Aqua­(4-nitro­phthalato-κO1)bis­[2-(1H-pyrazol-3-yl-κN2)pyridine-κN]­mangan­ese(II) hemihydrate

Ni, L.; Zhao, J.-L.; Wei, H.

doi:10.1107/S1600536810045952

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page m1550

https://doi.org/10.1107/S1600536810045952

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Aqua(4-nitrophthalato-κO¹)bis[2-(1H-pyrazol-3-yl-κN²)pyridine-κN]manganese(II) hemihydrate

Lei Ni,^a ^* Ji-Li Zhao ^a and Hong Wei ^a

^aCollege of Chemistry and Biology, Beihua University, Jilin 132013, People's Republic of China
^*Correspondence e-mail: nilei_bh@163.com

(Received 28 August 2010; accepted 8 November 2010; online 13 November 2010)

In the title compound, [Mn(C₈H₃NO₆)(C₈H₇N₃)₂(H₂O)]·0.5H₂O, the Mn²⁺ ion is octahedrally coordinated by two 2-(1H-pyrazol-3-yl)pyridine ligands, one 4-nitrophthalate ligand and one coordinated water molecule leading to an overall MnN₄O₂ coordination environment. The two 2-(1H-pyrazol-3-yl)pyridine ligands, which deviate from planarity by 0.0187 (2) and 0.0601 (2) Å, make a dihedral angle of 81.90 (6)°. An intramolecular N—H⋯O hydrogen bond occurs. Intermolecular π–π stacking interactions with a face-to-face separation of 3.61 (1) Å between the 2-(1H-pyrazol-3-yl)pyridine ligands is observed. Additionally, O—H⋯O hydrogen bonding involving the uncoordinated water (which is situated on an inversion center), coordinated water molecules and 2-(1H-pyrazol-3-yl)pyridine ligands leads to a three-dimensional network in the crystal structure.

Related literature

For the use of 4-nitro-phthalic acid for metal-organic frameworks, see: Xu et al. (2009 ); Guo & Guo (2007 ).

Experimental

Crystal data

[Mn(C₈H₃NO₆)(C₈H₇N₃)₂(H₂O)]·0.5H₂O
M_r = 581.41
Triclinic, $[P \overline 1]$
a = 10.5996 (7) Å
b = 11.2654 (7) Å
c = 11.9493 (7) Å
α = 96.275 (2)°
β = 112.485 (2)°
γ = 96.902 (2)°
V = 1289.94 (14) Å³
Z = 2
Mo Kα radiation
μ = 0.57 mm⁻¹
T = 294 K
0.12 × 0.10 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.935, T_max = 0.956
13775 measured reflections
4492 independent reflections
4112 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.107
S = 1.00
4492 reflections
364 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.67 e Å⁻³
Δρ_min = −0.56 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H2W⋯O4ⁱ	0.82 (2)	1.80 (2)	2.615 (2)	171 (3)
N1—H1A⋯O1	0.86	1.86	2.644 (3)	152
Symmetry code: (i) -x+2, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810045952/im2225sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810045952/im2225Isup2.hkl

checkCIF report

Comment top

The synthesis of metal-organic frameworks (MOFs) has attracted continuous research interest not only because of their appealing structural and topological novelty, but also due to their unusual optical, electronic, magnetic, and catalytic properties, as well as their potential medical application (Xu et al. (2009); Guo & Guo (2007)). Here, we describe the synthesis and structural characterization of the title compound.

Single crystal X-ray diffraction analysis revealed that the asymmetric unit of the title compound, [(Mn(C₈H₇N₃)₂(C₈H₃NO₆)(H₂O)] × 0.5 H₂O, consists of one Mn²⁺ ion that is octahedrally coordinated by two 2-(1H-pyrazol-3-yl)-pyridine ligands, one 4-nitro-phthalato ligand and one coordinated water molecule leading to an overall MnN₄O₂ coordination environment (Figure 1). Deviations of the two 2-(1H-pyrazol-3-yl)-pyridine moieties from planarity are 0.0187 (2) and 0.0601 (2) Å, respectively. The dihedral angle between the two 3-(2-pyridyl)-1H-pyrazole planes is 81.90 (6)°. The Mn-N and Mn-O bond distances are in the range of 2.200 (2)—2.359 (2) and 2.126 (2)—2.162 (2) Å, respectively. Intermolecular π-π stacking interactions with a face-to-face separation of 3.61 (1) Å between the 2-(1H-pyrazol-3-yl)-pyridine ligands is observed. Additionally, extensive hydrogen bonding involving solvent water (which are situated at a crystallographic center of inversion), coordinated water molecules and 2-(1H-pyrazol-3-yl)-pyridine ligands leads to a three dimensional network in the crystal structure (Figure 2).

Related literature top

For the use of 4-nitro-phthalic acid for metal-organic frameworks, see: Xu et al. (2009); Guo & Guo (2007).

Experimental top

A mixture of manganese sulfate hydrate (0.33 mmol, 0.050 g), 2-(1H-pyrazol-3-yl)-pyridine (0.32 mmoL, 0.05 g), and 4-nitrophthalic acid (0.24 mmoL, 0.05 g), gadolinium(III) nitrate pentahydrate (0.12 mmoL, 0.05 g), and 14 ml H₂O was sealed in a 25 ml Teflon-lined stainless steel autoclave at 433 K for three days. Pink crystals suitable for the X-ray experiment were obtained after cooling down to room temperature (yield: 76%). Anal. Calc. for C₄₈H₄₀Mn₂N₁₄O₁₅: C 49.53, H 3.44, N 16.85%; Found: C 49.36, H 3.32, N 16.72%.

Structure description top

For the use of 4-nitro-phthalic acid for metal-organic frameworks, see: Xu et al. (2009); Guo & Guo (2007).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level; H atoms are given as spheres of arbitrary radius.
	Fig. 2. Crystal packing of the title compound, displayed with hydrogen bonds as dashed lines.

Aqua(4-nitrophthalato-κO¹)bis[2-(1H-pyrazol-3-yl- κN²)pyridine-κN]manganese(II) hemihydrate top

Crystal data top

[Mn(C₈H₃NO₆)(C₈H₇N₃)₂(H₂O)]·0.5H₂O	Z = 2
M_r = 581.41	F(000) = 594
Triclinic, P1	D_x = 1.497 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.5996 (7) Å	Cell parameters from 4492 reflections
b = 11.2654 (7) Å	θ = 1.9–25.0°
c = 11.9493 (7) Å	µ = 0.57 mm⁻¹
α = 96.275 (2)°	T = 294 K
β = 112.485 (2)°	Block, pink
γ = 96.902 (2)°	0.12 × 0.10 × 0.08 mm
V = 1289.94 (14) Å³

Data collection top

Bruker APEXII CCD diffractometer	4492 independent reflections
Radiation source: fine-focus sealed tube	4112 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
phi and ω scans	θ_max = 25.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −12→12
T_min = 0.935, T_max = 0.956	k = −13→12
13775 measured reflections	l = −14→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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.065P)² + 0.6953P] where P = (F_o² + 2F_c²)/3
4492 reflections	(Δ/σ)_max = 0.001
364 parameters	Δρ_max = 0.67 e Å⁻³
3 restraints	Δρ_min = −0.56 e Å⁻³

Crystal data top

[Mn(C₈H₃NO₆)(C₈H₇N₃)₂(H₂O)]·0.5H₂O	γ = 96.902 (2)°
M_r = 581.41	V = 1289.94 (14) Å³
Triclinic, P1	Z = 2
a = 10.5996 (7) Å	Mo Kα radiation
b = 11.2654 (7) Å	µ = 0.57 mm⁻¹
c = 11.9493 (7) Å	T = 294 K
α = 96.275 (2)°	0.12 × 0.10 × 0.08 mm
β = 112.485 (2)°

Data collection top

Bruker APEXII CCD diffractometer	4492 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	4112 reflections with I > 2σ(I)
T_min = 0.935, T_max = 0.956	R_int = 0.016
13775 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	3 restraints
wR(F²) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.67 e Å⁻³
4492 reflections	Δρ_min = −0.56 e Å⁻³
364 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
C1	0.7173 (4)	0.2731 (3)	0.9226 (3)	0.0712 (8)
H1	0.6343	0.2568	0.9323	0.085*
C2	0.8448 (4)	0.3131 (3)	1.0143 (3)	0.0697 (8)
H2	0.8668	0.3294	1.0983	0.084*
C3	0.9359 (3)	0.3247 (2)	0.9554 (2)	0.0518 (6)
C4	1.0853 (3)	0.3638 (2)	1.0005 (2)	0.0537 (6)
C5	1.1703 (4)	0.4045 (3)	1.1239 (2)	0.0695 (8)
H5	1.1328	0.4073	1.1828	0.083*
C6	1.3098 (4)	0.4403 (3)	1.1578 (3)	0.0831 (10)
H6	1.3680	0.4673	1.2401	0.100*
C7	1.3632 (4)	0.4362 (3)	1.0692 (3)	0.0802 (9)
H7	1.4576	0.4607	1.0903	0.096*
C8	1.2730 (3)	0.3948 (3)	0.9483 (3)	0.0670 (7)
H8	1.3090	0.3916	0.8884	0.080*
C9	1.3004 (3)	0.2422 (3)	0.5695 (3)	0.0635 (7)
H9	1.3674	0.2662	0.5403	0.076*
C10	1.2660 (3)	0.1287 (3)	0.5905 (3)	0.0611 (7)
H10	1.3037	0.0604	0.5786	0.073*
C11	1.1618 (2)	0.13717 (19)	0.63382 (19)	0.0406 (4)
C12	1.0839 (2)	0.04615 (18)	0.67283 (18)	0.0404 (4)
C13	1.0928 (3)	−0.0766 (2)	0.6586 (2)	0.0526 (6)
H13	1.1490	−0.1049	0.6217	0.063*
C14	1.0177 (3)	−0.1549 (2)	0.6995 (3)	0.0663 (7)
H14	1.0218	−0.2372	0.6906	0.080*
C15	0.9309 (3)	0.0111 (2)	0.7633 (3)	0.0688 (8)
H15	0.8747	0.0405	0.7995	0.083*
C16	0.9367 (4)	−0.1107 (3)	0.7536 (3)	0.0761 (8)
H16	0.8861	−0.1620	0.7834	0.091*
C17	0.6605 (2)	0.2144 (2)	0.5118 (2)	0.0513 (6)
C18	0.5813 (2)	0.1929 (2)	0.3746 (2)	0.0427 (5)
C19	0.4714 (3)	0.0954 (2)	0.3232 (2)	0.0572 (6)
H19	0.4438	0.0523	0.3746	0.069*
C20	0.4030 (3)	0.0616 (2)	0.1979 (3)	0.0619 (7)
H20	0.3294	−0.0034	0.1639	0.074*
C21	0.4462 (2)	0.1264 (2)	0.1246 (2)	0.0545 (6)
C22	0.5544 (2)	0.2235 (2)	0.1721 (2)	0.0479 (5)
H22	0.5820	0.2648	0.1197	0.058*
C23	0.6216 (2)	0.25915 (18)	0.29779 (19)	0.0400 (4)
C24	0.7320 (2)	0.3719 (2)	0.3445 (2)	0.0462 (5)
Mn1	0.97367 (3)	0.28597 (3)	0.71009 (3)	0.03701 (12)
N1	0.7320 (2)	0.26121 (19)	0.8159 (2)	0.0564 (5)
H1A	0.6650	0.2366	0.7450	0.068*
N2	0.8652 (2)	0.29291 (17)	0.83442 (17)	0.0485 (4)
N3	1.1369 (2)	0.35929 (18)	0.91298 (18)	0.0528 (5)
N4	1.22077 (19)	0.31285 (17)	0.59823 (18)	0.0474 (4)
H4	1.2240	0.3884	0.5919	0.057*
N5	1.13476 (17)	0.25018 (15)	0.63847 (16)	0.0393 (4)
N6	1.0021 (2)	0.08928 (16)	0.72337 (18)	0.0467 (4)
N7	0.3749 (3)	0.0899 (3)	−0.0097 (2)	0.0805 (7)
O1	0.5935 (2)	0.2119 (4)	0.5746 (2)	0.1504 (16)
O2	0.78795 (15)	0.22449 (14)	0.54996 (14)	0.0475 (4)
O3	0.7370 (2)	0.44475 (15)	0.43391 (16)	0.0596 (4)
O4	0.8061 (2)	0.38723 (19)	0.2870 (2)	0.0791 (6)
O5	0.4122 (3)	0.1463 (3)	−0.0749 (2)	0.1086 (9)
O6	0.2814 (4)	0.0044 (3)	−0.0487 (3)	0.1654 (18)
O1W	0.96188 (16)	0.46463 (14)	0.66095 (15)	0.0479 (4)
O2W	0.5000	0.5000	0.5000	0.208 (3)
H1W	0.9011 (17)	0.454 (3)	0.5913 (10)	0.080*
H2W	1.0347 (14)	0.507 (2)	0.670 (2)	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.097 (2)	0.0723 (18)	0.0770 (19)	0.0202 (16)	0.0667 (19)	0.0216 (15)
C2	0.109 (2)	0.0717 (18)	0.0557 (16)	0.0283 (17)	0.0556 (18)	0.0216 (13)
C3	0.0855 (18)	0.0398 (11)	0.0455 (12)	0.0208 (11)	0.0388 (12)	0.0118 (9)
C4	0.0838 (18)	0.0380 (12)	0.0446 (12)	0.0213 (11)	0.0277 (12)	0.0100 (9)
C5	0.106 (2)	0.0573 (16)	0.0450 (14)	0.0253 (15)	0.0264 (15)	0.0096 (12)
C6	0.104 (3)	0.0694 (19)	0.0505 (16)	0.0196 (18)	0.0035 (17)	0.0064 (14)
C7	0.073 (2)	0.076 (2)	0.0705 (19)	0.0113 (16)	0.0083 (16)	0.0066 (15)
C8	0.0655 (17)	0.0692 (17)	0.0592 (16)	0.0113 (14)	0.0192 (13)	0.0037 (13)
C9	0.0590 (15)	0.0756 (18)	0.0797 (18)	0.0222 (13)	0.0481 (14)	0.0230 (14)
C10	0.0679 (16)	0.0625 (16)	0.0775 (17)	0.0340 (13)	0.0465 (14)	0.0217 (13)
C11	0.0430 (11)	0.0413 (11)	0.0400 (11)	0.0145 (9)	0.0174 (9)	0.0070 (8)
C12	0.0442 (11)	0.0390 (11)	0.0347 (10)	0.0117 (9)	0.0112 (9)	0.0057 (8)
C13	0.0630 (14)	0.0435 (12)	0.0492 (13)	0.0197 (11)	0.0175 (11)	0.0072 (10)
C14	0.0842 (19)	0.0372 (13)	0.0728 (17)	0.0156 (12)	0.0235 (15)	0.0146 (12)
C15	0.0821 (19)	0.0506 (14)	0.101 (2)	0.0164 (13)	0.0608 (17)	0.0260 (14)
C16	0.092 (2)	0.0478 (15)	0.105 (2)	0.0101 (14)	0.0540 (19)	0.0311 (15)
C17	0.0418 (12)	0.0668 (15)	0.0513 (13)	0.0064 (10)	0.0257 (10)	0.0111 (11)
C18	0.0337 (10)	0.0464 (12)	0.0515 (12)	0.0080 (9)	0.0206 (9)	0.0084 (9)
C19	0.0470 (13)	0.0583 (14)	0.0676 (16)	−0.0026 (11)	0.0259 (12)	0.0176 (12)
C20	0.0428 (13)	0.0561 (15)	0.0722 (17)	−0.0106 (11)	0.0149 (12)	0.0028 (12)
C21	0.0420 (12)	0.0584 (14)	0.0500 (13)	0.0027 (10)	0.0089 (10)	−0.0010 (11)
C22	0.0416 (11)	0.0532 (13)	0.0472 (12)	0.0032 (10)	0.0170 (10)	0.0096 (10)
C23	0.0338 (10)	0.0382 (11)	0.0475 (11)	0.0056 (8)	0.0162 (9)	0.0067 (9)
C24	0.0433 (11)	0.0391 (11)	0.0504 (12)	0.0008 (9)	0.0143 (10)	0.0085 (10)
Mn1	0.0428 (2)	0.03495 (19)	0.03942 (19)	0.00804 (13)	0.02298 (15)	0.00565 (13)
N1	0.0672 (13)	0.0579 (12)	0.0593 (12)	0.0069 (10)	0.0432 (11)	0.0088 (9)
N2	0.0655 (12)	0.0437 (10)	0.0483 (11)	0.0105 (9)	0.0356 (10)	0.0075 (8)
N3	0.0663 (13)	0.0466 (11)	0.0465 (11)	0.0141 (9)	0.0234 (10)	0.0048 (8)
N4	0.0476 (10)	0.0460 (10)	0.0576 (11)	0.0075 (8)	0.0302 (9)	0.0124 (8)
N5	0.0414 (9)	0.0379 (9)	0.0432 (9)	0.0072 (7)	0.0221 (8)	0.0062 (7)
N6	0.0541 (11)	0.0376 (9)	0.0570 (11)	0.0102 (8)	0.0298 (9)	0.0121 (8)
N7	0.0622 (15)	0.0935 (19)	0.0578 (15)	−0.0044 (14)	0.0031 (12)	−0.0036 (14)
O1	0.0515 (13)	0.342 (5)	0.0589 (13)	0.015 (2)	0.0337 (11)	0.016 (2)
O2	0.0402 (8)	0.0541 (9)	0.0470 (8)	0.0068 (7)	0.0177 (7)	0.0041 (7)
O3	0.0743 (12)	0.0413 (9)	0.0559 (10)	−0.0013 (8)	0.0228 (9)	0.0036 (8)
O4	0.0715 (13)	0.0731 (13)	0.0920 (14)	−0.0272 (10)	0.0501 (12)	−0.0099 (11)
O5	0.0866 (17)	0.167 (3)	0.0508 (12)	−0.0142 (17)	0.0190 (12)	0.0042 (14)
O6	0.160 (3)	0.160 (3)	0.0776 (18)	−0.088 (3)	−0.0201 (19)	−0.0018 (18)
O1W	0.0464 (9)	0.0414 (8)	0.0532 (9)	0.0005 (7)	0.0182 (7)	0.0109 (7)
O2W	0.190 (6)	0.278 (8)	0.248 (8)	0.101 (6)	0.165 (6)	0.066 (6)

Geometric parameters (Å, º) top

C1—N1	1.338 (3)	C15—H15	0.9300
C1—C2	1.357 (5)	C16—H16	0.9300
C1—H1	0.9300	C17—O1	1.216 (3)
C2—C3	1.398 (4)	C17—O2	1.235 (3)
C2—H2	0.9300	C17—C18	1.504 (3)
C3—N2	1.332 (3)	C18—C19	1.393 (3)
C3—C4	1.456 (4)	C18—C23	1.398 (3)
C4—N3	1.352 (3)	C19—C20	1.375 (4)
C4—C5	1.390 (4)	C19—H19	0.9300
C5—C6	1.370 (5)	C20—C21	1.370 (4)
C5—H5	0.9300	C20—H20	0.9300
C6—C7	1.378 (5)	C21—C22	1.378 (3)
C6—H6	0.9300	C21—N7	1.473 (3)
C7—C8	1.382 (4)	C22—C23	1.380 (3)
C7—H7	0.9300	C22—H22	0.9300
C8—N3	1.334 (4)	C23—C24	1.511 (3)
C8—H8	0.9300	C24—O4	1.235 (3)
C9—N4	1.337 (3)	C24—O3	1.253 (3)
C9—C10	1.364 (4)	Mn1—O2	2.1255 (15)
C9—H9	0.9300	Mn1—O1W	2.1619 (15)
C10—C11	1.396 (3)	Mn1—N2	2.1995 (17)
C10—H10	0.9300	Mn1—N5	2.2401 (16)
C11—N5	1.338 (3)	Mn1—N6	2.2861 (18)
C11—C12	1.465 (3)	Mn1—N3	2.359 (2)
C12—N6	1.338 (3)	N1—N2	1.339 (3)
C12—C13	1.393 (3)	N1—H1A	0.8600
C13—C14	1.370 (4)	N4—N5	1.347 (2)
C13—H13	0.9300	N4—H4	0.8600
C14—C16	1.364 (4)	N7—O6	1.203 (4)
C14—H14	0.9300	N7—O5	1.203 (4)
C15—N6	1.334 (3)	O1W—H1W	0.820 (12)
C15—C16	1.375 (4)	O1W—H2W	0.82 (2)

N1—C1—C2	108.0 (3)	C18—C19—H19	119.5
N1—C1—H1	126.0	C21—C20—C19	118.2 (2)
C2—C1—H1	126.0	C21—C20—H20	120.9
C1—C2—C3	105.2 (2)	C19—C20—H20	120.9
C1—C2—H2	127.4	C20—C21—C22	122.3 (2)
C3—C2—H2	127.4	C20—C21—N7	118.6 (2)
N2—C3—C2	109.7 (3)	C22—C21—N7	119.0 (2)
N2—C3—C4	117.4 (2)	C21—C22—C23	119.7 (2)
C2—C3—C4	132.9 (2)	C21—C22—H22	120.2
N3—C4—C5	121.6 (3)	C23—C22—H22	120.2
N3—C4—C3	115.1 (2)	C22—C23—C18	119.03 (19)
C5—C4—C3	123.3 (2)	C22—C23—C24	117.40 (19)
C6—C5—C4	119.2 (3)	C18—C23—C24	123.52 (19)
C6—C5—H5	120.4	O4—C24—O3	125.3 (2)
C4—C5—H5	120.4	O4—C24—C23	116.6 (2)
C5—C6—C7	119.5 (3)	O3—C24—C23	118.0 (2)
C5—C6—H6	120.2	O2—Mn1—O1W	86.45 (6)
C7—C6—H6	120.2	O2—Mn1—N2	93.74 (7)
C6—C7—C8	118.3 (3)	O1W—Mn1—N2	99.70 (7)
C6—C7—H7	120.9	O2—Mn1—N5	101.41 (6)
C8—C7—H7	120.9	O1W—Mn1—N5	95.17 (6)
N3—C8—C7	123.3 (3)	N2—Mn1—N5	159.38 (7)
N3—C8—H8	118.3	O2—Mn1—N6	89.68 (7)
C7—C8—H8	118.3	O1W—Mn1—N6	166.14 (7)
N4—C9—C10	108.0 (2)	N2—Mn1—N6	93.83 (7)
N4—C9—H9	126.0	N5—Mn1—N6	72.55 (6)
C10—C9—H9	126.0	O2—Mn1—N3	164.44 (7)
C9—C10—C11	105.0 (2)	O1W—Mn1—N3	94.04 (7)
C9—C10—H10	127.5	N2—Mn1—N3	70.82 (8)
C11—C10—H10	127.5	N5—Mn1—N3	94.05 (7)
N5—C11—C10	110.3 (2)	N6—Mn1—N3	93.24 (7)
N5—C11—C12	118.75 (18)	C1—N1—N2	110.7 (2)
C10—C11—C12	131.0 (2)	C1—N1—H1A	124.6
N6—C12—C13	121.9 (2)	N2—N1—H1A	124.6
N6—C12—C11	115.00 (18)	C3—N2—N1	106.40 (18)
C13—C12—C11	123.1 (2)	C3—N2—Mn1	120.74 (17)
C14—C13—C12	119.1 (2)	N1—N2—Mn1	132.63 (15)
C14—C13—H13	120.5	C8—N3—C4	118.0 (2)
C12—C13—H13	120.5	C8—N3—Mn1	126.27 (17)
C16—C14—C13	119.2 (2)	C4—N3—Mn1	115.70 (17)
C16—C14—H14	120.4	C9—N4—N5	111.07 (19)
C13—C14—H14	120.4	C9—N4—H4	124.5
N6—C15—C16	123.2 (3)	N5—N4—H4	124.5
N6—C15—H15	118.4	C11—N5—N4	105.65 (16)
C16—C15—H15	118.4	C11—N5—Mn1	116.41 (13)
C14—C16—C15	118.9 (3)	N4—N5—Mn1	137.92 (13)
C14—C16—H16	120.6	C15—N6—C12	117.8 (2)
C15—C16—H16	120.6	C15—N6—Mn1	125.06 (16)
O1—C17—O2	125.8 (2)	C12—N6—Mn1	116.60 (14)
O1—C17—C18	117.3 (2)	O6—N7—O5	123.3 (3)
O2—C17—C18	116.67 (19)	O6—N7—C21	117.6 (3)
C19—C18—C23	119.6 (2)	O5—N7—C21	119.1 (3)
C19—C18—C17	117.4 (2)	C17—O2—Mn1	142.44 (15)
C23—C18—C17	122.66 (19)	Mn1—O1W—H1W	106 (2)
C20—C19—C18	121.1 (2)	Mn1—O1W—H2W	117 (2)
C20—C19—H19	119.5	H1W—O1W—H2W	115 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H2W···O4ⁱ	0.82 (2)	1.80 (2)	2.615 (2)	171 (3)
N1—H1A···O1	0.86	1.86	2.644 (3)	152

Symmetry code: (i) −x+2, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[Mn(C₈H₃NO₆)(C₈H₇N₃)₂(H₂O)]·0.5H₂O
M_r	581.41
Crystal system, space group	Triclinic, P1
Temperature (K)	294
a, b, c (Å)	10.5996 (7), 11.2654 (7), 11.9493 (7)
α, β, γ (°)	96.275 (2), 112.485 (2), 96.902 (2)
V (Å³)	1289.94 (14)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.57
Crystal size (mm)	0.12 × 0.10 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.935, 0.956
No. of measured, independent and observed [I > 2σ(I)] reflections	13775, 4492, 4112
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.107, 1.00
No. of reflections	4492
No. of parameters	364
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.67, −0.56

Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H2W···O4ⁱ	0.82 (2)	1.80 (2)	2.615 (2)	171 (3)
N1—H1A···O1	0.86	1.86	2.644 (3)	151.7

Symmetry code: (i) −x+2, −y+1, −z+1.

Acknowledgements

The authors acknowledge financial support from the Science Foundation of Beihua University.

References

Bruker (2001). SAINT-Plus and SADABS. Bruker AXS Inc., Madison,Wisconsin, USA. Google Scholar
Bruker (2004). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Guo, M.-L. & Guo, C.-H. (2007). Acta Cryst. C63, m595–m597. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Xu, B.-Y., Xie, T., Lu, S.-J., Xue, B. & Li, W. (2009). Acta Cryst. E65, m856–m857. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar

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