Bis(μ-5-carboxyl­ato-1-carboxyl­ato­methyl-2-oxidopyridinium)-κ2O5:O1;κ2O1:O5-[diaqua­(phenan­throline-κ2N,N′)manganese(II)] dihydrate

Jiang, M.-X.; Feng, Y.-L.

doi:10.1107/S1600536809017668

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page m654

doi:10.1107/S1600536809017668

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Bis(μ-5-carboxylato-1-carboxylatomethyl-2-oxidopyridinium)-κ²O⁵:O¹;κ²O¹:O⁵-[diaqua(phenanthroline-κ²N,N′)manganese(II)] dihydrate

Mei-Xiang Jiang ^a and Yun-Long Feng ^a ^*

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

(Received 8 May 2009; accepted 11 May 2009; online 20 May 2009)

The centrosymmetric binuclear title complex, [Mn₂(C₈H₅NO₅)₂(C₁₂H₈N₂)₂(H₂O)₄]·2H₂O, was obtained by the reaction of manganese chloride with 5-carboxy-1-carboxymethyl-2-oxidopyridinium and 1,10-phenanthroline. The Mn^II atom is coordinated by two N atoms from the 1,10-phenanthroline ligand, two O atoms from two 5-carboxylato-1-carboxylatomethyl-2-oxidopyridinium ligands and two water molecules, leading to a distorted octahedral MnN₂O₄ environment. Intermolecular O—H⋯O hydrogen bonds link neighbouring molecules into a layer structure parallel to (001).

Related literature

For the synthesis of compounds with multicarboxylate ligands and metal centers, see: He et al. (2008 ); Huang et al. (2008 ); Jiang et al. (2009 ); Tong et al. (2005 ).

Experimental

Crystal data

[Mn₂(C₈H₅NO₅)₂(C₁₂H₈N₂)₂(H₂O)₄]·2H₂O
M_r = 968.64
Triclinic, $[P \overline 1]$
a = 7.7726 (11) Å
b = 9.9519 (14) Å
c = 15.411 (3) Å
α = 98.744 (10)°
β = 103.553 (10)°
γ = 110.252 (7)°
V = 1051.1 (3) Å³
Z = 1
Mo Kα radiation
μ = 0.68 mm⁻¹
T = 293 K
0.60 × 0.15 × 0.10 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.885, T_max = 0.934
19359 measured reflections
4779 independent reflections
3675 reflections with I > 2σ(I)
R_int = 0.171

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.141
S = 1.00
4779 reflections
307 parameters
9 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.81 e Å⁻³
Δρ_min = −0.79 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯O4ⁱ	0.831 (16)	1.967 (18)	2.773 (2)	163 (3)
O1W—H1WB⋯O3Wⁱⁱ	0.822 (15)	1.920 (15)	2.730 (2)	169 (3)
O2W—H2WA⋯O4	0.807 (16)	1.998 (15)	2.783 (2)	164 (2)
O2W—H2WA⋯O5	0.807 (16)	2.57 (3)	2.984 (2)	114 (2)
O2W—H2WB⋯O1ⁱⁱⁱ	0.856 (16)	1.959 (16)	2.806 (2)	170 (3)
O3W—H3WA⋯O1	0.833 (17)	1.962 (19)	2.775 (2)	165 (3)
Symmetry codes: (i) x-1, y, z; (ii) -x+1, -y+2, -z+1; (iii) -x+1, -y+1, -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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809017668/at2783sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809017668/at2783Isup2.hkl

checkCIF report

Comment top

There is intensely research on the synthesis of compounds with multicarboxylate ligands and metal centers for their potential applications and coloful coordination methods. A large number of these compounds have been synthesized (He et al., 2008; Huang et al., 2008; Jiang et al.,2009; Tong et al., 2005). As illustrated in Fig. 1, the Mn^II atom is coordinated by two nitrogen atoms from one 1,10-phenanthroline molecule, two oxygen atoms from two 5-carboxyl-1-carboxymethyl-2-oxidopyridinium ligands and two wate molecules. Four coordinated atoms of N2, N3, O5 and O2A constitute the base of the octahedral, whereas O1W and O2W atoms occupy the apical position. The intermolecular hydrogen bonds play an important role in the formation of the one-dimensional chain. As shown in Fig. 2. The intermolecular O—H···O hydrogen bonds link the neibouring molecules to a one-dimensional chain.

Related literature top

For the synthesis of compounds with multicarboxylate ligands and metal centers, see: He et al. (2008); Huang et al. (2008); Jiang et al. (2009); Tong et al. (2005).

Experimental top

A mixture of 0.5 mmol 5-carboxyl-1-carboxymethyl-2-oxidopyridinium, 0.5 mmol 1,10-phenanthroline and 0.5 mmol of manganese chloride in 10 ml distilled water was stirred for 30 min at 323 K, then the reaction mixture was filtered and well shaped yellow crystals of the title compound was obtained from the mother liquor by slow evaporation at room temperature for several 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: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are shown at the 30% probability level [Symmetry code: (A) -x + 1, -y + 1, -z + 1].
	Fig. 2. A view of the one-dimensional chain of the title compound. The O—H···O interactions are depicted by dashed lines.

Bis(µ-5-carboxylato-1-carboxylatomethyl-2-oxidopyridinium)- κ²O⁵:O¹;κ²O¹:O⁵- [diaqua(phenanthroline-κ²N,N')manganese(II)] dihydrate top

Crystal data top

[Mn₂(C₈H₅NO₅)₂(C₁₂H₈N₂)₂(H₂O)₄]·2H₂O	V = 1051.1 (3) Å³
M_r = 968.64	Z = 1
Triclinic, P1	F(000) = 498
Hall symbol: -P 1	D_x = 1.530 Mg m⁻³
a = 7.7726 (11) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.9519 (14) Å	θ = 2.8–27.5°
c = 15.411 (3) Å	µ = 0.68 mm⁻¹
α = 98.744 (10)°	T = 293 K
β = 103.553 (10)°	Block, yellow
γ = 110.252 (7)°	0.60 × 0.15 × 0.10 mm

Data collection top

Bruker APEXII area-detector diffractometer	4779 independent reflections
Radiation source: fine-focus sealed tube	3675 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.171
ω scans	θ_max = 27.5°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
T_min = 0.885, T_max = 0.934	k = −12→12
19359 measured reflections	l = −19→20

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.141	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.083P)² + 0.0025P] where P = (F_o² + 2F_c²)/3
4779 reflections	(Δ/σ)_max = 0.001
307 parameters	Δρ_max = 0.81 e Å⁻³
9 restraints	Δρ_min = −0.79 e Å⁻³

Crystal data top

[Mn₂(C₈H₅NO₅)₂(C₁₂H₈N₂)₂(H₂O)₄]·2H₂O	γ = 110.252 (7)°
M_r = 968.64	V = 1051.1 (3) Å³
Triclinic, P1	Z = 1
a = 7.7726 (11) Å	Mo Kα radiation
b = 9.9519 (14) Å	µ = 0.68 mm⁻¹
c = 15.411 (3) Å	T = 293 K
α = 98.744 (10)°	0.60 × 0.15 × 0.10 mm
β = 103.553 (10)°

Data collection top

Bruker APEXII area-detector diffractometer	4779 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3675 reflections with I > 2σ(I)
T_min = 0.885, T_max = 0.934	R_int = 0.171
19359 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	9 restraints
wR(F²) = 0.141	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.81 e Å⁻³
4779 reflections	Δρ_min = −0.79 e Å⁻³
307 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	0.34180 (4)	0.38197 (3)	0.24659 (2)	0.03192 (14)
C1	0.8430 (3)	0.9583 (2)	0.60141 (17)	0.0399 (5)
H1A	0.7365	0.9575	0.5533	0.048*
H1B	0.9335	1.0605	0.6284	0.048*
C2	0.7670 (3)	0.89610 (18)	0.67529 (14)	0.0334 (4)
C3	1.1327 (3)	0.9121 (2)	0.60386 (16)	0.0416 (5)
C4	1.2123 (3)	0.8185 (2)	0.56435 (17)	0.0447 (5)
H4	1.3421	0.8388	0.5905	0.054*
C5	1.1068 (3)	0.7009 (2)	0.49014 (16)	0.0397 (5)
H5	1.1640	0.6423	0.4663	0.048*
C6	0.9079 (3)	0.66801 (19)	0.44911 (15)	0.0350 (5)
C7	0.8321 (3)	0.75625 (19)	0.48720 (15)	0.0358 (5)
H7	0.7016	0.7344	0.4620	0.043*
C8	0.7808 (3)	0.5421 (2)	0.36561 (15)	0.0363 (5)
C9	−0.0500 (3)	0.1365 (2)	0.09487 (19)	0.0561 (7)
H9	−0.0641	0.0926	0.1433	0.067*
C10	−0.1881 (4)	0.0671 (3)	0.0077 (2)	0.0672 (9)
H10	−0.2900	−0.0226	−0.0012	0.081*
C11	−0.1736 (3)	0.1298 (2)	−0.06335 (19)	0.0565 (7)
H11	−0.2654	0.0839	−0.1212	0.068*
C12	−0.0184 (3)	0.2654 (2)	−0.04935 (16)	0.0413 (5)
C13	0.0048 (3)	0.3422 (3)	−0.11964 (18)	0.0506 (6)
H13	−0.0821	0.2997	−0.1789	0.061*
C14	0.1498 (3)	0.4747 (3)	−0.10162 (17)	0.0495 (6)
H14	0.1607	0.5238	−0.1481	0.059*
C15	0.2884 (3)	0.5414 (2)	−0.01126 (16)	0.0405 (5)
C16	0.4418 (4)	0.6812 (2)	0.01077 (19)	0.0509 (6)
H16	0.4584	0.7336	−0.0338	0.061*
C17	0.5659 (3)	0.7382 (2)	0.09913 (19)	0.0509 (6)
H17	0.6660	0.8312	0.1156	0.061*
C18	0.5416 (3)	0.6564 (2)	0.16410 (17)	0.0429 (5)
H18	0.6289	0.6962	0.2234	0.051*
C19	0.2732 (3)	0.46827 (18)	0.05867 (14)	0.0331 (4)
C20	0.1150 (3)	0.32712 (18)	0.04029 (14)	0.0338 (4)
O1W	0.2082 (2)	0.51934 (15)	0.30069 (13)	0.0469 (4)
H1WA	0.107 (3)	0.494 (3)	0.3146 (19)	0.056*
H1WB	0.262 (3)	0.6101 (18)	0.3185 (18)	0.056*
O1	0.6879 (2)	0.96382 (15)	0.71523 (12)	0.0473 (4)
O2W	0.5101 (2)	0.24567 (16)	0.20164 (12)	0.0439 (4)
H2WA	0.612 (3)	0.297 (2)	0.2403 (16)	0.053*
H2WB	0.459 (3)	0.177 (2)	0.2261 (16)	0.053*
O2	0.7879 (2)	0.78107 (15)	0.68951 (12)	0.0440 (4)
O3	1.2212 (2)	1.02222 (18)	0.67190 (14)	0.0640 (6)
O3W	0.5827 (3)	1.18225 (16)	0.65623 (18)	0.0688 (6)
H3WA	0.632 (4)	1.129 (3)	0.680 (2)	0.083*
H3WB	0.471 (3)	1.149 (3)	0.659 (2)	0.083*
O4	0.84928 (19)	0.46805 (15)	0.32338 (12)	0.0449 (4)
O5	0.6043 (2)	0.52140 (18)	0.34392 (12)	0.0526 (5)
N1	0.9381 (2)	0.87521 (16)	0.56051 (13)	0.0361 (4)
N2	0.3998 (2)	0.52424 (16)	0.14566 (13)	0.0351 (4)
N3	0.0999 (2)	0.26257 (16)	0.11052 (13)	0.0390 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.03112 (19)	0.02749 (17)	0.0329 (2)	0.00883 (12)	0.00698 (15)	0.00713 (12)
C1	0.0513 (11)	0.0308 (8)	0.0417 (13)	0.0170 (8)	0.0180 (10)	0.0135 (8)
C2	0.0322 (9)	0.0295 (8)	0.0345 (12)	0.0102 (7)	0.0072 (8)	0.0069 (7)
C3	0.0390 (10)	0.0365 (9)	0.0403 (13)	0.0071 (8)	0.0112 (9)	0.0057 (8)
C4	0.0306 (9)	0.0466 (10)	0.0455 (14)	0.0107 (8)	0.0024 (9)	0.0055 (9)
C5	0.0340 (9)	0.0377 (9)	0.0433 (13)	0.0132 (8)	0.0079 (9)	0.0079 (8)
C6	0.0318 (9)	0.0330 (8)	0.0348 (12)	0.0092 (7)	0.0055 (8)	0.0098 (8)
C7	0.0331 (9)	0.0334 (8)	0.0360 (12)	0.0088 (7)	0.0066 (8)	0.0118 (8)
C8	0.0336 (9)	0.0343 (8)	0.0361 (12)	0.0094 (7)	0.0079 (8)	0.0094 (8)
C9	0.0537 (13)	0.0374 (10)	0.0535 (17)	−0.0012 (9)	0.0010 (12)	0.0158 (10)
C10	0.0565 (14)	0.0399 (11)	0.066 (2)	−0.0090 (10)	−0.0065 (13)	0.0106 (12)
C11	0.0491 (12)	0.0441 (11)	0.0491 (17)	0.0073 (9)	−0.0067 (11)	−0.0029 (10)
C12	0.0399 (10)	0.0406 (9)	0.0383 (13)	0.0177 (8)	0.0041 (9)	0.0038 (8)
C13	0.0523 (12)	0.0593 (13)	0.0370 (14)	0.0270 (11)	0.0037 (10)	0.0076 (10)
C14	0.0587 (13)	0.0624 (13)	0.0383 (14)	0.0315 (11)	0.0165 (11)	0.0235 (11)
C15	0.0467 (11)	0.0407 (9)	0.0425 (13)	0.0223 (9)	0.0184 (10)	0.0151 (9)
C16	0.0622 (14)	0.0437 (11)	0.0559 (16)	0.0202 (10)	0.0270 (12)	0.0265 (10)
C17	0.0540 (13)	0.0328 (9)	0.0608 (18)	0.0071 (9)	0.0225 (12)	0.0149 (10)
C18	0.0422 (10)	0.0306 (8)	0.0455 (15)	0.0061 (8)	0.0113 (10)	0.0039 (8)
C19	0.0364 (9)	0.0291 (8)	0.0360 (12)	0.0156 (7)	0.0120 (8)	0.0068 (7)
C20	0.0350 (9)	0.0301 (8)	0.0347 (12)	0.0144 (7)	0.0076 (8)	0.0050 (7)
O1W	0.0401 (8)	0.0323 (6)	0.0712 (13)	0.0146 (6)	0.0243 (8)	0.0096 (7)
O1	0.0589 (9)	0.0417 (7)	0.0532 (11)	0.0275 (7)	0.0266 (8)	0.0131 (7)
O2W	0.0446 (8)	0.0401 (7)	0.0439 (11)	0.0140 (6)	0.0143 (7)	0.0084 (7)
O2	0.0562 (9)	0.0403 (7)	0.0529 (11)	0.0258 (6)	0.0295 (8)	0.0251 (7)
O3	0.0481 (9)	0.0496 (9)	0.0649 (14)	0.0037 (7)	0.0082 (8)	−0.0152 (8)
O3W	0.0591 (10)	0.0344 (7)	0.1180 (19)	0.0198 (7)	0.0337 (12)	0.0212 (9)
O4	0.0352 (7)	0.0413 (7)	0.0505 (11)	0.0110 (6)	0.0120 (7)	0.0020 (7)
O5	0.0323 (7)	0.0601 (9)	0.0504 (11)	0.0180 (7)	0.0006 (7)	−0.0080 (8)
N1	0.0384 (8)	0.0304 (7)	0.0386 (11)	0.0108 (6)	0.0135 (7)	0.0104 (7)
N2	0.0344 (8)	0.0282 (7)	0.0383 (11)	0.0085 (6)	0.0113 (7)	0.0058 (6)
N3	0.0376 (8)	0.0286 (7)	0.0411 (11)	0.0059 (6)	0.0063 (8)	0.0085 (7)

Geometric parameters (Å, º) top

Mn1—O5	2.0761 (14)	C10—C11	1.348 (4)
Mn1—O2ⁱ	2.1066 (15)	C10—H10	0.9300
Mn1—O1W	2.1643 (15)	C11—C12	1.409 (3)
Mn1—N2	2.2768 (18)	C11—H11	0.9300
Mn1—N3	2.2788 (17)	C12—C20	1.411 (3)
Mn1—O2W	2.3237 (17)	C12—C13	1.428 (3)
C1—N1	1.454 (3)	C13—C14	1.341 (3)
C1—C2	1.518 (3)	C13—H13	0.9300
C1—H1A	0.9700	C14—C15	1.436 (3)
C1—H1B	0.9700	C14—H14	0.9300
C2—O1	1.245 (2)	C15—C19	1.394 (3)
C2—O2	1.254 (2)	C15—C16	1.411 (3)
C3—O3	1.251 (2)	C16—C17	1.370 (4)
C3—N1	1.391 (3)	C16—H16	0.9300
C3—C4	1.423 (3)	C17—C18	1.390 (3)
C4—C5	1.356 (3)	C17—H17	0.9300
C4—H4	0.9300	C18—N2	1.327 (2)
C5—C6	1.423 (3)	C18—H18	0.9300
C5—H5	0.9300	C19—N2	1.361 (3)
C6—C7	1.352 (3)	C19—C20	1.444 (2)
C6—C8	1.503 (3)	C20—N3	1.348 (3)
C7—N1	1.356 (2)	O1W—H1WA	0.831 (16)
C7—H7	0.9300	O1W—H1WB	0.822 (15)
C8—O4	1.240 (3)	O2W—H2WA	0.807 (16)
C8—O5	1.267 (2)	O2W—H2WB	0.856 (16)
C9—N3	1.324 (2)	O2—Mn1ⁱ	2.1066 (15)
C9—C10	1.401 (3)	O3W—H3WA	0.833 (17)
C9—H9	0.9300	O3W—H3WB	0.833 (17)

O5—Mn1—O2ⁱ	105.32 (7)	C10—C11—C12	119.5 (2)
O5—Mn1—O1W	89.47 (6)	C10—C11—H11	120.2
O2ⁱ—Mn1—O1W	90.24 (6)	C12—C11—H11	120.2
O5—Mn1—N2	90.90 (7)	C11—C12—C20	116.6 (2)
O2ⁱ—Mn1—N2	163.71 (6)	C11—C12—C13	123.4 (2)
O1W—Mn1—N2	88.34 (7)	C20—C12—C13	120.00 (19)
O5—Mn1—N3	162.47 (8)	C14—C13—C12	121.1 (2)
O2ⁱ—Mn1—N3	91.35 (6)	C14—C13—H13	119.5
O1W—Mn1—N3	95.98 (7)	C12—C13—H13	119.5
N2—Mn1—N3	72.68 (6)	C13—C14—C15	120.6 (2)
O5—Mn1—O2W	85.20 (6)	C13—C14—H14	119.7
O2ⁱ—Mn1—O2W	89.67 (6)	C15—C14—H14	119.7
O1W—Mn1—O2W	174.44 (6)	C19—C15—C16	117.6 (2)
N2—Mn1—O2W	93.29 (6)	C19—C15—C14	120.02 (19)
N3—Mn1—O2W	89.58 (6)	C16—C15—C14	122.4 (2)
N1—C1—C2	112.73 (16)	C17—C16—C15	118.7 (2)
N1—C1—H1A	109.0	C17—C16—H16	120.7
C2—C1—H1A	109.0	C15—C16—H16	120.7
N1—C1—H1B	109.0	C16—C17—C18	119.7 (2)
C2—C1—H1B	109.0	C16—C17—H17	120.1
H1A—C1—H1B	107.8	C18—C17—H17	120.1
O1—C2—O2	126.3 (2)	N2—C18—C17	123.2 (2)
O1—C2—C1	116.48 (17)	N2—C18—H18	118.4
O2—C2—C1	117.18 (19)	C17—C18—H18	118.4
O3—C3—N1	118.6 (2)	N2—C19—C15	123.24 (17)
O3—C3—C4	126.2 (2)	N2—C19—C20	117.09 (18)
N1—C3—C4	115.20 (17)	C15—C19—C20	119.66 (18)
C5—C4—C3	122.79 (19)	N3—C20—C12	123.26 (18)
C5—C4—H4	118.6	N3—C20—C19	118.13 (17)
C3—C4—H4	118.6	C12—C20—C19	118.59 (19)
C4—C5—C6	119.4 (2)	Mn1—O1W—H1WA	128.8 (17)
C4—C5—H5	120.3	Mn1—O1W—H1WB	122.9 (17)
C6—C5—H5	120.3	H1WA—O1W—H1WB	108 (2)
C7—C6—C5	117.71 (18)	Mn1—O2W—H2WA	96 (2)
C7—C6—C8	119.05 (17)	Mn1—O2W—H2WB	93.0 (18)
C5—C6—C8	123.23 (19)	H2WA—O2W—H2WB	104 (2)
C6—C7—N1	122.87 (18)	C2—O2—Mn1ⁱ	134.18 (16)
C6—C7—H7	118.6	H3WA—O3W—H3WB	104 (2)
N1—C7—H7	118.6	C8—O5—Mn1	140.26 (15)
O4—C8—O5	124.86 (19)	C7—N1—C3	121.96 (18)
O4—C8—C6	120.83 (18)	C7—N1—C1	119.42 (17)
O5—C8—C6	114.31 (19)	C3—N1—C1	118.32 (17)
N3—C9—C10	122.1 (2)	C18—N2—C19	117.50 (19)
N3—C9—H9	118.9	C18—N2—Mn1	126.40 (15)
C10—C9—H9	118.9	C19—N2—Mn1	116.08 (12)
C11—C10—C9	120.2 (2)	C9—N3—C20	118.22 (18)
C11—C10—H10	119.9	C9—N3—Mn1	125.89 (16)
C9—C10—H10	119.9	C20—N3—Mn1	115.89 (12)

N1—C1—C2—O1	178.22 (17)	N2—Mn1—O5—C8	−84.9 (3)
N1—C1—C2—O2	−2.5 (3)	N3—Mn1—O5—C8	−64.8 (4)
O3—C3—C4—C5	−179.9 (3)	O2W—Mn1—O5—C8	8.3 (3)
N1—C3—C4—C5	−0.4 (3)	C6—C7—N1—C3	−2.2 (3)
C3—C4—C5—C6	0.0 (4)	C6—C7—N1—C1	−175.7 (2)
C4—C5—C6—C7	−0.6 (3)	O3—C3—N1—C7	−179.1 (2)
C4—C5—C6—C8	178.7 (2)	C4—C3—N1—C7	1.5 (3)
C5—C6—C7—N1	1.6 (3)	O3—C3—N1—C1	−5.4 (3)
C8—C6—C7—N1	−177.63 (18)	C4—C3—N1—C1	175.09 (19)
C7—C6—C8—O4	172.8 (2)	C2—C1—N1—C7	87.7 (2)
C5—C6—C8—O4	−6.4 (3)	C2—C1—N1—C3	−86.1 (2)
C7—C6—C8—O5	−6.9 (3)	C17—C18—N2—C19	−0.3 (3)
C5—C6—C8—O5	173.9 (2)	C17—C18—N2—Mn1	−178.77 (18)
N3—C9—C10—C11	−1.5 (5)	C15—C19—N2—C18	1.4 (3)
C9—C10—C11—C12	0.2 (5)	C20—C19—N2—C18	−177.59 (18)
C10—C11—C12—C20	0.3 (4)	C15—C19—N2—Mn1	−179.97 (16)
C10—C11—C12—C13	−177.8 (3)	C20—C19—N2—Mn1	1.1 (2)
C11—C12—C13—C14	176.6 (2)	O5—Mn1—N2—C18	−9.93 (18)
C20—C12—C13—C14	−1.5 (4)	O2ⁱ—Mn1—N2—C18	164.7 (2)
C12—C13—C14—C15	1.3 (4)	O1W—Mn1—N2—C18	79.51 (18)
C13—C14—C15—C19	0.2 (3)	N3—Mn1—N2—C18	176.30 (19)
C13—C14—C15—C16	−179.3 (2)	O2W—Mn1—N2—C18	−95.17 (18)
C19—C15—C16—C17	−0.7 (3)	O5—Mn1—N2—C19	171.54 (14)
C14—C15—C16—C17	178.9 (2)	O2ⁱ—Mn1—N2—C19	−13.9 (3)
C15—C16—C17—C18	1.7 (4)	O1W—Mn1—N2—C19	−99.02 (14)
C16—C17—C18—N2	−1.3 (4)	N3—Mn1—N2—C19	−2.23 (13)
C16—C15—C19—N2	−0.9 (3)	O2W—Mn1—N2—C19	86.30 (14)
C14—C15—C19—N2	179.6 (2)	C10—C9—N3—C20	2.0 (4)
C16—C15—C19—C20	178.02 (19)	C10—C9—N3—Mn1	−177.0 (2)
C14—C15—C19—C20	−1.5 (3)	C12—C20—N3—C9	−1.4 (3)
C11—C12—C20—N3	0.2 (3)	C19—C20—N3—C9	176.9 (2)
C13—C12—C20—N3	178.5 (2)	C12—C20—N3—Mn1	177.73 (16)
C11—C12—C20—C19	−178.11 (19)	C19—C20—N3—Mn1	−3.9 (2)
C13—C12—C20—C19	0.1 (3)	O5—Mn1—N3—C9	161.2 (2)
N2—C19—C20—N3	1.9 (3)	O2ⁱ—Mn1—N3—C9	−0.9 (2)
C15—C19—C20—N3	−177.08 (18)	O1W—Mn1—N3—C9	−91.3 (2)
N2—C19—C20—C12	−179.65 (18)	N2—Mn1—N3—C9	−177.7 (2)
C15—C19—C20—C12	1.4 (3)	O2W—Mn1—N3—C9	88.7 (2)
O1—C2—O2—Mn1ⁱ	17.7 (3)	O5—Mn1—N3—C20	−17.9 (3)
C1—C2—O2—Mn1ⁱ	−161.47 (15)	O2ⁱ—Mn1—N3—C20	179.98 (15)
O4—C8—O5—Mn1	1.0 (4)	O1W—Mn1—N3—C20	89.60 (15)
C6—C8—O5—Mn1	−179.30 (18)	N2—Mn1—N3—C20	3.23 (14)
O2ⁱ—Mn1—O5—C8	96.6 (3)	O2W—Mn1—N3—C20	−90.35 (15)
O1W—Mn1—O5—C8	−173.3 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O4ⁱⁱ	0.83 (2)	1.97 (2)	2.773 (2)	163 (3)
O1W—H1WB···O3Wⁱⁱⁱ	0.82 (2)	1.92 (2)	2.730 (2)	169 (3)
O2W—H2WA···O4	0.81 (2)	2.00 (2)	2.783 (2)	164 (2)
O2W—H2WA···O5	0.81 (2)	2.57 (3)	2.984 (2)	114 (2)
O2W—H2WB···O1ⁱ	0.86 (2)	1.96 (2)	2.806 (2)	170 (3)
O3W—H3WA···O1	0.83 (2)	1.96 (2)	2.775 (2)	165 (3)

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

Experimental details

Crystal data
Chemical formula	[Mn₂(C₈H₅NO₅)₂(C₁₂H₈N₂)₂(H₂O)₄]·2H₂O
M_r	968.64
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.7726 (11), 9.9519 (14), 15.411 (3)
α, β, γ (°)	98.744 (10), 103.553 (10), 110.252 (7)
V (Å³)	1051.1 (3)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.68
Crystal size (mm)	0.60 × 0.15 × 0.10

Data collection
Diffractometer	Bruker APEXII area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.885, 0.934
No. of measured, independent and observed [I > 2σ(I)] reflections	19359, 4779, 3675
R_int	0.171
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.141, 1.00
No. of reflections	4779
No. of parameters	307
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)	0.81, −0.79

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), 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—H1WA···O4ⁱ	0.831 (16)	1.967 (18)	2.773 (2)	163 (3)
O1W—H1WB···O3Wⁱⁱ	0.822 (15)	1.920 (15)	2.730 (2)	169 (3)
O2W—H2WA···O4	0.807 (16)	1.998 (15)	2.783 (2)	164 (2)
O2W—H2WA···O5	0.807 (16)	2.57 (3)	2.984 (2)	114 (2)
O2W—H2WB···O1ⁱⁱⁱ	0.856 (16)	1.959 (16)	2.806 (2)	170 (3)
O3W—H3WA···O1	0.833 (17)	1.962 (19)	2.775 (2)	165 (3)

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

References

Bruker (2006). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
He, Y. H., Feng, Y. L., Lan, Y. Z. & Wen, Y. H. (2008). Cryst. Growth Des. 8, 3586–3594. Web of Science CSD CrossRef CAS Google Scholar
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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tong, M. L., Hu, S., Wang, J., Kitagawa, S. & Ng, S. W. (2005). Cryst. Growth Des. 5, 837–839. Web of Science CSD CrossRef CAS Google Scholar

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