Bis(μ-3-carboxyl­ato­phenoxy­acetato)­bis­[(1H-imidazole)copper(II)] dihydrate

In the title centrosymmetric dinuclear complex, [Cu₂(3-CPOA)₂(C₃H₄N₂)₄]·2H₂O (3-CPOA²⁻ is the 3-carboxyl­ato­phenoxy­acetate dianion, C₉H₆O₅), each Cu^II ion is coordin­ated by three carboxyl O atoms, one ether O atom from two 3–CPOA²⁻ groups and two N atoms from two imidazole co-ligands, displaying an elongated square-pyramidal coordin­ation geometry with a based capped by one very long semicoordinate Cu—O_carboxyl bond [2.8191 (15) Å]. The two Cu^II ions are bridged by 3–CPOA²⁻ ligands, generating a macrocyclic ring motif, with a Cu...Cu separation of 6.879 (3) Å. The dinuclear motifs are further linked into a two-dimensional supramolecular network via hydrogen-bonding interactions.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.038
• wR factor = 0.099
• Data-to-parameter ratio = 16.5

checkCIF/PLATON results

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Computing details

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Bis(µ-3-carboxylatophenoxyacetato)bis[(1H-imidazole)copper(II)] dihydrate

Crystal data

[Cu2(C9H6O5)2(C3H4N2)4]·2H2O	F(000) = 844
Mr = 823.74	Dx = 1.551 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 15849 reflections
a = 9.997 (2) Å	θ = 3.1–27.4°
b = 16.422 (3) Å	µ = 1.28 mm^−1
c = 10.857 (2) Å	T = 293 K
β = 98.20 (3)°	Prism, blue
V = 1764.2 (6) Å^3	0.35 × 0.26 × 0.19 mm
Z = 2

Data collection

Rigaku R-AXIS RAPID diffractometer	3982 independent reflections
Radiation source: fine-focus sealed tube	3319 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
Detector resolution: 10 pixels mm^-1	θmax = 27.4°, θmin = 3.1°
ω scans	h = −12→12
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −21→21
Tmin = 0.663, Tmax = 0.793	l = −13→14
16077 measured reflections

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.099	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0558P)^2 + 0.5757P] where P = (Fo^2 + 2Fc^2)/3
3982 reflections	(Δ/σ)max = 0.001
241 parameters	Δρmax = 0.48 e Å^−3
3 restraints	Δρmin = −0.28 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.14180 (3)	0.625677 (16)	0.73660 (2)	0.04230 (11)
N1	0.2031 (2)	0.51828 (12)	0.80959 (19)	0.0506 (4)
N2	0.2494 (2)	0.38832 (13)	0.8197 (2)	0.0621 (6)
N3	0.08196 (19)	0.73278 (11)	0.66421 (18)	0.0468 (4)
N4	0.0060 (2)	0.82315 (13)	0.52347 (19)	0.0580 (5)
O1	0.29451 (16)	0.67706 (10)	0.83965 (14)	0.0506 (4)
O2	0.50898 (17)	0.71365 (11)	0.87529 (17)	0.0615 (5)
O3	0.31831 (17)	0.62502 (10)	0.61070 (16)	0.0541 (4)
O4	0.01582 (15)	0.43002 (9)	0.35865 (14)	0.0464 (3)
O5	0.11393 (18)	0.40470 (11)	0.19206 (16)	0.0574 (4)
O1W	0.2490 (2)	0.24494 (13)	0.6957 (3)	0.0853 (7)
C1	0.1796 (3)	0.44715 (15)	0.7545 (3)	0.0562 (6)
C2	0.2928 (3)	0.50325 (17)	0.9156 (2)	0.0605 (6)
C3	0.3218 (3)	0.42300 (18)	0.9233 (3)	0.0660 (7)
C4	0.0061 (3)	0.74458 (16)	0.5558 (2)	0.0562 (6)
C5	0.1319 (3)	0.80922 (15)	0.7008 (2)	0.0552 (6)
C6	0.0843 (3)	0.86452 (15)	0.6139 (3)	0.0582 (6)
C7	0.4088 (2)	0.68862 (13)	0.8054 (2)	0.0472 (5)
C8	0.4278 (2)	0.67252 (15)	0.6708 (2)	0.0510 (5)
C9	0.3300 (2)	0.58693 (13)	0.49955 (19)	0.0417 (4)
C10	0.4383 (2)	0.59762 (15)	0.4350 (2)	0.0500 (5)
C11	0.4397 (2)	0.55467 (16)	0.3251 (2)	0.0559 (6)
C12	0.3365 (2)	0.50259 (16)	0.2802 (2)	0.0498 (5)
C13	0.2271 (2)	0.49280 (12)	0.34492 (19)	0.0392 (4)
C14	0.2242 (2)	0.53554 (13)	0.45458 (19)	0.0398 (4)
C15	0.1119 (2)	0.43824 (13)	0.2944 (2)	0.0419 (5)
H1W1	0.217 (3)	0.1972 (11)	0.703 (4)	0.128*
H1W2	0.326 (2)	0.240 (2)	0.671 (4)	0.128*
H1	0.1223	0.4391	0.6802	0.067*
H2	0.3280	0.5424	0.9731	0.073*
H3	0.3790	0.3967	0.9859	0.079*
H4	−0.0409	0.7038	0.5083	0.067*
H5	0.1892	0.8205	0.7740	0.066*
H6	0.1020	0.9201	0.6158	0.070*
H8A	0.4319	0.7238	0.6272	0.061*
H8B	0.5122	0.6438	0.6685	0.061*
H10	0.5085	0.6328	0.4645	0.060*
H11	0.5121	0.5613	0.2809	0.067*
H12	0.3398	0.4740	0.2068	0.060*
H14	0.1511	0.5297	0.4981	0.048*
H16	0.2489	0.3376	0.8001	0.075*
H17	−0.0369	0.8438	0.4564	0.070*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.04254 (16)	0.04153 (16)	0.04086 (16)	−0.00437 (10)	−0.00078 (11)	−0.00196 (10)
N1	0.0484 (10)	0.0496 (11)	0.0527 (11)	−0.0017 (9)	0.0034 (9)	0.0033 (9)
N2	0.0626 (13)	0.0508 (12)	0.0765 (16)	0.0038 (10)	0.0220 (12)	0.0097 (10)
N3	0.0489 (10)	0.0445 (10)	0.0441 (10)	−0.0027 (8)	−0.0032 (8)	−0.0009 (8)
N4	0.0635 (12)	0.0576 (12)	0.0502 (11)	0.0068 (10)	−0.0010 (10)	0.0117 (10)
O1	0.0507 (9)	0.0520 (9)	0.0456 (8)	−0.0051 (7)	−0.0054 (7)	−0.0048 (7)
O2	0.0508 (9)	0.0635 (11)	0.0638 (11)	−0.0044 (8)	−0.0135 (8)	−0.0149 (9)
O3	0.0462 (9)	0.0656 (11)	0.0505 (9)	−0.0195 (7)	0.0075 (7)	−0.0191 (8)
O4	0.0436 (8)	0.0488 (8)	0.0462 (8)	−0.0093 (7)	0.0045 (7)	−0.0054 (7)
O5	0.0610 (10)	0.0626 (10)	0.0482 (9)	−0.0052 (8)	0.0062 (8)	−0.0184 (8)
O1W	0.0708 (13)	0.0620 (12)	0.124 (2)	−0.0040 (10)	0.0160 (14)	−0.0084 (13)
C1	0.0541 (13)	0.0477 (13)	0.0666 (16)	−0.0004 (11)	0.0083 (12)	0.0064 (11)
C2	0.0693 (16)	0.0610 (15)	0.0501 (14)	0.0043 (13)	0.0043 (12)	0.0060 (12)
C3	0.0686 (17)	0.0688 (18)	0.0613 (16)	0.0099 (14)	0.0115 (14)	0.0180 (14)
C4	0.0602 (14)	0.0547 (14)	0.0489 (13)	−0.0042 (11)	−0.0083 (11)	−0.0006 (11)
C5	0.0577 (14)	0.0469 (13)	0.0571 (14)	−0.0023 (11)	−0.0053 (11)	−0.0053 (11)
C6	0.0650 (16)	0.0427 (13)	0.0653 (16)	−0.0012 (11)	0.0037 (13)	0.0033 (11)
C7	0.0481 (12)	0.0342 (10)	0.0547 (13)	0.0011 (9)	−0.0081 (10)	−0.0033 (9)
C8	0.0438 (11)	0.0496 (13)	0.0570 (13)	−0.0111 (10)	−0.0021 (10)	−0.0070 (10)
C9	0.0427 (11)	0.0427 (11)	0.0390 (10)	−0.0023 (9)	0.0039 (9)	0.0009 (9)
C10	0.0429 (11)	0.0550 (13)	0.0515 (13)	−0.0113 (10)	0.0052 (10)	0.0027 (10)
C11	0.0457 (12)	0.0721 (16)	0.0527 (13)	−0.0085 (12)	0.0167 (11)	0.0006 (12)
C12	0.0501 (12)	0.0581 (14)	0.0425 (11)	0.0019 (10)	0.0105 (10)	−0.0008 (10)
C13	0.0378 (10)	0.0401 (10)	0.0390 (10)	0.0018 (8)	0.0033 (8)	0.0019 (8)
C14	0.0389 (10)	0.0436 (11)	0.0369 (10)	−0.0044 (8)	0.0058 (8)	0.0002 (8)
C15	0.0441 (11)	0.0386 (10)	0.0409 (11)	0.0021 (9)	−0.0011 (9)	−0.0014 (9)

Geometric parameters (Å, º)

Cu1—N1	1.994 (2)	O1W—H1W2	0.858 (10)
Cu1—N3	1.9837 (19)	C1—H1	0.9300
Cu1—O1	1.9513 (16)	C2—C3	1.350 (4)
Cu1—O3	2.3814 (18)	C2—H2	0.9300
Cu1—O4^i	1.9810 (15)	C3—H3	0.9300
Cu1—O5^i	2.8191 (15)	C4—H4	0.9300
O1—C7	1.266 (3)	C5—C6	1.347 (4)
O2—C7	1.238 (3)	C5—H5	0.9300
O4—C15	1.273 (3)	C6—H6	0.9300
O5—C15	1.243 (3)	C7—C8	1.523 (3)
N1—C1	1.318 (3)	C8—H8A	0.9700
N1—C2	1.377 (3)	C8—H8B	0.9700
N2—C1	1.334 (3)	C9—C10	1.382 (3)
N2—C3	1.372 (4)	C9—C14	1.386 (3)
N2—H16	0.8600	C10—C11	1.388 (3)
N3—C4	1.321 (3)	C10—H10	0.9300
N3—C5	1.388 (3)	C11—C12	1.375 (3)
N4—C4	1.337 (3)	C11—H11	0.9300
N4—C6	1.349 (3)	C12—C13	1.391 (3)
N4—H17	0.8600	C12—H12	0.9300
O3—C8	1.424 (3)	C13—C14	1.386 (3)
O3—C9	1.379 (3)	C13—C15	1.500 (3)
O4—Cu1^i	1.9810 (15)	C14—H14	0.9300
O1W—H1W1	0.856 (10)
N1—Cu1—O3	90.76 (7)	C2—C3—N2	105.7 (3)
N3—Cu1—N1	179.65 (8)	C2—C3—H3	127.1
N3—Cu1—O3	89.02 (7)	C3—N2—H16	126.0
O1—Cu1—N1	89.07 (8)	C3—C2—N1	109.6 (3)
O1—Cu1—N3	90.62 (8)	C3—C2—H2	125.2
O1—Cu1—O3	75.39 (6)	C4—N3—Cu1	125.85 (17)
O1—Cu1—O4^i	176.45 (7)	C4—N3—C5	105.1 (2)
O4^i—Cu1—N1	88.60 (8)	C4—N4—C6	108.5 (2)
O4^i—Cu1—N3	91.72 (7)	C4—N4—H17	125.8
O4^i—Cu1—O3	107.31 (6)	C5—N3—Cu1	127.80 (16)
O5^i—Cu1—N1	88.52 (7)	C5—C6—N4	106.3 (2)
O5^i—Cu1—N3	91.83 (7)	C5—C6—H6	126.9
O5^i—Cu1—O1	125.82 (7)	C6—N4—H17	125.8
O5^i—Cu1—O3	158.76 (6)	C6—C5—N3	109.4 (2)
O5^i—Cu1—O4^i	51.45 (6)	C6—C5—H5	125.3
N1—C1—N2	110.8 (2)	C7—O1—Cu1	124.16 (15)
N1—C1—H1	124.6	C7—C8—H8A	109.7
N1—C2—H2	125.2	C7—C8—H8B	109.7
N2—C1—H1	124.6	C8—O3—Cu1	108.58 (13)
N2—C3—H3	127.1	C9—O3—Cu1	131.81 (13)
N3—C4—N4	110.8 (2)	C9—O3—C8	119.59 (17)
N3—C4—H4	124.6	C9—C10—C11	118.5 (2)
N3—C5—H5	125.3	C9—C10—H10	120.8
N4—C4—H4	124.6	C9—C14—H14	119.9
N4—C6—H6	126.9	C10—C9—C14	120.8 (2)
O1—C7—C8	119.82 (19)	C10—C11—H11	119.3
O2—C7—O1	123.7 (2)	C11—C10—H10	120.8
O2—C7—C8	116.5 (2)	C11—C12—C13	119.8 (2)
O3—C8—C7	109.98 (19)	C11—C12—H12	120.1
O3—C8—H8A	109.7	C12—C11—C10	121.4 (2)
O3—C8—H8B	109.7	C12—C11—H11	119.3
O3—C9—C10	123.8 (2)	C12—C13—C15	120.13 (19)
O3—C9—C14	115.40 (18)	C13—C12—H12	120.1
O4—C15—C13	117.57 (18)	C13—C14—C9	120.18 (19)
O5—C15—O4	123.6 (2)	C13—C14—H14	119.9
O5—C15—C13	118.85 (19)	C14—C13—C12	119.3 (2)
C1—N1—C2	105.8 (2)	C14—C13—C15	120.53 (18)
C1—N1—Cu1	125.38 (17)	C15—O4—Cu1^i	111.66 (13)
C1—N2—C3	108.0 (2)	H1W1—O1W—H1W2	108.0 (16)
C1—N2—H16	126.0	H8A—C8—H8B	108.2
C2—N1—Cu1	128.13 (18)
Cu1—N1—C1—N2	171.33 (16)	O3—C9—C10—C11	178.8 (2)
Cu1—N1—C2—C3	−171.30 (18)	O3—C9—C14—C13	−178.59 (19)
Cu1—N3—C4—N4	−167.86 (17)	O4^i—Cu1—N1—C1	29.6 (2)
Cu1—N3—C5—C6	167.67 (19)	O4^i—Cu1—N1—C2	−161.0 (2)
Cu1—O1—C7—O2	−172.42 (17)	O4^i—Cu1—N3—C4	−26.0 (2)
Cu1—O1—C7—C8	8.4 (3)	O4^i—Cu1—N3—C5	169.0 (2)
Cu1—O3—C8—C7	14.1 (2)	O4^i—Cu1—O3—C8	173.59 (15)
Cu1—O3—C9—C10	175.81 (17)	O4^i—Cu1—O3—C9	−8.2 (2)
Cu1—O3—C9—C14	−4.3 (3)	C1—N1—C2—C3	−0.3 (3)
Cu1^i—O4—C15—O5	−10.1 (3)	C1—N2—C3—C2	−0.4 (3)
Cu1^i—O4—C15—C13	168.75 (14)	C2—N1—C1—N2	0.0 (3)
N1—Cu1—O1—C7	91.36 (18)	C3—N2—C1—N1	0.3 (3)
N1—Cu1—O3—C8	−97.64 (16)	C4—N3—C5—C6	0.2 (3)
N1—Cu1—O3—C9	80.6 (2)	C4—N4—C6—C5	0.2 (3)
N1—C2—C3—N2	0.4 (3)	C5—N3—C4—N4	−0.1 (3)
N3—Cu1—O1—C7	−88.49 (18)	C6—N4—C4—N3	−0.1 (3)
N3—Cu1—O3—C8	82.10 (16)	C8—O3—C9—C10	−6.1 (3)
N3—Cu1—O3—C9	−99.7 (2)	C8—O3—C9—C14	173.7 (2)
N3—C5—C6—N4	−0.3 (3)	C9—O3—C8—C7	−164.43 (19)
O1—Cu1—N1—C1	−153.1 (2)	C9—C10—C11—C12	0.1 (4)
O1—Cu1—N1—C2	16.3 (2)	C10—C9—C14—C13	1.3 (3)
O1—Cu1—N3—C4	156.7 (2)	C10—C11—C12—C13	0.6 (4)
O1—Cu1—N3—C5	−8.3 (2)	C11—C12—C13—C14	−0.4 (3)
O1—Cu1—O3—C8	−8.80 (15)	C11—C12—C13—C15	178.0 (2)
O1—Cu1—O3—C9	169.4 (2)	C12—C13—C14—C9	−0.5 (3)
O1—C7—C8—O3	−15.8 (3)	C12—C13—C15—O4	178.5 (2)
O2—C7—C8—O3	164.9 (2)	C12—C13—C15—O5	−2.7 (3)
O3—Cu1—N1—C1	−77.7 (2)	C14—C9—C10—C11	−1.0 (4)
O3—Cu1—N1—C2	91.7 (2)	C14—C13—C15—O4	−3.2 (3)
O3—Cu1—N3—C4	81.3 (2)	C14—C13—C15—O5	175.7 (2)
O3—Cu1—N3—C5	−83.7 (2)	C15—C13—C14—C9	−178.87 (19)
O3—Cu1—O1—C7	0.33 (17)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H16···O1W	0.86	1.90	2.712 (3)	158
N4—H17···O5^ii	0.86	1.96	2.812 (3)	171
O1W—H1W1···O5^iii	0.85 (2)	1.96 (3)	2.802 (3)	168 (4)
O1W—H1W2···O2^iv	0.85 (2)	1.84 (3)	2.691 (3)	172 (4)

Symmetry codes: (ii) −x, y+1/2, −z+1/2; (iii) x, −y+1/2, z+1/2; (iv) −x+1, y−1/2, −z+3/2.