Retracted: Poly[[aqua­(2,2-bipyrid­yl)(μ₃-pyridine-3,4-dicarboxyl­ato)manganese(II)] monohydrate]

In the title compound, {[Mn(C₇H₃NO₄)(C₁₀H₈N₂)(H₂O)]·H₂O}_n, the Mn(II) atom has a distorted fac-MnN₃O₃ octa­hedral coordination geometry, defined by one N,N′-chelating bipyridine mol­ecule, one N-bonded pyridine-3,4-dicarboxyl­ate (pdb) anion, two monodentate O-bonded pdb anions and one water mol­ecule. Adjacent Mn^II ions are bridged by pairs of pdb ligands to form distinctive squares, which are further linked by other pdb ligands to result in a layered coordination polymer exhibiting a wave-like structure. Hydrogen bonds involving both the coordinated and uncoordinated water mol­ecules help to consolidate the structure.

Key indicators

• Single-crystal X-ray study
• T = 292 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.034
• wR factor = 0.092
• Data-to-parameter ratio = 12.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT415_ALERT_2_C Short Inter D-H..H-X       H1W    ..  H16A    ..       2.13 Ang.

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Mn1         (2)       2.04

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 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
   0 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

Due to both their structural and topological novelty as well as for their potential applications as functional materials, the rational design of inorganic coordination networks has attracted much recent attention (Biradha et al., 2000, Moulton et al., 2001, Eddaoudi et al., 2001, Cao et al., 2003, Kortz et al., 2003). To date, a variety of extended frameworks have been obtained through the use of polydentate ligands, such as polycarboxylic acids (Pan et al., 2003, Noro et al., 2000). Herein, we report the crystal structure of the title compound, (I), which shows a layered polymeric structure.

The Mn^II ion in (I) has a distorted octahedral coordination geometry, defined by three N atoms and three carboxyl O atoms from chelating bipy, pyridine-3,4-dicarboxylate (pdb) ligands and one water molecule (Fig. 1, Table 1) The polymeric layers in (I) feature squares constructed from two Mn^II ions bridged by two pdb ligands. Such squares are further connected by pdb ligands, forming a sheet (Fig. 2). A network of O—H···O hydrogen bonds arising from the water molecules (Table 2) helps to consolidate the structure.

Related literature

For related literature, see: Biradha et al. (2000); Cao et al. (2003); Eddaoudi et al. (2001); Kortz et al. (2003); Moulton & Zaworotko (2001); Noro et al. (2000); Pan et al. (2003).

S2. Experimental

Compound (I) was prepared from a mixture of Mn(CH₃CO₂)₂^.4H₂O (0.120 g, 0.5 mmol), pyridine-3,4-dicarboxylic acid (0.083 g, 0.5 mmol), 2,2-bipyridine (0.078 g, 0.5 mmol) and H₂O (18 ml) in a 30 ml Teflon-lined autoclave under autogenous pressure at 423 K for 5 d. After cooling to room temperature, yellow crystals suitable for X-ray structure analysis were obtained. Analysis, calculated for C₁₇H₁₅MnN₃O₆: C 49.5, H 3.7, N 10.2%; found: C 49.4, H 3.6, N 10.0%.

S3. Refinement

The C-bonded H atoms and H4W were generated geometrically (C—H = 0.93 Å, O—H =0.82 Å) and refined as riding with U_iso(H)= 1.2U_eq(C) or U_iso(H4W) = 0.05 Ų. The other H atoms of the water molecules were located in difference maps and their positions and U_iso values were freely refined.

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The asymmetric unit of (I) expanded to show the coordination of the Mn atom drawn with 30% probability displacement ellipsoids (arbitrary spheres for the H atoms). Atoms O3I and N4I are at the symmetry positions (1 - x, -y, -z) and (1/2 - x, 3/2 - y, z) respectively.
	Fig. 2. Part of a polymeric layer in (I). Mn atoms are represented by green hatched spheres, N atoms by blue dotted spheres, O atoms by red grid spheres, and C atoms by grey spheres. H atoms have been omitted for clarity.

Poly[[aqua(2,2-bipyridyl)(µ₃pyridine-3,4-dicarboxylato)manganese(II)] monohydrate]

Crystal data

[Mn(C7H3NO4)(C10H8N2)(H2O)]·H2O	F(000) = 1688
Mr = 412.26	Dx = 1.669 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	θ = 2.4–26.1°
a = 15.614 (2) Å	µ = 0.85 mm^−1
b = 12.4561 (18) Å	T = 292 K
c = 16.870 (3) Å	Block, yellow
V = 3281.1 (8) Å^3	0.10 × 0.10 × 0.10 mm
Z = 8

Data collection

Bruker SMART CCD diffractometer	2562 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.073
Graphite monochromator	θmax = 26.1°, θmin = 2.4°
ω scans	h = −19→19
26510 measured reflections	k = −15→15
3249 independent reflections	l = −20→20

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0541P)^2] where P = (Fo^2 + 2Fc^2)/3
3249 reflections	(Δ/σ)max < 0.001
256 parameters	Δρmax = 0.55 e Å^−3
0 restraints	Δρmin = −0.55 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	0.43851 (2)	0.18948 (3)	−0.06880 (2)	0.02453 (12)
C13	0.31857 (13)	−0.12791 (17)	0.07018 (13)	0.0244 (5)
O2	0.30663 (11)	0.00140 (13)	−0.12384 (10)	0.0383 (4)
O1	0.38982 (9)	0.04326 (11)	−0.02127 (9)	0.0296 (4)
N2	0.51764 (11)	0.25010 (14)	0.03251 (11)	0.0264 (4)
O5	0.26473 (12)	0.13867 (14)	0.26106 (12)	0.0387 (4)
C16	0.22594 (13)	−0.15776 (17)	−0.04054 (13)	0.0257 (5)
H16A	0.2094	−0.1383	−0.0915	0.031*
N4	0.18302 (11)	−0.23754 (15)	−0.00607 (11)	0.0295 (4)
N1	0.49150 (11)	0.35320 (15)	−0.10606 (11)	0.0269 (4)
C14	0.27565 (14)	−0.21355 (18)	0.10597 (15)	0.0321 (5)
H14A	0.2913	−0.2358	0.1566	0.038*
C15	0.20980 (15)	−0.26556 (19)	0.06634 (14)	0.0331 (6)
H4A	0.1829	−0.3229	0.0914	0.040*
C1	0.52431 (15)	0.20098 (19)	0.10279 (15)	0.0339 (6)
H1A	0.4924	0.1391	0.1117	0.041*
C2	0.57649 (16)	0.2385 (2)	0.16233 (15)	0.0422 (6)
H2A	0.5797	0.2024	0.2105	0.051*
C12	0.29349 (13)	−0.10105 (16)	−0.00670 (12)	0.0227 (5)
C11	0.33328 (13)	−0.01213 (16)	−0.05444 (13)	0.0242 (5)
C10	0.47938 (15)	0.40019 (19)	−0.17620 (14)	0.0332 (5)
H10A	0.4357	0.3740	−0.2083	0.040*
C9	0.52727 (16)	0.48483 (19)	−0.20416 (15)	0.0368 (6)
H9A	0.5160	0.5157	−0.2532	0.044*
C5	0.56416 (13)	0.33975 (18)	0.01934 (13)	0.0255 (5)
C4	0.61805 (15)	0.38030 (19)	0.07749 (14)	0.0347 (6)
H4B	0.6503	0.4416	0.0677	0.042*
C3	0.62353 (16)	0.3293 (2)	0.14975 (16)	0.0428 (6)
H3A	0.6588	0.3564	0.1894	0.051*
C6	0.55396 (13)	0.39158 (18)	−0.05899 (13)	0.0261 (5)
C7	0.60589 (17)	0.4750 (2)	−0.08444 (15)	0.0442 (7)
H7A	0.6502	0.4993	−0.0522	0.053*
C8	0.59225 (18)	0.5219 (2)	−0.15697 (16)	0.0456 (7)
H8A	0.6268	0.5782	−0.1739	0.055*
C17	0.38450 (14)	−0.06848 (17)	0.11963 (12)	0.0263 (5)
O3	0.45903 (10)	−0.10620 (13)	0.12223 (10)	0.0372 (4)
O4	0.35811 (11)	0.00841 (14)	0.15903 (10)	0.0412 (4)
O6	0.36338 (11)	0.18742 (13)	−0.18066 (10)	0.0335 (4)
H4W	0.3344	0.1326	−0.1825	0.050*
H1W	0.2400 (18)	0.100 (2)	0.2944 (18)	0.053 (9)*
H2W	0.2883 (19)	0.093 (3)	0.2303 (18)	0.064 (10)*
H3W	0.322 (2)	0.241 (3)	−0.195 (2)	0.080 (11)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.02398 (19)	0.01951 (19)	0.0301 (2)	−0.00234 (13)	−0.00148 (14)	0.00011 (13)
C13	0.0207 (10)	0.0215 (11)	0.0309 (12)	0.0045 (8)	0.0042 (9)	−0.0009 (9)
O2	0.0512 (10)	0.0328 (9)	0.0309 (10)	−0.0135 (8)	−0.0092 (8)	0.0064 (7)
O1	0.0304 (8)	0.0228 (8)	0.0356 (9)	−0.0064 (7)	−0.0020 (7)	0.0023 (7)
N2	0.0245 (9)	0.0243 (10)	0.0304 (11)	−0.0005 (8)	0.0017 (8)	0.0009 (8)
O5	0.0482 (11)	0.0335 (10)	0.0342 (10)	0.0002 (9)	0.0064 (9)	0.0004 (9)
C16	0.0287 (11)	0.0239 (11)	0.0245 (11)	0.0004 (9)	0.0007 (9)	0.0005 (9)
N4	0.0278 (10)	0.0269 (10)	0.0337 (11)	−0.0040 (8)	−0.0004 (9)	0.0010 (8)
N1	0.0250 (10)	0.0260 (10)	0.0297 (11)	−0.0031 (8)	−0.0018 (8)	0.0023 (8)
C14	0.0333 (13)	0.0332 (13)	0.0297 (13)	−0.0003 (10)	−0.0022 (10)	0.0074 (10)
C15	0.0325 (13)	0.0280 (13)	0.0388 (14)	−0.0083 (10)	0.0009 (11)	0.0063 (10)
C1	0.0320 (12)	0.0322 (14)	0.0376 (14)	−0.0019 (10)	0.0020 (11)	0.0073 (11)
C2	0.0431 (15)	0.0502 (17)	0.0334 (15)	0.0013 (12)	−0.0033 (12)	0.0115 (12)
C12	0.0224 (10)	0.0181 (11)	0.0275 (12)	0.0005 (8)	0.0047 (9)	−0.0023 (9)
C11	0.0233 (11)	0.0176 (11)	0.0317 (13)	0.0013 (9)	0.0015 (9)	−0.0017 (9)
C10	0.0330 (13)	0.0352 (14)	0.0314 (13)	−0.0052 (10)	−0.0044 (10)	0.0013 (10)
C9	0.0444 (14)	0.0333 (14)	0.0328 (14)	−0.0035 (11)	0.0013 (11)	0.0069 (11)
C5	0.0223 (11)	0.0241 (11)	0.0301 (12)	0.0007 (9)	0.0012 (9)	−0.0026 (9)
C4	0.0347 (13)	0.0306 (13)	0.0387 (15)	−0.0080 (10)	−0.0065 (11)	−0.0003 (10)
C3	0.0401 (15)	0.0492 (17)	0.0391 (15)	−0.0034 (12)	−0.0112 (12)	−0.0023 (12)
C6	0.0250 (11)	0.0220 (11)	0.0311 (13)	−0.0016 (9)	0.0015 (9)	−0.0033 (9)
C7	0.0466 (16)	0.0447 (16)	0.0412 (16)	−0.0250 (13)	−0.0087 (12)	0.0040 (12)
C8	0.0552 (16)	0.0407 (16)	0.0408 (16)	−0.0225 (13)	−0.0001 (13)	0.0075 (12)
C17	0.0298 (12)	0.0271 (12)	0.0219 (12)	0.0013 (10)	0.0031 (9)	0.0041 (9)
O3	0.0258 (9)	0.0431 (10)	0.0428 (11)	0.0092 (7)	−0.0034 (7)	−0.0098 (8)
O4	0.0454 (10)	0.0365 (10)	0.0416 (11)	0.0110 (8)	−0.0012 (8)	−0.0153 (8)
O6	0.0355 (9)	0.0281 (9)	0.0370 (10)	−0.0046 (7)	−0.0038 (8)	−0.0006 (7)

Geometric parameters (Å, º)

Mn1—O3^i	2.1091 (16)	C15—H4A	0.9300
Mn1—O1	2.1303 (15)	C1—C2	1.375 (4)
Mn1—O6	2.2221 (17)	C1—H1A	0.9300
Mn1—N2	2.2401 (19)	C2—C3	1.365 (4)
Mn1—N1	2.2888 (18)	C2—H2A	0.9300
Mn1—N4^ii	2.3552 (18)	C12—C11	1.504 (3)
C13—C12	1.395 (3)	C10—C9	1.376 (3)
C13—C14	1.397 (3)	C10—H10A	0.9300
C13—C17	1.518 (3)	C9—C8	1.370 (4)
O2—C11	1.254 (3)	C9—H9A	0.9300
O1—C11	1.252 (2)	C5—C4	1.388 (3)
N2—C1	1.338 (3)	C5—C6	1.479 (3)
N2—C5	1.351 (3)	C4—C3	1.377 (4)
O5—H1W	0.83 (3)	C4—H4B	0.9300
O5—H2W	0.86 (3)	C3—H3A	0.9300
C16—N4	1.332 (3)	C6—C7	1.386 (3)
C16—C12	1.392 (3)	C7—C8	1.372 (4)
C16—H16A	0.9300	C7—H7A	0.9300
N4—C15	1.337 (3)	C8—H8A	0.9300
N4—Mn1^iii	2.3552 (18)	C17—O4	1.236 (3)
N1—C10	1.334 (3)	C17—O3	1.256 (2)
N1—C6	1.345 (3)	O3—Mn1^i	2.1091 (16)
C14—C15	1.387 (3)	O6—H4W	0.8200
C14—H14A	0.9300	O6—H3W	0.96 (3)
O3^i—Mn1—O1	90.63 (6)	C3—C2—C1	119.1 (2)
O3^i—Mn1—O6	91.82 (6)	C3—C2—H2A	120.4
O1—Mn1—O6	96.97 (6)	C1—C2—H2A	120.4
O3^i—Mn1—N2	94.21 (6)	C16—C12—C13	118.18 (19)
O1—Mn1—N2	101.41 (6)	C16—C12—C11	117.85 (19)
O6—Mn1—N2	160.57 (6)	C13—C12—C11	123.94 (19)
O3^i—Mn1—N1	92.67 (7)	O1—C11—O2	125.2 (2)
O1—Mn1—N1	173.81 (6)	O1—C11—C12	117.24 (19)
O6—Mn1—N1	88.16 (6)	O2—C11—C12	117.50 (18)
N2—Mn1—N1	73.13 (7)	N1—C10—C9	124.3 (2)
O3^i—Mn1—N4^ii	173.24 (7)	N1—C10—H10A	117.9
O1—Mn1—N4^ii	82.73 (6)	C9—C10—H10A	117.9
O6—Mn1—N4^ii	87.75 (6)	C8—C9—C10	117.5 (2)
N2—Mn1—N4^ii	88.36 (6)	C8—C9—H9A	121.3
N1—Mn1—N4^ii	94.06 (6)	C10—C9—H9A	121.3
C12—C13—C14	116.8 (2)	N2—C5—C4	120.7 (2)
C12—C13—C17	125.75 (19)	N2—C5—C6	116.74 (19)
C14—C13—C17	117.39 (19)	C4—C5—C6	122.5 (2)
C11—O1—Mn1	123.67 (14)	C3—C4—C5	119.7 (2)
C1—N2—C5	118.81 (19)	C3—C4—H4B	120.1
C1—N2—Mn1	124.39 (15)	C5—C4—H4B	120.1
C5—N2—Mn1	116.73 (15)	C2—C3—C4	119.1 (2)
H1W—O5—H2W	103 (3)	C2—C3—H3A	120.5
N4—C16—C12	125.5 (2)	C4—C3—H3A	120.5
N4—C16—H16A	117.2	N1—C6—C7	120.5 (2)
C12—C16—H16A	117.2	N1—C6—C5	116.75 (19)
C16—N4—C15	115.85 (19)	C7—C6—C5	122.7 (2)
C16—N4—Mn1^iii	119.81 (15)	C8—C7—C6	120.3 (2)
C15—N4—Mn1^iii	124.16 (15)	C8—C7—H7A	119.9
C10—N1—C6	118.1 (2)	C6—C7—H7A	119.9
C10—N1—Mn1	125.69 (15)	C9—C8—C7	119.3 (2)
C6—N1—Mn1	114.62 (14)	C9—C8—H8A	120.3
C15—C14—C13	120.3 (2)	C7—C8—H8A	120.3
C15—C14—H14A	119.9	O4—C17—O3	125.4 (2)
C13—C14—H14A	119.9	O4—C17—C13	116.58 (19)
N4—C15—C14	123.4 (2)	O3—C17—C13	117.72 (19)
N4—C15—H4A	118.3	C17—O3—Mn1^i	150.70 (16)
C14—C15—H4A	118.3	Mn1—O6—H4W	109.5
N2—C1—C2	122.5 (2)	Mn1—O6—H3W	124 (2)
N2—C1—H1A	118.7	H4W—O6—H3W	101.7
C2—C1—H1A	118.7

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H1W···O2^iv	0.84 (3)	2.01 (3)	2.838 (3)	174 (3)
O5—H2W···O4	0.85 (3)	1.93 (3)	2.779 (3)	170 (3)
O6—H3W···O5^v	0.96 (3)	1.90 (4)	2.834 (2)	165 (3)
O6—H4W···O2	0.82	1.96	2.659 (2)	143

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