A one-dimensional double-wavelike chain coordination polymer: catena-poly[[di­aqua­manganese(II)]-μ-(2,2′-bipyridyl-3,3′-di­carboxyl­ato-κ⁴N,N′:O,O′)]

The asymmetric unit of the title polymer, [Mn(C₁₂H₆N₂O₄)(H₂O)₂]_n, consists of an Mn^II ion, which lies on a twofold axis, one half of a 2,2′-bipyridine-3,3′-di­carboxyl­ate dianion and a coordinated water mol­ecule. The one-dimensional chains extend into two-dimensional sheets via O—H...O hydrogen-bonding interactions. The crystal packing of the two-dimensional sheets appears to be dominated by aromatic π–π interactions.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.035
• wR factor = 0.093
• Data-to-parameter ratio = 9.1

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

In recent years, the design and synthesis of new coordination polymers from transition metal ions and multidentate organic ligands have attracted great interest, owing to their intriguing molecular topologies and potential applications as functional materials (Batten et al., 1998; Hagrmann et al., 1999). The main and essential task of this domain is to make polymer structure controllable and predictable (Moulton et al., 2001). Researchers can then develop synthetic strategies to influence the arrangement of coordination polymers in the crystal (Yaghi et al., 1998; Batten et al., 2001). Before carring out further studies on more complicated systems, it is useful for researchers to initially model and investigate simple systems. Therefore, it is useful to investigate one-dimensional chain-like structures, which are the simplest topological type of coordination polymers.

In general, rigid linear multidentate ligands, such as 1,4-benzenedicarboxylic acid and 4,4'-bipyridine, can be used as a rod-like molecules to connect a metal center to construct an infinite structure. When these types of ligands coordinate to a metal ion, distortion of the ligand molecule can often occur and the ligand geometry changes. The resulting twist can make the ligand molecule behave as an efficient linker molecule when it is normally not considered one, as in the case of 2,2'-biprydine derivatives and binaphthyl compounds.

Here we present the structure of a novel one dimensional coordination polymer, [Mn(2,2'-bipryidine-3,3'-dicarboxylate)2(H₂O)]_n, (I). The asymmetric unit of the coordination polymer consists of a Mn^II ion (on a twofold axis), a half of a 2,2'-bipryidine-3,3'-dicarboxylate and a coordinated water molecule. The coordination geometry of the Mn^II ion is a distorted octahedron, in which the equatorial positions are occupied by two O atoms, O1 and O1ⁱ [symmetry code: (i) 1 − x, y, 1/2 − z], from two carboxyl groups and two N atoms, N1ⁱⁱ and N1ⁱⁱⁱ [symmetry codes: (ii) x, 1 + y, z; (iii) 1 − x, 1 + y, 1/2 − z], from 2,2'-bipyridine [Mn1—O1 = 2.157 (2) Å and Mn1—N1ⁱⁱ = 2.241 (3) Å]. The axial sites are occupied by two water molecules [O1Wⁱ—Mn—O1W = 172.52 (16)° and Mn1—O1W = 2.210 (2) Å]. Two carboxyl groups coordinate to Mn1 in monodentate mode and the two uncoordinated oxygen atoms from the carboxyl groups are located trans to each other. The 2,2'-bipyridine unit chelates the Mn ion as a bidentate ligand. In the biypyridyl ligand, the two pyridyl rings are not coplanar, but are twisted with a dihedral angle of 26.15 (1)°, and the unique carboxyl group is twisted from the pyridyl plane with a dihedral angle of 54.24 (3)°. The carboxyl groups and 2,2'-bipyridine units connect the Mn ion alternately to form a one-dimensional double-wavelike chain along the b axis direction. The three-dimensional packing arrangement of the double-wavelike chain in the lattice, is such that one chain runs in a carboxylate-Mn-biprydine-Mn-carboxylate order along the b axis directio, while another runs in a reversed order. Similar chains are connected by O—H···O hydrogen bonds with a distance of 1.97 (6)° for H1WB···O2(1/2 − x, 1/2 + y, 1/2 − z) to form extended two-dimensional sheets along the a axis direction, and a short intramolecular O—H···O hydrogen bond with a distance of 1.89 Å for H1WA···O2, controls, to some extent, the conformation of the one-dimensional chain. In the crystal lattice, the packing of the two-dimensional sheets appears to be controlled by aromatic π–π interactions between two pyridine cycles, with a centroid–centroid distance of 3.59 Å (Janiak et al., 2000).

S2. Experimental

Mn(Ac)₂·4H₂O (127.3 mg, 0.52 mmol), 2,2'-bipryidine-3,3'-dicarboxylic acid (122.8 mg, 0.50 mmol), and pyridine (0.2 ml) were dissolved in a mixture of 7 ml water and 4 ml e thanol. The mixture was placed in a Teflon-lined stainless steel vessel (25 ml). The vessel was sealed and heated at 403 K for 72 h and then cooled to room temperature. Large yellow block-shaped crystals were collected by filtration, followed by washing with water and ethanol in ca 72% yield.

S3. Refinement

H atoms were located from difference Fourier maps and refined independently with isotropic displacement parameters. The C—H distances ranged from 0.84 to 0.99A%.

Computing details

Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 2000); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. View of part of the one-dimensional polymeric chain structure of (I), with the asymmetric unit shown using open bonds. The displacement ellipsoids at the 30% probability level [symmetry codes: (i) x, 1 + y, z; (ii) 1 − x, 1 + y, 0.5 − z; (iii) 1 − x, y, 0.5 − z].
	Fig. 2. The molecular packing of (I), viewed along the b axis, showing the one-dimensional chains which are connected by hydrogen bonds to form the two-dimensional sheet structure. Dashed lines indicate the hydrogen-bonding interactions. Ellipsoids are drawn at the 30% probability level and H atoms have been omitted for clarity.

catena-poly-[[diaquamanganese(II)]-µ-(2,2'-bipyridyl-3,3'- dicarboxylato-κ⁴N,N':O,O')]

Crystal data

[Mn(C12H6N2O4)(H2O)2]	F(000) = 676
Mr = 333.16	Dx = 1.859 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 11.617 (2) Å	θ = 2.3–14.0°
b = 8.030 (2) Å	µ = 1.14 mm^−1
c = 12.961 (3) Å	T = 293 K
β = 100.17 (3)°	Block, yellow
V = 1190.1 (5) Å^3	0.40 × 0.30 × 0.30 mm
Z = 4

Data collection

Enraf-Nonius CAD-4 diffractometer	895 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.017
Graphite monochromator	θmax = 25.0°, θmin = 3.1°
ω scans	h = 0→13
Absorption correction: ψ scan (XCAD4; Harms & Wocadlo, 1995)	k = 0→9
Tmin = 0.670, Tmax = 0.710	l = −15→15
1103 measured reflections	3 standard reflections every 200 reflections
1051 independent reflections	intensity decay: 1.0%

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)] = 0.035	All H-atom parameters refined
wR(F^2) = 0.093	w = 1/[σ^2(Fo^2) + (0.0301P)^2 + 6.4486P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max < 0.001
1051 reflections	Δρmax = 0.32 e Å^−3
116 parameters	Δρmin = −0.38 e Å^−3
0 restraints

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	1.20243 (9)	0.2500	0.0200 (2)
O1W	0.3186 (2)	1.1845 (4)	0.2790 (2)	0.0319 (7)
H1WA	0.307 (4)	1.080 (6)	0.292 (3)	0.036 (12)*
H1WB	0.262 (5)	1.217 (7)	0.244 (4)	0.055 (16)*
O1	0.5304 (2)	1.0090 (3)	0.36710 (18)	0.0222 (6)
C1	0.4720 (3)	0.8756 (4)	0.3529 (2)	0.0178 (7)
N1	0.5712 (2)	0.4278 (3)	0.3417 (2)	0.0207 (7)
C2	0.5393 (3)	0.7140 (4)	0.3741 (2)	0.0174 (7)
O2	0.3644 (2)	0.8636 (3)	0.3260 (2)	0.0270 (6)
C3	0.6071 (3)	0.6967 (5)	0.4734 (3)	0.0224 (8)
H3	0.613 (3)	0.775 (5)	0.517 (3)	0.016 (9)*
C4	0.6558 (3)	0.5451 (5)	0.5066 (3)	0.0254 (8)
H4	0.705 (4)	0.528 (5)	0.574 (3)	0.037 (11)*
C5	0.5288 (3)	0.5780 (4)	0.3067 (2)	0.0162 (7)
C6	0.6323 (3)	0.4126 (5)	0.4394 (3)	0.0230 (8)
H6	0.661 (3)	0.300 (5)	0.461 (3)	0.029 (10)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0201 (4)	0.0105 (4)	0.0291 (4)	0.000	0.0036 (3)	0.000
O1W	0.0223 (15)	0.0237 (16)	0.0490 (18)	0.0033 (12)	0.0044 (13)	0.0094 (13)
O1	0.0265 (13)	0.0136 (12)	0.0245 (13)	−0.0030 (10)	−0.0014 (10)	0.0000 (10)
C1	0.0241 (18)	0.0143 (16)	0.0153 (17)	0.0007 (14)	0.0043 (14)	−0.0013 (13)
N1	0.0245 (15)	0.0134 (14)	0.0236 (16)	0.0010 (12)	0.0021 (12)	0.0017 (12)
C2	0.0187 (16)	0.0137 (16)	0.0207 (17)	−0.0018 (14)	0.0054 (13)	0.0018 (14)
O2	0.0201 (13)	0.0190 (13)	0.0404 (15)	−0.0006 (10)	0.0014 (11)	−0.0006 (11)
C3	0.0225 (18)	0.0235 (19)	0.0203 (18)	−0.0039 (16)	0.0013 (14)	−0.0034 (16)
C4	0.0212 (18)	0.030 (2)	0.0225 (19)	−0.0033 (16)	−0.0026 (15)	0.0033 (16)
C5	0.0131 (15)	0.0157 (16)	0.0201 (17)	−0.0004 (13)	0.0036 (13)	0.0011 (14)
C6	0.0191 (17)	0.0203 (18)	0.028 (2)	0.0065 (14)	0.0006 (14)	0.0082 (15)

Geometric parameters (Å, º)

Mn1—O1^i	2.157 (2)	N1—C6	1.344 (4)
Mn1—O1	2.157 (2)	N1—C5	1.351 (4)
Mn1—O1W^i	2.210 (3)	N1—Mn1^iv	2.241 (3)
Mn1—O1W	2.210 (3)	C2—C5	1.391 (5)
Mn1—N1^ii	2.241 (3)	C2—C3	1.391 (5)
Mn1—N1^iii	2.241 (3)	C3—C4	1.379 (5)
O1W—H1WA	0.87 (5)	C3—H3	0.84 (4)
O1W—H1WB	0.78 (5)	C4—C6	1.371 (5)
O1—C1	1.264 (4)	C4—H4	0.97 (4)
C1—O2	1.241 (4)	C5—C5^i	1.504 (6)
C1—C2	1.515 (4)	C6—H6	0.99 (4)
O1^i—Mn1—O1	87.88 (13)	O2—C1—C2	116.5 (3)
O1^i—Mn1—O1W^i	82.88 (11)	O1—C1—C2	116.9 (3)
O1—Mn1—O1W^i	91.72 (11)	C6—N1—C5	119.8 (3)
O1^i—Mn1—O1W	91.72 (11)	C6—N1—Mn1^iv	120.7 (2)
O1—Mn1—O1W	82.88 (11)	C5—N1—Mn1^iv	117.7 (2)
O1W^i—Mn1—O1W	172.52 (16)	C5—C2—C3	118.3 (3)
O1^i—Mn1—N1^ii	162.52 (10)	C5—C2—C1	125.0 (3)
O1—Mn1—N1^ii	102.05 (9)	C3—C2—C1	116.3 (3)
O1W^i—Mn1—N1^ii	82.48 (11)	C4—C3—C2	120.7 (3)
O1W—Mn1—N1^ii	103.66 (11)	C4—C3—H3	118 (2)
O1^i—Mn1—N1^iii	102.05 (9)	C2—C3—H3	121 (2)
O1—Mn1—N1^iii	162.52 (10)	C6—C4—C3	117.5 (3)
O1W^i—Mn1—N1^iii	103.66 (11)	C6—C4—H4	119 (3)
O1W—Mn1—N1^iii	82.48 (11)	C3—C4—H4	124 (3)
N1^ii—Mn1—N1^iii	72.34 (14)	N1—C5—C2	120.3 (3)
Mn1—O1W—H1WA	106 (3)	N1—C5—C5^i	113.63 (19)
Mn1—O1W—H1WB	128 (4)	C2—C5—C5^i	126.1 (2)
H1WA—O1W—H1WB	107 (5)	N1—C6—C4	122.8 (3)
C1—O1—Mn1	119.4 (2)	N1—C6—H6	116 (2)
O2—C1—O1	126.5 (3)	C4—C6—H6	121 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WB···O2^v	0.78 (5)	1.97 (6)	2.723 (4)	163 (5)
O1W—H1WA···O2	0.87 (5)	1.89 (5)	2.680 (4)	151 (4)

Symmetry code: (v) −x+1/2, y+1/2, −z+1/2.