Crystal structure and thermal properties of bis-[μ-2-(meth-oxy-carbonyl-hydrazinyl-idene)acetato-κ3 N 1,O:O]bis-[di-aqua-(thio-cyanato-κN)manganese(II)] tetra-hydrate.

The title compound, [Mn2(C4H5N2O4)2(NCS)2(H2O)4]·4H2O (I), exists as a centrosymmetric dimer. Each dimeric unit consists of tridentate (O,O,N)-chelating Schiff bases with symmetry-maintained μ-O-bridged carboxyl-ate anions, terminally bound thio-cyanate anions, and ligated and solvated water mol-ecules. The complex exhibits a distorted octa-hedron geometry and the centrosymmetric μ-O-bridged carboxyl-ate anions connect the two manganese atoms to form an M 2O2 ring. In the crystal, the mol-ecules are inter-linked via strong N-H⋯O and O-H⋯O hydrogen-bonding contacts and weak O-H⋯S inter-molecular inter-actions, forming a three-dimensional mol-ecular network.

Chemical context

Hydrazine, di­nitro­gen n class="Species">tetra­hydride (N2H4), is the simplest di­amine and parent of innumerable organic derivatives. Among them, carbaza­tes (esters of hydrazine­carb­oxy­lic acid, NH2-NH-COO-R, where R = CH3, C2H5, CH2C6H5 etc) are inter­esting as ligands in view of their variety of potential donor atoms such as oxygen and nitro­gen. Inter­estingly, these neutral mol­ecules can be expected to exhibit only one common coordination mode, i.e. N,O-chelating bidentate. This has been clearly observed in many metal complexes with a variety of anions such as formate (Srinivasan et al., 2011 ▸), benzoate (Kathiresan et al., 2012 ▸), thio­cyanate (Srinivasan et al., 2014a ▸,b ▸), nitrate (Zhang et al., 2005 ▸; Srinivasan et al., 2007 ▸,2008 ▸) and perchlorate (Chen et al., 2016 ▸, Sitong et al., 2016 ▸). Apart from their coordination ability, alkyl carbaza­tes can also undergo condensation reactions; the hydrazinic part of the terminal amine group can react with the carbonyl group of aldehydes or ketones to form Schiff bases. In this regard, Schiff bases and their CoIII, NiII, PdII and FeII complexes based on (2-phenyl­phosphino)benzaldehyde with ethyl carbazate (Milenković et al., 2013a ▸,b ▸, 2014 ▸) have been reported. Recently, we have also reported Schiff bases generated from analogous benzyl carbazate with alkyl and heteroaryl ketones, and their metal complexes (Nithya et al., 2016 ▸, 2017a ▸,b ▸, 2018a ▸,b ▸). However, no work involving Schiff base complexes of alkyl carbaza­tes with an aldehydic, or α-keto acid, has been reported so far, except from our own recent report of a Schiff base generated from methyl carbazate and α-ketoglutaric acid, and its silver(I) complex (Parveen et al., 2018 ▸). In a continuation of our investigations, the title complex (I) was prepared by a template method starting from manganese(II) nitrate with a Schiff base ligand. The product of condensation between methyl carbazate and glyoxylic acid, formed in situ in aqueous solution containing ammonium thio­cyanate.

Structural commentary

General structural details

The manganese title compound crystallizes in the monoclinic space group P2 and exists as a centrosymmetric dimer (Fig. 1 ▸). The asymmetric unit consists of an Mn atom, a tridentate n class="Chemical">Schiff base ligand, an N-bounded thio­cyanate moiety, and two ligated and two solvated water mol­ecules. The manganese atom is surrounded in a distorted octa­hedral geometry by symmetry-related μ-O-bridged carboxyl­ate anions, one azomethine nitro­gen, an N-bounded NCS anion and two ligated water mol­ecules with an MnN2O4 core. The axial sites are occupied by one of the coordinated water mol­ecules (O2W) and the N-bonded NCS anion, whereas the μ-O-bridged carboxyl­ate anions, azomethine nitro­gen atom and a coordinated water mol­ecule (O1W) occupy the equatorial positions. The two manganese atoms are connected via centrosymmetrically related μ-O-bridged carboxyl­ate anions, forming a rhomboidal Mn2O2 unit about an inversion centre.

Figure 1

Mol­ecular structure of the title complex (I), showing the atom-numbering scheme and displacement ellipsoids drawn at the 50% probability level. The mol­ecule is located about an inversion centre and the unlabelled atoms are generated by the symmetry operation (−x + 1, −y, −z + 1).

Specific structural details

The separation of the Mn atoms is 3.645 (3) Å. The Mn—N(iso­thio­cyanato) and Mn—n class="Chemical">N(azomethine) distances are 2.1289 (11) and 2.3388 (10) Å and the Mn—O distances involving the coordinated water mol­ecules and μ-O-bridged carboxyl­ate anions are 2.1448 (9), 2.1905 (9) and 2.2606 (8), 2.2985 (8) Å, respectively. The Mn—N—C—S torsion angle in the NCS moiety is 103.5 (4)° and the bond angles for the coordinated atoms vary from 68.99 (3)–132.57 (4)°, indicating a distorted geometry.

Supra­molecular features

The crystal structure of (I) contains both coordinated and solvated water mol­ecules. Inter- and intra-mol­ecular n class="Chemical">hydrogen-bonding inter­actions (Table 1 ▸) stabilize the supra­molecular three-dimensional network. The N2—H2N⋯O2v [2.7971 (13) Å] hydrogen bond between adjacent dimers forms chains extending along the ac diagonal. The weak O4W—H4W1⋯S1iv inter­action [3.3159 (12) Å] and O2W—H2W1⋯O4W hydrogen bond [2.7322 (14) Å] link the dimers, generating a two-dimensional network as shown in Fig. 2 ▸. The ligated and solvated water mol­ecules O1W, O3W and O4W are involved in O—H⋯O hydrogen-bonding inter­actions [2.733 (14)–3.2158 (15) Å, Table 1 ▸] that stack the complex mol­ecules along the b-axis direction. These contacts combine to generate several ring motifs (Fig. 3 ▸) viz. R 1 1(6), R 2 3(10) and R 4 4(14) that stabilize the three-dimensional supra­molecular network (Fig. 4 ▸).

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W1⋯O2i	0.83 (2)	1.92 (2)	2.7158 (13)	160 (2)
O1W—H1W2⋯O3W	0.80 (2)	2.07 (2)	2.8627 (15)	174 (2)
O2W—H2W1⋯O4W	0.79 (2)	1.94 (2)	2.7332 (14)	175 (2)
O2W—H2W2⋯O3ii	0.82 (3)	2.11 (3)	2.8852 (13)	159 (2)
O2W—H2W2⋯O1W ii	0.82 (3)	2.54 (2)	3.0865 (13)	125 (2)
O3W—H3W1⋯O4W ii	0.79 (2)	2.09 (3)	2.8264 (17)	155 (2)
O3W—H3W2⋯O4iii	0.80 (3)	2.54 (3)	3.2158 (15)	144 (2)
O4W—H4W1⋯S1iv	0.87 (3)	2.52 (3)	3.3159 (12)	153 (2)
O4W—H4W2⋯O3W iv	0.81 (2)	1.97 (2)	2.7754 (16)	173 (2)
N2—H2N⋯O2v	0.83 (2)	1.97 (2)	2.7971 (13)	174 (2)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .

Figure 2

View of a two-dimensional array of (I) showing N—H⋯O and O—H⋯O hydrogen bonds and weak O—H⋯S inter­molecular inter­actions (green lines) in a projection along the b axis.

Figure 3

View of hydrogen-bonding inter­actions (green lines) along the ac plane forming various ring motifs to further stabilize the three-dimensional network.

Figure 4

Overall packing view of the three-dimensional network for (I), viewed along the b axis, showing N—H⋯O and O—H⋯O hydrogen bonds and weak O—H⋯S inter­molecular inter­actions (green lines) and the stacking of (I) along the b axis.

Thermal properties

The thermal decomposition behaviour of the title complex was studied by simultaneous TG–n class="Chemical">DTG analyses recorded in a nitro­gen atmosphere in the temperature range 30–800°C, as shown in Fig. 5 ▸. The TG curve displays the combined mass loss of 20.5% (calculated 21.8%) in the temperature range 30–140°C corresponding to dehydration of both the solvated and coordinated water mol­ecules. The anhydrous compound then shows continuous decomposition between 140 and 600°C to give manganese sulfide as the end product (mass loss observed 73.6%, calculated 72.50%). The DTG curve shows a doublet (40 and 80°C) for dehydration and a multiplet (150, 164, 255 and 321°C) for the decomposition of the anhydrous compound in accordance with TG mass loss.

Figure 5

Simultaneous TG/DTG (N2 atmosphere) analysis of the title complex (I).

Database survey

There are a few structures of metal complexes in the crystallographic literature with simple n class="Chemical">hydrazones based on glyoxylic acid and salicyloyl hydrazine (Liu et al., 2010 ▸) and thio­semicarbazide (Dodoff et al., 2006 ▸; Huseynova et al., 2018 ▸). In the former salicyloyl hydrazone complex of cadmium, the Schiff base acts as a tetra­dentate (O,N,O,O) ligand with one of the carboxyl­ate oxygen atoms bridging the cadmium centers, leading to a dimer, whereas in the thio­semicarbazone complexes of Zn, Pd, Pt, Co, and Ni (Milenković et al., 2013a ▸,b ▸, 2014 ▸), the ligand adopts a tridentate (O,N,O) coordination mode. Recently, we have reported a silver(I) complex of 2-(meth­oxy­carbonyl­hydrazono)penta­nedioic acid in which the neutral as well as monoanionic Schiff base behaves as a tridentate (O,N,O) group, leading to an octa­hedral coordination of the silver atom (Parveen et al., 2018 ▸).

Synthesis and crystallization

Elemental analyses for carbon, hydrogen and nitro­gen were recorded using a Vario-ELIII elemental analyzer. The IR spectrum was recorded using a JASCO-4100 spectrophotometer and KBr pellets in the range of 4000–400.00 cm−1. Simultaneous TG/DTG (TG/DTG) analyses were carried out using a TA instrument, SDT Q600 thermal analyzer, in a flowing nitro­gen atmosphere with a heating rate of 10°C min−1.

Stoichiometric qu­anti­ties of glyoxylic acid (0.184 g, 2 mmol), ethyl­carbazate (0.208 g, 2 mmol) and ammonium thio­cyanate (0.152 g, 2 mmol) were dissolved in 30 mL of double-distilled n class="Chemical">water. To this homogeneous solution, Mn(NO3)2·6H2O (0.287 g, 1 mmol) dissolved in 10.00 mL of double-distilled water was added dropwise, the pH of the resulting solution was noted as 3.45. The above clear solution was kept over a water-bath until the solution was reduced to ca 15 mL and allowed to stand at room temperature for slow crystallization. After two days, colourless rod-shaped crystals were obtained and filtered off, washed with ice-cold water and air dried. The product is soluble in water, methanol and ethanol and insoluble in diethyl ether. In the absence of ammonium thio­cyanate, the reaction did not yield any desired product. Yield: 64%. Analysis calculated for C10H26Mn2N6O16S2 (I): C, 29.25, H, 3.44, N, 13.57; found: C, 29.20; H, 3.49; N, 13.55. Metal (%): calculated 14.27 (found: 14.06), FT–IR (KBr, cm−1): 3520 (b) [ν(O—H)], 3206 (b) [ν(N—H)], 2096 (s) [ν(C≡N)], 1705 (s) [ν(C=O], 1627 (m) [νasym (C=O)], 1555 (s) [ν(C=N)], 1397 (s) [νsym(C=O)], 1067 (s) [ν(N—N)].

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. H atoms attached to n class="Chemical">carbon atoms were positioned geometrically and constrained to ride on their parent atoms, with carbon–hydrogen bond lengths of 0.95 Å for alkene C—H and 0.98 Å for CH3 groups, respectively. Methyl H atoms were allowed to rotate but not to tip to best fit the experimental electron density. U iso(H) values were set to a multiple of U eq(C) with 1.5 for CH3 and 1.2 for C—H groups, respectively. Positions and U iso values of water and amine H atoms were freely refined.

Table 2

Experimental details

Crystal data
Chemical formula	[Mn2(C4H5N2O4)2(NCS)2(H2O)4]·4H2O
M r	660.37
Crystal system, space group	Monoclinic, P21/n
Temperature (K)	120
a, b, c (Å)	9.7060 (3), 8.3654 (3), 16.0082 (6)
β (°)	90.653 (2)
V (Å3)	1299.69 (8)
Z	2
Radiation type	Mo Kα
μ (mm−1)	1.21
Crystal size (mm)	0.46 × 0.24 × 0.17
Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996 ▸)
T min, T max	0.658, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	12223, 3915, 3408
R int	0.024
(sin θ/λ)max (Å−1)	0.715
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.025, 0.060, 1.05
No. of reflections	3915
No. of parameters	200
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)	0.49, −0.34

Computer programs: APEX2 and SAINT (Bruker, 2014 ▸), SIR92 (Altomare et al., 1993 ▸), SHELXL2018/3 (Sheldrick, 2015 ▸) and shelXle (Hübschle et al., 2011 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018014871/jj2203sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989018014871/jj2203Isup2.hkl

CCDC reference: 1870123

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Mn2(C4H5N2O4)2(NCS)2(H2O)4]·4H2O	F(000) = 676
Mr = 660.37	Dx = 1.687 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.7060 (3) Å	Cell parameters from 6980 reflections
b = 8.3654 (3) Å	θ = 2.5–30.6°
c = 16.0082 (6) Å	µ = 1.21 mm−1
β = 90.653 (2)°	T = 120 K
V = 1299.69 (8) Å3	Rod, colourless
Z = 2	0.46 × 0.24 × 0.17 mm

Bruker APEXII CCD diffractometer	3915 independent reflections
Radiation source: fine focus sealed tube	3408 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
ω and phi scans	θmax = 30.6°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→12
Tmin = 0.658, Tmax = 0.746	k = −11→11
12223 measured reflections	l = −22→22

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.025	Hydrogen site location: mixed
wR(F2) = 0.060	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0256P)2 + 0.5439P] where P = (Fo2 + 2Fc2)/3
3915 reflections	(Δ/σ)max = 0.003
200 parameters	Δρmax = 0.49 e Å−3
0 restraints	Δρmin = −0.34 e Å−3

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.

	x	y	z	Uiso*/Ueq
Mn1	0.59833 (2)	0.18522 (2)	0.50685 (2)	0.00920 (5)
S1	0.95128 (4)	−0.10626 (4)	0.66382 (2)	0.02029 (8)
O1	0.55108 (9)	−0.03030 (10)	0.42219 (5)	0.01108 (16)
O2	0.60023 (10)	−0.15606 (10)	0.30205 (5)	0.01546 (18)
O3	0.74296 (10)	0.44631 (11)	0.48516 (5)	0.01696 (18)
O4	0.87386 (10)	0.57439 (11)	0.38944 (6)	0.0191 (2)
O1W	0.57632 (11)	0.34713 (11)	0.61341 (6)	0.01577 (18)
H1W1	0.528 (2)	0.303 (3)	0.6488 (14)	0.046 (6)*
H1W2	0.646 (2)	0.379 (3)	0.6349 (14)	0.041 (6)*
O2W	0.42696 (10)	0.30284 (11)	0.44755 (6)	0.01524 (18)
H2W1	0.414 (2)	0.292 (2)	0.3989 (13)	0.028 (5)*
H2W2	0.396 (2)	0.389 (3)	0.4635 (15)	0.055 (7)*
O3W	0.82278 (12)	0.48163 (13)	0.68375 (7)	0.0247 (2)
H3W1	0.787 (3)	0.562 (3)	0.6975 (15)	0.053 (7)*
H3W2	0.887 (3)	0.509 (3)	0.6565 (16)	0.062 (8)*
O4W	0.38041 (13)	0.28790 (14)	0.27902 (7)	0.0265 (2)
H4W1	0.426 (3)	0.353 (3)	0.2471 (15)	0.057 (7)*
H4W2	0.370 (2)	0.206 (3)	0.2527 (14)	0.044 (6)*
N1	0.70220 (10)	0.21438 (11)	0.37662 (6)	0.01068 (19)
N2	0.77597 (11)	0.34553 (12)	0.35488 (6)	0.0123 (2)
H2N	0.8177 (18)	0.349 (2)	0.3097 (11)	0.018 (4)*
N11	0.77393 (12)	0.06901 (13)	0.55969 (7)	0.0184 (2)
C11	0.84668 (13)	−0.00547 (15)	0.60238 (8)	0.0140 (2)
C1	0.60689 (12)	−0.03982 (14)	0.35114 (7)	0.0107 (2)
C2	0.68949 (12)	0.10135 (14)	0.32384 (7)	0.0117 (2)
H2A	0.730139	0.106396	0.270198	0.014*
C3	0.79375 (13)	0.45612 (14)	0.41613 (7)	0.0125 (2)
C4	0.89246 (17)	0.70729 (17)	0.44739 (9)	0.0256 (3)
H4A	0.947018	0.791232	0.420758	0.038*
H4B	0.940626	0.669641	0.497796	0.038*
H4C	0.802229	0.750334	0.462554	0.038*

	U11	U22	U33	U12	U13	U23
Mn1	0.01079 (9)	0.00955 (9)	0.00729 (8)	0.00015 (6)	0.00089 (6)	−0.00039 (6)
S1	0.01857 (16)	0.02354 (17)	0.01866 (15)	0.00707 (12)	−0.00337 (12)	0.00329 (13)
O1	0.0138 (4)	0.0112 (4)	0.0083 (4)	−0.0019 (3)	0.0033 (3)	−0.0009 (3)
O2	0.0215 (5)	0.0138 (4)	0.0113 (4)	−0.0043 (3)	0.0066 (3)	−0.0045 (3)
O3	0.0233 (5)	0.0163 (4)	0.0114 (4)	−0.0045 (4)	0.0061 (3)	−0.0022 (3)
O4	0.0254 (5)	0.0149 (4)	0.0170 (4)	−0.0098 (4)	0.0085 (4)	−0.0039 (3)
O1W	0.0211 (5)	0.0149 (4)	0.0114 (4)	−0.0064 (4)	0.0040 (4)	−0.0029 (3)
O2W	0.0185 (5)	0.0151 (4)	0.0121 (4)	0.0051 (3)	−0.0019 (3)	−0.0013 (3)
O3W	0.0230 (6)	0.0228 (5)	0.0284 (5)	−0.0034 (4)	0.0049 (4)	0.0034 (4)
O4W	0.0377 (6)	0.0246 (5)	0.0171 (5)	−0.0057 (5)	−0.0050 (4)	0.0004 (4)
N1	0.0108 (5)	0.0092 (4)	0.0121 (4)	−0.0004 (3)	0.0019 (3)	0.0019 (4)
N2	0.0165 (5)	0.0102 (4)	0.0102 (4)	−0.0032 (4)	0.0058 (4)	0.0003 (4)
N11	0.0173 (6)	0.0175 (5)	0.0202 (5)	0.0004 (4)	−0.0033 (4)	0.0005 (4)
C11	0.0130 (6)	0.0140 (5)	0.0151 (5)	−0.0015 (4)	0.0009 (4)	−0.0018 (4)
C1	0.0115 (5)	0.0107 (5)	0.0098 (5)	−0.0003 (4)	0.0005 (4)	0.0002 (4)
C2	0.0139 (6)	0.0123 (5)	0.0090 (5)	−0.0004 (4)	0.0033 (4)	0.0002 (4)
C3	0.0125 (6)	0.0113 (5)	0.0136 (5)	−0.0009 (4)	0.0027 (4)	0.0004 (4)
C4	0.0331 (8)	0.0186 (6)	0.0254 (7)	−0.0131 (6)	0.0074 (6)	−0.0091 (5)

Mn1—N11	2.1289 (11)	O2W—H2W2	0.82 (3)
Mn1—O2W	2.1448 (9)	O3W—H3W1	0.79 (2)
Mn1—O1W	2.1905 (9)	O3W—H3W2	0.80 (3)
Mn1—O1i	2.2606 (8)	O4W—H4W1	0.87 (3)
Mn1—O1	2.2985 (8)	O4W—H4W2	0.81 (2)
Mn1—N1	2.3388 (10)	N1—C2	1.2731 (15)
Mn1—O3	2.6216 (9)	N1—N2	1.3576 (14)
S1—C11	1.6390 (13)	N2—C3	1.3577 (15)
O1—C1	1.2679 (13)	N2—H2N	0.833 (17)
O2—C1	1.2515 (14)	N11—C11	1.1588 (17)
O3—C3	1.2177 (14)	C1—C2	1.4955 (16)
O4—C3	1.3318 (14)	C2—H2A	0.9500
O4—C4	1.4578 (16)	C4—H4A	0.9800
O1W—H1W1	0.83 (2)	C4—H4B	0.9800
O1W—H1W2	0.80 (2)	C4—H4C	0.9800
O2W—H2W1	0.79 (2)
N11—Mn1—O2W	177.02 (4)	Mn1—O2W—H2W1	119.7 (14)
N11—Mn1—O1W	93.31 (4)	Mn1—O2W—H2W2	123.1 (17)
O2W—Mn1—O1W	88.79 (4)	H2W1—O2W—H2W2	111 (2)
N11—Mn1—O1i	93.09 (4)	H3W1—O3W—H3W2	105 (2)
O2W—Mn1—O1i	89.24 (3)	H4W1—O4W—H4W2	106 (2)
O1W—Mn1—O1i	83.93 (3)	C2—N1—N2	118.52 (10)
N11—Mn1—O1	91.69 (4)	C2—N1—Mn1	118.34 (8)
O2W—Mn1—O1	87.15 (3)	N2—N1—Mn1	123.15 (7)
O1W—Mn1—O1	157.45 (3)	N1—N2—C3	115.37 (10)
O1i—Mn1—O1	73.84 (3)	N1—N2—H2N	120.8 (12)
N11—Mn1—N1	92.90 (4)	C3—N2—H2N	123.0 (12)
O2W—Mn1—N1	84.12 (4)	C11—N11—Mn1	163.64 (10)
O1W—Mn1—N1	132.57 (4)	N11—C11—S1	178.43 (12)
O1i—Mn1—N1	142.48 (3)	O2—C1—O1	126.34 (11)
O1—Mn1—N1	68.99 (3)	O2—C1—C2	117.00 (10)
N11—Mn1—O3	90.32 (4)	O1—C1—C2	116.65 (10)
O2W—Mn1—O3	88.45 (3)	N1—C2—C1	116.15 (10)
O1W—Mn1—O3	69.22 (3)	N1—C2—H2A	121.9
O1i—Mn1—O3	153.09 (3)	C1—C2—H2A	121.9
O1—Mn1—O3	132.76 (3)	O3—C3—O4	125.80 (11)
N1—Mn1—O3	63.78 (3)	O3—C3—N2	124.05 (11)
C1—O1—Mn1i	134.25 (7)	O4—C3—N2	110.14 (10)
C1—O1—Mn1	119.59 (7)	O4—C4—H4A	109.5
Mn1i—O1—Mn1	106.16 (3)	O4—C4—H4B	109.5
C3—O3—Mn1	113.53 (8)	H4A—C4—H4B	109.5
C3—O4—C4	115.53 (10)	O4—C4—H4C	109.5
Mn1—O1W—H1W1	108.5 (15)	H4A—C4—H4C	109.5
Mn1—O1W—H1W2	116.8 (16)	H4B—C4—H4C	109.5
H1W1—O1W—H1W2	110 (2)
C2—N1—N2—C3	−175.42 (11)	O2—C1—C2—N1	−175.83 (11)
Mn1—N1—N2—C3	4.17 (14)	O1—C1—C2—N1	3.73 (16)
Mn1i—O1—C1—O2	−7.27 (19)	Mn1—O3—C3—O4	−178.58 (10)
Mn1—O1—C1—O2	173.28 (10)	Mn1—O3—C3—N2	1.36 (16)
Mn1i—O1—C1—C2	173.21 (8)	C4—O4—C3—O3	−4.53 (19)
Mn1—O1—C1—C2	−6.24 (13)	C4—O4—C3—N2	175.52 (12)
N2—N1—C2—C1	−179.86 (10)	N1—N2—C3—O3	−3.54 (18)
Mn1—N1—C2—C1	0.53 (14)	N1—N2—C3—O4	176.40 (10)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···O2i	0.83 (2)	1.92 (2)	2.7158 (13)	160 (2)
O1W—H1W2···O3W	0.80 (2)	2.07 (2)	2.8627 (15)	174 (2)
O2W—H2W1···O4W	0.79 (2)	1.94 (2)	2.7332 (14)	174.6 (19)
O2W—H2W2···O3ii	0.82 (3)	2.11 (3)	2.8852 (13)	159 (2)
O2W—H2W2···O1Wii	0.82 (3)	2.54 (2)	3.0865 (13)	125 (2)
O3W—H3W1···O4Wii	0.79 (2)	2.09 (3)	2.8264 (17)	155 (2)
O3W—H3W2···O4iii	0.80 (3)	2.54 (3)	3.2158 (15)	144 (2)
O4W—H4W1···S1iv	0.87 (3)	2.52 (3)	3.3159 (12)	153 (2)
O4W—H4W2···O3Wiv	0.81 (2)	1.97 (2)	2.7754 (16)	173 (2)
N2—H2N···O2v	0.833 (17)	1.967 (17)	2.7971 (13)	173.9 (17)