Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802002544/cf6150sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802002544/cf6150Isup2.hkl |
CCDC reference: 182581
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (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
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
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.
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).
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).
[Cu2(C2H3O2)4(C4H5N3)] | F(000) = 928 |
Mr = 458.36 | Dx = 1.735 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 15.096 (8) Å | Cell parameters from 25 reflections |
b = 13.585 (8) Å | θ = 12.8–17.0° |
c = 8.580 (4) Å | µ = 2.47 mm−1 |
β = 94.13 (5)° | T = 150 K |
V = 1755.0 (16) Å3 | Tablet, dark green |
Z = 4 | 0.53 × 0.45 × 0.20 mm |
Stoe Stadi-4 four-circle diffractometer | 1428 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.016 |
Graphite monochromator | θmax = 25.0°, θmin = 2.7° |
ω/θ scans | h = −17→17 |
Absorption correction: numerical (X-RED; Stoe & Cie, 1995) | k = 0→16 |
Tmin = 0.375, Tmax = 0.623 | l = −2→10 |
1980 measured reflections | 3 standard reflections every 60 min |
1517 independent reflections | intensity decay: none |
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)] = 0.024 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.064 | H 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 parameters | Δρmax = 0.32 e Å−3 |
1 restraint | Δρmin = −0.45 e Å−3 |
[Cu2(C2H3O2)4(C4H5N3)] | V = 1755.0 (16) Å3 |
Mr = 458.36 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 15.096 (8) Å | µ = 2.47 mm−1 |
b = 13.585 (8) Å | T = 150 K |
c = 8.580 (4) Å | 0.53 × 0.45 × 0.20 mm |
β = 94.13 (5)° |
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 = 0.623 | 3 standard reflections every 60 min |
1980 measured reflections | intensity decay: none |
1517 independent reflections |
R[F2 > 2σ(F2)] = 0.024 | 1 restraint |
wR(F2) = 0.064 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.15 | Δρmax = 0.32 e Å−3 |
1517 reflections | Δρmin = −0.45 e Å−3 |
120 parameters |
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 | ||
Cu1 | 0.180242 (17) | 0.28120 (2) | 0.56882 (3) | 0.01252 (12) | |
C1 | 0.16842 (17) | 0.27617 (17) | 0.2372 (3) | 0.0177 (5) | |
C11 | 0.12003 (19) | 0.2918 (2) | 0.0805 (3) | 0.0270 (6) | |
H11A | 0.0587 | 0.2743 | 0.0856 | 0.040* | |
H11B | 0.1461 | 0.2514 | 0.0042 | 0.040* | |
H11C | 0.1243 | 0.3598 | 0.0513 | 0.040* | |
O11 | 0.12790 (12) | 0.29606 (15) | 0.3558 (2) | 0.0269 (4) | |
O12 | 0.24662 (13) | 0.24461 (16) | 0.2392 (2) | 0.0293 (5) | |
C2 | 0.18900 (16) | 0.07504 (18) | 0.5111 (3) | 0.0177 (5) | |
C21 | 0.1577 (2) | −0.0303 (2) | 0.5196 (4) | 0.0326 (7) | |
H21A | 0.1646 | −0.0623 | 0.4215 | 0.049* | |
H21B | 0.0963 | −0.0313 | 0.5416 | 0.049* | |
H21C | 0.1924 | −0.0641 | 0.6011 | 0.049* | |
O21 | 0.14316 (12) | 0.14108 (13) | 0.5678 (2) | 0.0280 (4) | |
O22 | 0.26016 (12) | 0.08964 (13) | 0.4490 (2) | 0.0285 (5) | |
N11 | 0.06641 (12) | 0.34547 (14) | 0.6823 (2) | 0.0149 (4) | |
C12 | 0.0000 | 0.2989 (2) | 0.7500 | 0.0121 (6) | |
N12 | 0.0000 | 0.2004 (2) | 0.7500 | 0.0177 (6) | |
H12 | 0.0425 (14) | 0.1701 (19) | 0.708 (3) | 0.027* | |
C13 | 0.06495 (19) | 0.44346 (19) | 0.6845 (4) | 0.0324 (7) | |
H13 | 0.1101 | 0.4775 | 0.6394 | 0.039* | |
C14 | 0.0000 | 0.4964 (3) | 0.7500 | 0.0501 (15) | |
H14 | 0.0000 | 0.5649 | 0.7500 | 0.060* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.01110 (17) | 0.01386 (18) | 0.01312 (17) | 0.00103 (11) | 0.00451 (11) | −0.00030 (10) |
C1 | 0.0216 (13) | 0.0138 (12) | 0.0177 (12) | 0.0012 (9) | 0.0023 (10) | −0.0013 (9) |
C11 | 0.0311 (15) | 0.0312 (15) | 0.0179 (13) | 0.0113 (12) | −0.0028 (11) | −0.0027 (11) |
O11 | 0.0194 (9) | 0.0445 (12) | 0.0170 (9) | 0.0128 (8) | 0.0022 (7) | −0.0011 (8) |
O12 | 0.0223 (10) | 0.0511 (12) | 0.0146 (9) | 0.0145 (9) | 0.0025 (7) | −0.0011 (8) |
C2 | 0.0199 (13) | 0.0163 (12) | 0.0174 (11) | −0.0013 (10) | 0.0039 (10) | −0.0002 (10) |
C21 | 0.0331 (16) | 0.0183 (14) | 0.0483 (18) | −0.0051 (12) | 0.0162 (13) | −0.0023 (13) |
O21 | 0.0251 (10) | 0.0168 (9) | 0.0449 (11) | −0.0024 (8) | 0.0220 (8) | −0.0028 (8) |
O22 | 0.0229 (10) | 0.0168 (9) | 0.0485 (12) | −0.0036 (8) | 0.0214 (9) | −0.0070 (8) |
N11 | 0.0137 (10) | 0.0141 (10) | 0.0178 (10) | 0.0008 (8) | 0.0066 (8) | 0.0006 (8) |
C12 | 0.0116 (15) | 0.0170 (17) | 0.0075 (14) | 0.000 | −0.0011 (12) | 0.000 |
N12 | 0.0162 (15) | 0.0131 (15) | 0.0254 (16) | 0.000 | 0.0129 (12) | 0.000 |
C13 | 0.0278 (15) | 0.0149 (13) | 0.0580 (19) | −0.0016 (11) | 0.0287 (14) | 0.0037 (13) |
C14 | 0.045 (3) | 0.0120 (19) | 0.100 (4) | 0.000 | 0.053 (3) | 0.000 |
Cu1—Cu1i | 2.6281 (14) | N11—C12 | 1.352 (2) |
Cu1—N11 | 2.214 (2) | C12—N12 | 1.339 (4) |
Cu1—O11 | 1.949 (2) | C13—C14 | 1.369 (3) |
Cu1—O12i | 1.947 (2) | C11—H11A | 0.960 |
Cu1—O21 | 1.984 (2) | C11—H11B | 0.960 |
Cu1—O22i | 1.983 (2) | C11—H11C | 0.960 |
C1—O11 | 1.254 (3) | C21—H21A | 0.960 |
C1—O12 | 1.255 (3) | C21—H21B | 0.960 |
C1—C11 | 1.499 (4) | C21—H21C | 0.960 |
C2—O22 | 1.249 (3) | N12—H12 | 0.863 (10) |
C2—O21 | 1.252 (3) | C13—H13 | 0.930 |
C2—C21 | 1.510 (4) | C14—H14 | 0.930 |
N11—C13 | 1.331 (3) | ||
O12i—Cu1—O11 | 168.16 (8) | C13—N11—C12 | 116.6 (2) |
O12i—Cu1—O22i | 89.53 (9) | C13—N11—Cu1 | 114.49 (16) |
O11—Cu1—O22i | 89.52 (9) | C12—N11—Cu1 | 128.87 (17) |
O12i—Cu1—O21 | 88.49 (9) | N12—C12—N11 | 117.91 (15) |
O11—Cu1—O21 | 89.99 (9) | N12—C12—N11ii | 117.91 (15) |
O22i—Cu1—O21 | 168.01 (7) | N11—C12—N11ii | 124.2 (3) |
O12i—Cu1—N11 | 96.31 (8) | N11—C13—C14 | 123.0 (3) |
O11—Cu1—N11 | 95.53 (8) | C13ii—C14—C13 | 116.6 (4) |
O22i—Cu1—N11 | 93.19 (8) | C1—C11—H11A | 109.5 |
O21—Cu1—N11 | 98.78 (8) | C1—C11—H11B | 109.5 |
O12i—Cu1—Cu1i | 84.15 (7) | H11A—C11—H11B | 109.5 |
O11—Cu1—Cu1i | 84.03 (7) | C1—C11—H11C | 109.5 |
O22i—Cu1—Cu1i | 82.42 (6) | H11A—C11—H11C | 109.5 |
O21—Cu1—Cu1i | 85.61 (6) | H11B—C11—H11C | 109.5 |
N11—Cu1—Cu1i | 175.59 (5) | C2—C21—H21A | 109.5 |
O11—C1—O12 | 125.2 (2) | C2—C21—H21B | 109.5 |
O11—C1—C11 | 117.6 (2) | H21A—C21—H21B | 109.5 |
O12—C1—C11 | 117.3 (2) | C2—C21—H21C | 109.5 |
C1—O11—Cu1 | 123.38 (17) | H21A—C21—H21C | 109.5 |
C1—O12—Cu1i | 123.27 (17) | H21B—C21—H21C | 109.5 |
O22—C2—O21 | 124.6 (2) | C12—N12—H12 | 118 (2) |
O22—C2—C21 | 116.9 (2) | N11—C13—H13 | 118.5 |
O21—C2—C21 | 118.5 (2) | C14—C13—H13 | 118.5 |
C2—O21—Cu1 | 121.70 (16) | C13—C14—H14 | 121.7 |
C2—O22—Cu1i | 125.62 (17) | ||
C13—N11—C12—N12 | −179.75 (19) | C12—N11—C13—C14 | −0.5 (4) |
C13—N11—C12—N11ii | 0.25 (19) | N11—C13—C14—C13ii | 0.3 (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)] |
Mr | 458.36 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 150 |
a, b, c (Å) | 15.096 (8), 13.585 (8), 8.580 (4) |
β (°) | 94.13 (5) |
V (Å3) | 1755.0 (16) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.47 |
Crystal size (mm) | 0.53 × 0.45 × 0.20 |
Data collection | |
Diffractometer | Stoe Stadi-4 four-circle diffractometer |
Absorption correction | Numerical (X-RED; Stoe & Cie, 1995) |
Tmin, Tmax | 0.375, 0.623 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1980, 1517, 1428 |
Rint | 0.016 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.024, 0.064, 1.15 |
No. of reflections | 1517 |
No. of parameters | 120 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 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).
Cu1—Cu1i | 2.6281 (14) | Cu1—O12i | 1.947 (2) |
Cu1—N11 | 2.214 (2) | Cu1—O21 | 1.984 (2) |
Cu1—O11 | 1.949 (2) | Cu1—O22i | 1.983 (2) |
Symmetry code: (i) −x+1/2, −y+1/2, −z+1. |
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.