Poly[diaqua­(μ4-2,5-dicarb­oxy­benzene-1,4-dicarboxyl­ato-κ4O1:O2:O4:O5)(μ2-2,5-dicarb­oxy­benzene-1,4-dicarboxyl­ato-κ2O1:O4)bis­(1,10-phenanthroline-κ2N,N′)dimanganese(II)]

Zhong, K.-L.

doi:10.1107/S1600536812035441

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 9| September 2012| Pages m1184-m1185

doi:10.1107/S1600536812035441

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Poly[diaqua(μ₄-2,5-dicarboxybenzene-1,4-dicarboxylato-κ⁴O¹:O²:O⁴:O⁵)(μ₂-2,5-dicarboxybenzene-1,4-dicarboxylato-κ²O¹:O⁴)bis(1,10-phenanthroline-κ²N,N′)dimanganese(II)]

Kai-Long Zhong ^a ^*

^aDepartment of Applied Chemistry, Nanjing College of Chemical Technology, Nanjing 210048, People's Republic of China
^*Correspondence e-mail: zklong76@163.com

(Received 12 June 2012; accepted 10 August 2012; online 23 August 2012)

In the title compound, [Mn₂(C₁₀H₄O₈)₂(C₁₂H₈N₂)₂(H₂O)₂]_n, the Mn²⁺ ion has a slightly distorted octahedral N₂O₄ coordination geometry being coordinated by one aqua O atom, two N atoms of the chelating 1,10-phenanthroline ligand and three carboxyl O atoms from three 2,5-dicarboxybenzene-1,4-dicarboxylate (H₂btec²⁻) ligands. The H₂btec²⁻ anion exhibits two different coordination modes, viz. μ₂ and μ₄. Both of the H₂btec²⁻ anions are located on special positions (inversion centers). The μ₄-anion bridges adjacent Mn^II atoms, forming a chain along the a axis. Adjacent chains are further bridged by μ₂-anions, resulting in a two-dimensional layered polymer parallel to (011). In the crystal, extensive carboxy–carboxylate O—H⋯O and water–carboxylate O—H⋯O interactions lead to the formation of a three-dimensional supramolecular network.

Related literature

For isotypic structures, see: Hu et al. (2004 ); Yu et al. (2007 ). For background to manganese complexes and phenanthroline complexes, see: Zhu et al. (2006 ); Zhong et al. (2009 ); Cui et al. (2010 ); Zhong (2011 ). For background to coordination polymers, see: Batten & Robson (1998 ); Fabelo et al. (2008 ); Liu et al. (2007 ); Li et al. (2003 ); Zhang et al. (2010 ).

Experimental

Crystal data

[Mn₂(C₁₀H₄O₈)₂(C₁₂H₈N₂)₂(H₂O)₂]
M_r = 1010.58
Triclinic, $[P \overline 1]$
a = 9.880 (2) Å
b = 10.246 (2) Å
c = 11.272 (2) Å
α = 86.29 (3)°
β = 71.82 (3)°
γ = 65.32 (3)°
V = 982.2 (5) Å³
Z = 1
Mo Kα radiation
μ = 0.74 mm⁻¹
T = 223 K
0.50 × 0.50 × 0.30 mm

Data collection

Rigaku Mercury CCD diffractometer
Absorption correction: multi-scan (REQAB: Jacobson, 1998 ) T_min = 0.710, T_max = 0.810
9376 measured reflections
4403 independent reflections
3757 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.081
S = 1.05
4403 reflections
315 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Table 1
Selected bond lengths (Å)

Mn1—O1W	2.1576 (17)
Mn1—O5ⁱ	2.1830 (12)
Mn1—O7	2.1852 (13)
Mn1—O1	2.2001 (12)
Mn1—N2	2.2314 (14)
Mn1—N1	2.2317 (17)
Symmetry code: (i) -x, -y, -z+2.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O8—H8⋯O1	0.82	1.75	2.5176 (16)	155
O4—H4⋯O6ⁱⁱ	0.82	1.81	2.592 (2)	158
O1W—H1WB⋯O6ⁱ	0.79 (2)	1.95 (3)	2.7108 (19)	160 (2)
O1W—H1WA⋯O2ⁱⁱⁱ	0.80 (2)	1.94 (2)	2.7117 (18)	162 (2)
Symmetry codes: (i) -x, -y, -z+2; (ii) -x-1, -y+1, -z+2; (iii) -x, -y, -z+1.

Data collection: CrystalClear (Rigaku, 2007 ); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812035441/zq2172sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812035441/zq2172Isup2.hkl

checkCIF report

Comment top

Recently, the self-assembly of coordination polymers and the crystal engineering of metal-organic coordination frameworks have received much attention (Batten & Robson, 1998; Liu et al., 2007; Zhang et al., 2010). The 1,2,4,5-benzenetetracarboxylate acid and 1,10-phenanthroline (phen) have also been widely employed as polydentate ligands in coordination reactions and in the construction of supermolecular networks (Li et al., 2003; Fabelo et al., 2008). In the past few years, we have synthesized and reported many metal-Phen complexes such as manganese (Zhu et al., 2006), nickel (Zhong et al., 2009), zinc (Cui et al., 2010) and cadmium (Zhong, 2011) complexes . The title compound [Mn(phen)(µ₂ –H₂btec)_1/2(µ₄– H₂btec)_1/2(H₂O)], (I), was obtained during an attempt to synthesize a mixed-ligand complex of Mn^II with phen and 1,2,4,5-benzenetetracarboxylate ligand via a hydrothermal reaction.

The title compound is isomorphic with previously reported cobalt(II) and zinc(II) analogs (Hu et al., 2004; Yu et al., 2007). The X-ray diffraction study indicates that the Mn^II centers exhibit a slightly distorted octahedral MnN₂O₄ coordination environment. Atom Mn1 is coordinated by one aqua O atom (O1W), two N atoms (N1 and N2) from a bridging 1,10-phenanthroline ligand and three carboxyl O atoms (O1, O7 and O5D) from three H₂btec^2- anions. The N1, N2, O1W and O7 atoms occupy the equatorial sites, while O1 and O5D occupy the axial positions (Fig. 1 and Table 1). The Mn—N1 and Mn—N2 bond distances are 2.2317 (17) Å and 2.2314 (14) Å, respectively, and the N1—Ni—N2 bite angle is 75.32 (6)°. The bond lengths of Mn—O range from 2.1576 (17) Å to 2.2001 (12) Å. The H₂btec^2- anion exhibits two different coordination modes, µ₂-H₂btec^2- and µ₄-H₂btec^2-. The mean planes defined by µ₂-H₂btec^2- and its neighbour phenantroline ring are almost parallel [the dihedral angle is 5.18 (4)°], while the mean planes defined by µ₄-H₂btec^2- and its neighbour phenantroline ring are oriented at 64.33 (4)°, those are in agreement with that observed in [Co(C₁₀H₄O₈) (C₁₂H₈N₂)(H₂O)] (Hu et al., 2004). The µ₄-H₂btec^2- anions link neighbour Mn^II cations, giving rise to one-dimensional chains running along the a axis. The distances between two neighbour Mn atoms are 9.880 (2) Å [Mn1—Mn1 (1 + x, y, z)] and 5.880 (2) Å [Mn1—Mn1 (-x, -y, 2 - z)], respectively (Fig. 2). The adjacent one-dimensional chains are further crosslinked by bridging µ₂-H₂btec^2- anions, leading to a two-dimensional layered polymer (Fig. 3). Intermolecular O8—H8···O1 hydrogen bond and π-π interaction between the parallel phenantroline and µ₂-H₂btec^2- ligands help to further stabilize the layered structure (Fig.3 and Table 2). In the crystal structure, the two-dimensional polymeric layers are linked by carboxylic acid O—H···O carboxyl and water O—H···O carboxyl hydrogen bonds to form a three-dimensional supramolecular network structure (Fig.4).

Related literature top

For isotypic compounds, see: Hu et al. (2004); Yu et al. (2007). For background to manganese complexes and phenanthroline complexes, see: Zhu et al. (2006); Zhong et al. (2009); Cui et al. (2010); Zhong (2011). For background to coordination polymers, see: Batten & Robson (1998); Fabelo et al. (2008); Liu et al. (2007); Li et al. (2003); Zhang et al. (2010).

Experimental top

0.1 mmol MnSO₄^.2H₂O, 0.1 mmol phen, 0.1 mmol 1,2,4,5-benzenetetracarboxylic acid and 3.0 ml water were mixed and placed in a thick Pyrex tube, which was sealed and heated to 383 K for 72 h, whereupon pale-yellow block-shaped crystals were obtained.

Computing details top

Data collection: CrystalClear (Rigaku, 2007); cell refinement: CrystalClear (Rigaku, 2007); data reduction: CrystalClear (Rigaku, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of the title compound (displacement ellipsoids drawn at the 35% probability level). Unlabeled atoms are related to the labelled atoms by symmetry operators (symmetry codes: A = -x, 1 - y, 1 - z; B = 1 - x, -y, 2 - z; C = x - 1, y, z; D = -x, -y, 2 - z).
	Fig. 2. The one-dimensional chain structure of the title compound. Dashed lines indicate hydrogen bonds. All C atoms of the phenantroline and µ₂-H₂btec ligands have been omitted for clarity (symmetry codes: i = 1 + x, y, z; ii = -x, -y, 2 - z).
	Fig. 3. The two-dimensional layer structure of the title compound viewed along the a axis. All H atoms have been omitted for clarity.
	Fig. 4. Hydrogen-bonding interactions between adjacent layers of the title compound. Dashed lines indicate hydrogen bonds.

Poly[diaqua(µ₄-2,5-dicarboxybenzene-1,4-dicarboxylato-κ⁴O¹: O²:O⁴:O⁵)(µ₂-2,5-dicarboxybenzene-1,4- dicarboxylato-κ²O¹:O⁴)bis(1,10-phenanthroline- κ²N,N')dimanganese(II)] top

Crystal data top

[Mn₂(C₁₀H₄O₈)₂(C₁₂H₈N₂)₂(H₂O)₂]	Z = 1
M_r = 1010.58	F(000) = 514
Triclinic, P1	D_x = 1.708 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.880 (2) Å	Cell parameters from 4733 reflections
b = 10.246 (2) Å	θ = 3.5–27.5°
c = 11.272 (2) Å	µ = 0.74 mm⁻¹
α = 86.29 (3)°	T = 223 K
β = 71.82 (3)°	Prism, pale yellow
γ = 65.32 (3)°	0.50 × 0.50 × 0.30 mm
V = 982.2 (5) Å³

Data collection top

Rigaku Mercury CCD diffractometer	4403 independent reflections
Radiation source: fine-focus sealed tube	3757 reflections with I > 2σ(I)
Graphite Monochromator monochromator	R_int = 0.025
Detector resolution: 28.5714 pixels mm^-1	θ_max = 27.5°, θ_min = 3.5°
ω scans	h = −11→12
Absorption correction: multi-scan (REQAB: Jacobson, 1998)	k = −12→13
T_min = 0.710, T_max = 0.810	l = −13→14
9376 measured reflections

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.081	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0441P)²] where P = (F_o² + 2F_c²)/3
4403 reflections	(Δ/σ)_max < 0.001
315 parameters	Δρ_max = 0.42 e Å⁻³
0 restraints	Δρ_min = −0.45 e Å⁻³

Crystal data top

[Mn₂(C₁₀H₄O₈)₂(C₁₂H₈N₂)₂(H₂O)₂]	γ = 65.32 (3)°
M_r = 1010.58	V = 982.2 (5) Å³
Triclinic, P1	Z = 1
a = 9.880 (2) Å	Mo Kα radiation
b = 10.246 (2) Å	µ = 0.74 mm⁻¹
c = 11.272 (2) Å	T = 223 K
α = 86.29 (3)°	0.50 × 0.50 × 0.30 mm
β = 71.82 (3)°

Data collection top

Rigaku Mercury CCD diffractometer	4403 independent reflections
Absorption correction: multi-scan (REQAB: Jacobson, 1998)	3757 reflections with I > 2σ(I)
T_min = 0.710, T_max = 0.810	R_int = 0.025
9376 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.081	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.42 e Å⁻³
4403 reflections	Δρ_min = −0.45 e Å⁻³
315 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	0.03585 (3)	0.13877 (2)	0.76264 (2)	0.01653 (9)
O1	−0.07365 (14)	0.18231 (12)	0.61328 (10)	0.0203 (2)
O1W	0.19967 (17)	−0.06467 (13)	0.65855 (13)	0.0287 (3)
H1WB	0.235 (3)	−0.112 (2)	0.709 (2)	0.048 (7)*
H1WA	0.191 (3)	−0.113 (2)	0.610 (2)	0.051 (7)*
O2	−0.20089 (15)	0.27574 (12)	0.47561 (11)	0.0251 (3)
O3	−0.36828 (15)	0.48967 (13)	0.70890 (11)	0.0289 (3)
O4	−0.38216 (15)	0.71264 (12)	0.71302 (12)	0.0344 (3)
H4	−0.4697	0.7305	0.7625	0.052*
O5	−0.16064 (13)	−0.06578 (11)	1.09959 (10)	0.0196 (2)
O6	−0.32453 (13)	0.16588 (11)	1.15378 (10)	0.0201 (2)
O7	−0.15899 (14)	0.08266 (12)	0.86097 (10)	0.0230 (3)
O8	−0.24706 (16)	0.05474 (14)	0.70863 (10)	0.0302 (3)
H8	−0.1745	0.0730	0.6647	0.045*
N1	−0.10378 (17)	0.35804 (14)	0.86211 (12)	0.0201 (3)
N2	0.19008 (17)	0.25423 (14)	0.69255 (12)	0.0200 (3)
C1	−0.2460 (2)	0.40702 (19)	0.94468 (16)	0.0277 (4)
H1A	−0.2977	0.3468	0.9626	0.033*
C2	−0.3227 (3)	0.5448 (2)	1.00651 (18)	0.0380 (5)
H2A	−0.4231	0.5759	1.0636	0.046*
C3	−0.2453 (3)	0.63274 (19)	0.98044 (18)	0.0389 (5)
H3A	−0.2940	0.7250	1.0199	0.047*
C4	−0.0943 (2)	0.58473 (18)	0.89512 (16)	0.0298 (4)
C5	−0.0026 (3)	0.6674 (2)	0.86821 (19)	0.0396 (5)
H5A	−0.0461	0.7597	0.9068	0.048*
C6	0.1431 (3)	0.6146 (2)	0.78925 (19)	0.0394 (5)
H6A	0.1996	0.6706	0.7747	0.047*
C7	0.2162 (2)	0.4723 (2)	0.72534 (16)	0.0298 (4)
C8	0.3693 (3)	0.4120 (2)	0.64430 (18)	0.0376 (5)
H8A	0.4301	0.4641	0.6276	0.045*
C9	0.4304 (2)	0.2758 (2)	0.58920 (19)	0.0386 (5)
H9A	0.5329	0.2340	0.5354	0.046*
C10	0.3351 (2)	0.2004 (2)	0.61544 (17)	0.0289 (4)
H10A	0.3762	0.1085	0.5768	0.035*
C11	0.1296 (2)	0.38922 (17)	0.74896 (15)	0.0211 (4)
C12	−0.0266 (2)	0.44510 (17)	0.83610 (15)	0.0212 (4)
C13	0.08667 (19)	0.36364 (16)	0.44035 (14)	0.0169 (3)
H13A	0.1458	0.2719	0.3997	0.020*
C14	−0.06214 (19)	0.39624 (16)	0.52328 (13)	0.0152 (3)
C15	−0.15027 (19)	0.53453 (16)	0.58379 (14)	0.0161 (3)
C16	−0.39312 (18)	0.02498 (15)	1.04387 (13)	0.0144 (3)
C17	−0.37723 (18)	0.02458 (15)	0.91572 (14)	0.0149 (3)
C18	−0.48391 (18)	−0.00020 (15)	0.87421 (13)	0.0156 (3)
H16A	−0.4723	−0.0001	0.7891	0.019*
C19	−0.12121 (19)	0.27874 (16)	0.53878 (13)	0.0159 (3)
C20	−0.3108 (2)	0.57403 (17)	0.67429 (14)	0.0190 (3)
C21	−0.28096 (18)	0.04445 (16)	1.10044 (13)	0.0149 (3)
C22	−0.25052 (19)	0.05606 (16)	0.82447 (14)	0.0168 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.01545 (15)	0.01648 (14)	0.02046 (14)	−0.00844 (11)	−0.00689 (10)	0.00152 (9)
O1	0.0245 (7)	0.0232 (6)	0.0220 (6)	−0.0159 (5)	−0.0120 (5)	0.0094 (5)
O1W	0.0373 (9)	0.0203 (6)	0.0300 (7)	−0.0062 (6)	−0.0199 (6)	−0.0032 (6)
O2	0.0358 (8)	0.0259 (6)	0.0276 (6)	−0.0192 (6)	−0.0205 (6)	0.0070 (5)
O3	0.0233 (7)	0.0290 (6)	0.0343 (7)	−0.0167 (6)	0.0000 (6)	−0.0006 (5)
O4	0.0216 (7)	0.0234 (6)	0.0446 (8)	−0.0094 (6)	0.0095 (6)	−0.0094 (6)
O5	0.0162 (6)	0.0204 (6)	0.0216 (6)	−0.0043 (5)	−0.0095 (5)	−0.0006 (4)
O6	0.0176 (6)	0.0187 (6)	0.0255 (6)	−0.0074 (5)	−0.0079 (5)	−0.0029 (5)
O7	0.0228 (7)	0.0365 (7)	0.0204 (6)	−0.0216 (6)	−0.0092 (5)	0.0078 (5)
O8	0.0372 (8)	0.0556 (8)	0.0172 (6)	−0.0376 (7)	−0.0102 (5)	0.0109 (5)
N1	0.0202 (8)	0.0203 (7)	0.0195 (7)	−0.0068 (6)	−0.0082 (6)	0.0016 (5)
N2	0.0200 (8)	0.0213 (7)	0.0218 (7)	−0.0109 (6)	−0.0079 (6)	0.0041 (5)
C1	0.0222 (10)	0.0311 (9)	0.0241 (8)	−0.0055 (8)	−0.0072 (7)	−0.0014 (7)
C2	0.0318 (12)	0.0358 (11)	0.0286 (10)	0.0032 (9)	−0.0086 (9)	−0.0069 (8)
C3	0.0505 (14)	0.0212 (9)	0.0299 (10)	0.0043 (9)	−0.0186 (10)	−0.0056 (8)
C4	0.0493 (13)	0.0180 (8)	0.0249 (9)	−0.0098 (8)	−0.0217 (9)	0.0030 (7)
C5	0.0750 (18)	0.0220 (9)	0.0355 (11)	−0.0236 (11)	−0.0320 (12)	0.0078 (8)
C6	0.0758 (18)	0.0343 (10)	0.0394 (11)	−0.0414 (12)	−0.0366 (12)	0.0188 (9)
C7	0.0478 (13)	0.0364 (10)	0.0284 (9)	−0.0322 (10)	−0.0249 (9)	0.0169 (8)
C8	0.0450 (13)	0.0556 (13)	0.0389 (11)	−0.0404 (11)	−0.0245 (10)	0.0220 (10)
C9	0.0246 (11)	0.0605 (14)	0.0360 (10)	−0.0250 (10)	−0.0091 (9)	0.0158 (10)
C10	0.0230 (10)	0.0335 (10)	0.0291 (9)	−0.0128 (8)	−0.0063 (8)	0.0066 (8)
C11	0.0299 (10)	0.0228 (8)	0.0201 (8)	−0.0158 (8)	−0.0149 (7)	0.0074 (6)
C12	0.0304 (10)	0.0165 (8)	0.0198 (8)	−0.0084 (7)	−0.0145 (7)	0.0038 (6)
C13	0.0190 (9)	0.0149 (7)	0.0179 (7)	−0.0075 (6)	−0.0064 (6)	0.0006 (6)
C14	0.0179 (9)	0.0176 (7)	0.0146 (7)	−0.0097 (6)	−0.0082 (6)	0.0040 (6)
C15	0.0163 (8)	0.0184 (8)	0.0150 (7)	−0.0076 (6)	−0.0063 (6)	0.0024 (6)
C16	0.0143 (8)	0.0121 (7)	0.0181 (7)	−0.0055 (6)	−0.0067 (6)	0.0007 (6)
C17	0.0139 (8)	0.0144 (7)	0.0172 (7)	−0.0066 (6)	−0.0049 (6)	0.0022 (6)
C18	0.0167 (9)	0.0168 (7)	0.0142 (7)	−0.0073 (6)	−0.0057 (6)	0.0021 (6)
C19	0.0159 (9)	0.0166 (7)	0.0137 (7)	−0.0076 (6)	−0.0015 (6)	−0.0004 (6)
C20	0.0175 (9)	0.0222 (8)	0.0182 (7)	−0.0087 (7)	−0.0061 (7)	0.0003 (6)
C21	0.0147 (8)	0.0193 (8)	0.0133 (7)	−0.0101 (7)	−0.0038 (6)	0.0025 (6)
C22	0.0166 (9)	0.0171 (7)	0.0186 (7)	−0.0087 (7)	−0.0061 (6)	0.0033 (6)

Geometric parameters (Å, º) top

Mn1—O1W	2.1576 (17)	C4—C12	1.408 (2)
Mn1—O5ⁱ	2.1830 (12)	C4—C5	1.437 (3)
Mn1—O7	2.1852 (13)	C5—C6	1.331 (3)
Mn1—O1	2.2001 (12)	C5—H5A	0.9300
Mn1—N2	2.2314 (14)	C6—C7	1.448 (3)
Mn1—N1	2.2317 (17)	C6—H6A	0.9300
O1—C19	1.2858 (19)	C7—C8	1.391 (3)
O1W—H1WB	0.79 (2)	C7—C11	1.402 (2)
O1W—H1WA	0.80 (2)	C8—C9	1.368 (3)
O2—C19	1.2250 (19)	C8—H8A	0.9300
O3—C20	1.2040 (19)	C9—C10	1.405 (3)
O4—C20	1.325 (2)	C9—H9A	0.9300
O4—H4	0.8200	C10—H10A	0.9300
O5—C21	1.250 (2)	C11—C12	1.437 (3)
O5—Mn1ⁱ	2.1830 (12)	C13—C14	1.385 (2)
O6—C21	1.2581 (18)	C13—C15ⁱⁱ	1.400 (2)
O7—C22	1.2304 (19)	C13—H13A	0.9300
O8—C22	1.2963 (18)	C14—C15	1.398 (2)
O8—H8	0.8200	C14—C19	1.522 (2)
N1—C1	1.322 (2)	C15—C13ⁱⁱ	1.400 (2)
N1—C12	1.363 (2)	C15—C20	1.493 (2)
N2—C10	1.318 (2)	C16—C18ⁱⁱⁱ	1.386 (2)
N2—C11	1.364 (2)	C16—C17	1.404 (2)
C1—C2	1.399 (3)	C16—C21	1.522 (2)
C1—H1A	0.9300	C17—C18	1.393 (2)
C2—C3	1.372 (3)	C17—C22	1.490 (2)
C2—H2A	0.9300	C18—C16ⁱⁱⁱ	1.386 (2)
C3—C4	1.395 (3)	C18—H16A	0.9300
C3—H3A	0.9300

O1W—Mn1—O5ⁱ	85.93 (5)	C8—C7—C6	123.54 (17)
O1W—Mn1—O7	99.43 (6)	C11—C7—C6	118.32 (19)
O5ⁱ—Mn1—O7	96.43 (5)	C9—C8—C7	119.84 (17)
O1W—Mn1—O1	86.66 (6)	C9—C8—H8A	120.1
O5ⁱ—Mn1—O1	172.36 (4)	C7—C8—H8A	120.1
O7—Mn1—O1	82.92 (4)	C8—C9—C10	118.7 (2)
O1W—Mn1—N2	96.43 (6)	C8—C9—H9A	120.6
O5ⁱ—Mn1—N2	84.21 (5)	C10—C9—H9A	120.6
O7—Mn1—N2	164.13 (5)	N2—C10—C9	122.82 (18)
O1—Mn1—N2	98.51 (5)	N2—C10—H10A	118.6
O1W—Mn1—N1	171.56 (5)	C9—C10—H10A	118.6
O5ⁱ—Mn1—N1	91.39 (5)	N2—C11—C7	121.88 (17)
O7—Mn1—N1	88.81 (6)	N2—C11—C12	118.21 (14)
O1—Mn1—N1	96.21 (5)	C7—C11—C12	119.90 (16)
N2—Mn1—N1	75.32 (6)	N1—C12—C4	121.70 (17)
C19—O1—Mn1	141.94 (10)	N1—C12—C11	118.23 (14)
Mn1—O1W—H1WB	103.6 (17)	C4—C12—C11	120.05 (16)
Mn1—O1W—H1WA	131.1 (18)	C14—C13—C15ⁱⁱ	121.62 (14)
H1WB—O1W—H1WA	111 (2)	C14—C13—H13A	119.2
C20—O4—H4	109.5	C15ⁱⁱ—C13—H13A	119.2
C21—O5—Mn1ⁱ	131.34 (10)	C13—C14—C15	118.80 (14)
C22—O7—Mn1	132.25 (10)	C13—C14—C19	117.00 (13)
C22—O8—H8	109.5	C15—C14—C19	124.16 (14)
C1—N1—C12	118.72 (15)	C14—C15—C13ⁱⁱ	119.58 (15)
C1—N1—Mn1	127.15 (12)	C14—C15—C20	120.56 (14)
C12—N1—Mn1	114.05 (11)	C13ⁱⁱ—C15—C20	119.85 (14)
C10—N2—C11	118.60 (15)	C18ⁱⁱⁱ—C16—C17	118.29 (14)
C10—N2—Mn1	126.98 (11)	C18ⁱⁱⁱ—C16—C21	116.70 (12)
C11—N2—Mn1	113.96 (11)	C17—C16—C21	124.95 (14)
N1—C1—C2	123.36 (18)	C18—C17—C16	119.83 (14)
N1—C1—H1A	118.3	C18—C17—C22	119.82 (13)
C2—C1—H1A	118.3	C16—C17—C22	120.31 (14)
C3—C2—C1	118.06 (19)	C16ⁱⁱⁱ—C18—C17	121.88 (13)
C3—C2—H2A	121.0	C16ⁱⁱⁱ—C18—H16A	119.1
C1—C2—H2A	121.0	C17—C18—H16A	119.1
C2—C3—C4	120.50 (17)	O2—C19—O1	124.21 (14)
C2—C3—H3A	119.8	O2—C19—C14	119.47 (13)
C4—C3—H3A	119.8	O1—C19—C14	116.15 (13)
C3—C4—C12	117.66 (17)	O3—C20—O4	123.94 (16)
C3—C4—C5	123.69 (17)	O3—C20—C15	123.99 (15)
C12—C4—C5	118.61 (19)	O4—C20—C15	112.06 (13)
C6—C5—C4	121.33 (18)	O5—C21—O6	125.93 (14)
C6—C5—H5A	119.3	O5—C21—C16	116.50 (13)
C4—C5—H5A	119.3	O6—C21—C16	117.22 (14)
C5—C6—C7	121.77 (17)	O7—C22—O8	124.29 (14)
C5—C6—H6A	119.1	O7—C22—C17	120.20 (13)
C7—C6—H6A	119.1	O8—C22—C17	115.50 (14)
C8—C7—C11	118.12 (17)

O1W—Mn1—O1—C19	−130.08 (17)	C6—C7—C11—N2	−179.99 (15)
O7—Mn1—O1—C19	129.98 (17)	C8—C7—C11—C12	177.39 (15)
N2—Mn1—O1—C19	−34.06 (17)	C6—C7—C11—C12	−0.9 (2)
N1—Mn1—O1—C19	41.96 (17)	C1—N1—C12—C4	0.2 (2)
O1W—Mn1—O7—C22	−69.40 (15)	Mn1—N1—C12—C4	−176.96 (12)
O5ⁱ—Mn1—O7—C22	−156.33 (14)	C1—N1—C12—C11	178.22 (14)
O1—Mn1—O7—C22	16.00 (14)	Mn1—N1—C12—C11	1.03 (18)
N2—Mn1—O7—C22	112.2 (2)	C3—C4—C12—N1	−1.0 (2)
N1—Mn1—O7—C22	112.41 (15)	C5—C4—C12—N1	176.62 (15)
O5ⁱ—Mn1—N1—C1	−95.99 (14)	C3—C4—C12—C11	−178.99 (15)
O7—Mn1—N1—C1	0.42 (14)	C5—C4—C12—C11	−1.3 (2)
O1—Mn1—N1—C1	83.16 (14)	N2—C11—C12—N1	2.8 (2)
N2—Mn1—N1—C1	−179.63 (15)	C7—C11—C12—N1	−176.29 (14)
O5ⁱ—Mn1—N1—C12	80.91 (11)	N2—C11—C12—C4	−179.13 (14)
O7—Mn1—N1—C12	177.32 (11)	C7—C11—C12—C4	1.7 (2)
O1—Mn1—N1—C12	−99.93 (11)	C15ⁱⁱ—C13—C14—C15	0.1 (2)
N2—Mn1—N1—C12	−2.73 (10)	C15ⁱⁱ—C13—C14—C19	177.97 (13)
O1W—Mn1—N2—C10	−2.02 (15)	C13—C14—C15—C13ⁱⁱ	−0.1 (2)
O5ⁱ—Mn1—N2—C10	83.21 (14)	C19—C14—C15—C13ⁱⁱ	−177.80 (13)
O7—Mn1—N2—C10	176.37 (15)	C13—C14—C15—C20	−179.72 (13)
O1—Mn1—N2—C10	−89.58 (15)	C19—C14—C15—C20	2.6 (2)
N1—Mn1—N2—C10	176.18 (15)	C18ⁱⁱⁱ—C16—C17—C18	0.1 (2)
O1W—Mn1—N2—C11	−174.03 (11)	C21—C16—C17—C18	177.34 (13)
O5ⁱ—Mn1—N2—C11	−88.80 (11)	C18ⁱⁱⁱ—C16—C17—C22	177.73 (13)
O7—Mn1—N2—C11	4.4 (2)	C21—C16—C17—C22	−5.0 (2)
O1—Mn1—N2—C11	98.40 (11)	C16—C17—C18—C16ⁱⁱⁱ	−0.1 (2)
N1—Mn1—N2—C11	4.17 (10)	C22—C17—C18—C16ⁱⁱⁱ	−177.74 (14)
C12—N1—C1—C2	0.6 (3)	Mn1—O1—C19—O2	−168.79 (11)
Mn1—N1—C1—C2	177.34 (13)	Mn1—O1—C19—C14	16.0 (2)
N1—C1—C2—C3	−0.5 (3)	C13—C14—C19—O2	−93.97 (19)
C1—C2—C3—C4	−0.4 (3)	C15—C14—C19—O2	83.76 (19)
C2—C3—C4—C12	1.1 (3)	C13—C14—C19—O1	81.52 (17)
C2—C3—C4—C5	−176.44 (17)	C15—C14—C19—O1	−100.75 (18)
C3—C4—C5—C6	177.60 (18)	C14—C15—C20—O3	6.7 (2)
C12—C4—C5—C6	0.1 (3)	C13ⁱⁱ—C15—C20—O3	−172.92 (15)
C4—C5—C6—C7	0.8 (3)	C14—C15—C20—O4	−173.91 (14)
C5—C6—C7—C8	−178.54 (18)	C13ⁱⁱ—C15—C20—O4	6.5 (2)
C5—C6—C7—C11	−0.4 (3)	Mn1ⁱ—O5—C21—O6	31.1 (2)
C11—C7—C8—C9	0.8 (3)	Mn1ⁱ—O5—C21—C16	−141.87 (11)
C6—C7—C8—C9	178.96 (17)	C18ⁱⁱⁱ—C16—C21—O5	93.87 (17)
C7—C8—C9—C10	0.6 (3)	C17—C16—C21—O5	−83.45 (18)
C11—N2—C10—C9	0.2 (3)	C18ⁱⁱⁱ—C16—C21—O6	−79.70 (17)
Mn1—N2—C10—C9	−171.46 (13)	C17—C16—C21—O6	102.98 (18)
C8—C9—C10—N2	−1.1 (3)	Mn1—O7—C22—O8	0.8 (2)
C10—N2—C11—C7	1.2 (2)	Mn1—O7—C22—C17	−178.26 (10)
Mn1—N2—C11—C7	173.95 (12)	C18—C17—C22—O7	177.64 (14)
C10—N2—C11—C12	−177.90 (15)	C16—C17—C22—O7	0.0 (2)
Mn1—N2—C11—C12	−5.16 (18)	C18—C17—C22—O8	−1.5 (2)
C8—C7—C11—N2	−1.7 (2)	C16—C17—C22—O8	−179.20 (14)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O8—H8···O1	0.82	1.75	2.5176 (16)	155
O4—H4···O6^iv	0.82	1.81	2.592 (2)	158
O1W—H1WB···O6ⁱ	0.79 (2)	1.95 (3)	2.7108 (19)	160 (2)
O1W—H1WA···O2^v	0.80 (2)	1.94 (2)	2.7117 (18)	162 (2)

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

Experimental details

Crystal data
Chemical formula	[Mn₂(C₁₀H₄O₈)₂(C₁₂H₈N₂)₂(H₂O)₂]
M_r	1010.58
Crystal system, space group	Triclinic, P1
Temperature (K)	223
a, b, c (Å)	9.880 (2), 10.246 (2), 11.272 (2)
α, β, γ (°)	86.29 (3), 71.82 (3), 65.32 (3)
V (Å³)	982.2 (5)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.74
Crystal size (mm)	0.50 × 0.50 × 0.30

Data collection
Diffractometer	Rigaku Mercury CCD diffractometer
Absorption correction	Multi-scan (REQAB: Jacobson, 1998)
T_min, T_max	0.710, 0.810
No. of measured, independent and observed [I > 2σ(I)] reflections	9376, 4403, 3757
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.081, 1.05
No. of reflections	4403
No. of parameters	315
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.45

Computer programs: CrystalClear (Rigaku, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Mn1—O1W	2.1576 (17)	Mn1—O1	2.2001 (12)
Mn1—O5ⁱ	2.1830 (12)	Mn1—N2	2.2314 (14)
Mn1—O7	2.1852 (13)	Mn1—N1	2.2317 (17)

Symmetry code: (i) −x, −y, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O8—H8···O1	0.82	1.75	2.5176 (16)	154.5
O4—H4···O6ⁱⁱ	0.82	1.81	2.592 (2)	158.4
O1W—H1WB···O6ⁱ	0.79 (2)	1.95 (3)	2.7108 (19)	160 (2)
O1W—H1WA···O2ⁱⁱⁱ	0.80 (2)	1.94 (2)	2.7117 (18)	162 (2)

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

Acknowledgements

This work was supported by the Scientific Research Foundation of Nanjing College of Chemical Technology (grant No. NHKY-2010–17).

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