Poly[[diaqua­bis­(μ3-3,5-dicarb­oxy­benzo­ato-κ3O1:O3:O5)bis­(μ3-5-carb­oxy­ben­zene-1,3-dicarboxyl­ato-κ3O1:O3:O5)tetrakis(methylformamide-κO)tri­man­ganese(II)] dimethyl­formamide tetra­solvate]

Lei, J.-W.; Xie, C.-X.; Yang, H.

doi:10.1107/S1600536812017734

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 5| May 2012| Pages m697-m698

doi:10.1107/S1600536812017734

Open

access

Poly[[diaquabis(μ₃-3,5-dicarboxybenzoato-κ³O¹:O³:O⁵)bis(μ₃-5-carboxybenzene-1,3-dicarboxylato-κ³O¹:O³:O⁵)tetrakis(methylformamide-κO)trimanganese(II)] dimethylformamide tetrasolvate]

Jing-Wei Lei,^a Cai-Xia Xie ^a and Huai-xia Yang ^a ^*

^aPharmacy College, Henan University of Traditional Chinese Medicine, Zhengzhou 450008, People's Republic of China
^*Correspondence e-mail: 13623712409@139.com

(Received 10 April 2012; accepted 20 April 2012; online 28 April 2012)

In the title complex, {[Mn₃(C₉H₄O₆)₂(C₉H₅O₆)₂(C₃H₇NO)₄(H₂O)₂]·4C₃H₇NO}_n, one Mn^II ion sits on an inversion center, and is six-coordinated by four O atoms from four anions (monoanionic and dianionic) derived from benzene-1,3,5-tricarboxylic acid and by two dimethylformamide (DMF) molecules in a slightly distorted octahedral geometry. The other Mn^II ion is six-coordinated by four O atoms from four monoanionic and dianionic ligands, one DMF molecule and one water molecule in a distorted octahedral geometry. The monoanionic and dianionic ligands bridge the Mn^II ions, resulting in the formation of a layered structure parallel to (111) in which all of the carboxylate groups of the anionic ligands coordinate the Mn^II ions in a monodentate manner. Intra- and intermolecular O—H⋯O hydrogen bonds are present in the structure.

Related literature

For background information on complexes based on aromatic polycarboxylate ligands see: Hu et al. (2011 ); Prajapati et al. (2009 ).

Experimental

Crystal data

[Mn₃(C₉H₄O₆)₂(C₉H₅O₆)₂(C₃H₇NO)₄(H₂O)₂]·4C₃H₇NO
M_r = 1620.12
Triclinic, $[P \overline 1]$
a = 9.826 (2) Å
b = 13.290 (3) Å
c = 14.698 (3) Å
α = 73.22 (3)°
β = 83.32 (3)°
γ = 89.79 (3)°
V = 1824.2 (6) Å³
Z = 1
Mo Kα radiation
μ = 0.61 mm⁻¹
T = 293 K
0.19 × 0.15 × 0.13 mm

Data collection

Rigaku Saturn CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2004 ) T_min = 0.894, T_max = 0.925
18985 measured reflections
6589 independent reflections
5527 reflections with I > 2σ(I)
R_int = 0.041

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.116
S = 1.13
6589 reflections
478 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O8—H8⋯O2	0.82	1.67	2.448 (3)	157
O17—H2W⋯O16	0.85	1.85	2.694 (4)	176
O6—H6⋯O9ⁱ	0.82	1.69	2.452 (3)	153
O3—H3⋯O11ⁱⁱ	0.82	1.69	2.463 (3)	157
O17—H1W⋯O15ⁱⁱⁱ	0.85	1.92	2.713 (4)	155
Symmetry codes: (i) x, y-1, z+1; (ii) x+1, y-1, z; (iii) -x+1, -y+1, -z+1.

Data collection: CrystalClear (Rigaku/MSC, 2004); 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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812017734/pk2407sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812017734/pk2407Isup2.hkl

checkCIF report

Comment top

Aromatic polycarboxylate compounds, such as 1,3,5-benzenetricarboxylic acid and 1,2,4,5-benzenetetracarboxylic acid, have been proved to be effective ligands to design and synthesize open and rigid frameworks due to the versatile binding modes and high binding capacity of the carboxylate groups (Hu et al., 2011; Prajapati et al., 2009). In order to further explore metal-organic frameworks with new structures, we selected 1,3,5-benzenetricarboxylic acid (H₃btc) as ligand to self-assembly with MnCl₂ and obtained the title complex, {[Mn₃(C₉H₄O₆)₂(C₉H₅O₆)₂(DMF)₄)(H₂O)₂](DMF)₄}_n, of which the crystal structure is reported herein. As shown in Figure 1, there are two crystallographically independent manganese ions (Mn1 and Mn2), two crystallographically independent 1,3,5-benzenetricarboxylte groups (Hbtc and H₂btc), two crystallographically independent coordination DMF molecules, one coordination H₂O molecule, two crystallographically independent uncoordination DMF molecules in an asymmetric unit. Each Mn1 ion lies on an inversion center and displays a slightly distorted octahedral geometry defined by atoms O1, O1A, O7, O7A from four 1,3,5-benzenetricarboxylte anions in equatorial positions and by atoms O13, O13A from two DMF molecules in axial positions. The Mn2 ion is bound with six oxygen atoms from four 1,3,5-benzenetricarboxylte groups (O4A, O5B, O10, O12C), one DMF molecule (O14) and one H₂O molecule (O17) leading to a distorted octahedral geometry. As depicted in Figure 2, Mn1 and Mn2 ions are bridged by 1,3,5-benzenetricarboxylte ligands forming the two-dimensional layer structure in which all of the carboxylate groups of the 1,3,5-benzenetricarboxylte ligands coordinate to Mn^II ions in monodentate mode. In addition, intramolecular O—H···O hydrogen bonds between the carboxyl/carboxylate groups stabilize the molecular configuration whereas O—H···O hydrogen bonds between coordinated water molecules and solvent DMF molecules and between carboxyl/carboxylate groups of adjacent molecules consolidate the crystal packing.

Related literature top

For background information on complexes based on aromatic polycarboxylate ligands see: Hu et al. (2011); Prajapati et al. (2009).

Experimental top

A mixture of MnCl₂ (0.1 mmol), 1,3,5-benzenetricarboxylic acid (0.1 mmol), N,N'-dimethylformamide (2 ml) and water (8 ml) was placed in a 25 ml Teflon-lined stainless steel vessel and heated at 100 °C for 72 h, then cooled to room temperature. Pale yellow crystals were obtained from the filtrate and dried in air.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2004); cell refinement: CrystalClear (Rigaku/MSC, 2004); data reduction: CrystalClear (Rigaku/MSC, 2004); 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: publCIF (Westrip, 2010).

Figures top

	Fig. 1. View of the title complex showing 30% probability displacement ellipsoids. [Symmetry code A: -x + 2, -y, -z + 2; B: x, y + 1, z - 1; C: -x + 1, -y + 1, -z + 2.]
	Fig. 2. View of the two-dimensional structure of the title complex. Hydrogen atoms are omitted for clarity.

Poly[[diaquabis(µ₃-3,5- dicarboxybenzoato-κ³O¹:O³:O⁵)bis(µ₃-5- carboxybenzene-1,3-dicarboxylato- κ³O¹:O³:O⁵)tetrakis(methylformamide- κO)trimanganese(II)] dimethylformamide tetrasolvate] top

Crystal data top

[Mn₃(C₉H₄O₆)₂(C₉H₅O₆)₂(C₃H₇NO)₄(H₂O)₂]·4C₃H₇NO	Z = 1
M_r = 1620.12	F(000) = 841
Triclinic, P1	D_x = 1.475 Mg m⁻³
a = 9.826 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 13.290 (3) Å	Cell parameters from 4578 reflections
c = 14.698 (3) Å	θ = 2.1–27.9°
α = 73.22 (3)°	µ = 0.61 mm⁻¹
β = 83.32 (3)°	T = 293 K
γ = 89.79 (3)°	Prism, pale yellow
V = 1824.2 (6) Å³	0.19 × 0.15 × 0.13 mm

Data collection top

Rigaku Saturn CCD diffractometer	6589 independent reflections
Radiation source: fine-focus sealed tube	5527 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
Detector resolution: 28.6 pixels mm^-1	θ_max = 25.3°, θ_min = 1.5°
ω scans	h = −11→11
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2004)	k = −15→15
T_min = 0.894, T_max = 0.925	l = −17→17
18985 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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.116	H-atom parameters constrained
S = 1.13	w = 1/[σ²(F_o²) + (0.0375P)² + 1.4521P] where P = (F_o² + 2F_c²)/3
6589 reflections	(Δ/σ)_max = 0.001
478 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

[Mn₃(C₉H₄O₆)₂(C₉H₅O₆)₂(C₃H₇NO)₄(H₂O)₂]·4C₃H₇NO	γ = 89.79 (3)°
M_r = 1620.12	V = 1824.2 (6) Å³
Triclinic, P1	Z = 1
a = 9.826 (2) Å	Mo Kα radiation
b = 13.290 (3) Å	µ = 0.61 mm⁻¹
c = 14.698 (3) Å	T = 293 K
α = 73.22 (3)°	0.19 × 0.15 × 0.13 mm
β = 83.32 (3)°

Data collection top

Rigaku Saturn CCD diffractometer	6589 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2004)	5527 reflections with I > 2σ(I)
T_min = 0.894, T_max = 0.925	R_int = 0.041
18985 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	0 restraints
wR(F²) = 0.116	H-atom parameters constrained
S = 1.13	Δρ_max = 0.33 e Å⁻³
6589 reflections	Δρ_min = −0.33 e Å⁻³
478 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	1.0000	0.0000	1.0000	0.02695 (18)
Mn2	0.64081 (5)	0.63958 (4)	0.66415 (3)	0.02946 (15)
O1	1.0590 (2)	−0.06181 (19)	1.14191 (14)	0.0397 (6)
O2	0.8883 (3)	−0.04824 (19)	1.25050 (16)	0.0455 (7)
O3	1.3739 (2)	−0.35363 (17)	1.21994 (15)	0.0367 (6)
H3	1.4278	−0.3959	1.2067	0.044*
O4	1.3256 (2)	−0.48344 (17)	1.35625 (15)	0.0347 (6)
O5	0.8257 (2)	−0.31041 (18)	1.56693 (15)	0.0368 (6)
O6	0.9930 (2)	−0.42307 (18)	1.60883 (14)	0.0366 (6)
H6	0.9436	−0.4415	1.6601	0.044*
O7	0.9379 (2)	0.14743 (17)	1.02342 (16)	0.0399 (6)
O8	0.7940 (3)	0.11542 (18)	1.15860 (16)	0.0433 (6)
H8	0.8405	0.0635	1.1760	0.052*
O9	0.9107 (2)	0.49197 (19)	0.77771 (15)	0.0404 (6)
O10	0.7326 (2)	0.59048 (17)	0.79841 (14)	0.0352 (6)
O11	0.5417 (2)	0.55479 (17)	1.13690 (15)	0.0361 (6)
O12	0.5501 (2)	0.39777 (18)	1.24445 (15)	0.0371 (6)
O13	0.7895 (3)	−0.0676 (2)	1.03997 (18)	0.0452 (6)
O14	0.6417 (3)	0.8009 (2)	0.67832 (19)	0.0494 (7)
O15	0.7270 (3)	0.2236 (3)	0.4303 (3)	0.0780 (10)
O16	0.5669 (4)	0.7479 (2)	0.3566 (2)	0.0724 (10)
O17	0.5163 (3)	0.6835 (2)	0.54908 (16)	0.0487 (7)
H1W	0.4309	0.6935	0.5578	0.058*
H2W	0.5356	0.7017	0.4886	0.058*
N1	0.6125 (4)	−0.1482 (3)	0.9988 (3)	0.0671 (11)
N2	0.5441 (4)	0.9589 (3)	0.6541 (3)	0.0635 (11)
N3	0.9217 (3)	0.1958 (3)	0.3439 (3)	0.0556 (9)
N4	0.7209 (3)	0.6531 (3)	0.2913 (2)	0.0518 (9)
C1	0.9950 (3)	−0.0916 (2)	1.2233 (2)	0.0286 (7)
C2	1.3077 (3)	−0.3950 (2)	1.3036 (2)	0.0280 (7)
C3	0.9364 (3)	−0.3492 (2)	1.5497 (2)	0.0278 (7)
C4	1.0434 (3)	−0.1846 (2)	1.2955 (2)	0.0248 (7)
C5	1.1553 (3)	−0.2386 (2)	1.2693 (2)	0.0251 (7)
H5A	1.2024	−0.2142	1.2081	0.030*
C6	1.1979 (3)	−0.3284 (2)	1.3335 (2)	0.0249 (7)
C7	1.1277 (3)	−0.3631 (2)	1.4253 (2)	0.0267 (7)
H7A	1.1563	−0.4225	1.4692	0.032*
C8	1.0154 (3)	−0.3099 (2)	1.4523 (2)	0.0248 (7)
C9	0.9725 (3)	−0.2219 (2)	1.3868 (2)	0.0256 (7)
H9A	0.8956	−0.1874	1.4039	0.031*
C10	0.8490 (3)	0.1743 (2)	1.0777 (2)	0.0277 (7)
C11	0.8095 (3)	0.5173 (2)	0.8280 (2)	0.0294 (7)
C12	0.5792 (3)	0.4611 (2)	1.1633 (2)	0.0273 (7)
C13	0.7994 (3)	0.2843 (2)	1.0503 (2)	0.0255 (7)
C14	0.8347 (3)	0.3501 (2)	0.9576 (2)	0.0263 (7)
H14A	0.8927	0.3267	0.9139	0.032*
C15	0.7838 (3)	0.4499 (2)	0.9307 (2)	0.0261 (7)
C16	0.7011 (3)	0.4862 (2)	0.9972 (2)	0.0274 (7)
H16A	0.6671	0.5535	0.9789	0.033*
C17	0.6688 (3)	0.4234 (2)	1.0903 (2)	0.0241 (7)
C18	0.7168 (3)	0.3212 (2)	1.1157 (2)	0.0249 (7)
H18A	0.6930	0.2774	1.1774	0.030*
C19	0.7395 (4)	−0.1154 (3)	0.9906 (3)	0.0559 (11)
H19A	0.7990	−0.1296	0.9421	0.067*
C20	0.5644 (6)	−0.2077 (5)	0.9397 (5)	0.116 (2)
H20A	0.6388	−0.2159	0.8942	0.139*
H20B	0.4923	−0.1710	0.9064	0.139*
H20C	0.5303	−0.2757	0.9794	0.139*
C21	0.5122 (5)	−0.1282 (4)	1.0712 (4)	0.098 (2)
H21A	0.5550	−0.0888	1.1061	0.117*
H21B	0.4759	−0.1939	1.1144	0.117*
H21C	0.4392	−0.0888	1.0412	0.117*
C22	0.5480 (4)	0.8594 (3)	0.6588 (3)	0.0552 (11)
H22	0.4695	0.8301	0.6456	0.066*
C23	0.6581 (6)	1.0127 (4)	0.6741 (5)	0.114 (2)
H23A	0.7306	0.9646	0.6903	0.137*
H23B	0.6298	1.0402	0.7267	0.137*
H23C	0.6903	1.0695	0.6185	0.137*
C24	0.4228 (6)	1.0195 (5)	0.6292 (5)	0.127 (3)
H24A	0.3539	0.9750	0.6180	0.153*
H24B	0.4468	1.0768	0.5724	0.153*
H24C	0.3879	1.0467	0.6809	0.153*
C25	0.8121 (5)	0.2499 (4)	0.3601 (4)	0.0607 (12)
H25A	0.7995	0.3129	0.3142	0.073*
C26	1.0185 (5)	0.2309 (4)	0.2581 (3)	0.0760 (14)
H26A	0.9883	0.2951	0.2171	0.091*
H26B	1.0241	0.1780	0.2251	0.091*
H26C	1.1071	0.2427	0.2752	0.091*
C27	0.9503 (5)	0.0999 (4)	0.4130 (4)	0.0749 (14)
H27A	0.8797	0.0847	0.4664	0.090*
H27B	1.0372	0.1073	0.4346	0.090*
H27C	0.9533	0.0435	0.3842	0.090*
C28	0.6549 (5)	0.7381 (3)	0.2937 (3)	0.0561 (11)
H28	0.6772	0.7976	0.2421	0.067*
C29	0.8230 (5)	0.6526 (4)	0.2122 (4)	0.0839 (17)
H29A	0.8311	0.7212	0.1666	0.101*
H29B	0.7959	0.6020	0.1819	0.101*
H29C	0.9097	0.6342	0.2355	0.101*
C30	0.6934 (5)	0.5587 (4)	0.3695 (4)	0.0809 (16)
H30A	0.6237	0.5713	0.4161	0.097*
H30B	0.7757	0.5383	0.3986	0.097*
H30C	0.6625	0.5034	0.3461	0.097*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0340 (4)	0.0230 (4)	0.0199 (3)	0.0078 (3)	0.0035 (3)	−0.0028 (3)
Mn2	0.0318 (3)	0.0259 (3)	0.0237 (3)	0.0107 (2)	0.0054 (2)	0.0004 (2)
O1	0.0471 (14)	0.0431 (14)	0.0181 (11)	0.0165 (12)	0.0016 (10)	0.0054 (10)
O2	0.0545 (16)	0.0367 (14)	0.0310 (13)	0.0262 (12)	0.0112 (12)	0.0059 (11)
O3	0.0433 (14)	0.0298 (13)	0.0285 (12)	0.0131 (11)	0.0158 (11)	−0.0034 (10)
O4	0.0436 (14)	0.0260 (12)	0.0286 (12)	0.0148 (11)	0.0033 (10)	−0.0020 (10)
O5	0.0352 (13)	0.0341 (13)	0.0299 (12)	0.0105 (11)	0.0121 (10)	0.0019 (10)
O6	0.0400 (14)	0.0389 (14)	0.0187 (11)	0.0138 (11)	0.0079 (10)	0.0062 (10)
O7	0.0531 (15)	0.0250 (13)	0.0356 (13)	0.0154 (11)	0.0092 (12)	−0.0051 (10)
O8	0.0528 (16)	0.0280 (13)	0.0353 (13)	0.0196 (12)	0.0081 (12)	0.0069 (11)
O9	0.0427 (14)	0.0458 (15)	0.0214 (11)	0.0187 (12)	0.0107 (10)	0.0024 (11)
O10	0.0445 (14)	0.0304 (13)	0.0230 (12)	0.0138 (11)	−0.0003 (10)	0.0028 (10)
O11	0.0420 (14)	0.0272 (13)	0.0334 (13)	0.0096 (11)	0.0120 (11)	−0.0061 (10)
O12	0.0383 (13)	0.0415 (14)	0.0226 (12)	0.0127 (11)	0.0104 (10)	−0.0009 (11)
O13	0.0425 (15)	0.0472 (16)	0.0432 (15)	−0.0054 (12)	0.0042 (12)	−0.0125 (13)
O14	0.0489 (16)	0.0382 (15)	0.0610 (17)	0.0145 (13)	−0.0058 (13)	−0.0146 (13)
O15	0.059 (2)	0.100 (3)	0.083 (2)	0.029 (2)	−0.0168 (19)	−0.037 (2)
O16	0.106 (3)	0.063 (2)	0.0425 (16)	0.0293 (19)	0.0030 (17)	−0.0113 (15)
O17	0.0462 (15)	0.0636 (18)	0.0297 (13)	0.0191 (13)	−0.0018 (11)	−0.0045 (12)
N1	0.048 (2)	0.051 (2)	0.091 (3)	−0.0097 (18)	−0.018 (2)	0.001 (2)
N2	0.063 (2)	0.0298 (18)	0.093 (3)	0.0087 (17)	0.012 (2)	−0.0193 (19)
N3	0.050 (2)	0.059 (2)	0.061 (2)	0.0103 (18)	−0.0139 (18)	−0.0199 (19)
N4	0.050 (2)	0.049 (2)	0.062 (2)	0.0134 (17)	−0.0142 (17)	−0.0202 (18)
C1	0.0355 (18)	0.0255 (17)	0.0224 (16)	0.0061 (14)	−0.0014 (14)	−0.0039 (14)
C2	0.0293 (17)	0.0297 (18)	0.0245 (16)	0.0071 (14)	0.0000 (14)	−0.0083 (14)
C3	0.0346 (18)	0.0228 (16)	0.0219 (16)	0.0029 (14)	0.0041 (14)	−0.0032 (13)
C4	0.0301 (16)	0.0206 (16)	0.0205 (15)	0.0041 (13)	0.0000 (13)	−0.0020 (13)
C5	0.0311 (17)	0.0238 (16)	0.0178 (15)	0.0033 (13)	0.0024 (13)	−0.0042 (13)
C6	0.0261 (16)	0.0250 (16)	0.0213 (15)	0.0053 (13)	0.0038 (13)	−0.0059 (13)
C7	0.0312 (17)	0.0241 (16)	0.0206 (15)	0.0079 (14)	−0.0011 (13)	−0.0006 (13)
C8	0.0284 (16)	0.0267 (17)	0.0170 (15)	0.0047 (13)	0.0026 (13)	−0.0048 (13)
C9	0.0295 (17)	0.0245 (16)	0.0211 (15)	0.0082 (13)	0.0005 (13)	−0.0055 (13)
C10	0.0335 (18)	0.0233 (17)	0.0232 (16)	0.0077 (14)	−0.0033 (14)	−0.0021 (14)
C11	0.0358 (18)	0.0261 (17)	0.0216 (16)	0.0066 (15)	0.0011 (14)	−0.0013 (14)
C12	0.0258 (16)	0.0291 (18)	0.0240 (16)	0.0019 (14)	0.0036 (13)	−0.0058 (14)
C13	0.0294 (17)	0.0233 (16)	0.0221 (16)	0.0086 (13)	−0.0040 (13)	−0.0035 (13)
C14	0.0300 (17)	0.0287 (17)	0.0184 (15)	0.0101 (14)	0.0037 (13)	−0.0065 (13)
C15	0.0305 (17)	0.0259 (17)	0.0181 (15)	0.0093 (14)	−0.0003 (13)	−0.0012 (13)
C16	0.0304 (17)	0.0215 (16)	0.0258 (16)	0.0078 (13)	−0.0006 (14)	−0.0011 (13)
C17	0.0251 (16)	0.0260 (16)	0.0190 (15)	0.0056 (13)	0.0015 (13)	−0.0050 (13)
C18	0.0296 (16)	0.0229 (16)	0.0177 (15)	0.0032 (13)	0.0022 (13)	−0.0009 (13)
C19	0.053 (3)	0.045 (2)	0.062 (3)	0.003 (2)	−0.005 (2)	−0.005 (2)
C20	0.111 (5)	0.082 (4)	0.162 (6)	−0.023 (4)	−0.067 (5)	−0.027 (4)
C21	0.057 (3)	0.081 (4)	0.114 (5)	−0.011 (3)	0.006 (3)	0.030 (3)
C22	0.050 (2)	0.043 (2)	0.075 (3)	0.008 (2)	−0.003 (2)	−0.022 (2)
C23	0.108 (5)	0.063 (4)	0.181 (7)	−0.008 (3)	−0.005 (5)	−0.055 (4)
C24	0.102 (5)	0.064 (4)	0.218 (8)	0.044 (4)	−0.017 (5)	−0.045 (5)
C25	0.057 (3)	0.058 (3)	0.077 (3)	0.016 (2)	−0.036 (3)	−0.025 (3)
C26	0.059 (3)	0.086 (4)	0.082 (4)	−0.011 (3)	−0.011 (3)	−0.022 (3)
C27	0.076 (3)	0.065 (3)	0.086 (4)	0.027 (3)	−0.018 (3)	−0.021 (3)
C28	0.074 (3)	0.050 (3)	0.041 (2)	0.013 (2)	−0.006 (2)	−0.007 (2)
C29	0.051 (3)	0.100 (4)	0.116 (4)	0.006 (3)	0.008 (3)	−0.061 (4)
C30	0.092 (4)	0.048 (3)	0.104 (4)	0.023 (3)	−0.034 (3)	−0.014 (3)

Geometric parameters (Å, º) top

Mn1—O1ⁱ	2.156 (2)	C3—C8	1.496 (4)
Mn1—O1	2.156 (2)	C4—C5	1.388 (4)
Mn1—O7ⁱ	2.159 (2)	C4—C9	1.390 (4)
Mn1—O7	2.159 (2)	C5—C6	1.388 (4)
Mn1—O13ⁱ	2.204 (3)	C5—H5A	0.9300
Mn1—O13	2.204 (3)	C6—C7	1.392 (4)
Mn2—O12ⁱⁱ	2.146 (2)	C7—C8	1.389 (4)
Mn2—O17	2.146 (3)	C7—H7A	0.9300
Mn2—O5ⁱⁱⁱ	2.154 (2)	C8—C9	1.383 (4)
Mn2—O10	2.191 (2)	C9—H9A	0.9300
Mn2—O4ⁱ	2.199 (2)	C10—C13	1.496 (4)
Mn2—O14	2.213 (3)	C11—C15	1.509 (4)
O1—C1	1.239 (3)	C12—C17	1.504 (4)
O2—C1	1.274 (4)	C13—C18	1.383 (4)
O3—C2	1.290 (4)	C13—C14	1.394 (4)
O3—H3	0.8200	C14—C15	1.380 (4)
O4—C2	1.231 (4)	C14—H14A	0.9300
O4—Mn2ⁱ	2.199 (2)	C15—C16	1.390 (4)
O5—C3	1.233 (4)	C16—C17	1.382 (4)
O5—Mn2^iv	2.154 (2)	C16—H16A	0.9300
O6—C3	1.283 (4)	C17—C18	1.396 (4)
O6—H6	0.8200	C18—H18A	0.9300
O7—C10	1.236 (4)	C19—H19A	0.9300
O8—C10	1.278 (4)	C20—H20A	0.9600
O8—H8	0.8200	C20—H20B	0.9600
O9—C11	1.273 (4)	C20—H20C	0.9600
O10—C11	1.238 (4)	C21—H21A	0.9600
O11—C12	1.261 (4)	C21—H21B	0.9600
O12—C12	1.247 (4)	C21—H21C	0.9600
O12—Mn2ⁱⁱ	2.146 (2)	C22—H22	0.9300
O13—C19	1.234 (5)	C23—H23A	0.9600
O14—C22	1.210 (4)	C23—H23B	0.9600
O15—C25	1.215 (5)	C23—H23C	0.9600
O16—C28	1.226 (5)	C24—H24A	0.9600
O17—H1W	0.8500	C24—H24B	0.9600
O17—H2W	0.8500	C24—H24C	0.9600
N1—C19	1.304 (5)	C25—H25A	0.9300
N1—C21	1.446 (6)	C26—H26A	0.9600
N1—C20	1.448 (6)	C26—H26B	0.9600
N2—C22	1.304 (5)	C26—H26C	0.9600
N2—C23	1.434 (6)	C27—H27A	0.9600
N2—C24	1.459 (6)	C27—H27B	0.9600
N3—C25	1.330 (5)	C27—H27C	0.9600
N3—C27	1.432 (5)	C28—H28	0.9300
N3—C26	1.448 (5)	C29—H29A	0.9600
N4—C28	1.308 (5)	C29—H29B	0.9600
N4—C30	1.438 (5)	C29—H29C	0.9600
N4—C29	1.446 (5)	C30—H30A	0.9600
C1—C4	1.496 (4)	C30—H30B	0.9600
C2—C6	1.500 (4)	C30—H30C	0.9600

O1ⁱ—Mn1—O1	180.00 (5)	O8—C10—C13	115.1 (3)
O1ⁱ—Mn1—O7ⁱ	93.27 (9)	O10—C11—O9	125.0 (3)
O1—Mn1—O7ⁱ	86.73 (9)	O10—C11—C15	119.5 (3)
O1ⁱ—Mn1—O7	86.73 (9)	O9—C11—C15	115.5 (3)
O1—Mn1—O7	93.27 (9)	O12—C12—O11	125.8 (3)
O7ⁱ—Mn1—O7	180.00 (11)	O12—C12—C17	117.5 (3)
O1ⁱ—Mn1—O13ⁱ	94.50 (10)	O11—C12—C17	116.7 (3)
O1—Mn1—O13ⁱ	85.50 (10)	C18—C13—C14	119.3 (3)
O7ⁱ—Mn1—O13ⁱ	92.31 (10)	C18—C13—C10	120.6 (3)
O7—Mn1—O13ⁱ	87.69 (10)	C14—C13—C10	120.1 (3)
O1ⁱ—Mn1—O13	85.50 (10)	C15—C14—C13	120.2 (3)
O1—Mn1—O13	94.50 (10)	C15—C14—H14A	119.9
O7ⁱ—Mn1—O13	87.69 (10)	C13—C14—H14A	119.9
O7—Mn1—O13	92.31 (10)	C14—C15—C16	119.8 (3)
O13ⁱ—Mn1—O13	180.0	C14—C15—C11	120.4 (3)
O12ⁱⁱ—Mn2—O17	85.30 (9)	C16—C15—C11	119.7 (3)
O12ⁱⁱ—Mn2—O5ⁱⁱⁱ	175.24 (9)	C17—C16—C15	120.8 (3)
O17—Mn2—O5ⁱⁱⁱ	91.68 (9)	C17—C16—H16A	119.6
O12ⁱⁱ—Mn2—O10	84.37 (9)	C15—C16—H16A	119.6
O17—Mn2—O10	169.63 (9)	C16—C17—C18	118.8 (3)
O5ⁱⁱⁱ—Mn2—O10	98.57 (9)	C16—C17—C12	121.6 (3)
O12ⁱⁱ—Mn2—O4ⁱ	97.58 (9)	C18—C17—C12	119.6 (3)
O17—Mn2—O4ⁱ	91.90 (10)	C13—C18—C17	121.0 (3)
O5ⁱⁱⁱ—Mn2—O4ⁱ	86.18 (9)	C13—C18—H18A	119.5
O10—Mn2—O4ⁱ	90.35 (9)	C17—C18—H18A	119.5
O12ⁱⁱ—Mn2—O14	90.70 (10)	O13—C19—N1	127.2 (4)
O17—Mn2—O14	91.98 (10)	O13—C19—H19A	116.4
O5ⁱⁱⁱ—Mn2—O14	85.72 (10)	N1—C19—H19A	116.4
O10—Mn2—O14	87.24 (10)	N1—C20—H20A	109.5
O4ⁱ—Mn2—O14	171.11 (9)	N1—C20—H20B	109.5
C1—O1—Mn1	134.2 (2)	H20A—C20—H20B	109.5
C2—O3—H3	109.5	N1—C20—H20C	109.5
C2—O4—Mn2ⁱ	135.3 (2)	H20A—C20—H20C	109.5
C3—O5—Mn2^iv	136.4 (2)	H20B—C20—H20C	109.5
C3—O6—H6	109.5	N1—C21—H21A	109.5
C10—O7—Mn1	135.3 (2)	N1—C21—H21B	109.5
C10—O8—H8	109.5	H21A—C21—H21B	109.5
C11—O10—Mn2	130.3 (2)	N1—C21—H21C	109.5
C12—O12—Mn2ⁱⁱ	131.1 (2)	H21A—C21—H21C	109.5
C19—O13—Mn1	120.7 (3)	H21B—C21—H21C	109.5
C22—O14—Mn2	122.6 (3)	O14—C22—N2	127.6 (4)
Mn2—O17—H1W	122.8	O14—C22—H22	116.2
Mn2—O17—H2W	132.6	N2—C22—H22	116.2
H1W—O17—H2W	104.2	N2—C23—H23A	109.5
C19—N1—C21	120.3 (4)	N2—C23—H23B	109.5
C19—N1—C20	123.2 (5)	H23A—C23—H23B	109.5
C21—N1—C20	116.5 (4)	N2—C23—H23C	109.5
C22—N2—C23	121.5 (4)	H23A—C23—H23C	109.5
C22—N2—C24	121.2 (4)	H23B—C23—H23C	109.5
C23—N2—C24	117.3 (4)	N2—C24—H24A	109.5
C25—N3—C27	120.5 (4)	N2—C24—H24B	109.5
C25—N3—C26	122.5 (4)	H24A—C24—H24B	109.5
C27—N3—C26	116.9 (4)	N2—C24—H24C	109.5
C28—N4—C30	119.5 (4)	H24A—C24—H24C	109.5
C28—N4—C29	121.3 (4)	H24B—C24—H24C	109.5
C30—N4—C29	119.2 (4)	O15—C25—N3	125.2 (5)
O1—C1—O2	124.2 (3)	O15—C25—H25A	117.4
O1—C1—C4	119.2 (3)	N3—C25—H25A	117.4
O2—C1—C4	116.6 (3)	N3—C26—H26A	109.5
O4—C2—O3	125.1 (3)	N3—C26—H26B	109.5
O4—C2—C6	120.1 (3)	H26A—C26—H26B	109.5
O3—C2—C6	114.8 (3)	N3—C26—H26C	109.5
O5—C3—O6	125.7 (3)	H26A—C26—H26C	109.5
O5—C3—C8	119.5 (3)	H26B—C26—H26C	109.5
O6—C3—C8	114.8 (3)	N3—C27—H27A	109.5
C5—C4—C9	119.4 (3)	N3—C27—H27B	109.5
C5—C4—C1	119.6 (3)	H27A—C27—H27B	109.5
C9—C4—C1	120.8 (3)	N3—C27—H27C	109.5
C4—C5—C6	120.8 (3)	H27A—C27—H27C	109.5
C4—C5—H5A	119.6	H27B—C27—H27C	109.5
C6—C5—H5A	119.6	O16—C28—N4	127.1 (4)
C5—C6—C7	119.0 (3)	O16—C28—H28	116.5
C5—C6—C2	121.8 (3)	N4—C28—H28	116.5
C7—C6—C2	118.9 (3)	N4—C29—H29A	109.5
C8—C7—C6	120.7 (3)	N4—C29—H29B	109.5
C8—C7—H7A	119.6	H29A—C29—H29B	109.5
C6—C7—H7A	119.6	N4—C29—H29C	109.5
C9—C8—C7	119.5 (3)	H29A—C29—H29C	109.5
C9—C8—C3	119.5 (3)	H29B—C29—H29C	109.5
C7—C8—C3	120.9 (3)	N4—C30—H30A	109.5
C8—C9—C4	120.6 (3)	N4—C30—H30B	109.5
C8—C9—H9A	119.7	H30A—C30—H30B	109.5
C4—C9—H9A	119.7	N4—C30—H30C	109.5
O7—C10—O8	125.4 (3)	H30A—C30—H30C	109.5
O7—C10—C13	119.5 (3)	H30B—C30—H30C	109.5

O1ⁱ—Mn1—O1—C1	−5 (100)	O6—C3—C8—C9	−172.0 (3)
O7ⁱ—Mn1—O1—C1	−109.8 (3)	O5—C3—C8—C7	−169.0 (3)
O7—Mn1—O1—C1	70.2 (3)	O6—C3—C8—C7	10.8 (5)
O13ⁱ—Mn1—O1—C1	157.6 (3)	C7—C8—C9—C4	−2.0 (5)
O13—Mn1—O1—C1	−22.4 (3)	C3—C8—C9—C4	−179.3 (3)
O1ⁱ—Mn1—O7—C10	116.8 (3)	C5—C4—C9—C8	2.2 (5)
O1—Mn1—O7—C10	−63.2 (3)	C1—C4—C9—C8	178.0 (3)
O7ⁱ—Mn1—O7—C10	49 (100)	Mn1—O7—C10—O8	24.4 (5)
O13ⁱ—Mn1—O7—C10	−148.6 (3)	Mn1—O7—C10—C13	−156.3 (2)
O13—Mn1—O7—C10	31.4 (3)	Mn2—O10—C11—O9	42.7 (5)
O12ⁱⁱ—Mn2—O10—C11	117.4 (3)	Mn2—O10—C11—C15	−136.3 (3)
O17—Mn2—O10—C11	122.5 (5)	Mn2ⁱⁱ—O12—C12—O11	45.8 (5)
O5ⁱⁱⁱ—Mn2—O10—C11	−66.3 (3)	Mn2ⁱⁱ—O12—C12—C17	−135.1 (2)
O4ⁱ—Mn2—O10—C11	19.9 (3)	O7—C10—C13—C18	−169.7 (3)
O14—Mn2—O10—C11	−151.6 (3)	O8—C10—C13—C18	9.7 (5)
O1ⁱ—Mn1—O13—C19	47.3 (3)	O7—C10—C13—C14	11.2 (5)
O1—Mn1—O13—C19	−132.7 (3)	O8—C10—C13—C14	−169.4 (3)
O7ⁱ—Mn1—O13—C19	−46.2 (3)	C18—C13—C14—C15	−2.2 (5)
O7—Mn1—O13—C19	133.8 (3)	C10—C13—C14—C15	176.9 (3)
O13ⁱ—Mn1—O13—C19	76 (100)	C13—C14—C15—C16	2.3 (5)
O12ⁱⁱ—Mn2—O14—C22	−55.8 (3)	C13—C14—C15—C11	−173.6 (3)
O17—Mn2—O14—C22	29.6 (3)	O10—C11—C15—C14	158.2 (3)
O5ⁱⁱⁱ—Mn2—O14—C22	121.1 (3)	O9—C11—C15—C14	−20.9 (5)
O10—Mn2—O14—C22	−140.1 (3)	O10—C11—C15—C16	−17.7 (5)
O4ⁱ—Mn2—O14—C22	145.4 (5)	O9—C11—C15—C16	163.2 (3)
Mn1—O1—C1—O2	−37.4 (5)	C14—C15—C16—C17	−0.1 (5)
Mn1—O1—C1—C4	142.3 (3)	C11—C15—C16—C17	175.8 (3)
Mn2ⁱ—O4—C2—O3	−42.0 (5)	C15—C16—C17—C18	−2.2 (5)
Mn2ⁱ—O4—C2—C6	135.3 (3)	C15—C16—C17—C12	−179.9 (3)
Mn2^iv—O5—C3—O6	−25.9 (6)	O12—C12—C17—C16	176.9 (3)
Mn2^iv—O5—C3—C8	154.0 (2)	O11—C12—C17—C16	−3.9 (5)
O1—C1—C4—C5	−2.6 (5)	O12—C12—C17—C18	−0.8 (5)
O2—C1—C4—C5	177.0 (3)	O11—C12—C17—C18	178.4 (3)
O1—C1—C4—C9	−178.4 (3)	C14—C13—C18—C17	−0.2 (5)
O2—C1—C4—C9	1.2 (5)	C10—C13—C18—C17	−179.3 (3)
C9—C4—C5—C6	−0.7 (5)	C16—C17—C18—C13	2.3 (5)
C1—C4—C5—C6	−176.6 (3)	C12—C17—C18—C13	−179.9 (3)
C4—C5—C6—C7	−0.9 (5)	Mn1—O13—C19—N1	−171.1 (3)
C4—C5—C6—C2	172.7 (3)	C21—N1—C19—O13	0.9 (7)
O4—C2—C6—C5	−166.6 (3)	C20—N1—C19—O13	−177.4 (5)
O3—C2—C6—C5	11.0 (5)	Mn2—O14—C22—N2	−171.6 (3)
O4—C2—C6—C7	7.1 (5)	C23—N2—C22—O14	−0.8 (8)
O3—C2—C6—C7	−175.4 (3)	C24—N2—C22—O14	179.8 (5)
C5—C6—C7—C8	1.1 (5)	C27—N3—C25—O15	−2.2 (7)
C2—C6—C7—C8	−172.8 (3)	C26—N3—C25—O15	179.2 (4)
C6—C7—C8—C9	0.4 (5)	C30—N4—C28—O16	−1.1 (7)
C6—C7—C8—C3	177.6 (3)	C29—N4—C28—O16	−179.9 (4)
O5—C3—C8—C9	8.2 (5)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O8—H8···O2	0.82	1.67	2.448 (3)	157
O17—H2W···O16	0.85	1.85	2.694 (4)	176
O6—H6···O9^iv	0.82	1.69	2.452 (3)	153
O3—H3···O11^v	0.82	1.69	2.463 (3)	157
O17—H1W···O15^vi	0.85	1.92	2.713 (4)	155

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

Experimental details

Crystal data
Chemical formula	[Mn₃(C₉H₄O₆)₂(C₉H₅O₆)₂(C₃H₇NO)₄(H₂O)₂]·4C₃H₇NO
M_r	1620.12
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	9.826 (2), 13.290 (3), 14.698 (3)
α, β, γ (°)	73.22 (3), 83.32 (3), 89.79 (3)
V (Å³)	1824.2 (6)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.61
Crystal size (mm)	0.19 × 0.15 × 0.13

Data collection
Diffractometer	Rigaku Saturn CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2004)
T_min, T_max	0.894, 0.925
No. of measured, independent and observed [I > 2σ(I)] reflections	18985, 6589, 5527
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.116, 1.13
No. of reflections	6589
No. of parameters	478
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.33

Computer programs: CrystalClear (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O8—H8···O2	0.82	1.67	2.448 (3)	156.6
O17—H2W···O16	0.85	1.85	2.694 (4)	175.8
O6—H6···O9ⁱ	0.82	1.69	2.452 (3)	153.0
O3—H3···O11ⁱⁱ	0.82	1.69	2.463 (3)	156.8
O17—H1W···O15ⁱⁱⁱ	0.85	1.92	2.713 (4)	154.6

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

Acknowledgements

The study was supported by the Science and Technology Department of Henan Province (082102330003).

References

Hu, J.-S., Huang, L.-F., Yao, X.-Q., Qin, L., Li, Y.-Z., Guo, Z.-J., Zheng, H.-G. & Xue, Z.-L. (2011). Inorg. Chem. 50, 2404–2414. Web of Science CSD CrossRef CAS PubMed Google Scholar
Prajapati, R., Mishra, L., Kimura, K. & Raghavaiah, P. (2009). Polyhedron, 28, 600–608. Web of Science CSD CrossRef CAS Google Scholar
Rigaku/MSC (2004). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.