Poly[[hexa­aqua­bis(μ₃-trans-propene-1,2,3-tricarboxyl­ato)trimanganese(II)] 0.2-hydrate]

The title compound, {[Mn₃(C₆H₃O₆)₂(H₂O)₆]·0.2H₂O}_n, contains a three-dimensional open framework formed by each organic ligand μ₃-bridging three six-coordinated Mn^II atoms (one of which resides on a twofold crystallographic axis). Uncoordinated water mol­ecules are located in the channels of the framework along the c-axis direction. The primary O—H...O inter­molecular inter­actions have O...O distances ranging from 2.680 (4) to 3.020 (13) Å and O—H...O angles ranging from 125 (4) to 179 (4)°.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.006 Å
• Disorder in solvent or counterion
• R factor = 0.052
• wR factor = 0.076
• Data-to-parameter ratio = 10.8

checkCIF/PLATON results

No syntax errors found





Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.62
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      20.00 Perc.

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.619
            Tmax scaled      0.619 Tmin scaled      0.537
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          8

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   4 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

trans-Propene-1,2,3-tricarboxylic acid (trans-aconitic acid, H₃L) is a weak competitive inhibitor of the action of aconitase in the famous Krebs cycle (Thomson et al., 1966). Villagranca et al. detected an aconitase-manganous trans-aconitate complex by nuclear magnetic resonance (NMR) studies in 1972 (Villafranca & Mildvan, 1972), after which Dargay et al. reported the crystal structure of potassium dihydrogen trans-aconitate KH₂L and assumed that the active positions of L^3- ions in the aconitase-manganous trans-aconitate complex was the same as those in KH₂L (Dargay et al., 1972). We deem that it is helpful to understand the active mechanism by the direct synthesis and structural characterization of a Mn(II) complex of the L^3- ligand. Herein, we report the synthesis and crystal structure of Mn₃L₂(H₂O)₆.0.2H₂O (I, Scheme 1).

As shown in Fig. 1, the crystallographically independent unit of (I) consists of one L^3- ligand, 1.5 Mn^II atoms as well as three coordinated water molecules. The Mn1 and Mn2 atoms are in special and general positions, respectively. The coordination geometry of Mn1 atom is characteristic of a triangular prism, in which O1, O2 and O5 atoms comprise the base planes. The Mn2 atom locates in a slightly distorted octahedral environment, in which three water molecules are arranged in a mer- fashion. The mean Mn2—O bond distance of 2.178 (3) Å is 0.080 (3) Å shorter than that of Mn1—O bonds. The L^3- ligand is four coordinated by two Mn1 and two Mn2 atoms. The three carboxylate groups of L^3- ligand show two kinds of coordination modes: one is µ2-syn,trans- for carboxylate groups with C4 and C5 atoms and the other µ2-syn,syn- for the third carboxylate group. Additionally, the 1- and 3-carboxylate groups of L^3- ligand form an 8-membered ring. In our previous work, we have found 8 kinds of coordination modes for L^3- ligand (Wang et al., 2004; Wang et al., 2005). The coordination modes of L^3- ligand in present example differs from those previously found by our group, and represents a new type. The C1—C2 vinyl bond has a bond distance of 1.313 (5) Å, which is similar to the reported values by our group.

Fig. 2a depicts the 3-D metal-organic framework of (I) viewed along the b axis direction. This framework can be simplified as a (3,4)-connect network by treating the C2, C4 and C5 atoms in L^3- ligand as well as Mn2 atoms as 3-connected nodes while Mn1 atoms as 4-connected nodes. The resulting (3,4)-connected network has a short vertex symbol of (4.6.8)₂(4.10.12)₂(6².10².14²). Fig. 2 b shows a perspective view of the crystal structure of 1 along the c direction, which reveals an open metal-organic framework with channels hosting lattice water molecules. The O—H···O hydrogen bonds presented in the crystal structure are listed (Table 1). The O—H···O hydrogen bonds in the framework have O···O distances falling in the range of 2.680 (4)–2.921 (4) Å, which are shorter than those of host–guest hydrogen bonds (O4W—H···O3w, 3.02 (1) Å).

Related literature

For related literature, see: Dargay et al. (1972); Thomson et al. (1966); Villafranca & Mildvan (1972); Wang et al. (2004, 2005).

S2. Experimental

A mixture of H₃L (174 mg, 1 mmol) and Na₂CO₃ (159 mg, 1.5 mmol) was added into 8 ml water and reacted until no air bubbles appeared, after which MnCl₂.4H₂O (297 mg, 1.5 mmol) and pyridine (0.08 ml, 1 mmol) were added and let them react for further several minutes. Pale-yellow prismatic crystals of (I) suitable for single-crystal X-ray diffraction analysis were obtained by evaporation of the final solution under ambient environment.

S3. Refinement

Water H atoms were located in a difference Fourier map and refined as riding in their located positions, with U_iso(H) = 1.5Ueq(O). The DFIX commands were used to restrain the O—H bond distances of water molecules (Table 1). Other H atoms were allowed to ride on their respective parent atoms with C—H distances of 0.93 and 0.97 Å for methyne and methylene groups, respectively, and were included in the refinement with isotropic displacement parameters U_iso(H) = 1.2Ueq(C).

Computing details

Data collection: CrystalClear (Rigaku, 2002); cell refinement: CrystalClear (Rigaku, 2002); data reduction: CrystalClear (Rigaku, 2002); program(s) used to solve structure: SHELXTL (Siemens, 1994); program(s) used to refine structure: SHELXTL (Siemens, 1994); molecular graphics: SHELXTL (Siemens, 1994); software used to prepare material for publication: SHELXTL (Siemens, 1994).

Figures

	Fig. 1. ORTEP drawing with 30% probability displacement ellipsoids of the coordination environment of metal centers. Hydrogen atoms are omitted for clarity.
	Fig. 2. 3-D packing diagram viewed along the (a) b axis and (b) c axis directions. Hydrogen atoms are omitted for clarity.

Poly[[hexaaquabis(µ₃-trans-propene-1,2,3-tricarboxylato)trimanganese(II)] 0.2-hydrate]

Crystal data

[Mn3(C6H3O6)2(H2O)6]·0.2H2O	F(000) = 1244
Mr = 618.69	Dx = 2.011 Mg m^−3
Monoclinic, C2/c	Melting point: not measured K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 17.092 (7) Å	Cell parameters from 3076 reflections
b = 9.602 (2) Å	θ = 3.2–27.5°
c = 13.897 (5) Å	µ = 1.92 mm^−1
β = 116.367 (14)°	T = 293 K
V = 2043.4 (12) Å^3	Prism, pale yellow
Z = 4	0.4 × 0.26 × 0.25 mm

Data collection

Rigaku Mercury CCD diffractometer	1896 independent reflections
Radiation source: rotating-anode generator	1698 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
ω scans	θmax = 25.5°, θmin = 3.2°
Absorption correction: multi-scan (SPHERE in CrystalClear; Rigaku, 2002)	h = −15→20
Tmin = 0.868, Tmax = 1.000	k = −11→11
6731 measured reflections	l = −16→16

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.076	H atoms treated by a mixture of independent and constrained refinement
S = 1.25	w = 1/[σ^2(Fo^2) + (0.008P)^2 + 2.8742P] where P = (Fo^2 + 2Fc^2)/3
1896 reflections	(Δ/σ)max < 0.001
176 parameters	Δρmax = 0.38 e Å^−3
8 restraints	Δρmin = −0.42 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Mn1	0.5000	0.49519 (8)	0.7500	0.0217 (2)
Mn2	0.26523 (4)	0.24539 (6)	0.20029 (4)	0.01995 (18)
O1	0.50955 (18)	0.3760 (3)	0.6094 (2)	0.0342 (7)
O2	0.39711 (18)	0.3454 (3)	0.6427 (2)	0.0308 (7)
O3	0.2886 (2)	0.0620 (3)	0.2988 (2)	0.0360 (8)
O4	0.27903 (17)	−0.0846 (2)	0.41617 (19)	0.0258 (7)
O5	0.53149 (17)	0.3356 (3)	0.3676 (2)	0.0269 (7)
O6	0.38878 (16)	0.3483 (3)	0.30525 (19)	0.0246 (7)
O1W	0.1846 (2)	0.3148 (3)	0.2723 (3)	0.0501 (9)
H1	0.173 (3)	0.4081 (16)	0.273 (4)	0.075*
H2	0.155 (3)	0.264 (4)	0.303 (3)	0.075*
O2W	0.16551 (17)	0.1042 (3)	0.0844 (2)	0.0344 (8)
H3	0.131 (2)	0.058 (4)	0.109 (3)	0.052*
H4	0.1220 (17)	0.115 (4)	0.0161 (13)	0.052*
O3W	0.34376 (18)	0.1518 (3)	0.1290 (2)	0.0306 (7)
H5	0.386 (2)	0.213 (3)	0.130 (3)	0.046*
H6	0.314 (2)	0.120 (4)	0.0594 (14)	0.046*
C1	0.3347 (3)	0.1398 (4)	0.4788 (3)	0.0244 (9)
H1A	0.3044	0.1593	0.5186	0.029*
C2	0.4077 (3)	0.2074 (4)	0.5017 (3)	0.0235 (9)
C3	0.4660 (3)	0.1831 (4)	0.4463 (3)	0.0214 (9)
H3A	0.5260	0.1745	0.5008	0.026*
H3B	0.4497	0.0955	0.4077	0.026*
C4	0.4613 (3)	0.2976 (4)	0.3683 (3)	0.0181 (9)
C5	0.2982 (3)	0.0326 (4)	0.3917 (3)	0.0234 (9)
C6	0.4398 (3)	0.3152 (4)	0.5901 (3)	0.0221 (9)
O4W	0.5000	−0.033 (2)	0.2500	0.060 (8)	0.20
H7	0.447 (8)	0.01 (2)	0.22 (2)	0.090*	0.20

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0305 (5)	0.0170 (4)	0.0140 (4)	0.000	0.0068 (4)	0.000
Mn2	0.0234 (3)	0.0187 (3)	0.0162 (3)	−0.0010 (3)	0.0075 (3)	0.0022 (3)
O1	0.0338 (18)	0.0360 (18)	0.0361 (17)	−0.0123 (15)	0.0184 (15)	−0.0127 (14)
O2	0.0410 (18)	0.0291 (17)	0.0315 (17)	−0.0117 (14)	0.0246 (16)	−0.0096 (13)
O3	0.068 (2)	0.0178 (15)	0.0192 (16)	−0.0086 (15)	0.0172 (16)	−0.0011 (12)
O4	0.0398 (18)	0.0149 (14)	0.0187 (15)	−0.0076 (13)	0.0095 (14)	0.0001 (12)
O5	0.0249 (16)	0.0294 (16)	0.0327 (16)	0.0038 (13)	0.0184 (14)	0.0082 (13)
O6	0.0226 (16)	0.0228 (15)	0.0184 (14)	0.0004 (12)	0.0002 (13)	0.0020 (12)
O1W	0.082 (3)	0.0256 (18)	0.077 (2)	−0.0053 (19)	0.066 (2)	−0.0007 (18)
O2W	0.0234 (17)	0.050 (2)	0.0237 (16)	−0.0148 (15)	0.0053 (14)	−0.0003 (15)
O3W	0.0298 (18)	0.0356 (18)	0.0264 (16)	−0.0067 (14)	0.0123 (15)	−0.0121 (14)
C1	0.035 (3)	0.017 (2)	0.021 (2)	−0.0002 (19)	0.013 (2)	0.0011 (17)
C2	0.030 (2)	0.017 (2)	0.018 (2)	0.0010 (18)	0.0056 (19)	0.0043 (17)
C3	0.027 (2)	0.018 (2)	0.020 (2)	0.0072 (18)	0.0104 (19)	0.0047 (17)
C4	0.027 (2)	0.013 (2)	0.015 (2)	0.0014 (17)	0.0096 (19)	−0.0040 (16)
C5	0.030 (2)	0.019 (2)	0.018 (2)	−0.0017 (18)	0.0071 (19)	−0.0005 (18)
C6	0.029 (2)	0.016 (2)	0.017 (2)	−0.0005 (18)	0.005 (2)	0.0014 (17)
O4W	0.08 (2)	0.023 (13)	0.042 (15)	0.000	−0.008 (15)	0.000

Geometric parameters (Å, º)

Mn1—O5^i	2.195 (3)	O5—C4	1.259 (4)
Mn1—O5^ii	2.195 (3)	O5—Mn1^ii	2.195 (3)
Mn1—O2	2.248 (3)	O6—C4	1.255 (4)
Mn1—O2^iii	2.248 (3)	O1W—H1	0.919 (19)
Mn1—O1	2.332 (3)	O1W—H2	0.95 (5)
Mn1—O1^iii	2.332 (3)	O2W—H3	0.92 (4)
Mn1—C6	2.636 (4)	O2W—H4	0.915 (19)
Mn1—C6^iii	2.636 (4)	O3W—H5	0.93 (4)
Mn2—O1W	2.137 (3)	O3W—H6	0.92 (1)
Mn2—O3	2.156 (3)	C1—C2	1.313 (5)
Mn2—O4^iv	2.183 (2)	C1—C5	1.498 (5)
Mn2—O3W	2.184 (3)	C1—H1A	0.9300
Mn2—O6	2.197 (3)	C2—C6	1.511 (5)
Mn2—O2W	2.213 (3)	C2—C3	1.524 (5)
O1—C6	1.246 (4)	C3—C4	1.521 (5)
O2—C6	1.274 (4)	C3—H3A	0.9700
O3—C5	1.259 (4)	C3—H3B	0.9700
O4—C5	1.260 (4)	O4W—H7	0.928 (11)
O4—Mn2^v	2.183 (2)
O5^i—Mn1—O5^ii	84.49 (14)	O3W—Mn2—O2W	81.25 (11)
O5^i—Mn1—O2	145.92 (10)	O6—Mn2—O2W	163.96 (11)
O5^ii—Mn1—O2	96.82 (10)	C6—O1—Mn1	89.6 (2)
O5^i—Mn1—O2^iii	96.82 (10)	C6—O2—Mn1	92.7 (2)
O5^ii—Mn1—O2^iii	145.91 (10)	C5—O3—Mn2	137.5 (2)
O2—Mn1—O2^iii	100.48 (15)	C5—O4—Mn2^v	120.9 (2)
O5^i—Mn1—O1	154.37 (10)	C4—O5—Mn1^ii	107.5 (2)
O5^ii—Mn1—O1	79.91 (10)	C4—O6—Mn2	130.5 (2)
O2—Mn1—O1	57.01 (10)	Mn2—O1W—H1	120 (3)
O2^iii—Mn1—O1	85.24 (10)	Mn2—O1W—H2	130 (3)
O5^i—Mn1—O1^iii	79.91 (10)	H1—O1W—H2	110 (4)
O5^ii—Mn1—O1^iii	154.37 (10)	Mn2—O2W—H3	117 (2)
O2—Mn1—O1^iii	85.24 (10)	Mn2—O2W—H4	134 (3)
O2^iii—Mn1—O1^iii	57.01 (10)	H3—O2W—H4	95 (3)
O1—Mn1—O1^iii	121.24 (15)	Mn2—O3W—H5	111 (3)
O5^i—Mn1—C6	170.88 (11)	Mn2—O3W—H6	116 (3)
O5^ii—Mn1—C6	89.03 (11)	H5—O3W—H6	107 (3)
O2—Mn1—C6	28.86 (10)	C2—C1—C5	123.1 (4)
O2^iii—Mn1—C6	92.15 (11)	C2—C1—H1A	118.4
O1—Mn1—C6	28.19 (10)	C5—C1—H1A	118.4
O1^iii—Mn1—C6	103.78 (11)	C1—C2—C6	119.9 (4)
O5^i—Mn1—C6^iii	89.03 (11)	C1—C2—C3	124.4 (4)
O5^ii—Mn1—C6^iii	170.88 (11)	C6—C2—C3	115.6 (3)
O2—Mn1—C6^iii	92.15 (11)	C4—C3—C2	114.1 (3)
O2^iii—Mn1—C6^iii	28.86 (10)	C4—C3—H3A	108.7
O1—Mn1—C6^iii	103.78 (11)	C2—C3—H3A	108.7
O1^iii—Mn1—C6^iii	28.19 (10)	C4—C3—H3B	108.7
C6—Mn1—C6^iii	98.09 (16)	C2—C3—H3B	108.7
O1W—Mn2—O3	86.19 (12)	H3A—C3—H3B	107.6
O1W—Mn2—O4^iv	91.76 (12)	O6—C4—O5	122.1 (3)
O3—Mn2—O4^iv	170.60 (10)	O6—C4—C3	120.1 (3)
O1W—Mn2—O3W	173.89 (11)	O5—C4—C3	117.8 (3)
O3—Mn2—O3W	88.53 (11)	O3—C5—O4	123.1 (3)
O4^iv—Mn2—O3W	92.97 (11)	O3—C5—C1	119.5 (3)
O1W—Mn2—O6	100.26 (12)	O4—C5—C1	117.4 (3)
O3—Mn2—O6	95.35 (10)	O1—C6—O2	120.5 (3)
O4^iv—Mn2—O6	94.04 (10)	O1—C6—C2	117.6 (4)
O3W—Mn2—O6	83.28 (10)	O2—C6—C2	121.9 (4)
O1W—Mn2—O2W	94.79 (13)	O1—C6—Mn1	62.2 (2)
O3—Mn2—O2W	80.06 (11)	O2—C6—Mn1	58.41 (19)
O4^iv—Mn2—O2W	90.99 (10)	C2—C6—Mn1	177.6 (3)

Symmetry codes: (i) x, −y+1, z+1/2; (ii) −x+1, −y+1, −z+1; (iii) −x+1, y, −z+3/2; (iv) −x+1/2, y+1/2, −z+1/2; (v) −x+1/2, y−1/2, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1···O3^iv	0.92 (2)	2.05 (4)	2.687 (4)	125 (4)
O1W—H2···O2^vi	0.93 (5)	1.75 (5)	2.680 (4)	176 (5)
O2W—H3···O1^vii	0.92 (4)	2.18 (3)	2.843 (4)	129 (3)
O2W—H4···O5^vii	0.92 (2)	2.01 (1)	2.921 (4)	173 (4)
O3W—H6···O4^viii	0.92 (1)	1.84 (2)	2.735 (4)	163 (4)
O3W—H5···O5^ix	0.93 (4)	1.83 (3)	2.751 (4)	179 (4)
O4W—H7···O3W	0.92 (1)	2.12 (7)	3.020 (13)	162

Symmetry codes: (iv) −x+1/2, y+1/2, −z+1/2; (vi) −x+1/2, −y+1/2, −z+1; (vii) x−1/2, −y+1/2, z−1/2; (viii) x, −y, z−1/2; (ix) −x+1, y, −z+1/2.