Bis(2,2′-bipyrid­yl)(dichloro­acetato)copper(II) dichloro­acetate dihydrate

Abstract

In the title compound, [Cu(C₂HCl₂O₂)(C₁₀H₈N₂)₂](C₂HCl₂O₂)·2H₂O, the Cu^II ion is bonded to two N,N′-bidentate 2,2′-bipyridyl ligands and one O-monodentate 2,2-dichloro­acetate anion in a distorted CuON₄ trigonal-bipyramidal geometry, with the O atom occupying an equatorial site. In the crystal, the components are linked by O—H⋯O and O—H⋯Cl hydrogen bonds.

Related literature

For a related structure, see: Barszcz et al. (2004 ▶).

Experimental

Crystal data

• [Cu(C₂HCl₂O₂)(C₁₀H₈N₂)₂](C₂HCl₂O₂)·2H₂O

• M _r = 667.80

• Triclinic,

• a = 9.9710 (7) Å

• b = 11.7307 (9) Å

• c = 12.4736 (9) Å

• α = 105.407 (1)°

• β = 101.499 (1)°

• γ = 95.513 (1)°

• V = 1361.07 (17) ų

• Z = 2

• Mo Kα radiation

• μ = 1.24 mm⁻¹

• T = 293 K

• 0.22 × 0.20 × 0.18 mm

Data collection

• Bruker SMART CCD diffractometer

• 7789 measured reflections

• 5280 independent reflections

• 4592 reflections with I > 2σ(I)

• R _int = 0.033

Refinement

• R[F ² > 2σ(F ²)] = 0.034

• wR(F ²) = 0.097

• S = 1.06

• 5280 reflections

• 365 parameters

• 7 restraints

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.65 e Å⁻³

• Δρ_min = −0.64 e Å⁻³

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

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

Table 1. Selected bond lengths (Å).

Cu1—N1	1.9879 (18)
Cu1—N4	1.9889 (18)
Cu1—O1	2.0121 (16)
Cu1—N3	2.0711 (18)
Cu1—N2	2.1201 (18)

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1A⋯Cl2	0.84 (2)	2.79 (2)	3.571 (3)	155 (4)
O1W—H1B⋯O4	0.86 (2)	1.93 (2)	2.787 (4)	171 (4)
O2W—H2A⋯Cl1	0.88 (2)	2.76 (2)	3.511 (3)	144 (3)
O2W—H2B⋯O3i	0.87 (2)	1.89 (2)	2.757 (3)	172 (4)

Symmetry code: (i) .

supplementary crystallographic information

Experimental

Copper(II) 2,2-dicholoracetate, 0.32 g (1 mmol) and 2,2'-bipyridine 0.31 g (2 mmol) were added to 65 ml anhydrous alcohol under stirring. The mixture was refluxed for 7 h. The blue solution was filtered and the filtrate was left to stand undisturbed. Upon slow evaporation at room temperature, blue blocks of (I) appeared three days later and were separated by filtration.

Refinement

The water H atoms were located in a difference map and freely refined. The C-bonded H atoms were positioned geometrically (C—H = 0.93–0.98 Å) and refined as riding with U_iso(H) = 1.2U_eq(C).

Figures

Fig. 1.

The molecular structure for (I), with displacement ellipsoids drawn at the 30% probability level.

Crystal data

[Cu(C2HCl2O2)(C10H8N2)2](C2HCl2O2)·2H2O	Z = 2
Mr = 667.80	F(000) = 678
Triclinic, P1	Dx = 1.629 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.9710 (7) Å	Cell parameters from 2240 reflections
b = 11.7307 (9) Å	θ = 2.2–28.3°
c = 12.4736 (9) Å	µ = 1.24 mm−1
α = 105.407 (1)°	T = 293 K
β = 101.499 (1)°	Block, blue
γ = 95.513 (1)°	0.22 × 0.20 × 0.18 mm
V = 1361.07 (17) Å3

Data collection

Bruker SMART CCD diffractometer	4592 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.033
graphite	θmax = 26.0°, θmin = 1.8°
phi and ω scans	h = −11→12
7789 measured reflections	k = −13→14
5280 independent reflections	l = −15→14

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.034	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.097	w = 1/[σ2(Fo2) + (0.0542P)2 + 0.3598P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max < 0.001
5280 reflections	Δρmax = 0.65 e Å−3
365 parameters	Δρmin = −0.64 e Å−3
7 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0256 (15)

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
Cu1	0.02070 (3)	0.28505 (2)	0.24318 (2)	0.03074 (11)
Cl1	0.45242 (8)	0.39464 (9)	0.06435 (8)	0.0741 (3)
Cl2	0.50350 (6)	0.30032 (6)	0.25678 (6)	0.04867 (17)
O1	0.21727 (16)	0.36582 (14)	0.27220 (14)	0.0396 (4)
O2	0.17501 (17)	0.31459 (16)	0.08196 (15)	0.0459 (4)
N1	−0.06224 (19)	0.43199 (16)	0.24029 (15)	0.0318 (4)
N2	−0.05985 (19)	0.31277 (16)	0.39146 (15)	0.0326 (4)
N3	−0.13923 (19)	0.17107 (16)	0.11654 (15)	0.0328 (4)
N4	0.08416 (19)	0.12907 (17)	0.24147 (16)	0.0347 (4)
C1	−0.0573 (3)	0.4885 (2)	0.1606 (2)	0.0406 (5)
H1	−0.0007	0.4659	0.1103	0.049*
C2	−0.1329 (3)	0.5790 (2)	0.1503 (2)	0.0465 (6)
H2	−0.1280	0.6162	0.0936	0.056*
C3	−0.2157 (3)	0.6134 (2)	0.2255 (2)	0.0467 (6)
H3	−0.2691	0.6732	0.2193	0.056*
C4	−0.2185 (2)	0.5581 (2)	0.3104 (2)	0.0415 (5)
H4	−0.2722	0.5816	0.3629	0.050*
C5	−0.1403 (2)	0.46721 (18)	0.31641 (18)	0.0303 (4)
C6	−0.1365 (2)	0.40123 (18)	0.40308 (17)	0.0299 (4)
C7	−0.2055 (2)	0.4282 (2)	0.4908 (2)	0.0404 (5)
H6	−0.2572	0.4905	0.4982	0.049*
C8	−0.1960 (3)	0.3608 (2)	0.5670 (2)	0.0460 (6)
H8	−0.2415	0.3771	0.6263	0.055*
C9	−0.1187 (3)	0.2699 (2)	0.5541 (2)	0.0472 (6)
H9	−0.1114	0.2233	0.6041	0.057*
C10	−0.0515 (3)	0.2483 (2)	0.4653 (2)	0.0411 (5)
H10	0.0013	0.1868	0.4569	0.049*
C11	−0.2514 (2)	0.1998 (2)	0.0568 (2)	0.0405 (5)
H11	−0.2605	0.2802	0.0702	0.049*
C12	−0.3538 (3)	0.1155 (3)	−0.0237 (2)	0.0495 (6)
H12	−0.4300	0.1383	−0.0644	0.059*
C13	−0.3404 (3)	−0.0027 (3)	−0.0422 (2)	0.0525 (7)
H13	−0.4082	−0.0614	−0.0960	0.063*
C14	−0.2268 (3)	−0.0348 (2)	0.0188 (2)	0.0457 (6)
H14	−0.2175	−0.1150	0.0072	0.055*
C15	−0.1260 (2)	0.05451 (19)	0.09785 (18)	0.0334 (5)
C16	0.0007 (2)	0.0309 (2)	0.16703 (19)	0.0351 (5)
C17	0.0356 (3)	−0.0829 (2)	0.1571 (2)	0.0478 (6)
H17	−0.0222	−0.1500	0.1051	0.057*
C18	0.1576 (3)	−0.0946 (3)	0.2256 (3)	0.0571 (8)
H18	0.1831	−0.1698	0.2199	0.069*
C19	0.2412 (3)	0.0060 (3)	0.3024 (2)	0.0528 (7)
H19	0.3232	−0.0005	0.3495	0.063*
C20	0.2015 (3)	0.1165 (2)	0.3086 (2)	0.0450 (6)
H20	0.2577	0.1843	0.3607	0.054*
C21	0.2517 (2)	0.35388 (19)	0.1777 (2)	0.0341 (5)
C22	0.4076 (2)	0.3961 (2)	0.1938 (2)	0.0402 (5)
H22	0.4324	0.4778	0.2456	0.048*
Cl3	0.17481 (9)	0.06640 (8)	0.59492 (10)	0.0833 (3)
Cl4	0.36379 (9)	−0.04850 (8)	0.72163 (7)	0.0722 (2)
O3	0.4801 (3)	0.2075 (2)	0.7501 (2)	0.0807 (7)
O4	0.4943 (3)	0.1598 (2)	0.5687 (3)	0.0971 (9)
C23	0.3436 (3)	0.0293 (2)	0.6185 (2)	0.0466 (6)
H23A	0.3545	−0.0240	0.5466	0.056*
C24	0.4501 (3)	0.1442 (3)	0.6506 (3)	0.0550 (7)
O1W	0.4574 (3)	0.3842 (2)	0.5424 (2)	0.0744 (7)
H1A	0.455 (4)	0.384 (4)	0.4747 (19)	0.089*
H1B	0.467 (4)	0.312 (2)	0.543 (3)	0.089*
O2W	0.2759 (3)	0.6333 (2)	0.1579 (3)	0.0885 (8)
H2A	0.299 (3)	0.579 (2)	0.104 (2)	0.106*
H2B	0.349 (3)	0.686 (3)	0.192 (3)	0.106*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cu1	0.03054 (16)	0.02735 (16)	0.03555 (17)	0.00635 (10)	0.00873 (11)	0.00987 (11)
Cl1	0.0572 (4)	0.1167 (7)	0.0791 (5)	0.0245 (5)	0.0366 (4)	0.0615 (5)
Cl2	0.0370 (3)	0.0532 (4)	0.0565 (4)	0.0097 (3)	0.0046 (3)	0.0210 (3)
O1	0.0362 (8)	0.0390 (9)	0.0408 (9)	0.0010 (7)	0.0126 (7)	0.0062 (7)
O2	0.0399 (9)	0.0490 (10)	0.0437 (10)	0.0044 (8)	0.0057 (8)	0.0091 (8)
N1	0.0333 (9)	0.0273 (9)	0.0355 (9)	0.0062 (7)	0.0103 (8)	0.0083 (7)
N2	0.0341 (9)	0.0306 (9)	0.0314 (9)	0.0031 (7)	0.0070 (8)	0.0073 (7)
N3	0.0332 (9)	0.0300 (9)	0.0337 (9)	0.0034 (7)	0.0085 (8)	0.0070 (7)
N4	0.0354 (10)	0.0352 (10)	0.0375 (10)	0.0100 (8)	0.0118 (8)	0.0130 (8)
C1	0.0478 (14)	0.0352 (12)	0.0423 (13)	0.0085 (10)	0.0143 (11)	0.0140 (10)
C2	0.0562 (16)	0.0365 (13)	0.0501 (14)	0.0084 (11)	0.0097 (12)	0.0199 (11)
C3	0.0469 (14)	0.0349 (13)	0.0582 (16)	0.0147 (11)	0.0073 (12)	0.0140 (11)
C4	0.0384 (12)	0.0368 (13)	0.0480 (14)	0.0108 (10)	0.0112 (11)	0.0076 (10)
C5	0.0250 (10)	0.0268 (10)	0.0339 (11)	−0.0008 (8)	0.0038 (8)	0.0040 (8)
C6	0.0251 (10)	0.0287 (10)	0.0300 (10)	−0.0027 (8)	0.0036 (8)	0.0031 (8)
C7	0.0343 (12)	0.0429 (13)	0.0396 (12)	0.0027 (10)	0.0116 (10)	0.0034 (10)
C8	0.0433 (14)	0.0579 (16)	0.0347 (12)	−0.0009 (12)	0.0162 (11)	0.0078 (11)
C9	0.0540 (15)	0.0526 (15)	0.0374 (13)	−0.0002 (12)	0.0121 (11)	0.0191 (11)
C10	0.0464 (14)	0.0402 (13)	0.0401 (13)	0.0074 (10)	0.0115 (11)	0.0160 (10)
C11	0.0361 (12)	0.0399 (13)	0.0423 (13)	0.0057 (10)	0.0047 (10)	0.0100 (10)
C12	0.0372 (13)	0.0603 (17)	0.0445 (14)	0.0023 (12)	0.0023 (11)	0.0119 (12)
C13	0.0465 (15)	0.0520 (16)	0.0445 (14)	−0.0091 (12)	0.0039 (12)	0.0008 (12)
C14	0.0526 (15)	0.0332 (12)	0.0450 (14)	−0.0018 (11)	0.0142 (12)	0.0018 (10)
C15	0.0377 (12)	0.0306 (11)	0.0328 (11)	0.0034 (9)	0.0149 (9)	0.0068 (9)
C16	0.0426 (12)	0.0314 (11)	0.0382 (12)	0.0084 (10)	0.0209 (10)	0.0123 (9)
C17	0.0645 (17)	0.0339 (13)	0.0553 (15)	0.0157 (12)	0.0273 (13)	0.0179 (11)
C18	0.081 (2)	0.0492 (16)	0.0656 (18)	0.0368 (15)	0.0391 (17)	0.0323 (14)
C19	0.0521 (16)	0.0683 (19)	0.0564 (16)	0.0319 (14)	0.0212 (13)	0.0349 (15)
C20	0.0412 (13)	0.0545 (15)	0.0449 (13)	0.0157 (12)	0.0108 (11)	0.0207 (12)
C21	0.0345 (11)	0.0244 (10)	0.0450 (13)	0.0052 (9)	0.0116 (10)	0.0110 (9)
C22	0.0361 (12)	0.0368 (12)	0.0500 (14)	0.0044 (10)	0.0134 (11)	0.0148 (11)
Cl3	0.0527 (4)	0.0712 (5)	0.1169 (8)	0.0183 (4)	−0.0088 (5)	0.0304 (5)
Cl4	0.0675 (5)	0.0819 (6)	0.0722 (5)	0.0014 (4)	−0.0030 (4)	0.0485 (4)
O3	0.0808 (17)	0.0708 (16)	0.0752 (16)	−0.0105 (13)	0.0049 (13)	0.0133 (13)
O4	0.139 (3)	0.0615 (15)	0.108 (2)	0.0046 (15)	0.068 (2)	0.0287 (14)
C23	0.0518 (15)	0.0491 (15)	0.0428 (13)	0.0156 (12)	0.0092 (12)	0.0187 (11)
C24	0.0577 (17)	0.0466 (16)	0.0661 (19)	0.0142 (13)	0.0198 (15)	0.0196 (14)
O1W	0.0842 (16)	0.0731 (16)	0.0853 (17)	0.0306 (13)	0.0462 (15)	0.0298 (14)
O2W	0.0756 (17)	0.0565 (15)	0.130 (2)	0.0066 (12)	0.0219 (17)	0.0243 (15)

Geometric parameters (Å, °)

Cu1—N1	1.9879 (18)	C9—H9	0.9300
Cu1—N4	1.9889 (18)	C10—H10	0.9300
Cu1—O1	2.0121 (16)	C11—C12	1.378 (3)
Cu1—N3	2.0711 (18)	C11—H11	0.9300
Cu1—N2	2.1201 (18)	C12—C13	1.368 (4)
Cl1—C22	1.755 (3)	C12—H12	0.9300
Cl2—C22	1.780 (2)	C13—C14	1.377 (4)
O1—C21	1.268 (3)	C13—H13	0.9300
O2—C21	1.225 (3)	C14—C15	1.390 (3)
N1—C1	1.340 (3)	C14—H14	0.9300
N1—C5	1.352 (3)	C15—C16	1.476 (3)
N2—C10	1.333 (3)	C16—C17	1.391 (3)
N2—C6	1.341 (3)	C17—C18	1.382 (4)
N3—C11	1.339 (3)	C17—H17	0.9300
N3—C15	1.349 (3)	C18—C19	1.377 (4)
N4—C20	1.341 (3)	C18—H18	0.9300
N4—C16	1.350 (3)	C19—C20	1.379 (4)
C1—C2	1.378 (3)	C19—H19	0.9300
C1—H1	0.9300	C20—H20	0.9300
C2—C3	1.377 (4)	C21—C22	1.542 (3)
C2—H2	0.9300	C22—H22	0.9800
C3—C4	1.385 (4)	Cl3—C23	1.766 (3)
C3—H3	0.9300	Cl4—C23	1.757 (3)
C4—C5	1.388 (3)	O3—C24	1.225 (4)
C4—H4	0.9300	O4—C24	1.239 (4)
C5—C6	1.484 (3)	C23—C24	1.540 (4)
C6—C7	1.388 (3)	C23—H23A	0.9800
C7—C8	1.384 (4)	O1W—H1A	0.839 (18)
C7—H6	0.9300	O1W—H1B	0.861 (19)
C8—C9	1.369 (4)	O2W—H2A	0.884 (16)
C8—H8	0.9300	O2W—H2B	0.867 (18)
C9—C10	1.385 (3)
N1—Cu1—N4	174.19 (8)	C9—C10—H10	118.8
N1—Cu1—O1	94.77 (7)	N3—C11—C12	122.9 (2)
N4—Cu1—O1	91.01 (7)	N3—C11—H11	118.5
N1—Cu1—N3	94.63 (7)	C12—C11—H11	118.5
N4—Cu1—N3	80.37 (7)	C13—C12—C11	118.3 (3)
O1—Cu1—N3	142.56 (7)	C13—C12—H12	120.9
N1—Cu1—N2	79.44 (7)	C11—C12—H12	120.9
N4—Cu1—N2	98.73 (7)	C12—C13—C14	120.0 (2)
O1—Cu1—N2	114.17 (7)	C12—C13—H13	120.0
N3—Cu1—N2	103.17 (7)	C14—C13—H13	120.0
C21—O1—Cu1	109.56 (14)	C13—C14—C15	119.0 (2)
C1—N1—C5	119.18 (19)	C13—C14—H14	120.5
C1—N1—Cu1	123.79 (15)	C15—C14—H14	120.5
C5—N1—Cu1	116.62 (15)	N3—C15—C14	121.1 (2)
C10—N2—C6	118.93 (19)	N3—C15—C16	115.17 (19)
C10—N2—Cu1	127.95 (16)	C14—C15—C16	123.8 (2)
C6—N2—Cu1	112.90 (14)	N4—C16—C17	121.1 (2)
C11—N3—C15	118.69 (19)	N4—C16—C15	115.04 (19)
C11—N3—Cu1	127.97 (16)	C17—C16—C15	123.8 (2)
C15—N3—Cu1	113.30 (14)	C18—C17—C16	119.0 (3)
C20—N4—C16	119.4 (2)	C18—C17—H17	120.5
C20—N4—Cu1	124.53 (17)	C16—C17—H17	120.5
C16—N4—Cu1	116.08 (15)	C19—C18—C17	119.5 (2)
N1—C1—C2	122.5 (2)	C19—C18—H18	120.3
N1—C1—H1	118.7	C17—C18—H18	120.3
C2—C1—H1	118.7	C18—C19—C20	119.1 (3)
C3—C2—C1	118.8 (2)	C18—C19—H19	120.5
C3—C2—H2	120.6	C20—C19—H19	120.5
C1—C2—H2	120.6	N4—C20—C19	121.9 (3)
C2—C3—C4	119.2 (2)	N4—C20—H20	119.0
C2—C3—H3	120.4	C19—C20—H20	119.0
C4—C3—H3	120.4	O2—C21—O1	126.7 (2)
C3—C4—C5	119.4 (2)	O2—C21—C22	120.8 (2)
C3—C4—H4	120.3	O1—C21—C22	112.5 (2)
C5—C4—H4	120.3	C21—C22—Cl1	112.61 (17)
N1—C5—C4	120.8 (2)	C21—C22—Cl2	108.80 (16)
N1—C5—C6	115.24 (18)	Cl1—C22—Cl2	108.94 (13)
C4—C5—C6	123.9 (2)	C21—C22—H22	108.8
N2—C6—C7	121.7 (2)	Cl1—C22—H22	108.8
N2—C6—C5	114.97 (18)	Cl2—C22—H22	108.8
C7—C6—C5	123.4 (2)	C24—C23—Cl4	113.67 (19)
C8—C7—C6	118.9 (2)	C24—C23—Cl3	109.08 (18)
C8—C7—H6	120.6	Cl4—C23—Cl3	109.69 (15)
C6—C7—H6	120.6	C24—C23—H23A	108.1
C9—C8—C7	119.2 (2)	Cl4—C23—H23A	108.1
C9—C8—H8	120.4	Cl3—C23—H23A	108.1
C7—C8—H8	120.4	O3—C24—O4	128.5 (3)
C8—C9—C10	119.0 (2)	O3—C24—C23	118.1 (3)
C8—C9—H9	120.5	O4—C24—C23	113.4 (3)
C10—C9—H9	120.5	H1A—O1W—H1B	104 (4)
N2—C10—C9	122.3 (2)	H2A—O2W—H2B	107 (2)
N2—C10—H10	118.8

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1A···Cl2	0.84 (2)	2.79 (2)	3.571 (3)	155 (4)
O1W—H1B···O4	0.86 (2)	1.93 (2)	2.787 (4)	171 (4)
O2W—H2A···Cl1	0.88 (2)	2.76 (2)	3.511 (3)	144 (3)
O2W—H2B···O3i	0.87 (2)	1.89 (2)	2.757 (3)	172 (4)

Symmetry codes: (i) −x+1, −y+1, −z+1.