Synchrotron study of poly[[di-μ-aqua­(μ-2,2′-bipyridyl-5,5′-dicarboxyl­ato)di­potassium] dihydrate]

Bertke, J.A.; Oliver, A.G.; Henderson, K.W.

doi:10.1107/S1600536809038756

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 10| October 2009| Pages m1265-m1266

doi:10.1107/S1600536809038756

Open

access

Synchrotron study of poly[[di-μ-aqua(μ-2,2′-bipyridyl-5,5′-dicarboxylato)dipotassium] dihydrate]

Jeffrey A. Bertke,^a Allen G. Oliver ^a and Kenneth W. Henderson ^a ^*

^aUniversity of Notre Dame, Department of Chemistry and Biochemistry, 251 Nieuwland Science Hall, Notre Dame, IN 46556-5670, USA
^*Correspondence e-mail: khenders@nd.edu

(Received 8 September 2009; accepted 24 September 2009; online 30 September 2009)

The title compound, {[K₂(C₁₂H₆N₂O₄)(H₂O)₂]·2H₂O}_n, forms a three-dimensional coordination polymer in the solid state. The asymmetric unit consists of one K⁺ ion, half of a 2,2′-bipyridyl-5,5′-dicarboxylate ligand, one coordinated water molecule and one solvent water molecule. The K⁺ ion is 7-coordinated by the oxygen atoms of two water molecules and by five oxygen atoms of four carboxylate groups, one of which is chelating. The extended structure can be described as a binodal network in which each K⁺ is a six-connected node, bonding to four carboxylate groups and two bridging water molecules, and the 2,2′-bipyridyl-5,5′-dicarboxylate linkers are eight-connected nodes, with each carboxylate group bridging four metal centers. Overall, this arrangement generates a complex network with point symbol {3⁴.4¹².5¹²}{3⁴.4⁴.5⁴.6³}₂. Both of the bridging water molecules participate as donors in hydrogen-bonding interactions; one to solvent water molecules and a second to an oxygen atom of a carboxylate group.

Related literature

For topological analysis, see: Blatov (2007 ). For background to metal-organic frameworks (MOFs), see: MacDougall et al. (2005 ). The 2,2′-bipyridyl-5,5′-dicarboxylate ligand has been used as a linear linker for a variety of MOFs, see: Finn & Zubieta, (2002 ); Schoknecht & Kempe (2004 ); Szeto et al., (2008 ). It is a particularly interesting linker due to the fact that the pyridyl N atoms have the ability to act as Lewis bases for binding metal centers (Szeto et al., 2008). There has been only one structural example of this ligand bound to an alkali metal reported, viz. Rb (Hafizovic et al., 2007 ). For synthetic details, see: Anderson et al. (1985 ).

Experimental

Crystal data

[K₂(C₁₂H₆N₂O₄)(H₂O)₂]·2H₂O
M_r = 392.46
Monoclinic, P 2₁ /c
a = 3.6769 (6) Å
b = 8.2042 (14) Å
c = 26.292 (4) Å
β = 92.924 (2)°
V = 792.1 (2) Å³
Z = 2
Synchrotron radiation
λ = 0.77490 Å
μ = 0.76 mm⁻¹
T = 150 K
0.04 × 0.03 × 0.01 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a ) T_min = 0.654, T_max = 0.746
8561 measured reflections
1622 independent reflections
1301 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.128
S = 1.08
1622 reflections
117 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.03 e Å⁻³
Δρ_min = −0.51 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3A⋯O1ⁱ	0.84 (5)	1.93 (5)	2.770 (4)	177 (5)
O3—H3B⋯O4ⁱⁱ	0.84 (6)	2.15 (6)	2.976 (5)	169 (5)
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b); molecular graphics: SHELXTL (Sheldrick, 2008b); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809038756/wm2256sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809038756/wm2256Isup2.hkl

checkCIF report

Comment top

We are interested in using pre-assembled and structurally well defined aggregates as secondary building units (SBUs) to build coordination polymers or metal-organic frameworks (MOFs) (MacDougall et al., 2005). The title compound was synthesized as a precursor for use as a linker in the construction of MOFs. The 2,2'-bipyridyl-5,5'-dicarboxylate ligand has been used as a linear linker for a variety of MOFs (Finn & Zubieta, 2002; Schoknecht & Kempe, 2004); Szeto et al., 2008). It is a particularly interesting linker due to the fact that the pyridyl N atoms have the ability to act as Lewis bases for binding metal centers (Szeto et al., 2008).

The asymmetric unit consists of one K⁺ ion, half of a 2,2'-bipyridyl-5,5'-dicarboxylate ligand, one coordinated water molecule and one solvent water molecule (Fig. 1). The extended crystal structure of the title compound is composed of two-dimensional sheets consisting of potassium-carboxylate and potassium-water interactions. These sheets extend parallel to (001). The three-dimensional assembly is completed by connection of the sheets through the 2,2'-bipyridyl linkers (Fig. 2). Small channels run along the a axis and contain the disordered solvent water molecules. The geometry around the seven-coordinate potassium metal center can be described as a distorted monocapped trigonal-prism. The faces deviate from the ideal triangular, with angles of 49.69°(O1—O3—O2), 61.19° (O2—O1—O3) and 69.10° (O1—O2—O3). There is also a short contact distance of 2.826 (6) Å between O4 and N1, which is most likely due to a hydrogen bonding interaction. However, the hydrogen atoms on the solvent water molecule could not be located in the difference map.

For the topological analysis of the structure, the program TOPOS was used (Blatov, 2007). There has been only one structural example of the 2,2'-bipyridyl-5,5'-dicarboxylate ligand bound to an alkali metal reported, viz. Rb (Hafizovic et al., 2007).

Related literature top

For topological analysis, see: Blatov (2007). For background to metal-organic frameworks (MOFs), see: MacDougall et al. (2005). The 2,2'-bipyridyl-5,5'-dicarboxylate ligand has been used as a linear linker for a variety of MOFs, see: Finn & Zubieta, (2002); Schoknecht & Kempe (2004); Szeto et al., (2008). It is a particularly interesting linker due to the fact that the pyridyl N atoms have the ability to act as Lewis bases for binding metal centers (Szeto et al., 2008). There has been only one structural example of this ligand bound to an alkali metal reported, viz. Rb (Hafizovic et al., 2007). For synthetic details, see: Anderson et al. (1985).

Experimental top

The title complex was prepared using a modification of the method of Seddon and Pilling (Anderson et al., 1985) for the preparation of 2,2'-bipyridyl-4,4'-dicarboxylic acid. 5,5'-dimethyl-2,2'-bipyridine and K[MnO₄] were purchased from Aldrich and used without further purification. ¹H NMR data were collected on a Varian Unity Plus 300 spectrometer at 298 K. K[MnO₄] (10 g, 63 mmol) was added to a solution of 5,5'-dimethyl-2,2'-bipyridine (1.6 g, 8.7 mmol) in 100 mL H₂O. The mixture was heated to reflux for 12 h. Upon cooling, the mixture was filtered and the black precipitate was washed with water (2x 30 mL). The filtrate and the washings were combined and extracted with diethyl ether to remove unreacted starting material. The aqueous fraction was collected and the solvent was removed under vacuum, leaving a sticky white solid. The solid was heated under vacuum at 373 K overnight to give a fine white powder. Single crystals were grown from an aqueous solution upon slow evaporation of the solvent.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b); molecular graphics: SHELXTL (Sheldrick, 2008b); software used to prepare material for publication: SHELXTL (Sheldrick, 2008b).

Figures top

	Fig. 1. A portion of the polymeric structure of the title compound. All hydrogen atoms except those located on O3 have been omitted. Thermal ellipsoids are shown at the 50% probablility level.
	Fig. 2. Thermal ellipsoid plot of the asymmetric unit of the title compound. Thermal ellipsoids are shown at the 50% probablility level.

poly[[di-µ-aqua(µ-2,2'-bipyridyl-5,5'-dicarboxylato)dipotassium] dihydrate] top

Crystal data top

[K₂(C₁₂H₆N₂O₄)(H₂O)₂]·2H₂O	F(000) = 404
M_r = 392.46	D_x = 1.646 Mg m⁻³
Monoclinic, P2₁/c	Synchrotron radiation, λ = 0.77490 Å
Hall symbol: -P 2yc	Cell parameters from 1984 reflections
a = 3.6769 (6) Å	θ = 2.8–27.6°
b = 8.2042 (14) Å	µ = 0.76 mm⁻¹
c = 26.292 (4) Å	T = 150 K
β = 92.924 (2)°	Plate, colorless
V = 792.1 (2) Å³	0.04 × 0.03 × 0.01 mm
Z = 2

Data collection top

Bruker APEXII diffractometer	1622 independent reflections
Radiation source: synchrotron	1301 reflections with I > 2σ(I)
Channel-cut Si-<111> crystal monochromator	R_int = 0.045
Detector resolution: 83.33 pixels mm^-1	θ_max = 29.0°, θ_min = 2.8°
ω and ϕ scans	h = −4→4
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	k = −10→10
T_min = 0.654, T_max = 0.746	l = −32→32
8561 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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.128	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0609P)² + 1.2501P] where P = (F_o² + 2F_c²)/3
1622 reflections	(Δ/σ)_max < 0.001
117 parameters	Δρ_max = 1.03 e Å⁻³
0 restraints	Δρ_min = −0.51 e Å⁻³

Crystal data top

[K₂(C₁₂H₆N₂O₄)(H₂O)₂]·2H₂O	V = 792.1 (2) Å³
M_r = 392.46	Z = 2
Monoclinic, P2₁/c	Synchrotron radiation, λ = 0.77490 Å
a = 3.6769 (6) Å	µ = 0.76 mm⁻¹
b = 8.2042 (14) Å	T = 150 K
c = 26.292 (4) Å	0.04 × 0.03 × 0.01 mm
β = 92.924 (2)°

Data collection top

Bruker APEXII diffractometer	1622 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	1301 reflections with I > 2σ(I)
T_min = 0.654, T_max = 0.746	R_int = 0.045
8561 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.128	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 1.03 e Å⁻³
1622 reflections	Δρ_min = −0.51 e Å⁻³
117 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
K1	0.06233 (18)	0.72796 (8)	0.22289 (2)	0.0250 (2)
O1	0.5909 (6)	0.7368 (3)	0.30066 (8)	0.0257 (5)
O2	0.4216 (6)	0.4762 (3)	0.29578 (8)	0.0262 (5)
O3	0.5493 (7)	0.5466 (3)	0.16339 (11)	0.0359 (6)
H3A	0.499 (13)	0.454 (6)	0.1748 (18)	0.052 (14)*
H3B	0.528 (16)	0.539 (7)	0.132 (2)	0.080 (19)*
O4	0.537 (2)	0.0661 (6)	0.44962 (17)	0.154 (3)
N1	0.7659 (7)	0.3947 (3)	0.44667 (10)	0.0272 (6)
C1	0.9350 (8)	0.5168 (4)	0.47310 (10)	0.0216 (6)
C2	0.6527 (8)	0.4234 (4)	0.39788 (11)	0.0251 (7)
H2A	0.5352	0.3375	0.3792	0.030*
C3	0.6981 (8)	0.5704 (4)	0.37364 (11)	0.0225 (6)
C4	0.8744 (8)	0.6938 (4)	0.40162 (11)	0.0252 (7)
H4A	0.9138	0.7968	0.3863	0.030*
C5	0.9916 (8)	0.6669 (4)	0.45143 (11)	0.0209 (6)
H5A	1.1106	0.7510	0.4707	0.025*
C6	0.5582 (8)	0.5960 (4)	0.31898 (11)	0.0200 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
K1	0.0231 (3)	0.0293 (4)	0.0222 (4)	−0.0001 (3)	−0.0021 (2)	0.0022 (3)
O1	0.0312 (12)	0.0272 (12)	0.0182 (10)	0.0001 (9)	−0.0035 (9)	0.0015 (8)
O2	0.0310 (12)	0.0258 (12)	0.0209 (10)	−0.0008 (9)	−0.0053 (9)	−0.0028 (9)
O3	0.0432 (15)	0.0268 (14)	0.0371 (16)	−0.0043 (11)	−0.0035 (12)	0.0001 (11)
O4	0.345 (9)	0.055 (3)	0.059 (3)	0.017 (4)	−0.009 (4)	−0.001 (2)
N1	0.0293 (14)	0.0311 (15)	0.0209 (13)	−0.0025 (11)	−0.0025 (11)	−0.0005 (11)
C1	0.0182 (13)	0.0305 (16)	0.0159 (14)	0.0023 (12)	−0.0013 (11)	−0.0020 (12)
C2	0.0250 (16)	0.0316 (17)	0.0183 (14)	0.0008 (13)	−0.0024 (12)	−0.0005 (12)
C3	0.0176 (14)	0.0330 (16)	0.0168 (14)	0.0038 (12)	0.0003 (11)	−0.0008 (12)
C4	0.0225 (15)	0.0325 (17)	0.0205 (15)	0.0018 (12)	−0.0003 (11)	−0.0004 (12)
C5	0.0200 (14)	0.0256 (15)	0.0167 (14)	−0.0018 (11)	−0.0040 (11)	−0.0009 (11)
C6	0.0181 (14)	0.0261 (16)	0.0158 (14)	0.0029 (11)	0.0002 (11)	−0.0014 (11)

Geometric parameters (Å, º) top

K1—O2ⁱ	2.732 (2)	N1—C2	1.349 (4)
K1—O1ⁱⁱ	2.748 (2)	N1—C1	1.353 (4)
K1—O1	2.749 (2)	C1—C5	1.376 (4)
K1—O3ⁱⁱ	2.814 (3)	C1—C1^iv	1.496 (6)
K1—O2ⁱⁱⁱ	2.843 (2)	C2—C3	1.378 (5)
K1—O3	2.855 (3)	C2—H2A	0.9500
K1—O2	3.070 (2)	C3—C4	1.392 (4)
O1—C6	1.259 (4)	C3—C6	1.516 (4)
O2—C6	1.249 (4)	C4—C5	1.376 (4)
O3—H3A	0.84 (5)	C4—H4A	0.9500
O3—H3B	0.84 (6)	C5—H5A	0.9500

O2ⁱ—K1—O1ⁱⁱ	71.60 (7)	K1^vi—O2—K1	97.69 (6)
O2ⁱ—K1—O1	122.90 (7)	K1^vii—O2—K1	130.08 (8)
O1ⁱⁱ—K1—O1	83.96 (6)	K1^v—O3—K1	80.87 (7)
O2ⁱ—K1—O3ⁱⁱ	83.24 (8)	K1^v—O3—H3A	116 (3)
O1ⁱⁱ—K1—O3ⁱⁱ	89.84 (8)	K1—O3—H3A	97 (3)
O1—K1—O3ⁱⁱ	148.85 (8)	K1^v—O3—H3B	129 (4)
O2ⁱ—K1—O2ⁱⁱⁱ	82.49 (6)	K1—O3—H3B	124 (4)
O1ⁱⁱ—K1—O2ⁱⁱⁱ	124.15 (7)	H3A—O3—H3B	106 (5)
O1—K1—O2ⁱⁱⁱ	69.93 (6)	C2—N1—C1	118.1 (3)
O3ⁱⁱ—K1—O2ⁱⁱⁱ	135.82 (8)	N1—C1—C5	121.7 (3)
O2ⁱ—K1—O3	135.30 (8)	N1—C1—C1^iv	117.7 (3)
O1ⁱⁱ—K1—O3	149.13 (8)	C5—C1—C1^iv	120.6 (3)
O1—K1—O3	88.96 (7)	N1—C2—C3	123.6 (3)
O3ⁱⁱ—K1—O3	80.87 (7)	N1—C2—H2A	118.2
O2ⁱⁱⁱ—K1—O3	80.56 (7)	C3—C2—H2A	118.2
O2ⁱ—K1—O2	150.35 (3)	C2—C3—C4	117.2 (3)
O1ⁱⁱ—K1—O2	79.68 (6)	C2—C3—C6	121.1 (3)
O1—K1—O2	44.61 (6)	C4—C3—C6	121.7 (3)
O3ⁱⁱ—K1—O2	104.26 (7)	C5—C4—C3	120.0 (3)
O2ⁱⁱⁱ—K1—O2	108.66 (3)	C5—C4—H4A	120.0
O3—K1—O2	74.31 (7)	C3—C4—H4A	120.0
C6—O1—K1^v	109.68 (18)	C4—C5—C1	119.4 (3)
C6—O1—K1	100.52 (17)	C4—C5—H5A	120.3
K1^v—O1—K1	83.96 (6)	C1—C5—H5A	120.3
C6—O2—K1^vi	156.4 (2)	O2—C6—O1	125.4 (3)
C6—O2—K1^vii	113.13 (18)	O2—C6—C3	117.5 (3)
K1^vi—O2—K1^vii	82.49 (6)	O1—C6—C3	117.1 (3)
C6—O2—K1	85.69 (17)

O2ⁱ—K1—O1—C6	134.52 (17)	K1^vi—O2—C6—K1	−99.4 (5)
O1ⁱⁱ—K1—O1—C6	71.04 (18)	K1^vii—O2—C6—K1	132.06 (13)
O3ⁱⁱ—K1—O1—C6	−8.6 (3)	K1^vi—O2—C6—K1^v	−163.2 (4)
O2ⁱⁱⁱ—K1—O1—C6	−159.19 (19)	K1^vii—O2—C6—K1^v	68.29 (14)
O3—K1—O1—C6	−78.86 (18)	K1—O2—C6—K1^v	−63.77 (7)
O2—K1—O1—C6	−10.37 (16)	K1^vi—O2—C6—K1^vii	128.6 (5)
C6ⁱⁱ—K1—O1—C6	50.56 (15)	K1—O2—C6—K1^vii	−132.06 (13)
C6ⁱⁱⁱ—K1—O1—C6	−169.28 (16)	K1^v—O1—C6—O2	−64.9 (3)
K1ⁱⁱ—K1—O1—C6	71.04 (18)	K1—O1—C6—O2	22.4 (3)
K1^v—K1—O1—C6	−108.96 (18)	K1^v—O1—C6—C3	114.8 (2)
O2ⁱ—K1—O1—K1^v	−116.52 (7)	K1—O1—C6—C3	−157.9 (2)
O1ⁱⁱ—K1—O1—K1^v	180.0	K1^v—O1—C6—K1	−87.29 (11)
O3ⁱⁱ—K1—O1—K1^v	100.40 (15)	K1—O1—C6—K1^v	87.29 (11)
O2ⁱⁱⁱ—K1—O1—K1^v	−50.23 (6)	K1^v—O1—C6—K1^vii	−4.1 (3)
O3—K1—O1—K1^v	30.09 (7)	K1—O1—C6—K1^vii	83.2 (2)
O2—K1—O1—K1^v	98.58 (9)	C2—C3—C6—O2	−4.5 (4)
C6—K1—O1—K1^v	108.96 (18)	C4—C3—C6—O2	176.1 (3)
C6ⁱⁱ—K1—O1—K1^v	159.52 (7)	C2—C3—C6—O1	175.8 (3)
C6ⁱⁱⁱ—K1—O1—K1^v	−60.32 (6)	C4—C3—C6—O1	−3.7 (4)
K1ⁱⁱ—K1—O1—K1^v	180.0	C2—C3—C6—K1	108.6 (6)
O2ⁱ—K1—O2—C6	−67.1 (2)	C4—C3—C6—K1	−70.9 (7)
O1ⁱⁱ—K1—O2—C6	−81.54 (17)	C2—C3—C6—K1^v	−125.9 (3)
O1—K1—O2—C6	10.31 (16)	C4—C3—C6—K1^v	54.7 (4)
O3ⁱⁱ—K1—O2—C6	−168.72 (17)	C2—C3—C6—K1^vii	−47.7 (3)
O2ⁱⁱⁱ—K1—O2—C6	41.19 (16)	C4—C3—C6—K1^vii	132.8 (3)
O3—K1—O2—C6	115.25 (18)	O2ⁱ—K1—C6—O2	138.37 (12)
C6ⁱⁱ—K1—O2—C6	−94.85 (18)	O1ⁱⁱ—K1—C6—O2	93.78 (17)
C6ⁱⁱⁱ—K1—O2—C6	37.2 (2)	O1—K1—C6—O2	−160.9 (3)
K1ⁱⁱ—K1—O2—C6	−116.44 (16)	O3ⁱⁱ—K1—C6—O2	13.6 (2)
K1^v—K1—O2—C6	63.56 (16)	O2ⁱⁱⁱ—K1—C6—O2	−141.38 (15)
O2ⁱ—K1—O2—K1^vi	89.41 (15)	O3—K1—C6—O2	−60.97 (17)
O1ⁱⁱ—K1—O2—K1^vi	75.00 (7)	C6ⁱⁱ—K1—C6—O2	74.81 (17)
O1—K1—O2—K1^vi	166.84 (12)	C6ⁱⁱⁱ—K1—C6—O2	−149.60 (19)
O3ⁱⁱ—K1—O2—K1^vi	−12.18 (9)	K1ⁱⁱ—K1—C6—O2	74.81 (17)
O2ⁱⁱⁱ—K1—O2—K1^vi	−162.27 (8)	K1^v—K1—C6—O2	−105.19 (17)
O3—K1—O2—K1^vi	−88.21 (8)	O2ⁱ—K1—C6—O1	−60.7 (2)
C6—K1—O2—K1^vi	156.5 (2)	O1ⁱⁱ—K1—C6—O1	−105.34 (19)
C6ⁱⁱ—K1—O2—K1^vi	61.68 (7)	O3ⁱⁱ—K1—C6—O1	174.51 (17)
C6ⁱⁱⁱ—K1—O2—K1^vi	−166.30 (7)	O2ⁱⁱⁱ—K1—C6—O1	19.50 (18)
K1ⁱⁱ—K1—O2—K1^vi	40.09 (7)	O3—K1—C6—O1	99.91 (18)
K1^v—K1—O2—K1^vi	−139.91 (7)	O2—K1—C6—O1	160.9 (3)
O2ⁱ—K1—O2—K1^vii	176.04 (11)	C6ⁱⁱ—K1—C6—O1	−124.31 (16)
O1ⁱⁱ—K1—O2—K1^vii	161.63 (11)	C6ⁱⁱⁱ—K1—C6—O1	11.28 (17)
O1—K1—O2—K1^vii	−106.52 (13)	K1ⁱⁱ—K1—C6—O1	−124.31 (16)
O3ⁱⁱ—K1—O2—K1^vii	74.45 (11)	K1^v—K1—C6—O1	55.69 (16)
O2ⁱⁱⁱ—K1—O2—K1^vii	−75.64 (13)	O2ⁱ—K1—C6—C3	17.7 (6)
O3—K1—O2—K1^vii	−1.58 (10)	O1ⁱⁱ—K1—C6—C3	−26.9 (6)
C6—K1—O2—K1^vii	−116.8 (2)	O1—K1—C6—C3	78.4 (6)
C6ⁱⁱ—K1—O2—K1^vii	148.31 (12)	O3ⁱⁱ—K1—C6—C3	−107.0 (6)
C6ⁱⁱⁱ—K1—O2—K1^vii	−79.67 (12)	O2ⁱⁱⁱ—K1—C6—C3	97.9 (6)
K1ⁱⁱ—K1—O2—K1^vii	126.73 (8)	O3—K1—C6—C3	178.4 (6)
K1^v—K1—O2—K1^vii	−53.28 (8)	O2—K1—C6—C3	−120.7 (7)
O2ⁱ—K1—O3—K1^v	109.38 (9)	C6ⁱⁱ—K1—C6—C3	−45.9 (6)
O1ⁱⁱ—K1—O3—K1^v	−105.92 (13)	C6ⁱⁱⁱ—K1—C6—C3	89.7 (6)
O1—K1—O3—K1^v	−29.55 (7)	K1ⁱⁱ—K1—C6—C3	−45.9 (6)
O3ⁱⁱ—K1—O3—K1^v	180.0	K1^v—K1—C6—C3	134.1 (6)
O2ⁱⁱⁱ—K1—O3—K1^v	40.27 (6)	O2ⁱ—K1—C6—K1^v	−116.44 (9)
O2—K1—O3—K1^v	−72.29 (7)	O1ⁱⁱ—K1—C6—K1^v	−161.03 (6)
C6—K1—O3—K1^v	−51.77 (7)	O1—K1—C6—K1^v	−55.69 (16)
C6ⁱⁱ—K1—O3—K1^v	−107.38 (9)	O3ⁱⁱ—K1—C6—K1^v	118.82 (8)
C6ⁱⁱⁱ—K1—O3—K1^v	56.64 (7)	O2ⁱⁱⁱ—K1—C6—K1^v	−36.19 (6)
K1ⁱⁱ—K1—O3—K1^v	180.0	O3—K1—C6—K1^v	44.22 (6)
C2—N1—C1—C5	0.1 (4)	O2—K1—C6—K1^v	105.19 (17)
C2—N1—C1—C1^iv	−179.0 (3)	C6ⁱⁱ—K1—C6—K1^v	180.0
C1—N1—C2—C3	−0.4 (5)	C6ⁱⁱⁱ—K1—C6—K1^v	−44.41 (7)
N1—C2—C3—C4	0.7 (5)	K1ⁱⁱ—K1—C6—K1^v	180.0
N1—C2—C3—C6	−178.8 (3)	O2ⁱ—K1—C6—K1^vii	173.13 (8)
C2—C3—C4—C5	−0.7 (4)	O1ⁱⁱ—K1—C6—K1^vii	128.54 (9)
C6—C3—C4—C5	178.8 (3)	O1—K1—C6—K1^vii	−126.1 (2)
C3—C4—C5—C1	0.4 (4)	O3ⁱⁱ—K1—C6—K1^vii	48.39 (12)
N1—C1—C5—C4	−0.1 (5)	O2ⁱⁱⁱ—K1—C6—K1^vii	−106.62 (8)
C1^iv—C1—C5—C4	179.0 (3)	O3—K1—C6—K1^vii	−26.21 (8)
K1^vi—O2—C6—O1	−119.0 (4)	O2—K1—C6—K1^vii	34.76 (13)
K1^vii—O2—C6—O1	112.4 (3)	C6ⁱⁱ—K1—C6—K1^vii	109.57 (6)
K1—O2—C6—O1	−19.7 (3)	C6ⁱⁱⁱ—K1—C6—K1^vii	−114.84 (11)
K1^vi—O2—C6—C3	61.2 (6)	K1ⁱⁱ—K1—C6—K1^vii	109.57 (6)
K1^vii—O2—C6—C3	−67.3 (3)	K1^v—K1—C6—K1^vii	−70.43 (6)
K1—O2—C6—C3	160.6 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O1^vii	0.84 (5)	1.93 (5)	2.770 (4)	177 (5)
O3—H3B···O4ⁱⁱⁱ	0.84 (6)	2.15 (6)	2.976 (5)	169 (5)

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

Experimental details

Crystal data
Chemical formula	[K₂(C₁₂H₆N₂O₄)(H₂O)₂]·2H₂O
M_r	392.46
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	150
a, b, c (Å)	3.6769 (6), 8.2042 (14), 26.292 (4)
β (°)	92.924 (2)
V (Å³)	792.1 (2)
Z	2
Radiation type	Synchrotron, λ = 0.77490 Å
µ (mm⁻¹)	0.76
Crystal size (mm)	0.04 × 0.03 × 0.01

Data collection
Diffractometer	Bruker APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2008a)
T_min, T_max	0.654, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	8561, 1622, 1301
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.128, 1.08
No. of reflections	1622
No. of parameters	117
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.03, −0.51

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008b), SHELXL97 (Sheldrick, 2008b), SHELXTL (Sheldrick, 2008b).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O1ⁱ	0.84 (5)	1.93 (5)	2.770 (4)	177 (5)
O3—H3B···O4ⁱⁱ	0.84 (6)	2.15 (6)	2.976 (5)	169 (5)

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

Acknowledgements

Samples for synchrotron crystallographic analysis were submitted through the SCrALS (Service Crystallography at Advanced Light Source) program. Crystallographic data were collected at Beamline 11.3.1 at the Advanced Light Source (ALS), Lawrence Berkeley National Laboratory. The ALS is supported by the US Department of Energy, Office of Energy Sciences, under contract DE—AC02–05CH11231.

References

Anderson, S., Constable, E. C., Seddon, K. R., Turp, J. E., Baggott, J. E. & Pilling, M. J. (1985). J. Chem. Soc. Dalton Trans. pp. 2247-2261. CrossRef Web of Science Google Scholar
Blatov, V. A. (2007). http://www.topos.ssu.samara.ru/ . Google Scholar
Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Finn, R. C. & Zubieta, J. (2002). Solid State Sci. 4, 83–86. Web of Science CSD CrossRef CAS Google Scholar
Hafizovic, J., Olsbye, U. & Lillerud, K. P. (2007). Acta Cryst. E63, m962–m964. Web of Science CSD CrossRef IUCr Journals Google Scholar
MacDougall, D. J., Morris, J. J., Noll, B. C. & Henderson, K. W. (2005). Chem. Commun. pp. 456–458. Web of Science CSD CrossRef Google Scholar
Schoknecht, B. & Kempe, R. (2004). Z. Anorg. Allg. Chem. 630, 1377–1379. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008a). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008b). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Szeto, K. C., Kongshaug, K. O., Jakobsen, S., Tilset, M. & Lillerud, K. P. (2008). Dalton Trans. pp. 2054–2060. Web of Science CSD CrossRef PubMed 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.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 10| October 2009| Pages m1265-m1266

doi:10.1107/S1600536809038756

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Synchrotron study of poly[[di-μ-aqua­(μ-2,2′-bi­pyridyl-5,5′-di­carboxyl­ato)di­potassium] dihydrate]

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

Synchrotron study of poly[[di-μ-aqua(μ-2,2′-bipyridyl-5,5′-dicarboxylato)dipotassium] dihydrate]