Aqua-(2,2'-bipyridine-κN,N')bis-(thio-phene-2-carboxyl-ato-κO)copper(II).

In the title complex, [Cu(C(5)H(3)O(2)S)(2)(C(10)H(8)N(2))(H(2)O)], the Cu(II) atom is in a distorted square-pyramidal environment, with an Addison τ parameter of 0.07. The coordination geometry is defined by two nitro-gen donors from the 2,2'-bipyridine ligand, two O atoms from two monodentate thio-phene-2-carboxyl-ate ligands and one O atom from the aqua ligand. The latter occupies the elongated apical position. This is different from the related structure of aqua-(1,10-phenanthroline)bis-(thio-phene-2-carboxyl-ato)copper(II) where a carboxyl-ate O atom is in the apical position [Feng et al. (2005 ▶). Z. Kristallogr. New Cryst. Struct.220, 429-430]. The uncoordinated carboxyl-ate O atoms form intra- and inter-molecular hydrogen bonds to the aqua ligand. Two neighbouring 2,2'-bipyridine ligands form a π-stack, with a centroid-centroid distance of 3.683 (2) Å.

Related literature

Thio­phenes substituted in the 2-position are an important constituent of the drugs methapyrilene, temidap, tienilic acid and temocillin (Rance & Damani, 1989 ▶). Metal complexes containing the thio­phene unit have exhibited enhanced anti-amoebic activity (Bharti et al., 2003 ▶). For the use of thio­phene-2-carboxylic acid (Htpc) to prepare single mol­ecular magnet (SMM) and photoluminescence materials, see: Kuroda-Sowa et al. (2003 ▶); Teotonio et al. (2004 ▶). For the thermal behavior of metal–tpc complexes, see: Lumme & Korvola (1975 ▶). For the structures of 2-thio­phene­carboxyl­ate complexes, see: Feng et al. (2005 ▶); Panagoulis et al. (2007 ▶); Byrnes et al. (2004 ▶); Yin & Sun (2005 ▶); Yin et al. (2004 ▶). For hydrogen bonds from the aqua ligand to uncoordinated carboxyl O atoms, see: Habib & Janiak (2008 ▶); Wisser & Janiak (2007a ▶,b ▶); Janiak (2000 ▶). For details of the Addison τ parameter, see: Addison et al. (1984 ▶).

Experimental

Crystal data

[Cu(C5H3O2S)2(C10H8N2)(H2O)]

M = 492.01

Monoclinic,

a = 6.8458 (5) Å

b = 18.3799 (15) Å

c = 16.8421 (12) Å

β = 101.5164 (19)°

V = 2076.5 (3) Å3

Z = 4

Mo Kα radiation

μ = 1.29 mm−1

T = 123 K

0.35 × 0.22 × 0.18 mm

Data collection

Rigaku R-AXIS Spider image-plate detector diffractometer

Absorption correction: multi-scan (; Higashi, 1995 ▶) T min = 0.661, T max = 0.801

32855 measured reflections

4224 independent reflections

3637 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.099

S = 1.05

4224 reflections

277 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.64 e Å−3

Δρmin = −0.60 e Å−3

Data collection: CrystalClear (Rigaku, 2007 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Crystal Impact, 2009 ▶); software used to prepare material for publication: publCIF (Westrip, 2009 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809026713/fj2230sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809026713/fj2230Isup2.hkl

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

[Cu(C5H3O2S)2(C10H8N2)(H2O)]	F(000) = 1004
Mr = 492.01	Dx = 1.574 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 28386 reflections
a = 6.8458 (5) Å	θ = 3.0–27.5°
b = 18.3799 (15) Å	µ = 1.29 mm−1
c = 16.8421 (12) Å	T = 123 K
β = 101.5164 (19)°	Column, blue
V = 2076.5 (3) Å3	0.35 × 0.22 × 0.18 mm
Z = 4

Rigaku R-AXIS Spider image-plate detector diffractometer	4224 independent reflections
Radiation source: fine-focus sealed tube	3637 reflections with I > 2σ(I)
graphite	Rint = 0.034
ω scans	θmax = 26.4°, θmin = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −8→8
Tmin = 0.661, Tmax = 0.801	k = −22→22
32855 measured reflections	l = −21→21

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0489P)2 + 2.2127P] where P = (Fo2 + 2Fc2)/3
4224 reflections	(Δ/σ)max < 0.001
277 parameters	Δρmax = 0.64 e Å−3
0 restraints	Δρmin = −0.59 e Å−3

Experimental. IR (ATR): 3315 (m, br, νO-H, H-bonded), 3075 (m, sh, νC-H, aromatic), 3115 (m, sh) 1557 (s, sh, νasymCO2, ionically bonded to COO-Cu), 1520 (s, sh, νasymCO2, intramolecularly H-bonded), 1470 (m, sh) 1422 (s, sh) 1370 (s, sh, νsymCO2), 1336 (m, sh) (νC-O, free), 1312 (w, br, νC-O···H—O, H-bonded), 1224 (m, sh, νC-O), 1115 (s, sh, νC-N), 1056 (m, sh), 1026 (s, sh), 982 (m, sh), 911 (m, sh), 860 (s, sh), 808 (m, sh), 770 (s, sh), 713 (s, sh), 659 (w, sh), 631 (w, br), 539 (w, sh, νCu-O), 506 (m, sh), 461 (m, sh), 412 (s, sh, νCu-N) cm-1.

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
Cu	0.67488 (4)	0.151034 (16)	0.393556 (18)	0.02638 (11)
S1	0.63575 (13)	0.46085 (4)	0.37885 (5)	0.0465 (2)
S2	0.31914 (12)	0.17767 (6)	0.10820 (5)	0.0497 (2)
O1	0.5925 (3)	0.25157 (10)	0.40169 (12)	0.0373 (4)
O2	0.8271 (3)	0.31699 (10)	0.35780 (12)	0.0355 (4)
O3	0.5534 (3)	0.15076 (10)	0.27585 (11)	0.0331 (4)
O4	0.2930 (3)	0.12147 (11)	0.32959 (11)	0.0351 (4)
O5	0.9860 (3)	0.18398 (12)	0.38761 (14)	0.0391 (5)
H5A	0.964 (6)	0.221 (2)	0.374 (2)	0.059*
H5B	1.062 (6)	0.168 (2)	0.368 (2)	0.059*
N1	0.7125 (3)	0.04250 (12)	0.39954 (12)	0.0266 (4)
N2	0.7215 (3)	0.13725 (11)	0.51474 (12)	0.0277 (4)
C1	0.7038 (4)	−0.00185 (15)	0.33635 (17)	0.0340 (6)
H1	0.6855	0.0186	0.2836	0.041*
C2	0.7204 (4)	−0.07660 (16)	0.34483 (19)	0.0391 (6)
H2	0.7140	−0.1069	0.2987	0.047*
C3	0.7463 (4)	−0.10622 (15)	0.4214 (2)	0.0395 (7)
H3	0.7583	−0.1574	0.4288	0.047*
C4	0.7545 (4)	−0.06063 (14)	0.48737 (18)	0.0324 (6)
H4	0.7713	−0.0802	0.5405	0.039*
C5	0.7381 (3)	0.01361 (13)	0.47514 (15)	0.0256 (5)
C6	0.7470 (3)	0.06754 (13)	0.54036 (15)	0.0252 (5)
C7	0.7786 (4)	0.05039 (16)	0.62249 (16)	0.0331 (6)
H7	0.7931	0.0011	0.6398	0.040*
C8	0.7884 (4)	0.10584 (18)	0.67850 (17)	0.0398 (7)
H8	0.8117	0.0951	0.7348	0.048*
C9	0.7643 (5)	0.17670 (18)	0.65216 (18)	0.0423 (7)
H9	0.7712	0.2155	0.6899	0.051*
C10	0.7296 (4)	0.19039 (15)	0.56982 (17)	0.0371 (6)
H10	0.7108	0.2393	0.5516	0.045*
C11	0.6649 (4)	0.30992 (14)	0.37863 (14)	0.0289 (5)
C12	0.5375 (4)	0.37527 (14)	0.38065 (15)	0.0300 (5)
C13	0.3272 (5)	0.37346 (17)	0.38295 (17)	0.0406 (7)
H13	0.2457	0.3316	0.3830	0.049*
C14	0.2658 (5)	0.45070 (18)	0.3853 (2)	0.0508 (8)
H14	0.1336	0.4647	0.3878	0.061*
C15	0.4127 (5)	0.49975 (17)	0.3835 (2)	0.0488 (8)
H15	0.3930	0.5509	0.3847	0.059*
C16	0.3672 (4)	0.13855 (13)	0.27060 (15)	0.0285 (5)
C17	0.2351 (4)	0.14483 (13)	0.18962 (16)	0.0300 (5)
C18	0.0315 (4)	0.12344 (15)	0.16881 (17)	0.0351 (6)
H18	−0.0438	0.1036	0.2053	0.042*
C19	−0.0425 (5)	0.13653 (18)	0.0838 (2)	0.0492 (8)
H19	−0.1754	0.1259	0.0573	0.059*
C20	0.0926 (5)	0.1648 (2)	0.04594 (19)	0.0513 (8)
H20	0.0657	0.1767	−0.0101	0.062*

	U11	U22	U33	U12	U13	U23
Cu	0.02852 (17)	0.02612 (17)	0.02524 (17)	0.00260 (12)	0.00714 (12)	0.00575 (12)
S1	0.0513 (5)	0.0344 (4)	0.0543 (5)	0.0013 (3)	0.0115 (4)	0.0014 (3)
S2	0.0458 (4)	0.0696 (6)	0.0346 (4)	0.0073 (4)	0.0100 (3)	0.0159 (4)
O1	0.0436 (11)	0.0269 (9)	0.0451 (11)	0.0056 (8)	0.0177 (9)	0.0092 (8)
O2	0.0343 (10)	0.0339 (10)	0.0397 (11)	0.0042 (8)	0.0108 (8)	0.0075 (8)
O3	0.0298 (9)	0.0420 (11)	0.0278 (9)	0.0031 (8)	0.0064 (7)	0.0086 (8)
O4	0.0352 (10)	0.0409 (11)	0.0318 (10)	0.0069 (8)	0.0131 (8)	0.0117 (8)
O5	0.0311 (10)	0.0376 (11)	0.0523 (13)	0.0088 (9)	0.0172 (9)	0.0111 (10)
N1	0.0231 (10)	0.0294 (11)	0.0269 (11)	0.0020 (8)	0.0041 (8)	0.0024 (8)
N2	0.0280 (10)	0.0299 (11)	0.0261 (11)	−0.0029 (9)	0.0078 (8)	0.0020 (9)
C1	0.0312 (13)	0.0391 (14)	0.0308 (14)	0.0027 (11)	0.0042 (11)	−0.0032 (11)
C2	0.0318 (14)	0.0390 (15)	0.0462 (17)	0.0003 (12)	0.0070 (12)	−0.0111 (13)
C3	0.0303 (14)	0.0276 (13)	0.0612 (19)	−0.0002 (11)	0.0102 (13)	−0.0010 (13)
C4	0.0243 (12)	0.0282 (13)	0.0446 (15)	0.0018 (10)	0.0061 (11)	0.0085 (11)
C5	0.0163 (10)	0.0302 (12)	0.0298 (12)	−0.0006 (9)	0.0031 (9)	0.0050 (10)
C6	0.0186 (11)	0.0306 (12)	0.0265 (12)	−0.0020 (9)	0.0047 (9)	0.0050 (10)
C7	0.0273 (12)	0.0415 (15)	0.0300 (13)	−0.0001 (11)	0.0044 (10)	0.0094 (11)
C8	0.0358 (15)	0.0585 (18)	0.0254 (13)	−0.0037 (13)	0.0064 (11)	0.0026 (13)
C9	0.0448 (16)	0.0499 (17)	0.0327 (15)	−0.0066 (14)	0.0088 (12)	−0.0107 (13)
C10	0.0449 (16)	0.0333 (14)	0.0347 (15)	−0.0039 (12)	0.0115 (12)	−0.0035 (12)
C11	0.0346 (14)	0.0301 (13)	0.0207 (12)	0.0040 (11)	0.0024 (10)	0.0043 (10)
C12	0.0379 (14)	0.0268 (12)	0.0257 (12)	0.0017 (11)	0.0073 (10)	0.0048 (10)
C13	0.0475 (16)	0.0420 (16)	0.0388 (15)	0.0290 (14)	0.0243 (13)	0.0167 (13)
C14	0.0514 (19)	0.0436 (17)	0.064 (2)	0.0156 (15)	0.0272 (17)	0.0092 (15)
C15	0.063 (2)	0.0322 (15)	0.0548 (19)	0.0135 (14)	0.0199 (16)	0.0066 (14)
C16	0.0322 (13)	0.0258 (12)	0.0285 (13)	0.0059 (10)	0.0088 (10)	0.0048 (10)
C17	0.0350 (14)	0.0272 (12)	0.0280 (13)	0.0054 (11)	0.0067 (11)	0.0058 (10)
C18	0.0321 (13)	0.0338 (14)	0.0334 (14)	0.0017 (11)	−0.0081 (11)	0.0038 (11)
C19	0.0461 (17)	0.0504 (18)	0.0441 (18)	−0.0021 (15)	−0.0081 (14)	0.0014 (15)
C20	0.056 (2)	0.066 (2)	0.0277 (15)	0.0155 (17)	−0.0012 (14)	0.0041 (14)

Cu—O1	1.9447 (18)	C4—C5	1.381 (3)
Cu—O3	1.9909 (19)	C4—H4	0.9500
Cu—N1	2.011 (2)	C5—C6	1.472 (4)
Cu—N2	2.018 (2)	C6—C7	1.393 (3)
Cu—O5	2.236 (2)	C7—C8	1.381 (4)
S1—C15	1.702 (3)	C7—H7	0.9500
S1—C12	1.714 (3)	C8—C9	1.375 (4)
S2—C17	1.700 (3)	C8—H8	0.9500
S2—C20	1.706 (3)	C9—C10	1.383 (4)
O1—C11	1.274 (3)	C9—H9	0.9500
O2—C11	1.236 (3)	C10—H10	0.9500
O3—C16	1.280 (3)	C11—C12	1.489 (4)
O4—C16	1.243 (3)	C12—C13	1.448 (4)
O5—H5A	0.73 (4)	C13—C14	1.483 (4)
O5—H5B	0.73 (4)	C13—H13	0.9500
N1—C1	1.332 (3)	C14—C15	1.355 (5)
N1—C5	1.358 (3)	C14—H14	0.9500
N2—C10	1.340 (3)	C15—H15	0.9500
N2—C6	1.352 (3)	C16—C17	1.483 (4)
C1—C2	1.384 (4)	C17—C18	1.423 (4)
C1—H1	0.9500	C18—C19	1.440 (4)
C2—C3	1.378 (4)	C18—H18	0.9500
C2—H2	0.9500	C19—C20	1.330 (5)
C3—C4	1.384 (4)	C19—H19	0.9500
C3—H3	0.9500	C20—H20	0.9500
O1—Cu—O3	90.18 (8)	C8—C7—H7	120.4
O1—Cu—N1	167.13 (8)	C6—C7—H7	120.4
O3—Cu—N1	94.08 (8)	C9—C8—C7	119.5 (3)
O1—Cu—N2	92.15 (8)	C9—C8—H8	120.3
O3—Cu—N2	163.16 (8)	C7—C8—H8	120.3
N1—Cu—N2	80.33 (8)	C8—C9—C10	118.8 (3)
O1—Cu—O5	92.18 (8)	C8—C9—H9	120.6
O3—Cu—O5	99.70 (8)	C10—C9—H9	120.6
N1—Cu—O5	99.04 (8)	N2—C10—C9	122.5 (3)
N2—Cu—O5	96.87 (8)	N2—C10—H10	118.8
C15—S1—C12	91.48 (15)	C9—C10—H10	118.8
C17—S2—C20	91.96 (15)	O2—C11—O1	126.9 (2)
C11—O1—Cu	129.96 (17)	O2—C11—C12	119.0 (2)
C16—O3—Cu	106.35 (16)	O1—C11—C12	114.0 (2)
Cu—O5—H5A	97 (3)	C13—C12—C11	124.9 (2)
Cu—O5—H5B	133 (3)	C13—C12—S1	114.7 (2)
H5A—O5—H5B	110 (4)	C11—C12—S1	120.4 (2)
C1—N1—C5	119.1 (2)	C12—C13—C14	105.5 (3)
C1—N1—Cu	125.59 (18)	C12—C13—H13	127.3
C5—N1—Cu	115.21 (17)	C14—C13—H13	127.3
C10—N2—C6	119.0 (2)	C15—C14—C13	114.9 (3)
C10—N2—Cu	125.80 (18)	C15—C14—H14	122.5
C6—N2—Cu	115.21 (17)	C13—C14—H14	122.5
N1—C1—C2	122.4 (3)	C14—C15—S1	113.4 (2)
N1—C1—H1	118.8	C14—C15—H15	123.3
C2—C1—H1	118.8	S1—C15—H15	123.3
C3—C2—C1	118.8 (3)	O4—C16—O3	123.3 (2)
C3—C2—H2	120.6	O4—C16—C17	118.9 (2)
C1—C2—H2	120.6	O3—C16—C17	117.8 (2)
C2—C3—C4	119.3 (3)	C18—C17—C16	126.3 (2)
C2—C3—H3	120.4	C18—C17—S2	111.8 (2)
C4—C3—H3	120.4	C16—C17—S2	121.8 (2)
C5—C4—C3	119.3 (3)	C17—C18—C19	109.4 (3)
C5—C4—H4	120.4	C17—C18—H18	125.3
C3—C4—H4	120.4	C19—C18—H18	125.3
N1—C5—C4	121.2 (2)	C20—C19—C18	113.7 (3)
N1—C5—C6	114.5 (2)	C20—C19—H19	123.2
C4—C5—C6	124.3 (2)	C18—C19—H19	123.2
N2—C6—C7	121.1 (2)	C19—C20—S2	113.2 (2)
N2—C6—C5	114.6 (2)	C19—C20—H20	123.4
C7—C6—C5	124.3 (2)	S2—C20—H20	123.4
C8—C7—C6	119.2 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O2	0.73 (4)	1.99 (4)	2.682 (3)	160 (4)
O5—H5B···O4i	0.73 (4)	2.02 (4)	2.741 (3)	171 (4)

Cu—O1	1.9447 (18)
Cu—O3	1.9909 (19)
Cu—N1	2.011 (2)
Cu—N2	2.018 (2)
Cu—O5	2.236 (2)

O1—Cu—O3	90.18 (8)
O1—Cu—N1	167.13 (8)
O3—Cu—N1	94.08 (8)
O1—Cu—N2	92.15 (8)
O3—Cu—N2	163.16 (8)
N1—Cu—N2	80.33 (8)
O1—Cu—O5	92.18 (8)
O3—Cu—O5	99.70 (8)
N1—Cu—O5	99.04 (8)
N2—Cu—O5	96.87 (8)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5A⋯O2	0.73 (4)	1.99 (4)	2.682 (3)	160 (4)
O5—H5B⋯O4i	0.73 (4)	2.02 (4)	2.741 (3)	171 (4)

Symmetry code: (i) .