Bis(9-amino­acridinium) bis­(pyridine-2,6-dicarboxyl­ato-κ3O2,N,O6)manganate(II) trihydrate

Eshtiagh-Hosseini, H.; Mirzaei, M.; Eydizadeh, E.; Yousefi, Z.; Molčanov, K.

doi:10.1107/S1600536811036981

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 10| October 2011| Pages m1411-m1412

https://doi.org/10.1107/S1600536811036981

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Bis(9-aminoacridinium) bis(pyridine-2,6-dicarboxylato-κ³O²,N,O⁶)manganate(II) trihydrate

Hossien Eshtiagh-Hosseini,^a Masoud Mirzaei,^a ^* Ehsan Eydizadeh,^a Zakieh Yousefi ^a and Krešimir Molčanov ^b

^aDepartment of Chemistry, Ferdowsi University of Mashhad, 917791436 Mashhad, Iran, and ^bLaboratory of Chemical Crystallography and Biocrystallography, Department of Physical Chemistry, Rudjer Bošković Institute, Bijenička 54, HR-10000 Zagreb, Croatia
^*Correspondence e-mail: mirzaeesh@um.ac.ir

(Received 4 July 2011; accepted 12 September 2011; online 30 September 2011)

The asymmetric unit of the title compound, (C₁₃H₁₁N₂)₂[Mn(C₇H₃NO₄)₂]·3H₂O, consists of a discrete mononuclear [Mn(2,6-pydc)₂]²⁻ anionic complex (2,6-pydc is pyridine-2,6-dicarboxylate) associated with two 9-aminoacridinium counter-ions for neutralization of charge and three uncoordinated water molecules. The Mn^II atom is six-coordinated by (2,6-pydc)²⁻ anions in a tridentate fashion and is at the centre of a distorted octahedron formed by the MnO₄N₂ bonding set. In the crystal, various intermolecular interactions between different moieties can be found, such as different kinds of hydrogen bonds, offset or slipped π–π [centroid–centroid distances in the range 3.3704 (12) to 3.8674 (13)Å] and C=O⋯π [3.563 Å] interactions, which lead to the formation of a three-dimensional supramolecular network.

Related literature

For complexes derived from Mn(II) atoms and pyridine-2,6-dicarboxlic acid, see: Aghabozorg et al. (2010 , 2011 ). For similar compounds, see: Mirzaei et al. (2011 ); Derikvand et al. (2010 ); Eshtiagh-Hosseini, Aghabozorg et al. (2010 ); Eshtiagh-Hosseini, Alfi et al. (2010 ); Eshtiagh-Hosseini, Gschwind et al. (2010 ); Eshtiagh-Hosseini, Yousefi et al. (2010 ) ; Mei & Wolf (2004 ); MacDonald et al. (2000 ); Aghabozorg et al. (2008 ).

Experimental

Crystal data

(C₁₃H₁₁N₂)₂[Mn(C₇H₃NO₄)₂]·3H₂O
M_r = 829.67
Triclinic, $[P \overline 1]$
a = 10.8202 (4) Å
b = 13.5186 (5) Å
c = 13.9844 (5) Å
α = 102.351 (3)°
β = 103.466 (3)°
γ = 104.868 (3)°
V = 1839.42 (12) Å³
Z = 2
Cu Kα radiation
μ = 3.55 mm⁻¹
T = 293 K
0.20 × 0.12 × 0.10 mm

Data collection

Oxford Diffraction Xcalibur Nova diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.538, T_max = 0.718
17948 measured reflections
7606 independent reflections
6791 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.114
S = 1.08
7606 reflections
572 parameters
9 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3N⋯O2	0.88 (2)	1.86 (2)	2.736 (2)	178 (2)
N4—H4A⋯O4ⁱ	0.85 (3)	2.22 (3)	2.994 (2)	152 (3)
N4—H4B⋯O10ⁱⁱ	0.93 (3)	2.01 (3)	2.884 (3)	156 (2)
N5—H5N⋯O11	0.84 (3)	1.87 (3)	2.706 (2)	171 (3)
N6—H6A⋯O6	0.90 (2)	1.92 (3)	2.801 (2)	164 (2)
N6—H6B⋯O1ⁱⁱⁱ	0.89 (3)	2.20 (3)	3.029 (2)	155 (3)
O9—H9A⋯O4	0.94 (3)	1.89 (3)	2.815 (2)	171 (3)
O9—H9B⋯O4^iv	0.93 (3)	1.93 (3)	2.851 (3)	172 (3)
O10—H10A⋯O3^v	0.92 (2)	2.02 (2)	2.926 (2)	168 (3)
O10—H10B⋯O8	0.92 (3)	1.89 (3)	2.805 (3)	175 (4)
O11—H11A⋯O6^vi	0.92 (3)	1.88 (3)	2.790 (3)	170 (4)
O11—H11B⋯O9^vii	0.92 (3)	1.85 (3)	2.756 (3)	169 (2)
Symmetry codes: (i) x-1, y, z-1; (ii) -x+1, -y+1, -z; (iii) -x+1, -y+1, -z+1; (iv) -x+2, -y, -z+1; (v) -x+2, -y+1, -z+1; (vi) -x+1, -y+1, -z+2; (vii) x, y+1, z+1.

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS86 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON (Spek; 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536811036981/om2447sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811036981/om2447Isup2.hkl

checkCIF report

Comment top

Acridine derivatives with two benzene rings fused to pyridine are highly fluorescent agents. These compounds are used as topical antiseptics and experimentally as mutagens, intracellular pH indicators and as MALDI matrices (Derikvand et al. 2010). Acridine and related derivatives bind to DNA and RNA due to their abilitiy to intercalate. In the viewpoint of crystal engineering, acridine and its 9-amino derivative are very interesting because of their capability for hydrogen bonding via N atom of the ring and π-π stacking since they possess three rings (Aghabozorg et al. 2010, Mei & Wolf, 2004).

In continuation of our study on proton transfer compounds and their complexes (Mirzaei et al., 2011; Eshtiagh-Hosseini, Aghabozorg et al., 2010; Eshtiagh-Hosseini, Alfi et al., 2010; Eshtiagh-Hosseini, Gschwind et al., 2010; Eshtiagh-Hosseini, Yousefi et al., 2010), here we describe the crystal structure of a new coordination compound based upon Mn^II atom, 2,6-pydcH₂, and 9aa (abbreviation for 9-aminoacridine) fragments. The asymmetric unit of 1 comprises an anionic complex [Mn(2,6-pydc)₂]^2–, two monoprotonated (9aaH⁺), and three uncoordinated water molecules (Fig. 1). The Mn^II atom is six-coordinated via two tridentate (2,6-pydc)^2– with polyhedron MnO₄N₂ which adopts a distorted octahedral geometry. Indeed, in anionic fragment two rigid (2,6-pydc)^2– are almost perpendicular to each other. The geometry, bond distances and angles of title compound are comprable with similar compounds in reported litratures (Aghabozorg et al., 2008; MacDonald et al. 2000) It is interesting to point out that in the crystal structure of 1, two cationic fragments participate in different H-bonds, that is, one of them takes part in three H-bonds via NH₂ group and an N atom located in the ring with anionic complex fragments and water molecule, while, the other partakes in H-bond with a water molecule and an anionic moiety via with NH₂ group and with another complex via N atom of ring. Also, there is a H-bond pattern with graph set R⁴₂(8) created by two water molecules and two complex fragments. Alongside different H-bonds, π-π stacking interactions play an important role in the stability of 1. As claimed before, 9aa can establish several π-π stacking interactions, and this point is evident in this structure, as well as the intermolecular π-π interaction which occurs between the two symmetry-related anionic fragments (2,6-pydc)^2–. Distances between centroids of aromatic rings range from 3.3704 (12)Å to 3.8674 (13)Å (Cg1—Cg2= 3.703 Å, Cg1=C16—C17—C18—C19—C20—C21 and Cg2= C34—C35—C36—C37—C39—C40; Cg1—Cg3= 3.515 Å, Cg3=C28—C29—C34—C35—C40—N5; Cg2—Cg3=3.370 Å) as calculated by PLATON (Spek, 2009). In addition to these intermolecular interactions, some weak interactions such as C=O···π (Cg4—O= 3.563 Å, Cg4=C8—C9—C10—C11—C12—N2), aid to construct a three-dimensional supramolecular network (Fig. 2).

Related literature top

For complexes containing a Mn(II) atom and pyridine-2,6-dicarboxlic acid, see: Aghabozorg et al. (2010, 2011). For similar compounds, see: Mirzaei et al. (2011); Derikvand et al. (2010); Eshtiagh-Hosseini, Aghabozorg et al. (2010); Eshtiagh-Hosseini, Alfi et al. (2010); Eshtiagh-Hosseini, Gschwind et al. (2010); Eshtiagh-Hosseini, Yousefi et al. (2010 ); Mei & Wolf (2004); MacDonald et al. (2000); Aghabozorg et al. (2008).

Experimental top

To an aqeous solution of pydcH₂ (0.0167 g, 0.1 mmol) a solution of 9a-ac (0.02 g,0.1 mmol) in methanol was added dropwise, then a soution of MnCl₂.2H₂O(0.0167 g, 0.1 mmol)) in water was added and the resultant solution was heated and stirred for 3 hrs at 60 °C. The yellow crystals were obtained by slow evaporation at room temprature after 3 days.

Structure description top

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS86 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek; 2009).

Figures top

Fig. 1. ORTEP view of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

Fig. 2. Packing diagram of the title compoud showing extensive π···π stacking interaction between aromatic rings of (9aaH)⁺ ions and carbonyl···π interactions (Cg1—Cg2= 3.703 Å, Cg1=C16—C17—C18—C19—C20—C21 and Cg2= C34—C35—C36—C37—C39—C40; Cg1—Cg3= 3.515 Å, Cg3=C28—C29—C34—C35—C40—N5; Cg2—Cg3=3.370 Å; Cg4—O= 3.563 Å, Cg4=C8—C9—C10—C11—C12—N2).

Bis(9-aminoacridinium) bis(pyridine-2,6-dicarboxylato- κ³O²,N,O⁶)manganate(II) trihydrate top

Crystal data top

(C₁₃H₁₁N₂)₂[Mn(C₇H₃NO₄)₂]·3H₂O	Z = 2
M_r = 829.67	F(000) = 858
Triclinic, P1	D_x = 1.498 Mg m⁻³
a = 10.8202 (4) Å	Cu Kα radiation, λ = 1.54184 Å
b = 13.5186 (5) Å	Cell parameters from 11391 reflections
c = 13.9844 (5) Å	θ = 3.4–75.9°
α = 102.351 (3)°	µ = 3.55 mm⁻¹
β = 103.466 (3)°	T = 293 K
γ = 104.868 (3)°	Prism, yellow
V = 1839.42 (12) Å³	0.20 × 0.12 × 0.10 mm

Data collection top

Oxford Diffraction Xcalibur Nova diffractometer	7606 independent reflections
Radiation source: Enhance (Cu) X-ray Source	6791 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
Detector resolution: 10.4323 pixels mm^-1	θ_max = 76.1°, θ_min = 3.4°
ω scans	h = −13→13
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −17→16
T_min = 0.538, T_max = 0.718	l = −17→12
17948 measured reflections

Refinement top

Refinement on F²	H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.0654P)² + 0.2228P] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.038	(Δ/σ)_max < 0.001
wR(F²) = 0.114	Δρ_max = 0.25 e Å⁻³
S = 1.08	Δρ_min = −0.31 e Å⁻³
7606 reflections	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
572 parameters	Extinction coefficient: 0.00077 (19)
9 restraints

Crystal data top

(C₁₃H₁₁N₂)₂[Mn(C₇H₃NO₄)₂]·3H₂O	γ = 104.868 (3)°
M_r = 829.67	V = 1839.42 (12) Å³
Triclinic, P1	Z = 2
a = 10.8202 (4) Å	Cu Kα radiation
b = 13.5186 (5) Å	µ = 3.55 mm⁻¹
c = 13.9844 (5) Å	T = 293 K
α = 102.351 (3)°	0.20 × 0.12 × 0.10 mm
β = 103.466 (3)°

Data collection top

Oxford Diffraction Xcalibur Nova diffractometer	7606 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	6791 reflections with I > 2σ(I)
T_min = 0.538, T_max = 0.718	R_int = 0.029
17948 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	9 restraints
wR(F²) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.25 e Å⁻³
7606 reflections	Δρ_min = −0.31 e Å⁻³
572 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Mn1	0.64063 (3)	0.25673 (2)	0.40959 (2)	0.04394 (10)
O1	0.44381 (15)	0.20160 (11)	0.28655 (10)	0.0518 (3)
O2	0.26457 (17)	0.05818 (15)	0.19184 (12)	0.0669 (4)
O3	0.79344 (15)	0.20184 (11)	0.50812 (11)	0.0535 (3)
O4	0.84704 (14)	0.06026 (11)	0.53782 (11)	0.0529 (3)
N1	0.56149 (14)	0.08499 (11)	0.37675 (10)	0.0360 (3)
C1	0.43716 (17)	0.03411 (14)	0.31346 (11)	0.0377 (3)
C2	0.37476 (18)	−0.07366 (15)	0.29815 (13)	0.0451 (4)
H2	0.2881	−0.1084	0.2535	0.054*
C3	0.44423 (19)	−0.12868 (14)	0.35074 (14)	0.0447 (4)
H3	0.4042	−0.2009	0.3422	0.054*
C4	0.57380 (18)	−0.07533 (13)	0.41616 (12)	0.0404 (3)
H4	0.6221	−0.1111	0.4517	0.048*
C5	0.62957 (16)	0.03236 (13)	0.42732 (11)	0.0356 (3)
C6	0.37496 (19)	0.10379 (16)	0.25923 (13)	0.0444 (4)
C7	0.76853 (18)	0.10354 (14)	0.49707 (12)	0.0407 (3)
O5	0.54528 (17)	0.30295 (10)	0.52945 (11)	0.0543 (3)
O6	0.52901 (17)	0.43798 (12)	0.64314 (11)	0.0581 (4)
O7	0.76616 (18)	0.31403 (12)	0.31869 (11)	0.0609 (4)
O8	0.91391 (19)	0.45506 (14)	0.30369 (13)	0.0657 (4)
N2	0.71790 (16)	0.42813 (11)	0.47040 (10)	0.0416 (3)
C8	0.67712 (19)	0.47705 (14)	0.54468 (12)	0.0425 (4)
C9	0.7249 (2)	0.58709 (15)	0.58508 (14)	0.0528 (4)
H9	0.6945	0.6213	0.6354	0.063*
C10	0.8191 (3)	0.64496 (16)	0.54865 (17)	0.0605 (5)
H10	0.8542	0.719	0.5757	0.073*
C11	0.8613 (2)	0.59309 (16)	0.47198 (16)	0.0567 (5)
H11	0.9251	0.6313	0.4474	0.068*
C12	0.8062 (2)	0.48295 (14)	0.43303 (13)	0.0453 (4)
C13	0.5753 (2)	0.40030 (14)	0.57584 (12)	0.0435 (4)
C14	0.8333 (2)	0.41252 (16)	0.34409 (14)	0.0493 (4)
N3	0.14305 (15)	0.10470 (12)	0.02023 (11)	0.0411 (3)
H3N	0.181 (2)	0.0906 (19)	0.0761 (19)	0.050 (6)*
N4	−0.01292 (19)	0.18331 (17)	−0.24082 (13)	0.0553 (4)
H4A	−0.029 (3)	0.141 (2)	−0.300 (2)	0.065 (7)*
H4B	−0.029 (3)	0.248 (2)	−0.236 (2)	0.073 (8)*
C15	0.03526 (17)	0.15624 (15)	−0.15714 (13)	0.0428 (4)
C16	0.05018 (16)	0.22265 (14)	−0.05743 (13)	0.0397 (3)
C17	0.01312 (18)	0.31667 (16)	−0.04250 (15)	0.0475 (4)
H17	−0.0232	0.3373	−0.0991	0.057*
C18	0.0302 (2)	0.37710 (17)	0.05400 (17)	0.0525 (4)
H18	0.0065	0.4391	0.0627	0.063*
C19	0.0832 (2)	0.34669 (18)	0.14030 (15)	0.0539 (4)
H19	0.0924	0.3879	0.2056	0.065*
C20	0.12132 (19)	0.25721 (16)	0.12938 (14)	0.0468 (4)
H20	0.1576	0.238	0.187	0.056*
C21	0.10539 (16)	0.19399 (14)	0.03001 (12)	0.0389 (3)
C22	0.12958 (16)	0.03901 (14)	−0.07291 (13)	0.0414 (3)
C23	0.1714 (2)	−0.05174 (16)	−0.07770 (16)	0.0500 (4)
H23	0.2069	−0.0672	−0.0175	0.06*
C24	0.1597 (2)	−0.11733 (17)	−0.17090 (18)	0.0589 (5)
H24	0.1881	−0.177	−0.1737	0.071*
C25	0.1055 (2)	−0.09545 (19)	−0.26169 (17)	0.0628 (5)
H25	0.0982	−0.1406	−0.3246	0.075*
C26	0.0634 (2)	−0.00866 (19)	−0.25909 (15)	0.0586 (5)
H26	0.0271	0.0046	−0.3204	0.07*
C27	0.07390 (17)	0.06234 (15)	−0.16393 (13)	0.0445 (4)
N5	0.66357 (16)	0.67352 (14)	1.11671 (11)	0.0465 (3)
H5N	0.677 (3)	0.680 (2)	1.180 (2)	0.073 (8)*
N6	0.54690 (18)	0.61190 (14)	0.80226 (11)	0.0475 (3)
H6A	0.556 (2)	0.5560 (19)	0.7592 (19)	0.053 (6)*
H6B	0.523 (3)	0.661 (2)	0.7753 (19)	0.060 (7)*
C28	0.58159 (16)	0.62845 (13)	0.90294 (12)	0.0375 (3)
C29	0.56236 (17)	0.71798 (13)	0.96725 (12)	0.0393 (3)
C30	0.4940 (2)	0.78319 (15)	0.92699 (14)	0.0466 (4)
H30	0.4611	0.7694	0.8562	0.056*
C31	0.4756 (2)	0.86606 (17)	0.99064 (18)	0.0569 (5)
H31	0.4295	0.9079	0.963	0.068*
C32	0.5257 (3)	0.88850 (18)	1.09755 (18)	0.0627 (6)
H32	0.5154	0.9468	1.1403	0.075*
C33	0.5889 (2)	0.82645 (17)	1.13944 (15)	0.0559 (5)
H33	0.6208	0.8416	1.2105	0.067*
C34	0.60641 (17)	0.73838 (15)	1.07472 (13)	0.0424 (4)
C35	0.67653 (16)	0.58457 (15)	1.05882 (13)	0.0424 (4)
C36	0.73090 (19)	0.51809 (18)	1.10862 (17)	0.0542 (5)
H36	0.7585	0.5358	1.18	0.065*
C37	0.7427 (2)	0.42785 (19)	1.05168 (19)	0.0594 (5)
H37	0.7766	0.3832	1.0846	0.071*
C38	0.7046 (2)	0.40105 (17)	0.94423 (19)	0.0584 (5)
H38	0.7144	0.3395	0.9065	0.07*
C39	0.65279 (19)	0.46540 (15)	0.89438 (15)	0.0476 (4)
H39	0.6283	0.4474	0.823	0.057*
C40	0.63637 (16)	0.55866 (14)	0.95048 (13)	0.0396 (3)
O9	0.88560 (18)	−0.13804 (14)	0.47029 (16)	0.0717 (4)
H9A	0.866 (3)	−0.0741 (19)	0.486 (3)	0.096 (11)*
H9B	0.971 (2)	−0.119 (3)	0.463 (3)	0.103 (12)*
O10	1.0899 (2)	0.63986 (16)	0.28914 (14)	0.0766 (5)
H10A	1.135 (3)	0.684 (2)	0.3551 (16)	0.087 (10)*
H10B	1.036 (3)	0.580 (2)	0.298 (3)	0.114 (13)*
O11	0.6811 (2)	0.69942 (17)	1.31723 (11)	0.0742 (5)
H11A	0.618 (3)	0.657 (2)	1.338 (3)	0.100 (11)*
H11B	0.744 (3)	0.750 (2)	1.3740 (19)	0.089 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0648 (2)	0.03080 (15)	0.03618 (15)	0.01615 (12)	0.01555 (12)	0.00863 (10)
O1	0.0674 (8)	0.0479 (7)	0.0453 (7)	0.0261 (6)	0.0124 (6)	0.0202 (6)
O2	0.0601 (9)	0.0752 (10)	0.0585 (8)	0.0199 (8)	−0.0034 (7)	0.0314 (8)
O3	0.0560 (8)	0.0393 (7)	0.0511 (7)	0.0095 (6)	0.0022 (6)	0.0079 (5)
O4	0.0479 (7)	0.0520 (7)	0.0527 (7)	0.0204 (6)	0.0020 (6)	0.0123 (6)
N1	0.0452 (7)	0.0343 (6)	0.0295 (6)	0.0150 (5)	0.0110 (5)	0.0090 (5)
C1	0.0442 (8)	0.0426 (8)	0.0285 (7)	0.0162 (7)	0.0117 (6)	0.0118 (6)
C2	0.0437 (9)	0.0473 (9)	0.0385 (8)	0.0089 (7)	0.0084 (7)	0.0120 (7)
C3	0.0532 (10)	0.0353 (8)	0.0447 (9)	0.0101 (7)	0.0160 (7)	0.0140 (7)
C4	0.0518 (9)	0.0385 (8)	0.0370 (8)	0.0207 (7)	0.0147 (7)	0.0146 (6)
C5	0.0426 (8)	0.0364 (8)	0.0303 (7)	0.0162 (6)	0.0126 (6)	0.0091 (6)
C6	0.0491 (9)	0.0548 (10)	0.0344 (7)	0.0223 (8)	0.0115 (7)	0.0180 (7)
C7	0.0457 (9)	0.0409 (8)	0.0348 (7)	0.0157 (7)	0.0103 (6)	0.0091 (6)
O5	0.0814 (10)	0.0353 (6)	0.0494 (7)	0.0152 (6)	0.0312 (7)	0.0112 (5)
O6	0.0752 (9)	0.0496 (8)	0.0451 (7)	0.0153 (7)	0.0266 (7)	0.0016 (6)
O7	0.0890 (11)	0.0468 (7)	0.0525 (8)	0.0196 (7)	0.0377 (8)	0.0110 (6)
O8	0.0794 (10)	0.0665 (10)	0.0610 (9)	0.0203 (8)	0.0370 (8)	0.0254 (7)
N2	0.0566 (8)	0.0335 (7)	0.0335 (6)	0.0140 (6)	0.0127 (6)	0.0090 (5)
C8	0.0561 (10)	0.0368 (8)	0.0304 (7)	0.0147 (7)	0.0081 (6)	0.0067 (6)
C9	0.0733 (13)	0.0380 (9)	0.0383 (8)	0.0150 (8)	0.0125 (8)	0.0021 (7)
C10	0.0792 (14)	0.0332 (9)	0.0544 (11)	0.0049 (9)	0.0154 (10)	0.0046 (8)
C11	0.0662 (12)	0.0426 (10)	0.0539 (11)	0.0062 (9)	0.0169 (9)	0.0143 (8)
C12	0.0567 (10)	0.0401 (9)	0.0375 (8)	0.0130 (7)	0.0112 (7)	0.0147 (7)
C13	0.0600 (10)	0.0402 (9)	0.0304 (7)	0.0182 (7)	0.0130 (7)	0.0089 (6)
C14	0.0649 (11)	0.0473 (10)	0.0409 (9)	0.0198 (8)	0.0193 (8)	0.0177 (7)
N3	0.0403 (7)	0.0457 (8)	0.0354 (7)	0.0127 (6)	0.0078 (5)	0.0137 (6)
N4	0.0621 (10)	0.0606 (10)	0.0367 (8)	0.0191 (8)	0.0042 (7)	0.0139 (7)
C15	0.0351 (8)	0.0483 (9)	0.0374 (8)	0.0065 (7)	0.0050 (6)	0.0123 (7)
C16	0.0316 (7)	0.0459 (9)	0.0396 (8)	0.0097 (6)	0.0087 (6)	0.0144 (7)
C17	0.0403 (8)	0.0532 (10)	0.0501 (9)	0.0169 (7)	0.0096 (7)	0.0198 (8)
C18	0.0466 (10)	0.0519 (10)	0.0625 (11)	0.0214 (8)	0.0195 (8)	0.0137 (9)
C19	0.0554 (11)	0.0572 (11)	0.0465 (9)	0.0188 (9)	0.0175 (8)	0.0066 (8)
C20	0.0484 (9)	0.0531 (10)	0.0375 (8)	0.0139 (8)	0.0130 (7)	0.0131 (7)
C21	0.0326 (7)	0.0431 (8)	0.0385 (8)	0.0083 (6)	0.0102 (6)	0.0125 (7)
C22	0.0359 (8)	0.0415 (8)	0.0418 (8)	0.0070 (6)	0.0107 (6)	0.0098 (7)
C23	0.0471 (9)	0.0464 (10)	0.0556 (10)	0.0140 (8)	0.0146 (8)	0.0152 (8)
C24	0.0576 (11)	0.0439 (10)	0.0700 (13)	0.0145 (9)	0.0218 (10)	0.0063 (9)
C25	0.0663 (13)	0.0557 (12)	0.0523 (11)	0.0120 (10)	0.0180 (9)	−0.0030 (9)
C26	0.0613 (12)	0.0601 (12)	0.0390 (9)	0.0110 (9)	0.0072 (8)	0.0027 (8)
C27	0.0390 (8)	0.0477 (9)	0.0383 (8)	0.0067 (7)	0.0080 (6)	0.0083 (7)
N5	0.0428 (7)	0.0589 (9)	0.0324 (7)	0.0093 (7)	0.0104 (6)	0.0122 (6)
N6	0.0635 (10)	0.0470 (8)	0.0335 (7)	0.0255 (7)	0.0120 (6)	0.0086 (6)
C28	0.0350 (7)	0.0380 (8)	0.0348 (7)	0.0078 (6)	0.0097 (6)	0.0074 (6)
C29	0.0392 (8)	0.0391 (8)	0.0360 (8)	0.0085 (6)	0.0124 (6)	0.0074 (6)
C30	0.0515 (10)	0.0445 (9)	0.0450 (9)	0.0162 (8)	0.0169 (7)	0.0119 (7)
C31	0.0651 (12)	0.0478 (10)	0.0647 (12)	0.0238 (9)	0.0276 (10)	0.0147 (9)
C32	0.0794 (15)	0.0491 (11)	0.0640 (12)	0.0218 (10)	0.0390 (11)	0.0054 (9)
C33	0.0649 (12)	0.0561 (11)	0.0404 (9)	0.0106 (9)	0.0237 (8)	0.0037 (8)
C34	0.0385 (8)	0.0474 (9)	0.0356 (8)	0.0063 (7)	0.0142 (6)	0.0069 (7)
C35	0.0317 (7)	0.0504 (9)	0.0428 (8)	0.0067 (6)	0.0102 (6)	0.0183 (7)
C36	0.0397 (9)	0.0676 (13)	0.0569 (11)	0.0109 (8)	0.0109 (8)	0.0333 (10)
C37	0.0427 (9)	0.0623 (12)	0.0828 (14)	0.0169 (9)	0.0170 (9)	0.0431 (11)
C38	0.0491 (10)	0.0470 (10)	0.0811 (14)	0.0169 (8)	0.0191 (10)	0.0219 (10)
C39	0.0438 (9)	0.0434 (9)	0.0532 (10)	0.0139 (7)	0.0122 (7)	0.0126 (8)
C40	0.0341 (7)	0.0402 (8)	0.0404 (8)	0.0076 (6)	0.0092 (6)	0.0111 (6)
O9	0.0588 (9)	0.0509 (9)	0.0911 (12)	0.0094 (7)	0.0181 (8)	0.0069 (8)
O10	0.0891 (13)	0.0703 (11)	0.0565 (9)	0.0100 (9)	0.0071 (8)	0.0260 (8)
O11	0.0774 (11)	0.0874 (12)	0.0363 (7)	−0.0017 (9)	0.0132 (7)	0.0133 (7)

Geometric parameters (Å, º) top

Mn1—N2	2.1501 (14)	C18—H18	0.93
Mn1—N1	2.1622 (14)	C19—C20	1.365 (3)
Mn1—O7	2.1786 (15)	C19—H19	0.93
Mn1—O5	2.2254 (13)	C20—C21	1.413 (2)
Mn1—O1	2.2319 (15)	C20—H20	0.93
Mn1—O3	2.2780 (14)	C22—C23	1.406 (3)
O1—C6	1.263 (2)	C22—C27	1.412 (3)
O2—C6	1.243 (2)	C23—C24	1.368 (3)
O3—C7	1.254 (2)	C23—H23	0.93
O4—C7	1.249 (2)	C24—C25	1.395 (4)
N1—C1	1.333 (2)	C24—H24	0.93
N1—C5	1.338 (2)	C25—C26	1.360 (4)
C1—C2	1.385 (2)	C25—H25	0.93
C1—C6	1.519 (2)	C26—C27	1.425 (3)
C2—C3	1.387 (3)	C26—H26	0.93
C2—H2	0.93	N5—C34	1.351 (3)
C3—C4	1.387 (3)	N5—C35	1.358 (3)
C3—H3	0.93	N5—H5N	0.84 (3)
C4—C5	1.384 (2)	N6—C28	1.323 (2)
C4—H4	0.93	N6—H6A	0.90 (2)
C5—C7	1.520 (2)	N6—H6B	0.90 (3)
O5—C13	1.255 (2)	C28—C40	1.434 (2)
O6—C13	1.241 (2)	C28—C29	1.438 (2)
O7—C14	1.268 (3)	C29—C34	1.408 (2)
O8—C14	1.233 (3)	C29—C30	1.413 (3)
N2—C12	1.330 (2)	C30—C31	1.363 (3)
N2—C8	1.334 (2)	C30—H30	0.93
C8—C9	1.382 (3)	C31—C32	1.402 (3)
C8—C13	1.520 (3)	C31—H31	0.93
C9—C10	1.383 (3)	C32—C33	1.354 (4)
C9—H9	0.93	C32—H32	0.93
C10—C11	1.387 (3)	C33—C34	1.416 (3)
C10—H10	0.93	C33—H33	0.93
C11—C12	1.384 (3)	C35—C36	1.410 (3)
C11—H11	0.93	C35—C40	1.412 (2)
C12—C14	1.532 (3)	C36—C37	1.360 (4)
N3—C21	1.360 (2)	C36—H36	0.93
N3—C22	1.363 (2)	C37—C38	1.400 (3)
N3—H3N	0.88 (2)	C37—H37	0.93
N4—C15	1.331 (2)	C38—C39	1.373 (3)
N4—H4A	0.85 (3)	C38—H38	0.93
N4—H4B	0.93 (3)	C39—C40	1.412 (3)
C15—C27	1.426 (3)	C39—H39	0.93
C15—C16	1.436 (2)	O9—H9A	0.933 (18)
C16—C21	1.408 (2)	O9—H9B	0.926 (18)
C16—C17	1.417 (3)	O10—H10A	0.924 (18)
C17—C18	1.363 (3)	O10—H10B	0.922 (18)
C17—H17	0.93	O11—H11A	0.923 (18)
C18—C19	1.402 (3)	O11—H11B	0.914 (18)

N2—Mn1—N1	169.44 (5)	C18—C17—H17	119.7
N2—Mn1—O7	73.33 (5)	C16—C17—H17	119.7
N1—Mn1—O7	115.96 (5)	C17—C18—C19	120.64 (19)
N2—Mn1—O5	72.69 (5)	C17—C18—H18	119.7
N1—Mn1—O5	98.33 (5)	C19—C18—H18	119.7
O7—Mn1—O5	145.68 (5)	C20—C19—C18	120.60 (18)
N2—Mn1—O1	112.02 (5)	C20—C19—H19	119.7
N1—Mn1—O1	72.97 (5)	C18—C19—H19	119.7
O7—Mn1—O1	97.13 (6)	C19—C20—C21	119.58 (18)
O5—Mn1—O1	91.08 (6)	C19—C20—H20	120.2
N2—Mn1—O3	103.37 (5)	C21—C20—H20	120.2
N1—Mn1—O3	71.55 (5)	N3—C21—C16	120.66 (15)
O7—Mn1—O3	96.10 (6)	N3—C21—C20	118.95 (16)
O5—Mn1—O3	96.27 (6)	C16—C21—C20	120.38 (17)
O1—Mn1—O3	144.44 (5)	N3—C22—C23	119.67 (17)
C6—O1—Mn1	118.13 (11)	N3—C22—C27	119.93 (17)
C7—O3—Mn1	118.29 (11)	C23—C22—C27	120.40 (17)
C1—N1—C5	120.32 (14)	C24—C23—C22	120.0 (2)
C1—N1—Mn1	118.51 (11)	C24—C23—H23	120
C5—N1—Mn1	120.76 (11)	C22—C23—H23	120
N1—C1—C2	121.49 (15)	C23—C24—C25	120.5 (2)
N1—C1—C6	114.05 (15)	C23—C24—H24	119.7
C2—C1—C6	124.43 (16)	C25—C24—H24	119.7
C1—C2—C3	118.59 (16)	C26—C25—C24	120.59 (19)
C1—C2—H2	120.7	C26—C25—H25	119.7
C3—C2—H2	120.7	C24—C25—H25	119.7
C2—C3—C4	119.62 (16)	C25—C26—C27	121.0 (2)
C2—C3—H3	120.2	C25—C26—H26	119.5
C4—C3—H3	120.2	C27—C26—H26	119.5
C5—C4—C3	118.45 (15)	C22—C27—C26	117.47 (19)
C5—C4—H4	120.8	C22—C27—C15	119.44 (16)
C3—C4—H4	120.8	C26—C27—C15	123.06 (18)
N1—C5—C4	121.53 (15)	C34—N5—C35	122.46 (15)
N1—C5—C7	112.96 (14)	C34—N5—H5N	120 (2)
C4—C5—C7	125.51 (15)	C35—N5—H5N	117 (2)
O2—C6—O1	127.50 (17)	C28—N6—H6A	122.2 (15)
O2—C6—C1	116.80 (17)	C28—N6—H6B	120.0 (16)
O1—C6—C1	115.68 (15)	H6A—N6—H6B	117 (2)
O4—C7—O3	125.91 (17)	N6—C28—C40	121.98 (16)
O4—C7—C5	118.23 (16)	N6—C28—C29	119.49 (16)
O3—C7—C5	115.85 (15)	C40—C28—C29	118.52 (15)
C13—O5—Mn1	118.71 (12)	C34—C29—C30	118.19 (16)
C14—O7—Mn1	119.60 (12)	C34—C29—C28	119.07 (16)
C12—N2—C8	121.52 (16)	C30—C29—C28	122.64 (15)
C12—N2—Mn1	118.88 (12)	C31—C30—C29	120.82 (18)
C8—N2—Mn1	119.60 (12)	C31—C30—H30	119.6
N2—C8—C9	120.87 (18)	C29—C30—H30	119.6
N2—C8—C13	113.30 (15)	C30—C31—C32	120.3 (2)
C9—C8—C13	125.81 (17)	C30—C31—H31	119.9
C8—C9—C10	118.25 (19)	C32—C31—H31	119.9
C8—C9—H9	120.9	C33—C32—C31	120.89 (19)
C10—C9—H9	120.9	C33—C32—H32	119.6
C9—C10—C11	120.29 (18)	C31—C32—H32	119.6
C9—C10—H10	119.9	C32—C33—C34	119.79 (19)
C11—C10—H10	119.9	C32—C33—H33	120.1
C12—C11—C10	118.25 (19)	C34—C33—H33	120.1
C12—C11—H11	120.9	N5—C34—C29	120.45 (16)
C10—C11—H11	120.9	N5—C34—C33	119.60 (17)
N2—C12—C11	120.78 (18)	C29—C34—C33	119.95 (18)
N2—C12—C14	113.29 (16)	N5—C35—C36	118.89 (17)
C11—C12—C14	125.90 (18)	N5—C35—C40	120.82 (16)
O6—C13—O5	125.91 (18)	C36—C35—C40	120.29 (19)
O6—C13—C8	118.40 (16)	C37—C36—C35	119.61 (19)
O5—C13—C8	115.69 (15)	C37—C36—H36	120.2
O8—C14—O7	126.68 (19)	C35—C36—H36	120.2
O8—C14—C12	118.80 (18)	C36—C37—C38	121.07 (19)
O7—C14—C12	114.51 (16)	C36—C37—H37	119.5
C21—N3—C22	122.48 (15)	C38—C37—H37	119.5
C21—N3—H3N	118.6 (15)	C39—C38—C37	120.2 (2)
C22—N3—H3N	118.9 (15)	C39—C38—H38	119.9
C15—N4—H4A	119.1 (19)	C37—C38—H38	119.9
C15—N4—H4B	121.4 (18)	C38—C39—C40	120.57 (19)
H4A—N4—H4B	119 (2)	C38—C39—H39	119.7
N4—C15—C27	121.37 (17)	C40—C39—H39	119.7
N4—C15—C16	119.93 (18)	C39—C40—C35	118.27 (17)
C27—C15—C16	118.70 (16)	C39—C40—C28	123.25 (16)
C21—C16—C17	118.15 (16)	C35—C40—C28	118.48 (16)
C21—C16—C15	118.76 (16)	H9A—O9—H9B	105 (3)
C17—C16—C15	123.09 (16)	H10A—O10—H10B	104 (3)
C18—C17—C16	120.63 (18)	H11A—O11—H11B	108 (3)

N2—Mn1—O1—C6	−165.89 (13)	Mn1—O5—C13—O6	178.93 (16)
N1—Mn1—O1—C6	4.23 (13)	Mn1—O5—C13—C8	−0.7 (2)
O7—Mn1—O1—C6	119.25 (13)	N2—C8—C13—O6	−178.68 (17)
O5—Mn1—O1—C6	−94.15 (13)	C9—C8—C13—O6	0.3 (3)
O3—Mn1—O1—C6	8.22 (18)	N2—C8—C13—O5	1.0 (2)
N2—Mn1—O3—C7	173.32 (13)	C9—C8—C13—O5	179.98 (19)
N1—Mn1—O3—C7	2.96 (13)	Mn1—O7—C14—O8	175.59 (18)
O7—Mn1—O3—C7	−112.41 (14)	Mn1—O7—C14—C12	−5.7 (2)
O5—Mn1—O3—C7	99.67 (14)	N2—C12—C14—O8	−179.84 (19)
O1—Mn1—O3—C7	−1.07 (19)	C11—C12—C14—O8	2.1 (3)
N2—Mn1—N1—C1	112.5 (3)	N2—C12—C14—O7	1.3 (3)
O7—Mn1—N1—C1	−97.01 (12)	C11—C12—C14—O7	−176.8 (2)
O5—Mn1—N1—C1	81.29 (12)	N4—C15—C16—C21	−178.00 (17)
O1—Mn1—N1—C1	−7.29 (11)	C27—C15—C16—C21	1.5 (2)
O3—Mn1—N1—C1	175.16 (12)	N4—C15—C16—C17	1.4 (3)
N2—Mn1—N1—C5	−60.2 (4)	C27—C15—C16—C17	−179.12 (16)
O7—Mn1—N1—C5	90.30 (12)	C21—C16—C17—C18	−0.3 (3)
O5—Mn1—N1—C5	−91.40 (12)	C15—C16—C17—C18	−179.62 (17)
O1—Mn1—N1—C5	−179.98 (12)	C16—C17—C18—C19	−0.8 (3)
O3—Mn1—N1—C5	2.47 (11)	C17—C18—C19—C20	1.4 (3)
C5—N1—C1—C2	0.1 (2)	C18—C19—C20—C21	−0.9 (3)
Mn1—N1—C1—C2	−172.62 (12)	C22—N3—C21—C16	−0.1 (2)
C5—N1—C1—C6	−178.14 (13)	C22—N3—C21—C20	179.29 (16)
Mn1—N1—C1—C6	9.13 (17)	C17—C16—C21—N3	−179.84 (15)
N1—C1—C2—C3	0.3 (2)	C15—C16—C21—N3	−0.4 (2)
C6—C1—C2—C3	178.37 (16)	C17—C16—C21—C20	0.8 (2)
C1—C2—C3—C4	−0.6 (3)	C15—C16—C21—C20	−179.84 (16)
C2—C3—C4—C5	0.4 (3)	C19—C20—C21—N3	−179.59 (17)
C1—N1—C5—C4	−0.3 (2)	C19—C20—C21—C16	−0.2 (3)
Mn1—N1—C5—C4	172.30 (11)	C21—N3—C22—C23	179.56 (16)
C1—N1—C5—C7	−179.10 (13)	C21—N3—C22—C27	−0.4 (2)
Mn1—N1—C5—C7	−6.54 (17)	N3—C22—C23—C24	−179.19 (18)
C3—C4—C5—N1	0.0 (2)	C27—C22—C23—C24	0.8 (3)
C3—C4—C5—C7	178.68 (15)	C22—C23—C24—C25	−0.5 (3)
Mn1—O1—C6—O2	−179.12 (17)	C23—C24—C25—C26	−0.1 (4)
Mn1—O1—C6—C1	−1.0 (2)	C24—C25—C26—C27	0.3 (4)
N1—C1—C6—O2	173.11 (17)	N3—C22—C27—C26	179.45 (17)
C2—C1—C6—O2	−5.1 (3)	C23—C22—C27—C26	−0.5 (3)
N1—C1—C6—O1	−5.2 (2)	N3—C22—C27—C15	1.5 (2)
C2—C1—C6—O1	176.59 (16)	C23—C22—C27—C15	−178.46 (16)
Mn1—O3—C7—O4	172.80 (14)	C25—C26—C27—C22	0.0 (3)
Mn1—O3—C7—C5	−7.1 (2)	C25—C26—C27—C15	177.8 (2)
N1—C5—C7—O4	−171.07 (15)	N4—C15—C27—C22	177.46 (17)
C4—C5—C7—O4	10.1 (2)	C16—C15—C27—C22	−2.0 (2)
N1—C5—C7—O3	8.9 (2)	N4—C15—C27—C26	−0.4 (3)
C4—C5—C7—O3	−169.90 (16)	C16—C15—C27—C26	−179.86 (17)
N2—Mn1—O5—C13	0.21 (14)	N6—C28—C29—C34	−176.52 (16)
N1—Mn1—O5—C13	174.50 (15)	C40—C28—C29—C34	4.4 (2)
O7—Mn1—O5—C13	−8.2 (2)	N6—C28—C29—C30	7.2 (3)
O1—Mn1—O5—C13	−112.55 (15)	C40—C28—C29—C30	−171.89 (16)
O3—Mn1—O5—C13	102.30 (15)	C34—C29—C30—C31	2.4 (3)
N2—Mn1—O7—C14	5.78 (16)	C28—C29—C30—C31	178.69 (18)
N1—Mn1—O7—C14	−168.81 (15)	C29—C30—C31—C32	0.6 (3)
O5—Mn1—O7—C14	14.2 (2)	C30—C31—C32—C33	−2.3 (4)
O1—Mn1—O7—C14	116.70 (17)	C31—C32—C33—C34	0.8 (3)
O3—Mn1—O7—C14	−96.39 (17)	C35—N5—C34—C29	−2.7 (3)
N1—Mn1—N2—C12	147.6 (3)	C35—N5—C34—C33	176.34 (17)
O7—Mn1—N2—C12	−4.85 (14)	C30—C29—C34—N5	175.17 (16)
O5—Mn1—N2—C12	−179.90 (15)	C28—C29—C34—N5	−1.3 (2)
O1—Mn1—N2—C12	−95.92 (14)	C30—C29—C34—C33	−3.8 (3)
O3—Mn1—N2—C12	87.60 (14)	C28—C29—C34—C33	179.73 (16)
N1—Mn1—N2—C8	−32.1 (4)	C32—C33—C34—N5	−176.72 (19)
O7—Mn1—N2—C8	175.43 (15)	C32—C33—C34—C29	2.3 (3)
O5—Mn1—N2—C8	0.38 (13)	C34—N5—C35—C36	−176.67 (16)
O1—Mn1—N2—C8	84.37 (14)	C34—N5—C35—C40	3.3 (3)
O3—Mn1—N2—C8	−92.12 (14)	N5—C35—C36—C37	179.03 (17)
C12—N2—C8—C9	0.4 (3)	C40—C35—C36—C37	−1.0 (3)
Mn1—N2—C8—C9	−179.87 (14)	C35—C36—C37—C38	1.5 (3)
C12—N2—C8—C13	179.48 (16)	C36—C37—C38—C39	−0.8 (3)
Mn1—N2—C8—C13	−0.8 (2)	C37—C38—C39—C40	−0.5 (3)
N2—C8—C9—C10	−1.9 (3)	C38—C39—C40—C35	1.0 (3)
C13—C8—C9—C10	179.18 (19)	C38—C39—C40—C28	−179.30 (17)
C8—C9—C10—C11	1.4 (3)	N5—C35—C40—C39	179.74 (16)
C9—C10—C11—C12	0.5 (4)	C36—C35—C40—C39	−0.3 (2)
C8—N2—C12—C11	1.6 (3)	N5—C35—C40—C28	0.0 (2)
Mn1—N2—C12—C11	−178.14 (15)	C36—C35—C40—C28	−179.99 (15)
C8—N2—C12—C14	−176.62 (16)	N6—C28—C40—C39	−2.5 (3)
Mn1—N2—C12—C14	3.7 (2)	C29—C28—C40—C39	176.53 (16)
C10—C11—C12—N2	−2.0 (3)	N6—C28—C40—C35	177.18 (16)
C10—C11—C12—C14	176.0 (2)	C29—C28—C40—C35	−3.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···O2	0.88 (2)	1.86 (2)	2.736 (2)	178 (2)
N4—H4A···O4ⁱ	0.85 (3)	2.22 (3)	2.994 (2)	152 (3)
N4—H4B···O10ⁱⁱ	0.93 (3)	2.01 (3)	2.884 (3)	156 (2)
N5—H5N···O11	0.84 (3)	1.87 (3)	2.706 (2)	171 (3)
N6—H6A···O6	0.90 (2)	1.92 (3)	2.801 (2)	164 (2)
N6—H6B···O1ⁱⁱⁱ	0.89 (3)	2.20 (3)	3.029 (2)	155 (3)
O9—H9A···O4	0.94 (3)	1.89 (3)	2.815 (2)	171 (3)
O9—H9B···O4^iv	0.93 (3)	1.93 (3)	2.851 (3)	172 (3)
O10—H10A···O3^v	0.92 (2)	2.02 (2)	2.926 (2)	168 (3)
O10—H10B···O8	0.92 (3)	1.89 (3)	2.805 (3)	175 (4)
O11—H11A···O6^vi	0.92 (3)	1.88 (3)	2.790 (3)	170 (4)
O11—H11B···O9^vii	0.92 (3)	1.85 (3)	2.756 (3)	169 (2)

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

Experimental details

Crystal data
Chemical formula	(C₁₃H₁₁N₂)₂[Mn(C₇H₃NO₄)₂]·3H₂O
M_r	829.67
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	10.8202 (4), 13.5186 (5), 13.9844 (5)
α, β, γ (°)	102.351 (3), 103.466 (3), 104.868 (3)
V (Å³)	1839.42 (12)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	3.55
Crystal size (mm)	0.20 × 0.12 × 0.10

Data collection
Diffractometer	Oxford Diffraction Xcalibur Nova
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)
T_min, T_max	0.538, 0.718
No. of measured, independent and observed [I > 2σ(I)] reflections	17948, 7606, 6791
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.629

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.114, 1.08
No. of reflections	7606
No. of parameters	572
No. of restraints	9
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.31

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), SHELXS86 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999) and PLATON (Spek; 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···O2	0.88 (2)	1.86 (2)	2.736 (2)	178 (2)
N4—H4A···O4ⁱ	0.85 (3)	2.22 (3)	2.994 (2)	152 (3)
N4—H4B···O10ⁱⁱ	0.93 (3)	2.01 (3)	2.884 (3)	156 (2)
N5—H5N···O11	0.84 (3)	1.87 (3)	2.706 (2)	171 (3)
N6—H6A···O6	0.90 (2)	1.92 (3)	2.801 (2)	164 (2)
N6—H6B···O1ⁱⁱⁱ	0.89 (3)	2.20 (3)	3.029 (2)	155 (3)
O9—H9A···O4	0.94 (3)	1.89 (3)	2.815 (2)	171 (3)
O9—H9B···O4^iv	0.93 (3)	1.93 (3)	2.851 (3)	172 (3)
O10—H10A···O3^v	0.92 (2)	2.02 (2)	2.926 (2)	168 (3)
O10—H10B···O8	0.92 (3)	1.89 (3)	2.805 (3)	175 (4)
O11—H11A···O6^vi	0.92 (3)	1.88 (3)	2.790 (3)	170 (4)
O11—H11B···O9^vii	0.92 (3)	1.85 (3)	2.756 (3)	169 (2)

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

Acknowledgements

The authors wish to thank the Ferdowsi University of Mashhad for financial support of this article (grant No. 15606/.3). This research was supported by the Ministry of Science, Education and Sports of Croatia (grant No. 098–1191344-2943).

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