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The solvent effect on the mol­ecular structures of copper(II) complexes produced from the reaction between CuBr2 and 1,10-phenanthroline is evident. The momomeric title compound, [CuBr2(C12H8N2)(C2H6OS)], which consists of discrete units, is produced from this reaction in dimethyl sulfoxide (DMSO), whereas a polymeric copper(II) compound is known to be produced from the same reaction in the poor coordinating solvent ethanol. The geometry around the copper(II) ion in the title compound is best described as trigonal–bipyramidal distorted square-based pyramidal, with a τ value of 0.37. The two phenanthroline N atoms, the DMSO O atom and one of the Br atoms occupy the four basal positions, while the second Br atom occupies the axial position. The magnetic susceptibility data also indicate that the title compound is monomeric, but there is still a weak antiferromagnetic inter­action between paramagnetic copper(II) centers via the inter­molecular `Cu—Br...Br—Cu' contact pathway.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108005003/av3138sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108005003/av3138Isup2.hkl
Contains datablock I

CCDC reference: 686414

Comment top

The polymeric [Cu(phen)Br2] (phen is 1,10-phenanthroline) is produced when anhydrous CuBr2 reacts with an equimolar amount of 1,10-phenanthroline in ethanol. This polymer consists of chains linked by Cu—Br bonds, in which the Cu atom displays tetragonally elongated (4 + 2)-coordination (Garland et al., 1988). However, the same reaction proceeded in dimethylsulfoxide (DMSO), a coordinating solvent, produces the monomeric and five-coordinate title CuII complex, [Cu(phen)Br2(DMSO)], (I). In this work, we report the preparation of (I) and the determination of its single-crystal structure. Selected bond distances and angles for (I) are listed in Table 1.

The coordination geometry around the Cu atom is best described as trigonal–bipyramidal distorted square-based pyramidal, with a τ value of 0.37 (Addison et al., 1984; Harrison et al., 1981; Nagle et al., 1990); two N atoms of the 1,10-phenanthroline molecule, one Br atom and one O atom of DMSO occupy the four basal positions, while the other Br atom occupies the axial position. The basal bond distance Cu—Br2 is considerably shorter than the axial bond distance Cu—Br1, but both distances are longer than the terminal Cu—Br distances observed in the polymeric [Cu(phen)Br2] compound. The unequal Cu—N bond distances (Table 1) and distortion of the normally symmetric 1,10-phenanthroline ligand in (I) is attributable to the coordination of the large DMSO molecule to the Cu atom. The Cu—ODMSO (Cu—O15) distance in (I) is similar to those in [Cu(DMSO)4](ClO4)2 [1.934 (6)–1.954 (6) Å; Blake et al., 1996], but is significantly shorter than those in [Cu(C9H5N2O3)(DMSO)2] [2.336 (5) or 2.418 (7) Å; Popović et al., 2007] or the Zn—ODMSO distances in a similar Zn–DMSO complex [2.045 (5) and 2.066 (5) Å; Che et al., 2006]. The intermolecular distance between the two parallel aromatic rings N1/C2–C5/C14 and C5i–C8i/C13i/C14i [symmetry code: (i) -x + 1, -y + 2, -z] of the coordinated 1,10-phenanthroline ligands in the packing structure [3.4 (s.u. value available?) Å] is much shorter than 4.11 Å, indicating the existence of significant ππ interactions between them (Fig. 2).

Magnetic data of (I) were collected as a function of temperature (2–300 K). Fig. 3 shows a plot of magnetic susceptibility versus temperature. The room-temperature magnetic moment of (I), estimated from ueff = 2.828(χM)1/2, is 1.9 M. [define units] and the Neel temperature TN is observed at 4.0 K, indicating the presence of a very weak antiferromagnetic interaction between paramagnetic CuII centers. The distance between the two nearest Cu atoms in the packing structure is 7.228 (s.u. value?) Å, which is too long for a pair of CuII centers to interact magnetically. In view of the magnetic exchange mechanism of the monomeric copper(II)–bromide system, the `bromide–bromide contact' or Cu—Br···Br—Cu contact is known to be an important pathway for antiferromagnetic interaction (Dyrek et al., 1987; Bond et al., 1995). The Br···Br intermolecular contact distance in (I) is 5.180 (s.u.?) Å. This contact distance is considerably longer than the sum of the van der Walls radii of two Br atoms (3.90 Å), but is in the range of the typical Br···Br contact distances (3.90–5.61 Å) observed for many di- and tetrabromocuprate compounds that exhibit the antiferromagnetisn at low temperature (Kang et al., 2004; Van der Bilt et al., 1981). The observed weak antiferromagnetism of the title compound in the crystalline state is most probably due to magnetic exchange via the `Cu—Br···Br—Cu contact' pathway.

Related literature top

For related literature, see: Addison et al. (1984); Blake et al. (1996); Bond et al. (1995); Che et al. (2006); Garland et al. (1988); Harrison et al. (1981); Kang et al. (2004); Nagle et al. (1990); Popović et al. (2007); Van der Bilt, Joung, Carlin & De Jongh (1981).

Experimental top

Dibromo(1,10-phenanthroline)copper(II), [Cu(phen)Br2], was prepared according to the methods described by Garland et al. (1988). The chocolate-colored precipitates (0.5 mmol) were dissolved in DMSO. Green single crystals were obtained by slow evaporation in DMSO solution for 3 d. Analysis calculated for C14H14Br2CuN2OS: C 34.91, H 2.93, N 5.82%; found C 34.79, H 2.61, N 5.81%.

Refinement top

H atoms were positioned geometrically and constrained to ride on their attached atoms. Their Uiso(H) values were fixed at 1.2 or 1.5 times Ueq of their parent atoms.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. An ORTEP-3 (Farrugia, 1997) diagram of (I), showing the atom-numbering scheme and 30% probability displacement ellipsoids.
[Figure 2] Fig. 2. ππ stacking interaction between two 1,10-phenanthroline ligands of (I). Views parallel (a) and perpendicular (b) to the ππ stacking interaction are shown. [a = N1···C7i = 3.411 (7) Å, b = C3···C9i = 3.414 (8) Å and c = C5···C13i = 3.466 (7) Å; symmetry code: (i) -x + 1, -y + 2, -z)].
[Figure 3] Fig. 3. A plot of magnetic susceptibilities versus temperature in the temperature region 2–300 K for (I).
Dibromido(dimethyl sulfoxide-κO)(1,10-phenanthroline-κ2N,N')copper(II) top
Crystal data top
[CuBr2(C12H8N2)(C2H6OS)]F(000) = 940
Mr = 481.69Dx = 1.947 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2276 reflections
a = 8.3984 (2) Åθ = 2.9–23.4°
b = 14.0857 (3) ŵ = 6.32 mm1
c = 14.5004 (3) ÅT = 295 K
β = 106.667 (2)°Block, green
V = 1643.29 (6) Å30.15 × 0.09 × 0.06 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer
3778 independent reflections
Radiation source: fine-focus sealed tube2381 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.074
ϕ and ω scansθmax = 27.5°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Bruker, 2002)
h = 1010
Tmin = 0.511, Tmax = 0.685k = 1818
22691 measured reflectionsl = 1818
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)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.127H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0607P)2 + 0.0896P]
where P = (Fo2 + 2Fc2)/3
3778 reflections(Δ/σ)max = 0.001
190 parametersΔρmax = 0.53 e Å3
0 restraintsΔρmin = 0.48 e Å3
Crystal data top
[CuBr2(C12H8N2)(C2H6OS)]V = 1643.29 (6) Å3
Mr = 481.69Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.3984 (2) ŵ = 6.32 mm1
b = 14.0857 (3) ÅT = 295 K
c = 14.5004 (3) Å0.15 × 0.09 × 0.06 mm
β = 106.667 (2)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
3778 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2002)
2381 reflections with I > 2σ(I)
Tmin = 0.511, Tmax = 0.685Rint = 0.074
22691 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0380 restraints
wR(F2) = 0.127H-atom parameters constrained
S = 1.06Δρmax = 0.53 e Å3
3778 reflectionsΔρmin = 0.48 e Å3
190 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
Cu0.78965 (8)0.93879 (4)0.23195 (4)0.04082 (19)
Br11.02804 (7)0.81705 (4)0.28156 (4)0.0614 (2)
Br20.63347 (8)0.93850 (5)0.35260 (4)0.0573 (2)
N10.7946 (5)0.9958 (3)0.1011 (3)0.0397 (10)
C20.8745 (7)1.0708 (4)0.0821 (4)0.0492 (13)
H20.93891.10690.13290.059*
C30.8648 (8)1.0976 (4)0.0131 (5)0.0613 (17)
H30.92321.15040.02400.074*
C40.7693 (8)1.0461 (5)0.0900 (5)0.0607 (17)
H40.76421.06300.15280.073*
C50.6809 (7)0.9685 (4)0.0720 (4)0.0497 (14)
C60.5693 (8)0.9093 (5)0.1449 (4)0.0589 (17)
H60.55570.92270.20960.071*
C70.4857 (8)0.8363 (5)0.1220 (4)0.0580 (16)
H70.41350.80170.17110.070*
C80.5045 (6)0.8101 (4)0.0240 (4)0.0466 (13)
C90.4236 (7)0.7341 (4)0.0054 (4)0.0546 (15)
H90.35300.69530.04040.066*
C100.4476 (7)0.7169 (4)0.0995 (4)0.0543 (14)
H100.39510.66600.11930.065*
C110.5528 (7)0.7766 (4)0.1674 (4)0.0512 (14)
H110.56760.76460.23240.061*
N120.6320 (5)0.8493 (3)0.1435 (3)0.0389 (9)
C130.6098 (6)0.8655 (4)0.0488 (3)0.0387 (11)
C140.6983 (6)0.9451 (4)0.0248 (3)0.0384 (11)
O150.9210 (5)1.0472 (3)0.2908 (3)0.0587 (11)
S161.04181 (17)1.04119 (10)0.39217 (9)0.0432 (3)
C171.2383 (9)1.0542 (5)0.3729 (5)0.082 (2)
H17A1.26630.99690.34520.122*
H17B1.32021.06630.43320.122*
H17C1.23541.10630.32980.122*
C181.0206 (9)1.1531 (4)0.4417 (4)0.0690 (18)
H18A0.91621.15600.45630.103*
H18B1.02431.20190.39610.103*
H18C1.10971.16230.49960.103*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu0.0456 (4)0.0384 (4)0.0355 (3)0.0042 (3)0.0069 (3)0.0016 (3)
Br10.0580 (4)0.0518 (4)0.0641 (4)0.0151 (3)0.0012 (3)0.0045 (3)
Br20.0572 (4)0.0750 (5)0.0423 (3)0.0086 (3)0.0184 (3)0.0036 (3)
N10.041 (2)0.037 (2)0.044 (2)0.0076 (19)0.0168 (19)0.0066 (19)
C20.045 (3)0.041 (3)0.065 (3)0.008 (3)0.021 (3)0.012 (3)
C30.065 (4)0.049 (4)0.083 (4)0.019 (3)0.043 (4)0.027 (3)
C40.073 (4)0.065 (4)0.057 (4)0.029 (3)0.039 (3)0.021 (3)
C50.053 (3)0.059 (4)0.044 (3)0.027 (3)0.024 (3)0.015 (3)
C60.064 (4)0.082 (5)0.029 (3)0.027 (4)0.010 (3)0.002 (3)
C70.056 (4)0.074 (5)0.039 (3)0.017 (3)0.007 (3)0.015 (3)
C80.040 (3)0.058 (4)0.040 (3)0.017 (3)0.007 (2)0.008 (2)
C90.045 (3)0.049 (4)0.064 (4)0.003 (3)0.005 (3)0.014 (3)
C100.051 (3)0.043 (3)0.063 (4)0.001 (3)0.006 (3)0.000 (3)
C110.055 (3)0.050 (3)0.044 (3)0.001 (3)0.007 (2)0.010 (3)
N120.044 (2)0.036 (2)0.035 (2)0.0004 (19)0.0083 (18)0.0042 (18)
C130.038 (3)0.043 (3)0.034 (2)0.013 (2)0.007 (2)0.005 (2)
C140.036 (3)0.044 (3)0.038 (2)0.017 (2)0.015 (2)0.004 (2)
O150.072 (3)0.044 (2)0.048 (2)0.017 (2)0.0035 (19)0.0030 (17)
S160.0482 (8)0.0414 (8)0.0399 (6)0.0051 (6)0.0124 (5)0.0001 (5)
C170.066 (4)0.117 (7)0.068 (4)0.024 (4)0.028 (4)0.019 (4)
C180.090 (5)0.053 (4)0.056 (4)0.015 (3)0.010 (3)0.003 (3)
Geometric parameters (Å, º) top
Cu—N12.071 (4)C8—C91.398 (8)
Cu—N122.003 (4)C8—C131.403 (7)
Cu—Br12.5769 (8)C9—C101.343 (8)
Cu—Br22.4692 (8)C9—H90.9300
Cu—O151.933 (4)C10—C111.400 (7)
N1—C21.322 (6)C10—H100.9300
N1—C141.370 (6)C11—N121.320 (6)
C2—C31.411 (8)C11—H110.9300
C2—H20.9300N12—C131.351 (6)
C3—C41.379 (9)C13—C141.442 (7)
C3—H30.9300O15—S161.531 (4)
C4—C51.388 (8)S16—C171.760 (7)
C4—H40.9300S16—C181.762 (6)
C5—C141.408 (7)C17—H17A0.9600
C5—C61.457 (8)C17—H17B0.9600
C6—C71.339 (9)C17—H17C0.9600
C6—H60.9300C18—H18A0.9600
C7—C81.433 (8)C18—H18B0.9600
C7—H70.9300C18—H18C0.9600
N1—Cu—N1280.84 (16)C10—C9—C8120.2 (5)
N1—Cu—Br1107.20 (11)C10—C9—H9119.9
N1—Cu—Br2143.48 (11)C8—C9—H9119.9
N1—Cu—O1586.51 (17)C9—C10—C11119.1 (6)
N12—Cu—Br194.47 (12)C9—C10—H10120.4
N12—Cu—Br293.71 (12)C11—C10—H10120.4
N12—Cu—O15165.55 (16)N12—C11—C10123.1 (5)
Br1—Cu—O1595.93 (13)N12—C11—H11118.5
Br2—Cu—O1592.31 (13)C10—C11—H11118.5
Br2—Cu—Br1109.22 (3)C11—N12—C13117.7 (4)
C2—N1—C14117.7 (4)C11—N12—Cu127.6 (3)
C2—N1—Cu130.2 (4)C13—N12—Cu114.7 (3)
C14—N1—Cu112.0 (3)N12—C13—C8122.9 (5)
N1—C2—C3121.9 (6)N12—C13—C14116.5 (4)
N1—C2—H2119.1C8—C13—C14120.6 (4)
C3—C2—H2119.1N1—C14—C5123.5 (5)
C4—C3—C2120.5 (6)N1—C14—C13115.9 (4)
C4—C3—H3119.7C5—C14—C13120.6 (5)
C2—C3—H3119.7S16—O15—Cu121.2 (2)
C3—C4—C5118.7 (5)O15—S16—C17103.6 (3)
C3—C4—H4120.7O15—S16—C18103.0 (3)
C5—C4—H4120.7C17—S16—C18100.4 (3)
C4—C5—C14117.7 (6)S16—C17—H17A109.5
C4—C5—C6125.5 (5)S16—C17—H17B109.5
C14—C5—C6116.8 (5)H17A—C17—H17B109.5
C7—C6—C5122.2 (5)S16—C17—H17C109.5
C7—C6—H6118.9H17A—C17—H17C109.5
C5—C6—H6118.9H17B—C17—H17C109.5
C6—C7—C8121.9 (5)S16—C18—H18A109.5
C6—C7—H7119.1S16—C18—H18B109.5
C8—C7—H7119.1H18A—C18—H18B109.5
C9—C8—C13117.0 (5)S16—C18—H18C109.5
C9—C8—C7125.1 (5)H18A—C18—H18C109.5
C13—C8—C7117.9 (5)H18B—C18—H18C109.5
O15—Cu—N1—C25.2 (4)N1—Cu—N12—C131.8 (3)
N12—Cu—N1—C2178.2 (5)Br2—Cu—N12—C13145.5 (3)
Br2—Cu—N1—C294.4 (5)Br1—Cu—N12—C13104.9 (3)
Br1—Cu—N1—C289.9 (4)C11—N12—C13—C81.5 (7)
O15—Cu—N1—C14175.0 (3)Cu—N12—C13—C8179.9 (4)
N12—Cu—N1—C142.0 (3)C11—N12—C13—C14179.8 (4)
Br2—Cu—N1—C1485.8 (3)Cu—N12—C13—C141.4 (5)
Br1—Cu—N1—C1489.9 (3)C9—C8—C13—N121.5 (7)
C14—N1—C2—C31.1 (7)C7—C8—C13—N12177.5 (5)
Cu—N1—C2—C3178.6 (4)C9—C8—C13—C14179.8 (4)
N1—C2—C3—C40.5 (9)C7—C8—C13—C141.1 (7)
C2—C3—C4—C51.1 (9)C2—N1—C14—C50.2 (7)
C3—C4—C5—C141.9 (8)Cu—N1—C14—C5179.6 (4)
C3—C4—C5—C6177.3 (5)C2—N1—C14—C13178.4 (4)
C4—C5—C6—C7178.8 (5)Cu—N1—C14—C131.8 (5)
C14—C5—C6—C70.4 (8)C4—C5—C14—N11.4 (7)
C5—C6—C7—C81.8 (9)C6—C5—C14—N1177.9 (4)
C6—C7—C8—C9178.9 (6)C4—C5—C14—C13179.8 (4)
C6—C7—C8—C132.1 (8)C6—C5—C14—C130.5 (7)
C13—C8—C9—C100.3 (8)N12—C13—C14—N10.3 (6)
C7—C8—C9—C10178.6 (5)C8—C13—C14—N1178.4 (4)
C8—C9—C10—C110.7 (9)N12—C13—C14—C5178.9 (4)
C9—C10—C11—N120.7 (9)C8—C13—C14—C50.2 (7)
C10—C11—N12—C130.4 (8)N12—Cu—O15—S16179.6 (6)
C10—C11—N12—Cu178.5 (4)N1—Cu—O15—S16151.5 (3)
O15—Cu—N12—C11150.8 (7)Br2—Cu—O15—S1665.0 (3)
N1—Cu—N12—C11180.0 (5)Br1—Cu—O15—S1644.6 (3)
Br2—Cu—N12—C1136.4 (4)Cu—O15—S16—C17113.5 (4)
Br1—Cu—N12—C1173.3 (4)Cu—O15—S16—C18142.2 (3)
O15—Cu—N12—C1331.1 (9)

Experimental details

Crystal data
Chemical formula[CuBr2(C12H8N2)(C2H6OS)]
Mr481.69
Crystal system, space groupMonoclinic, P21/c
Temperature (K)295
a, b, c (Å)8.3984 (2), 14.0857 (3), 14.5004 (3)
β (°) 106.667 (2)
V3)1643.29 (6)
Z4
Radiation typeMo Kα
µ (mm1)6.32
Crystal size (mm)0.15 × 0.09 × 0.06
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2002)
Tmin, Tmax0.511, 0.685
No. of measured, independent and
observed [I > 2σ(I)] reflections
22691, 3778, 2381
Rint0.074
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.127, 1.06
No. of reflections3778
No. of parameters190
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.53, 0.48

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top
Cu—N12.071 (4)Cu—Br22.4692 (8)
Cu—N122.003 (4)Cu—O151.933 (4)
Cu—Br12.5769 (8)
N1—Cu—N1280.84 (16)N12—Cu—Br293.71 (12)
N1—Cu—Br1107.20 (11)N12—Cu—O15165.55 (16)
N1—Cu—Br2143.48 (11)Br1—Cu—O1595.93 (13)
N1—Cu—O1586.51 (17)Br2—Cu—O1592.31 (13)
N12—Cu—Br194.47 (12)Br2—Cu—Br1109.22 (3)
 

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