Synchrotron study of poly[[di-μ-aqua-(μ-2,2'-bipyridyl-5,5'-dicarboxyl-ato)di-potassium] dihydrate].

The title compound, {[K(2)(C(12)H(6)N(2)O(4))(H(2)O)(2)]·2H(2)O}(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'-dicarboxyl-ate ligand, one coordinated water mol-ecule and one solvent water mol-ecule. The K(+) ion is 7-coordinated by the oxygen atoms of two water mol-ecules and by five oxygen atoms of four carboxyl-ate 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 carboxyl-ate groups and two bridging water mol-ecules, and the 2,2'-bipyridyl-5,5'-dicarboxyl-ate linkers are eight-connected nodes, with each carboxyl-ate group bridging four metal centers. Overall, this arrangement generates a complex network with point symbol {3(4).4(12).5(12)}{3(4).4(4).5(4).6(3)}(2). Both of the bridging water mol-ecules participate as donors in hydrogen-bonding inter-actions; one to solvent water mol-ecules and a second to an oxygen atom of a carboxyl-ate 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 = 392.46

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.128

S = 1.08

1622 reflections

117 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.03 e Å−3

Δρmin = −0.51 e Å−3

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.

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[K2(C12H6N2O4)(H2O)2]·2H2O	F(000) = 404
Mr = 392.46	Dx = 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

Bruker APEXII diffractometer	1622 independent reflections
Radiation source: synchrotron	1301 reflections with I > 2σ(I)
channel-cut Si-<111> crystal	Rint = 0.045
Detector resolution: 83.33 pixels mm-1	θmax = 29.0°, θmin = 2.8°
ω and φ scans	h = −4→4
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	k = −10→10
Tmin = 0.654, Tmax = 0.746	l = −32→32
8561 measured reflections

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(Fo2) + (0.0609P)2 + 1.2501P] where P = (Fo2 + 2Fc2)/3
1622 reflections	(Δ/σ)max < 0.001
117 parameters	Δρmax = 1.03 e Å−3
0 restraints	Δρmin = −0.51 e Å−3

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.

	x	y	z	Uiso*/Ueq
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)

	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)

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—C1iv	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)	K1vi—O2—K1	97.69 (6)
O2i—K1—O1	122.90 (7)	K1vii—O2—K1	130.08 (8)
O1ii—K1—O1	83.96 (6)	K1v—O3—K1	80.87 (7)
O2i—K1—O3ii	83.24 (8)	K1v—O3—H3A	116 (3)
O1ii—K1—O3ii	89.84 (8)	K1—O3—H3A	97 (3)
O1—K1—O3ii	148.85 (8)	K1v—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—C1iv	117.7 (3)
O1ii—K1—O3	149.13 (8)	C5—C1—C1iv	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—K1v	109.68 (18)	C4—C5—C1	119.4 (3)
C6—O1—K1	100.52 (17)	C4—C5—H5A	120.3
K1v—O1—K1	83.96 (6)	C1—C5—H5A	120.3
C6—O2—K1vi	156.4 (2)	O2—C6—O1	125.4 (3)
C6—O2—K1vii	113.13 (18)	O2—C6—C3	117.5 (3)
K1vi—O2—K1vii	82.49 (6)	O1—C6—C3	117.1 (3)
C6—O2—K1	85.69 (17)
O2i—K1—O1—C6	134.52 (17)	K1vi—O2—C6—K1	−99.4 (5)
O1ii—K1—O1—C6	71.04 (18)	K1vii—O2—C6—K1	132.06 (13)
O3ii—K1—O1—C6	−8.6 (3)	K1vi—O2—C6—K1v	−163.2 (4)
O2iii—K1—O1—C6	−159.19 (19)	K1vii—O2—C6—K1v	68.29 (14)
O3—K1—O1—C6	−78.86 (18)	K1—O2—C6—K1v	−63.77 (7)
O2—K1—O1—C6	−10.37 (16)	K1vi—O2—C6—K1vii	128.6 (5)
C6ii—K1—O1—C6	50.56 (15)	K1—O2—C6—K1vii	−132.06 (13)
C6iii—K1—O1—C6	−169.28 (16)	K1v—O1—C6—O2	−64.9 (3)
K1ii—K1—O1—C6	71.04 (18)	K1—O1—C6—O2	22.4 (3)
K1v—K1—O1—C6	−108.96 (18)	K1v—O1—C6—C3	114.8 (2)
O2i—K1—O1—K1v	−116.52 (7)	K1—O1—C6—C3	−157.9 (2)
O1ii—K1—O1—K1v	180.0	K1v—O1—C6—K1	−87.29 (11)
O3ii—K1—O1—K1v	100.40 (15)	K1—O1—C6—K1v	87.29 (11)
O2iii—K1—O1—K1v	−50.23 (6)	K1v—O1—C6—K1vii	−4.1 (3)
O3—K1—O1—K1v	30.09 (7)	K1—O1—C6—K1vii	83.2 (2)
O2—K1—O1—K1v	98.58 (9)	C2—C3—C6—O2	−4.5 (4)
C6—K1—O1—K1v	108.96 (18)	C4—C3—C6—O2	176.1 (3)
C6ii—K1—O1—K1v	159.52 (7)	C2—C3—C6—O1	175.8 (3)
C6iii—K1—O1—K1v	−60.32 (6)	C4—C3—C6—O1	−3.7 (4)
K1ii—K1—O1—K1v	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—K1v	−125.9 (3)
O1—K1—O2—C6	10.31 (16)	C4—C3—C6—K1v	54.7 (4)
O3ii—K1—O2—C6	−168.72 (17)	C2—C3—C6—K1vii	−47.7 (3)
O2iii—K1—O2—C6	41.19 (16)	C4—C3—C6—K1vii	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)
K1v—K1—O2—C6	63.56 (16)	O2iii—K1—C6—O2	−141.38 (15)
O2i—K1—O2—K1vi	89.41 (15)	O3—K1—C6—O2	−60.97 (17)
O1ii—K1—O2—K1vi	75.00 (7)	C6ii—K1—C6—O2	74.81 (17)
O1—K1—O2—K1vi	166.84 (12)	C6iii—K1—C6—O2	−149.60 (19)
O3ii—K1—O2—K1vi	−12.18 (9)	K1ii—K1—C6—O2	74.81 (17)
O2iii—K1—O2—K1vi	−162.27 (8)	K1v—K1—C6—O2	−105.19 (17)
O3—K1—O2—K1vi	−88.21 (8)	O2i—K1—C6—O1	−60.7 (2)
C6—K1—O2—K1vi	156.5 (2)	O1ii—K1—C6—O1	−105.34 (19)
C6ii—K1—O2—K1vi	61.68 (7)	O3ii—K1—C6—O1	174.51 (17)
C6iii—K1—O2—K1vi	−166.30 (7)	O2iii—K1—C6—O1	19.50 (18)
K1ii—K1—O2—K1vi	40.09 (7)	O3—K1—C6—O1	99.91 (18)
K1v—K1—O2—K1vi	−139.91 (7)	O2—K1—C6—O1	160.9 (3)
O2i—K1—O2—K1vii	176.04 (11)	C6ii—K1—C6—O1	−124.31 (16)
O1ii—K1—O2—K1vii	161.63 (11)	C6iii—K1—C6—O1	11.28 (17)
O1—K1—O2—K1vii	−106.52 (13)	K1ii—K1—C6—O1	−124.31 (16)
O3ii—K1—O2—K1vii	74.45 (11)	K1v—K1—C6—O1	55.69 (16)
O2iii—K1—O2—K1vii	−75.64 (13)	O2i—K1—C6—C3	17.7 (6)
O3—K1—O2—K1vii	−1.58 (10)	O1ii—K1—C6—C3	−26.9 (6)
C6—K1—O2—K1vii	−116.8 (2)	O1—K1—C6—C3	78.4 (6)
C6ii—K1—O2—K1vii	148.31 (12)	O3ii—K1—C6—C3	−107.0 (6)
C6iii—K1—O2—K1vii	−79.67 (12)	O2iii—K1—C6—C3	97.9 (6)
K1ii—K1—O2—K1vii	126.73 (8)	O3—K1—C6—C3	178.4 (6)
K1v—K1—O2—K1vii	−53.28 (8)	O2—K1—C6—C3	−120.7 (7)
O2i—K1—O3—K1v	109.38 (9)	C6ii—K1—C6—C3	−45.9 (6)
O1ii—K1—O3—K1v	−105.92 (13)	C6iii—K1—C6—C3	89.7 (6)
O1—K1—O3—K1v	−29.55 (7)	K1ii—K1—C6—C3	−45.9 (6)
O3ii—K1—O3—K1v	180.0	K1v—K1—C6—C3	134.1 (6)
O2iii—K1—O3—K1v	40.27 (6)	O2i—K1—C6—K1v	−116.44 (9)
O2—K1—O3—K1v	−72.29 (7)	O1ii—K1—C6—K1v	−161.03 (6)
C6—K1—O3—K1v	−51.77 (7)	O1—K1—C6—K1v	−55.69 (16)
C6ii—K1—O3—K1v	−107.38 (9)	O3ii—K1—C6—K1v	118.82 (8)
C6iii—K1—O3—K1v	56.64 (7)	O2iii—K1—C6—K1v	−36.19 (6)
K1ii—K1—O3—K1v	180.0	O3—K1—C6—K1v	44.22 (6)
C2—N1—C1—C5	0.1 (4)	O2—K1—C6—K1v	105.19 (17)
C2—N1—C1—C1iv	−179.0 (3)	C6ii—K1—C6—K1v	180.0
C1—N1—C2—C3	−0.4 (5)	C6iii—K1—C6—K1v	−44.41 (7)
N1—C2—C3—C4	0.7 (5)	K1ii—K1—C6—K1v	180.0
N1—C2—C3—C6	−178.8 (3)	O2i—K1—C6—K1vii	173.13 (8)
C2—C3—C4—C5	−0.7 (4)	O1ii—K1—C6—K1vii	128.54 (9)
C6—C3—C4—C5	178.8 (3)	O1—K1—C6—K1vii	−126.1 (2)
C3—C4—C5—C1	0.4 (4)	O3ii—K1—C6—K1vii	48.39 (12)
N1—C1—C5—C4	−0.1 (5)	O2iii—K1—C6—K1vii	−106.62 (8)
C1iv—C1—C5—C4	179.0 (3)	O3—K1—C6—K1vii	−26.21 (8)
K1vi—O2—C6—O1	−119.0 (4)	O2—K1—C6—K1vii	34.76 (13)
K1vii—O2—C6—O1	112.4 (3)	C6ii—K1—C6—K1vii	109.57 (6)
K1—O2—C6—O1	−19.7 (3)	C6iii—K1—C6—K1vii	−114.84 (11)
K1vi—O2—C6—C3	61.2 (6)	K1ii—K1—C6—K1vii	109.57 (6)
K1vii—O2—C6—C3	−67.3 (3)	K1v—K1—C6—K1vii	−70.43 (6)
K1—O2—C6—C3	160.6 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O1vii	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)

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) ; (ii) .