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The title compound, [4′-(4-bromo­phenyl)-2,2′:6′,2′′-ter­pyri­dine]­chlorido(trifluoro­methane­sulfonato)­copper(II), [Cu(CF3O3S)Cl(C21H14BrN3)], is a new copper complex containing a polypyridyl-based ligand. The CuII centre is five-coordinated in a square-pyramidal manner by one substituted 2,2′:6′,2′′-ter­pyridine ligand, one chloride ligand and a coordinated trifluoro­methane­sulfonate anion. The Cu—N bond lengths differ by 0.1 Å for the peripheral and central pyridine rings [2.032 (2) (mean) and 1.9345 (15) Å, respectively]. The presence of the trifluoro­methane­sulfonate anion coordinated to the metal centre allows Br...F halogen–halogen inter­actions, giving rise to the formation of a dimer about an inversion centre. This work also demonstrates that the rigidity of the ligand allows the formation of other types of nonclassical inter­actions (C—H...Cl and C—H...O), yielding a three-dimensional network.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270111004641/gg3247sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270111004641/gg3247Isup2.hkl
Contains datablock I

CCDC reference: 824029

Comment top

Polypyridine ligands, e.g. 2,2':6',2''-terpyridine (tpy), have been the focus of much attention due to their incorporation into devices with many potential applications, such as electrochromic materials, anion-recognition devices and solar photovoltaic cells (Han et al., 2008; Bhaumik et al., 2010). In particular, several ruthenium(II) complexes based on polypyridine ligands have been prepared and structurally characterized. Heteroleptic complexes are designed to increase the excited-state lifetime of ruthenium(II) bis(tpy) complexes for use in such devices (Rajeshwar et al., 2008). In the literature there are, however, fewer examples of CuII complexes of substituted tpy ligands and their derivatives (Chen et al., 2010; McMurtrie & Dance, 2009; Uma et al., 2005; Medlycott et al., 2008; Wang et al., 2009). Previous work by our group has described the synthesis of new homoleptic tridentate complexes containing one central triazine ring that may be applied to the development of new redox mediators (Medlycott et al., 2007, 2008). As an extension of this study, we are currently investigating the supramolecular reactivity of the tridentate pyridyl-substituted ligand tpy to form copper complexes. Against this background, we present here the structure of the title copper–tpy complex, (I).

The CuII centre in (I) is coordinated in a slightly distorted square-pyramidal environment by three N donors from the tridentate ligand. The Cl atom occupies the fourth coordination site of the basal plane. The three N atoms and Cl atom of the basal plane are nearly coplanar, with the largest deviation from the least-squares plane being 0.0524 (8) Å for atom N2. The Cu atom is displaced by 0.1420 (7) Å out of the basal plane.

The Cu—N and Cu—Cl distances (Table 1) are comparable with those found in the Cambridge Structural Database (CSD, Version?; Allen, 2002) for 230 other Cu complexes having the same core as (I). In (I), the Cu—N bond lengths involving the peripheral pyridine rings are about 0.1 Å longer than that of the and central pyridine ring. These values compare well with those found in a copper complex containing 4'-p-tolyl-2,2':6',2''-terpyridine and two chloride ligands [Cu—N(peripheral) = 2.052 (3) and 2.035 (3) Å, Cu—N(central) = 1.940 (3) Å and Cu—Cl = 2.228 (1) Å, for the four atoms that form the base of the square-pyramidal coordination around the metal centre; Wang et al., 2009]. On the other hand, the CuN6 core of a homoleptic copper complex exhibits an even greater difference between the peripheral Cu—N and central Cu—N bond lengths [2.205 (4) versus 1.981 (5) Å; Uma et al., 2005]. The trans N2—Cu1—Cl1 angle in (I) deviates slightly from linearity, while the cis N1—Cu1—N2 and N2—Cu1—N3 angles have very similar values deviating by about 10° from 90° because of the bite constrictions of the ligand.

Fig. 1 shows the molecular structure of (I). The axial position of the square-pyramidal CuII coordination environment is occupied by one O atom of the triflate ligand, with an elongated Cu1—O1 distance of 2.4635 (14) Å. In addition, the triflate ligand extends almost perpendicular to the basal plane of the complex complex, as shown by the Cl1—Cu1—O1 and N2—Cu1—O1 angles (Table 1). Another interesting structural feature of (I) is the dihedral angle of 22.40 (7)° formed between the mean plane through the three pyridine rings and the plane of the bromophenyl group. A similar conformation was found in the two p-tolylterpyridine complexes mentioned above (Wang et al., 2009; Uma et al., 2005) [see Note 2]. The planes of the three pyridyl rings very slightly tilted with respect to each other to give dihedral angles between the pairs of rings containing atoms N1/N2, N2/N3 and N1/N3 of 6.4 (1), 3.7 (1) and 6.1 (1)°, respectively. The tilt between the planes of the central pyridyl and the bromophenyl ring is 24.62 (9)°.

As illustrated in Figs. 2–4, the crystal packing of (I) is effected by halogen–halogen interactions and weak hydrogen bonds. In Fig. 2, two molecules are paired by two halogen interactions to form a dimer about an inversion centre. The shortest intermolecular distance involving F and Br atoms is 3.148 (1) Å, while the predicted sum of the van der Waals radii for fluorine and bromine is 3.32 Å (Bondi, 1964). Thus, this interaction is rather weak. A survey of similar contacts in the CSD showed 171 reported cases, covering a range of 2.90–3.40 Å with a median (maximum occurrence) at 3.15 Å. Furthermore, the dimeric subunits of (I) are linked to each other across centres of inversion between the dimers by duplex C—H···Cl bonds (Table 2 and Fig. 3) involving the Cl atom and one of the pyridyl rings of the tpy ligand in an adjacent molecule (C15—H; Table 2 and Fig. 3). The C—H···Cl and Br···F interactions serve to link the molecules into extended chains which run parallel to the [120] direction.

Given that (I) has a nearly planar organic ligand, the crystal structure might have been expected to present several aromatic ππ interactions, particularly between the tpy ring systems. However, only one potential interaction is observed, maybe due the blocking caused by the presence of the triflate ligand. The bromophenyl rings from two centrosymmetrically-disposed molecules display a weak ππ interaction such that the centroids of the rings are separated by 3.7333 (11) Å, the perpendicular distance from the centroid of one ring to the plane of the other is 3.4034 (8) Å and the slippage of the centroids is 1.54 Å. Several weak C—H···O interactions (Table 2) appear to provide some support to the vertical alignment of the triflate ligand, and crosslink the above-mentioned chains to give a three-dimensional network. The planarity of the tpy ring system clearly facilitates the formation of these C—H···O interactions (Fig. 4).

In summary, the packing of the title copper complex shows that the presence of the trifluoromethanesulfonate anion plays an active role in the intermolecular interactions. The close Br···F contacts in (I) may be stabilizing interactions but they are apparently not structure-determining, since other weak C—H···Cl and C—H···O interactions contribute to the packing pattern.

Related literature top

For related literature, see: Allen (2002); Bhaumik et al. (2010); Bondi (1964); Chen et al. (2010); Han et al. (2008); McMurtrie & Dance (2009); Medlycott et al. (2007, 2008); Rajeshwar et al. (2008); Uma et al. (2005); Wang et al. (2009).

Experimental top

A round-bottomed flask was charged with Cu(CF3SO3)2 (1 equivalent, 0.28 mmol, 101 mg) and bromophenylterpyridine (1 equivalent, 0.28 mmol, 109 mg) in acetonitrile (10 ml) with a stirring bar. To increase the solubility of the organic ligand, chloroform (5 ml) was added to the reaction mixture. The reaction was heated at 358 K for 3 h and then slowly cooled to room temperature under magnetic stirring. A deep-green [Blue given in CIF - please clarify] crystalline solid was formed. The crystals were filtered off and characterized as the title compound (yield 80 mg; 45%). HRMS (ESI): m/z = 486.93614 (C21H14BrClCuN3 requires 487.25896).

Although the reaction procedure does not involve the Cl- anion, it seems that the presence of copper and air photocatalysed the decomposition of the chloroform solvent to form the chloride anion, which was then available to coordinate to the metal centre so as to give rise to the title compound.

Refinement top

The H atoms were generated geometrically, with C—H = 0.95 Å, and were included in the refinement in the riding-model approximation, with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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: UdMX (Maris, 2004) and XPREP (Bruker, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. A view of the halogen-bonding interactions in (I), indicated by dotted lines.
[Figure 3] Fig. 3. A view of the C—H···Cl interactions in (I) (dotted lines), showing the two-dimensional supramolecular network with packing. [Symmetry code: (*) -x, -y + 2, -z + 1.]
[Figure 4] Fig. 4. A view of the C—H···O interactions in (I) (dotted lines), showing their influence on the crystal packing and formation of the supramolecular assembly. [Symmetry codes: (*) x + 1/2, -y + 3/2, z + 1/2; (**) x + 1, y, z; (***) x - 1/2, -y + 3/2, z + 1/2.]
[4'-(4-bromophenyl)-2,2':6',2''- terpyridine]chlorido(trifluoromethanesulfonato)copper(II) top
Crystal data top
[Cu(CF3O3S)Cl(C21H14BrN3)]F(000) = 1260
Mr = 636.32Dx = 1.829 Mg m3
Monoclinic, P21/nCu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ynCell parameters from 28837 reflections
a = 7.7841 (2) Åθ = 3.6–69.4°
b = 16.3043 (4) ŵ = 5.78 mm1
c = 18.2533 (4) ÅT = 150 K
β = 93.884 (1)°Block, blue
V = 2311.28 (10) Å30.10 × 0.06 × 0.06 mm
Z = 4
Data collection top
Bruker Microstar
diffractometer
4344 independent reflections
Radiation source: rotating anode4016 reflections with I > 2σ(I)
Helios optics monochromatorRint = 0.039
Detector resolution: 8.3 pixels mm-1θmax = 69.6°, θmin = 3.6°
ω scansh = 89
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
k = 1919
Tmin = 0.452, Tmax = 0.707l = 2222
47414 measured reflections
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)] = 0.026Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.073H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0486P)2 + 0.8516P]
where P = (Fo2 + 2Fc2)/3
4344 reflections(Δ/σ)max = 0.002
316 parametersΔρmax = 0.71 e Å3
0 restraintsΔρmin = 0.33 e Å3
Crystal data top
[Cu(CF3O3S)Cl(C21H14BrN3)]V = 2311.28 (10) Å3
Mr = 636.32Z = 4
Monoclinic, P21/nCu Kα radiation
a = 7.7841 (2) ŵ = 5.78 mm1
b = 16.3043 (4) ÅT = 150 K
c = 18.2533 (4) Å0.10 × 0.06 × 0.06 mm
β = 93.884 (1)°
Data collection top
Bruker Microstar
diffractometer
4344 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
4016 reflections with I > 2σ(I)
Tmin = 0.452, Tmax = 0.707Rint = 0.039
47414 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0260 restraints
wR(F2) = 0.073H-atom parameters constrained
S = 1.07Δρmax = 0.71 e Å3
4344 reflectionsΔρmin = 0.33 e Å3
316 parameters
Special details top

Experimental. X-ray crystallographic data for (I) were collected from a single-crystal sample, which was mounted on a loop fiber. Data were collected using a Bruker Microstar diffractometer equipped with a Platinum 135 CCD detector, Helios optics and a Kappa goniometer. The crystal-to-detector distance was 4.0 cm, and the data collection was carried out in 512 × 512 pixel mode. The initial unit-cell parameters were determined by a least-squares fit of the angular setting of strong reflections, collected by a 3.0 degree scan in 33 frames over three different parts of the reciprocal space (99 frames total).

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
Cu10.40934 (3)0.905424 (16)0.454742 (14)0.02276 (9)
Cl10.23317 (6)1.00983 (3)0.43312 (3)0.03348 (12)
Br11.37255 (3)0.442745 (14)0.598587 (12)0.03687 (9)
N10.57990 (19)0.92948 (9)0.37810 (8)0.0231 (3)
N20.58819 (18)0.82762 (9)0.48463 (8)0.0209 (3)
N30.31217 (19)0.85826 (10)0.54644 (8)0.0236 (3)
C10.5655 (3)0.98667 (12)0.32572 (10)0.0285 (4)
H10.46411.01920.32080.034*
C20.6944 (3)0.99998 (13)0.27832 (11)0.0327 (4)
H20.68101.04090.24130.039*
C30.8423 (3)0.95322 (13)0.28537 (11)0.0340 (4)
H30.93250.96200.25370.041*
C40.8578 (2)0.89316 (13)0.33935 (11)0.0287 (4)
H40.95830.86010.34510.034*
C50.7237 (2)0.88245 (11)0.38458 (10)0.0228 (4)
C60.7257 (2)0.82202 (11)0.44488 (9)0.0215 (4)
C70.8529 (2)0.76442 (11)0.46223 (10)0.0224 (4)
H70.94880.75950.43300.027*
C80.8381 (2)0.71359 (11)0.52336 (10)0.0219 (4)
C90.6976 (2)0.72503 (11)0.56646 (10)0.0226 (4)
H90.68790.69390.61000.027*
C100.5732 (2)0.78236 (11)0.54474 (9)0.0217 (4)
C110.4136 (2)0.80105 (11)0.58155 (10)0.0227 (4)
C120.3674 (2)0.76315 (12)0.64508 (10)0.0273 (4)
H120.44160.72420.66960.033*
C130.2098 (3)0.78326 (13)0.67239 (11)0.0320 (4)
H130.17450.75780.71570.038*
C140.1061 (2)0.84039 (14)0.63582 (11)0.0331 (4)
H140.00230.85430.65340.040*
C150.1608 (2)0.87752 (13)0.57309 (11)0.0290 (4)
H150.08940.91750.54840.035*
C160.9671 (2)0.64860 (11)0.54150 (10)0.0232 (4)
C171.1343 (2)0.65440 (12)0.51783 (10)0.0256 (4)
H171.16510.70060.48980.031*
C181.2551 (2)0.59374 (12)0.53468 (11)0.0288 (4)
H181.36870.59850.51920.035*
C191.2083 (2)0.52629 (12)0.57431 (10)0.0274 (4)
C201.0431 (3)0.51764 (13)0.59721 (11)0.0308 (4)
H201.01210.47030.62360.037*
C210.9241 (2)0.57916 (13)0.58098 (10)0.0280 (4)
H210.81100.57400.59700.034*
F10.02448 (14)0.67842 (8)0.30605 (7)0.0362 (3)
F20.21350 (18)0.64436 (8)0.23121 (7)0.0474 (3)
F30.25878 (18)0.62114 (8)0.34733 (8)0.0482 (3)
O10.25040 (16)0.79914 (9)0.38212 (7)0.0283 (3)
O20.47382 (19)0.75758 (12)0.30338 (10)0.0505 (5)
O30.2102 (2)0.82285 (10)0.25089 (8)0.0436 (4)
S30.29491 (6)0.77536 (3)0.30915 (2)0.02805 (12)
C220.1937 (2)0.67463 (13)0.29795 (11)0.0302 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.01972 (14)0.02611 (16)0.02256 (15)0.00442 (10)0.00220 (10)0.00067 (10)
Cl10.0314 (2)0.0307 (2)0.0384 (3)0.01190 (18)0.00304 (19)0.00048 (19)
Br10.03649 (14)0.04247 (15)0.03127 (13)0.02009 (9)0.00053 (9)0.00149 (9)
N10.0211 (7)0.0266 (8)0.0214 (7)0.0012 (6)0.0001 (6)0.0001 (6)
N20.0172 (7)0.0260 (8)0.0195 (7)0.0003 (6)0.0013 (5)0.0015 (6)
N30.0192 (7)0.0299 (8)0.0216 (7)0.0017 (6)0.0018 (6)0.0049 (6)
C10.0296 (9)0.0301 (10)0.0252 (9)0.0030 (8)0.0031 (7)0.0017 (7)
C20.0404 (11)0.0328 (10)0.0245 (10)0.0000 (9)0.0000 (8)0.0064 (8)
C30.0350 (11)0.0402 (11)0.0276 (10)0.0014 (9)0.0072 (8)0.0062 (9)
C40.0241 (9)0.0362 (10)0.0262 (9)0.0024 (8)0.0052 (7)0.0046 (8)
C50.0214 (8)0.0265 (9)0.0203 (8)0.0001 (7)0.0004 (7)0.0004 (7)
C60.0177 (8)0.0273 (9)0.0195 (8)0.0025 (7)0.0014 (6)0.0024 (7)
C70.0186 (8)0.0280 (9)0.0208 (8)0.0009 (7)0.0033 (6)0.0001 (7)
C80.0186 (8)0.0265 (9)0.0205 (8)0.0004 (7)0.0002 (6)0.0020 (7)
C90.0217 (8)0.0277 (9)0.0184 (8)0.0007 (7)0.0016 (7)0.0006 (7)
C100.0180 (8)0.0287 (9)0.0184 (8)0.0022 (7)0.0015 (6)0.0025 (7)
C110.0182 (8)0.0294 (9)0.0208 (8)0.0010 (7)0.0024 (7)0.0058 (7)
C120.0233 (9)0.0365 (10)0.0222 (9)0.0007 (8)0.0026 (7)0.0005 (8)
C130.0273 (10)0.0457 (12)0.0240 (10)0.0046 (8)0.0094 (8)0.0036 (8)
C140.0217 (9)0.0460 (12)0.0324 (10)0.0005 (8)0.0079 (8)0.0097 (9)
C150.0205 (9)0.0368 (10)0.0300 (10)0.0037 (8)0.0024 (7)0.0076 (8)
C160.0213 (8)0.0293 (9)0.0188 (8)0.0024 (7)0.0007 (7)0.0005 (7)
C170.0221 (9)0.0279 (9)0.0270 (9)0.0005 (7)0.0023 (7)0.0018 (7)
C180.0210 (9)0.0360 (11)0.0296 (10)0.0022 (7)0.0033 (7)0.0048 (8)
C190.0262 (9)0.0324 (10)0.0232 (9)0.0098 (8)0.0018 (7)0.0035 (7)
C200.0323 (10)0.0334 (10)0.0265 (10)0.0038 (8)0.0006 (8)0.0064 (8)
C210.0220 (9)0.0363 (10)0.0260 (10)0.0040 (8)0.0035 (7)0.0060 (8)
F10.0244 (6)0.0415 (7)0.0428 (7)0.0069 (5)0.0021 (5)0.0005 (5)
F20.0514 (8)0.0493 (8)0.0426 (7)0.0129 (6)0.0124 (6)0.0241 (6)
F30.0442 (7)0.0413 (7)0.0578 (9)0.0095 (6)0.0045 (6)0.0075 (6)
O10.0230 (6)0.0386 (7)0.0237 (7)0.0012 (5)0.0037 (5)0.0085 (5)
O20.0244 (7)0.0729 (12)0.0563 (10)0.0121 (7)0.0174 (7)0.0336 (9)
O30.0623 (10)0.0418 (9)0.0266 (8)0.0140 (8)0.0024 (7)0.0012 (6)
S30.0239 (2)0.0375 (3)0.0235 (2)0.00757 (18)0.00693 (17)0.00897 (18)
C220.0251 (9)0.0362 (11)0.0294 (10)0.0006 (8)0.0026 (8)0.0047 (8)
Geometric parameters (Å, º) top
Cu1—N12.0311 (16)C9—H90.9500
Cu1—N21.9345 (15)C10—C111.483 (2)
Cu1—N32.0338 (16)C11—C121.383 (3)
Cu1—Cl12.2048 (5)C12—C131.394 (3)
Cu1—O12.4635 (14)C12—H120.9500
Br1—C191.8998 (18)C13—C141.376 (3)
N1—C11.335 (2)C13—H130.9500
N1—C51.355 (2)C14—C151.387 (3)
N2—C101.334 (2)C14—H140.9500
N2—C61.336 (2)C15—H150.9500
N3—C151.342 (2)C16—C211.395 (3)
N3—C111.355 (2)C16—C171.402 (3)
C1—C21.385 (3)C17—C181.385 (3)
C1—H10.9500C17—H170.9500
C2—C31.380 (3)C18—C191.379 (3)
C2—H20.9500C18—H180.9500
C3—C41.389 (3)C19—C201.386 (3)
C3—H30.9500C20—C211.384 (3)
C4—C51.385 (3)C20—H200.9500
C4—H40.9500C21—H210.9500
C5—C61.476 (2)F1—C221.337 (2)
C6—C71.386 (3)F2—C221.333 (2)
C7—C81.401 (3)F3—C221.329 (3)
C7—H70.9500O1—S31.4515 (13)
C8—C91.403 (2)O2—S31.4334 (16)
C8—C161.482 (3)O3—S31.4387 (17)
C9—C101.385 (3)S3—C221.827 (2)
N1—Cu1—Cl198.93 (5)N2—C10—C11112.44 (15)
N2—Cu1—Cl1169.69 (5)C9—C10—C11126.87 (16)
N3—Cu1—Cl1100.24 (5)N3—C11—C12121.89 (16)
N1—Cu1—O195.34 (5)N3—C11—C10113.96 (16)
N1—Cu1—N280.18 (6)C12—C11—C10124.14 (17)
N1—Cu1—N3159.51 (6)C11—C12—C13118.67 (18)
N2—Cu1—O190.92 (5)C11—C12—H12120.7
N2—Cu1—N379.67 (6)C13—C12—H12120.7
N3—Cu1—O188.61 (5)C14—C13—C12119.17 (19)
Cl1—Cu1—O199.39 (4)C14—C13—H13120.4
C1—N1—C5119.10 (16)C12—C13—H13120.4
C1—N1—Cu1126.97 (13)C13—C14—C15119.55 (18)
C5—N1—Cu1113.90 (12)C13—C14—H14120.2
C10—N2—C6121.81 (15)C15—C14—H14120.2
C10—N2—Cu1119.55 (12)N3—C15—C14121.53 (18)
C6—N2—Cu1118.63 (12)N3—C15—H15119.2
C15—N3—C11119.17 (16)C14—C15—H15119.2
C15—N3—Cu1126.47 (13)C21—C16—C17118.32 (17)
C11—N3—Cu1114.35 (12)C21—C16—C8120.87 (16)
N1—C1—C2121.86 (18)C17—C16—C8120.79 (17)
N1—C1—H1119.1C18—C17—C16120.93 (18)
C2—C1—H1119.1C18—C17—H17119.5
C3—C2—C1119.35 (19)C16—C17—H17119.5
C3—C2—H2120.3C19—C18—C17119.11 (17)
C1—C2—H2120.3C19—C18—H18120.4
C2—C3—C4119.16 (19)C17—C18—H18120.4
C2—C3—H3120.4C18—C19—C20121.53 (18)
C4—C3—H3120.4C18—C19—Br1119.78 (14)
C5—C4—C3118.65 (19)C20—C19—Br1118.69 (15)
C5—C4—H4120.7C21—C20—C19118.90 (19)
C3—C4—H4120.7C21—C20—H20120.5
N1—C5—C4121.86 (17)C19—C20—H20120.5
N1—C5—C6114.17 (15)C20—C21—C16121.19 (18)
C4—C5—C6123.93 (17)C20—C21—H21119.4
N2—C6—C7120.55 (16)C16—C21—H21119.4
N2—C6—C5113.02 (15)O2—S3—O3116.96 (11)
C7—C6—C5126.43 (16)O2—S3—O1114.51 (9)
C6—C7—C8119.16 (16)O3—S3—O1114.12 (9)
C6—C7—H7120.4O2—S3—C22102.91 (10)
C8—C7—H7120.4O3—S3—C22103.22 (9)
C7—C8—C9118.50 (16)O1—S3—C22102.41 (9)
C7—C8—C16120.69 (16)F3—C22—F2108.33 (17)
C9—C8—C16120.80 (16)F3—C22—F1106.75 (16)
C10—C9—C8119.09 (16)F2—C22—F1107.08 (16)
C10—C9—H9120.5F3—C22—S3111.87 (14)
C8—C9—H9120.5F2—C22—S3111.08 (14)
N2—C10—C9120.68 (16)F1—C22—S3111.51 (14)
N2—Cu1—N1—C1177.44 (17)Cu1—N2—C10—C9178.65 (13)
N3—Cu1—N1—C1167.07 (16)C6—N2—C10—C11177.79 (15)
Cl1—Cu1—N1—C17.86 (16)Cu1—N2—C10—C110.9 (2)
N2—Cu1—N1—C50.45 (13)C8—C9—C10—N21.6 (3)
N3—Cu1—N1—C510.8 (3)C8—C9—C10—C11177.87 (17)
Cl1—Cu1—N1—C5170.04 (12)C15—N3—C11—C121.5 (3)
N1—Cu1—N2—C10176.27 (14)Cu1—N3—C11—C12179.57 (14)
N3—Cu1—N2—C100.06 (13)C15—N3—C11—C10177.20 (16)
Cl1—Cu1—N2—C1090.4 (3)Cu1—N3—C11—C101.77 (19)
N1—Cu1—N2—C62.41 (13)N2—C10—C11—N31.7 (2)
N3—Cu1—N2—C6178.74 (14)C9—C10—C11—N3177.75 (17)
Cl1—Cu1—N2—C688.3 (3)N2—C10—C11—C12179.66 (17)
N2—Cu1—N3—C15177.83 (16)C9—C10—C11—C120.9 (3)
N1—Cu1—N3—C15171.78 (17)N3—C11—C12—C131.6 (3)
Cl1—Cu1—N3—C1512.65 (16)C10—C11—C12—C13176.90 (17)
N2—Cu1—N3—C111.06 (12)C11—C12—C13—C140.5 (3)
N1—Cu1—N3—C119.3 (3)C12—C13—C14—C150.7 (3)
Cl1—Cu1—N3—C11168.46 (12)C11—N3—C15—C140.2 (3)
C5—N1—C1—C20.8 (3)Cu1—N3—C15—C14179.02 (14)
Cu1—N1—C1—C2177.03 (15)C13—C14—C15—N30.9 (3)
N1—C1—C2—C30.3 (3)C7—C8—C16—C21154.31 (18)
C1—C2—C3—C40.8 (3)C9—C8—C16—C2125.0 (3)
C2—C3—C4—C50.2 (3)C7—C8—C16—C1724.1 (3)
C1—N1—C5—C41.3 (3)C9—C8—C16—C17156.65 (17)
Cu1—N1—C5—C4176.73 (15)C21—C16—C17—C181.6 (3)
C1—N1—C5—C6179.39 (16)C8—C16—C17—C18179.98 (17)
Cu1—N1—C5—C61.31 (19)C16—C17—C18—C191.1 (3)
C3—C4—C5—N10.9 (3)C17—C18—C19—C200.4 (3)
C3—C4—C5—C6178.70 (18)C17—C18—C19—Br1179.57 (14)
C10—N2—C6—C74.4 (3)C18—C19—C20—C211.3 (3)
Cu1—N2—C6—C7176.90 (13)Br1—C19—C20—C21178.66 (15)
C10—N2—C6—C5174.92 (15)C19—C20—C21—C160.8 (3)
Cu1—N2—C6—C53.7 (2)C17—C16—C21—C200.6 (3)
N1—C5—C6—N23.2 (2)C8—C16—C21—C20179.05 (18)
C4—C5—C6—N2174.81 (18)O2—S3—C22—F356.95 (16)
N1—C5—C6—C7177.48 (17)O3—S3—C22—F3179.07 (14)
C4—C5—C6—C74.5 (3)O1—S3—C22—F362.15 (15)
N2—C6—C7—C81.9 (3)O2—S3—C22—F264.24 (16)
C5—C6—C7—C8177.43 (17)O3—S3—C22—F257.88 (16)
C6—C7—C8—C92.3 (3)O1—S3—C22—F2176.66 (13)
C6—C7—C8—C16177.01 (16)O2—S3—C22—F1176.41 (14)
C7—C8—C9—C103.9 (3)O3—S3—C22—F161.47 (16)
C16—C8—C9—C10175.35 (16)O1—S3—C22—F157.31 (15)
C6—N2—C10—C92.7 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C4—H4···O1i0.952.533.461 (2)166
C7—H7···O1i0.952.663.556 (2)157
C9—H9···O3ii0.952.583.451 (2)152
C12—H12···O3ii0.952.603.481 (2)155
C13—H13···O2iii0.952.323.183 (2)150
C15—H15···Cl1iv0.952.823.5696 (19)137
C17—H17···O1i0.952.663.581 (2)164
Symmetry codes: (i) x+1, y, z; (ii) x+1/2, y+3/2, z+1/2; (iii) x1/2, y+3/2, z+1/2; (iv) x, y+2, z+1.

Experimental details

Crystal data
Chemical formula[Cu(CF3O3S)Cl(C21H14BrN3)]
Mr636.32
Crystal system, space groupMonoclinic, P21/n
Temperature (K)150
a, b, c (Å)7.7841 (2), 16.3043 (4), 18.2533 (4)
β (°) 93.884 (1)
V3)2311.28 (10)
Z4
Radiation typeCu Kα
µ (mm1)5.78
Crystal size (mm)0.10 × 0.06 × 0.06
Data collection
DiffractometerBruker Microstar
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.452, 0.707
No. of measured, independent and
observed [I > 2σ(I)] reflections
47414, 4344, 4016
Rint0.039
(sin θ/λ)max1)0.608
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.026, 0.073, 1.07
No. of reflections4344
No. of parameters316
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.71, 0.33

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), UdMX (Maris, 2004) and XPREP (Bruker, 2008).

Selected geometric parameters (Å, º) top
Cu1—N12.0311 (16)Cu1—Cl12.2048 (5)
Cu1—N21.9345 (15)Cu1—O12.4635 (14)
Cu1—N32.0338 (16)
N1—Cu1—Cl198.93 (5)N1—Cu1—N3159.51 (6)
N2—Cu1—Cl1169.69 (5)N2—Cu1—O190.92 (5)
N3—Cu1—Cl1100.24 (5)N2—Cu1—N379.67 (6)
N1—Cu1—O195.34 (5)N3—Cu1—O188.61 (5)
N1—Cu1—N280.18 (6)Cl1—Cu1—O199.39 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C4—H4···O1i0.952.533.461 (2)166.1
C7—H7···O1i0.952.663.556 (2)157
C9—H9···O3ii0.952.583.451 (2)152.3
C12—H12···O3ii0.952.603.481 (2)155.1
C13—H13···O2iii0.952.323.183 (2)150.0
C15—H15···Cl1iv0.952.823.5696 (19)136.8
C17—H17···O1i0.952.663.581 (2)164
Symmetry codes: (i) x+1, y, z; (ii) x+1/2, y+3/2, z+1/2; (iii) x1/2, y+3/2, z+1/2; (iv) x, y+2, z+1.
 

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