Hexa­kis­(prop-2-enamide)­copper(II) bis­(perchlorate) and hexa­kis­(prop-2-enamide)­manganese(II) bis­(per­chlorate)

The structures of [Cu(AA)₆](ClO₄)₂, (I), and [Mn(AA)₆](ClO₄)₂, (II) (AA is acryl­amide, also known as prop-2-en­amide; C₃H₅NO), display both intra- and inter­molecular N—H...O hydrogen bonding. A three-dimensional network is propagated via the perchlorate counter-ions. There are two crystallographically independent mol­ecules in the copper complex, with the most significant difference between them being the conformation of one symmetry-related pair of AA ligands which are in the unusual syn conformation. The copper complex exhibits syn/anti disorder of the =CH₂ group in one pair of symmetry-related AA ligands. The Cu^II and Mn^II centres are both situated on centres of inversion. The copper complex cation has octa­hedral coordination geometry with typical Jahn–Teller distortions.

S1. Comment

Acrylamide (AA) is a versatile nucleophile containing olefinic, carbonyl and amine groups. Consequently, AA can form a variety of metal complexes (Reedijk, 1971; Girma et al., 2005a), predominantly coordinating through the carbonyl O atom, with the monodentate geometries of divalent transition metals being octahedral for [M(AA)₆] species. [MX₂(AA)₄] species also adopt an octahedral geometry, with counterions or, in some cases, water molecules, occupying the ancillary coordinating positions (Girma et al., 2005a,b,c,d, 2006a,b). As yet, the copper(II) and manganese(II) AA complexes, (I) and (II), have not been published and both structures are described herein.

AA has sparked worldwide debate within food safety circles due to its discovery within thermally treated foodstuffs (Rosen & Hellenas, 2002; Tareke et al., 2002; Mottram et al., 2002). It has been classified as a probable human carcinogen by the International Agency for Research on Cancer (1994) and is implicated in tumour formation (Rice, 2005), neurotoxicity (Chen et al., 2009) and mutagenesis (Martins et al., 2007; Baum et al. 2005). While AA and its metabolites, especially glycidamide, have been the subject of intensive investigations, the possibility of any of these species forming metal complexes in vivo through interaction with either free metal ions or metal cations within metalloenzymes has yet to be investigated. Given the relative ease with which metal adducts of AA are formed, along with their apparent water solubility, makes us believe that compounds of this type may be worthy of further investigation from both synthetic and toxicological standpoints.

The crystal structure of (I) consists of two crystallographically independent Cu^II centres, both situated on centres of inversion (Figs. 1 and 2). The Cu—O distances in the two molecules occur in two distinct ranges, one short [1.9340 (10)–1.9736 (10) Å] and the other long [2.4534 (10)–2.5241 (10) Å]. This is typical of Jahn–Teller distortions observed in d⁹ metal centres. Copper centre Cu2 has the greater spread of Cu—O distances but it is the other crystallographically independent molecule containing Cu1 which has disorder in the ═CH₂ group. In this disordered group there are two possible positions for the ═CH₂ group, the major component being occupied 68% of the time. The major component has the ═CH₂ group anti with respect to NH₂, whereas the minor component is of the unusual syn conformation. In the other crystallographically independent molecule, one pair of AA ligands exists solely in this syn form. None of the AA complexes found in the May 2010 version of the Cambridge Structural Database (Allen, 2002) have the syn form. Several ═CH₂ C-atom displacement ellipsoids are rather anisotropic, but there is no residual electron density greater than 0.5 e Å^-3 associated with the AA atoms. One perchlorate ion is noticeably disordered and was modelled with two O4 orientations, yet four of the eight O-atom positions take part in hydrogen bonding. Three of the four the O atoms in the other ordered perchlorate take part in hydrogen bonding.

The manganese complex, (II), also exhibits the same combination of intra- and intermolecular N—H···O hydrogen bonding as seen in the copper species. The Mn^II centre also lies on a centre of inversion but with the six Mn—O bond lengths being in a tighter range [2.1357 (9)–2.1976 (9) Å], as would be expected for an Mn^II ion. All AA ligands are in the usual anti conformation (Fig. 3).

All amine H atoms of (I) and (II) participate in hydrogen bonding, either intermolecularly with perchlorate O atoms to form a three-dimensional network, or intramolecularly with neighbouring AA O atoms. The N—H···O hydrogen bonds involving amides bound to the Cu2 centre of (I) are closer to linearity than those emanating from the molecule containing Cu1 (see Table 1). In (I), (II), and the cobalt (Girma et al., 2005b) and iron (Girma et al., 2006a) hexaacrylamide-O analogues, the intermolecular hydrogen bonds all involve the counterion. There are no direct complex-to-complex contacts in any of these four species. In (I) and (II), only four of the six amine groups take part in intramolecular hydrogen bonding (see Figs. 1, 2 and 3). These form six-membered rings with the graph-set notation S¹₁(6) (Bernstein et al., 1995). The H atoms of the other two amines take part in intermolecular hydrogen bonding only. This is also the case in the Fe^II analogue (Girma et al. 2006b), while in the Co^II, Ni^II and Zn^II structures (Girma et al. 2006b) all amines are involved in intermolecular hydrogen bonding. The solely intermolecularly hydrogen-bonded ligand (and its symmetry equivalent) in (I) have the longest Cu—O distance at both Cu centres, whereas conversely in (II) the shortest Mn—O bonds are made by the solely intermolecularly hydrogen-bonded ligand.

The three shortest N···O distances are all intramolecular hydrogen bonds in (I), but there is no such distinction in (II). Two pairs of O atoms in (I) do not participate in hydrogen bonding (O3, O4 and their symmetry equivalents), whereas atoms O2 and O6 make bifurcated hydrogen bonds with neighbouring amine groups (see Figs. 1 and 2). The pattern in (II) differs subtly in that although one pair of O atoms (O3 and its symmetry equivalent) is not involved in N—H···O hydrogen bonding, no bifurcated hydrogen bonds are made by the other O atoms. The torsion angles M—O—C—N in (I) and (II) vary such that when this intramolecular hydrogen bond is present the range of values is 3.33 (19)–19.9 (2)°, but when the amine does not make this type of bond the torsion angle is between -80.88 (16) and -107.35 (14)°. The Fe^II species with the perchlorate counterion (Girma et al., 2006b) has a similar combination of intra- and intermolecular hydrogen-bonding patterns as the Cu^II and Mn^II structures described here. However, in the Fe^II analogue with µ₂-oxo-hexachloridodiiron(III) as the counterion (Girma et al., 2008), the amides all have intramolecular N—H..O contacts, although in addition two NH₂ groups make intermolecular contacts with the bridging oxo atom in the counterion.

The intermolecular hydrogen bonding in (I) and (II) is extensive and propagates in three dimensions (see Figs. 4 and 5 and Tables 1 and 2). The N—H···O links joining the complexes to the counterions form a series of rings. One type of ring [R²₄(20)] involves one perchlorate O atom in a bifurcated hydrogen bond as the link between complexes, and another requires two O atoms in the counterion to form the ring [R⁴₄(24)]. Both these rings are over centres of inversion and involve two identical Cu^II centres. Complexes containing Cu1 and Cu2 are joined to form dimers via perchlorate O atoms, with graph-set notation D³₃(14). In (II), the intermolecular hydrogen bonding differs from (I) in that chains are more apparent than rings. The smallest ring which includes the metal centres has graph-set notation R⁸₈(36), where four manganese complexes are needed to form a ring with four perchlorates.

In conclusion, metal complexes of AA display a significant degree of variation in intramolecular hydrogen bonding, even between chemically identical molecules. Such variation increases the capacity for yet more diversity in intermolecular interactions for complexes containing relatively simple ligands.

S2. Experimental

[Cu(AA)₆](ClO₄)₂, (I), was prepared as follows. To a solution of copper(II) perchlorate hexahydrate (1.0 g, 2.7 mmol) in a 50:50 mixture of acetonitrile and triethylorthoformate (14 ml) was added acrylamide (1.15 g, 16.2 mmol). The resulting blue solution was stirred at room temperature for 1 h and then allowed to stand for 1 week, resulting in the formation of the product as blue crystals (yield 1.17 g, 63%). Analysis, calculated: C 31.38, H 4.39, N 12.20, Cl 10.29%; found: C 31.38, H 4.36, N 12.04, Cl 10.04%. Spectroscopic analysis: IR (KBr, ν, cm^-1): 3335, 3196, 1667, 1429, 1353, 1281, 1089, 985, 811, 626, 508; Raman (cm^-1): 3103, 3033, 3011, 2923, 1682, 1637, 1588, 1435, 1284, 1144, 1052, 959, 941, 844, 812, 627, 506, 462, 303, 126, 98. Solubility: water. UV–Vis: λ_d-d = 808 nm, ε = 12 dm³ mol^-1 cm^-1.

[Mn(AA)₆](ClO₄)₂, (II), was prepared as follows. To a solution of manganese(II) perchlorate hexahydrate (1.0 g, 2.8 mmol) in a 50:50 mixture of acetonitrile and triethylorthoformate (14 ml) was added acrylamide (1.17 g, 16.6 mmol). The resulting colourless solution was stirred at room temperature for 1 h and then allowed to stand for 1 week, resulting in the formation of the product as colourless crystals which were stored at 253 K (yield 1.21 g, 64%). Analysis, calculated: C 31.78, H 4.44, N 12.35, Cl 10.42%; found: C 29.68, H 4.74, N 11.05, Cl 7.65. Spectroscopic analysis: IR (KBr, ν, cm^-1): 3333, 3189, 2745, 1665, 1621, 1589, 1436, 1436, 1360, 1282, 1105, 979, 811, 629; Raman (cm^-1): 3363, 2932, 1667, 1606, 1459, 1324, 1122, 933, 842, 764, 624, 458, 134. Solubility: water.

S3. Refinement

In (I), the CH₂ group in one of the unique AA ligands was disordered through an approximately 180° rotation about the C21—C22 bond, with relative occupancies of the two orientations of 0.644 (5) and 0.356 (5), and these were labelled as C23B and C23C, respectively. The displacement parameters of the following atoms were restrained using rigid-bond restraints (DELU; Sheldrick, 2008), namely (C31/C32/C33), (C41/C42/C43) and (C21/C22/C23C/C23B) or similarity restraints (SIMU) (C22/C23C/C23B), (C32/C33) and (C42/C43); atoms in parentheses were restrained together. All Cl—O and O···O distances in both perchlorate anions were restrained to be similar within a standard deviation of 0.02 Å. One perchlorate anion has disordered O atoms and two orientations were modelled for all four O atoms with occupancies of 0.74 (2) for the major component. For both (I) and (II), all amine H atoms were located in difference Fourier maps. Their coordinates were refined in (I), with N—H distances restrained to 0.85 (2) Å, but fixed in geometrically idealized positions in (II) and treated as riding on the parent N atom, with U_iso(H) = 1.2U_eq(N). The positions of all H atoms bound to C atoms were calculated and constrained to idealized geometries, with C—H = 0.95? and U_iso(H) = 1.2U_eq(C).

Computing details

For both compounds, data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. A perspective view of one of the crystallographically independent molecules in (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. The suffix A denotes the symmetry operation (-x + 2, -y + 1, -z). Counterions and the minor component of disorder in the ═CH2 fragment have been omitted for clarity. H atoms are shown as small spheres of arbitrary radii. Intramolecular hydrogen bonds are shown as dashed lines.
	Fig. 2. A perspective view of the second crystallographically independent molecule of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. The suffix A denotes the symmetry operation (-x, -y + 2, -z + 1). H atoms are shown as small spheres of arbitrary radii. Intramolecular hydrogen bonds are shown as dashed lines.
	Fig. 3. A perspective view of (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. The suffix A denotes the symmetry operation (-x, -y, -z + 2). H atoms are shown as small spheres of arbitrary radii. Intramolecular hydrogen bonds are shown as dashed lines.
	Fig. 4. The hydrogen bonding of (I), showing both intra- and intermolecular hydrogen bonds (dashed lines).
	Fig. 5. The hydrogen bonding of (II), showing both intra- and intermolecular hydrogen bonds (dashed lines).

(I) Hexakis(prop-2-enamide)copper(II) bis(perchlorate)

Crystal data

[Cu(C3H5NO)6](ClO4)2	Z = 2
Mr = 688.92	F(000) = 710
Triclinic, P1	Dx = 1.554 Mg m^−3
a = 8.4577 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.8762 (6) Å	Cell parameters from 9880 reflections
c = 17.7889 (11) Å	θ = 2.3–30.8°
α = 88.392 (3)°	µ = 1.00 mm^−1
β = 85.871 (3)°	T = 100 K
γ = 83.690 (3)°	Block, blue
V = 1472.77 (15) Å^3	0.80 × 0.58 × 0.32 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	9130 independent reflections
Radiation source: fine-focus sealed tube	7503 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
ϕ and ω scans	θmax = 31.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −12→10
Tmin = 0.503, Tmax = 0.741	k = −13→14
34176 measured reflections	l = −25→25

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.081	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0404P)^2 + 0.555P] where P = (Fo^2 + 2Fc^2)/3
9130 reflections	(Δ/σ)max < 0.001
457 parameters	Δρmax = 0.52 e Å^−3
165 restraints	Δρmin = −0.58 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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)
Cu1	0.0000	0.5000	0.0000	0.01213 (6)
Cu2	0.0000	1.0000	0.5000	0.01163 (6)
O1	−0.01583 (11)	0.57494 (10)	0.10228 (5)	0.01557 (19)
N1	−0.25570 (15)	0.70257 (14)	0.10231 (7)	0.0175 (2)
H1A	−0.283 (2)	0.6586 (17)	0.0667 (9)	0.021*
H1B	−0.321 (2)	0.7630 (16)	0.1215 (10)	0.021*
O2	0.28733 (12)	0.51742 (11)	−0.00127 (6)	0.0176 (2)
N2	0.36002 (17)	0.64070 (16)	−0.10357 (8)	0.0261 (3)
H2A	0.342 (2)	0.5808 (18)	−0.1327 (10)	0.031*
H2B	0.392 (2)	0.7125 (17)	−0.1213 (11)	0.031*
O3	0.02512 (12)	0.31633 (10)	0.04194 (5)	0.0163 (2)
N3	0.22902 (16)	0.32158 (15)	0.11740 (8)	0.0233 (3)
H3B	0.250 (2)	0.3964 (16)	0.0993 (11)	0.028*
H3A	0.284 (2)	0.2833 (19)	0.1520 (10)	0.028*
O4	0.08485 (11)	0.81076 (10)	0.49090 (5)	0.01515 (19)
N4	0.25499 (15)	0.81301 (13)	0.38591 (7)	0.0164 (2)
H4B	0.219 (2)	0.8935 (15)	0.3752 (10)	0.020*
H4A	0.3291 (19)	0.7717 (17)	0.3596 (9)	0.020*
O5	0.21430 (11)	1.05827 (10)	0.48963 (5)	0.01432 (19)
N5	0.22285 (15)	1.15928 (13)	0.60198 (7)	0.0174 (2)
H5A	0.155 (2)	1.1113 (17)	0.6238 (10)	0.021*
H5B	0.276 (2)	1.2038 (17)	0.6283 (9)	0.021*
O6	−0.00145 (12)	0.96692 (10)	0.64125 (6)	0.0168 (2)
N6	0.15985 (15)	0.80137 (13)	0.69553 (7)	0.0190 (2)
H6B	0.232 (2)	0.8542 (17)	0.7005 (10)	0.023*
H6A	0.176 (2)	0.7193 (15)	0.7118 (10)	0.023*
C11	−0.11579 (16)	0.66668 (14)	0.13028 (7)	0.0145 (3)
C12	−0.08098 (18)	0.74078 (15)	0.19716 (8)	0.0199 (3)
H12	−0.1602	0.8075	0.2181	0.024*
C13	0.0551 (2)	0.71793 (19)	0.22867 (10)	0.0328 (4)
H13A	0.1358	0.6516	0.2085	0.039*
H13B	0.0730	0.7677	0.2716	0.039*
C21	0.33517 (16)	0.62348 (16)	−0.03001 (8)	0.0186 (3)
C22	0.3658 (2)	0.7376 (2)	0.01783 (12)	0.0365 (4)
H22	0.4079	0.8135	−0.0072	0.044*	0.644 (5)
H22A	0.3582	0.7116	0.0697	0.044*	0.356 (5)
C23B	0.3420 (3)	0.7429 (3)	0.08581 (16)	0.0351 (8)	0.644 (5)
H23A	0.3530	0.8245	0.1110	0.042*	0.644 (5)
H23B	0.3123	0.6653	0.1139	0.042*	0.644 (5)
C23C	0.3959 (7)	0.8480 (5)	0.0105 (3)	0.0331 (14)	0.356 (5)
H23C	0.3940	0.9037	0.0533	0.040*	0.356 (5)
H23D	0.4229	0.8836	−0.0383	0.040*	0.356 (5)
C31	0.11260 (17)	0.26269 (15)	0.09149 (8)	0.0180 (3)
C32	0.0857 (2)	0.12560 (18)	0.12153 (11)	0.0316 (4)
H32	0.1477	0.0857	0.1605	0.038*
C33	−0.0222 (3)	0.0588 (2)	0.09509 (17)	0.0606 (8)
H33A	−0.0844	0.0982	0.0561	0.073*
H33B	−0.0385	−0.0294	0.1148	0.073*
C41	0.19121 (16)	0.75233 (14)	0.44610 (8)	0.0145 (3)
C42	0.24768 (19)	0.60784 (15)	0.46059 (9)	0.0248 (3)
H42	0.3269	0.5617	0.4271	0.030*
C43	0.1885 (3)	0.54265 (19)	0.51990 (13)	0.0512 (6)
H43B	0.1093	0.5886	0.5535	0.061*
H43A	0.2251	0.4496	0.5291	0.061*
C51	0.27699 (16)	1.13482 (13)	0.53165 (8)	0.0133 (2)
C52	0.41753 (16)	1.20190 (15)	0.50235 (8)	0.0171 (3)
H52	0.4541	1.2693	0.5319	0.021*
C53	0.49382 (18)	1.17150 (17)	0.43678 (9)	0.0229 (3)
H53A	0.4590	1.1044	0.4065	0.027*
H53B	0.5837	1.2167	0.4198	0.027*
C61	0.02339 (16)	0.84728 (14)	0.66649 (7)	0.0148 (3)
C62	−0.10360 (18)	0.75546 (16)	0.66486 (8)	0.0200 (3)
H62	−0.1928	0.7865	0.6371	0.024*
C63	−0.1044 (2)	0.63500 (17)	0.69831 (10)	0.0258 (3)
H63B	−0.0177	0.5996	0.7268	0.031*
H63A	−0.1916	0.5834	0.6940	0.031*
Cl1	0.50368 (4)	0.02522 (3)	0.220890 (18)	0.01470 (7)
Cl2	0.56337 (4)	0.53537 (3)	0.28424 (2)	0.01881 (8)
O1S	0.47834 (13)	0.17200 (11)	0.21175 (6)	0.0239 (2)
O2S	0.61844 (14)	−0.00887 (11)	0.27602 (7)	0.0266 (3)
O3S	0.35713 (14)	−0.02654 (13)	0.24450 (8)	0.0318 (3)
O4S	0.56577 (16)	−0.03050 (14)	0.14941 (7)	0.0355 (3)
O5S	0.4498 (7)	0.5492 (7)	0.2255 (3)	0.0399 (10)	0.74 (2)
O6S	0.5626 (10)	0.6639 (6)	0.3175 (4)	0.0296 (10)	0.74 (2)
O7S	0.5114 (6)	0.4371 (3)	0.3383 (3)	0.0354 (9)	0.74 (2)
O8S	0.7178 (7)	0.4874 (9)	0.2500 (5)	0.0212 (14)	0.74 (2)
O5T	0.581 (2)	0.6834 (17)	0.3027 (12)	0.025 (3)	0.26 (2)
O6T	0.569 (3)	0.466 (2)	0.3584 (11)	0.060 (7)	0.26 (2)
O7T	0.4375 (15)	0.5255 (19)	0.2486 (16)	0.045 (4)	0.26 (2)
O8T	0.717 (2)	0.491 (3)	0.2429 (12)	0.019 (4)	0.26 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.01253 (11)	0.01234 (11)	0.01078 (10)	0.00158 (9)	−0.00071 (8)	0.00122 (8)
Cu2	0.00883 (10)	0.01072 (11)	0.01514 (11)	0.00036 (8)	−0.00115 (8)	−0.00126 (8)
O1	0.0150 (5)	0.0165 (5)	0.0143 (4)	0.0027 (4)	−0.0015 (4)	−0.0004 (4)
N1	0.0137 (5)	0.0214 (6)	0.0166 (6)	0.0029 (5)	−0.0018 (4)	−0.0048 (5)
O2	0.0144 (5)	0.0211 (5)	0.0175 (5)	−0.0028 (4)	−0.0009 (4)	−0.0006 (4)
N2	0.0273 (7)	0.0273 (7)	0.0241 (7)	−0.0088 (6)	0.0020 (5)	0.0030 (6)
O3	0.0176 (5)	0.0147 (5)	0.0161 (5)	0.0011 (4)	−0.0024 (4)	0.0033 (4)
N3	0.0222 (6)	0.0243 (7)	0.0229 (7)	0.0010 (5)	−0.0071 (5)	0.0071 (5)
O4	0.0131 (4)	0.0125 (4)	0.0191 (5)	0.0010 (4)	0.0009 (4)	−0.0009 (4)
N4	0.0154 (6)	0.0162 (6)	0.0165 (6)	0.0025 (5)	0.0003 (4)	−0.0019 (5)
O5	0.0110 (4)	0.0157 (5)	0.0163 (5)	−0.0013 (4)	−0.0013 (3)	−0.0015 (4)
N5	0.0179 (6)	0.0203 (6)	0.0154 (6)	−0.0065 (5)	−0.0031 (4)	−0.0003 (5)
O6	0.0163 (5)	0.0154 (5)	0.0187 (5)	−0.0014 (4)	−0.0024 (4)	0.0030 (4)
N6	0.0157 (6)	0.0161 (6)	0.0254 (6)	−0.0020 (5)	−0.0055 (5)	0.0037 (5)
C11	0.0159 (6)	0.0139 (6)	0.0135 (6)	−0.0012 (5)	−0.0004 (5)	0.0018 (5)
C12	0.0226 (7)	0.0198 (7)	0.0171 (7)	0.0000 (6)	−0.0030 (5)	−0.0043 (5)
C13	0.0331 (9)	0.0334 (9)	0.0332 (9)	0.0025 (8)	−0.0148 (7)	−0.0122 (7)
C21	0.0108 (6)	0.0219 (7)	0.0231 (7)	−0.0013 (5)	−0.0005 (5)	−0.0040 (6)
C22	0.0223 (8)	0.0330 (10)	0.0564 (12)	−0.0067 (7)	−0.0041 (8)	−0.0207 (9)
C23B	0.0290 (14)	0.0433 (17)	0.0353 (16)	−0.0112 (13)	0.0012 (11)	−0.0219 (13)
C23C	0.044 (3)	0.022 (2)	0.035 (3)	−0.006 (2)	−0.012 (2)	0.000 (2)
C31	0.0173 (6)	0.0188 (7)	0.0156 (6)	0.0046 (6)	0.0026 (5)	0.0036 (5)
C32	0.0288 (9)	0.0255 (8)	0.0388 (10)	0.0016 (7)	−0.0050 (7)	0.0173 (7)
C33	0.0571 (15)	0.0298 (11)	0.100 (2)	−0.0170 (10)	−0.0336 (14)	0.0364 (12)
C41	0.0110 (6)	0.0144 (6)	0.0185 (6)	−0.0003 (5)	−0.0038 (5)	−0.0028 (5)
C42	0.0243 (8)	0.0148 (7)	0.0325 (8)	0.0048 (6)	0.0076 (6)	−0.0013 (6)
C43	0.0643 (15)	0.0172 (8)	0.0616 (14)	0.0155 (9)	0.0324 (11)	0.0114 (8)
C51	0.0111 (6)	0.0120 (6)	0.0163 (6)	0.0023 (5)	−0.0038 (5)	0.0024 (5)
C52	0.0128 (6)	0.0167 (7)	0.0228 (7)	−0.0036 (5)	−0.0047 (5)	0.0019 (5)
C53	0.0147 (6)	0.0246 (8)	0.0289 (8)	−0.0029 (6)	0.0006 (6)	0.0041 (6)
C61	0.0147 (6)	0.0167 (6)	0.0123 (6)	−0.0004 (5)	0.0006 (5)	0.0006 (5)
C62	0.0169 (6)	0.0222 (7)	0.0216 (7)	−0.0043 (6)	−0.0037 (5)	0.0039 (6)
C63	0.0218 (7)	0.0226 (8)	0.0337 (9)	−0.0073 (6)	−0.0019 (6)	0.0062 (7)
Cl1	0.01473 (14)	0.01386 (15)	0.01537 (14)	0.00070 (12)	−0.00360 (11)	0.00005 (11)
Cl2	0.01791 (16)	0.01546 (15)	0.02119 (16)	0.00188 (13)	0.00519 (12)	0.00113 (12)
O1S	0.0254 (6)	0.0145 (5)	0.0312 (6)	0.0006 (4)	−0.0047 (5)	0.0054 (4)
O2S	0.0312 (6)	0.0201 (5)	0.0303 (6)	−0.0006 (5)	−0.0200 (5)	0.0029 (5)
O3S	0.0203 (6)	0.0307 (7)	0.0447 (7)	−0.0081 (5)	−0.0028 (5)	0.0146 (6)
O4S	0.0405 (7)	0.0398 (7)	0.0241 (6)	0.0071 (6)	−0.0008 (5)	−0.0134 (5)
O5S	0.0235 (17)	0.058 (2)	0.0366 (17)	0.0127 (14)	−0.0105 (12)	−0.0130 (14)
O6S	0.0204 (17)	0.0201 (16)	0.049 (2)	−0.0055 (11)	0.0032 (15)	−0.0113 (13)
O7S	0.0440 (18)	0.0211 (10)	0.0374 (16)	−0.0042 (11)	0.0211 (12)	0.0040 (10)
O8S	0.014 (2)	0.021 (2)	0.027 (2)	0.0050 (16)	0.0044 (14)	0.0023 (16)
O5T	0.017 (4)	0.011 (4)	0.046 (6)	−0.004 (3)	0.003 (4)	−0.016 (4)
O6T	0.077 (11)	0.050 (8)	0.036 (6)	0.037 (8)	0.035 (7)	0.031 (5)
O7T	0.012 (3)	0.044 (6)	0.083 (10)	−0.015 (3)	0.001 (5)	−0.038 (6)
O8T	0.015 (6)	0.025 (7)	0.016 (4)	0.001 (5)	0.000 (3)	0.000 (4)

Geometric parameters (Å, º)

Cu1—O3	1.9376 (10)	C22—C23B	1.213 (3)
Cu1—O3^i	1.9376 (10)	C22—H22	0.9500
Cu1—O1	1.9735 (10)	C22—H22A	0.9500
Cu1—O1^i	1.9735 (10)	C23B—H23A	0.9500
Cu2—O4	1.9338 (9)	C23B—H23B	0.9500
Cu2—O4^ii	1.9338 (9)	C23C—H23C	0.9500
Cu2—O5	1.9558 (10)	C23C—H23D	0.9500
Cu2—O5^ii	1.9558 (10)	C31—C32	1.476 (2)
O1—C11	1.2570 (16)	C32—C33	1.305 (3)
N1—C11	1.3252 (18)	C32—H32	0.9500
N1—H1A	0.839 (14)	C33—H33A	0.9500
N1—H1B	0.831 (14)	C33—H33B	0.9500
O2—C21	1.2473 (18)	C41—C42	1.476 (2)
N2—C21	1.320 (2)	C42—C43	1.317 (2)
N2—H2A	0.831 (15)	C42—H42	0.9500
N2—H2B	0.831 (15)	C43—H43B	0.9500
O3—C31	1.2597 (17)	C43—H43A	0.9500
N3—C31	1.314 (2)	C51—C52	1.4791 (19)
N3—H3B	0.829 (14)	C52—C53	1.318 (2)
N3—H3A	0.851 (14)	C52—H52	0.9500
O4—C41	1.2594 (16)	C53—H53A	0.9500
N4—C41	1.3223 (18)	C53—H53B	0.9500
N4—H4B	0.841 (14)	C61—C62	1.482 (2)
N4—H4A	0.831 (14)	C62—C63	1.316 (2)
O5—C51	1.2603 (17)	C62—H62	0.9500
N5—C51	1.3204 (18)	C63—H63B	0.9500
N5—H5A	0.848 (14)	C63—H63A	0.9500
N5—H5B	0.835 (14)	Cl1—O3S	1.4234 (12)
O6—C61	1.2534 (16)	Cl1—O2S	1.4366 (11)
N6—C61	1.3275 (18)	Cl1—O4S	1.4405 (12)
N6—H6B	0.857 (14)	Cl1—O1S	1.4482 (11)
N6—H6A	0.853 (14)	Cl2—O7T	1.291 (16)
C11—C12	1.478 (2)	Cl2—O6S	1.415 (5)
C12—C13	1.311 (2)	Cl2—O7S	1.429 (3)
C12—H12	0.9500	Cl2—O8S	1.438 (5)
C13—H13A	0.9500	Cl2—O5S	1.463 (4)
C13—H13B	0.9500	Cl2—O6T	1.468 (10)
C21—C22	1.487 (2)	Cl2—O8T	1.474 (13)
C22—C23C	1.148 (5)	Cl2—O5T	1.533 (14)
O3—Cu1—O3^i	180.00 (6)	C33—C32—C31	120.68 (16)
O3—Cu1—O1	90.39 (4)	C33—C32—H32	119.7
O3^i—Cu1—O1	89.61 (4)	C31—C32—H32	119.7
O3—Cu1—O1^i	89.61 (4)	C32—C33—H33A	120.0
O3^i—Cu1—O1^i	90.39 (4)	C32—C33—H33B	120.0
O1—Cu1—O1^i	180.00 (2)	H33A—C33—H33B	120.0
O4—Cu2—O4^ii	180.0	O4—C41—N4	123.60 (13)
O4—Cu2—O5	91.45 (4)	O4—C41—C42	118.73 (13)
O4^ii—Cu2—O5	88.55 (4)	N4—C41—C42	117.67 (12)
O4—Cu2—O5^ii	88.55 (4)	C43—C42—C41	120.16 (14)
O4^ii—Cu2—O5^ii	91.45 (4)	C43—C42—H42	119.9
O5—Cu2—O5^ii	180.00 (5)	C41—C42—H42	119.9
C11—O1—Cu1	128.63 (9)	C42—C43—H43B	120.0
C11—N1—H1A	119.5 (13)	C42—C43—H43A	120.0
C11—N1—H1B	122.0 (13)	H43B—C43—H43A	120.0
H1A—N1—H1B	118.3 (18)	O5—C51—N5	122.97 (13)
C21—N2—H2A	120.3 (14)	O5—C51—C52	119.78 (12)
C21—N2—H2B	120.3 (14)	N5—C51—C52	117.25 (13)
H2A—N2—H2B	119 (2)	C53—C52—C51	122.34 (14)
C31—O3—Cu1	131.37 (10)	C53—C52—H52	118.8
C31—N3—H3B	119.2 (14)	C51—C52—H52	118.8
C31—N3—H3A	120.8 (13)	C52—C53—H53A	120.0
H3B—N3—H3A	120.1 (19)	C52—C53—H53B	120.0
C41—O4—Cu2	131.56 (9)	H53A—C53—H53B	120.0
C41—N4—H4B	118.6 (13)	O6—C61—N6	121.61 (13)
C41—N4—H4A	120.0 (12)	O6—C61—C62	119.18 (13)
H4B—N4—H4A	121.4 (18)	N6—C61—C62	119.21 (13)
C51—O5—Cu2	128.70 (9)	C63—C62—C61	126.12 (14)
C51—N5—H5A	120.3 (12)	C63—C62—H62	116.9
C51—N5—H5B	118.2 (13)	C61—C62—H62	116.9
H5A—N5—H5B	118.7 (18)	C62—C63—H63B	120.0
C61—N6—H6B	121.1 (13)	C62—C63—H63A	120.0
C61—N6—H6A	120.9 (13)	H63B—C63—H63A	120.0
H6B—N6—H6A	118.0 (18)	O3S—Cl1—O2S	110.14 (7)
O1—C11—N1	122.84 (13)	O3S—Cl1—O4S	110.47 (8)
O1—C11—C12	120.63 (13)	O2S—Cl1—O4S	109.33 (8)
N1—C11—C12	116.53 (12)	O3S—Cl1—O1S	109.90 (7)
C13—C12—C11	122.48 (14)	O2S—Cl1—O1S	109.02 (7)
C13—C12—H12	118.8	O4S—Cl1—O1S	107.94 (8)
C11—C12—H12	118.8	O7T—Cl2—O6S	112.9 (8)
C12—C13—H13A	120.0	O7T—Cl2—O7S	89.0 (10)
C12—C13—H13B	120.0	O6S—Cl2—O7S	110.9 (2)
H13A—C13—H13B	120.0	O7T—Cl2—O8S	119.7 (9)
O2—C21—N2	122.20 (14)	O6S—Cl2—O8S	112.0 (4)
O2—C21—C22	120.98 (15)	O7S—Cl2—O8S	110.0 (4)
N2—C21—C22	116.82 (16)	O6S—Cl2—O5S	108.2 (3)
C23C—C22—C23B	94.7 (3)	O7S—Cl2—O5S	107.2 (2)
C23C—C22—C21	138.7 (3)	O8S—Cl2—O5S	108.2 (3)
C23B—C22—C21	126.0 (2)	O7T—Cl2—O6T	116.1 (7)
C23B—C22—H22	117.0	O6S—Cl2—O6T	91.1 (12)
C21—C22—H22	117.0	O8S—Cl2—O6T	101.0 (7)
C23C—C22—H22A	110.7	O5S—Cl2—O6T	134.8 (14)
C21—C22—H22A	110.7	O7T—Cl2—O8T	115.7 (12)
H22—C22—H22A	131.0	O6S—Cl2—O8T	112.6 (13)
C22—C23B—H23A	120.0	O7S—Cl2—O8T	113.7 (10)
C22—C23B—H23B	120.0	O5S—Cl2—O8T	103.6 (10)
H23A—C23B—H23B	120.0	O6T—Cl2—O8T	105.8 (10)
C22—C23C—H23C	120.0	O7T—Cl2—O5T	112.0 (9)
C22—C23C—H23D	120.0	O7S—Cl2—O5T	124.0 (7)
H23C—C23C—H23D	120.0	O8S—Cl2—O5T	103.2 (10)
O3—C31—N3	123.41 (14)	O5S—Cl2—O5T	103.3 (8)
O3—C31—C32	118.79 (14)	O6T—Cl2—O5T	102.7 (10)
N3—C31—C32	117.79 (14)	O8T—Cl2—O5T	102.9 (10)
O3—Cu1—O1—C11	−132.92 (12)	N2—C21—C22—C23B	176.0 (2)
O3^i—Cu1—O1—C11	47.08 (12)	Cu1—O3—C31—N3	−11.6 (2)
O1—Cu1—O3—C31	−47.02 (12)	Cu1—O3—C31—C32	169.47 (11)
O1^i—Cu1—O3—C31	132.98 (12)	O3—C31—C32—C33	2.8 (3)
O5—Cu2—O4—C41	−45.01 (12)	N3—C31—C32—C33	−176.2 (2)
O5^ii—Cu2—O4—C41	134.99 (12)	Cu2—O4—C41—N4	−9.9 (2)
O4—Cu2—O5—C51	−128.14 (11)	Cu2—O4—C41—C42	170.69 (10)
O4^ii—Cu2—O5—C51	51.86 (11)	O4—C41—C42—C43	−0.8 (3)
Cu1—O1—C11—N1	19.9 (2)	N4—C41—C42—C43	179.76 (19)
Cu1—O1—C11—C12	−159.92 (10)	Cu2—O5—C51—N5	19.60 (19)
O1—C11—C12—C13	2.1 (2)	Cu2—O5—C51—C52	−160.29 (9)
N1—C11—C12—C13	−177.78 (16)	O5—C51—C52—C53	−9.0 (2)
O2—C21—C22—C23C	−172.0 (5)	N5—C51—C52—C53	171.09 (14)
N2—C21—C22—C23C	7.6 (5)	O6—C61—C62—C63	−169.90 (16)
O2—C21—C22—C23B	−3.5 (3)	N6—C61—C62—C63	9.2 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O4S^iii	0.83 (1)	2.21 (2)	2.9997 (18)	159 (2)
N1—H1A···O2^i	0.84 (1)	2.12 (2)	2.9049 (17)	155 (2)
N2—H2A···O8T^iv	0.83 (2)	2.21 (3)	2.97 (2)	153 (2)
N2—H2B···O1S^iv	0.83 (2)	2.24 (2)	2.9952 (18)	151 (2)
N3—H3B···O2	0.83 (1)	2.15 (2)	2.8759 (17)	147 (2)
N3—H3A···O1S	0.85 (1)	2.20 (2)	3.0219 (17)	162 (2)
N4—H4A···O6S	0.83 (1)	2.23 (2)	3.037 (8)	164 (2)
N4—H4A···O5T	0.83 (1)	2.38 (2)	3.19 (2)	166 (2)
N4—H4B···O6^ii	0.84 (1)	2.21 (2)	2.9362 (16)	145 (2)
N5—H5B···O6S^v	0.84 (1)	2.27 (2)	3.100 (6)	171 (2)
N5—H5B···O5T^v	0.84 (1)	2.19 (2)	3.027 (15)	179 (2)
N5—H5A···O6	0.85 (1)	2.05 (2)	2.8676 (17)	161 (2)
N6—H6B···O2S^vi	0.86 (1)	2.15 (2)	3.0019 (18)	170 (2)
N6—H6A···O8S^vi	0.85 (1)	2.25 (2)	3.080 (9)	166 (2)
N6—H6A···O8T^vi	0.85 (1)	2.32 (3)	3.15 (2)	166 (2)

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

(II) Hexakis(prop-2-enamide)manganese(II) bis(perchlorate)

Crystal data

[Mn(C3H5NO)6](ClO4)2	F(000) = 702
Mr = 680.32	Dx = 1.536 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9895 reflections
a = 9.2804 (6) Å	θ = 2.4–31.4°
b = 15.9533 (10) Å	µ = 0.70 mm^−1
c = 10.6876 (7) Å	T = 100 K
β = 111.642 (3)°	Block, colourless
V = 1470.79 (16) Å^3	0.64 × 0.58 × 0.42 mm
Z = 2

Data collection

Bruker APEXII CCD area-detector diffractometer	5063 independent reflections
Radiation source: fine-focus sealed tube	4083 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
ϕ and ω scans	θmax = 31.9°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −13→13
Tmin = 0.662, Tmax = 0.757	k = −23→23
43193 measured reflections	l = −15→15

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.090	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0455P)^2 + 0.2932P] where P = (Fo^2 + 2Fc^2)/3
5063 reflections	(Δ/σ)max = 0.001
187 parameters	Δρmax = 0.52 e Å^−3
0 restraints	Δρmin = −0.52 e Å^−3

Special details

Experimental. 2009–07-07 # Formatted by publCIF

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
O1S	0.43853 (12)	0.24537 (7)	0.49636 (10)	0.0312 (2)
Mn1	0.0000	0.0000	1.0000	0.01459 (7)
O1	−0.06157 (10)	0.09332 (6)	1.12036 (9)	0.01835 (18)
O2	0.24984 (10)	0.01682 (6)	1.11141 (9)	0.02028 (19)
O3	0.00353 (11)	0.09964 (6)	0.86770 (9)	0.02174 (19)
N1	−0.27987 (13)	0.15609 (7)	0.97851 (11)	0.0227 (2)
H1A	−0.2835	0.1231	0.9114	0.034*
H1B	−0.3514	0.1947	0.9665	0.034*
N2	0.26722 (13)	0.13792 (8)	1.22531 (13)	0.0270 (3)
H2A	0.1664	0.1395	1.2053	0.040*
H2B	0.3266	0.1780	1.2744	0.040*
N3	0.18662 (13)	0.15153 (8)	0.79767 (12)	0.0244 (2)
H3A	0.2376	0.1736	0.8772	0.037*
H3B	0.2218	0.1575	0.7322	0.037*
C10	−0.16687 (13)	0.14752 (8)	1.09754 (12)	0.0170 (2)
C11	−0.16807 (15)	0.20521 (9)	1.20582 (14)	0.0226 (3)
H11	−0.2397	0.2504	1.1846	0.027*
C12	−0.07136 (16)	0.19492 (9)	1.33133 (14)	0.0260 (3)
H12A	0.0007	0.1499	1.3536	0.031*
H12B	−0.0738	0.2325	1.3994	0.031*
C20	0.32968 (14)	0.07527 (8)	1.18153 (12)	0.0182 (2)
C21	0.50067 (14)	0.07737 (9)	1.22113 (14)	0.0237 (3)
H21	0.5571	0.1226	1.2748	0.028*
C22	0.57686 (16)	0.01872 (9)	1.18446 (16)	0.0274 (3)
H22A	0.5223	−0.0270	1.1308	0.033*
H22B	0.6864	0.0221	1.2117	0.033*
C30	0.05653 (15)	0.10918 (8)	0.77646 (13)	0.0194 (2)
C31	−0.02246 (17)	0.07554 (9)	0.63896 (14)	0.0258 (3)
H31	0.0279	0.0790	0.5762	0.031*
C32	−0.16160 (18)	0.04076 (10)	0.60134 (15)	0.0307 (3)
H32A	−0.2131	0.0370	0.6632	0.037*
H32B	−0.2099	0.0196	0.5125	0.037*
Cl1S	0.42725 (3)	0.17867 (2)	0.58438 (3)	0.02065 (8)
O2S	0.48644 (13)	0.20707 (8)	0.72143 (10)	0.0356 (3)
O3S	0.26695 (12)	0.15732 (9)	0.54845 (11)	0.0396 (3)
O4S	0.5118 (2)	0.10871 (10)	0.56775 (18)	0.0666 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1S	0.0268 (5)	0.0381 (6)	0.0249 (5)	−0.0100 (4)	0.0052 (4)	0.0100 (4)
Mn1	0.01184 (12)	0.01729 (13)	0.01538 (12)	−0.00017 (9)	0.00587 (9)	−0.00068 (9)
O1	0.0149 (4)	0.0218 (4)	0.0191 (4)	0.0030 (3)	0.0070 (3)	−0.0011 (3)
O2	0.0140 (4)	0.0234 (5)	0.0227 (4)	−0.0017 (3)	0.0058 (3)	−0.0039 (4)
O3	0.0255 (5)	0.0207 (5)	0.0238 (4)	0.0013 (4)	0.0147 (4)	0.0032 (4)
N1	0.0186 (5)	0.0223 (6)	0.0240 (5)	0.0041 (4)	0.0041 (4)	0.0005 (4)
N2	0.0164 (5)	0.0291 (6)	0.0352 (6)	−0.0038 (4)	0.0093 (5)	−0.0136 (5)
N3	0.0223 (5)	0.0288 (6)	0.0252 (6)	−0.0018 (5)	0.0124 (5)	0.0000 (5)
C10	0.0136 (5)	0.0179 (6)	0.0214 (6)	−0.0011 (4)	0.0085 (4)	0.0011 (4)
C11	0.0182 (6)	0.0197 (6)	0.0312 (7)	0.0021 (5)	0.0105 (5)	−0.0045 (5)
C12	0.0258 (6)	0.0276 (7)	0.0265 (7)	−0.0002 (5)	0.0121 (5)	−0.0072 (5)
C20	0.0146 (5)	0.0212 (6)	0.0186 (5)	−0.0014 (4)	0.0057 (4)	0.0002 (4)
C21	0.0140 (5)	0.0244 (7)	0.0307 (7)	−0.0033 (5)	0.0057 (5)	−0.0013 (5)
C22	0.0165 (6)	0.0256 (7)	0.0407 (8)	−0.0008 (5)	0.0113 (6)	0.0023 (6)
C30	0.0205 (6)	0.0176 (6)	0.0223 (6)	0.0037 (5)	0.0104 (5)	0.0039 (5)
C31	0.0282 (7)	0.0298 (7)	0.0221 (6)	−0.0031 (5)	0.0126 (5)	0.0001 (5)
C32	0.0318 (7)	0.0345 (8)	0.0247 (7)	−0.0053 (6)	0.0092 (6)	−0.0007 (6)
Cl1S	0.01625 (13)	0.02367 (16)	0.02388 (15)	−0.00034 (11)	0.00956 (11)	0.00255 (11)
O2S	0.0325 (6)	0.0470 (7)	0.0187 (5)	−0.0121 (5)	−0.0008 (4)	0.0044 (4)
O3S	0.0232 (5)	0.0687 (9)	0.0278 (5)	−0.0216 (5)	0.0104 (4)	−0.0045 (5)
O4S	0.0859 (11)	0.0495 (9)	0.0910 (12)	0.0380 (8)	0.0640 (10)	0.0210 (8)

Geometric parameters (Å, º)

O1S—Cl1S	1.4494 (11)	C10—C11	1.4819 (18)
Mn1—O3	2.1357 (9)	C11—C12	1.321 (2)
Mn1—O3^i	2.1357 (9)	C11—H11	0.9500
Mn1—O1^i	2.1771 (9)	C12—H12A	0.9500
Mn1—O1	2.1771 (9)	C12—H12B	0.9500
Mn1—O2	2.1976 (9)	C20—C21	1.4842 (17)
Mn1—O2^i	2.1976 (9)	C21—C22	1.317 (2)
O1—C10	1.2595 (14)	C21—H21	0.9500
O2—C20	1.2532 (15)	C22—H22A	0.9500
O3—C30	1.2529 (15)	C22—H22B	0.9500
N1—C10	1.3239 (16)	C30—C31	1.4800 (19)
N1—H1A	0.8800	C31—C32	1.324 (2)
N1—H1B	0.8800	C31—H31	0.9500
N2—C20	1.3245 (17)	C32—H32A	0.9500
N2—H2A	0.8800	C32—H32B	0.9500
N2—H2B	0.8800	Cl1S—O4S	1.4124 (13)
N3—C30	1.3280 (17)	Cl1S—O3S	1.4336 (11)
N3—H3A	0.8800	Cl1S—O2S	1.4350 (11)
N3—H3B	0.8800
O3—Mn1—O3^i	180.0	C12—C11—C10	121.20 (12)
O3—Mn1—O1^i	92.65 (4)	C12—C11—H11	119.4
O3^i—Mn1—O1^i	87.35 (4)	C10—C11—H11	119.4
O3—Mn1—O1	87.35 (4)	C11—C12—H12A	120.0
O3^i—Mn1—O1	92.65 (4)	C11—C12—H12B	120.0
O1^i—Mn1—O1	180.0	H12A—C12—H12B	120.0
O3—Mn1—O2	89.83 (4)	O2—C20—N2	122.24 (11)
O3^i—Mn1—O2	90.17 (4)	O2—C20—C21	121.43 (12)
O1^i—Mn1—O2	87.09 (3)	N2—C20—C21	116.32 (12)
O1—Mn1—O2	92.91 (3)	C22—C21—C20	122.29 (13)
O3—Mn1—O2^i	90.17 (4)	C22—C21—H21	118.9
O3^i—Mn1—O2^i	89.83 (4)	C20—C21—H21	118.9
O1^i—Mn1—O2^i	92.91 (3)	C21—C22—H22A	120.0
O1—Mn1—O2^i	87.09 (3)	C21—C22—H22B	120.0
O2—Mn1—O2^i	180.00 (3)	H22A—C22—H22B	120.0
C10—O1—Mn1	135.15 (8)	O3—C30—N3	121.47 (12)
C20—O2—Mn1	133.46 (8)	O3—C30—C31	122.41 (12)
C30—O3—Mn1	135.40 (9)	N3—C30—C31	116.12 (11)
C10—N1—H1A	120.0	C32—C31—C30	121.59 (13)
C10—N1—H1B	120.0	C32—C31—H31	119.2
H1A—N1—H1B	120.0	C30—C31—H31	119.2
C20—N2—H2A	120.0	C31—C32—H32A	120.0
C20—N2—H2B	120.0	C31—C32—H32B	120.0
H2A—N2—H2B	120.0	H32A—C32—H32B	120.0
C30—N3—H3A	120.0	O4S—Cl1S—O3S	110.37 (10)
C30—N3—H3B	120.0	O4S—Cl1S—O2S	110.89 (10)
H3A—N3—H3B	120.0	O3S—Cl1S—O2S	108.49 (7)
O1—C10—N1	122.69 (12)	O4S—Cl1S—O1S	108.79 (8)
O1—C10—C11	120.26 (11)	O3S—Cl1S—O1S	108.47 (7)
N1—C10—C11	117.06 (11)	O2S—Cl1S—O1S	109.79 (7)
O3—Mn1—O1—C10	54.79 (12)	Mn1—O1—C10—C11	−176.62 (9)
O3^i—Mn1—O1—C10	−125.21 (12)	O1—C10—C11—C12	−8.2 (2)
O2^i—Mn1—O1—C10	−35.51 (11)	N1—C10—C11—C12	171.83 (13)
O3—Mn1—O2—C20	65.08 (12)	Mn1—O2—C20—N2	14.2 (2)
O3^i—Mn1—O2—C20	−114.92 (12)	Mn1—O2—C20—C21	−166.40 (9)
O1^i—Mn1—O2—C20	157.74 (12)	O2—C20—C21—C22	0.4 (2)
O1—Mn1—O2—C20	−22.26 (12)	N2—C20—C21—C22	179.81 (14)
O1^i—Mn1—O3—C30	−16.17 (13)	Mn1—O3—C30—N3	−102.43 (15)
O1—Mn1—O3—C30	163.83 (13)	Mn1—O3—C30—C31	78.62 (17)
O2—Mn1—O3—C30	70.91 (13)	O3—C30—C31—C32	6.9 (2)
O2^i—Mn1—O3—C30	−109.09 (13)	N3—C30—C31—C32	−172.10 (14)
Mn1—O1—C10—N1	3.33 (19)

Symmetry code: (i) −x, −y, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2^i	0.88	2.28	2.9678 (15)	135
N1—H1B···O1S^ii	0.88	2.30	3.1153 (15)	155
N2—H2A···O1	0.88	2.10	2.9241 (14)	155
N2—H2B···O1S^iii	0.88	2.46	3.2343 (16)	147
N2—H2B···O2S^iv	0.88	2.55	3.2121 (18)	133
N3—H3A···O1S^iv	0.88	2.24	3.0030 (16)	145
N3—H3B···O3S	0.88	2.15	3.0206 (16)	168

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