 2; C1/N1, C2/N2, C3/N3, C1ⁱ/N1ⁱ, C2ⁱ/N2ⁱ and C3ⁱ/N3ⁱ; symmetry code: (i) -x + 1, -y + 1, -z]. The Li⁺ cation is four-coordinated by two N atoms of bridging cyanide groups and by two water molecules, and adopts a distorted tetra­hedral geometry. The Li—N bond lengths are 2.011 (2) Å, a little longer than the Li—O bond lengths, which are 1.962 (3) Å. The N1—Li1—N1ⁱⁱ and O1—Li1—O1ⁱⁱ bond angles are 120.9 (2) and 99.58 (18)°, respectively, while the N1—Li1—O1 bond angles are in the range 108.57 (7)–108.59 (6)° [symmetry code: (ii) -x + 1, y, -z + 1/2]. These values are comparable with those in [Cu(en)₂Li(H₂O)][Co(CN)₆] (en is ethyl­enedi­amine), (NMe₄)₂Li(H₂O)₂[M(CN)₆] (Me = methyl, M = Cr, Mn, Fe, Co) and (NMe₄)₃Li[Mo(CN)₈].3.5H₂O, where the Li—O and Li—N bond lengths are in the ranges 1.898 (2)–1.944 (4) and 2.034 (8)–2.140 (2) Å, respectively, and the N—Li—N, O—Li—O and N—Li—O bond angles are in the ranges 108.35 (3)–114.31 (3), 91.81 (2)–95.55 (4) and 103.40 (3)–120.35 (3)°, respectiely (Sima & Zhang, 2011; Schwarten et al., 2000; Meske & Babel, 1998; Witzel et al., 1988).

In the crystal structure of (I), neighbouring [Co(CN)₆]^3- anionic units are linked by Li⁺ cations through the bridging cyanide groups in a trans mode, forming a one-dimensional {[{Co(CN)₄}(µ-CN){Li(H₂O)₂}(µ-CN)]^2-}_n zigzag chain extending along the c axis (Fig. 2), with the Co³⁺ cations collinear with the chain direction. The distances between two nearest Co³⁺ or Li⁺ cations within the chain are 8.405 (4) and 10.062 (5) Å, respectively. The chains are crosslinked into a three-dimensional network by a range of hydrogen-bonding inter­actions (Table 3) involving the imidazole cations, the cyanide ligands and the coordinated water molecules (Fig. 3). The nearest distance between the Co³⁺/Li⁺ cations in two neighbouring chains is 7.857 (6) Å. Similar one-dimensional zigzag Li—N≡C—Co chains were found in an [N(CH₃)₄]-containing compound, namely [N(CH₃)₄]₂{Li(H₂O)₂[M(CN)₆]} (Witzel et al., 1988; Schwarten et al., 2000).

The structure of (I) is further stabilized by weak CN···π inter­actions between the imidazolium cations and the cyanide ligands. The C3^iv—N4^iv···Cg1 (Cg1 is the centroid of the N4/C4/N5/C5/C6 ring) separation is 3.5181 (14) Å [symmetry code: (iv) x - 1/2, y - 1/2, z] (Fig. 4).

In summary, an organic–inorganic hybrid compound, {(C₃H₅N₂)₂[CoLi(CN)₆(H₂O)₂]}_n, was synthesized by the reaction of Li₃[Co(CN)₆] with imidazolium chloride in aqueous solution. It crystallizes in the monoclinic space group C2/c at 273 K. Neighbouring [Co(CN)₆]^3- anions are linked by Li⁺ cations through cyanide groups in a trans mode, forming a one-dimensional zigzag chain structure along the c axis. The chains are involved in a three-dimensional hydrogen-bonding network together with imidazolium cations.

Related literature

For related literature, see: Atanasov et al. (2006); Cernak et al. (2002); Meske & Babel (1998); Ohba & Okawa (2000); Schwarten et al. (2000); Sima & Zhang (2011); Witzel et al. (1988, 2000); Zhang & Xiong (2012); Zhou et al. (2012).

Structure description

Organic–inorganic hybrids are important materials which have rich magnetic, electrical, optical and porous properties, and they have potential applications in areas as diverse as biology, crystal engineering and materials science (Zhou et al., 2012; Zhang & Xiong, 2012). Cyano­metallates, e.g. [M(CN)₆]^3- (M = Cr, Mn, Fe, Co), are commonly used as building blocks for the assembly of multidimensional organic–inorganic hybrid architectures, varying from clusters through one-dimensional chains and two-dimensional layers to three-dimensional frameworks (Ohba & Okawa, 2000; Cernak et al., 2002). Although there have been numerous compounds synthesized from the combination of [M(CN)₆]^3- and transition metal ions, the number of alkali metal hexa­cyano­metallates is still small (Witzel et al., 1988, 2000; Schwarten et al., 2000; Meske & Babel, 1998; Atanasov et al., 2006; Sima & Zhang, 2011). In this paper, we report the structure of an Li^I-containing hexa­cyano­cobaltate-based inorganic–organic hybrid compound, catena-poly[bis­(3H-imidazol-1-ium) [[tetra­cyanido-κ⁴C-cobalt(III)]-µ-cyanido-κ²C:N-[di­aqua­lithium(I)]-κ²N:C], (I), in which the Li⁺ cations link the hexa­cyano­cobaltate units to form one-dimensional zigzag chains.

Compound (I) crystallizes in the monoclinic space group C2/c (data collected at 273 K). The asymmetric unit contains one half of an [LiCo(CN)₆]^2- anion, one free imidazolium cation and one coordinated water molecule (Fig. 1). Atom Co1 is o­cta­hedrally coordinated by six cyanide groups with Co—C distances in the range 1.8913 (18)–1.8964 (16) Å [Table 2; C1/N1, C2/N2, C3/N3, C1ⁱ/N1ⁱ, C2ⁱ/N2ⁱ and C3ⁱ/N3ⁱ; symmetry code: (i) -x + 1, -y + 1, -z]. The Li⁺ cation is four-coordinated by two N atoms of bridging cyanide groups and by two water molecules, and adopts a distorted tetra­hedral geometry. The Li—N bond lengths are 2.011 (2) Å, a little longer than the Li—O bond lengths, which are 1.962 (3) Å. The N1—Li1—N1ⁱⁱ and O1—Li1—O1ⁱⁱ bond angles are 120.9 (2) and 99.58 (18)°, respectively, while the N1—Li1—O1 bond angles are in the range 108.57 (7)–108.59 (6)° [symmetry code: (ii) -x + 1, y, -z + 1/2]. These values are comparable with those in [Cu(en)₂Li(H₂O)][Co(CN)₆] (en is ethyl­enedi­amine), (NMe₄)₂Li(H₂O)₂[M(CN)₆] (Me = methyl, M = Cr, Mn, Fe, Co) and (NMe₄)₃Li[Mo(CN)₈].3.5H₂O, where the Li—O and Li—N bond lengths are in the ranges 1.898 (2)–1.944 (4) and 2.034 (8)–2.140 (2) Å, respectively, and the N—Li—N, O—Li—O and N—Li—O bond angles are in the ranges 108.35 (3)–114.31 (3), 91.81 (2)–95.55 (4) and 103.40 (3)–120.35 (3)°, respectiely (Sima & Zhang, 2011; Schwarten et al., 2000; Meske & Babel, 1998; Witzel et al., 1988).

In the crystal structure of (I), neighbouring [Co(CN)₆]^3- anionic units are linked by Li⁺ cations through the bridging cyanide groups in a trans mode, forming a one-dimensional {[{Co(CN)₄}(µ-CN){Li(H₂O)₂}(µ-CN)]^2-}_n zigzag chain extending along the c axis (Fig. 2), with the Co³⁺ cations collinear with the chain direction. The distances between two nearest Co³⁺ or Li⁺ cations within the chain are 8.405 (4) and 10.062 (5) Å, respectively. The chains are crosslinked into a three-dimensional network by a range of hydrogen-bonding inter­actions (Table 3) involving the imidazole cations, the cyanide ligands and the coordinated water molecules (Fig. 3). The nearest distance between the Co³⁺/Li⁺ cations in two neighbouring chains is 7.857 (6) Å. Similar one-dimensional zigzag Li—N≡C—Co chains were found in an [N(CH₃)₄]-containing compound, namely [N(CH₃)₄]₂{Li(H₂O)₂[M(CN)₆]} (Witzel et al., 1988; Schwarten et al., 2000).

The structure of (I) is further stabilized by weak CN···π inter­actions between the imidazolium cations and the cyanide ligands. The C3^iv—N4^iv···Cg1 (Cg1 is the centroid of the N4/C4/N5/C5/C6 ring) separation is 3.5181 (14) Å [symmetry code: (iv) x - 1/2, y - 1/2, z] (Fig. 4).

In summary, an organic–inorganic hybrid compound, {(C₃H₅N₂)₂[CoLi(CN)₆(H₂O)₂]}_n, was synthesized by the reaction of Li₃[Co(CN)₆] with imidazolium chloride in aqueous solution. It crystallizes in the monoclinic space group C2/c at 273 K. Neighbouring [Co(CN)₆]^3- anions are linked by Li⁺ cations through cyanide groups in a trans mode, forming a one-dimensional zigzag chain structure along the c axis. The chains are involved in a three-dimensional hydrogen-bonding network together with imidazolium cations.

For related literature, see: Atanasov et al. (2006); Cernak et al. (2002); Meske & Babel (1998); Ohba & Okawa (2000); Schwarten et al. (2000); Sima & Zhang (2011); Witzel et al. (1988, 2000); Zhang & Xiong (2012); Zhou et al. (2012).

Synthesis and crystallization

The title compound, (I), was synthesized by combining Li₃[Co(CN)₆] (0.236 g, 1 mmol), imidazolium chloride (0.204 g, 3 mmol) and H₂O (10 ml). The resulting solution was evaporated slowly at room temperature over a period of several days, affording pale-yellow crystals of (I). Spectroscopic analysis: IR (KBr pellet, ν, cm^-1): 2999 (w, C—H), 2133 (vs, C≡ N), 1593 (s, C═C and C═N).

Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms bonded to C and N atoms were placed in calculated positions, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C), and N—H = 0.86 Å and U_iso(H) = 1.2U_eq(N). H atoms bonded to N atoms were refined freely [Contradicts previous sentence] with isotropic displacement parameters. The water H atoms were located in a difference Fourier synthesis and refined with an O—H distance restraint of 0.82(s.u.?) Å and with U_iso(H) = 1.5U_eq(O).

Computing details

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

Fig. 1. The structural unit of (I), showing the atom-numbering scheme and hydrogen-bonding interactions. Displacement ellipsoids are drawn at the 50% probability level. Dashed lines denote hydrogen bonds. [Symmetry codes: (i) -x + 1, -y + 1, -z; (ii) -x + 1, y, -z + 1/2; (iii) -x + 1/2, y + 1/2, -z + 1/2; (iv) x - 1/2, y - 1/2, z; (v) x, y - 1, z.]

Fig. 2. (a) The one-dimensional chain of anionic building blocks in (I). (b) A view of the two-dimensional layer structure formed by the assembly of the one-dimensional zigzag chains through hydrogen bonds (dashed lines).

Fig. 3. The crystal packing of (I), showing the hydrogen-bonding interactions (dashed lines) among the imidazolium cations and inorganic chains.

Fig. 4. A view of the CN···π interactions in (I), denoted by violet dashed lines. [Symmetry code: (iv) x - 1/2, y - 1/2, z.]

catena-Poly[bis(3H-imidazol-1-ium) [[tetracyanido-κ⁴C-cobalt(III)]-µ-cyanido-κ²C:N-[diaqualithium(I)]-κ²N:C]

Crystal data

(C3H5N2)2[CoLi(CN)6(H2O)2]	F(000) = 808
Mr = 396.20	Dx = 1.391 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2169 reflections
a = 15.581 (7) Å	θ = 2.8–27.5°
b = 7.857 (2) Å	µ = 0.94 mm^−1
c = 16.809 (8) Å	T = 273 K
β = 113.20 (3)°	Block, yellow
V = 1891.4 (14) Å^3	0.38 × 0.34 × 0.3 mm
Z = 4

Data collection

Rigaku SCXmini diffractometer	1932 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.031
Graphite monochromator	θmax = 27.5°, θmin = 2.8°
ω scans	h = −20→20
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −10→10
Tmin = 0.733, Tmax = 0.792	l = −21→21
9863 measured reflections	3 standard reflections every 180 reflections
2169 independent reflections	intensity decay: none

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) = 0.073	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ^2(Fo^2) + (0.0342P)^2 + 1.0124P] where P = (Fo^2 + 2Fc^2)/3
2169 reflections	(Δ/σ)max < 0.001
128 parameters	Δρmax = 0.24 e Å^−3
3 restraints	Δρmin = −0.27 e Å^−3

Special details

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

	x	y	z	Uiso*/Ueq
C1	0.50829 (10)	0.3558 (2)	0.09322 (10)	0.0244 (3)
C2	0.48223 (11)	0.6862 (2)	0.06366 (10)	0.0260 (3)
C3	0.63101 (11)	0.53016 (19)	0.04951 (9)	0.0247 (3)
C4	0.15916 (16)	0.4749 (3)	0.08239 (15)	0.0507 (5)
H4A	0.1004	0.4722	0.0374	0.061*
C5	0.30872 (16)	0.4865 (4)	0.15278 (17)	0.0715 (9)
H5A	0.3722	0.4942	0.1650	0.086*
C6	0.26938 (17)	0.4709 (4)	0.20993 (15)	0.0697 (8)
H6A	0.3002	0.4651	0.2698	0.084*
Co1	0.5000	0.5000	0.0000	0.01768 (10)
H1A	0.3447 (9)	0.017 (3)	0.1682 (12)	0.061 (8)*
H1B	0.4217 (13)	−0.078 (2)	0.1810 (12)	0.061 (7)*
Li1	0.5000	0.1479 (5)	0.2500	0.0259 (7)
N1	0.51240 (10)	0.27415 (19)	0.15103 (9)	0.0364 (3)
N2	0.46940 (12)	0.7963 (2)	0.10225 (11)	0.0449 (4)
N3	0.71095 (10)	0.5450 (2)	0.07754 (10)	0.0387 (4)
N4	0.17615 (12)	0.4652 (2)	0.16416 (11)	0.0467 (4)
H4B	0.1348	0.4563	0.1859	0.056*
N5	0.23838 (14)	0.4889 (2)	0.07388 (12)	0.0524 (5)
H5B	0.2448	0.4984	0.0255	0.063*
O1	0.39593 (8)	−0.01333 (15)	0.20292 (7)	0.0290 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0226 (7)	0.0289 (8)	0.0241 (7)	0.0024 (6)	0.0119 (6)	0.0022 (6)
C2	0.0241 (7)	0.0316 (8)	0.0250 (7)	−0.0003 (6)	0.0124 (6)	−0.0006 (7)
C3	0.0257 (8)	0.0335 (9)	0.0171 (7)	0.0017 (6)	0.0109 (6)	0.0010 (6)
C4	0.0405 (11)	0.0646 (14)	0.0440 (11)	0.0042 (9)	0.0134 (9)	0.0103 (10)
C5	0.0379 (12)	0.125 (3)	0.0621 (16)	−0.0003 (13)	0.0305 (12)	−0.0045 (14)
C6	0.0481 (13)	0.128 (3)	0.0323 (11)	−0.0017 (13)	0.0155 (10)	−0.0046 (12)
Co1	0.01768 (15)	0.02238 (16)	0.01505 (14)	0.00157 (10)	0.00867 (10)	0.00134 (10)
Li1	0.0307 (19)	0.0275 (19)	0.0230 (17)	0.000	0.0143 (15)	0.000
N1	0.0413 (8)	0.0407 (8)	0.0321 (7)	0.0047 (7)	0.0195 (7)	0.0130 (6)
N2	0.0501 (9)	0.0433 (9)	0.0474 (9)	0.0008 (7)	0.0257 (8)	−0.0165 (8)
N3	0.0227 (7)	0.0634 (10)	0.0294 (7)	−0.0005 (7)	0.0098 (6)	0.0001 (7)
N4	0.0409 (9)	0.0632 (11)	0.0494 (10)	0.0058 (8)	0.0323 (8)	0.0030 (8)
N5	0.0654 (12)	0.0664 (12)	0.0396 (9)	0.0017 (9)	0.0360 (9)	0.0046 (8)
O1	0.0214 (6)	0.0409 (7)	0.0248 (6)	0.0023 (5)	0.0093 (5)	−0.0062 (5)

Geometric parameters (Å, º)

C1—N1	1.145 (2)	C6—H6A	0.9300
C1—Co1	1.8963 (16)	Co1—C3^i	1.8913 (18)
C2—N2	1.145 (2)	Co1—C1^i	1.8963 (16)
C2—Co1	1.8964 (16)	Co1—C2^i	1.8964 (16)
C3—N3	1.151 (2)	Li1—O1	1.962 (3)
C3—Co1	1.8913 (18)	Li1—O1^ii	1.962 (3)
C4—N4	1.295 (3)	Li1—N1^ii	2.011 (2)
C4—N5	1.302 (3)	Li1—N1	2.011 (2)
C4—H4A	0.9300	Li1—H1B	2.21 (2)
C5—C6	1.333 (3)	N4—H4B	0.8599
C5—N5	1.347 (3)	N5—H5B	0.8600
C5—H5A	0.9300	O1—H1A	0.818 (9)
C6—N4	1.350 (3)	O1—H1B	0.822 (9)
N1—C1—Co1	177.29 (15)	C1—Co1—C2^i	91.59 (7)
N2—C2—Co1	178.07 (15)	C1^i—Co1—C2^i	88.41 (7)
N3—C3—Co1	177.71 (14)	C2—Co1—C2^i	180.00 (8)
N4—C4—N5	108.4 (2)	O1—Li1—O1^ii	99.58 (18)
N4—C4—H4A	125.8	O1—Li1—N1^ii	108.59 (6)
N5—C4—H4A	125.8	O1^ii—Li1—N1^ii	108.57 (7)
C6—C5—N5	106.5 (2)	O1—Li1—N1	108.57 (7)
C6—C5—H5A	126.8	O1^ii—Li1—N1	108.59 (6)
N5—C5—H5A	126.8	N1^ii—Li1—N1	120.9 (2)
C5—C6—N4	106.8 (2)	O1—Li1—H1B	21.7 (3)
C5—C6—H6A	126.6	O1^ii—Li1—H1B	83.7 (4)
N4—C6—H6A	126.6	N1^ii—Li1—H1B	128.2 (4)
C3^i—Co1—C3	180.00 (4)	N1—Li1—H1B	100.1 (6)
C3^i—Co1—C1	89.95 (7)	C1—N1—Li1	170.84 (15)
C3—Co1—C1	90.05 (7)	C4—N4—C6	109.08 (18)
C3^i—Co1—C1^i	90.05 (7)	C4—N4—H4B	125.5
C3—Co1—C1^i	89.95 (7)	C6—N4—H4B	125.4
C1—Co1—C1^i	180.00 (9)	C4—N5—C5	109.23 (18)
C3^i—Co1—C2	88.44 (7)	C4—N5—H5B	125.4
C3—Co1—C2	91.56 (7)	C5—N5—H5B	125.4
C1—Co1—C2	88.41 (7)	Li1—O1—H1A	121.1 (16)
C1^i—Co1—C2	91.59 (7)	Li1—O1—H1B	96.3 (16)
C3^i—Co1—C2^i	91.56 (7)	H1A—O1—H1B	112.1 (15)
C3—Co1—C2^i	88.44 (7)
N5—C5—C6—N4	−0.3 (3)	N2—C2—Co1—C3	−146 (5)
N3—C3—Co1—C3^i	158 (100)	N2—C2—Co1—C1	−56 (5)
N3—C3—Co1—C1	106 (4)	N2—C2—Co1—C1^i	124 (5)
N3—C3—Co1—C1^i	−74 (4)	N2—C2—Co1—C2^i	19 (4)
N3—C3—Co1—C2	−166 (4)	Co1—C1—N1—Li1	47 (4)
N3—C3—Co1—C2^i	14 (4)	O1—Li1—N1—C1	68.2 (11)
N1—C1—Co1—C3^i	−83 (3)	O1^ii—Li1—N1—C1	175.6 (10)
N1—C1—Co1—C3	97 (3)	N1^ii—Li1—N1—C1	−58.1 (10)
N1—C1—Co1—C1^i	−164 (100)	N5—C4—N4—C6	−0.8 (3)
N1—C1—Co1—C2	6 (3)	C5—C6—N4—C4	0.7 (3)
N1—C1—Co1—C2^i	−174 (100)	N4—C4—N5—C5	0.6 (3)
N2—C2—Co1—C3^i	34 (5)	C6—C5—N5—C4	−0.2 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4B···O1^iii	0.86	2.12	2.874 (2)	146
N5—H5B···N3^i	0.86	2.13	2.959 (3)	162
O1—H1A···N3^iv	0.82 (1)	2.05 (1)	2.859 (2)	169 (2)
O1—H1B···N2^v	0.82 (1)	2.01 (1)	2.817 (2)	166 (2)

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