Di­aqua­bis­(hexa­methyl­enetetr­amine-N)­bis­(iso­thiocyanato)­manganese(II) tetra­aqua­bis­(iso­thio­cyanato)­manganese(II) dihydrate

The crystal structure of the title compound, [Mn(NCS)₂(hmt)₂(H₂O)₂]·[Mn(NCS)₂(H₂O)₄]·2H₂O, where hmt is hexa­methyl­ene­tetr­amine (C₆H₁₂N₄), shows that each Mn atom is in an octahedral coordination enviroment, and that the independent uncharged components [Mn(NCS)₂(hmt)₂(H₂O)₂], [Mn(NCS)₂(H₂O)₄] and H₂O are linked together by three kinds of hydrogen bonds (O—H...N, O—H...O and O—H...S) to form a three-dimensional supramolecular structure.

Key indicators

• Single-crystal X-ray study
• T = 288 K
• Mean [sigma](N-C) = 0.002 Å
• R factor = 0.024
• wR factor = 0.062
• Data-to-parameter ratio = 14.7

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level B:



PLAT_731  Alert B Bond    Calc     0.82(3), Rep    0.819(5) ....       6.00 s.u-Ratio
                     O4   -H4OA    1.555   1.555

Author response: Hydrogen atoms sites solution of water was used the method of difference Fourier map. O-H distance was restraint with "DFix.82" instruction during the refinement.

PLAT_735  Alert B D-H     Calc     0.82(3), Rep    0.819(5) ....       6.00 s.u-Ratio
                     O4   -H4OA    1.555   1.555

Author response: Hydrogen atoms sites solution of water was used the method of difference Fourier map. O-H distance was restraint with "DFix.82" instruction during the refinement.

PLAT_736  Alert B H...A   Calc     2.00(3), Rep    2.001(6) ....       5.00 s.u-Ratio
                     H4OA -N4      1.555   1.555

Author response: Hydrogen atoms sites solution of water was used the method of difference Fourier map. O-H distance was restraint with "DFix.82" instruction during the refinement.

 Alert Level C:



PLAT_420  Alert C D-H Without Acceptor       O1     -   H1OB              ?

PLAT_731  Alert C Bond    Calc   0.818(17), Rep    0.818(5) ....       3.40 s.u-Ratio
                     O1   -H1OA    1.555   1.555

PLAT_731  Alert C Bond    Calc     0.82(2), Rep    0.818(5) ....       4.00 s.u-Ratio
                     O1   -H1OB    1.555   1.555

PLAT_731  Alert C Bond    Calc   0.823(18), Rep    0.823(5) ....       3.60 s.u-Ratio
                     O2   -H2OA    1.555   1.555

PLAT_731  Alert C Bond    Calc     0.82(2), Rep    0.822(5) ....       4.00 s.u-Ratio
                     O2   -H2OB    1.555   1.555

PLAT_731  Alert C Bond    Calc   0.815(14), Rep    0.815(5) ....       2.80 s.u-Ratio
                     O3   -H3OA    1.555   1.555

PLAT_731  Alert C Bond    Calc   0.817(12), Rep    0.816(5) ....       2.40 s.u-Ratio
                     O3   -H3OB    1.555   1.555

PLAT_731  Alert C Bond    Calc   0.819(18), Rep    0.818(5) ....       3.60 s.u-Ratio
                     O4   -H4OB    1.555   1.555

PLAT_735  Alert C D-H     Calc   0.819(18), Rep    0.818(5) ....       3.60 s.u-Ratio
                     O4   -H4OB    1.555   1.555

PLAT_735  Alert C D-H     Calc     0.82(2), Rep    0.822(5) ....       4.00 s.u-Ratio
                     O2   -H2OB    1.555   1.555

PLAT_735  Alert C D-H     Calc   0.823(18), Rep    0.823(5) ....       3.60 s.u-Ratio
                     O2   -H2OA    1.555   1.555

PLAT_735  Alert C D-H     Calc   0.817(12), Rep    0.816(5) ....       2.40 s.u-Ratio
                     O3   -H3OB    1.555   1.555

PLAT_735  Alert C D-H     Calc   0.815(14), Rep    0.815(5) ....       2.80 s.u-Ratio
                     O3   -H3OA    1.555   1.555

PLAT_735  Alert C D-H     Calc   0.818(17), Rep    0.818(5) ....       3.40 s.u-Ratio
                     O1   -H1OA    1.555   1.555

PLAT_736  Alert C H...A   Calc   1.991(18), Rep    1.992(7) ....       2.57 s.u-Ratio
                     H2OA -N3      1.555   1.555

PLAT_736  Alert C H...A   Calc   1.925(16), Rep    1.925(6) ....       2.67 s.u-Ratio
                     H1OA -O4      1.555   2.666

General Notes



FORMU_01  There is a discrepancy between the atom counts in the
          _chemical_formula_sum and _chemical_formula_moiety. This is
          usually due to the moiety formula being in the wrong format.
          Atom count from _chemical_formula_sum:   C16 H40 Mn2 N12 O8 S4
          Atom count from _chemical_formula_moiety:C16 H40 Mn1 N12 O8 S4


 0 Alert Level A = Potentially serious problem

 3 Alert Level B = Potential problem

 16 Alert Level C = Please check

---

S1. Comment

Metal complexes that assemble into specific supramolecular structures in the crystal lattice have generated considerable interest because of their potential use in developing new materials with magnetic, optical and catalytic properties (Lehn, 1990). Materials with multidimensional supramolecular architectures have been organized by coordinate, covalent or hydrogen bonding (Gemma & Jonathan, 1999). The vast majority of current work centers around the controlled assembly of donor and acceptor building blocks (particularly involving hydrogen-bond acid–base pairs, e.g. nucleobase) in order to generate an entirely supramolecular polymer, i.e. a material held together solely by non-covalent interactions. With this in mind, considering hexamethylenetetramine (hmt) as a potential tetradentate ligand or hydrogen-bond acceptor, and suitable for the self-assembly of supramolecular architectures (Stuart et al., 1998), we sought to synthesize a multidimensional supramolecular compound containing it. Herein we report the three-dimensional supramolecular architecture of [Mn(hmt)₂(H₂O)₂(NCS)₂]·[Mn(H₂O)₄(NCS)₂]·2H₂O, (I).

The molecular structure of (I) is shown in Fig. 1. The geometry around Mn1 is octahedral; the two O atoms of the coordinated water molecules and the two N atoms from two NCS^- define the equatorial positions, whereas an N atom from each of the hmt ligands occupies the axial ones. The axial Mn1—N1 bond distance of 2.4213 (13) Å is significantly longer than the equatorial Mn1—O1 bonds of 2.1865 (12) Å and the Mn1—N5 bonds of 2.1342 (15) Å. Mn2 is also in an octahedral environment. The coordination polyhedron is formed by two NCS^- and four water molecules, elongated along the axis defined by the water molecules; the axial Mn2—O2 distance is 2.2132 (13) Å. Both Mn1- and Mn2-containing species are located on inversion centres. In Fig. 2, both the interlayer Mn1···Mn1 and Mn2···Mn2 distances are 7.969 Å, the distance of Mn1···Mn1 between adjacent chains is 9.280 Å in the same layer, the shortest intermolecular Mn1···Mn2 distance is 7.296 Å and the shorter intermolecular Mn1···Mn2 distance is 8.640 Å. The independent moieties [Mn(hmt)₂(H₂O)₂(NCS)₂] and [Mn(H₂O)₄(NCS)₂] are connected by four hydrogen bonds (Table 2) to form a two-dimensional structure. Adjacent two-dimensional chains are connected by further hydrogen bonds to form a three-dimensional supramolecular architecture.

S2. Experimental

To 1 mmol of hmt and 2 mmol of MnCl₂·4H₂O in 3.5 ml of water solution, 2 ml aqueous solution of NH₄SCN was added and the mixture stirred for ca 10 min. The resulting solution was allowed to stand for 2 d. Colorless crystals were collected in 34% yield.

S3. Refinement

H atoms were placed in calculated positions (C—H = 0.97 Å), assigned fixed isotropic displacement parameters at 1.2 times the equivalent U_iso of the atoms to which they are attached and were allowed to ride on their respective parent atoms.

Computing details

Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: SHELXTL (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The molecular structure of the title compound showing 40% probability displacement ellipsoids and some neighbouring atoms linked by hydrogen bonds.
	Fig. 2. Packing diagram of the title compound, viewed along the a axis.

(I)

Crystal data

[Mn(NCS)2(C6H12N4)2(H2O)2]·[Mn(NCS)2(H2O)4]·2H2O	Z = 1
Mr = 766.72	F(000) = 398
Triclinic, P1	Dx = 1.507 Mg m^−3
a = 7.969 (1) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.111 (1) Å	Cell parameters from 26 reflections
c = 13.076 (2) Å	θ = 2.8–17.2°
α = 94.34 (1)°	µ = 1.05 mm^−1
β = 96.83 (1)°	T = 288 K
γ = 115.16 (1)°	Block, colourless
V = 844.76 (19) Å^3	0.48 × 0.48 × 0.40 mm

Data collection

Siemens P4 diffractometer	2853 reflections with I > 2σ(I)
Radiation source: normal-focus sealed tube	Rint = 0.010
Graphite monochromator	θmax = 26.0°, θmin = 1.6°
ω scans	h = 0→9
Absorption correction: ψ scan (XSCANS; Siemens, 1994)	k = −11→10
Tmin = 0.615, Tmax = 0.653	l = −16→16
3694 measured reflections	3 standard reflections every 97 reflections
3316 independent reflections	intensity decay: 3.5%

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)] = 0.024	H-atom parameters constrained
wR(F^2) = 0.062	w = 1/[σ^2(Fo^2) + (0.0321P)^2 + 0.1263P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
3316 reflections	Δρmax = 0.33 e Å^−3
226 parameters	Δρmin = −0.27 e Å^−3
12 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0364 (17)

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
Mn1	0.5000	0.0000	0.5000	0.02889 (10)
Mn2	0.0000	−0.5000	0.0000	0.03183 (11)
S1	−0.16159 (7)	−0.37686 (7)	0.44188 (4)	0.05815 (16)
S2	0.66791 (6)	−0.21450 (6)	0.17286 (4)	0.05044 (14)
N1	0.42844 (17)	0.09081 (14)	0.33825 (9)	0.0284 (3)
N2	0.5533 (2)	0.22801 (17)	0.19114 (11)	0.0383 (3)
N3	0.2372 (2)	0.00512 (16)	0.16372 (10)	0.0354 (3)
N4	0.3028 (2)	0.26803 (16)	0.26084 (11)	0.0391 (3)
N5	0.2048 (2)	−0.1341 (2)	0.49683 (12)	0.0475 (4)
N6	0.2969 (2)	−0.37415 (18)	0.07137 (12)	0.0453 (4)
O1	0.4996 (2)	0.21088 (15)	0.59150 (10)	0.0433 (3)
O2	−0.03956 (19)	−0.27697 (16)	0.03734 (11)	0.0463 (3)
O3	0.0833 (2)	−0.4221 (2)	−0.14557 (10)	0.0612 (4)
O4	0.1863 (2)	0.50706 (16)	0.32481 (11)	0.0467 (3)
C1	0.5968 (2)	0.1713 (2)	0.28886 (12)	0.0344 (4)
H1A	0.6912	0.2641	0.3368	0.041*
H1B	0.6490	0.0946	0.2748	0.041*
C2	0.2858 (2)	−0.04843 (18)	0.26183 (12)	0.0337 (4)
H2A	0.3343	−0.1277	0.2473	0.040*
H2B	0.1730	−0.1020	0.2919	0.040*
C3	0.3508 (2)	0.2099 (2)	0.35709 (12)	0.0358 (4)
H3A	0.2388	0.1591	0.3883	0.043*
H3B	0.4423	0.3030	0.4060	0.043*
C4	0.4101 (3)	0.0862 (2)	0.11935 (13)	0.0401 (4)
H4A	0.4601	0.0083	0.1040	0.048*
H4B	0.3802	0.1221	0.0546	0.048*
C5	0.4729 (3)	0.3427 (2)	0.21334 (14)	0.0440 (4)
H5A	0.4418	0.3794	0.1491	0.053*
H5B	0.5661	0.4380	0.2600	0.053*
C6	0.1634 (2)	0.1252 (2)	0.18730 (14)	0.0413 (4)
H6A	0.0499	0.0732	0.2171	0.050*
H6B	0.1309	0.1617	0.1233	0.050*
C7	0.0528 (2)	−0.2347 (2)	0.47418 (12)	0.0347 (4)
C8	0.4509 (2)	−0.30931 (19)	0.11229 (13)	0.0330 (3)
H1OA	0.5946 (17)	0.2925 (18)	0.6187 (17)	0.071 (8)*
H1OB	0.4048 (18)	0.210 (3)	0.610 (2)	0.105 (11)*
H2OA	0.0512 (19)	−0.196 (2)	0.0704 (16)	0.085 (9)*
H2OB	−0.1345 (18)	−0.294 (3)	0.0629 (17)	0.085 (9)*
H3OA	0.1931 (10)	−0.367 (2)	−0.1501 (15)	0.072 (8)*
H3OB	0.013 (2)	−0.457 (2)	−0.2016 (8)	0.065 (7)*
H4OA	0.215 (4)	0.436 (2)	0.3025 (17)	0.087 (9)*
H4OB	0.145 (3)	0.488 (3)	0.3792 (11)	0.081 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.02875 (18)	0.02442 (17)	0.02892 (18)	0.00741 (14)	0.00444 (13)	0.00397 (13)
Mn2	0.02604 (18)	0.03186 (19)	0.03127 (19)	0.00747 (14)	0.00344 (14)	0.00213 (14)
S1	0.0347 (3)	0.0591 (3)	0.0584 (3)	0.0038 (2)	0.0001 (2)	−0.0058 (2)
S2	0.0278 (2)	0.0529 (3)	0.0610 (3)	0.0132 (2)	−0.0016 (2)	−0.0058 (2)
N1	0.0315 (7)	0.0236 (6)	0.0278 (6)	0.0102 (5)	0.0045 (5)	0.0029 (5)
N2	0.0368 (8)	0.0362 (7)	0.0350 (7)	0.0084 (6)	0.0058 (6)	0.0130 (6)
N3	0.0400 (8)	0.0270 (7)	0.0296 (7)	0.0077 (6)	−0.0010 (6)	0.0022 (5)
N4	0.0454 (8)	0.0309 (7)	0.0394 (8)	0.0186 (7)	−0.0039 (6)	0.0021 (6)
N5	0.0328 (8)	0.0511 (9)	0.0477 (9)	0.0072 (7)	0.0066 (7)	0.0133 (7)
N6	0.0311 (8)	0.0449 (9)	0.0506 (9)	0.0104 (7)	0.0004 (7)	0.0006 (7)
O1	0.0457 (8)	0.0363 (7)	0.0462 (7)	0.0183 (6)	0.0058 (6)	−0.0035 (6)
O2	0.0381 (7)	0.0374 (7)	0.0547 (8)	0.0121 (6)	0.0021 (6)	−0.0073 (6)
O3	0.0342 (7)	0.0901 (11)	0.0368 (8)	0.0044 (8)	0.0056 (6)	0.0191 (7)
O4	0.0542 (8)	0.0436 (7)	0.0440 (8)	0.0244 (7)	0.0067 (7)	0.0002 (6)
C1	0.0324 (8)	0.0349 (8)	0.0328 (8)	0.0110 (7)	0.0052 (7)	0.0097 (7)
C2	0.0388 (9)	0.0250 (8)	0.0304 (8)	0.0077 (7)	0.0041 (7)	0.0042 (6)
C3	0.0420 (9)	0.0327 (8)	0.0326 (8)	0.0183 (7)	0.0015 (7)	−0.0006 (7)
C4	0.0496 (10)	0.0399 (9)	0.0285 (8)	0.0167 (8)	0.0074 (7)	0.0074 (7)
C5	0.0515 (11)	0.0259 (8)	0.0422 (10)	0.0080 (8)	−0.0056 (8)	0.0093 (7)
C6	0.0377 (9)	0.0390 (9)	0.0410 (9)	0.0142 (8)	−0.0046 (7)	0.0036 (7)
C7	0.0353 (9)	0.0420 (9)	0.0285 (8)	0.0170 (8)	0.0090 (7)	0.0083 (7)
C8	0.0336 (9)	0.0289 (8)	0.0368 (9)	0.0132 (7)	0.0092 (7)	0.0052 (7)

Geometric parameters (Å, º)

Mn1—N5^i	2.1341 (15)	N4—C3	1.473 (2)
Mn1—N5	2.1341 (15)	N4—C6	1.476 (2)
Mn1—O1^i	2.1866 (12)	N5—C7	1.151 (2)
Mn1—O1	2.1866 (12)	N6—C8	1.149 (2)
Mn1—N1	2.4213 (13)	O1—H1OA	0.818 (5)
Mn1—N1^i	2.4213 (13)	O1—H1OB	0.818 (5)
Mn2—O3	2.1616 (13)	O2—H2OA	0.823 (5)
Mn2—O3^ii	2.1616 (13)	O2—H2OB	0.822 (5)
Mn2—N6^ii	2.1886 (15)	O3—H3OA	0.815 (5)
Mn2—N6	2.1886 (15)	O3—H3OB	0.816 (5)
Mn2—O2^ii	2.2132 (13)	O4—H4OA	0.819 (5)
Mn2—O2	2.2132 (13)	O4—H4OB	0.818 (5)
S1—C7	1.6244 (17)	C1—H1A	0.97
S2—C8	1.6324 (17)	C1—H1B	0.97
N1—C3	1.479 (2)	C2—H2A	0.97
N1—C1	1.482 (2)	C2—H2B	0.97
N1—C2	1.4871 (19)	C3—H3A	0.97
N2—C5	1.468 (2)	C3—H3B	0.97
N2—C4	1.470 (2)	C4—H4A	0.97
N2—C1	1.472 (2)	C4—H4B	0.97
N3—C4	1.473 (2)	C5—H5A	0.97
N3—C2	1.474 (2)	C5—H5B	0.97
N3—C6	1.475 (2)	C6—H6A	0.97
N4—C5	1.471 (2)	C6—H6B	0.97
N5^i—Mn1—N5	180.0	Mn1—O1—H1OB	122.8 (16)
N5^i—Mn1—O1^i	90.22 (6)	H1OA—O1—H1OB	112.3 (13)
N5—Mn1—O1^i	89.78 (6)	Mn2—O2—H2OA	117.3 (17)
N5^i—Mn1—O1	89.78 (6)	Mn2—O2—H2OB	113.5 (17)
N5—Mn1—O1	90.22 (6)	H2OA—O2—H2OB	110.5 (13)
O1^i—Mn1—O1	180.00 (6)	Mn2—O3—H3OA	121.6 (14)
N5^i—Mn1—N1	91.80 (5)	Mn2—O3—H3OB	123.9 (14)
N5—Mn1—N1	88.20 (5)	H3OA—O3—H3OB	113.8 (13)
O1^i—Mn1—N1	88.28 (5)	H4OA—O4—H4OB	111.5 (13)
O1—Mn1—N1	91.72 (5)	N2—C1—N1	112.23 (13)
N5^i—Mn1—N1^i	88.20 (5)	N2—C1—H1A	109.2
N5—Mn1—N1^i	91.80 (5)	N1—C1—H1A	109.2
O1^i—Mn1—N1^i	91.72 (5)	N2—C1—H1B	109.2
O1—Mn1—N1^i	88.28 (5)	N1—C1—H1B	109.2
N1—Mn1—N1^i	180.0	H1A—C1—H1B	107.9
O3—Mn2—O3^ii	180.000 (1)	N3—C2—N1	112.10 (12)
O3—Mn2—N6^ii	91.79 (6)	N3—C2—H2A	109.2
O3^ii—Mn2—N6^ii	88.21 (6)	N1—C2—H2A	109.2
O3—Mn2—N6	88.21 (6)	N3—C2—H2B	109.2
O3^ii—Mn2—N6	91.79 (6)	N1—C2—H2B	109.2
N6^ii—Mn2—N6	180.00 (9)	H2A—C2—H2B	107.9
O3—Mn2—O2^ii	89.78 (6)	N4—C3—N1	112.35 (13)
O3^ii—Mn2—O2^ii	90.22 (6)	N4—C3—H3A	109.1
N6^ii—Mn2—O2^ii	91.64 (5)	N1—C3—H3A	109.1
N6—Mn2—O2^ii	88.36 (5)	N4—C3—H3B	109.1
O3—Mn2—O2	90.22 (6)	N1—C3—H3B	109.1
O3^ii—Mn2—O2	89.78 (6)	H3A—C3—H3B	107.9
N6^ii—Mn2—O2	88.36 (5)	N2—C4—N3	111.58 (13)
N6—Mn2—O2	91.64 (5)	N2—C4—H4A	109.3
O2^ii—Mn2—O2	180.0	N3—C4—H4A	109.3
C3—N1—C1	107.72 (12)	N2—C4—H4B	109.3
C3—N1—C2	107.55 (12)	N3—C4—H4B	109.3
C1—N1—C2	107.60 (12)	H4A—C4—H4B	108.0
C3—N1—Mn1	110.08 (9)	N2—C5—N4	112.13 (13)
C1—N1—Mn1	112.35 (9)	N2—C5—H5A	109.2
C2—N1—Mn1	111.33 (9)	N4—C5—H5A	109.2
C5—N2—C4	107.96 (14)	N2—C5—H5B	109.2
C5—N2—C1	108.65 (13)	N4—C5—H5B	109.2
C4—N2—C1	108.52 (12)	H5A—C5—H5B	107.9
C4—N3—C2	108.35 (13)	N3—C6—N4	111.32 (13)
C4—N3—C6	108.71 (13)	N3—C6—H6A	109.4
C2—N3—C6	108.43 (13)	N4—C6—H6A	109.4
C5—N4—C3	108.69 (13)	N3—C6—H6B	109.4
C5—N4—C6	107.74 (14)	N4—C6—H6B	109.4
C3—N4—C6	108.49 (13)	H6A—C6—H6B	108.0
C7—N5—Mn1	160.59 (15)	N5—C7—S1	179.83 (19)
C8—N6—Mn2	177.51 (15)	N6—C8—S2	178.40 (16)
Mn1—O1—H1OA	124.3 (15)
N5—Mn1—N1—C3	71.47 (10)	C6—N3—C2—N1	−59.01 (17)
N5^i—Mn1—N1—C3	−108.53 (10)	C3—N1—C2—N3	57.98 (17)
O1—Mn1—N1—C3	−18.70 (10)	C1—N1—C2—N3	−57.83 (17)
O1^i—Mn1—N1—C3	161.30 (10)	Mn1—N1—C2—N3	178.66 (10)
N5—Mn1—N1—C1	−168.48 (11)	C5—N4—C3—N1	−57.98 (17)
N5^i—Mn1—N1—C1	11.52 (11)	C6—N4—C3—N1	58.90 (18)
O1—Mn1—N1—C1	101.36 (10)	C1—N1—C3—N4	57.78 (16)
O1^i—Mn1—N1—C1	−78.64 (10)	C2—N1—C3—N4	−57.94 (16)
N5—Mn1—N1—C2	−47.71 (11)	Mn1—N1—C3—N4	−179.40 (10)
N5^i—Mn1—N1—C2	132.29 (11)	C5—N2—C4—N3	−58.58 (17)
O1—Mn1—N1—C2	−137.88 (10)	C1—N2—C4—N3	59.01 (18)
O1^i—Mn1—N1—C2	42.12 (10)	C2—N3—C4—N2	−59.06 (17)
O1—Mn1—N5—C7	167.5 (4)	C6—N3—C4—N2	58.59 (17)
O1^i—Mn1—N5—C7	−12.5 (4)	C4—N2—C5—N4	59.58 (17)
N1^i—Mn1—N5—C7	−104.2 (4)	C1—N2—C5—N4	−57.93 (17)
N1—Mn1—N5—C7	75.8 (4)	C3—N4—C5—N2	57.73 (17)
C5—N2—C1—N1	58.35 (17)	C6—N4—C5—N2	−59.63 (17)
C4—N2—C1—N1	−58.80 (17)	C4—N3—C6—N4	−58.62 (17)
C3—N1—C1—N2	−57.94 (16)	C2—N3—C6—N4	58.98 (17)
C2—N1—C1—N2	57.75 (16)	C5—N4—C6—N3	58.67 (17)
Mn1—N1—C1—N2	−179.36 (10)	C3—N4—C6—N3	−58.82 (18)
C4—N3—C2—N1	58.82 (17)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4OB···S1^iii	0.82 (1)	2.63 (1)	3.3533 (16)	148 (2)
O2—H2OB···S2^iv	0.82 (1)	2.54 (1)	3.2949 (15)	154 (2)
O4—H4OA···N4	0.82 (1)	2.00 (1)	2.817 (2)	174 (3)
O2—H2OA···N3	0.82 (1)	1.99 (1)	2.8055 (19)	170 (2)
O3—H3OB···O4^v	0.82 (1)	2.00 (1)	2.797 (2)	166 (2)
O3—H3OA···N2^vi	0.82 (1)	2.04 (1)	2.843 (2)	169 (2)
O1—H1OA···O4^vii	0.82 (1)	1.93 (1)	2.7424 (19)	176 (2)

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