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The basic architectural motif of the title compound, [Cu2(C2H3O2)4(C4H5N3)], is a chain of alternating tetrakis(μ-acetato)­dicopper(II) and 2-amino­pyrimidine moieties in which square-pyramidal copper(II) centres are alternately linked by four bridging acetate anions [Cu—O = 1.947 (2)–1.984 (2) Å] and a single bridging 2-amino­pyrimidine mol­ecule [Cu—N 2.214 (2) Å]. N—H...O and C—H...O hydrogen bonds support the Cu—N coordination to generate the chains, which align perpendicular to the (10\overline 1) plane. The dinuclear copper unit has crystallographic inversion symmetry, and the 2-amino­pyrimidine bridging ligand has twofold rotation symmetry.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802002544/cf6150sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536802002544/cf6150Isup2.hkl
Contains datablock I

CCDC reference: 182581

Key indicators

  • Single-crystal X-ray study
  • T = 150 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.024
  • wR factor = 0.064
  • Data-to-parameter ratio = 12.6

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
PLAT_213 Alert C Atom C14 has ADP max/min Ratio ........... 3.20 prolate General Notes
ABSTM_02 The ratio of expected to reported Tmax/Tmin(RR) is > 1.10 Tmin and Tmax reported: 0.375 0.623 Tmin and Tmax expected: 0.283 0.616 RR = 1.310 Please check that your absorption correction is appropriate.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check

Comment top

The structure of the title compound, (I), has been reported at 296 K (Smith et al., 1991). Continuing our studies of the coordination chemistry of the tetrakis(acetato)dicopper(II) moiety with nitrogen bases (Begley et al., 1993), we now report its structure at 150 K. The asymmetric unit of the title compound comprises half a tetrakis(acetato)dicopper(II) moiety, the complete dinuclear unit being located on an inversion centre, and half a 2-aminopyrimidine ligand, which is located on a twofold symmetry axis passing through N12, C12 and C14 (Fig. 1). The square-pyramidal coordination geometry of the copper(II) centre comprises four basal O atoms from four bridging acetate anions [Cu—O 1.947 (2), 1.948 (2), 1.983 (2) and, 1.984 (2) Å] and an axial N atom from a single bridging 2-aminopyrimidine molecule [Cu—N 2.214 (2) Å].

The basic architectural motif of the extended structure is a zigzag chain (Fig. 2) of alternating tetrakis(acetato)dicopper(II) and 2-aminopyrimidine moieties. The zigzag motif of the chains, which pack perpendicular to the (101) plane (Fig. 3) with alternating copper(II)–copper(II) separations of 2.6281 (14) and 6.4589 (14) Å, results from the 120° angle between the σ-donor orbitals of the pyrimidine heterocyclic N atoms. Two hydrogen-bonding contacts, one N—H···O and one C—H···O, support the Cu—N coordination to generate the chain structure. The significance of the hydrogen-bonding interactions comes, not from their dimensions [N—H 0.86 (2), H···O 2.04 (2), N···O 2.872 (3) Å and N—H···O 161 (3)°; C—H 0.93, H···O 2.34, C···O 2.987 (3) Å and C—H···O 127°], which are moderated by the Cu—N coordination, but from the low value of the dihedral angle (7.2°) between the plane containing the copper centres and the pyrimidine molecule and the plane containing the copper centres and the two acetate anions providing the hydrogen-bond acceptors.

Experimental top

Careful layering of a methanol solution (5 ml) of Cu(OAc)2·H2O (0.079 g, 0.396 mmol) with a dichloromethane solution (5 ml) of N,N'-bis(pyrimidin-2-yl)thiourea (0.090 g, 0.387 mmol), previously prepared by reaction of 2-aminopyrimidine (2.02 g, 21.2 mol) with carbon disulfide (2.41 g, 31.7 mmol) and sulfur (0.178 g, 5.55 mmol) in ethanol (50 ml), yielded, over a period of 7 d, two sets of large chunky crystals, which proved to be Cu(OAc)2·H2O (located at the bottom of the vial) and the title compound (located on the walls of the vial). The latter was assumed to arise via ligand decomposition.

Refinement top

Amino H atoms were located from ΔF syntheses and refined with the N—H distance restrained to be 0.88 (1) Å and with Uiso(H) = 1.5Ueq(N). Methyl H atoms were located from ΔF syntheses and refined as part of a rigid rotating group with C—H = 0.96 Å and with Uiso(H) = 1.5Ueq(C). After location from ΔF syntheses, aromatic H atoms were placed geometrically and refined with a riding model for which the C—H distance was constrained to be 0.93 Å and Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: STADI4 (Stoe & Cie, 1995); cell refinement: STADI-4; data reduction: X-RED (Stoe & Cie, 1995); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2002).

Figures top
[Figure 1] Fig. 1. A view of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probablility level. [Symmetry codes: (i) 1/2 - x, 1/2 - y, 1 - z; (ii) -x, y, 3/2 - z.]
[Figure 2] Fig. 2. A view of the zigzag chain of alternating tetrakis(acetato)dicopper(II) and 2-aminopyrimidine moieties. Atoms are identified as follows: Cu, large blue circles; C, black circles; N, blue circles; O, red circles; H, small yellow circles. [Symmetry code: (i) 1/2 - x, 1/2 - y, 1 - z.]
[Figure 3] Fig. 3. A view of the extended structure of the title compound perpendicular to the (101) plane, showing the packing of the chains. Atoms are identified as in Fig. 2.
catena-Poly[[tetrakis(µ-acetato-κO:κO')dicopper(II)]-µ-2-aminopyrimidine- κ2N:N'] top
Crystal data top
[Cu2(C2H3O2)4(C4H5N3)]F(000) = 928
Mr = 458.36Dx = 1.735 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 15.096 (8) ÅCell parameters from 25 reflections
b = 13.585 (8) Åθ = 12.8–17.0°
c = 8.580 (4) ŵ = 2.47 mm1
β = 94.13 (5)°T = 150 K
V = 1755.0 (16) Å3Tablet, dark green
Z = 40.53 × 0.45 × 0.20 mm
Data collection top
Stoe Stadi-4 four-circle
diffractometer
1428 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.016
Graphite monochromatorθmax = 25.0°, θmin = 2.7°
ω/θ scansh = 1717
Absorption correction: numerical
(X-RED; Stoe & Cie, 1995)
k = 016
Tmin = 0.375, Tmax = 0.623l = 210
1980 measured reflections3 standard reflections every 60 min
1517 independent reflections intensity decay: none
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.024Hydrogen site location: difference Fourier map
wR(F2) = 0.064H atoms treated by a mixture of independent and constrained refinement
S = 1.15 w = 1/[σ2(Fo2) + (0.03P)2 + 4.087P]
where P = (Fo2 + 2Fc2)/3
1517 reflections(Δ/σ)max = 0.001
120 parametersΔρmax = 0.32 e Å3
1 restraintΔρmin = 0.45 e Å3
Crystal data top
[Cu2(C2H3O2)4(C4H5N3)]V = 1755.0 (16) Å3
Mr = 458.36Z = 4
Monoclinic, C2/cMo Kα radiation
a = 15.096 (8) ŵ = 2.47 mm1
b = 13.585 (8) ÅT = 150 K
c = 8.580 (4) Å0.53 × 0.45 × 0.20 mm
β = 94.13 (5)°
Data collection top
Stoe Stadi-4 four-circle
diffractometer
1428 reflections with I > 2σ(I)
Absorption correction: numerical
(X-RED; Stoe & Cie, 1995)
Rint = 0.016
Tmin = 0.375, Tmax = 0.6233 standard reflections every 60 min
1980 measured reflections intensity decay: none
1517 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0241 restraint
wR(F2) = 0.064H atoms treated by a mixture of independent and constrained refinement
S = 1.15Δρmax = 0.32 e Å3
1517 reflectionsΔρmin = 0.45 e Å3
120 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
xyzUiso*/Ueq
Cu10.180242 (17)0.28120 (2)0.56882 (3)0.01252 (12)
C10.16842 (17)0.27617 (17)0.2372 (3)0.0177 (5)
C110.12003 (19)0.2918 (2)0.0805 (3)0.0270 (6)
H11A0.05870.27430.08560.040*
H11B0.14610.25140.00420.040*
H11C0.12430.35980.05130.040*
O110.12790 (12)0.29606 (15)0.3558 (2)0.0269 (4)
O120.24662 (13)0.24461 (16)0.2392 (2)0.0293 (5)
C20.18900 (16)0.07504 (18)0.5111 (3)0.0177 (5)
C210.1577 (2)0.0303 (2)0.5196 (4)0.0326 (7)
H21A0.16460.06230.42150.049*
H21B0.09630.03130.54160.049*
H21C0.19240.06410.60110.049*
O210.14316 (12)0.14108 (13)0.5678 (2)0.0280 (4)
O220.26016 (12)0.08964 (13)0.4490 (2)0.0285 (5)
N110.06641 (12)0.34547 (14)0.6823 (2)0.0149 (4)
C120.00000.2989 (2)0.75000.0121 (6)
N120.00000.2004 (2)0.75000.0177 (6)
H120.0425 (14)0.1701 (19)0.708 (3)0.027*
C130.06495 (19)0.44346 (19)0.6845 (4)0.0324 (7)
H130.11010.47750.63940.039*
C140.00000.4964 (3)0.75000.0501 (15)
H140.00000.56490.75000.060*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.01110 (17)0.01386 (18)0.01312 (17)0.00103 (11)0.00451 (11)0.00030 (10)
C10.0216 (13)0.0138 (12)0.0177 (12)0.0012 (9)0.0023 (10)0.0013 (9)
C110.0311 (15)0.0312 (15)0.0179 (13)0.0113 (12)0.0028 (11)0.0027 (11)
O110.0194 (9)0.0445 (12)0.0170 (9)0.0128 (8)0.0022 (7)0.0011 (8)
O120.0223 (10)0.0511 (12)0.0146 (9)0.0145 (9)0.0025 (7)0.0011 (8)
C20.0199 (13)0.0163 (12)0.0174 (11)0.0013 (10)0.0039 (10)0.0002 (10)
C210.0331 (16)0.0183 (14)0.0483 (18)0.0051 (12)0.0162 (13)0.0023 (13)
O210.0251 (10)0.0168 (9)0.0449 (11)0.0024 (8)0.0220 (8)0.0028 (8)
O220.0229 (10)0.0168 (9)0.0485 (12)0.0036 (8)0.0214 (9)0.0070 (8)
N110.0137 (10)0.0141 (10)0.0178 (10)0.0008 (8)0.0066 (8)0.0006 (8)
C120.0116 (15)0.0170 (17)0.0075 (14)0.0000.0011 (12)0.000
N120.0162 (15)0.0131 (15)0.0254 (16)0.0000.0129 (12)0.000
C130.0278 (15)0.0149 (13)0.0580 (19)0.0016 (11)0.0287 (14)0.0037 (13)
C140.045 (3)0.0120 (19)0.100 (4)0.0000.053 (3)0.000
Geometric parameters (Å, º) top
Cu1—Cu1i2.6281 (14)N11—C121.352 (2)
Cu1—N112.214 (2)C12—N121.339 (4)
Cu1—O111.949 (2)C13—C141.369 (3)
Cu1—O12i1.947 (2)C11—H11A0.960
Cu1—O211.984 (2)C11—H11B0.960
Cu1—O22i1.983 (2)C11—H11C0.960
C1—O111.254 (3)C21—H21A0.960
C1—O121.255 (3)C21—H21B0.960
C1—C111.499 (4)C21—H21C0.960
C2—O221.249 (3)N12—H120.863 (10)
C2—O211.252 (3)C13—H130.930
C2—C211.510 (4)C14—H140.930
N11—C131.331 (3)
O12i—Cu1—O11168.16 (8)C13—N11—C12116.6 (2)
O12i—Cu1—O22i89.53 (9)C13—N11—Cu1114.49 (16)
O11—Cu1—O22i89.52 (9)C12—N11—Cu1128.87 (17)
O12i—Cu1—O2188.49 (9)N12—C12—N11117.91 (15)
O11—Cu1—O2189.99 (9)N12—C12—N11ii117.91 (15)
O22i—Cu1—O21168.01 (7)N11—C12—N11ii124.2 (3)
O12i—Cu1—N1196.31 (8)N11—C13—C14123.0 (3)
O11—Cu1—N1195.53 (8)C13ii—C14—C13116.6 (4)
O22i—Cu1—N1193.19 (8)C1—C11—H11A109.5
O21—Cu1—N1198.78 (8)C1—C11—H11B109.5
O12i—Cu1—Cu1i84.15 (7)H11A—C11—H11B109.5
O11—Cu1—Cu1i84.03 (7)C1—C11—H11C109.5
O22i—Cu1—Cu1i82.42 (6)H11A—C11—H11C109.5
O21—Cu1—Cu1i85.61 (6)H11B—C11—H11C109.5
N11—Cu1—Cu1i175.59 (5)C2—C21—H21A109.5
O11—C1—O12125.2 (2)C2—C21—H21B109.5
O11—C1—C11117.6 (2)H21A—C21—H21B109.5
O12—C1—C11117.3 (2)C2—C21—H21C109.5
C1—O11—Cu1123.38 (17)H21A—C21—H21C109.5
C1—O12—Cu1i123.27 (17)H21B—C21—H21C109.5
O22—C2—O21124.6 (2)C12—N12—H12118 (2)
O22—C2—C21116.9 (2)N11—C13—H13118.5
O21—C2—C21118.5 (2)C14—C13—H13118.5
C2—O21—Cu1121.70 (16)C13—C14—H14121.7
C2—O22—Cu1i125.62 (17)
C13—N11—C12—N12179.75 (19)C12—N11—C13—C140.5 (4)
C13—N11—C12—N11ii0.25 (19)N11—C13—C14—C13ii0.3 (2)
Symmetry codes: (i) x+1/2, y+1/2, z+1; (ii) x, y, z+3/2.

Experimental details

Crystal data
Chemical formula[Cu2(C2H3O2)4(C4H5N3)]
Mr458.36
Crystal system, space groupMonoclinic, C2/c
Temperature (K)150
a, b, c (Å)15.096 (8), 13.585 (8), 8.580 (4)
β (°) 94.13 (5)
V3)1755.0 (16)
Z4
Radiation typeMo Kα
µ (mm1)2.47
Crystal size (mm)0.53 × 0.45 × 0.20
Data collection
DiffractometerStoe Stadi-4 four-circle
diffractometer
Absorption correctionNumerical
(X-RED; Stoe & Cie, 1995)
Tmin, Tmax0.375, 0.623
No. of measured, independent and
observed [I > 2σ(I)] reflections
1980, 1517, 1428
Rint0.016
(sin θ/λ)max1)0.594
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.024, 0.064, 1.15
No. of reflections1517
No. of parameters120
No. of restraints1
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.32, 0.45

Computer programs: STADI4 (Stoe & Cie, 1995), STADI-4, X-RED (Stoe & Cie, 1995), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), CAMERON (Watkin et al., 1996), SHELXL97 and PLATON (Spek, 2002).

Selected bond lengths (Å) top
Cu1—Cu1i2.6281 (14)Cu1—O12i1.947 (2)
Cu1—N112.214 (2)Cu1—O211.984 (2)
Cu1—O111.949 (2)Cu1—O22i1.983 (2)
Symmetry code: (i) x+1/2, y+1/2, z+1.
 

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