Aqua(dipicolinato-κ³O²,N,O⁶)(1,10-phenanthroline-κ²N,N′)manganese(II) monohydrate

In the title compound [systematic name: aqua(1,10-phenanthroline-κ²N,N′)(pyridine-2,6-di­carboxyl­ato-κ³O²,N,O⁶)manganese(II) monohydrate, [Mn(C₇H₃NO₄)(C₁₂H₈N₂)(H₂O)]·H₂O, the manganese(II) centre is surrounded by one bidentate phenanthroline ligand [Mn—N = 2.248 (3) and 2.278 (3) Å], one tridentate dipicolinate ligand [Mn—N = 2.179 (3) Å, and Mn—O = 2.237 (2) and 2.266 (2) Å] and one water mol­ecule [Mn—O = 2.117 (3) Å], and it exhibits a strongly distorted octahedral geometry, with trans angles ranging from 144.12 (9) to 158.88 (11)°. Extensive intermolecular hydrogen-bonding interactions involving coordinated and uncoordinated water mol­ecules and the carboxyl O atoms of the dipicolinate ligand, as well as a stacking interaction involving the phenanthroline rings, are observed in the crystal structure.

S1. Comment

It is well established that Mn is one of the trace elements in biosystems and it plays an important role in the active sites of various redox-based enzymes (Weighardt, 1989). In addition to the best known oxygen-evolving complex, which is believed to contain a tetranuclear Mn cluster catalyzing the oxidation of water to yield O₂ during photosynthesis (Debus, 1992), there are three enzymes containing a mononuclear Mn site, viz. superoxide dismutase, peroxidase and dioxygenase, which participate in the redox changes of biological systems (Law et al., 1999). Based on the knowledge that the sphere of Mn centres in these enzymes is dominated by N,O donors from available amino acid residues (Pecoraro & Butler, 1986), N,O-containing ligands are often employed to prepare model compounds for the better understanding of their exact nature and mechanism of action. As part of our systematic study on Mn chemistry, we have selected dipicolinic acid as the primary ligand to react with Mn²⁺ salts in participation with diimine ligands. Dipicolinic acid possesses versatile yet unpredictable coordination modes (Herring et al., 1979; Quaglieri et al., 1972; Starynowicz, 1992; Lawrence & Tuyetha, 2000) and diverse biological activities (Church & Halvorson, 1959; Chung et al., 1971; Scapin al., 1997), and we have obtained the title compound, (I), which represents a new example of mononuclear Mn with mixed ligands. \sch

Compound (I) (Fig. 1) consists of a neutral [Mn(dpc)(phen)(H₂O)] unit and one solvate water molecule (dpc is dipicolinate and phen is phenanthroline). The octahedral sphere on the Mn centre is severely distorted because of the chelation of two rigid planar lidands (phen and dpc) (Table 1). The mean Mn—N(phen) bond length [2.263 (15) Å] is in agreement with that reported in other Mn-phen complexes, e.g. in [Mn(phen)(H₂O)₄]²⁺ [2.263 (9) Å; Ma et al., 2002], and the N1—Mn—N2 phen chelate angle of 73.50 (1)° is as expected for Mn complexes (Drew et al., 1989; McCann et al., 1997; Ramalakshmi et al., 1999; Wang et al., 2000; Deng et al., 2000).

The Mn—N3 distance of 2.179 (3) Å, significantly smaller than that for Mn—N1 (or N2), indicates that N3 is a stronger donor, since the two carboxylate groups in ortho positions enhance the electron density on N3. The average Mn—O(dpc) distance [2.252 (15) Å] and the dpc chelate angles are comparable with those found in other Mn complexes (Limburg et al., 1997; Chandra et al., 1992; Okabe & Oya, 2000). The phen ligand is reasonably planar, with a mean deviation of 0.044 (1) Å, and bond distances and angles are consistent with those in the free base (Nishigaki et al., 1978). All atoms in the dpc ligand are also nearly coplanar, with a maximum deviation of 0.075 (1) Å for O2. The dihedral angle between the phen and dpc planes is 81.5 (1)°.

As listed in Table 2, two normal hydrogen bonds link the coordinated water molecule O5 and two carboxyl O atoms (O2 and O4) of symmetry-related molecules to generate a two-dimensional network sheet (Fig. 2). Two weaker hydrogen bonds link the uncoordinated water molecule to carboxyl atom O4 and to a symmetry-related carboxyl atom O3 to generate centrosymmetric dimers (Fig. 3), and overall give rise to a three-dimensional hydrogen-bonded network. In addition, there are π–π stacking interactions between inversion-related phen ligands along the a direction (Fig. 4), with perpendicular ring separations of 3.455 (2) and 3.405 (6) Å, which are comparable with the sum of the van der Waals contact radii of two C atoms (3.4 Å; Bondi, 1964).

S2. Experimental

To an EtOH-H₂O solution (30 ml, ca 1:1 v/v) containing MnCl₂·4H₂O (1 mmol) and disodium dipicolinate (2 mmol), 1,10-phenathroline (1 mmol) was added slowly with continuous stirring. The resulting solution was refluxed for 1 h and then filtered. The yellow filtrate was left for 21 d at room temperature, after which time yellow crystals of (I) suitable for X-ray diffraction analysis were obtained.

S3. Refinement

H atoms bonded to C atoms were placed in calculated positions with C—H distances of 0.93 Å, and treated as riding atoms. Water H-atom coordinates were located from difference maps and refined isotropically; the four O—H distances involving the water molecules were refined with a DFIX restraint of 0.85 (2) Å Please clarify - largest value in CIF tables is 0.88 (4).

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1994); data reduction: XPREP in SHELXTL (Siemens, 1994); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL (Bruker? Different version?); software used to prepare material for publication: SHELXTL (Bruker? Different version?).

Figures

	Fig. 1. A view of the molecule of (I), with the atomic labelling scheme and 30% probability displacement ellipsoids.
	Fig. 2. A packing diagram for (I), showing part of the two-dimensional hydrogen-bonded network. Atoms labelled with a hash (#), dollar sign (add) or ampersand (add) are at the symmetry positions (x - 1,y,z), (1 + x,y,z) and (x,3/2 - y,1/2 + z), respectively.
	Fig. 3. A diagram showing the centrosymmetric dimers produced by the lattice water molecules of (I). Atoms labelled with an asterisk (*) are at the symmetry position (-x,1 - y,1 - z).
	Fig. 4. A diagram showing part of the π-π stacking interactions in (I).

aqua(1,10-phenanthroline-κ²N,N')(pyridine-2,6-dicarboxylato- κ³O²,N,O⁶)manganese(II) monohydrate

Crystal data

[Mn(C7H3NO4)(C12H8N2)(H2O)]·H2O	F(000) = 892
Mr = 436.28	Dx = 1.590 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2918 reflections
a = 7.6006 (6) Å	θ = 1.9–25.1°
b = 21.1600 (16) Å	µ = 0.77 mm^−1
c = 11.4733 (9) Å	T = 293 K
β = 98.916 (1)°	Needle, yellow
V = 1822.9 (2) Å^3	0.59 × 0.20 × 0.16 mm
Z = 4

Data collection

Make Model CCD area-detector diffractometer	3198 independent reflections
Radiation source: fine-focus sealed tube	2264 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
ϕ and ω scans	θmax = 25.1°, θmin = 1.9°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −8→9
Tmin = 0.630, Tmax = 0.880	k = −21→25
6177 measured reflections	l = −13→9

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.125	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0658P)^2] where P = (Fo^2 + 2Fc^2)/3
3198 reflections	(Δ/σ)max = 0.001
278 parameters	Δρmax = 0.26 e Å^−3
3 restraints	Δρmin = −0.37 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
Mn	0.34349 (7)	0.62456 (2)	0.23754 (4)	0.03415 (19)
O1	0.4295 (3)	0.70244 (12)	0.1272 (2)	0.0477 (7)
O2	0.3427 (4)	0.79208 (13)	0.0320 (3)	0.0669 (9)
O3	0.1305 (3)	0.59408 (11)	0.3438 (2)	0.0381 (6)
O4	−0.1305 (3)	0.61805 (11)	0.3984 (2)	0.0457 (6)
O5	0.5263 (4)	0.65387 (15)	0.3860 (3)	0.0550 (8)
H5B	0.491 (6)	0.6747 (18)	0.439 (3)	0.072 (15)*
H5C	0.641 (6)	0.6452 (19)	0.400 (4)	0.070 (15)*
O6	−0.1307 (6)	0.54305 (17)	0.6042 (3)	0.0757 (10)
H6B	−0.078 (7)	0.551 (3)	0.546 (4)	0.11 (2)*
H6C	−0.130 (8)	0.5040 (10)	0.593 (6)	0.13 (3)*
N1	0.4490 (4)	0.52516 (13)	0.2531 (2)	0.0357 (7)
N2	0.2399 (4)	0.57577 (13)	0.0635 (2)	0.0347 (7)
N3	0.1386 (4)	0.69738 (12)	0.2231 (2)	0.0320 (7)
C1	0.5473 (5)	0.49974 (18)	0.3479 (3)	0.0421 (9)
H1A	0.5858	0.5258	0.4120	0.051*
C2	0.5955 (5)	0.43620 (19)	0.3559 (4)	0.0513 (10)
H2A	0.6634	0.4202	0.4239	0.062*
C3	0.5405 (5)	0.39785 (19)	0.2613 (4)	0.0496 (10)
H3A	0.5709	0.3552	0.2649	0.060*
C4	0.4387 (5)	0.42228 (16)	0.1593 (3)	0.0402 (9)
C5	0.3824 (5)	0.38556 (17)	0.0544 (4)	0.0490 (10)
H5A	0.4130	0.3430	0.0534	0.059*
C6	0.2868 (5)	0.41140 (18)	−0.0418 (4)	0.0493 (10)
H6A	0.2547	0.3867	−0.1087	0.059*
C7	0.2330 (5)	0.47657 (17)	−0.0437 (3)	0.0383 (9)
C8	0.1303 (5)	0.50542 (19)	−0.1404 (3)	0.0460 (10)
H8A	0.0928	0.4824	−0.2089	0.055*
C9	0.0852 (5)	0.56739 (19)	−0.1341 (3)	0.0457 (9)
H9A	0.0168	0.5872	−0.1981	0.055*
C10	0.1425 (5)	0.60083 (18)	−0.0308 (3)	0.0432 (9)
H10A	0.1107	0.6432	−0.0279	0.052*
C11	0.2868 (4)	0.51414 (16)	0.0581 (3)	0.0329 (8)
C12	0.3939 (4)	0.48647 (15)	0.1600 (3)	0.0329 (8)
C13	0.1563 (5)	0.74804 (15)	0.1556 (3)	0.0363 (8)
C14	0.0279 (6)	0.79453 (18)	0.1408 (4)	0.0504 (10)
H14A	0.0412	0.8298	0.0947	0.060*
C15	−0.1202 (6)	0.78803 (18)	0.1951 (4)	0.0570 (11)
H15A	−0.2088	0.8188	0.1853	0.068*
C16	−0.1367 (5)	0.73537 (17)	0.2645 (4)	0.0474 (10)
H16A	−0.2359	0.7304	0.3019	0.057*
C17	−0.0033 (4)	0.69048 (15)	0.2770 (3)	0.0325 (8)
C18	0.3244 (5)	0.74770 (17)	0.0998 (3)	0.0426 (9)
C19	−0.0011 (4)	0.62951 (15)	0.3462 (3)	0.0323 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn	0.0340 (3)	0.0339 (3)	0.0352 (3)	0.0010 (2)	0.0075 (2)	−0.0025 (2)
O1	0.0485 (17)	0.0445 (16)	0.0553 (17)	−0.0059 (13)	0.0248 (14)	−0.0043 (13)
O2	0.093 (2)	0.0531 (18)	0.064 (2)	−0.0129 (16)	0.0391 (18)	0.0167 (15)
O3	0.0385 (14)	0.0334 (13)	0.0440 (15)	0.0051 (11)	0.0108 (11)	0.0068 (11)
O4	0.0369 (14)	0.0512 (15)	0.0529 (16)	0.0007 (12)	0.0193 (12)	0.0124 (13)
O5	0.0358 (17)	0.082 (2)	0.0475 (17)	0.0012 (15)	0.0077 (14)	−0.0298 (16)
O6	0.119 (3)	0.058 (2)	0.049 (2)	−0.009 (2)	0.009 (2)	0.0040 (18)
N1	0.0345 (17)	0.0389 (17)	0.0346 (17)	0.0021 (13)	0.0083 (13)	−0.0005 (13)
N2	0.0366 (16)	0.0347 (16)	0.0333 (17)	−0.0016 (13)	0.0074 (13)	−0.0007 (13)
N3	0.0388 (17)	0.0298 (15)	0.0281 (15)	−0.0011 (12)	0.0070 (13)	0.0019 (12)
C1	0.040 (2)	0.050 (2)	0.036 (2)	0.0007 (18)	0.0056 (17)	−0.0021 (18)
C2	0.049 (2)	0.052 (2)	0.054 (3)	0.014 (2)	0.010 (2)	0.015 (2)
C3	0.050 (2)	0.041 (2)	0.062 (3)	0.0103 (18)	0.018 (2)	0.012 (2)
C4	0.039 (2)	0.035 (2)	0.050 (2)	−0.0028 (17)	0.0171 (18)	−0.0014 (17)
C5	0.051 (2)	0.036 (2)	0.063 (3)	0.0014 (18)	0.019 (2)	−0.007 (2)
C6	0.052 (2)	0.047 (2)	0.051 (3)	−0.008 (2)	0.014 (2)	−0.020 (2)
C7	0.031 (2)	0.045 (2)	0.040 (2)	−0.0091 (16)	0.0091 (16)	−0.0062 (17)
C8	0.043 (2)	0.065 (3)	0.031 (2)	−0.013 (2)	0.0075 (17)	−0.0091 (19)
C9	0.044 (2)	0.058 (3)	0.033 (2)	−0.0065 (19)	−0.0012 (17)	0.0053 (18)
C10	0.042 (2)	0.046 (2)	0.041 (2)	−0.0027 (18)	0.0021 (18)	0.0034 (18)
C11	0.0310 (19)	0.038 (2)	0.0322 (19)	−0.0040 (15)	0.0125 (15)	−0.0039 (16)
C12	0.0300 (19)	0.0343 (19)	0.037 (2)	−0.0039 (15)	0.0120 (16)	−0.0019 (16)
C13	0.048 (2)	0.0303 (18)	0.0312 (19)	−0.0038 (16)	0.0084 (16)	−0.0006 (15)
C14	0.062 (3)	0.038 (2)	0.051 (2)	0.0035 (19)	0.011 (2)	0.0136 (19)
C15	0.054 (3)	0.039 (2)	0.079 (3)	0.0169 (19)	0.014 (2)	0.012 (2)
C16	0.043 (2)	0.042 (2)	0.060 (3)	0.0090 (18)	0.016 (2)	0.0093 (19)
C17	0.0347 (19)	0.0316 (18)	0.0320 (18)	−0.0025 (15)	0.0076 (15)	−0.0015 (15)
C18	0.059 (3)	0.035 (2)	0.037 (2)	−0.0107 (19)	0.0171 (18)	−0.0062 (18)
C19	0.0312 (19)	0.0326 (18)	0.0324 (18)	−0.0046 (16)	0.0030 (15)	0.0007 (15)

Geometric parameters (Å, º)

Mn—N1	2.248 (3)	C2—H2A	0.9300
Mn—N2	2.278 (3)	C3—C4	1.398 (5)
Mn—N3	2.179 (3)	C3—H3A	0.9300
Mn—O1	2.237 (2)	C4—C12	1.401 (4)
Mn—O3	2.266 (2)	C4—C5	1.441 (5)
Mn—O5	2.117 (3)	C5—C6	1.340 (5)
O1—C18	1.255 (4)	C5—H5A	0.9300
O2—C18	1.241 (4)	C6—C7	1.438 (5)
O3—C19	1.254 (4)	C6—H6A	0.9300
O4—C19	1.252 (4)	C7—C8	1.395 (5)
O5—O2^i	2.605 (4)	C7—C11	1.420 (5)
O5—O4^ii	2.699 (4)	C8—C9	1.360 (5)
O5—H5B	0.83 (4)	C8—H8A	0.9300
O5—H5C	0.88 (4)	C9—C10	1.391 (5)
O6—O3^iii	2.962 (4)	C9—H9A	0.9300
O6—H6B	0.85 (5)	C10—H10A	0.9300
O6—H6C	0.84 (2)	C11—C12	1.441 (5)
N1—C1	1.334 (4)	C13—C14	1.378 (5)
N1—C12	1.359 (4)	C13—C18	1.515 (5)
N2—C10	1.323 (4)	C14—C15	1.375 (5)
N2—C11	1.356 (4)	C14—H14A	0.9300
N3—C17	1.332 (4)	C15—C16	1.386 (5)
N3—C13	1.341 (4)	C15—H15A	0.9300
C1—C2	1.393 (5)	C16—C17	1.380 (5)
C1—H1A	0.9300	C16—H16A	0.9300
C2—C3	1.367 (6)	C17—C19	1.513 (5)
O5—Mn—N3	103.07 (11)	C6—C5—H5A	119.3
O5—Mn—O1	91.54 (12)	C4—C5—H5A	119.3
N3—Mn—O1	72.79 (10)	C5—C6—C7	121.4 (4)
O5—Mn—N1	91.65 (12)	C5—C6—H6A	119.3
N3—Mn—N1	155.45 (10)	C7—C6—H6A	119.3
O1—Mn—N1	127.03 (10)	C8—C7—C11	117.6 (3)
O5—Mn—O3	94.88 (10)	C8—C7—C6	123.7 (3)
N3—Mn—O3	71.36 (9)	C11—C7—C6	118.7 (3)
O1—Mn—O3	144.12 (9)	C9—C8—C7	119.6 (3)
N1—Mn—O3	88.09 (9)	C9—C8—H8A	120.2
O5—Mn—N2	158.88 (11)	C7—C8—H8A	120.2
N3—Mn—N2	96.20 (10)	C8—C9—C10	119.2 (4)
O1—Mn—N2	85.93 (10)	C8—C9—H9A	120.4
N1—Mn—N2	73.50 (10)	C10—C9—H9A	120.4
O3—Mn—N2	99.43 (9)	N2—C10—C9	123.7 (4)
C18—O1—Mn	118.2 (2)	N2—C10—H10A	118.2
C19—O3—Mn	118.7 (2)	C9—C10—H10A	118.2
Mn—O5—H5B	120 (3)	N2—C11—C7	122.1 (3)
Mn—O5—H5C	126 (3)	N2—C11—C12	118.3 (3)
O2^i—O5—H5C	126 (3)	C7—C11—C12	119.6 (3)
H5B—O5—H5C	114 (4)	N1—C12—C4	122.9 (3)
H6B—O6—H6C	94 (5)	N1—C12—C11	117.3 (3)
C1—N1—C12	117.6 (3)	C4—C12—C11	119.8 (3)
C1—N1—Mn	126.1 (2)	N3—C13—C14	120.6 (3)
C12—N1—Mn	116.0 (2)	N3—C13—C18	114.0 (3)
C10—N2—C11	117.8 (3)	C14—C13—C18	125.4 (3)
C10—N2—Mn	127.5 (2)	C15—C14—C13	119.1 (3)
C11—N2—Mn	114.7 (2)	C15—C14—H14A	120.4
C17—N3—C13	121.1 (3)	C13—C14—H14A	120.4
C17—N3—Mn	120.5 (2)	C14—C15—C16	119.6 (4)
C13—N3—Mn	118.3 (2)	C14—C15—H15A	120.2
N1—C1—C2	123.5 (4)	C16—C15—H15A	120.2
N1—C1—H1A	118.3	C17—C16—C15	118.9 (4)
C2—C1—H1A	118.3	C17—C16—H16A	120.6
C3—C2—C1	118.4 (4)	C15—C16—H16A	120.6
C3—C2—H2A	120.8	N3—C17—C16	120.7 (3)
C1—C2—H2A	120.8	N3—C17—C19	113.1 (3)
C2—C3—C4	120.4 (4)	C16—C17—C19	126.1 (3)
C2—C3—H3A	119.8	O2—C18—O1	127.3 (4)
C4—C3—H3A	119.8	O2—C18—C13	116.4 (4)
C3—C4—C12	117.2 (3)	O1—C18—C13	116.3 (3)
C3—C4—C5	123.7 (4)	O4—C19—O3	125.7 (3)
C12—C4—C5	119.1 (3)	O4—C19—C17	118.0 (3)
C6—C5—C4	121.4 (3)	O3—C19—C17	116.2 (3)
O5—Mn—O1—C18	−108.4 (3)	C12—C4—C5—C6	−0.7 (5)
N3—Mn—O1—C18	−5.2 (3)	C4—C5—C6—C7	−1.4 (6)
N1—Mn—O1—C18	158.4 (2)	C5—C6—C7—C8	−178.5 (4)
O3—Mn—O1—C18	−7.9 (3)	C5—C6—C7—C11	1.5 (5)
N2—Mn—O1—C18	92.6 (3)	C11—C7—C8—C9	−0.2 (5)
O5—Mn—O3—C19	102.7 (2)	C6—C7—C8—C9	179.8 (3)
N3—Mn—O3—C19	0.5 (2)	C7—C8—C9—C10	−0.1 (5)
O1—Mn—O3—C19	3.3 (3)	C11—N2—C10—C9	0.5 (5)
N1—Mn—O3—C19	−165.8 (2)	Mn—N2—C10—C9	179.8 (3)
N2—Mn—O3—C19	−92.9 (2)	C8—C9—C10—N2	−0.1 (6)
N3—Mn—O5—O2^i	33.45 (16)	C10—N2—C11—C7	−0.8 (5)
O1—Mn—O5—O2^i	106.14 (14)	Mn—N2—C11—C7	179.8 (2)
N1—Mn—O5—O2^i	−126.75 (14)	C10—N2—C11—C12	179.5 (3)
O3—Mn—O5—O2^i	−38.52 (14)	Mn—N2—C11—C12	0.1 (4)
N2—Mn—O5—O2^i	−171.2 (3)	C8—C7—C11—N2	0.7 (5)
N3—Mn—O5—O4^ii	−153.52 (14)	C6—C7—C11—N2	−179.4 (3)
O1—Mn—O5—O4^ii	−80.83 (15)	C8—C7—C11—C12	−179.6 (3)
N1—Mn—O5—O4^ii	46.29 (16)	C6—C7—C11—C12	0.3 (5)
O3—Mn—O5—O4^ii	134.51 (15)	C1—N1—C12—C4	−1.2 (5)
N2—Mn—O5—O4^ii	1.9 (4)	Mn—N1—C12—C4	−175.9 (2)
O5—Mn—N1—C1	17.5 (3)	C1—N1—C12—C11	179.6 (3)
N3—Mn—N1—C1	−109.9 (3)	Mn—N1—C12—C11	4.9 (4)
O1—Mn—N1—C1	110.7 (3)	C3—C4—C12—N1	1.8 (5)
O3—Mn—N1—C1	−77.3 (3)	C5—C4—C12—N1	−176.7 (3)
N2—Mn—N1—C1	−177.7 (3)	C3—C4—C12—C11	−179.0 (3)
O5—Mn—N1—C12	−168.3 (2)	C5—C4—C12—C11	2.5 (5)
N3—Mn—N1—C12	64.3 (4)	N2—C11—C12—N1	−3.4 (4)
O1—Mn—N1—C12	−75.2 (3)	C7—C11—C12—N1	176.9 (3)
O3—Mn—N1—C12	96.8 (2)	N2—C11—C12—C4	177.4 (3)
N2—Mn—N1—C12	−3.6 (2)	C7—C11—C12—C4	−2.3 (5)
O5—Mn—N2—C10	−130.7 (4)	C17—N3—C13—C14	0.3 (5)
N3—Mn—N2—C10	25.2 (3)	Mn—N3—C13—C14	178.1 (3)
O1—Mn—N2—C10	−47.0 (3)	C17—N3—C13—C18	−179.2 (3)
N1—Mn—N2—C10	−177.6 (3)	Mn—N3—C13—C18	−1.4 (4)
O3—Mn—N2—C10	97.3 (3)	N3—C13—C14—C15	−0.7 (6)
O5—Mn—N2—C11	48.6 (4)	C18—C13—C14—C15	178.7 (4)
N3—Mn—N2—C11	−155.5 (2)	C13—C14—C15—C16	0.7 (6)
O1—Mn—N2—C11	132.4 (2)	C14—C15—C16—C17	−0.2 (6)
N1—Mn—N2—C11	1.8 (2)	C13—N3—C17—C16	0.2 (5)
O3—Mn—N2—C11	−83.4 (2)	Mn—N3—C17—C16	−177.5 (3)
O5—Mn—N3—C17	−91.5 (3)	C13—N3—C17—C19	178.5 (3)
O1—Mn—N3—C17	−179.0 (3)	Mn—N3—C17—C19	0.7 (4)
N1—Mn—N3—C17	34.0 (4)	C15—C16—C17—N3	−0.3 (6)
O3—Mn—N3—C17	−0.7 (2)	C15—C16—C17—C19	−178.3 (4)
N2—Mn—N3—C17	97.2 (3)	Mn—O1—C18—O2	−173.7 (3)
O5—Mn—N3—C13	90.7 (3)	Mn—O1—C18—C13	6.1 (4)
O1—Mn—N3—C13	3.2 (2)	N3—C13—C18—O2	176.6 (3)
N1—Mn—N3—C13	−143.9 (3)	C14—C13—C18—O2	−2.8 (6)
O3—Mn—N3—C13	−178.5 (3)	N3—C13—C18—O1	−3.2 (5)
N2—Mn—N3—C13	−80.6 (2)	C14—C13—C18—O1	177.4 (4)
C12—N1—C1—C2	−0.1 (5)	Mn—O3—C19—O4	178.0 (3)
Mn—N1—C1—C2	174.0 (3)	Mn—O3—C19—C17	−0.4 (4)
N1—C1—C2—C3	0.6 (6)	N3—C17—C19—O4	−178.7 (3)
C1—C2—C3—C4	0.1 (6)	C16—C17—C19—O4	−0.6 (5)
C2—C3—C4—C12	−1.3 (5)	N3—C17—C19—O3	−0.2 (4)
C2—C3—C4—C5	177.2 (4)	C16—C17—C19—O3	177.9 (3)
C3—C4—C5—C6	−179.1 (4)

Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) x+1, y, z; (iii) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5B···O2^i	0.83 (4)	1.81 (2)	2.605 (4)	160 (4)
O5—H5C···O4^ii	0.88 (4)	1.83 (4)	2.699 (4)	168 (4)
O6—H6B···O4	0.85 (5)	2.20 (4)	2.845 (4)	133 (5)
O6—H6C···O3^iii	0.84 (2)	2.20 (4)	2.962 (4)	152 (6)

Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) x+1, y, z; (iii) −x, −y+1, −z+1.