trans-Cyano(6-methyl-1,4,8,11-tetraazacyclotetradecan-6-amine)cobalt(III) bis(perchlorate) hydrate and trans-hydroxo(6-methyl-1,4,8,11-tetraazacyclotetradecan-6-amine)cobalt(III) bis(perchlorate)

The crystal structures of a pair of closely related macrocyclic cyano- and hydroxopenta­amine­cobalt(III) complexes, as their perchlorate salts, are reported. Although the two complexes, [Co(CN)(C₁₁H₂₇N₅)](ClO₄)₂·H₂O and [Co(OH)(C₁₁H₂₇N₅)](ClO₄)₂, exhibit similar conformations, significant differences in the Co-N bond lengths arise from the influence of the sixth ligand (cyano as opposed to hydroxo). The ensuing hydrogen-bonding patterns are also distinctly different. Disorder in the perchlorate anions was clearly resolved and this was rationalized on the basis of distinct hydrogen-bonding motifs involving the anion O atoms and the N-H and O-H donors.

S1. Comment

The pendant amino-substitutued cyclam 6-methyl-1,4,8,11-tetraazacyclotetradecane-6-amine (L¹) has the capability of binding as a pentadentate ligand via its four secondary amine and single primary amine N-donors. The ligand may coordinate in a folded (cis) (Lawrance et al., 1992) or planar (trans) configuration (Hambley et al., 1992). Within the trans form, there are two possible N-based isomeric forms, RSRS (trans-I) (Bernhardt et al., 2000), with all amine H atoms on the same side of the macrocyclic plane, and RRSS (trans-III) (Hambley et al., 1992), with two H atoms up and two down. In six-coordinate complexes of L¹, the trans-I form has been most commonly encountered in complexes bearing the [CoL¹] moiety (Bernhardt et al., 2000; Bernhardt et al., 2002). \sch

The related hexaamine L² may bind in a hexadentate (Bernhardt et al., 1989; Bernhardt, Comba et al., 1990; Bernhardt et al., 1991), pentadentate (Bernhardt, Lawrance, Comba et al., 1990; Curtis et al., 1993) or tetradentate (Curtis et al., 1992; Bernhardt, Lawrance, Patalinghug et al., 1990) mode, depending on the protonation state of the pendant amines and the preferred coordination geometry of the metal ion. When bulky substituents are attached to one of the pendant amines of L² (e.g. L^3a-c), coordination of the substituted amine is disfavoured on steric grounds (Bernhardt & Hayes, 2002). Pentadentate coordination by ligands such as L^3a-c has obvious parallels with the chemistry of L¹.

In this work, we report the crystal structures of trans-[CoL¹CN](ClO₄)₂·H₂O, (I), and trans-[CoL¹OH](ClO₄)₂, (II), where both complexes are in the trans-I configuration. These structures represent rare examples of structurally characterized cyano- and hydroxopentaaminecobalt(III) complexes.

The structure of (I) (Fig. 1) reveals the expected scorpionate conformation of the macrocyclic ligand, with the pendant amine tail coordinating above the CoN₄ plane and trans to the cyano ligand. The trans-I N-based isomer is apparent. As expected, the Co—CN coordinate bond is the shortest (Table 1). The four secondary amine coordinate bonds are similar, and the Co—N bond to the pendant amine is significantly longer. For comparison, in all other high-resolution crystal structures of Co^III complexes containing the pentadentate-coordinated L¹ moiety, including derivatives such as L^3a-c, the five Co—N bonds lie within a relatively narrow range (1.94–1.96 Å). In (I), there is a significant increase in the average Co—N bond length. Upon closer inspection, the four in-plane Co—N bonds span the range 1.956 (3)–1.975 (3) Å, while the bond to the pendant amine is significantly longer [1.990 (2) Å]. This axial elongation may be attributed to the trans influence of the cyano ligand, as no significant differences between the bond lengths involving the secondary or primary amines have been seen in chloro (Bernhardt et al., 2000; Bernhardt & Macpherson, 2003), N-bound ferrocyanide (Bernhardt et al., 2000) or ferricyanide (Bernhardt et al., 2002) complexes bearing the (CoL¹) moiety. Furthermore, in Na[CoL^3bCN](ClO₄)₃, the only other cyanopentaaminecobalt(III) complex to be structurally characterized to date, a similar trans influence of the cyano ligand on the pendant amine coordinate bond length [2.001 (5) Å] was observed (Bernhardt & Hayes, 2002).

Hydrogen bonding is a feature of the structure of (I) (Fig. 2). The complex cations are arranged into a linear polymeric hydrogen-bonded array, with the pendant amino group as donor and the cyano ligand as acceptor (Table 2). All remaining N—H groups participate in hydrogen bonds to either the perchlorate anions or the water molecule. Of note is the bifurcated hydrogen bond formed between the water atom O1 and the pair of adjacent secondary amines (N2 and N3).

Disorder in the positions of perchlorate atoms O1B, O1C and O1D (O1B'', O1C'' and O1D'') was resolved and two distinct orientations of the anion were identified, related by a ca 70° rotation of the anion about the Cl1—O1A bond. The complementary occupancies of the two contributors were 83% and 17%, and no geometric restraints were used in refinement. The hydrogen bonds present in these two orientations are illustrated in Fig. 3. In the major contributor, atoms O1C and O1D participate in strong hydrogen-bonding interactions with the pendant amine and the water molecule (Table 2). Although these two interactions remain in the alternate minor orientation, they are somewhat more acute and hence weaker. To compensate for this misalignment, the minor contributor gains an extra hydrogen bond, with atom O1B'' as acceptor for a water molecule, whereas atom O1B has no partner in the major form.

The structure of (II) (Fig. 4) has also been determined. The conformation of the macrocycle is identical to that seen in (I), but the Co—N bond lengths (Table 3) now lie within the normal range for Co^III complexes of L¹ and pentadentate-coordinated L², and the Co—N5 bond length is not particularly long.

Substitution of cyano (a hydrogen-bond acceptor) with hydroxo (both a donor and an acceptor) results in a quite different hydrogen-bonding pattern for (II) (Fig. 5). Unlike the polymeric hydrogen-bonded chain seen in (I), the cations in (II) form centrosymmetric dimers, with the hydroxo O atom on one cation participating in a bifurcated hydrogen-bond with the secondary amine groups N2 and N3 on an adjacent complex (Table 4). This motif is reminiscent of that seen in (I), where the water molecule plays the role of acceptor in place of the hydroxo ligand. All other amine H atoms (except that attached to N1) and the hydroxo ligand participate in hydrogen bonding with the perchlorate anions.

Disorder was identified in both perchlorate anions in (II) (O1B, O1C and O1D/O1B'', O1C'' and O1D'', and O2B, O2C and O2D/O2B'', O2C'' and O2D''). The contributors were again refined with complementary occupancies (91% and 9%) without geometrical restraints. The two contributors (Fig. 6) to disorder in anion 1 are related by a ca 40° rotation about Cl1—O1A. In the major orientation, atoms O1B and O1D accept strong hydrogen bonds from N4—H4 and O1—H1C. In the minor contributor, only atom O2D'' is hydrogen-bonded, in a bifurcated motif with both N4—H4 and O1—H1C. Anion 2 bridges the pendant amines of adjacent cations. Rotation about Cl2—O2A, again by ca 40°, generates the two contributors, each of which forms a pair of hydrogen bonds of similar strength to two different complex cations.

In conclusion, some interesting variations in the structures of two closely related macrocyclic pentaamine complexes of Co^III have been identified. Introduction of a cyano ligand into the sixth coordination site, (I), leads to a lengthening of the Co—N bonds and a significant extension of the Co—N bond trans to the cyano ligand. By comparison, the coordinate bonds in the hydroxo analogue, (II), are typical of other complexes bearing the [CoL¹] or pentadentate-coordinated [CoL²] moiety. Perchlorate disorder was resolved and rationalized on the basis of distinct hydrogen-bonding patterns.

S2. Experimental

The precursor, trans-I-[CoL¹Cl](ClO₄)₂ (Bernhardt et al., 2000), was converted to the cyano complex by boiling an aqueous solution of the complex in the presence of a stoichiometric amount of KCN in a well ventilated fume hood. The compound was purified by cation-exchange chromatography and then crystallized as (I) by slow evaporation of a concentrated NaClO₄ solution of the complex. The hydroxo analogue, (II), was prepared by base hydrolysis of trans-I-[CoL¹Cl](ClO₄)₂ (pH 10) at room temperature, followed by slow evaporation of the solution at this pH.

Computing details

For both compounds, data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS86 (Sheldrick, 1985); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLUTON (Spek, 1990); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. A view of the complex cation in (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A plot of the hydrogen bonding in (I). Alkyl H atoms have been omitted. See Table 2 for symmetry codes.
	Fig. 3. A plot of the perchlorate disorder in (I). Alkyl H atoms have been omitted. See Table 2 for the perchlorate symmetry code. Atoms labelled with an asterisk (*) are at symmetry position (1 − x, 1/2 + y, 1 − z) and atoms labelled with a hash sign (#) are at symmetry position (x − 1, y + 1, z).
	Fig. 4. A view of the complex cation in (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 5. A plot of the hydrogen bonding in (II). Alkyl H atoms have been omitted. See Table 4 for symmetry codes.
	Fig. 6. A plot of the perchlorate disorder in (II). Alkyl H atoms have been omitted. The atom labelled with an asterisk (*) is at symmetry position (1/2 − x, 1/2 + y, 1/2 − z).

(I) trans-cyano(6-methyl-1,4,8,11-tetraazacyclotetradecane-6-amine)cobalt(III) bis(perchlorate) hydrate

Crystal data

[Co(CN)(C11H27N5)](ClO4)2·H2O	F(000) = 552
Mr = 531.24	Dx = 1.667 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 25 reflections
a = 7.4158 (5) Å	θ = 10.8–14.2°
b = 8.9373 (8) Å	µ = 1.12 mm^−1
c = 16.228 (2) Å	T = 293 K
β = 100.218 (7)°	Prism, yellow
V = 1058.49 (18) Å^3	0.5 × 0.2 × 0.2 mm
Z = 2

Data collection

Enraf-Nonius CAD-4 diffractometer	2111 reflections with I > 2σ(I)
Radiation source: Enraf-Nonius FR590	Rint = 0.028
Graphite monochromator	θmax = 25.0°, θmin = 2.6°
non–profiled ω/2θ scans	h = −1→8
Absorption correction: ψ scan (North et al., 1968) Number of ψ-scan sets used was 5 Theta correction was applied. Averaged transmission function was used. No Fourier smoothing was applied.	k = −1→10
Tmin = 0.686, Tmax = 0.799	l = −19→19
2789 measured reflections	3 standard reflections every 120 min
2240 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.029	w = 1/[σ^2(Fo^2) + (0.0567P)^2 + 0.0357P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.075	(Δ/σ)max = 0.001
S = 1.11	Δρmax = 0.29 e Å^−3
2240 reflections	Δρmin = −0.46 e Å^−3
285 parameters	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.046 (3)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 193 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.036 (15)

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	Occ. (<1)
C1	0.5981 (5)	0.7815 (5)	0.9156 (2)	0.0317 (9)
H1A	0.4672	0.7827	0.8947	0.038*
H1B	0.6179	0.7667	0.9758	0.038*
C2	0.6880 (5)	0.6571 (5)	0.8743 (2)	0.0332 (8)
H2A	0.8148	0.6457	0.9014	0.04*
H2B	0.6248	0.5633	0.879	0.04*
C3	0.5047 (5)	0.6595 (4)	0.7272 (2)	0.0321 (8)
H3A	0.4129	0.6294	0.7597	0.039*
H3B	0.5254	0.5763	0.6916	0.039*
C4	0.4359 (4)	0.7946 (4)	0.6732 (2)	0.0307 (8)
C5	0.5625 (5)	0.8400 (5)	0.6126 (2)	0.0328 (8)
H5A	0.5785	0.7563	0.5765	0.039*
H5B	0.5082	0.9221	0.5777	0.039*
C6	0.8202 (5)	1.0286 (5)	0.6328 (2)	0.0375 (9)
H6A	0.7913	1.0361	0.5722	0.045*
H6B	0.9524	1.0302	0.6496	0.045*
C7	0.7364 (6)	1.1574 (5)	0.6719 (2)	0.0374 (9)
H7A	0.7971	1.25	0.6617	0.045*
H7B	0.6075	1.1662	0.6477	0.045*
C8	0.6471 (5)	1.2338 (4)	0.8056 (2)	0.0365 (8)
H8A	0.5192	1.2244	0.7798	0.044*
H8B	0.685	1.3357	0.7972	0.044*
C9	0.6671 (6)	1.2033 (5)	0.8984 (2)	0.0389 (9)
H9A	0.6112	1.2847	0.9244	0.047*
H9B	0.7963	1.2012	0.9227	0.047*
C10	0.5802 (5)	1.0574 (5)	0.9178 (2)	0.0333 (9)
H10A	0.5755	1.0535	0.9771	0.04*
H10B	0.4554	1.0532	0.8872	0.04*
C11	0.2415 (5)	0.7701 (5)	0.6267 (2)	0.0416 (9)
H11A	0.2014	0.8569	0.5936	0.062*
H11B	0.1616	0.7534	0.6663	0.062*
H11C	0.2386	0.6845	0.5907	0.062*
C12	0.9769 (4)	0.8861 (4)	0.8121 (2)	0.0286 (8)
Co	0.72008 (5)	0.91291 (5)	0.77850 (2)	0.02164 (15)
N1	0.6831 (3)	0.9264 (4)	0.89511 (15)	0.0257 (6)
H1	0.7964	0.9305	0.9276	0.031*
N2	0.6782 (4)	0.6974 (4)	0.78448 (17)	0.0281 (7)
H2	0.7714	0.6497	0.7656	0.034*
N3	0.7445 (4)	0.8869 (4)	0.66107 (17)	0.0285 (7)
H3	0.8265	0.8122	0.6581	0.034*
N4	0.7582 (4)	1.1293 (4)	0.76398 (18)	0.0291 (7)
H4	0.8776	1.1483	0.7859	0.035*
N5	0.4524 (3)	0.9221 (4)	0.73397 (15)	0.0262 (5)
H5C	0.3855	0.9067	0.7744	0.031*
H5D	0.4199	1.0097	0.7082	0.031*
N6	1.1317 (4)	0.8715 (4)	0.8275 (2)	0.0436 (9)
Cl1	0.21918 (13)	0.27347 (13)	0.58617 (5)	0.0407 (3)
O1A	0.3584 (6)	0.3828 (5)	0.5814 (2)	0.0762 (12)
O1B	0.0425 (7)	0.3196 (9)	0.5517 (5)	0.103 (2)	0.828 (10)
O1C	0.2293 (7)	0.2149 (8)	0.6694 (3)	0.085 (2)	0.828 (10)
O1D	0.2616 (9)	0.1436 (7)	0.5403 (4)	0.090 (2)	0.828 (10)
O1B''	0.157 (3)	0.325 (3)	0.6623 (14)	0.063 (7)*	0.172 (10)
O1C''	0.271 (3)	0.134 (3)	0.6025 (15)	0.057 (7)*	0.172 (10)
O1D''	0.108 (5)	0.285 (4)	0.5103 (19)	0.095 (10)*	0.172 (10)
Cl2	0.12881 (11)	0.40451 (14)	0.86750 (5)	0.0369 (2)
O2A	0.0032 (4)	0.4608 (5)	0.79759 (18)	0.0620 (10)
O2B	0.3084 (4)	0.4602 (4)	0.8684 (2)	0.0631 (10)
O2C	0.1316 (5)	0.2443 (4)	0.8623 (3)	0.0713 (11)
O2D	0.0657 (4)	0.4478 (5)	0.94231 (17)	0.0616 (11)
O1	0.8552 (4)	0.5732 (4)	0.6376 (2)	0.0553 (8)
H1C	0.8517	0.5875	0.5779	0.066*
H1D	0.9601	0.5271	0.6736	0.066*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0275 (19)	0.034 (2)	0.0345 (18)	−0.0044 (18)	0.0076 (15)	0.0070 (18)
C2	0.0316 (19)	0.029 (2)	0.0377 (18)	−0.0012 (16)	0.0034 (15)	0.0064 (17)
C3	0.0293 (18)	0.030 (2)	0.0373 (17)	−0.0075 (16)	0.0061 (14)	−0.0019 (17)
C4	0.0237 (16)	0.032 (2)	0.0357 (16)	−0.0013 (16)	0.0045 (13)	−0.0038 (17)
C5	0.0339 (17)	0.039 (2)	0.0259 (14)	−0.0009 (18)	0.0058 (13)	−0.0034 (16)
C6	0.0343 (18)	0.041 (2)	0.0398 (18)	−0.0034 (18)	0.0149 (15)	0.0029 (18)
C7	0.040 (2)	0.031 (2)	0.0432 (19)	−0.0053 (18)	0.0116 (16)	0.0087 (18)
C8	0.0360 (19)	0.0199 (18)	0.055 (2)	0.0028 (16)	0.0132 (17)	−0.0021 (18)
C9	0.040 (2)	0.032 (2)	0.047 (2)	0.0015 (18)	0.0139 (17)	−0.0094 (19)
C10	0.033 (2)	0.035 (2)	0.0338 (18)	0.0024 (19)	0.0120 (16)	−0.0063 (19)
C11	0.0305 (19)	0.046 (2)	0.0438 (19)	−0.0057 (19)	−0.0044 (16)	−0.007 (2)
C12	0.0210 (15)	0.028 (2)	0.0381 (16)	−0.0007 (14)	0.0092 (12)	0.0006 (15)
Co	0.0158 (2)	0.0223 (2)	0.0277 (2)	−0.0008 (2)	0.00654 (14)	−0.0003 (2)
N1	0.0216 (11)	0.0286 (16)	0.0274 (11)	−0.0034 (15)	0.0054 (9)	−0.0010 (15)
N2	0.0226 (14)	0.0255 (17)	0.0378 (15)	−0.0005 (14)	0.0092 (12)	−0.0015 (13)
N3	0.0214 (12)	0.033 (2)	0.0323 (12)	0.0023 (13)	0.0075 (10)	0.0016 (14)
N4	0.0236 (14)	0.0245 (16)	0.0403 (15)	−0.0032 (14)	0.0087 (12)	0.0007 (14)
N5	0.0207 (11)	0.0285 (14)	0.0300 (11)	0.0002 (16)	0.0058 (9)	0.0004 (16)
N6	0.0230 (15)	0.050 (2)	0.0581 (19)	0.0031 (14)	0.0086 (13)	0.0018 (17)
Cl1	0.0365 (5)	0.0491 (6)	0.0363 (4)	0.0032 (5)	0.0058 (3)	0.0025 (4)
O1A	0.085 (2)	0.066 (3)	0.079 (2)	−0.027 (2)	0.0163 (19)	−0.002 (2)
O1B	0.050 (3)	0.120 (5)	0.127 (5)	0.030 (3)	−0.016 (3)	0.021 (5)
O1C	0.074 (3)	0.126 (6)	0.052 (2)	−0.014 (4)	0.004 (2)	0.025 (3)
O1D	0.117 (5)	0.061 (3)	0.101 (5)	0.000 (3)	0.042 (4)	−0.021 (3)
Cl2	0.0275 (4)	0.0401 (5)	0.0414 (4)	−0.0008 (5)	0.0018 (3)	0.0017 (5)
O2A	0.0548 (18)	0.080 (3)	0.0470 (15)	0.0197 (18)	−0.0033 (13)	0.0050 (17)
O2B	0.0367 (15)	0.070 (3)	0.084 (2)	−0.0169 (16)	0.0133 (15)	0.003 (2)
O2C	0.062 (2)	0.041 (2)	0.107 (3)	−0.0013 (18)	0.007 (2)	−0.003 (2)
O2D	0.0459 (16)	0.094 (3)	0.0432 (14)	0.0144 (19)	0.0029 (12)	−0.0062 (19)
O1	0.0514 (18)	0.053 (2)	0.0637 (18)	0.0066 (17)	0.0154 (15)	−0.0032 (17)

Geometric parameters (Å, º)

C1—N1	1.503 (5)	C10—H10A	0.97
C1—C2	1.512 (6)	C10—H10B	0.97
C1—H1A	0.97	C11—H11A	0.96
C1—H1B	0.97	C11—H11B	0.96
C2—N2	1.491 (5)	C11—H11C	0.96
C2—H2A	0.97	C12—N6	1.138 (4)
C2—H2B	0.97	Co—N1	1.963 (2)
C3—N2	1.487 (4)	Co—N2	1.956 (3)
C3—C4	1.526 (5)	Co—N3	1.960 (3)
C3—H3A	0.97	Co—N4	1.975 (3)
C3—H3B	0.97	Co—N5	1.990 (2)
C4—N5	1.498 (5)	Co—C12	1.901 (3)
C4—C11	1.520 (5)	N1—H1	0.91
C4—C5	1.530 (5)	N2—H2	0.91
C5—N3	1.496 (4)	N3—H3	0.91
C5—H5A	0.97	N4—H4	0.91
C5—H5B	0.97	N5—H5C	0.9
C6—N3	1.491 (5)	N5—H5D	0.9
C6—C7	1.502 (6)	Cl1—O1C''	1.32 (2)
C6—H6A	0.97	Cl1—O1D''	1.36 (3)
C6—H6B	0.97	Cl1—O1B	1.393 (5)
C7—N4	1.495 (5)	Cl1—O1A	1.434 (4)
C7—H7A	0.97	Cl1—O1C	1.438 (4)
C7—H7B	0.97	Cl1—O1D	1.444 (6)
C8—N4	1.485 (5)	Cl1—O1B''	1.47 (2)
C8—C9	1.512 (6)	Cl2—O2B	1.419 (3)
C8—H8A	0.97	Cl2—O2A	1.426 (3)
C8—H8B	0.97	Cl2—O2D	1.430 (3)
C9—C10	1.512 (6)	Cl2—O2C	1.435 (4)
C9—H9A	0.97	O1—H1C	0.9728
C9—H9B	0.97	O1—H1D	0.9773
C10—N1	1.480 (5)
N1—C1—C2	107.5 (3)	N6—C12—Co	176.0 (3)
N1—C1—H1A	110.2	N1—Co—N2	87.82 (14)
C2—C1—H1A	110.2	N1—Co—N3	175.76 (14)
N1—C1—H1B	110.2	N1—Co—N4	95.88 (14)
C2—C1—H1B	110.2	N1—Co—N5	92.67 (10)
H1A—C1—H1B	108.5	N1—Co—C12	92.04 (12)
N2—C2—C1	107.9 (3)	N2—Co—N3	88.52 (12)
N2—C2—H2A	110.1	N2—Co—N4	176.06 (13)
C1—C2—H2A	110.1	N2—Co—N5	84.37 (15)
N2—C2—H2B	110.1	N2—Co—C12	91.22 (14)
C1—C2—H2B	110.1	N3—Co—N4	87.73 (13)
H2A—C2—H2B	108.4	N3—Co—N5	84.84 (11)
N2—C3—C4	110.1 (3)	N3—Co—C12	90.17 (12)
N2—C3—H3A	109.6	N4—Co—N5	94.06 (15)
C4—C3—H3A	109.6	N4—Co—C12	90.02 (14)
N2—C3—H3B	109.6	N5—Co—C12	173.41 (15)
C4—C3—H3B	109.6	C10—N1—C1	111.8 (2)
H3A—C3—H3B	108.2	C10—N1—Co	117.1 (2)
N5—C4—C11	113.3 (3)	C1—N1—Co	107.2 (2)
N5—C4—C3	104.1 (3)	C10—N1—H1	106.7
C11—C4—C3	111.3 (3)	C1—N1—H1	106.7
N5—C4—C5	103.5 (3)	Co—N1—H1	106.7
C11—C4—C5	110.8 (3)	C3—N2—C2	116.3 (3)
C3—C4—C5	113.5 (3)	C3—N2—Co	108.7 (2)
N3—C5—C4	109.7 (3)	C2—N2—Co	107.8 (2)
N3—C5—H5A	109.7	C3—N2—H2	107.9
C4—C5—H5A	109.7	C2—N2—H2	107.9
N3—C5—H5B	109.7	Co—N2—H2	107.9
C4—C5—H5B	109.7	C6—N3—C5	115.5 (3)
H5A—C5—H5B	108.2	C6—N3—Co	107.7 (2)
N3—C6—C7	108.3 (3)	C5—N3—Co	108.29 (19)
N3—C6—H6A	110	C6—N3—H3	108.4
C7—C6—H6A	110	C5—N3—H3	108.4
N3—C6—H6B	110	Co—N3—H3	108.4
C7—C6—H6B	110	C8—N4—C7	112.2 (3)
H6A—C6—H6B	108.4	C8—N4—Co	117.3 (2)
N4—C7—C6	108.3 (3)	C7—N4—Co	106.9 (2)
N4—C7—H7A	110	C8—N4—H4	106.6
C6—C7—H7A	110	C7—N4—H4	106.6
N4—C7—H7B	110	Co—N4—H4	106.6
C6—C7—H7B	110	C4—N5—Co	99.6 (2)
H7A—C7—H7B	108.4	C4—N5—H5C	111.8
N4—C8—C9	112.0 (3)	Co—N5—H5C	111.8
N4—C8—H8A	109.2	C4—N5—H5D	111.8
C9—C8—H8A	109.2	Co—N5—H5D	111.8
N4—C8—H8B	109.2	H5C—N5—H5D	109.6
C9—C8—H8B	109.2	O1C''—Cl1—O1D''	111.3 (19)
H8A—C8—H8B	107.9	O1C''—Cl1—O1A	118.0 (10)
C8—C9—C10	113.1 (3)	O1D''—Cl1—O1A	103.0 (15)
C8—C9—H9A	108.9	O1B—Cl1—O1A	114.3 (4)
C10—C9—H9A	108.9	O1B—Cl1—O1C	111.9 (4)
C8—C9—H9B	108.9	O1A—Cl1—O1C	112.4 (3)
C10—C9—H9B	108.9	O1B—Cl1—O1D	107.8 (4)
H9A—C9—H9B	107.8	O1A—Cl1—O1D	107.2 (3)
N1—C10—C9	111.9 (3)	O1C—Cl1—O1D	102.3 (4)
N1—C10—H10A	109.2	O1C''—Cl1—O1B''	104.6 (15)
C9—C10—H10A	109.2	O1D''—Cl1—O1B''	120.4 (18)
N1—C10—H10B	109.2	O1A—Cl1—O1B''	99.7 (9)
C9—C10—H10B	109.2	O2B—Cl2—O2A	111.3 (2)
H10A—C10—H10B	107.9	O2B—Cl2—O2D	110.1 (2)
C4—C11—H11A	109.5	O2A—Cl2—O2D	108.32 (19)
C4—C11—H11B	109.5	O2B—Cl2—O2C	109.1 (2)
H11A—C11—H11B	109.5	O2A—Cl2—O2C	108.6 (2)
C4—C11—H11C	109.5	O2D—Cl2—O2C	109.3 (3)
H11A—C11—H11C	109.5	H1C—O1—H1D	121.9
H11B—C11—H11C	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2D^i	0.91	2.18	2.954 (4)	142
N2—H2···O1	0.91	2.37	3.122 (4)	140
N2—H2···O2A^ii	0.91	2.4	3.185 (5)	145
N3—H3···O1	0.91	2.18	2.965 (5)	144
N4—H4···O2C^iii	0.91	2.23	3.115 (5)	163
N5—H5C···N6^iv	0.9	2.23	3.073 (4)	156
N5—H5D···O1C′′^v	0.9	2.17	2.99 (2)	150
N5—H5D···O1C^v	0.9	2.33	3.173 (8)	155
O1—H1C···O1D^vi	0.97	2.02	2.930 (7)	156
O1—H1C···O1D′′^vi	0.97	2.33	3.11 (4)	137
O1—H1D···O2A^ii	0.98	2.07	2.819 (5)	132
O1—H1D···O1B′′^ii	0.98	2.35	3.12 (3)	136

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

(II) trans-hydroxo(6-methyl-1,4,8,11-tetraazacyclotetradecane-6-amine)cobalt(III) bis(perchlorate)

Crystal data

[Co(OH)(C11H27N5)](ClO4)2	F(000) = 1048
Mr = 504.21	Dx = 1.71 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 23 reflections
a = 14.817 (5) Å	θ = 11.2–13.4°
b = 9.535 (2) Å	µ = 1.21 mm^−1
c = 15.409 (8) Å	T = 293 K
β = 115.91 (3)°	Prism, red
V = 1958.1 (13) Å^3	0.5 × 0.3 × 0.3 mm
Z = 4

Data collection

Enraf-Nonius CAD-4 diffractometer	Rint = 0.071
Radiation source: Enraf-Nonius FR590	θmax = 25.0°, θmin = 1.6°
Graphite monochromator	h = 0→17
non–profiled ω scans	k = 0→11
3569 measured reflections	l = −18→16
3430 independent reflections	3 standard reflections every 120 min
2406 reflections with I > 2σ(I)	intensity decay: −8%

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.142	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0915P)^2] where P = (Fo^2 + 2Fc^2)/3
3430 reflections	(Δ/σ)max = 0.001
278 parameters	Δρmax = 0.70 e Å^−3
0 restraints	Δρmin = −0.69 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	Occ. (<1)
C1	0.5703 (3)	−0.0728 (5)	0.2888 (3)	0.0415 (11)
H1A	0.5222	−0.1153	0.3078	0.05*
H1B	0.6354	−0.0722	0.3443	0.05*
C2	0.5754 (3)	−0.1554 (5)	0.2075 (3)	0.0404 (11)
H2A	0.6322	−0.1243	0.1969	0.048*
H2B	0.5841	−0.2543	0.2237	0.048*
C3	0.3969 (3)	−0.2301 (5)	0.1051 (3)	0.0386 (11)
H3A	0.4132	−0.282	0.1642	0.046*
H3B	0.3872	−0.2967	0.0542	0.046*
C4	0.3010 (3)	−0.1457 (5)	0.0789 (3)	0.0378 (10)
C5	0.2643 (3)	−0.0713 (5)	−0.0176 (3)	0.0431 (11)
H5A	0.2544	−0.1389	−0.068	0.052*
H5B	0.2006	−0.0259	−0.0328	0.052*
C6	0.2986 (4)	0.1759 (5)	−0.0513 (3)	0.0462 (12)
H6A	0.233	0.1661	−0.1055	0.055*
H6B	0.3424	0.2238	−0.0735	0.055*
C7	0.2903 (4)	0.2590 (6)	0.0277 (4)	0.0489 (13)
H7A	0.2737	0.3559	0.0078	0.059*
H7B	0.2379	0.2204	0.0424	0.059*
C8	0.3836 (4)	0.3114 (6)	0.2004 (4)	0.0536 (14)
H8A	0.3325	0.2624	0.2119	0.064*
H8B	0.3641	0.4092	0.1883	0.064*
C9	0.4833 (4)	0.3008 (6)	0.2902 (4)	0.0530 (13)
H9A	0.535	0.3446	0.2769	0.064*
H9B	0.4784	0.3529	0.342	0.064*
C10	0.5145 (4)	0.1534 (6)	0.3234 (3)	0.0487 (13)
H10A	0.5727	0.1556	0.3857	0.058*
H10B	0.4607	0.1067	0.3317	0.058*
C11	0.2183 (4)	−0.2363 (6)	0.0838 (4)	0.0511 (13)
H11A	0.2434	−0.2819	0.1455	0.077*
H11B	0.1975	−0.3057	0.0337	0.077*
H11C	0.1622	−0.1782	0.0754	0.077*
Co	0.43752 (4)	0.05913 (6)	0.12043 (4)	0.0297 (2)
N1	0.5393 (3)	0.0718 (4)	0.2545 (2)	0.0368 (9)
H1	0.5937	0.1142	0.2531	0.044*
N2	0.4802 (2)	−0.1330 (4)	0.1183 (2)	0.0324 (8)
H2	0.494	−0.1426	0.0666	0.039*
N3	0.3401 (3)	0.0356 (4)	−0.0129 (3)	0.0355 (8)
H3	0.3727	0.0026	−0.0469	0.043*
N4	0.3886 (3)	0.2510 (4)	0.1138 (3)	0.0415 (9)
H4	0.4313	0.3067	0.101	0.05*
N5	0.3345 (3)	−0.0291 (4)	0.1516 (2)	0.0332 (8)
H5C	0.361	−0.062	0.2124	0.04*
H5D	0.2841	0.0305	0.1426	0.04*
O1	0.5297 (2)	0.1177 (3)	0.0731 (2)	0.0368 (7)
H1C	0.5571	0.1861	0.0928	0.044*
Cl1	0.65270 (9)	0.46674 (13)	0.15831 (9)	0.0466 (3)
O1A	0.7207 (3)	0.5556 (4)	0.2301 (4)	0.0951 (18)
O1B	0.5509 (3)	0.5001 (6)	0.1324 (4)	0.0764 (17)	0.912 (8)
O1C	0.6720 (5)	0.4720 (9)	0.0774 (5)	0.107 (2)	0.912 (8)
O1D	0.6702 (4)	0.3253 (5)	0.1926 (4)	0.0799 (18)	0.912 (8)
O1B''	0.571 (3)	0.568 (4)	0.093 (3)	0.044 (11)*	0.088 (8)
O1D''	0.608 (4)	0.377 (6)	0.184 (4)	0.072 (16)*	0.088 (8)
O1C''	0.688 (3)	0.388 (5)	0.105 (3)	0.050 (12)*	0.088 (8)
Cl2	0.08366 (9)	0.18053 (14)	0.12128 (9)	0.0465 (3)
O2A	−0.0004 (3)	0.1448 (4)	0.1379 (3)	0.0652 (11)
O2B	0.0637 (5)	0.1649 (8)	0.0243 (4)	0.102 (3)	0.912 (8)
O2C	0.1651 (4)	0.0881 (6)	0.1781 (5)	0.0862 (19)	0.912 (8)
O2D	0.1163 (4)	0.3212 (6)	0.1522 (5)	0.0688 (15)	0.912 (8)
O2B''	0.036 (3)	0.276 (6)	0.035 (3)	0.060 (14)*	0.088 (8)
O2C''	0.129 (4)	0.082 (5)	0.091 (4)	0.058 (13)*	0.088 (8)
O2D''	0.142 (3)	0.274 (4)	0.184 (3)	0.021 (9)*	0.088 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.033 (2)	0.053 (3)	0.036 (2)	0.002 (2)	0.013 (2)	0.004 (2)
C2	0.031 (2)	0.048 (3)	0.038 (2)	0.006 (2)	0.0107 (19)	0.004 (2)
C3	0.032 (2)	0.041 (3)	0.044 (3)	−0.007 (2)	0.018 (2)	−0.006 (2)
C4	0.026 (2)	0.046 (3)	0.041 (2)	−0.009 (2)	0.0150 (19)	−0.004 (2)
C5	0.029 (2)	0.060 (3)	0.037 (2)	−0.006 (2)	0.012 (2)	−0.005 (2)
C6	0.047 (3)	0.049 (3)	0.043 (3)	0.013 (2)	0.020 (2)	0.012 (2)
C7	0.050 (3)	0.049 (3)	0.055 (3)	0.017 (2)	0.030 (3)	0.008 (2)
C8	0.068 (3)	0.047 (3)	0.061 (3)	0.003 (3)	0.042 (3)	−0.012 (3)
C9	0.066 (3)	0.053 (3)	0.051 (3)	−0.007 (3)	0.036 (3)	−0.016 (3)
C10	0.054 (3)	0.064 (3)	0.035 (3)	−0.013 (3)	0.026 (2)	−0.018 (2)
C11	0.037 (3)	0.065 (4)	0.053 (3)	−0.017 (3)	0.022 (2)	−0.007 (3)
Co	0.0266 (3)	0.0359 (3)	0.0307 (3)	−0.0012 (3)	0.0164 (2)	−0.0026 (3)
N1	0.0331 (19)	0.047 (2)	0.0338 (19)	−0.0062 (17)	0.0177 (16)	−0.0097 (18)
N2	0.0283 (18)	0.036 (2)	0.0356 (19)	0.0008 (16)	0.0166 (15)	−0.0021 (16)
N3	0.0316 (18)	0.045 (2)	0.0316 (19)	0.0022 (17)	0.0154 (16)	0.0010 (17)
N4	0.049 (2)	0.040 (2)	0.048 (2)	0.0012 (19)	0.032 (2)	−0.0039 (19)
N5	0.0292 (18)	0.039 (2)	0.0327 (19)	0.0041 (16)	0.0144 (15)	0.0007 (16)
O1	0.0378 (16)	0.0366 (17)	0.0448 (18)	−0.0086 (14)	0.0260 (14)	−0.0051 (14)
Cl1	0.0363 (6)	0.0441 (7)	0.0543 (7)	−0.0008 (5)	0.0153 (5)	−0.0063 (6)
O1A	0.065 (3)	0.060 (3)	0.110 (4)	0.006 (2)	−0.008 (3)	−0.037 (3)
O1B	0.036 (2)	0.093 (4)	0.090 (4)	0.014 (2)	0.019 (2)	0.005 (3)
O1C	0.107 (5)	0.148 (7)	0.088 (4)	−0.012 (5)	0.063 (4)	0.014 (4)
O1D	0.063 (3)	0.040 (3)	0.102 (4)	−0.005 (2)	0.005 (3)	0.005 (2)
Cl2	0.0432 (6)	0.0575 (8)	0.0481 (7)	0.0000 (6)	0.0285 (6)	−0.0067 (6)
O2A	0.052 (2)	0.070 (3)	0.092 (3)	−0.005 (2)	0.049 (2)	−0.008 (2)
O2B	0.124 (5)	0.144 (6)	0.054 (3)	−0.056 (5)	0.054 (3)	−0.030 (3)
O2C	0.061 (3)	0.090 (4)	0.120 (5)	0.028 (3)	0.051 (3)	0.028 (3)
O2D	0.066 (3)	0.062 (4)	0.093 (4)	−0.003 (3)	0.048 (3)	−0.008 (3)

Geometric parameters (Å, º)

C1—N1	1.476 (6)	C10—H10A	0.97
C1—C2	1.510 (6)	C10—H10B	0.97
C1—H1A	0.97	C11—H11A	0.96
C1—H1B	0.97	C11—H11B	0.96
C2—N2	1.493 (5)	C11—H11C	0.96
C2—H2A	0.97	Co—N1	1.958 (4)
C2—H2B	0.97	Co—N2	1.943 (4)
C3—N2	1.485 (6)	Co—N3	1.940 (4)
C3—C4	1.526 (6)	Co—N4	1.954 (4)
C3—H3A	0.97	Co—N5	1.976 (4)
C3—H3B	0.97	Co—O1	1.892 (3)
C4—N5	1.500 (6)	N1—H1	0.91
C4—C5	1.517 (7)	N2—H2	0.91
C4—C11	1.528 (6)	N3—H3	0.91
C5—N3	1.495 (6)	N4—H4	0.91
C5—H5A	0.97	N5—H5C	0.9
C5—H5B	0.97	N5—H5D	0.9
C6—N3	1.483 (6)	O1—H1C	0.7581
C6—C7	1.503 (7)	Cl1—O1D''	1.25 (5)
C6—H6A	0.97	Cl1—O1C''	1.38 (5)
C6—H6B	0.97	Cl1—O1C	1.397 (6)
C7—N4	1.483 (6)	Cl1—O1A	1.409 (4)
C7—H7A	0.97	Cl1—O1B	1.418 (4)
C7—H7B	0.97	Cl1—O1D	1.430 (5)
C8—N4	1.485 (6)	Cl1—O1B''	1.53 (4)
C8—C9	1.523 (7)	Cl2—O2D''	1.33 (4)
C8—H8A	0.97	Cl2—O2C''	1.35 (4)
C8—H8B	0.97	Cl2—O2B	1.399 (5)
C9—C10	1.498 (7)	Cl2—O2A	1.419 (4)
C9—H9A	0.97	Cl2—O2D	1.435 (5)
C9—H9B	0.97	Cl2—O2C	1.441 (5)
C10—N1	1.486 (6)	Cl2—O2B''	1.50 (5)
N1—C1—C2	108.1 (4)	N1—Co—N4	95.42 (16)
N1—C1—H1A	110.1	N1—Co—N5	95.21 (15)
C2—C1—H1A	110.1	N1—Co—O1	92.01 (14)
N1—C1—H1B	110.1	N2—Co—N3	88.29 (15)
C2—C1—H1B	110.1	N2—Co—N4	176.32 (16)
H1A—C1—H1B	108.4	N2—Co—N5	83.94 (15)
N2—C2—C1	108.6 (4)	N2—Co—O1	88.66 (14)
N2—C2—H2A	110	N3—Co—N4	88.03 (16)
C1—C2—H2A	110	N3—Co—N5	84.92 (15)
N2—C2—H2B	110	N3—Co—O1	87.41 (14)
C1—C2—H2B	110	N4—Co—N5	95.95 (15)
H2A—C2—H2B	108.3	N4—Co—O1	90.97 (15)
N2—C3—C4	109.3 (4)	N5—Co—O1	169.48 (14)
N2—C3—H3A	109.8	C1—N1—C10	111.6 (4)
C4—C3—H3A	109.8	C1—N1—Co	107.2 (3)
N2—C3—H3B	109.8	C10—N1—Co	118.0 (3)
C4—C3—H3B	109.8	C1—N1—H1	106.5
H3A—C3—H3B	108.3	C10—N1—H1	106.5
N5—C4—C5	104.2 (4)	Co—N1—H1	106.5
N5—C4—C3	103.1 (3)	C3—N2—C2	115.6 (4)
C5—C4—C3	113.6 (4)	C3—N2—Co	109.4 (3)
N5—C4—C11	113.2 (4)	C2—N2—Co	107.6 (3)
C5—C4—C11	111.2 (4)	C3—N2—H2	108
C3—C4—C11	111.3 (4)	C2—N2—H2	108
N3—C5—C4	109.3 (3)	Co—N2—H2	108
N3—C5—H5A	109.8	C6—N3—C5	115.1 (4)
C4—C5—H5A	109.8	C6—N3—Co	107.8 (3)
N3—C5—H5B	109.8	C5—N3—Co	109.0 (3)
C4—C5—H5B	109.8	C6—N3—H3	108.2
H5A—C5—H5B	108.3	C5—N3—H3	108.2
N3—C6—C7	108.6 (4)	Co—N3—H3	108.2
N3—C6—H6A	110	C7—N4—C8	111.6 (4)
C7—C6—H6A	110	C7—N4—Co	107.0 (3)
N3—C6—H6B	110	C8—N4—Co	118.6 (3)
C7—C6—H6B	110	C7—N4—H4	106.3
H6A—C6—H6B	108.4	C8—N4—H4	106.3
N4—C7—C6	107.5 (4)	Co—N4—H4	106.3
N4—C7—H7A	110.2	C4—N5—Co	100.0 (2)
C6—C7—H7A	110.2	C4—N5—H5C	111.8
N4—C7—H7B	110.2	Co—N5—H5C	111.8
C6—C7—H7B	110.2	C4—N5—H5D	111.8
H7A—C7—H7B	108.5	Co—N5—H5D	111.8
N4—C8—C9	112.4 (4)	H5C—N5—H5D	109.5
N4—C8—H8A	109.1	Co—O1—H1C	116.7
C9—C8—H8A	109.1	O1D''—Cl1—O1C''	102 (3)
N4—C8—H8B	109.1	O1D''—Cl1—O1A	117 (2)
C9—C8—H8B	109.1	O1C''—Cl1—O1A	118.0 (19)
H8A—C8—H8B	107.9	O1C—Cl1—O1A	108.9 (4)
C10—C9—C8	113.9 (5)	O1C—Cl1—O1B	110.4 (4)
C10—C9—H9A	108.8	O1A—Cl1—O1B	113.2 (3)
C8—C9—H9A	108.8	O1C—Cl1—O1D	106.8 (4)
C10—C9—H9B	108.8	O1A—Cl1—O1D	109.0 (3)
C8—C9—H9B	108.8	O1B—Cl1—O1D	108.3 (3)
H9A—C9—H9B	107.7	O1D''—Cl1—O1B''	106 (3)
N1—C10—C9	112.5 (4)	O1C''—Cl1—O1B''	110 (2)
N1—C10—H10A	109.1	O1A—Cl1—O1B''	102.9 (15)
C9—C10—H10A	109.1	O2D''—Cl2—O2C''	118 (3)
N1—C10—H10B	109.1	O2D''—Cl2—O2A	111.7 (17)
C9—C10—H10B	109.1	O2C''—Cl2—O2A	119.8 (19)
H10A—C10—H10B	107.8	O2B—Cl2—O2A	112.0 (3)
C4—C11—H11A	109.5	O2B—Cl2—O2D	109.7 (4)
C4—C11—H11B	109.5	O2A—Cl2—O2D	111.1 (3)
H11A—C11—H11B	109.5	O2B—Cl2—O2C	108.3 (4)
C4—C11—H11C	109.5	O2A—Cl2—O2C	108.2 (3)
H11A—C11—H11C	109.5	O2D—Cl2—O2C	107.4 (4)
H11B—C11—H11C	109.5	O2D''—Cl2—O2B''	98 (2)
N1—Co—N2	88.25 (15)	O2C''—Cl2—O2B''	104 (3)
N1—Co—N3	176.51 (16)	O2A—Cl2—O2B''	100.8 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1^i	0.91	2.04	2.892 (5)	156
N3—H3···O1^i	0.91	2.02	2.878 (5)	157
N4—H4···O1B	0.91	2.46	3.301 (7)	155
N5—H5C···O2D′′^ii	0.9	2.24	3.04 (4)	148
N5—H5C···O2D^ii	0.9	2.26	3.128 (7)	163
N5—H5D···O2C	0.9	2.13	2.935 (6)	148
N5—H5D···O2C′′	0.9	2.14	2.97 (5)	153
O1—H1C···O1D	0.76	2.16	2.879 (5)	158
O1—H1C···O1D′′	0.76	2.22	2.94 (5)	159
N4—H4···O1D′′	0.91	2.45	3.18 (6)	137

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