Poly[[bis­(2,2-bipyridine)­bis­[μ6-5-(carboxyl­atometh­oxy)benzene-1,3-dicarboxyl­ato]trimanganese(II)] monohydrate]

Jiang, Z.-G.; Chen, J.; Feng, Y.-L.

doi:10.1107/S1600536811002819

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 2| February 2011| Pages m259-m260

doi:10.1107/S1600536811002819

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Poly[[bis(2,2-bipyridine)bis[μ₆-5-(carboxylatomethoxy)benzene-1,3-dicarboxylato]trimanganese(II)] monohydrate]

Zhan-Guo Jiang,^a Jing Chen ^a and Yun-Long Feng ^a ^*

^aZhejiang Key Laboratory for Reactive Chemistry on Solid Surfaces, College of Chemistry and Life Science, Zhejiang Normal University, Jinhua, Zhejiang 321004, People's Republic of China
^*Correspondence e-mail: sky37@zjnu.cn

(Received 6 January 2011; accepted 20 January 2011; online 26 January 2011)

The title compound, {[Mn₃(C₁₀H₅O₇)₂(C₁₀H₈N₂)₂]·H₂O}_n, was synthesized under hydrothermal conditions. Six carboxylate groups of six 5-(carboxylatomethoxy)benzene-1,3-dicarboxylate anions (OABDC³⁻) join three Mn^II ions into a trinuclear centrosymmetric [Mn₃(μ₂-COO)₆] unit with one Mn site situated on a centre of inversion. The latter Mn^II ion exhibits a distorted MnO₆ coordination, whereas the other Mn^II ion has a trigonal–bipyramidal MnN₂O₃ coordination environment resulting from three carboxylate O atoms and the two N atoms of the bipyridine ligand. Adjacent units are linked to each other by OABDC³⁻ ligands into a layer parallel to (010). Within the layer, O—H⋯O hydrogen-bonding interactions involving the uncoordinated and half-occupied water molecule and the free carboxylate O atoms are observed. The layers stack along [010], constructing a three-dimensional structure through π–π interactions between adjacent pyridine rings, with a centroid–centroid distance of 3.473 (5) Å.

Related literature

For the construction of metal-organic frameworks with polycarboxylate ligands, see: Xing et al. (2010 ); Cao et al. (2004 , 2007 ).

Experimental

Crystal data

[Mn₃(C₁₀H₅O₇)₂(C₁₀H₈N₂)₂]·H₂O
M_r = 969.48
Monoclinic, P 2₁ /n
a = 8.5683 (1) Å
b = 25.2280 (4) Å
c = 9.7685 (1) Å
β = 114.633 (1)°
V = 1919.41 (4) Å³
Z = 2
Mo Kα radiation
μ = 1.05 mm⁻¹
T = 296 K
0.37 × 0.19 × 0.09 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.786, T_max = 0.907
16528 measured reflections
3350 independent reflections
3012 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.123
S = 1.10
3350 reflections
292 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.11 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Table 1
Selected bond lengths (Å)

Mn1—O7ⁱ	2.100 (2)
Mn1—O3ⁱⁱ	2.148 (2)
Mn1—O1	2.175 (2)
Mn1—N2	2.228 (3)
Mn1—N1	2.251 (3)
Mn2—O4ⁱⁱⁱ	2.108 (2)
Mn2—O6^iv	2.159 (2)
Mn2—O1	2.322 (2)
Symmetry codes: (i) x+1, y, z+1; (ii) x, y, z+1; (iii) -x, -y, -z-1; (iv) -x-1, -y, -z-1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WB⋯O2ⁱⁱⁱ	0.85 (1)	2.19 (2)	3.015 (5)	164 (6)
Symmetry code: (iii) -x, -y, -z-1.

Data collection: APEX2 (Bruker, 2006 ); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2008 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811002819/wm2447sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811002819/wm2447Isup2.hkl

checkCIF report

Comment top

Aromatic polycarboxylic acids like 1,3,5-benzenetricarboxylate (H₃btc) and 1,2,4,5-benzenetetracarboxylate (H₄btec) are widely used to construct metal-organic frameworks (Xing et al., 2010). Aromatic polycarboxylate ligands with rigid and flexible carboxyl group are less reported. 5-oxyacetato-1,3-benzenebiscarboxylic acid (H₃OABDC) is a ligand with two rigid carboxyl groups and one flexible oxyacetato group. Previous structural studies including this ligand have also been reported (Cao et al., 2004, 2007).

The title compound, [Mn₃(C₁₀H₅O₇)₂(C₁₀H₈N₂)₂]^.H₂O, crystallizes with two Mn^II ions (Mn1 on a general position, Mn2 on a centre of inversion), one OABDC^3- trianion, one chelating 2,2-bipyridine (bipy) ligand and one water molecule (half-occupied) in the asymmetric unit. Mn1 is five-coordinated by two N atoms from the bipy ligand, one O atom from one flexible carboxyl group of the OABDC^3- anion and two O atoms from two rigid carboxyl groups of the OABDC^3- anion to form a distorted trigonal-bipyramidal environment. Mn2 is six-coordinated by two O atoms from two flexible carboxyl groups of the OABDC^3- anion and four oxygen atoms from four rigid carboxyl groups of adjacent OABDC^3- anions to form a distorted octahedral environment (Table 1, Fig. 1).

Six OABDC^3- anions join three Mn^II ions through their carboxyl groups. As a result, trinuclear [Mn₃(µ₂-COO)₆]_n layers are formed in which Mn2 sits on a centre of inversion of each trinuclear unit. These layers are oriented parallel to (010). Uncoordinated water molecules interact with non-bonded O atoms of the carboxylate groups within the layers through relatively weak O—H···O hydrogen-bonding interactions (Table 2, Fig. 2).

The bipy ligands decorate the top and bottom of each layer. Between parallel pyridine rings of adjacent layers exist π–π interactions with a centroid- centroid distance of 3.473 (5) Å that consolidate the packing of the structure along [010] into a three-dimensional framework (Fig. 3).

Related literature top

For the construction of metal-organic frameworks with polycarboxylate ligands, see: Xing et al. (2010); Cao et al. (2004, 2007).

Experimental top

All reagents were purchased commercially and used without further purification. A mixture of 5-oxyacetato-1,3-benzenebiscarboxylic acid (H₃OABDC; 0.1205 g, 0.5 mmol), MnCl₂^.4H₂O (0.0976 g, 0.5 mmol), bipyridine (0.0786 g, 0.5 mmol), was dissolved with NaOH (0.0101 g, 0.25 mmol) in water (15 ml) and loaded in a 25 ml stainless steel reactor with a telflon liner. The autoclave was heated at 433 K for 72 h, and then cooled to room temperature over 3 days with a cooling rate of 5 K per hour. Yellow single crystals of the title compound were obtained by slow evaporation of the filtrate over a few days.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXS97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2008); software used to prepare material for publication: SHELXTL (Brandenburg, 2008).

Figures top

	Fig. 1. The molecular structure of title the compound. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (1) x + 1,y,z + 1; (2) x,y,z + 1; (3) -x,-y,-z - 1; (4) -x - 1,-y,-z - 1; (5) -x,-y,-z.]
	Fig. 2. two-dimensional layered structure (bipys are omitted for clarity).
	Fig. 3. View of π–π interactions between layers.

Poly[[bis(2,2-bipyridine)bis[µ₆-5-(carboxylatomethoxy)benzene-1,3- dicarboxylato]trimanganese(II)] monohydrate] top

Crystal data top

[Mn₃(C₁₀H₅O₇)₂(C₁₀H₈N₂)₂]·H₂O	F(000) = 982
M_r = 969.48	D_x = 1.677 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 8045 reflections
a = 8.5683 (1) Å	θ = 2.4–27.7°
b = 25.2280 (4) Å	µ = 1.05 mm⁻¹
c = 9.7685 (1) Å	T = 296 K
β = 114.633 (1)°	Block, yellow
V = 1919.41 (4) Å³	0.37 × 0.19 × 0.09 mm
Z = 2

Data collection top

Bruker APEXII area-detector diffractometer	3350 independent reflections
Radiation source: fine-focus sealed tube	3012 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ω scans	θ_max = 25.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→8
T_min = 0.786, T_max = 0.907	k = −24→30
16528 measured reflections	l = −11→11

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.123	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ²(F_o²) + (0.0743P)² + 1.9128P] where P = (F_o² + 2F_c²)/3
3350 reflections	(Δ/σ)_max < 0.001
292 parameters	Δρ_max = 1.11 e Å⁻³
6 restraints	Δρ_min = −0.47 e Å⁻³

Crystal data top

[Mn₃(C₁₀H₅O₇)₂(C₁₀H₈N₂)₂]·H₂O	V = 1919.41 (4) Å³
M_r = 969.48	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.5683 (1) Å	µ = 1.05 mm⁻¹
b = 25.2280 (4) Å	T = 296 K
c = 9.7685 (1) Å	0.37 × 0.19 × 0.09 mm
β = 114.633 (1)°

Data collection top

Bruker APEXII area-detector diffractometer	3350 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3012 reflections with I > 2σ(I)
T_min = 0.786, T_max = 0.907	R_int = 0.023
16528 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	6 restraints
wR(F²) = 0.123	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	Δρ_max = 1.11 e Å⁻³
3350 reflections	Δρ_min = −0.47 e Å⁻³
292 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	Occ. (<1)
Mn1	0.23443 (6)	0.121021 (17)	0.11506 (5)	0.02566 (17)
Mn2	0.0000	0.0000	0.0000	0.02189 (18)
O1W	−0.6212 (6)	−0.12729 (17)	−0.9008 (6)	0.0426 (12)	0.50
H1WB	−0.5137 (17)	−0.130 (3)	−0.874 (7)	0.051*	0.50
H1WA	−0.659 (7)	−0.111 (3)	−0.984 (5)	0.051*	0.50
O1	0.0588 (3)	0.08005 (8)	−0.0861 (2)	0.0297 (5)
O2	0.2531 (3)	0.12144 (9)	−0.1396 (2)	0.0353 (5)
O3	0.1568 (3)	0.11891 (9)	−0.7023 (3)	0.0416 (6)
O4	0.0038 (3)	0.04991 (9)	−0.8255 (2)	0.0387 (6)
O5	−0.3626 (3)	0.00513 (9)	−0.5459 (2)	0.0337 (5)
O6	−0.7274 (3)	−0.01469 (9)	−0.8866 (2)	0.0337 (5)
O7	−0.5860 (3)	0.06004 (9)	−0.7894 (3)	0.0408 (6)
N1	0.1153 (4)	0.20221 (11)	0.0619 (3)	0.0344 (6)
N2	0.4486 (3)	0.17919 (10)	0.1761 (3)	0.0308 (6)
C1	0.0167 (3)	0.08164 (10)	−0.3438 (3)	0.0207 (6)
C2	0.0778 (4)	0.09280 (10)	−0.4528 (3)	0.0213 (6)
H2	0.1769	0.1128	−0.4285	0.026*
C3	−0.0115 (4)	0.07361 (10)	−0.5978 (3)	0.0217 (6)
C4	−0.1610 (4)	0.04408 (11)	−0.6359 (3)	0.0227 (6)
H4	−0.2187	0.0308	−0.7330	0.027*
C5	−0.2231 (3)	0.03463 (11)	−0.5281 (3)	0.0228 (6)
C6	−0.1349 (4)	0.05419 (11)	−0.3831 (3)	0.0232 (6)
H6	−0.1786	0.0487	−0.3116	0.028*
C7	0.1182 (4)	0.09562 (10)	−0.1816 (3)	0.0237 (6)
C8	0.0547 (4)	0.08148 (12)	−0.7170 (3)	0.0269 (6)
C9	−0.4589 (4)	−0.02186 (12)	−0.6826 (3)	0.0306 (7)
H9A	−0.5073	−0.0537	−0.6605	0.037*
H9B	−0.3821	−0.0326	−0.7277	0.037*
C10	−0.6025 (4)	0.01101 (12)	−0.7951 (3)	0.0264 (6)
C11	−0.0531 (5)	0.21147 (17)	0.0082 (4)	0.0468 (9)
H11	−0.1278	0.1827	−0.0174	0.056*
C12	−0.1217 (6)	0.2624 (2)	−0.0112 (4)	0.0587 (12)
H12	−0.2397	0.2678	−0.0514	0.070*
C13	−0.0103 (6)	0.30430 (18)	0.0307 (5)	0.0613 (12)
H13	−0.0521	0.3388	0.0210	0.074*
C14	0.1621 (6)	0.29541 (15)	0.0868 (4)	0.0514 (10)
H14	0.2382	0.3238	0.1155	0.062*
C15	0.2239 (4)	0.24397 (13)	0.1008 (3)	0.0342 (7)
C16	0.4077 (4)	0.23094 (12)	0.1557 (3)	0.0318 (7)
C17	0.5338 (5)	0.26898 (13)	0.1875 (4)	0.0440 (9)
H17	0.5040	0.3046	0.1724	0.053*
C18	0.7043 (5)	0.25413 (15)	0.2416 (4)	0.0479 (9)
H18	0.7899	0.2796	0.2644	0.057*
C19	0.7455 (5)	0.20131 (15)	0.2613 (4)	0.0456 (9)
H19	0.8589	0.1900	0.2968	0.055*
C20	0.6131 (4)	0.16548 (13)	0.2268 (4)	0.0381 (8)
H20	0.6403	0.1296	0.2397	0.046*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0318 (3)	0.0250 (3)	0.0198 (3)	−0.00594 (17)	0.0103 (2)	−0.00228 (16)
Mn2	0.0203 (3)	0.0264 (3)	0.0174 (3)	−0.0036 (2)	0.0062 (2)	−0.0038 (2)
O1W	0.031 (2)	0.022 (2)	0.081 (4)	−0.0176 (19)	0.030 (3)	−0.026 (2)
O1	0.0381 (12)	0.0346 (11)	0.0175 (9)	−0.0066 (9)	0.0128 (9)	−0.0019 (8)
O2	0.0355 (13)	0.0405 (13)	0.0266 (11)	−0.0142 (10)	0.0096 (10)	−0.0066 (9)
O3	0.0529 (15)	0.0437 (14)	0.0397 (13)	−0.0147 (11)	0.0308 (12)	−0.0004 (10)
O4	0.0457 (14)	0.0523 (14)	0.0230 (11)	−0.0026 (11)	0.0191 (10)	−0.0108 (10)
O5	0.0225 (11)	0.0500 (13)	0.0265 (11)	−0.0143 (9)	0.0081 (9)	−0.0015 (9)
O6	0.0240 (11)	0.0355 (12)	0.0331 (11)	−0.0025 (9)	0.0036 (9)	−0.0045 (9)
O7	0.0329 (12)	0.0268 (12)	0.0507 (14)	−0.0042 (9)	0.0056 (11)	0.0036 (10)
N1	0.0399 (16)	0.0386 (15)	0.0291 (13)	0.0006 (12)	0.0188 (12)	0.0027 (11)
N2	0.0389 (15)	0.0249 (13)	0.0306 (13)	−0.0035 (11)	0.0164 (12)	−0.0029 (10)
C1	0.0251 (14)	0.0191 (13)	0.0180 (13)	0.0014 (11)	0.0091 (11)	0.0008 (10)
C2	0.0230 (14)	0.0194 (13)	0.0215 (13)	−0.0018 (11)	0.0093 (11)	−0.0003 (10)
C3	0.0256 (14)	0.0219 (14)	0.0192 (13)	0.0039 (11)	0.0110 (11)	0.0018 (10)
C4	0.0222 (14)	0.0259 (14)	0.0168 (12)	−0.0006 (11)	0.0050 (11)	−0.0017 (10)
C5	0.0181 (13)	0.0262 (14)	0.0225 (13)	0.0007 (11)	0.0069 (11)	0.0039 (11)
C6	0.0233 (14)	0.0288 (14)	0.0181 (13)	0.0016 (11)	0.0091 (11)	0.0034 (11)
C7	0.0302 (15)	0.0199 (13)	0.0200 (13)	0.0019 (12)	0.0096 (12)	−0.0011 (11)
C8	0.0298 (16)	0.0321 (16)	0.0214 (14)	0.0043 (13)	0.0132 (12)	0.0056 (12)
C9	0.0236 (15)	0.0301 (16)	0.0330 (16)	−0.0061 (12)	0.0067 (13)	−0.0023 (13)
C10	0.0220 (15)	0.0307 (16)	0.0273 (15)	−0.0029 (12)	0.0111 (12)	−0.0002 (12)
C11	0.044 (2)	0.062 (2)	0.0393 (19)	0.0037 (18)	0.0220 (16)	0.0068 (17)
C12	0.057 (2)	0.085 (3)	0.042 (2)	0.029 (2)	0.0267 (19)	0.013 (2)
C13	0.081 (3)	0.052 (3)	0.053 (2)	0.029 (2)	0.030 (2)	0.008 (2)
C14	0.068 (3)	0.0360 (19)	0.051 (2)	0.0100 (19)	0.025 (2)	0.0001 (16)
C15	0.050 (2)	0.0301 (16)	0.0258 (15)	0.0028 (14)	0.0192 (14)	0.0017 (12)
C16	0.0471 (19)	0.0265 (15)	0.0246 (15)	−0.0049 (14)	0.0177 (14)	−0.0018 (12)
C17	0.063 (3)	0.0251 (16)	0.048 (2)	−0.0093 (16)	0.0268 (18)	−0.0055 (14)
C18	0.053 (2)	0.046 (2)	0.052 (2)	−0.0217 (18)	0.0289 (18)	−0.0113 (17)
C19	0.041 (2)	0.048 (2)	0.051 (2)	−0.0097 (17)	0.0229 (17)	−0.0070 (17)
C20	0.0378 (19)	0.0321 (17)	0.0450 (19)	−0.0029 (14)	0.0179 (15)	−0.0035 (14)

Geometric parameters (Å, º) top

Mn1—O7ⁱ	2.100 (2)	C1—C2	1.396 (4)
Mn1—O3ⁱⁱ	2.148 (2)	C1—C7	1.498 (4)
Mn1—O1	2.175 (2)	C2—C3	1.386 (4)
Mn1—N2	2.228 (3)	C2—H2	0.9300
Mn1—N1	2.251 (3)	C3—C4	1.392 (4)
Mn2—O4ⁱⁱ	2.108 (2)	C3—C8	1.506 (4)
Mn2—O4ⁱⁱⁱ	2.108 (2)	C4—C5	1.384 (4)
Mn2—O6^iv	2.159 (2)	C4—H4	0.9300
Mn2—O6ⁱ	2.159 (2)	C5—C6	1.389 (4)
Mn2—O1^v	2.322 (2)	C6—H6	0.9300
Mn2—O1	2.322 (2)	C9—C10	1.511 (4)
O1W—H1WB	0.849 (2)	C9—H9A	0.9700
O1W—H1WA	0.849 (2)	C9—H9B	0.9700
O1—C7	1.296 (3)	C11—C12	1.394 (6)
O2—C7	1.238 (4)	C11—H11	0.9300
O3—C8	1.254 (4)	C12—C13	1.366 (7)
O3—Mn1^vi	2.148 (2)	C12—H12	0.9300
O4—C8	1.250 (4)	C13—C14	1.363 (6)
O4—Mn2^vi	2.108 (2)	C13—H13	0.9300
O5—C5	1.356 (3)	C14—C15	1.387 (5)
O5—C9	1.417 (4)	C14—H14	0.9300
O6—C10	1.252 (4)	C15—C16	1.474 (5)
O6—Mn2^vii	2.159 (2)	C16—C17	1.380 (5)
O7—C10	1.244 (4)	C17—C18	1.382 (6)
O7—Mn1^vii	2.100 (2)	C17—H17	0.9300
N1—C11	1.334 (5)	C18—C19	1.371 (5)
N1—C15	1.351 (4)	C18—H18	0.9300
N2—C20	1.330 (4)	C19—C20	1.378 (5)
N2—C16	1.345 (4)	C19—H19	0.9300
C1—C6	1.378 (4)	C20—H20	0.9300

O7ⁱ—Mn1—O3ⁱⁱ	92.04 (10)	O5—C5—C4	126.5 (2)
O7ⁱ—Mn1—O1	99.00 (9)	O5—C5—C6	113.7 (2)
O3ⁱⁱ—Mn1—O1	113.65 (9)	C4—C5—C6	119.7 (3)
O7ⁱ—Mn1—N2	89.68 (9)	C1—C6—C5	120.8 (3)
O3ⁱⁱ—Mn1—N2	107.44 (9)	C1—C6—H6	119.6
O1—Mn1—N2	137.52 (8)	C5—C6—H6	119.6
O7ⁱ—Mn1—N1	161.31 (10)	O2—C7—O1	120.9 (2)
O3ⁱⁱ—Mn1—N1	86.93 (9)	O2—C7—C1	121.6 (2)
O1—Mn1—N1	98.49 (9)	O1—C7—C1	117.5 (2)
N2—Mn1—N1	72.92 (10)	O4—C8—O3	123.8 (3)
O4ⁱⁱ—Mn2—O4ⁱⁱⁱ	180.00 (12)	O4—C8—C3	117.5 (3)
O4ⁱⁱ—Mn2—O6^iv	87.76 (9)	O3—C8—C3	118.7 (3)
O4ⁱⁱⁱ—Mn2—O6^iv	92.24 (9)	O5—C9—C10	113.6 (2)
O4ⁱⁱ—Mn2—O6ⁱ	92.24 (9)	O5—C9—H9A	108.9
O4ⁱⁱⁱ—Mn2—O6ⁱ	87.76 (9)	C10—C9—H9A	108.9
O6^iv—Mn2—O6ⁱ	180.00 (11)	O5—C9—H9B	108.9
O4ⁱⁱ—Mn2—O1^v	99.16 (8)	C10—C9—H9B	108.9
O4ⁱⁱⁱ—Mn2—O1^v	80.84 (8)	H9A—C9—H9B	107.7
O6^iv—Mn2—O1^v	89.06 (8)	O7—C10—O6	126.5 (3)
O6ⁱ—Mn2—O1^v	90.94 (8)	O7—C10—C9	118.0 (3)
O4ⁱⁱ—Mn2—O1	80.84 (8)	O6—C10—C9	115.5 (3)
O4ⁱⁱⁱ—Mn2—O1	99.16 (8)	N1—C11—C12	122.7 (4)
O6^iv—Mn2—O1	90.94 (8)	N1—C11—H11	118.6
O6ⁱ—Mn2—O1	89.06 (8)	C12—C11—H11	118.6
O1^v—Mn2—O1	180.00 (5)	C13—C12—C11	118.1 (4)
H1WB—O1W—H1WA	105.3 (4)	C13—C12—H12	121.0
C7—O1—Mn1	100.06 (17)	C11—C12—H12	121.0
C7—O1—Mn2	137.20 (18)	C14—C13—C12	119.8 (4)
Mn1—O1—Mn2	105.02 (8)	C14—C13—H13	120.1
C8—O3—Mn1^vi	111.51 (19)	C12—C13—H13	120.1
C8—O4—Mn2^vi	161.5 (2)	C13—C14—C15	119.9 (4)
C5—O5—C9	121.3 (2)	C13—C14—H14	120.0
C10—O6—Mn2^vii	134.2 (2)	C15—C14—H14	120.0
C10—O7—Mn1^vii	131.3 (2)	N1—C15—C14	120.8 (3)
C11—N1—C15	118.6 (3)	N1—C15—C16	115.8 (3)
C11—N1—Mn1	124.2 (3)	C14—C15—C16	123.4 (3)
C15—N1—Mn1	116.8 (2)	N2—C16—C17	120.7 (3)
C20—N2—C16	118.6 (3)	N2—C16—C15	116.3 (3)
C20—N2—Mn1	123.7 (2)	C17—C16—C15	123.0 (3)
C16—N2—Mn1	117.7 (2)	C16—C17—C18	120.1 (3)
C6—C1—C2	119.9 (2)	C16—C17—H17	120.0
C6—C1—C7	118.5 (2)	C18—C17—H17	120.0
C2—C1—C7	121.5 (2)	C19—C18—C17	119.1 (3)
C3—C2—C1	119.1 (2)	C19—C18—H18	120.5
C3—C2—H2	120.5	C17—C18—H18	120.5
C1—C2—H2	120.5	C18—C19—C20	117.8 (4)
C2—C3—C4	121.0 (2)	C18—C19—H19	121.1
C2—C3—C8	121.3 (2)	C20—C19—H19	121.1
C4—C3—C8	117.7 (2)	N2—C20—C19	123.8 (3)
C5—C4—C3	119.4 (2)	N2—C20—H20	118.1
C5—C4—H4	120.3	C19—C20—H20	118.1
C3—C4—H4	120.3

O7ⁱ—Mn1—O1—C7	−94.71 (18)	Mn1—O1—C7—C1	−172.1 (2)
O3ⁱⁱ—Mn1—O1—C7	169.05 (17)	Mn2—O1—C7—C1	62.5 (4)
N2—Mn1—O1—C7	4.8 (2)	C6—C1—C7—O2	−178.1 (3)
N1—Mn1—O1—C7	78.69 (18)	C2—C1—C7—O2	6.0 (4)
O7ⁱ—Mn1—O1—Mn2	50.28 (10)	C6—C1—C7—O1	1.3 (4)
O3ⁱⁱ—Mn1—O1—Mn2	−45.96 (12)	C2—C1—C7—O1	−174.6 (2)
N2—Mn1—O1—Mn2	149.75 (11)	Mn2^vi—O4—C8—O3	36.8 (8)
N1—Mn1—O1—Mn2	−136.32 (9)	Mn2^vi—O4—C8—C3	−143.2 (6)
O4ⁱⁱ—Mn2—O1—C7	162.4 (3)	Mn1^vi—O3—C8—O4	−0.7 (4)
O4ⁱⁱⁱ—Mn2—O1—C7	−17.6 (3)	Mn1^vi—O3—C8—C3	179.27 (19)
O6^iv—Mn2—O1—C7	−110.0 (3)	C2—C3—C8—O4	157.0 (3)
O6ⁱ—Mn2—O1—C7	70.0 (3)	C4—C3—C8—O4	−19.8 (4)
O4ⁱⁱ—Mn2—O1—Mn1	38.66 (9)	C2—C3—C8—O3	−23.0 (4)
O4ⁱⁱⁱ—Mn2—O1—Mn1	−141.34 (9)	C4—C3—C8—O3	160.2 (3)
O6^iv—Mn2—O1—Mn1	126.24 (9)	C5—O5—C9—C10	−89.4 (3)
O6ⁱ—Mn2—O1—Mn1	−53.76 (9)	Mn1^vii—O7—C10—O6	15.9 (5)
O7ⁱ—Mn1—N1—C11	−156.2 (3)	Mn1^vii—O7—C10—C9	−164.6 (2)
O3ⁱⁱ—Mn1—N1—C11	−68.9 (3)	Mn2^vii—O6—C10—O7	−32.8 (5)
O1—Mn1—N1—C11	44.5 (3)	Mn2^vii—O6—C10—C9	147.6 (2)
N2—Mn1—N1—C11	−178.2 (3)	O5—C9—C10—O7	27.3 (4)
O7ⁱ—Mn1—N1—C15	17.3 (4)	O5—C9—C10—O6	−153.1 (3)
O3ⁱⁱ—Mn1—N1—C15	104.6 (2)	C15—N1—C11—C12	0.8 (5)
O1—Mn1—N1—C15	−141.9 (2)	Mn1—N1—C11—C12	174.2 (3)
N2—Mn1—N1—C15	−4.7 (2)	N1—C11—C12—C13	−1.7 (6)
O7ⁱ—Mn1—N2—C20	9.9 (3)	C11—C12—C13—C14	1.2 (6)
O3ⁱⁱ—Mn1—N2—C20	102.0 (3)	C12—C13—C14—C15	0.1 (6)
O1—Mn1—N2—C20	−93.1 (3)	C11—N1—C15—C14	0.6 (4)
N1—Mn1—N2—C20	−177.0 (3)	Mn1—N1—C15—C14	−173.3 (2)
O7ⁱ—Mn1—N2—C16	−172.2 (2)	C11—N1—C15—C16	−178.5 (3)
O3ⁱⁱ—Mn1—N2—C16	−80.2 (2)	Mn1—N1—C15—C16	7.6 (3)
O1—Mn1—N2—C16	84.7 (2)	C13—C14—C15—N1	−1.1 (5)
N1—Mn1—N2—C16	0.9 (2)	C13—C14—C15—C16	178.0 (3)
C6—C1—C2—C3	−3.2 (4)	C20—N2—C16—C17	−0.4 (4)
C7—C1—C2—C3	172.6 (2)	Mn1—N2—C16—C17	−178.3 (2)
C1—C2—C3—C4	0.7 (4)	C20—N2—C16—C15	−179.4 (3)
C1—C2—C3—C8	−176.0 (2)	Mn1—N2—C16—C15	2.7 (3)
C2—C3—C4—C5	1.3 (4)	N1—C15—C16—N2	−6.8 (4)
C8—C3—C4—C5	178.1 (2)	C14—C15—C16—N2	174.1 (3)
C9—O5—C5—C4	2.6 (4)	N1—C15—C16—C17	174.2 (3)
C9—O5—C5—C6	−174.3 (2)	C14—C15—C16—C17	−4.9 (5)
C3—C4—C5—O5	−177.4 (3)	N2—C16—C17—C18	−0.3 (5)
C3—C4—C5—C6	−0.7 (4)	C15—C16—C17—C18	178.6 (3)
C2—C1—C6—C5	3.8 (4)	C16—C17—C18—C19	0.8 (5)
C7—C1—C6—C5	−172.1 (2)	C17—C18—C19—C20	−0.5 (5)
O5—C5—C6—C1	175.2 (2)	C16—N2—C20—C19	0.6 (5)
C4—C5—C6—C1	−1.9 (4)	Mn1—N2—C20—C19	178.4 (3)
Mn1—O1—C7—O2	7.3 (3)	C18—C19—C20—N2	−0.2 (6)
Mn2—O1—C7—O2	−118.1 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WB···O2ⁱⁱⁱ	0.85 (1)	2.19 (2)	3.015 (5)	164 (6)

Symmetry code: (iii) −x, −y, −z−1.

Experimental details

Crystal data
Chemical formula	[Mn₃(C₁₀H₅O₇)₂(C₁₀H₈N₂)₂]·H₂O
M_r	969.48
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	8.5683 (1), 25.2280 (4), 9.7685 (1)
β (°)	114.633 (1)
V (Å³)	1919.41 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.05
Crystal size (mm)	0.37 × 0.19 × 0.09

Data collection
Diffractometer	Bruker APEXII area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.786, 0.907
No. of measured, independent and observed [I > 2σ(I)] reflections	16528, 3350, 3012
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.123, 1.10
No. of reflections	3350
No. of parameters	292
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.11, −0.47

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2008), SHELXTL (Brandenburg, 2008).

Selected bond lengths (Å) top

Mn1—O7ⁱ	2.100 (2)	Mn1—N1	2.251 (3)
Mn1—O3ⁱⁱ	2.148 (2)	Mn2—O4ⁱⁱⁱ	2.108 (2)
Mn1—O1	2.175 (2)	Mn2—O6^iv	2.159 (2)
Mn1—N2	2.228 (3)	Mn2—O1	2.322 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WB···O2ⁱⁱⁱ	0.849 (2)	2.190 (19)	3.015 (5)	164 (6)

Symmetry code: (iii) −x, −y, −z−1.

References

Brandenburg, K. (2008). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2006). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cao, X.-Y., Zhang, J., Cheng, J.-K., Kang, Y. & Yao, Y.-G. (2004). CrystEngComm. 6, 315–317. Web of Science CSD CrossRef CAS Google Scholar
Cao, X.-Y., Zhang, J., Li, Z.-J., Cheng, J.-K. & Yao, Y.-G. (2007). CrystEngComm. 9, 806–814. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Xing, X.-Y., Song, X.-Y., Yang, P.-P., Liu, R.-N., Li, L.-C. & Liao, D.-Z. (2010). J. Mol. Struct. 967, 196–200. Web of Science CSD CrossRef CAS Google Scholar

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ISSN: 2056-9890

Volume 67| Part 2| February 2011| Pages m259-m260

doi:10.1107/S1600536811002819

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