Mixed cobalt(III) complexes with aromatic amino acids and di­amines. III. Absolute structure of Λ-trans(O)-(1,2-di­amino­ethane-κ²N,N)­bis(S-tyrosinato)­cobalt(III) chloride tetrahydrate

The title compound, [Co(C₉H₁₀NO₃)₂(C₂H₈N₂)]Cl·4H₂O, is one of six possible diastereomers of the (1,2-di­amino­ethane)­bis(S-tyrosinato)­cobalt(III) complex. The cobalt(III) ion has an octahedral coordination, with three five-membered chelate rings which have deformed coordination angles and coordinated O atoms in trans positions. In comparison with the previously reported crystal structure of the Δ-C₁-cis(O) diastereomer [Miodragović et al. (2001). Enantiomer, 6, 299–308], the compound presented in this paper has more planar five-membered amino­carboxyl­ate rings. Complex cations, chloride anions and water mol­ecules of crystallization are linked together by a network of hydrogen bonds. The chloride anions lie approximately between two Co atoms and form hydrogen bonds with all coordinated NH₂ groups. In the crystal structure, there is a weak intermolecular π...π interaction between the phenyl rings.

S1. Comment

The crystal structure of the title compound, (I), represents further work in our investigation the the structure and stereochemistry of cobalt(III) complexes with aromatic amino acids (Miodragović et al., 2001). Complexes of cobalt(III) with aromatic amino acids are interesting as a simple model system for the investigation of non-covalent interactions in which aromatic amino acids are involved (Jitsukawa et al., 1997; Kumita et al., 1998, 2001), because it is known that their side chains, through non-covalent interactions, play an important role in molecular recognition in vivo (Fontecave et al., 1996; Ma & Dougherty, 1997; Pomponi et al., 1998; Hofstädter et al., 1999). Mixed (1,2-diaminoethane)bis(S-aminocarboxylato)cobalt(III) complexescan occur in the form of three geometrical isomers, and each of them has an optical counterpart.

In our previous paper (Miodragović et al., 2001), we described the synthesis and characterization of five out of six theoretically possible diastereomers of the (1,2-diaminoethane)bis(S-tyrosinato)cobalt(III) complex and presented the X-ray crystal structure of the Δ—C₁-cis(O) diastereomer, (II). By a subsequent recrystallization of the diastereomers, high quality monocrystals of the Λ-trans(O) diastereomer, (I), were obtained, whose crystal structure is presented in this paper (Fig. 1).

The greatest differences between complexes (I) and (II) are in different coordination of the O and N atoms of the S-tyrosinato ligands. Namely, complex (II) has a cis(O),cis(N) configuration, while complex (I) has a trans(O),trans(N) configuration, leading to different Co—O bond lengths. Hence, in complex (I), Co—O1 = 1.886 (2) Å and Co—O4 = 1.892 (2) Å, which are shorter than the in (II) [Co—O1 = 1.912 (6) Å and Co—O4 = 1.909 (5) Å]. There are also differences in the Co—N(S-tyrosinato) bond lengths, i.e. in (II), they are different [Co—N1 = 1.93 (7) Å and Co—N1 = 1.965 (6) Å], while in the title complex (I), they are almost the same, i.e. Co—N1 = 1.959 (2) Å and Co—N2 = 1.960 (2) Å.

In addition to the differences in coordination, the complexes also exhibit differences in the conformation of the amino acidic chelate rings. Namely, although these chelate rings exhibit the same conformation (envelope), in (I), the rings are less puckered. The puckering parameters for the Co—O1—C1—C2—N1 (q2) and Co—O4—C10—C11—N2 (q2') chelate rings for complex (I) are q2 = 0.267 (2) Å and q2' = 0.230 (3) Å, while for complex (II), the puckering parameters are q2 = 0.65 (8) Å and q2' = 0.323 (7) Å (Cremer & Pople, 1975). Such a difference in the planarity of the amino acidic chelate rings leads to somewhat smaller H—N1—C2—H and H—N2—C11—H torsion angles in complex (I), namely, the H atoms bonded to chelate-ring N and C atoms are closer to eclipsed positions in complex (I).

The puckering parameters of the diamine five-membered chelate ring (Co—N3—C19—C20—N4) are q2 = 0.446 (3) Å and ϕ = -99.0 (3)°. There are no remarkable differences between the conformations of the chelate rings of the 1,2-diaminoethane ligands in both complexes. In both cases, this chelate ring adopts a conformation which is intermediate between half-chair (with a local pseudo-twofold axis along Co and the midpoint of the C19—C20 bond) and envelope (with a local pseudo-mirror along C19 and the midpoint of the Co—N4 bond).

Due to the formation of three five-membered chelate rings, the coordinate angles deviate markedly from the ideal values of 90 and 180° (Table 1). The crystal structure is stabilized by a great number of hydrogen bonds (Table 2). In the crystal lattice of (I), the chloride anions are located approximately between two neighboring Co atoms [Co···Cl = 4.120 (2) Å and Cl···Coⁱ = 4.132 (2) Å; symmetry code: (i) x - 1, y, z], forming hydrogen bonds with the NH₂ groups coordinated to the Co atoms. However, in the crystal lattice of complex (II), the complex cations also form intermolecular hydrogen bonds, but these are directly through the COO and NH₂ groups from the coordination sphere of the Co atom.

In the crystal lattice of complex (I), there is a weak intermolecular π···π interaction between the phenyl rings of the amino acidic ligands. The phenyl rings are oriented in such a way that the perpendicular distance from the C4–C9 ring to the C13ⁱ–C18ⁱ ring is 3.88 Å, with the closest distance being C8···C17ⁱ of 3.672 (6) Å. The distance between the ring centroids is 4.142 (3) Å. An unhomogeneous arrangement of π-electron density through the phenyl ring is probably responsible for mutual orientation of the phenyl rings (Fig. 2) and the PD (parallel-displaced) type of π···π interactions (Kamishima et al., 2001).

It was subsequently established (i.e. it had not been published earlier) that in (II), the phenyl rings of tyrosine are involved in the formation of intermolecular C—H···π interactions with the following geometrical parameters: (i) the distance between an H atom bonded to atom C14 and the centre of the C4–C9 aromatic ring is 2.67 Å; (ii) the distance between an H atom bonded to atom C14 and the plane of the C4–C9 aromatic ring is 2.66 Å; (iii) the angle between the line connecting an H atom and the centre of the ring, and the normal to the C4–C9 plane is 4.6°; (iv) the angle C14—H···M (M = ring center) is 172°.

From the results presented in this paper, it can be concluded that the phenyl rings of amino acids present in the same complex, but having different geometrical configurations, can form two kinds of interactions, that is, C—H···π and π···π interactions. It can also be concluded that in both complexes, the complex cations form intermolecular hydrogen bonds of different type. In complex (II), the hydrogen bonds are formed through coordinated COO and NH₂ groups, while in complex (I), a chloride anion is positioned centrally between two complex cations and forms multiple hydrogen bonds with coordinated NH₂ groups.

S2. Experimental

The investigated diastereomer was obtained by the action of the S-tyrosinate ligand on trans-dichlorobis(1,2-diaminoethane)cobalt(III) chloride according to Miodragović et al. (2001). Red crystals of (I) were recrystallized from water in a 62% yield.

S3. Refinement

All H atoms of the complex cation were placed at calculated positions (C—H = 0.93–0.98 Å and N—H = 0.90 Å) using a riding model and isotropic displacement parameters were set equal to 1.2 times the equivalent isotropic displacement parameter of the parent atoms. Water and hydroxyl H-atom positions were determined by the HYDROGEN program (Nardelli, 1999) and were refined using a riding model with a fixed O—H bond length of 0.85 Å; isotropic displacement parameters were set equal to 1.5 times the equivalent isotropic displacement parameter of the parent atoms. It should be noted that all calculated data for water and hydroxyl H atoms are on the basis of an approximate model. A Gaussian-type absorption correction based on the crystal morphology was applied (Spek, 1990, 1998).

Computing details

Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: CAD-4 EXPRESS (Enraf-Nonius, 1994); program(s) used to solve structure: SHELXS97 (Scheldrick, 1997); program(s) used to refine structure: SHELXL97 (Scheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97, PARST (Nardelli, 1995) and WinGX (Farrugia, 1999).

Figures

	Fig. 1. A view of the molecular structure of the complex [Co(C9H10O3N)2(C2H8N2)]^+ cation with the atom labels. Displacement ellipsoids are shown at the 50% probability level.
	Fig. 2. Two projections of the crystal structure fragments, showing π···π interactions between phenyl rings. Displacement ellipsoids are shown at the 30% probability level.

Λ-trans(O)-(1,2-diaminoethane)bis(S-tyrosinato)cobalt(III) chloride tetrahydrate

Crystal data

[Co(C9H10NO3)2(C2H8N2)]Cl·4H2O	F(000) = 616
Mr = 586.91	Dx = 1.468 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 8.232 (3) Å	Cell parameters from 25 reflections
b = 15.348 (5) Å	θ = 11.3–15.6°
c = 10.539 (3) Å	µ = 0.81 mm^−1
β = 94.50 (2)°	T = 293 K
V = 1327.4 (8) Å^3	Prismatic, red
Z = 2	0.29 × 0.14 × 0.11 mm

Data collection

Enraf-Nonius CAD-4 diffractometer	4768 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.011
Graphite monochromator	θmax = 27.0°, θmin = 1.9°
ω/2θ scans	h = 0→10
Absorption correction: gaussian (Spek, 1990, 1998)	k = −18→18
Tmin = 0.882, Tmax = 0.926	l = −13→13
11424 measured reflections	2 standard reflections every 60 min
5323 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.032	H-atom parameters constrained
wR(F^2) = 0.088	w = 1/[σ^2(Fo^2) + (0.045P)^2 + 0.7052P] where P = (Fo^2 + 2Fc^2)/3
S = 1.10	(Δ/σ)max = 0.001
5323 reflections	Δρmax = 0.32 e Å^−3
325 parameters	Δρmin = −0.30 e Å^−3
1 restraint	Absolute structure: (Flack, 1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.008 (12)

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

	x	y	z	Uiso*/Ueq
Co	0.36432 (4)	−0.184147 (19)	0.56184 (3)	0.02179 (8)
N3	0.2004 (2)	−0.1885 (2)	0.41807 (19)	0.0283 (4)
H1N3	0.1008	−0.1957	0.4462	0.034*
H2N3	0.2007	−0.1383	0.3741	0.034*
N4	0.4974 (3)	−0.25376 (16)	0.4539 (2)	0.0296 (5)
H1N4	0.5967	−0.2295	0.4521	0.035*
H2N4	0.5099	−0.3079	0.4861	0.035*
C19	0.2381 (4)	−0.2619 (2)	0.3353 (3)	0.0386 (7)
H19A	0.1787	−0.2562	0.2526	0.046*
H19B	0.2085	−0.3167	0.3730	0.046*
C20	0.4174 (4)	−0.2583 (2)	0.3229 (3)	0.0371 (7)
H20A	0.4529	−0.3098	0.2796	0.044*
H20B	0.4447	−0.2073	0.2745	0.044*
O1	0.4563 (2)	−0.08050 (13)	0.50342 (19)	0.0281 (4)
O2	0.4296 (3)	0.06246 (14)	0.4927 (2)	0.0437 (6)
N1	0.2256 (3)	−0.10611 (15)	0.6532 (2)	0.0254 (5)
H1N1	0.1238	−0.1276	0.6510	0.031*
H2N1	0.2646	−0.1016	0.7352	0.031*
C1	0.3811 (4)	−0.00906 (18)	0.5258 (3)	0.0285 (6)
C2	0.2236 (3)	−0.01889 (18)	0.5917 (3)	0.0271 (6)
H2	0.1328	−0.0179	0.5258	0.032*
C3	0.1990 (4)	0.0564 (2)	0.6832 (3)	0.0356 (7)
H3A	0.2950	0.0610	0.7424	0.043*
H3B	0.1903	0.1102	0.6346	0.043*
C4	0.0507 (4)	0.0483 (2)	0.7588 (3)	0.0334 (6)
C5	−0.0999 (4)	0.0209 (2)	0.7060 (3)	0.0362 (7)
H5	−0.1103	0.0027	0.6216	0.043*
C6	−0.2358 (4)	0.0198 (2)	0.7758 (3)	0.0372 (7)
H6	−0.3359	0.0012	0.7384	0.045*
C7	−0.2214 (4)	0.0465 (2)	0.9014 (3)	0.0378 (7)
O3	−0.3595 (3)	0.04689 (19)	0.9668 (2)	0.0509 (7)
H1O3	−0.3548	0.0891	1.0193	0.076*
C8	−0.0729 (5)	0.0721 (2)	0.9562 (3)	0.0465 (8)
H8	−0.0628	0.0895	1.0410	0.056*
C9	0.0628 (4)	0.0724 (2)	0.8858 (3)	0.0438 (8)
H9	0.1634	0.0890	0.9246	0.053*
O4	0.2741 (2)	−0.28452 (13)	0.6334 (2)	0.0293 (4)
O5	0.3062 (3)	−0.38214 (15)	0.7868 (2)	0.0403 (5)
N2	0.5316 (3)	−0.19277 (19)	0.7042 (2)	0.0270 (5)
H1N2	0.6305	−0.1827	0.6764	0.032*
H2N2	0.5132	−0.1525	0.7635	0.032*
C10	0.3574 (4)	−0.31985 (18)	0.7274 (3)	0.0292 (6)
C11	0.5269 (3)	−0.28214 (19)	0.7612 (3)	0.0306 (6)
H11	0.6056	−0.3184	0.7202	0.037*
C12	0.5732 (4)	−0.2835 (2)	0.9042 (3)	0.0404 (7)
H12A	0.4867	−0.2559	0.9470	0.048*
H12B	0.5799	−0.3437	0.9322	0.048*
C13	0.7325 (4)	−0.2387 (2)	0.9457 (3)	0.0354 (7)
C14	0.8717 (4)	−0.2525 (2)	0.8825 (3)	0.0420 (7)
H14	0.8661	−0.2885	0.8113	0.050*
C15	1.0184 (4)	−0.2142 (2)	0.9230 (3)	0.0441 (8)
H15	1.1101	−0.2243	0.8789	0.053*
C16	1.0291 (4)	−0.1612 (2)	1.0282 (3)	0.0407 (8)
O6	1.1780 (3)	−0.1256 (2)	1.0665 (3)	0.0553 (7)
H1O6	1.2108	−0.1462	1.1389	0.083*
C17	0.8917 (5)	−0.1464 (3)	1.0930 (3)	0.0503 (9)
H17	0.8976	−0.1107	1.1645	0.060*
C18	0.7455 (4)	−0.1852 (3)	1.0508 (3)	0.0454 (7)
H18	0.6536	−0.1747	1.0946	0.055*
Cl	−0.13650 (9)	−0.19990 (7)	0.54624 (9)	0.0531 (3)
O1W	0.4064 (3)	−0.0795 (2)	0.9008 (2)	0.0504 (6)
H11W	0.4627	−0.0351	0.9241	0.076*
H21W	0.3531	−0.0950	0.9629	0.076*
O2W	−0.0286 (4)	−0.3968 (2)	0.6341 (3)	0.0707 (9)
H12W	−0.0810	−0.3493	0.6229	0.106*
H22W	0.0546	−0.3939	0.5914	0.106*
O3W	−0.2111 (4)	−0.5173 (2)	0.7437 (3)	0.0681 (8)
H13W	−0.1500	−0.4794	0.7127	0.102*
H23W	−0.2230	−0.5029	0.8203	0.102*
O4W	0.4509 (5)	−0.5448 (2)	0.7442 (3)	0.0788 (10)
H14W	0.4313	−0.5735	0.6757	0.118*
H24W	0.5242	−0.5075	0.7315	0.118*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co	0.02055 (14)	0.01730 (15)	0.02802 (15)	−0.00076 (16)	0.00508 (11)	0.00091 (16)
N3	0.0253 (10)	0.0263 (11)	0.0336 (10)	−0.0029 (13)	0.0043 (8)	0.0013 (13)
N4	0.0272 (11)	0.0243 (12)	0.0381 (13)	0.0019 (10)	0.0087 (10)	−0.0018 (10)
C19	0.0436 (17)	0.0340 (17)	0.0374 (16)	−0.0019 (14)	−0.0019 (13)	−0.0082 (13)
C20	0.0468 (18)	0.0314 (16)	0.0344 (15)	0.0015 (14)	0.0120 (13)	−0.0054 (12)
O1	0.0272 (10)	0.0209 (10)	0.0374 (11)	−0.0014 (8)	0.0104 (8)	0.0028 (8)
O2	0.0558 (14)	0.0208 (10)	0.0572 (14)	−0.0083 (11)	0.0209 (12)	0.0011 (9)
N1	0.0234 (11)	0.0244 (13)	0.0291 (12)	0.0009 (9)	0.0062 (9)	0.0009 (9)
C1	0.0336 (14)	0.0216 (14)	0.0306 (13)	−0.0003 (12)	0.0052 (11)	−0.0012 (11)
C2	0.0282 (13)	0.0204 (13)	0.0331 (14)	0.0044 (11)	0.0057 (11)	0.0016 (11)
C3	0.0387 (16)	0.0229 (14)	0.0460 (17)	0.0009 (13)	0.0092 (13)	−0.0060 (12)
C4	0.0376 (16)	0.0228 (14)	0.0405 (16)	0.0071 (12)	0.0080 (12)	−0.0026 (12)
C5	0.0447 (17)	0.0313 (15)	0.0327 (15)	0.0060 (14)	0.0048 (13)	−0.0066 (12)
C6	0.0356 (16)	0.0367 (17)	0.0391 (16)	−0.0006 (14)	0.0023 (13)	−0.0083 (13)
C7	0.0415 (17)	0.0317 (16)	0.0421 (17)	0.0003 (14)	0.0146 (13)	−0.0054 (13)
O3	0.0470 (14)	0.0568 (16)	0.0515 (14)	−0.0098 (12)	0.0206 (11)	−0.0214 (12)
C8	0.052 (2)	0.051 (2)	0.0372 (17)	−0.0046 (17)	0.0083 (15)	−0.0171 (15)
C9	0.0414 (18)	0.046 (2)	0.0443 (18)	−0.0046 (16)	0.0052 (14)	−0.0148 (15)
O4	0.0275 (10)	0.0232 (10)	0.0375 (11)	−0.0042 (9)	0.0052 (8)	0.0052 (9)
O5	0.0456 (13)	0.0321 (11)	0.0440 (12)	−0.0052 (10)	0.0101 (10)	0.0114 (10)
N2	0.0241 (10)	0.0257 (13)	0.0312 (10)	−0.0018 (11)	0.0028 (8)	0.0025 (11)
C10	0.0319 (14)	0.0223 (13)	0.0346 (14)	0.0013 (12)	0.0111 (11)	0.0026 (11)
C11	0.0291 (14)	0.0252 (14)	0.0376 (15)	0.0030 (12)	0.0026 (12)	0.0057 (12)
C12	0.0398 (17)	0.0439 (19)	0.0372 (16)	−0.0035 (15)	0.0018 (13)	0.0119 (14)
C13	0.0359 (15)	0.0379 (17)	0.0317 (14)	0.0040 (14)	−0.0017 (12)	0.0093 (12)
C14	0.0443 (18)	0.0439 (19)	0.0379 (16)	0.0006 (16)	0.0030 (13)	−0.0057 (14)
C15	0.0389 (17)	0.050 (2)	0.0445 (18)	−0.0009 (15)	0.0098 (14)	−0.0033 (14)
C16	0.0381 (16)	0.044 (2)	0.0401 (16)	−0.0025 (13)	0.0041 (13)	0.0021 (13)
O6	0.0459 (14)	0.0674 (18)	0.0528 (15)	−0.0146 (13)	0.0043 (11)	−0.0086 (13)
C17	0.052 (2)	0.060 (2)	0.0398 (18)	0.0030 (18)	0.0070 (16)	−0.0111 (16)
C18	0.0411 (15)	0.0567 (19)	0.0395 (14)	0.004 (2)	0.0093 (11)	0.000 (2)
Cl	0.0273 (3)	0.0690 (9)	0.0643 (5)	−0.0078 (4)	0.0120 (3)	−0.0044 (5)
O1W	0.0471 (14)	0.0614 (17)	0.0433 (13)	−0.0054 (13)	0.0080 (10)	−0.0125 (12)
O2W	0.0552 (17)	0.062 (2)	0.096 (2)	−0.0185 (15)	0.0097 (17)	−0.0191 (17)
O3W	0.076 (2)	0.071 (2)	0.0554 (16)	0.0012 (17)	−0.0073 (15)	0.0161 (15)
O4W	0.109 (3)	0.060 (2)	0.073 (2)	0.0163 (19)	0.0432 (19)	0.0090 (16)

Geometric parameters (Å, º)

Co—O1	1.886 (2)	O3—H1O3	0.8500
Co—O4	1.892 (2)	C8—C9	1.388 (5)
Co—N3	1.950 (2)	C8—H8	0.9300
Co—N4	1.957 (2)	C9—H9	0.9300
Co—N1	1.959 (2)	O4—C10	1.281 (4)
Co—N2	1.960 (2)	O5—C10	1.235 (4)
N3—C19	1.472 (4)	N2—C11	1.499 (4)
N3—H1N3	0.9000	N2—H1N2	0.9000
N3—H2N3	0.9000	N2—H2N2	0.9000
N4—C20	1.484 (4)	C10—C11	1.527 (4)
N4—H1N4	0.9000	C11—C12	1.526 (4)
N4—H2N4	0.9000	C11—H11	0.9800
C19—C20	1.493 (5)	C12—C13	1.515 (5)
C19—H19A	0.9700	C12—H12A	0.9700
C19—H19B	0.9700	C12—H12B	0.9700
C20—H20A	0.9700	C13—C18	1.376 (5)
C20—H20B	0.9700	C13—C14	1.386 (5)
O1—C1	1.290 (4)	C14—C15	1.381 (5)
O2—C1	1.228 (4)	C14—H14	0.9300
N1—C2	1.487 (4)	C15—C16	1.372 (5)
N1—H1N1	0.9000	C15—H15	0.9300
N1—H2N1	0.9000	C16—O6	1.373 (4)
C1—C2	1.526 (4)	C16—C17	1.385 (5)
C2—C3	1.529 (4)	O6—H1O6	0.8500
C2—H2	0.9800	C17—C18	1.384 (5)
C3—C4	1.514 (4)	C17—H17	0.9300
C3—H3A	0.9700	C18—H18	0.9300
C3—H3B	0.9700	O1W—H11W	0.85
C4—C9	1.385 (4)	O1W—H21W	0.85
C4—C5	1.384 (5)	O2W—H12W	0.85
C5—C6	1.386 (5)	O2W—H22W	0.85
C5—H5	0.9300	O3W—H13W	0.85
C6—C7	1.381 (4)	O3W—H23W	0.85
C6—H6	0.9300	O4W—H14W	0.85
C7—C8	1.368 (5)	O4W—H24W	0.85
C7—O3	1.376 (4)
O1—Co—O4	175.55 (10)	C5—C4—C3	123.2 (3)
O1—Co—N3	92.66 (11)	C4—C5—C6	121.7 (3)
O4—Co—N3	90.71 (10)	C4—C5—H5	119.2
O1—Co—N4	90.77 (11)	C6—C5—H5	119.2
O4—Co—N4	92.41 (10)	C7—C6—C5	119.5 (3)
N3—Co—N4	85.09 (11)	C7—C6—H6	120.2
O1—Co—N1	84.79 (9)	C5—C6—H6	120.2
O4—Co—N1	92.29 (10)	C8—C7—O3	122.2 (3)
N3—Co—N1	90.49 (11)	C8—C7—C6	119.8 (3)
N4—Co—N1	173.59 (11)	O3—C7—C6	118.0 (3)
O1—Co—N2	91.77 (10)	C7—O3—H1O3	109.4
O4—Co—N2	85.07 (10)	C7—C8—C9	120.3 (3)
N3—Co—N2	174.08 (14)	C7—C8—H8	119.8
N4—Co—N2	90.94 (11)	C9—C8—H8	119.8
N1—Co—N2	93.81 (11)	C4—C9—C8	121.0 (3)
C19—N3—Co	108.73 (19)	C4—C9—H9	119.5
C19—N3—H1N3	109.9	C8—C9—H9	119.5
Co—N3—H1N3	109.9	C10—O4—Co	116.76 (19)
C19—N3—H2N3	109.9	C11—N2—Co	109.27 (18)
Co—N3—H2N3	109.9	C11—N2—H1N2	109.8
H1N3—N3—H2N3	108.3	Co—N2—H1N2	109.8
C20—N4—Co	109.79 (18)	C11—N2—H2N2	109.8
C20—N4—H1N4	109.7	Co—N2—H2N2	109.8
Co—N4—H1N4	109.7	H1N2—N2—H2N2	108.3
C20—N4—H2N4	109.7	O5—C10—O4	122.5 (3)
Co—N4—H2N4	109.7	O5—C10—C11	121.2 (3)
H1N4—N4—H2N4	108.2	O4—C10—C11	116.3 (2)
N3—C19—C20	106.3 (2)	N2—C11—C10	107.8 (2)
N3—C19—H19A	110.5	N2—C11—C12	113.4 (3)
C20—C19—H19A	110.5	C10—C11—C12	112.2 (2)
N3—C19—H19B	110.5	N2—C11—H11	107.8
C20—C19—H19B	110.5	C10—C11—H11	107.8
H19A—C19—H19B	108.7	C12—C11—H11	107.8
N4—C20—C19	106.8 (2)	C13—C12—C11	115.0 (3)
N4—C20—H20A	110.4	C13—C12—H12A	108.5
C19—C20—H20A	110.4	C11—C12—H12A	108.5
N4—C20—H20B	110.4	C13—C12—H12B	108.5
C19—C20—H20B	110.4	C11—C12—H12B	108.5
H20A—C20—H20B	108.6	H12A—C12—H12B	107.5
C1—O1—Co	116.53 (18)	C18—C13—C14	117.6 (3)
C2—N1—Co	108.85 (17)	C18—C13—C12	121.0 (3)
C2—N1—H1N1	109.9	C14—C13—C12	121.4 (3)
Co—N1—H1N1	109.9	C15—C14—C13	121.5 (3)
C2—N1—H2N1	109.9	C15—C14—H14	119.3
Co—N1—H2N1	109.9	C13—C14—H14	119.3
H1N1—N1—H2N1	108.3	C16—C15—C14	120.1 (3)
O2—C1—O1	122.5 (3)	C16—C15—H15	120.0
O2—C1—C2	121.6 (3)	C14—C15—H15	120.0
O1—C1—C2	115.9 (2)	O6—C16—C15	118.2 (3)
N1—C2—C1	107.9 (2)	O6—C16—C17	122.3 (3)
N1—C2—C3	113.8 (2)	C15—C16—C17	119.5 (3)
C1—C2—C3	111.8 (2)	C16—O6—H1O6	109.2
N1—C2—H2	107.7	C16—C17—C18	119.6 (3)
C1—C2—H2	107.7	C16—C17—H17	120.2
C3—C2—H2	107.7	C18—C17—H17	120.2
C4—C3—C2	114.9 (3)	C13—C18—C17	121.7 (3)
C4—C3—H3A	108.5	C13—C18—H18	119.1
C2—C3—H3A	108.5	C17—C18—H18	119.1
C4—C3—H3B	108.5	H11W—O1W—H21W	107.7
C2—C3—H3B	108.5	H12W—O2W—H22W	107.7
H3A—C3—H3B	107.5	H13W—O3W—H23W	107.7
C9—C4—C5	117.6 (3)	H14W—O4W—H24W	107.7
C9—C4—C3	119.1 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1N3···Cl	0.90	2.29	3.183 (2)	170
N3—H2N3···O3W^i	0.90	2.24	3.138 (5)	176
N1—H1N1···Cl	0.90	2.58	3.421 (3)	155
N1—H2N1···O1W	0.90	2.05	2.929 (4)	165
N2—H2N2···O1W	0.90	2.08	2.951 (4)	163
N4—H1N4···Cl^ii	0.90	2.38	3.202 (3)	152
N2—H1N2···Cl^ii	0.90	2.46	3.311 (2)	158
N4—H2N4···O2^iii	0.90	2.06	2.929 (3)	162
O3—H1O3···O5^iv	0.85	2.10	2.818 (3)	142
O6—H1O6···O3W^v	0.85	2.33	2.599 (4)	98
O1W—H11W···O3^ii	0.85	1.96	2.784 (4)	165
O1W—H21W···O6^vi	0.85	1.93	2.758 (4)	163
O2W—H12W···Cl	0.85	2.46	3.263 (4)	157
O2W—H22W···O4	0.85	2.48	3.030 (4)	123
O3W—H13W···O2W	0.85	1.85	2.699 (5)	176
O3W—H23W···O6^vii	0.85	2.24	2.599 (4)	105
O4W—H14W···O1^iii	0.85	2.17	2.830 (4)	134
O4W—H24W···O3W^ii	0.85	2.18	2.815 (5)	132

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