catena-Poly[[trans-diaqua­manganese(II)]-di-μ-3-pyrid­ylacetato]

The title manganese(II) coordination polymer, [Mn(C₇H₆NO₂)₂(H₂O)₂]_n, which was obtained from a solvothermal reaction of 3-pyridylacetic acid hydro­chloride with Mn(ClO₄)₂·6H₂O, is centrosymmetric, so pairs of equivalent ligands lie trans to each other in a slightly distorted octa­hedral geometry such that the Mn^II center is coordinated by two pyridyl N atoms [Mn—N = 2.287 (4) Å], two carboxyl­ate O atoms [Mn—O = 2.129 (3) Å] and two water mol­ecules [Mn—O = 2.179 (3) Å]. Each unit is further extended into two-dimensional sheets with a rhombic grid through sharing Mn^II ions, 3-pyridylacetate anionic ligands and intra­molecular O—H...O hydrogen bonds with angles at hydrogen of 147°. Adjacent two-dimensional layers are connected via inter­molecular O—H...O and weak C—H...O hydrogen-bonding contacts, resulting in a three-dimensional framework with oxygen as a trifurcated acceptor atom.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.008 Å
• R factor = 0.072
• wR factor = 0.138
• Data-to-parameter ratio = 12.0

checkCIF/PLATON results

No syntax errors found



Alert level B
RINTA01_ALERT_3_B  The value of Rint is greater than 0.15
            Rint given   0.170
PLAT020_ALERT_3_B The value of Rint is greater than 0.10 .........       0.17

Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.97
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          8
PLAT415_ALERT_2_C Short Inter D-H..H-X       H7     ..  H9      ..       2.13 Ang.

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Mn1         (2)       2.11

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

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

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S1. Comment

The molecule of the title complex (I), which is similar to the described for [M(Hpya)₂(H₂O)₂]_n (M = Cu, Co, Mn, Ni, Zn, Cd; Hpya = 4-pyridylacetic acid) (Li et al., 2004; Du et al.,

2006) and [M(3-pyridylacetato)₂(H₂O)₂]_n (M = Ni, Co) (Martin et al., 2007), is centrosymmetric, so pairs of equivalent ligands lie trans to each other in a slightly distorted octahedral geometry. The Mn^II center is six-coordinated by two pyridyl nitrogen atoms from two 3-pyridylacetate ligands in the axial positions, two carboxylate oxygen atoms from another two 3-pyridylacetate ligands and two oxygen atoms from two water molecules in the equatorial plane. Each 3-pyridylacetate anion uses its pyridine nitrogen atom and one carboxylate oxygen atom to connect two Mn^II ions. Four 3-pyridylacetate anionic ligands and four Mn^II ions form a tetragon with a side length of 8.763 Å and a diagonal measurement of 15.199 * 8.728 Å based on the Mn—Mn distances. The tetragon is further extended into a two-dimensional framework with a rhombic grid through sharing Mn^II ions, 3-pyridylacetate anionic ligands and intramolecular O—H···O hydrogen bonds with angles at hydrogen of 147 ° (Fig. 1).

Adjacent two-dimensional layers are connected via intermolecular O—H···O and weak C—H···O hydrogen-bonding contacts, resulting in a three-dimensional framework structure with oxygen as a trifurcated acceptor atom (Fig. 2).

Related literature

Related complexes of 4-pyridylacetate and 3-pyridylacetate have been reported (Li et al., 2004; Du et al., 2006; Martin et al., 2007).

S2. Experimental

A mixture of 3-pyridylacetic acid hydrochloride (0.0174 g, 0.1 mmol), Mn(ClO₄)₂.6H₂O(0.0181 g, 0.05 mmol), NaClO₄.6H₂O (0.0150 g, 0.07 mmol), NaOH (0.0080 g, 0.2 mmol), THF (5 ml) and water (2.5 ml) was sealed in a 25 ml Teflon-lined stainless-steel reactor and heated to 333 K for 96 h, yielding colourless crystals of (I) suitable for X-ray analysis. Elemental analysis for C₁₄H₁₆MnN₂O₆, calculated: C 46.29, H 4.44, N 7.71%; found: C 45.09, H 4.97, N 7.15%.

S3. Refinement

H atoms of the water molecules were located in a difference map. H atoms bonded to C atoms were placed at calulated positions and treated using a riding-model approximation [C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C)].

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. Principal connectivity of the coordination polymer two-dimensional structure (I), showing 50% probability displacement ellipsoids. All H atoms except H9 have been omitted for clarity. Symmetry codes: (i) 1 - x,-y,-z; (ii) 1/2 - x,y - 1/2,1/2 - z; (iii) 1/2 + x,1/2 - y,z - 1/2.
	Fig. 2. Intermolecular hydrogen bonding contacts between the two-dimensional polymer layers in ac plane. For clarity, only H5, H8 and H9 were used. Symmetry codes: (i) x - 1,2 + y,z; (ii) -x,2 - y,1 - z; (iii) -1/2 - x,1/2 + y,1/2 - z.

catena-Poly[[trans-diaquamanganese(II)]-di-µ-(3-pyridyl)acetato]

Crystal data

[Mn(C7H6NO2)2(H2O)2]	F(000) = 374
Mr = 363.23	Dx = 1.612 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1227 reflections
a = 9.260 (2) Å	θ = 2.6–28.0°
b = 8.7283 (18) Å	µ = 0.92 mm^−1
c = 9.671 (2) Å	T = 298 K
β = 106.788 (3)°	Block, colourless
V = 748.3 (3) Å^3	0.10 × 0.08 × 0.06 mm
Z = 2

Data collection

Bruker SMART CCD area-detector diffractometer	1274 independent reflections
Radiation source: fine-focus sealed tube	770 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.170
φ and ω scans	θmax = 25.0°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −10→7
Tmin = 0.914, Tmax = 0.947	k = −10→10
3717 measured reflections	l = −11→11

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)] = 0.072	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.138	H-atom parameters constrained
S = 0.99	w = 1/[σ^2(Fo^2) + (0.0532P)^2] where P = (Fo^2 + 2Fc^2)/3
1274 reflections	(Δ/σ)max < 0.001
106 parameters	Δρmax = 0.48 e Å^−3
0 restraints	Δρmin = −0.56 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
Mn1	0.5000	0.0000	0.0000	0.0273 (4)
N1	0.2917 (5)	0.0792 (5)	0.0622 (4)	0.0297 (11)
O1	0.0346 (5)	0.2775 (4)	0.4250 (4)	0.0376 (10)
O2	0.1985 (5)	0.1665 (4)	0.6121 (4)	0.0433 (11)
O3	0.6360 (4)	0.0553 (4)	0.2185 (4)	0.0375 (10)
H8	0.7067	0.0017	0.2725	0.056*
H9	0.6703	0.1460	0.2219	0.056*
C1	0.1243 (7)	0.1730 (6)	0.4810 (6)	0.0284 (13)
C2	0.1421 (8)	0.0417 (6)	0.3840 (6)	0.0387 (16)
H2A	0.2328	−0.0146	0.4328	0.046*
H2B	0.0574	−0.0275	0.3721	0.046*
C3	0.2762 (7)	0.0467 (6)	0.1934 (5)	0.0283 (14)
H3A	0.3539	−0.0058	0.2588	0.034*
C4	0.1512 (6)	0.0869 (6)	0.2364 (5)	0.0269 (13)
C5	0.0392 (7)	0.1676 (6)	0.1404 (6)	0.0341 (14)
H5	−0.0462	0.1982	0.1653	0.041*
C6	0.0546 (7)	0.2029 (6)	0.0071 (6)	0.0376 (15)
H6	−0.0205	0.2573	−0.0594	0.045*
C7	0.1825 (7)	0.1567 (6)	−0.0273 (6)	0.0347 (15)
H7	0.1918	0.1816	−0.1178	0.042*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0316 (8)	0.0291 (6)	0.0210 (6)	−0.0029 (7)	0.0074 (5)	−0.0003 (6)
N1	0.030 (3)	0.035 (2)	0.022 (2)	0.003 (3)	0.004 (2)	0.002 (2)
O1	0.053 (3)	0.028 (2)	0.027 (2)	0.009 (2)	0.005 (2)	−0.0021 (17)
O2	0.052 (3)	0.039 (2)	0.032 (2)	0.008 (2)	0.001 (2)	−0.0002 (19)
O3	0.041 (3)	0.038 (2)	0.027 (2)	−0.001 (2)	−0.0010 (18)	−0.0040 (16)
C1	0.029 (4)	0.027 (3)	0.031 (3)	−0.005 (3)	0.012 (3)	0.001 (3)
C2	0.054 (4)	0.032 (3)	0.035 (3)	0.007 (3)	0.021 (3)	0.005 (2)
C3	0.034 (4)	0.029 (3)	0.021 (3)	0.004 (3)	0.007 (3)	0.002 (2)
C4	0.033 (4)	0.025 (3)	0.021 (3)	−0.001 (3)	0.005 (3)	−0.002 (2)
C5	0.027 (4)	0.038 (3)	0.034 (3)	0.003 (3)	0.004 (3)	−0.006 (3)
C6	0.039 (4)	0.033 (3)	0.033 (3)	0.014 (3)	−0.002 (3)	0.001 (3)
C7	0.042 (4)	0.037 (3)	0.024 (3)	0.002 (3)	0.008 (3)	0.006 (3)

Geometric parameters (Å, º)

Mn1—O1^i	2.129 (3)	C1—C2	1.520 (7)
Mn1—O1^ii	2.129 (3)	C2—C4	1.507 (6)
Mn1—O3	2.179 (3)	C2—H2A	0.9700
Mn1—O3^iii	2.179 (3)	C2—H2B	0.9700
Mn1—N1^iii	2.287 (4)	C3—C4	1.383 (7)
Mn1—N1	2.287 (4)	C3—H3A	0.9300
N1—C7	1.313 (7)	C4—C5	1.370 (7)
N1—C3	1.348 (6)	C5—C6	1.372 (7)
O1—C1	1.247 (6)	C5—H5	0.9300
O1—Mn1^iv	2.129 (3)	C6—C7	1.380 (8)
O2—C1	1.257 (7)	C6—H6	0.9300
O3—H8	0.8500	C7—H7	0.9300
O3—H9	0.8500
O1^i—Mn1—O1^ii	180	O1—C1—C2	117.4 (5)
O1^i—Mn1—O3	88.47 (14)	O2—C1—C2	117.6 (5)
O1^ii—Mn1—O3	91.53 (14)	C4—C2—C1	115.7 (4)
O1^i—Mn1—O3^iii	91.53 (14)	C4—C2—H2A	108.4
O1^ii—Mn1—O3^iii	88.47 (14)	C1—C2—H2A	108.4
O3—Mn1—O3^iii	180	C4—C2—H2B	108.4
O1^i—Mn1—N1^iii	92.02 (15)	C1—C2—H2B	108.4
O1^ii—Mn1—N1^iii	87.98 (15)	H2A—C2—H2B	107.4
O3—Mn1—N1^iii	91.54 (15)	N1—C3—C4	123.8 (5)
O3^iii—Mn1—N1^iii	88.46 (15)	N1—C3—H3A	118.1
O1^i—Mn1—N1	87.98 (15)	C4—C3—H3A	118.1
O1^ii—Mn1—N1	92.02 (15)	C5—C4—C3	117.5 (5)
O3—Mn1—N1	88.46 (15)	C5—C4—C2	122.5 (5)
O3^iii—Mn1—N1	91.54 (15)	C3—C4—C2	120.0 (5)
N1^iii—Mn1—N1	180	C4—C5—C6	119.2 (5)
C7—N1—C3	117.2 (5)	C4—C5—H5	120.4
C7—N1—Mn1	122.0 (3)	C6—C5—H5	120.4
C3—N1—Mn1	120.8 (4)	C5—C6—C7	119.4 (6)
C1—O1—Mn1^iv	131.8 (3)	C5—C6—H6	120.3
Mn1—O3—H8	126.9	C7—C6—H6	120.3
Mn1—O3—H9	110.4	N1—C7—C6	122.9 (5)
H8—O3—H9	106.1	N1—C7—H7	118.6
O1—C1—O2	124.9 (5)	C6—C7—H7	118.6
O1^i—Mn1—N1—C7	−130.5 (4)	C7—N1—C3—C4	1.7 (8)
O1^ii—Mn1—N1—C7	49.5 (4)	Mn1—N1—C3—C4	−177.9 (4)
O3—Mn1—N1—C7	141.0 (4)	N1—C3—C4—C5	−1.6 (8)
O3^iii—Mn1—N1—C7	−39.0 (4)	N1—C3—C4—C2	178.3 (5)
O1^i—Mn1—N1—C3	49.1 (4)	C1—C2—C4—C5	−58.4 (7)
O1^ii—Mn1—N1—C3	−130.9 (4)	C1—C2—C4—C3	121.7 (6)
O3—Mn1—N1—C3	−39.4 (4)	C3—C4—C5—C6	0.8 (8)
O3^iii—Mn1—N1—C3	140.6 (4)	C2—C4—C5—C6	−179.1 (5)
Mn1^iv—O1—C1—O2	14.6 (8)	C4—C5—C6—C7	−0.2 (8)
Mn1^iv—O1—C1—C2	−166.9 (4)	C3—N1—C7—C6	−1.0 (8)
O1—C1—C2—C4	42.5 (7)	Mn1—N1—C7—C6	178.7 (4)
O2—C1—C2—C4	−139.0 (5)	C5—C6—C7—N1	0.3 (9)

Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) x+1/2, −y+1/2, z−1/2; (iii) −x+1, −y, −z; (iv) −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
O3—H9···O2^ii	0.85	2.01	2.763 (5)	147
O3—H8···O2^v	0.85	1.90	2.707 (5)	158
C5—H5···O2^vi	0.93	2.56	3.409 (7)	152

Symmetry codes: (ii) x+1/2, −y+1/2, z−1/2; (v) −x+1, −y, −z+1; (vi) x−1/2, −y+1/2, z−1/2.