Second-sphere coordination in anion binding: cis-diazido­bis(ethyl­ene­diamine-κ²N,N′)cobalt(III) picrate

In the title compound, [Co(N₃)₂(C₂H₈N₂)₂](C₆H₂N₃O₇), the cations share NH₂...NH₂ edges with picrate anions via second-sphere N—H...O hydrogen bonds.

S1. Comment

We are currently engaged in studies to explore cobalt(III) complexes as potential anion receptors and have previously reported the crystal structures of some cis-diazidobis(ethylenediamine)cobalt(III) salts (Sharma et al., 2003). The [cis-Co(en)₂(N₃)₂]⁺ cation (en is ethylenediamine) has also been characterized as a nitrate salt (Padmanabhan et al., 1968; Kastner et al., 1989). In continuation of our interest in this class of compounds, we describe here the synthesis and crystal structure of the title complex salt, [cis-Co(en)₂(N₃)₂]⁺(C₆H₂N₃O₇⁻), (I) (Fig. 1).

The cation and anion moieties in (I) are segregated into layers lying approximately in the (004) plane. The [cis-Co(en)₂(N₃)₂]⁺ cations form bilayers, into which the azido ligands interdigitate (Fig. 2). Within these bilayers, several N—H···N hydrogen bonds are formed with acceptor N atoms in the azide moieties (Table 1). The interactions N8—H8B···N3 and N7—H7A···N6 are formed to the terminal (non-coordinated) N atom of each azide moiety, with the N—H vector in each case being close to collinear with the N₃ axis. Interactions N10—H10A···N1 and N10—H10B···N4 are formed with acceptor N atoms bound directly to atom Co1. In these cases, the geometry at the N acceptor is such that the interaction can be envisaged as involving a lone pair of electrons on an sp²-hybridized N atom.

In the layers of picrate anions, the phenyl rings lie approximately perpendicular to the layer planes, forming a herring-bone-type arrangement (Fig. 3). One NO₂ group of each anion lies approximately in the plane, and the C—O⁻ bonds in adjacent molecules project alternately above and below the plane.

Of most interest from the perspective of anion–cation recognition is the arrangement of the second-sphere hydrogen-bond interactions at the interface between the picrate layers and the [cis-Co(en)₂(N₃)₂]⁺ bilayers. The edge of each picrate anion that contains the phenoxo O atom interacts with an NH₂···NH₂ edge of an adjacent [cis-Co(en)₂(N₃)₂]⁺ cation, forming complementary sets of N—H···O hydrogen bonds that are bifurcated at the N—H donor (Table 1 and Fig. 4). The remaining NO₂ group also interacts essentially with a single NH₂···NH₂ edge, accepting N—H···O hydrogen bonds from N7—H7 that are bifurcated at the donor (Table 1 and Fig. 4). Atom O4 of this nitrate group lies approximately along the bisector of the H9A—N9—H9B angle, slightly displaced towards H9B, so that it accepts N—H···O hydrogen bonds that are bifurcated at the acceptor.

S2. Experimental

The complex salt [cis-Co(en)₂(N₃)₂]NO₃ was prepared according to the literature method of Staples & Tobe (1960). [cis-Co(en)₂(N₃)₂]NO₃ (1 g, 0.003 mol) was dissolved in water (100 ml) in a beaker. In a second beaker, NaOH (0.1362 g, 0.003 mol) was dissolved in a minimum amount of water, and picric acid, C₆H₃N₃O₇ (0.7116 g, 0.003 mol), was added to it. The two clear solutions were mixed and the resulting brown precipitate was filtered and dried in air. This solid was dissolved in 3:1 acetone–water mixture and slow evaporation at room temperature afforded reddish–black single crystals of (I) suitable for X-ray structure determination within one week. The complex salt (m.p. 453 K) is soluble in water and dimethylsulfoxide and fairly soluble in acetone. Elemental analysis, found: Co 12.04, C 24.80, H 3.82, N 37.25%; calculated for C₁₀H₁₈CoN₁₃O₇: Co 12.00, C 24.42, H 3.66, N 37.04%.

S3. Refinement

The largest peak in the difference density map lies in the vicinity of atom Co1. All H atoms were placed in calculated positions and allowed to ride during subsequent refinement, with C—H = 0.95 Å and N—H = 0.92 Å, and with U_iso(H) = 1.2 U_eq(C,N).

Computing details

Data collection: APEX2 (Bruker Nonius, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The molecular units in (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radius.
	Fig. 2. A projection along [100], showing bilayers of [trans-Co(en)2(N3)2]^+ cations and layers of picrate anions lying approximately in (004). N—H···N hydrogen bonds are depicted as dashed lines in the central [trans-Co(en)2(N3)2]^+ bilayer and the acceptor atoms are labelled. Atoms N1, N3 and N4 are at the symmetry positions (1/2 − x, 1 − y, 1/2 + z), (1 − x, 1/2 + y, 1/2 − z) and (x, 1/2 − y, 1/2 + z), respectively. H atoms bound to C atoms have been omitted for clarity.
	Fig. 3. A projection along [001] onto the plane of a single layer of picrate anions, showing the herring-bone-type arrangement.
	Fig. 4. Second-sphere hydrogen-bond interactions between the cationic and anionic moieties. [Symmetry code: (i) −x, 1/2 + y, 1/2 − z.]

cis-diazidobis(ethylenediamine-κ²N,N')cobalt(III) picrate

Crystal data

[Co(C2H8N2)2(N3)2](C6H2N3O7)	F(000) = 2016
Mr = 491.30	Dx = 1.799 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 6972 reflections
a = 9.1229 (3) Å	θ = 2.7–31.3°
b = 12.0980 (5) Å	µ = 1.02 mm^−1
c = 32.8793 (12) Å	T = 180 K
V = 3628.9 (2) Å^3	Block, red-black
Z = 8	0.25 × 0.25 × 0.20 mm

Data collection

Bruker Nonius X8 APEX-II CCD area-detector diffractometer	4649 independent reflections
Radiation source: fine-focus sealed tube	3930 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
thin–slice ω and ϕ scans	θmax = 29.5°, θmin = 3.6°
Absorption correction: multi-scan (SADABS version 2.10; Sheldrick, 2003) Ratio of minimum to maximum apparent transmission = 0.855478	h = −12→12
Tmin = 0.703, Tmax = 0.822	k = −15→13
20066 measured reflections	l = −43→44

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.115	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0559P)^2 + 4.5267P] where P = (Fo^2 + 2Fc^2)/3
4649 reflections	(Δ/σ)max < 0.001
280 parameters	Δρmax = 1.39 e Å^−3
0 restraints	Δρmin = −0.43 e Å^−3

Special details

Experimental. All H atoms placed geometrically and refined using a riding model.

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
Co1	0.09138 (3)	0.25250 (2)	0.061765 (8)	0.02026 (10)
N1	−0.0235 (2)	0.27566 (16)	0.01206 (5)	0.0272 (4)
N2	0.0140 (2)	0.34764 (18)	−0.01103 (5)	0.0315 (4)
N3	0.0433 (3)	0.4157 (2)	−0.03437 (7)	0.0515 (7)
N4	0.1962 (2)	0.12737 (16)	0.03752 (5)	0.0276 (4)
N5	0.1718 (2)	0.09472 (17)	0.00394 (6)	0.0283 (4)
N6	0.1588 (3)	0.0594 (2)	−0.02838 (7)	0.0493 (6)
N7	−0.0647 (2)	0.15235 (17)	0.07961 (6)	0.0280 (4)
H7A	−0.0891	0.1048	0.0589	0.034*
H7B	−0.0331	0.1111	0.1014	0.034*
N8	−0.0199 (2)	0.36823 (17)	0.08980 (6)	0.0290 (4)
H8A	0.0414	0.4079	0.1066	0.035*
H8B	−0.0599	0.4160	0.0711	0.035*
N9	0.2157 (2)	0.22658 (15)	0.11012 (5)	0.0232 (4)
H9A	0.1762	0.2617	0.1324	0.028*
H9B	0.2207	0.1521	0.1156	0.028*
N10	0.2450 (2)	0.35599 (16)	0.04524 (5)	0.0268 (4)
H10A	0.2977	0.3264	0.0240	0.032*
H10B	0.2030	0.4209	0.0364	0.032*
C1	−0.1944 (3)	0.2189 (3)	0.09141 (8)	0.0416 (6)
H1A	−0.2484	0.2436	0.0669	0.050*
H1B	−0.2615	0.1745	0.1085	0.050*
C2	−0.1394 (3)	0.3153 (3)	0.11441 (8)	0.0429 (6)
H2A	−0.1007	0.2913	0.1411	0.051*
H2B	−0.2198	0.3687	0.1191	0.051*
C3	0.3646 (2)	0.2706 (2)	0.10168 (7)	0.0271 (4)
H3A	0.4203	0.2183	0.0844	0.033*
H3B	0.4191	0.2815	0.1274	0.033*
C4	0.3448 (2)	0.3791 (2)	0.08002 (7)	0.0298 (5)
H4A	0.3010	0.4347	0.0985	0.036*
H4B	0.4402	0.4074	0.0702	0.036*
O1	0.1538 (2)	0.40324 (16)	0.16432 (5)	0.0394 (4)
O2	−0.0152 (3)	0.57057 (17)	0.14385 (5)	0.0506 (6)
O3	−0.1548 (2)	0.6410 (2)	0.18950 (6)	0.0528 (6)
O4	−0.0664 (3)	0.5959 (2)	0.32876 (6)	0.0584 (6)
O5	0.0804 (2)	0.47089 (19)	0.35122 (5)	0.0459 (5)
O6	0.3140 (3)	0.24616 (19)	0.19832 (6)	0.0608 (7)
O7	0.3777 (2)	0.27011 (15)	0.26040 (5)	0.0360 (4)
N11	−0.0554 (2)	0.57939 (16)	0.17922 (6)	0.0294 (4)
N12	0.0209 (2)	0.51990 (19)	0.32298 (6)	0.0351 (5)
N13	0.3002 (2)	0.29272 (16)	0.23090 (5)	0.0257 (4)
C5	0.1236 (2)	0.42980 (18)	0.19980 (6)	0.0235 (4)
C6	0.0195 (2)	0.51616 (17)	0.21078 (6)	0.0229 (4)
C7	−0.0144 (2)	0.54450 (18)	0.25007 (7)	0.0245 (4)
H7	−0.0833	0.6015	0.2555	0.029*
C8	0.0533 (2)	0.48890 (19)	0.28174 (6)	0.0257 (4)
C9	0.1561 (2)	0.40692 (18)	0.27486 (6)	0.0237 (4)
H9	0.2026	0.3707	0.2970	0.028*
C10	0.1896 (2)	0.37874 (17)	0.23555 (6)	0.0223 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.02115 (15)	0.02316 (17)	0.01646 (15)	−0.00189 (10)	0.00146 (9)	−0.00117 (10)
N1	0.0293 (9)	0.0302 (10)	0.0222 (8)	−0.0003 (8)	−0.0037 (7)	0.0032 (7)
N2	0.0320 (9)	0.0400 (12)	0.0226 (9)	−0.0046 (9)	−0.0044 (7)	−0.0001 (8)
N3	0.0617 (15)	0.0595 (16)	0.0332 (11)	−0.0290 (13)	−0.0074 (11)	0.0142 (11)
N4	0.0302 (9)	0.0281 (10)	0.0246 (8)	0.0024 (8)	−0.0004 (7)	−0.0026 (7)
N5	0.0298 (9)	0.0272 (10)	0.0279 (9)	0.0050 (8)	−0.0028 (7)	−0.0028 (7)
N6	0.0536 (14)	0.0535 (15)	0.0409 (12)	0.0195 (12)	−0.0149 (10)	−0.0215 (11)
N7	0.0293 (9)	0.0313 (10)	0.0235 (8)	−0.0056 (8)	0.0012 (7)	0.0030 (7)
N8	0.0329 (9)	0.0298 (10)	0.0241 (8)	0.0062 (8)	0.0001 (7)	−0.0023 (7)
N9	0.0271 (9)	0.0227 (9)	0.0199 (8)	−0.0005 (7)	0.0001 (6)	0.0000 (7)
N10	0.0298 (9)	0.0284 (10)	0.0222 (8)	−0.0058 (8)	0.0006 (7)	0.0023 (7)
C1	0.0301 (12)	0.0544 (17)	0.0402 (13)	−0.0022 (12)	0.0090 (10)	0.0040 (12)
C2	0.0330 (12)	0.0558 (18)	0.0398 (14)	0.0054 (12)	0.0121 (10)	−0.0071 (12)
C3	0.0234 (10)	0.0350 (12)	0.0230 (10)	−0.0018 (9)	0.0005 (8)	−0.0028 (8)
C4	0.0295 (10)	0.0353 (13)	0.0247 (10)	−0.0104 (9)	−0.0005 (8)	0.0005 (9)
O1	0.0514 (11)	0.0466 (11)	0.0202 (7)	0.0175 (9)	0.0005 (7)	−0.0059 (7)
O2	0.0873 (16)	0.0390 (11)	0.0254 (9)	0.0220 (11)	−0.0040 (9)	0.0032 (8)
O3	0.0474 (12)	0.0616 (14)	0.0494 (12)	0.0283 (11)	−0.0001 (9)	0.0083 (10)
O4	0.0758 (15)	0.0641 (15)	0.0355 (10)	0.0290 (12)	0.0110 (10)	−0.0164 (10)
O5	0.0572 (12)	0.0603 (13)	0.0201 (8)	0.0061 (10)	0.0001 (7)	−0.0043 (8)
O6	0.0820 (17)	0.0650 (15)	0.0353 (10)	0.0461 (13)	−0.0121 (11)	−0.0203 (9)
O7	0.0349 (8)	0.0369 (10)	0.0363 (9)	0.0089 (8)	−0.0066 (7)	0.0003 (7)
N11	0.0351 (10)	0.0234 (10)	0.0296 (9)	−0.0006 (8)	−0.0055 (8)	0.0001 (8)
N12	0.0388 (11)	0.0407 (12)	0.0259 (9)	−0.0002 (9)	0.0058 (8)	−0.0106 (9)
N13	0.0256 (8)	0.0242 (9)	0.0274 (9)	0.0014 (7)	0.0008 (7)	−0.0021 (7)
C5	0.0255 (9)	0.0248 (11)	0.0203 (9)	−0.0009 (8)	0.0010 (8)	−0.0030 (8)
C6	0.0249 (9)	0.0202 (10)	0.0237 (9)	−0.0008 (8)	−0.0008 (7)	0.0001 (8)
C7	0.0244 (9)	0.0214 (10)	0.0277 (10)	−0.0007 (8)	0.0023 (8)	−0.0044 (8)
C8	0.0293 (10)	0.0266 (11)	0.0211 (9)	−0.0027 (9)	0.0037 (8)	−0.0049 (8)
C9	0.0252 (9)	0.0255 (11)	0.0205 (9)	−0.0024 (8)	−0.0004 (7)	−0.0013 (8)
C10	0.0214 (9)	0.0218 (10)	0.0238 (9)	−0.0005 (8)	0.0011 (7)	−0.0045 (8)

Geometric parameters (Å, º)

Co1—N10	1.9560 (18)	C2—H2A	0.990
Co1—N7	1.9594 (19)	C2—H2B	0.990
Co1—N8	1.9595 (19)	C3—C4	1.505 (3)
Co1—N4	1.9602 (19)	C3—H3A	0.990
Co1—N1	1.9613 (18)	C3—H3B	0.990
Co1—N9	1.9779 (17)	C4—H4A	0.990
N1—N2	1.205 (3)	C4—H4B	0.990
N2—N3	1.157 (3)	O1—C5	1.241 (3)
N4—N5	1.194 (3)	O2—N11	1.224 (3)
N5—N6	1.151 (3)	O3—N11	1.221 (3)
N7—C1	1.483 (3)	O4—N12	1.231 (3)
N7—H7A	0.920	O5—N12	1.228 (3)
N7—H7B	0.920	O6—N13	1.217 (3)
N8—C2	1.501 (3)	O7—N13	1.231 (2)
N8—H8A	0.920	N11—C6	1.459 (3)
N8—H8B	0.920	N12—C8	1.438 (3)
N9—C3	1.485 (3)	N13—C10	1.457 (3)
N9—H9A	0.920	C5—C6	1.457 (3)
N9—H9B	0.920	C5—C10	1.458 (3)
N10—C4	1.489 (3)	C6—C7	1.372 (3)
N10—H10A	0.920	C7—C8	1.385 (3)
N10—H10B	0.920	C7—H7	0.950
C1—C2	1.477 (4)	C8—C9	1.384 (3)
C1—H1A	0.990	C9—C10	1.371 (3)
C1—H1B	0.990	C9—H9	0.950
N10—Co1—N7	178.14 (8)	N7—C1—H1B	110.3
N10—Co1—N8	92.53 (8)	H1A—C1—H1B	108.6
N7—Co1—N8	85.68 (9)	C1—C2—N8	107.9 (2)
N10—Co1—N4	91.83 (8)	C1—C2—H2A	110.1
N7—Co1—N4	89.93 (8)	N8—C2—H2A	110.1
N8—Co1—N4	174.78 (8)	C1—C2—H2B	110.1
N10—Co1—N1	93.43 (8)	N8—C2—H2B	110.1
N7—Co1—N1	87.11 (8)	H2A—C2—H2B	108.4
N8—Co1—N1	90.76 (8)	N9—C3—C4	106.94 (18)
N4—Co1—N1	91.84 (8)	N9—C3—H3A	110.3
N10—Co1—N9	85.07 (7)	C4—C3—H3A	110.3
N7—Co1—N9	94.47 (8)	N9—C3—H3B	110.3
N8—Co1—N9	91.84 (8)	C4—C3—H3B	110.3
N4—Co1—N9	85.68 (8)	H3A—C3—H3B	108.6
N1—Co1—N9	177.05 (8)	N10—C4—C3	105.85 (18)
N2—N1—Co1	118.49 (15)	N10—C4—H4A	110.6
N3—N2—N1	176.4 (2)	C3—C4—H4A	110.6
N5—N4—Co1	122.72 (16)	N10—C4—H4B	110.6
N6—N5—N4	174.7 (2)	C3—C4—H4B	110.6
C1—N7—Co1	108.81 (16)	H4A—C4—H4B	108.7
C1—N7—H7A	109.9	O3—N11—O2	122.6 (2)
Co1—N7—H7A	109.9	O3—N11—C6	118.09 (19)
C1—N7—H7B	109.9	O2—N11—C6	119.3 (2)
Co1—N7—H7B	109.9	O5—N12—O4	122.0 (2)
H7A—N7—H7B	108.3	O5—N12—C8	119.8 (2)
C2—N8—Co1	108.96 (16)	O4—N12—C8	118.3 (2)
C2—N8—H8A	109.9	O6—N13—O7	122.1 (2)
Co1—N8—H8A	109.9	O6—N13—C10	119.64 (19)
C2—N8—H8B	109.9	O7—N13—C10	118.25 (18)
Co1—N8—H8B	109.9	O1—C5—C6	124.3 (2)
H8A—N8—H8B	108.3	O1—C5—C10	123.8 (2)
C3—N9—Co1	108.51 (13)	C6—C5—C10	111.92 (17)
C3—N9—H9A	110.0	C7—C6—C5	124.01 (19)
Co1—N9—H9A	110.0	C7—C6—N11	115.66 (19)
C3—N9—H9B	110.0	C5—C6—N11	120.33 (18)
Co1—N9—H9B	110.0	C6—C7—C8	119.1 (2)
H9A—N9—H9B	108.4	C6—C7—H7	120.5
C4—N10—Co1	110.20 (13)	C8—C7—H7	120.5
C4—N10—H10A	109.6	C9—C8—C7	121.83 (19)
Co1—N10—H10A	109.6	C9—C8—N12	118.7 (2)
C4—N10—H10B	109.6	C7—C8—N12	119.4 (2)
Co1—N10—H10B	109.6	C10—C9—C8	118.9 (2)
H10A—N10—H10B	108.1	C10—C9—H9	120.5
C2—C1—N7	106.9 (2)	C8—C9—H9	120.5
C2—C1—H1A	110.3	C9—C10—N13	115.54 (19)
N7—C1—H1A	110.3	C9—C10—C5	124.21 (19)
C2—C1—H1B	110.3	N13—C10—C5	120.25 (17)
N10—Co1—N1—N2	−7.77 (19)	N9—C3—C4—N10	−52.3 (2)
N7—Co1—N1—N2	170.45 (19)	O1—C5—C6—C7	179.4 (2)
N8—Co1—N1—N2	84.81 (19)	C10—C5—C6—C7	−1.2 (3)
N4—Co1—N1—N2	−99.71 (19)	O1—C5—C6—N11	−1.0 (3)
N10—Co1—N4—N5	−94.89 (19)	C10—C5—C6—N11	178.33 (18)
N7—Co1—N4—N5	85.71 (19)	O3—N11—C6—C7	−9.5 (3)
N1—Co1—N4—N5	−1.4 (2)	O2—N11—C6—C7	169.2 (2)
N9—Co1—N4—N5	−179.8 (2)	O3—N11—C6—C5	170.9 (2)
N8—Co1—N7—C1	17.55 (16)	O2—N11—C6—C5	−10.4 (3)
N4—Co1—N7—C1	−165.29 (16)	C5—C6—C7—C8	0.1 (3)
N1—Co1—N7—C1	−73.44 (16)	N11—C6—C7—C8	−179.43 (19)
N9—Co1—N7—C1	109.06 (16)	C6—C7—C8—C9	1.2 (3)
N10—Co1—N8—C2	−169.39 (16)	C6—C7—C8—N12	178.5 (2)
N7—Co1—N8—C2	10.09 (16)	O5—N12—C8—C9	−2.6 (3)
N1—Co1—N8—C2	97.14 (16)	O4—N12—C8—C9	177.2 (2)
N9—Co1—N8—C2	−84.25 (16)	O5—N12—C8—C7	179.9 (2)
N10—Co1—N9—C3	−15.77 (14)	O4—N12—C8—C7	−0.3 (3)
N7—Co1—N9—C3	166.03 (14)	C7—C8—C9—C10	−1.2 (3)
N8—Co1—N9—C3	−108.16 (15)	N12—C8—C9—C10	−178.6 (2)
N4—Co1—N9—C3	76.44 (14)	C8—C9—C10—N13	179.25 (19)
N8—Co1—N10—C4	78.06 (16)	C8—C9—C10—C5	0.0 (3)
N4—Co1—N10—C4	−99.07 (16)	O6—N13—C10—C9	164.2 (2)
N1—Co1—N10—C4	168.98 (15)	O7—N13—C10—C9	−16.2 (3)
N9—Co1—N10—C4	−13.57 (15)	O6—N13—C10—C5	−16.5 (3)
Co1—N7—C1—C2	−41.8 (2)	O7—N13—C10—C5	163.1 (2)
N7—C1—C2—N8	50.5 (3)	O1—C5—C10—C9	−179.5 (2)
Co1—N8—C2—C1	−35.9 (3)	C6—C5—C10—C9	1.2 (3)
Co1—N9—C3—C4	41.44 (19)	O1—C5—C10—N13	1.3 (3)
Co1—N10—C4—C3	39.3 (2)	C6—C5—C10—N13	−178.07 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N7—H7A···N6^i	0.92	2.31	3.184 (3)	158
N8—H8B···N3^ii	0.92	2.37	3.194 (3)	149
N10—H10A···N1^iii	0.92	2.37	3.248 (3)	161
N10—H10B···N4^iv	0.92	2.66	3.336 (3)	131
N8—H8A···O1	0.92	2.16	2.948 (3)	143
N8—H8A···O2	0.92	2.38	3.025 (3)	128
N9—H9A···O1	0.92	2.02	2.839 (2)	148
N9—H9A···O6	0.92	2.51	3.045 (3)	117
N9—H9A···O4^v	0.92	2.58	2.897 (3)	101
N9—H9B···O4^v	0.92	2.41	2.897 (3)	113
N7—H7B···O4^v	0.92	2.48	3.312 (3)	151
N7—H7B···O5^v	0.92	2.34	3.164 (3)	149

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