Linkage isomeric oxamate chelates: rac-bis­(ethane-1,2-diamine)oxamatocobalt(III) bis­(trifluoro­methane­sulfonate) dihydrate and Λ(+)₅₇₈-bis­(ethane-1,2-diamine)[oxamato(2−)]cobalt(III) trifluoro­methane­sulfonate

The structures of rac-bis­(ethane-1,2-diamine)(oxamato-κ²O¹,O²)cobalt(III) bis­(trifluoro­methane­sulfonate) dihydrate, [Co(C₂H₂NO₃)(C₂H₈N₂)₂](CF₃SO₃)₂·2H₂O, (I), and Λ(+)₅₇₈-bis­(ethane-1,2-diamine)[oxamato(2−)-κ²N,O¹]cobalt(III) trifluoro­methane­sulfonate, [Co(C₂HNO₃)(C₂H₈N₂)₂]CF₃SO₃, (II), are compared. Together, the two complexes constitute the first pair of linkage isomers of bidentate oxamate available for structural comparison.

S1. Comment

The production of multidimensional magnetic materials through self-assembly of paramagnetic metal ions with small anionic ligands has to a large degree relied on oxalate as the bridging ligand (Pilkington & Decurtins, 2004; Kou et al., 2008, and references therein). However, anionic forms of derivatives such as oxamide (H₂NCOCONH₂), dithiooxamide (H₂NCSCSNH₂), oxamic acid (H₂NCOCO₂H) and their derivatives are also employed in bridging capacities, due to the structural and electronic variation offered by such species (Verdaguer et al., 1985; Kahn, 2000; Cangussu et al., 2008).

The unsymmetrical nature of oxamic acid, whether singly or doubly deprotonated, gives rise to different coordination modes for the oxamate entity in both bridging and non-bridging roles (Novosad et al., 2000; Rodrígez-Martín et al., 2001). For bidentate oxamate in mononuclear systems, both the O,O'- and N,O-coordination modes are possible. However, essentially all reported crystal structures of mononuclear oxamate complexes have the ligand O,O' bound at a labile metal centre (Braibanti et al., 1971; Pellinghelli et al., 1972; Skoulika et al., 1988a,b; Veltsistas et al., 1995, 1999; Papadimitriou et al., 1998; Novosad et al., 2000; Rodrígez-Martín et al., 2001; Wang et al., 2003). The sole example of a robust metal centre is the cobalt(III) complex p-[Co(tren)(O₂CCONH₂-O,O')]Cl₂.2H₂O (tren is what?; Chun et al., 1999).

The two cobalt(III) complexes of this study constitute oxamate linkage isomers covering both coordination modes. However, the two complexes do differ with respect to the level of deprotonation of the oxamate ligand. Thus, the O,O' isomer, rac-[Co(en)₂(O₂CCONH₂-O,O')](O₃SCF₃)₂.2H₂O, (I), comprises the oxamate monoanion, whereas the N,O isomer, Λ(+)₅₇₈-[Co(en)₂(O₂CCONH-N,O)](O₃SCF₃), (II), comprises the dianion, with the oxamate also deprotonated at the N atom, as expected for an N-bound amide (Sigel & Martin, 1982). Reprotonation of (II), presumably at the amide exo-O atom, only occurs in strong acids, consistent with a pK_a value of 0.7 for the protonated form, as determined spectrophotometrically for the chloride salt (Grøndahl, Hammershøi et al., 1995).

To our knowledge, compound (II) represents the first structurally unambiguous example of an N,O-linkage isomer of oxamate in a mononuclear complex. Together, complexes (I) and (II) constitute the first pair of linkage isomers of bidentate oxamate available for structural comparison (Tables 1 and 3). The two isomers differ significantly with respect to the bond distances of their oxamate amide segments. These segments are both polarized by coordination to the metal, but to different degrees in each linkage isomer. A valid comparison of these differences should take unbound oxamate as the point of reference. Aakeröy et al. (1996) reported structures of six independent oxamate salts in which the oxamate anion is not coordinated. The C—O and C—N bond distances of the oxamate amide moieties of these structures are all very similar (±0.01 Å), averaging 1.236 and 1.320 Å, respectively. Comparing these values with those from the chelated compounds, it transpires that the O-bound amide moiety of (I) has the C1—O1 bond length [1.2657 (11) Å] increased by ca 0.03 Å and the C1—N1 bond length [1.2979 (12) Å] decreased by ca 0.02 Å relative to the unbound anion. This is consistent with a relative shift of double-bond character from the C1—O1 bond towards the C1—N1 bond, induced by the metal. The same trend, albeit less pronounced, is evident in (II), with C1—O1 and C1—N1 bond lengths of 1.2578 (9) and 1.3139 (9) Å, respectively. In (II), the metal centre has formally replaced an H atom at the amidic N atom. The smaller charge-to-radius ratio of the cobalt(III) centre renders it less polarizing than an H atom (Dixon & Sargeson, 1993), and the relative effect of such an H⁺/Co^III replacement would be to release electron density into the N—C bond, albeit on a minor scale, as judged from the small bond-length changes compared with the unbound anion. The Co1—N1(amide) bond distance of 1.9039 (7) Å is the shortest such bond in (II), with the other Co1—N(primary amine) distances ranging from 1.9444 (7) to 1.9699 (6) Å. The structure of the closely related 2-thiooxamate complex, [Co(en)₂(O₂CCSNH-N,O)]O₃SCF₃.H₂O (Grøndahl, Hammershøi & Larsen, 1995) shows the same features, with thioamide Co—N and C—N bond distances of 1.896 (2) and 1.310 (4) Å, respectively, which closely match those of (II). The Co1—N1 distance of 1.9039 (7) Å in (II) is significantly shorter than the corresponding distance of 1.960 (2) Å in the N-formyloxamate complex, Λ(+)₅₇₈-[Co(en)₂(O₂CCONCHO-N,O)]ClO₄ (Grøndahl, Hammershøi et al., 1995). Thus, the introduction of a formyl group has a dramatic effect on the Co—N distance. A parallel trend holds for 2-iminoacetate versus 2-methyliminoacetate as ligands. Thus, the introduction of a methyl group at the imine N atom increases the Co—N(imine) distance from 1.904 (4) Å in [Co(en)₂(O₂CC═ NH)]Br₂.H₂O to 1.951 (2) Å in [Co(en)₂(O₂CC=NCH₃)]S₂O₆.1.5H₂O (Bendahl et al., 2002). The oxamate and oxamate-to-metal bond parameters of (I) are almost identical to those of the corresponding tren complex, p-[Co(tren)(O₂CCONH₂-O,O')]Cl₂.2H₂O.

The study of Chun et al. (1999) was initiated against the background that certain racemic halide salts of the [Co(en)₂(ox)]⁺ cation were known to display conglomerate crystallization (spontaneous resolution) from aqueous solution (Yamanari et al., 1973). Therefore, it was of interest to detect whether this property is retained if the oxalate ligand is replaced by structurally related ligands, e.g. oxamate. Indeed, the racemic chloride salt of (II), rac-[Co(en)₂(O₂CCONH-N,O)]Cl.H₂O, has been demonstrated to display conglomerate crystallization from a comparison of the X-ray powder diffraction pattern of the racemate with that of one enantiomer, Λ(+)₅₇₈-[Co(en)₂(O₂CCONH-N,O)]Cl.H₂O (Grøndahl, Hammershøi et al., 1995). These patterns are identical, implying that the racemate must crystallize in the same noncentrosymmetric space group as the enantiomer (Galsbøl et al., 1978).

The structures of both (I) and (III) are characterized by extensive hydrogen-bonding networks; for details, see Tables 2 and 4. [Do you wish to add any comment on the nature of these networks? e.g. two- or three-dimensional, ribbons, chains, sheets etc. Also, do you wish to add hydrogen-bond diagrams?]

S2. Experimental

The O,O' isomer, (I), was synthesized here anew. Earlier attempts at producing this complex from trans-[Co(en)₂Cl₂]Cl by reaction with sodium oxamate in water only resulted in the oxalate complex, [Co(en)₂(ox)]Cl.4H₂O (Chun et al., 1999), evidently due to adverse hydrolysis of oxamate in the aqueous conditions. This difficulty was circumvented here by allowing ethyl oxamate in acetone to replace the coordinated trifluoromethanesulfonate ions in cis-[Co(en)₂(O₃SCF₃)₂]O₃SCF₃ (Barfod et al., 2005). During aqueous work-up, the ester part of ethyl oxamate, once coordinated, readily hydrolyzes (Browne et al., 2000). Thus, for the synthesis of (I), a solution of cis-[Co(en)₂(O₃SCF₃)₂]O₃SCF₃ (4.82 g, 10.0 mmol) and ethyl oxamate (2.34 g, 20.0 mmol) in acetone (20 ml) was stirred at 313–318 K for 0.5 h. The solvent was then removed by rotary evaporation, the resulting residue taken up in water (15 ml) and the solution extracted with diethyl ether (2 × 20 ml). The aqueous phase was concentrated almost to dryness and the resulting residue redissolved in water (ca 5 ml). Gradual addition of LiCl (1.7 g) and EtOH (10 ml), followed by cooling in ice, deposited the chloride salt, rac-[Co(en)₂(O₂CCONH₂)]Cl₂.2H₂O, as red crystals (1.81 g). These were recrystallized from hot water (5.5 ml) and EtOH (10 ml) (1.64 g, 44%). Large ruby-coloured crystals of the trifluoromethanesulfonate salt, (I), suitable for X-ray crystallography, were grown from an aqueous solution of the chloride salt to which was added excess NaO₃SCF₃.H₂O. The N,O isomer, (II), was obtained from the known chloride salt (Grøndahl, Hammershøi et al., 1995). A solution of Λ(+)₅₇₈-[Co(en)₂(O₂CCONH-N,O)]Cl.H₂O (0.25 g) and KO₃SCF₃ (0.50 g) in hot water (5 ml, 323 K) was cooled slowly to 298 K, depositing orange–red crystals (0.28 g). These were recrystallized from boiling water (15 ml) to produce crystals of (II) (0.10 g) of crystallographic quality.

S3. Refinement

Space groups were determined from analysis of the systematically absent reflections. H atoms were found in a difference Fourier map and included in the refinement as constrained idealized H atoms riding on the parent atom, with C—H = 0.99 and N—H = 0.92 Å. In the final refinement of (I) and (II), the H atoms at the oxamate N atom were refined semi-free, with U_iso(H) = 1.2U_eq(N). The H atoms of the solvent water molecules in (I) were also refined semi-free, with a distance restraint [Please state O—H restraint used] and with U_iso(H) = 1.5U_eq(O).

Computing details

For both compounds, data collection: COLLECT (Nonius, 1999); cell refinement: COLLECT (Nonius, 1999); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. A view of the molecular structure of (I), with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A view of the molecular structure of (II), with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.

(I) rac-bis(ethane-1,2-diamine)(oxamato- κ²O¹,O²)cobalt(III) bis(trifluoromethanesulfonate) dihydrate

Crystal data

[Co(C2H2NO3)(C2H8N2)2](CF3SO3)2·2H2O	Z = 2
Mr = 601.36	F(000) = 612
Triclinic, P1	Dx = 1.846 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.2621 (9) Å	Cell parameters from 27593 reflections
b = 10.6826 (7) Å	θ = 1.9–45.0°
c = 16.4111 (6) Å	µ = 1.10 mm^−1
α = 92.214 (5)°	T = 122 K
β = 94.350 (5)°	Prism, red
γ = 98.257 (7)°	0.35 × 0.23 × 0.06 mm
V = 1081.95 (18) Å^3

Data collection

Nonius KappaCCD area-detector diffractometer	13446 independent reflections
Radiation source: fine-focus sealed tube	10801 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.044
ω and ϕ scans	θmax = 40.1°, θmin = 2.2°
Absorption correction: integration Gaussian integration (Coppens, 1970)	h = −11→11
Tmin = 0.693, Tmax = 0.933	k = −19→19
68590 measured reflections	l = −29→29

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.079	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0217P)^2 + 0.6052P] where P = (Fo^2 + 2Fc^2)/3
13446 reflections	(Δ/σ)max = 0.001
316 parameters	Δρmax = 0.70 e Å^−3
6 restraints	Δρmin = −0.70 e Å^−3

Special details

Experimental. General: NMR spectra (¹³C) were recorded on a Bruker (400 MHz) spectrometer using 1,4-dioxane (δ = 69.14 relative to Me₄Si) in D₂O as internal standard. [Co(en)₂(O₃SCF₃)₂]O₃SCF₃ (Barfod et al., 2005) was synthesized according to a published procedure. NaO₃SCF₃.H₂O and KO₃SCF₃ were obtained from aqueous HO₃SCF₃ and NaOH or KOH, respectively, followed by evaporation and recrystallization from EtOH. Routine concentration of solutions was carried out at reduced pressure (ca 20 Torr) in a Büchi rotary evaporator using a vacuum pump and water bath (ca 50 °C).

Synthesis of rac-[Co(en)₂(O₂CCONH₂-O,O')]Cl₂.2H₂O: a solution of cis-[Co(en)₂(O₃SCF₃)₂]O₃SCF₃ (4.82 g, 10.0 mmol) and ethyl oxamate (2.34 g, 20.0 mmol) in acetone (20 ml) was stirred at 40–45 °C for 0.5 h while the colour changed from purple to deep red. The solvent was removed by rotary evaporation and the resulting residue was taken up in water (15 ml). The solution was extracted with diethylether (2 × 20 ml) before the aqueous phase was concentrated to almost dryness. The residue was redissolved in water (ca 5 ml) followed by gradual addition of LiCl (1.7 g) and EtOH (10 ml) followed by cooling in ice. The red crystals (1.81 g) that separated were collected and recrystallized from hot water (5.5 ml) and EtOH (10 ml). After cooling in ice the crystals were collected and washed with EtOH, Et₂O and airdried. Yield: 1.64 g, 44%. C₆H₁₈Cl₂CoN₅O₃ (374.11): calcd. C 19.26, H 5.93, Cl 18.95, Co 15.75, N 18.72; found C 19.1, H 6.1, Cl 18.7, Co 15.7 N 18.8. ¹³C NMR (400 MHz, D₂O): δ = 172.6, 169.7 (C═O); 48.5, 48.4, 46.2, 46.0 (4 × CH₂).

Synthesis of rac-[Co(en)₂(O₂CCONH₂-O,O')](O₃SCF₃)₂.2H₂O, (I): Crystals of the trifluoromethanesulfonate salt suitable for X-ray crystallography were grown from an aqueous solution of rac-[Co(en)₂(O₂CCONH₂-O,O')]Cl₂.2H₂O to which was added excess NaO₃SCF₃.H₂O. The large ruby coloured crystals were dried between filter paper. C₈H₂₂CoF₆N₅O₁₁S₂ (601.36): calcd. C 15.98, H 3.69, Co 9.80, N 11.65; found C 15.8, H 3.2, Co 9.5 N 11.0.

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	0.58257 (2)	0.558060 (12)	0.247322 (7)	0.00964 (3)
O1	0.52488 (11)	0.46540 (7)	0.14387 (4)	0.01245 (11)
O2	0.86506 (11)	0.61190 (7)	0.21181 (4)	0.01336 (12)
N2	0.65704 (13)	0.66399 (8)	0.34608 (5)	0.01381 (13)
H2A	0.5585	0.6419	0.3838	0.017*
H2B	0.7921	0.6534	0.3684	0.017*
N3	0.29795 (13)	0.48869 (8)	0.27774 (5)	0.01239 (12)
H3A	0.2363	0.5511	0.3033	0.015*
H3B	0.2101	0.4585	0.2316	0.015*
N4	0.47283 (14)	0.70318 (8)	0.19963 (5)	0.01354 (13)
H4A	0.5626	0.7359	0.1614	0.016*
H4B	0.3370	0.6779	0.1738	0.016*
N5	0.68243 (14)	0.40949 (9)	0.29510 (5)	0.01425 (13)
H5A	0.7761	0.3774	0.2621	0.017*
H5B	0.7541	0.4315	0.3458	0.017*
C1	0.68708 (14)	0.48048 (9)	0.10181 (5)	0.01163 (13)
N1	0.68787 (14)	0.42549 (9)	0.02993 (5)	0.01440 (13)
H1A	0.575 (2)	0.3727 (14)	0.0114 (10)	0.017*
H1B	0.802 (2)	0.4403 (16)	0.0031 (10)	0.017*
C2	0.88950 (14)	0.56700 (9)	0.13995 (6)	0.01223 (14)
O3	1.05471 (12)	0.58539 (8)	0.10379 (5)	0.01639 (13)
C21	0.65566 (19)	0.79857 (10)	0.32557 (7)	0.01879 (17)
H21A	0.7911	0.8318	0.3013	0.023*
H21B	0.6439	0.8513	0.3755	0.023*
C31	0.31784 (16)	0.38387 (10)	0.33392 (6)	0.01604 (16)
H31A	0.1782	0.3270	0.3334	0.019*
H31B	0.3611	0.4182	0.3906	0.019*
C41	0.46228 (19)	0.80178 (10)	0.26493 (7)	0.01824 (17)
H41A	0.3260	0.7834	0.2920	0.022*
H41B	0.4686	0.8862	0.2416	0.022*
C51	0.48942 (17)	0.31302 (10)	0.30262 (7)	0.01683 (16)
H51A	0.5249	0.2488	0.3414	0.020*
H51B	0.4385	0.2697	0.2488	0.020*
S1	0.19943 (4)	0.68254 (2)	0.482812 (14)	0.01360 (4)
O11	0.10287 (13)	0.64823 (8)	0.40011 (5)	0.01720 (13)
O12	0.07976 (14)	0.62913 (9)	0.54759 (5)	0.02102 (15)
O13	0.42959 (13)	0.67880 (9)	0.49207 (5)	0.02202 (16)
C61	0.1749 (2)	0.85089 (11)	0.49388 (7)	0.0228 (2)
F11	0.26565 (16)	0.90144 (8)	0.56570 (5)	0.03358 (19)
F12	0.2688 (2)	0.91590 (9)	0.43535 (6)	0.0427 (2)
F13	−0.03322 (16)	0.86529 (9)	0.48914 (7)	0.0385 (2)
S2	0.87661 (4)	0.18319 (2)	0.133795 (16)	0.01574 (4)
O21	0.96896 (13)	0.30076 (8)	0.17845 (5)	0.01883 (14)
O22	0.64444 (14)	0.15369 (9)	0.13392 (6)	0.02658 (18)
O23	0.96088 (16)	0.16275 (9)	0.05572 (5)	0.02525 (17)
C71	0.9767 (2)	0.06338 (11)	0.19693 (8)	0.0239 (2)
F21	0.90012 (16)	−0.05303 (7)	0.16606 (6)	0.03400 (19)
F22	1.19123 (16)	0.07597 (9)	0.20275 (7)	0.0406 (2)
F23	0.9135 (2)	0.07378 (10)	0.27244 (6)	0.0448 (3)
O60	0.67060 (14)	0.74754 (8)	0.03708 (5)	0.02022 (15)
H60A	0.610 (3)	0.8087 (16)	0.0389 (12)	0.030*
H60B	0.772 (3)	0.7646 (18)	0.0099 (11)	0.030*
O70	0.39841 (17)	0.91299 (10)	0.07357 (6)	0.02724 (18)
H70A	0.445 (3)	0.9930 (15)	0.0834 (13)	0.041*
H70B	0.280 (3)	0.910 (2)	0.0409 (12)	0.041*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.00763 (4)	0.01407 (5)	0.00712 (5)	0.00144 (4)	0.00104 (3)	−0.00097 (4)
O1	0.0096 (2)	0.0182 (3)	0.0093 (2)	0.0013 (2)	0.0018 (2)	−0.0021 (2)
O2	0.0100 (2)	0.0198 (3)	0.0096 (3)	0.0000 (2)	0.0017 (2)	−0.0025 (2)
N2	0.0125 (3)	0.0185 (3)	0.0100 (3)	0.0012 (3)	0.0013 (2)	−0.0022 (3)
N3	0.0099 (3)	0.0160 (3)	0.0113 (3)	0.0019 (2)	0.0018 (2)	−0.0007 (2)
N4	0.0135 (3)	0.0161 (3)	0.0113 (3)	0.0028 (3)	0.0015 (2)	0.0007 (2)
N5	0.0126 (3)	0.0190 (4)	0.0120 (3)	0.0049 (3)	0.0018 (2)	0.0009 (3)
C1	0.0097 (3)	0.0166 (4)	0.0087 (3)	0.0028 (3)	0.0008 (2)	−0.0008 (3)
N1	0.0126 (3)	0.0205 (4)	0.0097 (3)	0.0014 (3)	0.0018 (2)	−0.0034 (3)
C2	0.0095 (3)	0.0172 (4)	0.0099 (3)	0.0021 (3)	0.0009 (2)	−0.0006 (3)
O3	0.0106 (3)	0.0253 (4)	0.0129 (3)	0.0004 (2)	0.0040 (2)	−0.0018 (3)
C21	0.0218 (4)	0.0162 (4)	0.0168 (4)	−0.0007 (3)	0.0007 (3)	−0.0036 (3)
C31	0.0154 (4)	0.0191 (4)	0.0140 (4)	0.0018 (3)	0.0045 (3)	0.0024 (3)
C41	0.0225 (4)	0.0168 (4)	0.0162 (4)	0.0056 (3)	0.0027 (3)	−0.0013 (3)
C51	0.0181 (4)	0.0163 (4)	0.0167 (4)	0.0032 (3)	0.0037 (3)	0.0016 (3)
S1	0.01436 (9)	0.01734 (10)	0.00975 (8)	0.00448 (7)	0.00205 (7)	−0.00117 (7)
O11	0.0188 (3)	0.0222 (3)	0.0112 (3)	0.0066 (3)	0.0001 (2)	−0.0028 (2)
O12	0.0231 (4)	0.0263 (4)	0.0136 (3)	0.0012 (3)	0.0056 (3)	0.0006 (3)
O13	0.0157 (3)	0.0355 (5)	0.0163 (3)	0.0092 (3)	0.0016 (3)	−0.0010 (3)
C61	0.0292 (5)	0.0194 (5)	0.0201 (5)	0.0065 (4)	0.0001 (4)	−0.0037 (4)
F11	0.0446 (5)	0.0263 (4)	0.0277 (4)	0.0068 (4)	−0.0072 (4)	−0.0127 (3)
F12	0.0710 (7)	0.0226 (4)	0.0354 (5)	0.0033 (4)	0.0145 (5)	0.0070 (3)
F13	0.0336 (4)	0.0341 (5)	0.0500 (6)	0.0212 (4)	−0.0069 (4)	−0.0119 (4)
S2	0.01498 (9)	0.01595 (10)	0.01560 (10)	0.00039 (8)	0.00241 (8)	−0.00314 (8)
O21	0.0190 (3)	0.0155 (3)	0.0208 (3)	0.0009 (3)	−0.0001 (3)	−0.0042 (3)
O22	0.0151 (3)	0.0292 (4)	0.0337 (5)	−0.0004 (3)	0.0029 (3)	−0.0091 (4)
O23	0.0283 (4)	0.0289 (4)	0.0177 (4)	−0.0005 (3)	0.0079 (3)	−0.0045 (3)
C71	0.0288 (5)	0.0166 (4)	0.0246 (5)	0.0000 (4)	−0.0009 (4)	−0.0004 (4)
F21	0.0442 (5)	0.0145 (3)	0.0400 (5)	−0.0031 (3)	−0.0016 (4)	−0.0028 (3)
F22	0.0292 (4)	0.0259 (4)	0.0648 (7)	0.0070 (3)	−0.0132 (4)	0.0003 (4)
F23	0.0786 (8)	0.0339 (5)	0.0212 (4)	0.0030 (5)	0.0080 (4)	0.0055 (3)
O60	0.0193 (3)	0.0217 (4)	0.0185 (3)	−0.0015 (3)	0.0028 (3)	0.0000 (3)
O70	0.0294 (5)	0.0255 (4)	0.0255 (4)	0.0025 (4)	−0.0017 (3)	−0.0021 (3)

Geometric parameters (Å, º)

Co1—O1	1.9150 (7)	C21—H21B	0.9900
Co1—O2	1.9208 (7)	C31—C51	1.5094 (15)
Co1—N2	1.9280 (8)	C31—H31A	0.9900
Co1—N3	1.9389 (8)	C31—H31B	0.9900
Co1—N4	1.9510 (9)	C41—H41A	0.9900
Co1—N5	1.9575 (9)	C41—H41B	0.9900
C1—O1	1.2657 (11)	C51—H51A	0.9900
C1—N1	1.2979 (12)	C51—H51B	0.9900
C2—O2	1.2841 (11)	S1—O12	1.4360 (9)
C2—O3	1.2268 (11)	S1—O13	1.4442 (9)
N2—C21	1.4904 (15)	S1—O11	1.4545 (8)
N2—H2A	0.9200	S1—C61	1.8301 (12)
N2—H2B	0.9200	C61—F11	1.3285 (14)
N3—C31	1.4906 (13)	C61—F12	1.3306 (16)
N3—H3A	0.9200	C61—F13	1.3309 (16)
N3—H3B	0.9200	S2—O22	1.4428 (9)
N4—C41	1.4853 (13)	S2—O23	1.4429 (9)
N4—H4A	0.9200	S2—O21	1.4509 (8)
N4—H4B	0.9200	S2—C71	1.8271 (13)
N5—C51	1.4876 (14)	C71—F22	1.3267 (16)
N5—H5A	0.9200	C71—F21	1.3328 (14)
N5—H5B	0.9200	C71—F23	1.3344 (16)
C1—C2	1.5334 (13)	O60—H60A	0.803 (14)
N1—H1A	0.865 (13)	O60—H60B	0.809 (14)
N1—H1B	0.864 (13)	O70—H70A	0.867 (15)
C21—C41	1.5131 (16)	O70—H70B	0.878 (15)
C21—H21A	0.9900
O1—Co1—O2	85.49 (3)	N2—C21—C41	107.26 (8)
O1—Co1—N2	174.45 (3)	N2—C21—H21A	110.3
O2—Co1—N2	90.03 (3)	C41—C21—H21A	110.3
O1—Co1—N3	90.11 (3)	N2—C21—H21B	110.3
O2—Co1—N3	174.65 (3)	C41—C21—H21B	110.3
N2—Co1—N3	94.53 (4)	H21A—C21—H21B	108.5
O1—Co1—N4	90.20 (3)	N3—C31—C51	106.23 (8)
O2—Co1—N4	91.19 (4)	N3—C31—H31A	110.5
N2—Co1—N4	86.61 (4)	C51—C31—H31A	110.5
N3—Co1—N4	91.87 (4)	N3—C31—H31B	110.5
O1—Co1—N5	89.26 (3)	C51—C31—H31B	110.5
O2—Co1—N5	90.66 (4)	H31A—C31—H31B	108.7
N2—Co1—N5	94.08 (4)	N4—C41—C21	106.39 (9)
N3—Co1—N5	86.24 (4)	N4—C41—H41A	110.4
N4—Co1—N5	178.03 (4)	C21—C41—H41A	110.4
C1—O1—Co1	111.65 (6)	N4—C41—H41B	110.4
C2—O2—Co1	113.20 (6)	C21—C41—H41B	110.4
C21—N2—Co1	108.67 (6)	H41A—C41—H41B	108.6
C21—N2—H2A	110.0	N5—C51—C31	106.25 (8)
Co1—N2—H2A	110.0	N5—C51—H51A	110.5
C21—N2—H2B	110.0	C31—C51—H51A	110.5
Co1—N2—H2B	110.0	N5—C51—H51B	110.5
H2A—N2—H2B	108.3	C31—C51—H51B	110.5
C31—N3—Co1	109.46 (6)	H51A—C51—H51B	108.7
C31—N3—H3A	109.8	O12—S1—O13	115.24 (5)
Co1—N3—H3A	109.8	O12—S1—O11	115.92 (5)
C31—N3—H3B	109.8	O13—S1—O11	113.43 (5)
Co1—N3—H3B	109.8	O12—S1—C61	102.84 (6)
H3A—N3—H3B	108.2	O13—S1—C61	104.62 (6)
C41—N4—Co1	109.72 (6)	O11—S1—C61	102.48 (5)
C41—N4—H4A	109.7	F11—C61—F12	108.06 (11)
Co1—N4—H4A	109.7	F11—C61—F13	107.99 (10)
C41—N4—H4B	109.7	F12—C61—F13	108.13 (12)
Co1—N4—H4B	109.7	F11—C61—S1	111.31 (9)
H4A—N4—H4B	108.2	F12—C61—S1	111.45 (9)
C51—N5—Co1	107.98 (6)	F13—C61—S1	109.78 (9)
C51—N5—H5A	110.1	O22—S2—O23	115.00 (6)
Co1—N5—H5A	110.1	O22—S2—O21	114.17 (5)
C51—N5—H5B	110.1	O23—S2—O21	115.15 (5)
Co1—N5—H5B	110.1	O22—S2—C71	103.54 (6)
H5A—N5—H5B	108.4	O23—S2—C71	103.96 (6)
O1—C1—N1	122.93 (9)	O21—S2—C71	102.79 (5)
O1—C1—C2	116.93 (8)	F22—C71—F21	108.06 (11)
N1—C1—C2	120.14 (8)	F22—C71—F23	107.83 (12)
C1—N1—H1A	118.3 (11)	F21—C71—F23	107.94 (11)
C1—N1—H1B	119.4 (11)	F22—C71—S2	111.61 (9)
H1A—N1—H1B	122.2 (15)	F21—C71—S2	111.10 (9)
O3—C2—O2	126.11 (9)	F23—C71—S2	110.16 (9)
O3—C2—C1	121.14 (8)	H60A—O60—H60B	107.0 (19)
O2—C2—C1	112.73 (8)	H70A—O70—H70B	105 (2)
O1—C1—C2—O2	0.78 (13)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O60^i	0.87 (1)	1.95 (1)	2.8181 (12)	176 (2)
N1—H1B···O3^ii	0.86 (1)	2.06 (1)	2.8281 (11)	148 (2)
N2—H2A···O13	0.92	2.05	2.8890 (12)	150
N2—H2B···O11^iii	0.92	1.98	2.8947 (12)	170
N3—H3A···O11	0.92	2.15	3.0225 (11)	158
N3—H3B···O21^iv	0.92	2.20	2.9966 (12)	145
N4—H4A···O60	0.92	2.20	3.0504 (12)	153
N4—H4B···O3^iv	0.92	2.13	3.0313 (12)	167
N5—H5A···O21	0.92	2.11	3.0301 (12)	175
N5—H5B···O12^v	0.92	2.14	2.9543 (12)	147
O60—H60A···O70	0.80 (1)	1.95 (2)	2.7067 (14)	157 (2)
O60—H60B···O23^ii	0.81 (1)	2.13 (2)	2.9280 (13)	172 (2)
O70—H70A···O22^vi	0.87 (2)	2.08 (2)	2.8984 (14)	158 (2)
O70—H70B···O23^i	0.88 (2)	2.14 (2)	2.9730 (14)	158 (2)

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

(II) Λ(+)₅₇₈-bis(ethane-1,2-diamine)[oxamato(2-)- κ²N,O¹]cobalt(III) trifluoromethanesulfonate

Crystal data

[Co(C2HNO3)(C2H8N2)2](CF3SO3)	F(000) = 424
Mr = 415.25	Dx = 1.930 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 29543 reflections
a = 6.6398 (4) Å	θ = 1.7–50.0°
b = 11.6663 (8) Å	µ = 1.42 mm^−1
c = 9.2846 (10) Å	T = 122 K
β = 96.517 (11)°	Prism, orange red
V = 714.55 (10) Å^3	0.20 × 0.13 × 0.06 mm
Z = 2

Data collection

Nonius KappaCCD area-detector diffractometer	8895 independent reflections
Radiation source: fine-focus sealed tube	8611 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
ω and ϕ scans	θmax = 40.1°, θmin = 2.8°
Absorption correction: integration Gaussian integration (Coppens, 1970)	h = −12→11
Tmin = 0.714, Tmax = 0.919	k = −21→21
35436 measured reflections	l = −16→16

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)] = 0.019	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.047	w = 1/[σ^2(Fo^2) + (0.0149P)^2 + 0.1524P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.002
8895 reflections	Δρmax = 0.48 e Å^−3
211 parameters	Δρmin = −0.75 e Å^−3
1 restraint	Absolute structure: Flack (1983), with 4283 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.000 (4)

Special details

Experimental. General: Optical rotations were measured on a Perkin–Elmer P22 polarimeter (±0.002°) in a 1 dm quartz cell; within experimental error all listed values for specific rotations ([α]_λ, in units of 10^-1 ° cm² g^-1) of the chiral product did not change on further recrystallization, and this was taken as evidence of optical purity. Synthesis of Λ(+)₅₇₈Co(en)₂(O₂CCONH-N,O)](O₃SCF₃) (II): A solution of Λ(+)₅₇₈Co(en)₂(O₂CCONH-N,O)]Cl.H₂O (0.25 g) (Grøndahl, Hammershøi et al., 1995) and KO₃SCF₃ (0.50 g) in hot water (5 ml, 50 °C) was slowly cooled to 25 °C whereby orange–red crystals (0.28 g) deposited. These were recrystallized from boiling water (15 ml) to produce crystals (0.10 g) of crystallographic quality. [α]₅₇₈ 800, [α]₅₄₆ 1280, [α]₄₃₆ -1660, [α]₃₆₄ -1500, [α]₃₁₃ -1760; C₇H₁₇CoF₃N₅O₆S (415.17): calcd. C 20.25, H 4.13, Co 14.19, N 16.87; found C 20.1, H 4.0, Co 14.1, N 16.7.

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	0.174374 (13)	0.001318 (8)	0.537607 (10)	0.00677 (2)
N1	0.44856 (9)	−0.02313 (5)	0.61600 (7)	0.00922 (9)
H1	0.527 (2)	0.0286 (13)	0.6563 (16)	0.011*
N2	−0.10023 (9)	0.00975 (7)	0.43266 (7)	0.00985 (9)
H2A	−0.1733	−0.0542	0.4524	0.012*
H2B	−0.1665	0.0734	0.4621	0.012*
N3	0.16535 (11)	0.15728 (6)	0.61048 (8)	0.01126 (10)
H3A	0.2939	0.1815	0.6443	0.014*
H3B	0.1140	0.2058	0.5372	0.014*
N4	0.26676 (10)	0.05468 (6)	0.35651 (7)	0.01059 (10)
H4A	0.3587	0.1132	0.3757	0.013*
H4B	0.3305	−0.0043	0.3140	0.013*
N5	0.07523 (10)	−0.04527 (6)	0.72081 (7)	0.00990 (9)
H5A	−0.0562	−0.0710	0.7030	0.012*
H5B	0.1538	−0.1041	0.7623	0.012*
O1	0.70271 (8)	−0.15963 (5)	0.61593 (7)	0.01192 (9)
O2	0.18307 (8)	−0.15761 (5)	0.48554 (6)	0.00942 (8)
O3	0.38798 (9)	−0.30953 (5)	0.51618 (7)	0.01139 (9)
C2	0.35527 (10)	−0.20579 (6)	0.52516 (8)	0.00804 (9)
C1	0.52292 (10)	−0.12468 (6)	0.59115 (8)	0.00829 (10)
C21	−0.08354 (11)	0.01674 (7)	0.27406 (8)	0.01256 (12)
H21A	−0.2104	0.0476	0.2219	0.015*
H21B	−0.0585	−0.0602	0.2348	0.015*
C31	0.03376 (12)	0.15925 (7)	0.72986 (9)	0.01249 (11)
H31A	−0.1109	0.1582	0.6898	0.015*
H31B	0.0595	0.2295	0.7889	0.015*
C41	0.09210 (13)	0.09580 (7)	0.25582 (9)	0.01359 (12)
H41A	0.1252	0.0936	0.1545	0.016*
H41B	0.0576	0.1756	0.2796	0.016*
C51	0.08452 (13)	0.05417 (7)	0.82150 (9)	0.01278 (11)
H51A	0.2219	0.0612	0.8746	0.015*
H51B	−0.0142	0.0445	0.8928	0.015*
S1	0.58537 (3)	0.297614 (17)	0.86318 (2)	0.01214 (3)
O11	0.57971 (13)	0.17529 (6)	0.84105 (9)	0.02082 (13)
O12	0.46085 (12)	0.36143 (7)	0.75216 (8)	0.02138 (13)
O13	0.78102 (11)	0.34777 (8)	0.90628 (10)	0.02459 (15)
C11	0.45637 (13)	0.31675 (8)	1.02577 (9)	0.01527 (13)
F11	0.44080 (12)	0.42713 (6)	1.05828 (8)	0.02451 (13)
F12	0.56277 (12)	0.26538 (7)	1.13906 (7)	0.02750 (14)
F13	0.27067 (11)	0.27239 (8)	1.01103 (8)	0.02872 (15)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.00602 (3)	0.00596 (3)	0.00827 (3)	0.00011 (3)	0.00057 (2)	−0.00038 (3)
N1	0.0078 (2)	0.0080 (2)	0.0116 (2)	−0.00110 (15)	−0.00006 (17)	−0.00100 (17)
N2	0.00806 (18)	0.0097 (2)	0.0117 (2)	0.00078 (19)	0.00079 (16)	0.0005 (2)
N3	0.0134 (2)	0.0085 (2)	0.0118 (2)	−0.00030 (19)	0.00118 (19)	−0.00099 (19)
N4	0.0104 (2)	0.0111 (2)	0.0103 (2)	−0.00168 (19)	0.00144 (18)	−0.00015 (19)
N5	0.0090 (2)	0.0100 (2)	0.0106 (2)	0.00011 (17)	0.00080 (18)	0.00027 (18)
O1	0.00647 (19)	0.0122 (2)	0.0167 (2)	0.00086 (16)	−0.00049 (17)	−0.00014 (19)
O2	0.00674 (18)	0.00807 (18)	0.0131 (2)	0.00059 (15)	−0.00046 (15)	−0.00130 (16)
O3	0.0102 (2)	0.00708 (19)	0.0165 (2)	0.00027 (15)	−0.00019 (17)	−0.00053 (17)
C2	0.0070 (2)	0.0076 (2)	0.0096 (2)	−0.00017 (18)	0.00113 (18)	0.00002 (19)
C1	0.0069 (2)	0.0082 (2)	0.0096 (2)	−0.00082 (18)	0.00057 (18)	0.00048 (19)
C21	0.0113 (2)	0.0146 (3)	0.0112 (2)	−0.0018 (2)	−0.0015 (2)	−0.0002 (2)
C31	0.0134 (3)	0.0120 (3)	0.0120 (3)	0.0034 (2)	0.0009 (2)	−0.0027 (2)
C41	0.0145 (3)	0.0141 (3)	0.0116 (3)	−0.0027 (2)	−0.0008 (2)	0.0029 (2)
C51	0.0144 (3)	0.0140 (3)	0.0098 (3)	0.0013 (2)	0.0009 (2)	−0.0012 (2)
S1	0.01220 (7)	0.01227 (7)	0.01242 (7)	−0.00151 (6)	0.00341 (6)	−0.00148 (6)
O11	0.0303 (4)	0.0130 (2)	0.0203 (3)	−0.0022 (2)	0.0077 (3)	−0.0046 (2)
O12	0.0239 (3)	0.0262 (3)	0.0148 (3)	0.0068 (3)	0.0051 (2)	0.0051 (2)
O13	0.0143 (3)	0.0281 (4)	0.0323 (4)	−0.0077 (3)	0.0065 (3)	−0.0096 (3)
C11	0.0166 (3)	0.0181 (3)	0.0114 (3)	−0.0033 (3)	0.0026 (2)	−0.0032 (2)
F11	0.0309 (3)	0.0201 (3)	0.0236 (3)	0.0017 (2)	0.0079 (3)	−0.0086 (2)
F12	0.0369 (4)	0.0331 (4)	0.0118 (2)	0.0070 (3)	−0.0004 (2)	0.0012 (2)
F13	0.0209 (3)	0.0449 (4)	0.0222 (3)	−0.0162 (3)	0.0101 (2)	−0.0094 (3)

Geometric parameters (Å, º)

Co1—N1	1.9039 (7)	N5—H5A	0.9200
Co1—O2	1.9185 (6)	N5—H5B	0.9200
Co1—N2	1.9699 (6)	C2—C1	1.5347 (10)
Co1—N3	1.9444 (7)	C21—C41	1.5114 (11)
Co1—N4	1.9558 (7)	C21—H21A	0.9900
Co1—N5	1.9689 (7)	C21—H21B	0.9900
C1—O1	1.2578 (9)	C31—C51	1.5084 (12)
C1—N1	1.3139 (9)	C31—H31A	0.9900
C2—O2	1.2896 (9)	C31—H31B	0.9900
C2—O3	1.2340 (9)	C41—H41A	0.9900
N1—H1	0.856 (15)	C41—H41B	0.9900
N2—C21	1.4915 (10)	C51—H51A	0.9900
N2—H2A	0.9200	C51—H51B	0.9900
N2—H2B	0.9200	S1—O13	1.4395 (8)
N3—C31	1.4874 (11)	S1—O11	1.4416 (8)
N3—H3A	0.9200	S1—O12	1.4516 (8)
N3—H3B	0.9200	S1—C11	1.8320 (9)
N4—C41	1.4843 (11)	C11—F11	1.3293 (11)
N4—H4A	0.9200	C11—F13	1.3299 (11)
N4—H4B	0.9200	C11—F12	1.3402 (11)
N5—C51	1.4868 (11)
N1—Co1—O2	84.07 (3)	O3—C2—O2	124.42 (7)
N1—Co1—N3	94.19 (3)	O3—C2—C1	120.43 (6)
O2—Co1—N3	174.22 (3)	O2—C2—C1	115.12 (6)
N1—Co1—N4	89.81 (3)	O1—C1—N1	128.90 (7)
O2—Co1—N4	93.99 (3)	O1—C1—C2	120.24 (6)
N3—Co1—N4	91.51 (3)	N1—C1—C2	110.86 (6)
N1—Co1—N5	91.57 (3)	N2—C21—C41	106.78 (6)
O2—Co1—N5	88.48 (3)	N2—C21—H21A	110.4
N3—Co1—N5	86.05 (3)	C41—C21—H21A	110.4
N4—Co1—N5	177.28 (3)	N2—C21—H21B	110.4
N1—Co1—N2	171.06 (3)	C41—C21—H21B	110.4
O2—Co1—N2	88.64 (3)	H21A—C21—H21B	108.6
N3—Co1—N2	93.56 (3)	N3—C31—C51	107.17 (6)
N4—Co1—N2	85.52 (3)	N3—C31—H31A	110.3
N5—Co1—N2	93.42 (3)	C51—C31—H31A	110.3
C1—N1—Co1	115.47 (5)	N3—C31—H31B	110.3
C1—N1—H1	119.3 (10)	C51—C31—H31B	110.3
Co1—N1—H1	124.9 (10)	H31A—C31—H31B	108.5
C21—N2—Co1	108.83 (4)	N4—C41—C21	106.85 (6)
C21—N2—H2A	109.9	N4—C41—H41A	110.4
Co1—N2—H2A	109.9	C21—C41—H41A	110.4
C21—N2—H2B	109.9	N4—C41—H41B	110.4
Co1—N2—H2B	109.9	C21—C41—H41B	110.4
H2A—N2—H2B	108.3	H41A—C41—H41B	108.6
C31—N3—Co1	108.52 (5)	N5—C51—C31	106.78 (6)
C31—N3—H3A	110.0	N5—C51—H51A	110.4
Co1—N3—H3A	110.0	C31—C51—H51A	110.4
C31—N3—H3B	110.0	N5—C51—H51B	110.4
Co1—N3—H3B	110.0	C31—C51—H51B	110.4
H3A—N3—H3B	108.4	H51A—C51—H51B	108.6
C41—N4—Co1	110.21 (5)	O13—S1—O11	116.75 (5)
C41—N4—H4A	109.6	O13—S1—O12	114.35 (6)
Co1—N4—H4A	109.6	O11—S1—O12	113.76 (5)
C41—N4—H4B	109.6	O13—S1—C11	102.30 (5)
Co1—N4—H4B	109.6	O11—S1—C11	103.36 (4)
H4A—N4—H4B	108.1	O12—S1—C11	103.93 (4)
C51—N5—Co1	109.50 (5)	F11—C11—F13	107.78 (8)
C51—N5—H5A	109.8	F11—C11—F12	107.61 (7)
Co1—N5—H5A	109.8	F13—C11—F12	107.87 (8)
C51—N5—H5B	109.8	F11—C11—S1	111.15 (6)
Co1—N5—H5B	109.8	F13—C11—S1	112.49 (6)
H5A—N5—H5B	108.2	F12—C11—S1	109.77 (6)
C2—O2—Co1	113.60 (5)
N1—C1—C2—O2	10.18 (9)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O11	0.856 (15)	2.421 (15)	3.1733 (10)	147.1 (12)
N2—H2A···O1^i	0.92	2.19	3.0029 (9)	148
N2—H2B···O3^ii	0.92	2.03	2.9202 (9)	161
N3—H3A···O11	0.92	2.48	3.2955 (12)	148
N3—H3A···O12	0.92	2.53	3.2660 (11)	138
N3—H3B···O1^iii	0.92	2.52	3.1887 (10)	130
N3—H3B···O2^ii	0.92	2.53	3.2160 (9)	132
N4—H4A···O3^iii	0.92	2.07	2.9236 (9)	155
N4—H4B···O12^iv	0.92	2.22	3.1282 (11)	168
N5—H5A···O1^i	0.92	2.00	2.8809 (9)	160
N5—H5B···F12^v	0.92	2.51	3.4117 (11)	166

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