(Acetyl­acetonato-κ2O,O′)­aqua­[salicyl­aldehyde nicotinoylhydrazonato(2−)-κ3O,N,O′]manganese(III)

Wang, Z.-Y.; Liu, S.-X.; Fu, Z.-W.

doi:10.1107/S1600536807060734

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Pages m371-m372

doi:10.1107/S1600536807060734

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(Acetylacetonato-κ²O,O′)aqua[salicylaldehyde nicotinoylhydrazonato(2−)-κ³O,N,O′]manganese(III)

Zeng-You Wang,^a Shi-Xiong Liu ^a ^* and Zhong-Wu Fu ^a

^aDepartment of Chemistry, Fuzhou University, Fuzhou, Fujian, 350002, People's Republic of China
^*Correspondence e-mail: shixiongliu@yahoo.com

(Received 8 November 2007; accepted 19 November 2007; online 18 January 2008)

The Mn^III atom in the title complex, [Mn(C₁₃H₉N₃O₂)(C₅H₇O₂)(H₂O)], is coordinated by three donors from a dianionic ligand, salicylaldehyde nicotylhydrazone, two O atoms from an acetylacetonate anion and a water molecule in a distorted octahedral geometry. There is an extended two-dimensional supramolecular motif resulting from O—H⋯N hydrogen bonds between the coordinated water molecule and a hydrazine N or pyridine N atom, and from C—H⋯O hydrogen bonds between a CH group and the phenolate O atom.

Related literature

For general background, see: Janiak (2003 ); Kitagawa et al. (2004 ); Graham & Pike (2000 ); Niu et al. (2005 ); Adams et al. (2000 ); Ranford et al. (1998 ); Batten & Robson (1998 ); Hagrman et al. (1999 ). For related structures, see: Kessissoglou et al. (2002 ); Sailaja et al. (2003 ); Zhang et al. (2001 ); Clérac et al. (2002 ); Mitra et al. (2006 ); Hoshino et al. (2003 ); Nakamura et al. (2001 ); Liu et al. (2001 ).

Experimental

Crystal data

[Mn(C₁₃H₉N₃O₂)(C₅H₇O₂)(H₂O)]
M_r = 411.29
Monoclinic, P 2₁ /c
a = 17.462 (2) Å
b = 9.5286 (18) Å
c = 11.529 (3) Å
β = 106.798 (5)°
V = 1836.4 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.75 mm⁻¹
T = 293 (2) K
0.58 × 0.49 × 0.10 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: multi-scan (TEXRAY; Molecular Structure Corporation, 1999 ) T_min = 0.598, T_max = 0.932
17468 measured reflections
4203 independent reflections
3380 reflections with I > 2σ(I)
R_int = 0.047

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.105
S = 1.06
4203 reflections
246 parameters
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5B⋯N2ⁱ	0.90	2.14	3.013 (2)	164
O5—H5C⋯N1ⁱⁱ	0.88	1.92	2.784 (3)	165
C7—H7A⋯O2ⁱⁱⁱ	0.93	2.27	3.160 (2)	160
C13—H13A⋯O2ⁱⁱⁱ	0.93	2.59	3.390 (3)	145
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z+1; (iii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: TEXRAY (Molecular Structure Corporation, 1999); cell refinement: TEXRAY; data reduction: TEXSAN (Molecular Structure Corporation, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEX (McArdle, 1995 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807060734/xu2362sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536807060734/xu2362Isup2.hkl

checkCIF report

Comment top

Metal-organic supramolecular complexes with various fascinating topologies have been studied widely for their versatile chemical and physical properties and potential applications as functional materials (Janiak, 2003; Kitagawa et al., 2004). Self-assembly based on molecular building blocks has become an effective approach to construct these functional materials. In the development of supramolecular chemistry, hydrogen-bonding plays an important role in selfassembling multi-dimensional metal-organic supramolecular frameworks or networks (Graham & Pike, 2000). Some nicotylhydrazone derivatives and aroylhydrazone derivatives had led to a number of complexes with multidimensional structures or extended multidimensional structures. (Niu et al., 2005; Adams et al., 2000; Ranford et al., 1998). The syntheses and characterization of these complexes has been an area of rapid growth in recent years.(Batten & Robson, 1998; Hagrman et al., 1999). Herein, we report the synthesis and crystal structure of the title manganese(III) complex.

Complex (I) crystallizes in the space group P2₁/c. The crystal structure reveals that complex (I) consists of a neutral Mn(C₁₃H₉N₃O₂)(C₅H₇O₂)(H₂O) unit. As shown in Fig. 1, compound (I) is composed of one salicylaldehyde-nicotylhydrazone dianion, one acetylacetone anion, one coordinated water molecule and one Mn^III cations. The manganese(III) atom exists in a distorted octahedral environment defined by one carbonyl oxygen atom O1, one hydrazine nitrogen atom N3 and one phenolate oxygen atom O2 of the deprotonated Schiff base ligand, the two oxygen atoms (O3 and O4) of the acetylacetonate (acac) anion and one oxygen atom O5 of the coordinated water molecule. O1, N3, O2 and O4 atoms are located in the equatorial plane, while O3 and O5 occupy the axial positions. The bond length of Mn1—O1 (carbonyl oxygen) in complex (I) is 1.935 (2) Å, while the corresponding values in the similar known complexes are between 1.959 (2) and 1.971 (1)Å (Kessissoglou et al., 2002). The bond length of Mn1—O2(phenolic oxygen) in complex (I) is 1.886 (2) Å, while the corresponding values in the known complexes are between 1.844 (3) and 1.923 (3)Å (Sailaja et al., 2003; Zhang et al., 2001; Clérac et al., 2002) The bond length of Mn1—N3(hydrazone nitrogen) in complex (I) is 1.972 (2) Å, which is similar to the corresponding values 1.968 (4)–1.999 (7)Å of the known complexes (Mitra et al., 2006; Hoshino et al., 2003). The bond distance of axial Mn1—O3 (acac^-) (2.122 (2) Å) is 0.20 Å longer than that of the equatorial Mn1—O4(acac^-) (1.920 (1) Å), O3 and O4 being from the same acac^- ligand. This typical Jahn-Teller elongation along the z axis of the manganese(III) ion was also observed in some manganese(III) compounds (Nakamura et al., 2001; Liu et al., 2001). The title complex molecules are linked by hydrogen bonds (Table 1) into a two-dimensional supramolecular network. As illustrated in Fig. 2, one complex molecule connected to two neighboring complex molecules via hydrogen bonds of O—H(H₂O)···N(hydrazine) type and C—H···O(phenolate) type, resulting in an extended chain along the c axis. These hydrogen bonds are marked with green color in Fig. 2. A t the same time, the neighboring extended chains are combined by O—H(H₂O)···N(pyridine) hydrogen bonds with pink color, forming an extended two-dimensional network.

Related literature top

For general background, see: Janiak (2003); Kitagawa et al. (2004); Graham & Pike (2000); Niu et al. (2005); Adams et al. (2000); Ranford et al. (1998); Batten & Robson (1998); Hagrman et al. (1999). For related structures, see: Kessissoglou et al. (2002); Sailaja et al. (2003); Zhang et al. (2001); Clérac et al. (2002); Mitra et al. (2006); Hoshino et al. (2003); Nakamura et al. (2001); Liu et al. (2001).

Please provide captions for figures for Supplementary Material.

Experimental top

A DMF solution of salicylaldehyde-nicotylhydrazone ligand (24 mg, 0.1 mmol) and a methanol solution of Mn(acac)₃ (35 mg, 0.1 mmol) were mixed and stirred for 3 h. The resulting solution was then left for aerial evaporation at room temperature. Black block crystals of (I), suitable in size for single-crystal X-ray diffraction, appeared after two weeks.

Computing details top

Data collection: TEXRAY (Molecular Structure Corporation, 1999); cell refinement: TEXRAY (Molecular Structure Corporation, 1999); data reduction: TEXSAN (Molecular Structure Corporation, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEX (McArdle, 1995); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top

	Fig. 1. The molecular structure of (I), with the atom-numbering scheme and 30% probability displacement ellipsoids.
	Fig. 2. A plot illustrating extended two-dimensional structure of (I), hydrogen bonds are drawn as dashed lines. H atoms not-involved in hydrogen bonding have been omitted.
	Fig. 3. The extended two-dimensional net-work connected by hydrogen bonds, which are drawn as dashed lines. H atoms not-involved in hydrogen bonding have been omitted.

(Acetylacetonato-κ²O,O')aqua[salicylaldehyde nicotinoylhydrazonato(2-)-κ³O,N,O']manganese(III) top

Crystal data top

[Mn(C₁₃H₉N₃O₂)(C₅H₇O₂)(H₂O)]	F(000) = 848
M_r = 411.29	D_x = 1.488 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 17468 reflections
a = 17.462 (2) Å	θ = 3.2–27.5°
b = 9.5286 (18) Å	µ = 0.75 mm⁻¹
c = 11.529 (3) Å	T = 293 K
β = 106.798 (5)°	Block, black
V = 1836.4 (6) Å³	0.58 × 0.49 × 0.10 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	4203 independent reflections
Radiation source: fine-focus sealed tube	3380 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.047
ω scans	θ_max = 27.5°, θ_min = 3.2°
Absorption correction: multi-scan (TEXRAY; Molecular Structure Corporation, 1999)	h = −22→22
T_min = 0.598, T_max = 0.932	k = −12→12
17468 measured reflections	l = −12→14

Refinement top

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.105	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.056P)² + 0.2426P] where P = (F_o² + 2F_c²)/3
4203 reflections	(Δ/σ)_max < 0.001
246 parameters	Δρ_max = 0.40 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

[Mn(C₁₃H₉N₃O₂)(C₅H₇O₂)(H₂O)]	V = 1836.4 (6) Å³
M_r = 411.29	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 17.462 (2) Å	µ = 0.75 mm⁻¹
b = 9.5286 (18) Å	T = 293 K
c = 11.529 (3) Å	0.58 × 0.49 × 0.10 mm
β = 106.798 (5)°

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	4203 independent reflections
Absorption correction: multi-scan (TEXRAY; Molecular Structure Corporation, 1999)	3380 reflections with I > 2σ(I)
T_min = 0.598, T_max = 0.932	R_int = 0.047
17468 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.105	H-atom parameters constrained
S = 1.06	Δρ_max = 0.40 e Å⁻³
4203 reflections	Δρ_min = −0.26 e Å⁻³
246 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Mn1	0.249798 (18)	0.57337 (3)	0.43657 (2)	0.03214 (11)
O1	0.34284 (9)	0.48904 (15)	0.40574 (12)	0.0409 (3)
O2	0.15564 (9)	0.67021 (14)	0.43678 (12)	0.0384 (3)
O3	0.19055 (11)	0.37673 (16)	0.40212 (15)	0.0509 (4)
O4	0.27874 (10)	0.52725 (15)	0.60578 (12)	0.0419 (3)
O5	0.32467 (9)	0.77095 (14)	0.50465 (13)	0.0405 (3)
H5B	0.3069	0.8261	0.5550	0.061*
H5C	0.3709	0.7356	0.5472	0.061*
N1	0.53617 (13)	0.3198 (2)	0.3250 (2)	0.0579 (5)
N2	0.29071 (10)	0.57484 (16)	0.21251 (15)	0.0343 (4)
N3	0.23512 (10)	0.63091 (16)	0.26725 (13)	0.0302 (3)
C1	0.47353 (14)	0.3815 (2)	0.3467 (2)	0.0463 (5)
H1B	0.4732	0.3895	0.4269	0.056*
C2	0.40938 (13)	0.43433 (19)	0.25884 (19)	0.0373 (4)
C3	0.41031 (18)	0.4214 (3)	0.1385 (2)	0.0572 (7)
H3A	0.3677	0.4534	0.0753	0.069*
C4	0.4756 (2)	0.3604 (3)	0.1159 (3)	0.0716 (9)
H4A	0.4781	0.3518	0.0367	0.086*
C5	0.53676 (18)	0.3125 (3)	0.2098 (3)	0.0658 (7)
H5A	0.5810	0.2730	0.1928	0.079*
C6	0.34313 (12)	0.50249 (19)	0.29342 (17)	0.0343 (4)
C7	0.18497 (12)	0.7207 (2)	0.20497 (17)	0.0337 (4)
H7A	0.1885	0.7435	0.1283	0.040*
C8	0.12392 (12)	0.78839 (19)	0.24536 (17)	0.0332 (4)
C9	0.11051 (12)	0.75715 (18)	0.35741 (17)	0.0331 (4)
C10	0.04471 (14)	0.8204 (2)	0.3828 (2)	0.0440 (5)
H10A	0.0341	0.8006	0.4556	0.053*
C11	−0.00431 (15)	0.9108 (2)	0.3023 (2)	0.0490 (6)
H11A	−0.0482	0.9499	0.3207	0.059*
C12	0.01056 (15)	0.9450 (2)	0.1939 (2)	0.0511 (6)
H12A	−0.0224	1.0081	0.1407	0.061*
C13	0.07387 (14)	0.8852 (2)	0.1662 (2)	0.0436 (5)
H13A	0.0843	0.9086	0.0939	0.052*
C14	0.1360 (2)	0.1594 (3)	0.4358 (3)	0.0801 (9)
H14A	0.1246	0.1535	0.3493	0.120*
H14B	0.0867	0.1641	0.4569	0.120*
H14C	0.1655	0.0779	0.4724	0.120*
C15	0.18474 (15)	0.2891 (2)	0.4808 (2)	0.0499 (6)
C16	0.22056 (18)	0.3043 (2)	0.6060 (2)	0.0586 (7)
H16A	0.2100	0.2300	0.6570	0.070*
C17	0.26526 (15)	0.4158 (2)	0.6601 (2)	0.0449 (5)
C18	0.3042 (2)	0.4170 (3)	0.7940 (2)	0.0728 (9)
H18A	0.3610	0.4275	0.8098	0.109*
H18B	0.2930	0.3304	0.8284	0.109*
H18C	0.2836	0.4940	0.8297	0.109*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.03229 (18)	0.03714 (17)	0.02695 (16)	0.00286 (12)	0.00849 (12)	0.00486 (11)
O1	0.0407 (9)	0.0492 (8)	0.0326 (7)	0.0147 (7)	0.0103 (6)	0.0088 (6)
O2	0.0359 (8)	0.0488 (8)	0.0325 (7)	0.0063 (6)	0.0132 (6)	0.0050 (6)
O3	0.0556 (11)	0.0453 (8)	0.0487 (9)	−0.0095 (7)	0.0102 (8)	−0.0057 (7)
O4	0.0515 (10)	0.0417 (7)	0.0303 (7)	−0.0014 (7)	0.0081 (6)	0.0076 (6)
O5	0.0358 (8)	0.0441 (7)	0.0390 (7)	−0.0016 (6)	0.0068 (6)	0.0023 (6)
N1	0.0410 (12)	0.0618 (12)	0.0654 (13)	0.0187 (10)	0.0068 (10)	−0.0026 (11)
N2	0.0316 (9)	0.0408 (8)	0.0320 (8)	0.0060 (7)	0.0114 (7)	0.0021 (7)
N3	0.0281 (9)	0.0343 (7)	0.0285 (7)	0.0030 (6)	0.0085 (7)	0.0023 (6)
C1	0.0413 (13)	0.0515 (11)	0.0425 (12)	0.0088 (10)	0.0065 (10)	−0.0033 (10)
C2	0.0362 (11)	0.0349 (9)	0.0403 (11)	0.0063 (8)	0.0105 (9)	−0.0002 (8)
C3	0.0633 (17)	0.0670 (15)	0.0411 (12)	0.0315 (13)	0.0148 (12)	0.0041 (11)
C4	0.082 (2)	0.0829 (19)	0.0559 (15)	0.0405 (17)	0.0301 (15)	0.0051 (14)
C5	0.0575 (18)	0.0671 (15)	0.0785 (19)	0.0266 (13)	0.0286 (15)	−0.0014 (14)
C6	0.0331 (11)	0.0338 (9)	0.0349 (10)	0.0011 (8)	0.0083 (8)	−0.0006 (8)
C7	0.0321 (10)	0.0404 (9)	0.0286 (9)	0.0020 (8)	0.0085 (8)	0.0036 (8)
C8	0.0309 (10)	0.0344 (9)	0.0334 (9)	0.0025 (8)	0.0079 (8)	0.0000 (8)
C9	0.0298 (10)	0.0333 (9)	0.0350 (9)	−0.0024 (7)	0.0077 (8)	−0.0033 (8)
C10	0.0406 (13)	0.0499 (11)	0.0453 (11)	0.0033 (10)	0.0187 (10)	−0.0017 (9)
C11	0.0386 (13)	0.0503 (12)	0.0609 (14)	0.0122 (10)	0.0188 (11)	−0.0025 (11)
C12	0.0458 (14)	0.0495 (12)	0.0545 (14)	0.0175 (10)	0.0088 (11)	0.0057 (10)
C13	0.0438 (13)	0.0443 (10)	0.0417 (11)	0.0098 (9)	0.0108 (10)	0.0044 (9)
C14	0.083 (2)	0.0524 (14)	0.104 (2)	−0.0233 (15)	0.026 (2)	−0.0089 (15)
C15	0.0479 (14)	0.0353 (10)	0.0687 (15)	−0.0019 (9)	0.0199 (12)	−0.0020 (10)
C16	0.0756 (19)	0.0434 (11)	0.0589 (15)	−0.0054 (12)	0.0228 (14)	0.0148 (11)
C17	0.0494 (14)	0.0463 (11)	0.0412 (11)	0.0074 (10)	0.0166 (10)	0.0130 (9)
C18	0.101 (3)	0.0729 (17)	0.0410 (14)	−0.0015 (16)	0.0143 (15)	0.0194 (12)

Geometric parameters (Å, º) top

Mn1—O2	1.8860 (14)	C5—H5A	0.9300
Mn1—O4	1.9195 (14)	C7—C8	1.434 (3)
Mn1—O1	1.9354 (14)	C7—H7A	0.9300
Mn1—N3	1.9718 (16)	C8—C9	1.410 (3)
Mn1—O3	2.1216 (16)	C8—C13	1.410 (3)
Mn1—O5	2.2971 (14)	C9—C10	1.401 (3)
O1—C6	1.303 (2)	C10—C11	1.370 (3)
O2—C9	1.315 (2)	C10—H10A	0.9300
O3—C15	1.259 (3)	C11—C12	1.388 (3)
O4—C17	1.289 (2)	C11—H11A	0.9300
O5—H5B	0.9021	C12—C13	1.361 (3)
O5—H5C	0.8812	C12—H12A	0.9300
N1—C1	1.327 (3)	C13—H13A	0.9300
N1—C5	1.333 (4)	C14—C15	1.505 (3)
N2—C6	1.300 (3)	C14—H14A	0.9600
N2—N3	1.407 (2)	C14—H14B	0.9600
N3—C7	1.285 (2)	C14—H14C	0.9600
C1—C2	1.370 (3)	C15—C16	1.405 (4)
C1—H1B	0.9300	C16—C17	1.358 (3)
C2—C3	1.398 (3)	C16—H16A	0.9713
C2—C6	1.478 (3)	C17—C18	1.497 (4)
C3—C4	1.370 (4)	C18—H18A	0.9600
C3—H3A	0.9300	C18—H18B	0.9600
C4—C5	1.361 (4)	C18—H18C	0.9600
C4—H4A	0.9300

O2—Mn1—O4	94.83 (6)	O1—C6—C2	116.94 (17)
O2—Mn1—O1	169.05 (6)	N3—C7—C8	124.64 (17)
O4—Mn1—O1	95.92 (6)	N3—C7—H7A	117.7
O2—Mn1—N3	90.07 (6)	C8—C7—H7A	117.7
O4—Mn1—N3	172.13 (7)	C9—C8—C13	119.71 (18)
O1—Mn1—N3	79.02 (6)	C9—C8—C7	122.60 (17)
O2—Mn1—O3	93.11 (7)	C13—C8—C7	117.64 (17)
O4—Mn1—O3	87.65 (6)	O2—C9—C10	119.25 (17)
O1—Mn1—O3	89.36 (7)	O2—C9—C8	123.10 (17)
N3—Mn1—O3	98.24 (6)	C10—C9—C8	117.64 (18)
O2—Mn1—O5	90.51 (6)	C11—C10—C9	121.3 (2)
O4—Mn1—O5	83.32 (6)	C11—C10—H10A	119.4
O1—Mn1—O5	88.73 (6)	C9—C10—H10A	119.4
N3—Mn1—O5	90.50 (6)	C10—C11—C12	121.0 (2)
O3—Mn1—O5	170.53 (6)	C10—C11—H11A	119.5
C6—O1—Mn1	112.73 (12)	C12—C11—H11A	119.5
C9—O2—Mn1	130.91 (12)	C13—C12—C11	119.3 (2)
C15—O3—Mn1	125.99 (15)	C13—C12—H12A	120.3
C17—O4—Mn1	130.61 (15)	C11—C12—H12A	120.3
Mn1—O5—H5B	115.4	C12—C13—C8	121.0 (2)
Mn1—O5—H5C	102.5	C12—C13—H13A	119.5
H5B—O5—H5C	107.1	C8—C13—H13A	119.5
C1—N1—C5	117.0 (2)	C15—C14—H14A	109.5
C6—N2—N3	108.27 (16)	C15—C14—H14B	109.5
C7—N3—N2	116.70 (15)	H14A—C14—H14B	109.5
C7—N3—Mn1	127.66 (13)	C15—C14—H14C	109.5
N2—N3—Mn1	115.42 (11)	H14A—C14—H14C	109.5
N1—C1—C2	124.5 (2)	H14B—C14—H14C	109.5
N1—C1—H1B	117.8	O3—C15—C16	124.6 (2)
C2—C1—H1B	117.8	O3—C15—C14	116.8 (2)
C1—C2—C3	117.4 (2)	C16—C15—C14	118.6 (2)
C1—C2—C6	119.89 (19)	C17—C16—C15	125.3 (2)
C3—C2—C6	122.7 (2)	C17—C16—H16A	118.4
C4—C3—C2	118.3 (2)	C15—C16—H16A	116.2
C4—C3—H3A	120.8	O4—C17—C16	125.7 (2)
C2—C3—H3A	120.8	O4—C17—C18	113.7 (2)
C5—C4—C3	119.7 (2)	C16—C17—C18	120.6 (2)
C5—C4—H4A	120.1	C17—C18—H18A	109.5
C3—C4—H4A	120.1	C17—C18—H18B	109.5
N1—C5—C4	123.0 (2)	H18A—C18—H18B	109.5
N1—C5—H5A	118.5	C17—C18—H18C	109.5
C4—C5—H5A	118.5	H18A—C18—H18C	109.5
N2—C6—O1	124.14 (18)	H18B—C18—H18C	109.5
N2—C6—C2	118.88 (17)

O2—Mn1—O1—C6	−10.2 (4)	C3—C4—C5—N1	1.1 (5)
O4—Mn1—O1—C6	−179.52 (14)	N3—N2—C6—O1	−1.1 (3)
N3—Mn1—O1—C6	−5.61 (13)	N3—N2—C6—C2	−178.91 (16)
O3—Mn1—O1—C6	92.91 (14)	Mn1—O1—C6—N2	5.6 (3)
O5—Mn1—O1—C6	−96.37 (14)	Mn1—O1—C6—C2	−176.53 (13)
O4—Mn1—O2—C9	164.44 (17)	C1—C2—C6—N2	167.1 (2)
O1—Mn1—O2—C9	−4.9 (4)	C3—C2—C6—N2	−12.4 (3)
N3—Mn1—O2—C9	−9.40 (17)	C1—C2—C6—O1	−10.8 (3)
O3—Mn1—O2—C9	−107.66 (17)	C3—C2—C6—O1	169.6 (2)
O5—Mn1—O2—C9	81.10 (17)	N2—N3—C7—C8	179.71 (17)
O2—Mn1—O3—C15	−92.8 (2)	Mn1—N3—C7—C8	−6.0 (3)
O4—Mn1—O3—C15	1.9 (2)	N3—C7—C8—C9	−3.1 (3)
O1—Mn1—O3—C15	97.8 (2)	N3—C7—C8—C13	179.7 (2)
N3—Mn1—O3—C15	176.63 (19)	Mn1—O2—C9—C10	−177.10 (14)
O2—Mn1—O4—C17	95.0 (2)	Mn1—O2—C9—C8	4.3 (3)
O1—Mn1—O4—C17	−87.0 (2)	C13—C8—C9—O2	−178.60 (19)
O3—Mn1—O4—C17	2.1 (2)	C7—C8—C9—O2	4.2 (3)
O5—Mn1—O4—C17	−175.0 (2)	C13—C8—C9—C10	2.8 (3)
C6—N2—N3—C7	171.09 (17)	C7—C8—C9—C10	−174.42 (19)
C6—N2—N3—Mn1	−3.94 (19)	O2—C9—C10—C11	−179.5 (2)
O2—Mn1—N3—C7	10.08 (18)	C8—C9—C10—C11	−0.8 (3)
O1—Mn1—N3—C7	−169.04 (18)	C9—C10—C11—C12	−1.3 (4)
O3—Mn1—N3—C7	103.23 (18)	C10—C11—C12—C13	1.4 (4)
O5—Mn1—N3—C7	−80.43 (18)	C11—C12—C13—C8	0.6 (4)
O2—Mn1—N3—N2	−175.53 (13)	C9—C8—C13—C12	−2.7 (3)
O1—Mn1—N3—N2	5.34 (12)	C7—C8—C13—C12	174.6 (2)
O3—Mn1—N3—N2	−82.38 (13)	Mn1—O3—C15—C16	−3.4 (4)
O5—Mn1—N3—N2	93.96 (13)	Mn1—O3—C15—C14	176.78 (19)
C5—N1—C1—C2	1.7 (4)	O3—C15—C16—C17	1.0 (4)
N1—C1—C2—C3	0.2 (4)	C14—C15—C16—C17	−179.2 (3)
N1—C1—C2—C6	−179.3 (2)	Mn1—O4—C17—C16	−4.8 (4)
C1—C2—C3—C4	−1.6 (4)	Mn1—O4—C17—C18	175.20 (19)
C6—C2—C3—C4	178.0 (2)	C15—C16—C17—O4	3.3 (4)
C2—C3—C4—C5	1.0 (5)	C15—C16—C17—C18	−176.7 (3)
C1—N1—C5—C4	−2.4 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5B···N2ⁱ	0.90	2.14	3.013 (2)	164
O5—H5C···N1ⁱⁱ	0.88	1.92	2.784 (3)	165
C7—H7A···O2ⁱⁱⁱ	0.93	2.27	3.160 (2)	160
C13—H13A···O2ⁱⁱⁱ	0.93	2.59	3.390 (3)	145

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

Experimental details

Crystal data
Chemical formula	[Mn(C₁₃H₉N₃O₂)(C₅H₇O₂)(H₂O)]
M_r	411.29
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	17.462 (2), 9.5286 (18), 11.529 (3)
β (°)	106.798 (5)
V (Å³)	1836.4 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.75
Crystal size (mm)	0.58 × 0.49 × 0.10

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP diffractometer
Absorption correction	Multi-scan (TEXRAY; Molecular Structure Corporation, 1999)
T_min, T_max	0.598, 0.932
No. of measured, independent and observed [I > 2σ(I)] reflections	17468, 4203, 3380
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.105, 1.06
No. of reflections	4203
No. of parameters	246
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.26

Computer programs: TEXRAY (Molecular Structure Corporation, 1999), TEXSAN (Molecular Structure Corporation, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEX (McArdle, 1995).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5B···N2ⁱ	0.90	2.14	3.013 (2)	163.5
O5—H5C···N1ⁱⁱ	0.88	1.92	2.784 (3)	164.9
C7—H7A···O2ⁱⁱⁱ	0.93	2.27	3.160 (2)	160.4
C13—H13A···O2ⁱⁱⁱ	0.93	2.59	3.390 (3)	144.6

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

Acknowledgements

The authors are grateful for financial support from the National Natural Science Foundation of China (grant Nos. 20431010 and 20171012).

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