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The crystal packing of the title compound, C24H18Br2N2S2, is rationalized using the PIXEL method, which allows a separation of the inter­molecular inter­action energy into Coulombic, polarization, dispersion and repulsion contributions. Infinite (\overline{1}01) mol­ecular planes are formed through π–π stacking and other minor inter­actions, including a Br...S contact, with the σ hole of the Br atom pointing towards the S-atom lone pair. The title compound has crystallographically imposed twofold symmetry, with the twofold axis at the mid-point of the central C—C bond.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112048196/fg3278sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270112048196/fg3278Isup2.hkl
Contains datablock I

CCDC reference: 925264

Comment top

Functionalized 4,4'-bipyridine building blocks are of great interest in designing coordination polymers (Biradha et al., 2006) and are also useful intermediates in viologen chemistry (Benniston et al., 2007). However, the known methods for their preparation often require long reaction sequences (Swahn et al., 2006). Recently, a new one-step procedure was described for the preparation of a series of 4,4'-bipyridines bearing four halogen atoms in their structure, which can serve for further functionalization by using cross-coupling reactions (Abboud, Mamane et al., 2010). Therefore, the nonsymmetrical bipyridine 4-(5,5'-dibromo-2'-chloro-4,4'-bipyridin-2-yl)benzaldehyde could be prepared by a selective Suzuki reaction on a single halogen atom (Abboud, Kadimi et al., 2010). Here, we report on the structural analysis of a symmetrical derivative, namely 5,5'-dibromo-2,2'-bis[4-(methylsulfanyl)phenyl]-4,4'-bipyridine, (I). Its preparation involves a selective Suzuki reaction on the C2 and C2' positions of 2,2',5,5'-tetrabromo-4,4'-bipyridine, due to the increased reactivity of Br atoms in proximity to N atoms (Abboud et al., 2012). Crystals of (I) suitable for X-ray analysis were obtained by evaporation from dichloromethane at room temperature.

Compound (I) crystallizes in the C2/c space group, with half the molecule in the asymmetric unit (Fig. 1). The molecule lies on the crystallographic twofold symmetry axis. The dihedral angle between the pyridine rings is 85.43 (4)°, leading to an intramolecular Br1···Br1(-x + 1, y, -z + 3/2) separation [4.2745 (4) Å] shorter than the corresponding distance found in a previously reported partially functionalized bipyridine [4.29549 (3)Å; Abboud, Kadimi et al., 2010] but still significantly longer than twice the van der Waals radius of bromine (1.85 Å; Bondi, 1964). The methylsulfanyl group is essentially coplanar with the phenyl ring [C11—C10—S13—C14 = -0.1 (2)°], but the latter makes a dihedral angle of 19.88 (9)° with the attached pyridine ring.

The intermolecular interactions in (I) were analysed using the PIXEL method (OPiX; Gavezzotti, 2003a,b), which allows the separation of the intermolecular interaction energies between pairs of molecules into the individual Coulombic, polarization, dispersion and repulsion contributions. In this PIXEL method, all symmetry-related molecules within 22 Å of a reference molecule were considered. Atomic coordinates derived from the X-ray diffraction experiment were used, except for H atoms, which were located at standard average distances derived from neutron diffraction (Allen et al., 1995). Molecular charge densities from a quantum chemical calculation (MP2 level with 6-31G** basis set using GAUSSIAN03; Frisch et al., 2003) and tabulated atomic polarizabilities were used to compute the Coulombic, polarization, dispersion and repulsion terms. Table 1 reports the intermolecular interaction energies for all molecular pairs with an energy below -1.0 kJ mol-1.

It can be seen [Where?] that (I) forms infinite molecular columns parallel to [010]. Indeed, the molecules are tightly bonded (entry 1; intermolecular interaction energy 60.0 kJ mol-1) through ππ stacking (Table 2) between the benzene and pyridine rings. The cohesion of this molecular arrangement is also effected through a C3—H3···Br1iv hydrogen bond (Table 3) and methyl···π contacts [C14—H14B···π(C9i) H···A = 2.70 Å and D—H···A = 146°; symmetry code: (i) x, y - 1, z]. This particular molecular interaction is characterized by a very large dispersion contribution, which may also result in part from the proximity between the pyridine ring π-cloud and the polarizable atom Br1i [C3···Br1i = 4.256 (2) Å and C3···Br1i—C5i = 85.96 (6)°].

These neighbouring columns interact through slightly weaker ππ stacking between the pyridine rings, viz. C14—H14C···π(C7ii) [H···A = 2.76 Å and D—H···A = 150°; symmetry code: (ii) -x + 1/2, -y - 1/2, -z + 1] and C14—H14A···Br1vii [H···A = 3.00 Å and D—H···A = 172°; symmetry code: (vii) x - 1/2, -y - 1/2, z - 1/2 [should this be (ii)?] contacts (Table 1, entry 2), forming infinite (101) molecular planes (Fig. 2). This lower interaction energy compared with the first dimer, where two ππ interactions are present (Table 1, entry 1), may be related to fact that in this second dimer only one such interaction is present.

Of the less stabilizing interactions listed in Table 1, entries 5 and 7 also participate in the internal cohesion of these molecular planes. The former is characterized by two crystallographically equivalent C5—Br1···S13(x + 1/2, -y + 1/2, z + 1/2) contacts (Fig. 3). Although the Br···S distance [3.8173 (6) Å] is slightly larger than the sum of the corresponding van der Waals radii [rvdW(Br) = 1.85 Å, rvdW(S) = 1.80 Å; Bondi, 1964], these atoms show a favourable mutual orientation, with the positive σ hole of the halogen atom pointing towards one of the S-atom lone pairs [C5—Br1···S13 = 170.72 (5)°]. Interestingly, a search of the Cambridge Structural Database (CSD, Version 5.33 of November 2011 plus three updates; Allen, 2002) for Br···S intermolecular contacts reveals a sharp peak centred at 3.9 Å in the normalized contact distribution function (Gavezzotti, 2010) calculated from these data (Fig. 4) (the search was for C—Br···SXY contacts < vdW + 3 Å with three-dimensional coordinates determined, with no errors and no disorder, yielding 678 structures and 4454 contacts). Thus, although this distance is slightly longer than the sum of the van der Waals radii of Br and S atoms, it corresponds to a preferential statistical geometric relationship between these two atoms. Scatter plots of the C—Br···S and Br···S—Cg angles versus Br···S distance (where Cg is the centroid of S, X and Y atoms of the SXY fragment) show that, as the Br···S distance increases, the observed ranges for these angles widen (Figs. 5 and 6). More precisely, for the C—Br···S angle there is first a rapid widening for Br···S ranging from 3.3 to 3.6 Å, and then a smooth enlarging of the observed contact angles. At the observed contact distance (nearly corresponding to the peak in the contact distribution function, i.e. 3.9 Å) the observed range is about 60–180°. Thus, this type of contact is not strongly directional at this interatomic distance, the positive σ hole of the Br atom not being systematically oriented towards the S atom. For the Br···S—Cg angle, the observed range is about 80–180° for the shortest distances, and about 0–180° for Br···S distances above 5.6 Å. Thus, from this CSD survey it appears that the observed orientation of the C—Br···S contact in (I), with the Br σ hole pointing towards the S-atom lone pair, results more from a coincidence induced by the packing than from the anisotropy of the electron density around the Br and S atoms. Moreover, the situation within the structure of (I) is additionally complicated: the two molecules involved in this Br···S contact interact with two other molecules at (-x + 1, y + 1, -z + 3/2) and (x + 1/2, -y - 1/2, z + 1/2) through the two strongest interactions (entries 1 and 2 of Table 1). The interaction listed in entry 7 is characterized by a cyclic methyl···aromatic H atom C14···H11(-x + 1/2, -y - 3/2, -z + 1) contact. The dispersion term is the leading contribution, arising from the proximity of the benzene rings and S atoms.

All the other interactions listed in Table 1 ensure cohesion between adjacent (101) molecular planes. The strongest (Table 1, entry 3) corresponds to ππ stacking involving half the molecule through the pyridine and benzene rings (Table 2). In this dimer, a C—Br···S contact is observed with a significantly longer Br···S distance than the previous one [C5—Br1···S13(-x + 1, -y, -z + 1); Br···S = 4.1194 (5) Å and C—Br···S = 104.90 (4)°], falling on the right-hand side of the peak in the Br···S distance distribution (Fig. 4). In this latter case, the mutual orientation of the Br and S atoms is not favourable according to the σ-hole model, the lone pairs of the two atoms being approximately oriented towards each other. Contrary to the first two ππ interactions mentioned above, this particular contact has relatively small Coulombic and polarization contributions besides the large dispersion term; in the first two cases, C—H···π/Br interactions also contribute to the total energy. In comparison, the cyclic R22(6) (Bernstein et al., 1995) C6—H6···N1(-x + 1, -y + 1, -z + 1) hydrogen bonds (Table 1, entry 4) have a Coulombic plus polarization term almost twice as large; the dispersion contribution is smaller but is still the leading term, resulting from the close proximity of the parallel pyridine rings (distance between ring centroids = 5.591 Å) (Fig. 7). Aromatic atom H9 is involved in hydrogen bonding with atom S13, viz. C9—H9···S13(-x + 1/2, y + 1/2, -z + 1/2) (Table 3), giving four such contacts per molecule (Table 1, entry 6). The last two interactions listed in Table 1 (entries 8 and 9) involve distant molecules belonging to the second interaction shell.

The lattice energy of (I) was computed using the PIXEL method as the sum of pair contributions to a central molecule embedded in a crystal cluster of radius 22 Å. This cohesion energy reached -198.1 kJ mol-1, which is significantly larger than the corresponding value obtained in a similar calculation performed on 4-(5,5'-dibromo-2'-chloro-4,4'-bipyridin-2-yl)benzaldehyde (-135.0 kJ mol-1; Abboud, Kadimi et al., 2010). This is in line with the larger melting point measured for (I) (488–489 K) compared with 4-(5,5'-dibromo-2'-chloro-4,4' bipyridin-2-yl)benzaldehyde (443–444 K).

Related literature top

For related literature, see: Abboud et al. (2012); Abboud, Kadimi, Mamane & Aubert (2010); Abboud, Mamane, Aubert, Lecomte & Fort (2010); Allen (2002); Allen et al. (1995); Benniston et al. (2007); Bernstein et al. (1995); Biradha et al. (2006); Bondi (1964); Frisch (2003); Gavezzotti (2003a, 2003b, 2010); Swahn et al. (2006).

Experimental top

To a degassed toluene solution (6 ml) containing Pd(PPh3)4 (87 mg, 0.075 mmol) and 2,2',5,5'-tetrabromo-4,4'-bipyridine (575 mg, 1.5 mmol) were successively added degassed solutions of 4-(methylsulfanyl)phenylboronic acid (450 mg, 3 mmol) in methanol (3 ml) and Na2CO3 (636 mg, 6 mmol) in water (3 ml). After heating for 15 h at 373 K, the reaction mixture was cooled to room temperature, extracted with ethyl acetate and dried over MgSO4. After concentration [By heating? Under vacuum?], the residue was purified by chromatography on silica gel (hexanes–ethyl acetate 9:1 v/v) to give compound (I) as a yellow powder (yield 136 mg, 45%). Crystals of (I) were obtained by slow evaporation from dichloromethane at room temperature and in air (m.p. 488–489 K).

Refinement top

H atoms were located from difference Fourier maps. The final structure was constructed using riding models for C—H bonds, with C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C) for all aromatic H atoms, and with C—H = 0.98 Å and 1.5Ueq(C) for all methyl H atoms.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
Fig. 1. A molecular view of (I), showing the atom-numbering scheme for the asymmetric unit; the molecule displays a twofold symmetry axis. Displacement ellipsoids are drawn at the 50% probability level.

Fig. 2. A packing diagram showing the (101) plane; ππ, S13···Br1 and H3···Br1 interactions are shown as dashed lines. [Symmetry codes: (i) x, y, z (reference molecule); (ii) x, y - 1, z; (iii) -x + 1, y - 1, -z + 3/2; (iv) -x + 1/2, -y - 1/2, -z + 1; (v) x - 1/2, -y - 1/2, z - 1/2.]

Fig. 3. A molecular view showing the Br···S contact (dashed line), with the σ hole of the Br atom pointing toward the S-atom lone pair. [Symmetry codes: (i) x, y, z (reference molecule); (ii) x + 1/2, -y + 1/2, x + 1/2.]

Fig. 4. Contact distribution function (CDF) for Br···S intermolecular contacts extracted from the CSD, plotted as a function of Br···S distances (Å) (see Comment).

Fig. 5. A scatter plot of C—Br···S angles (°) as a function of Br···S distances (Å) extracted from the CSD (see Comment).

Fig. 6. A scatter plot of Br···SCg angles (°) as a function of Br···S distances (Å) extracted from the CSD (see Comment).

Fig. 7. A packing diagram showing the (010) plane; traces of (101) planes are displayed as dotted–dashed lines. Br···S contacts participating in the internal cohesion of the (101) planes and N···H hydrogen bonds participating in the cohesion between adjacent (101) planes are shown as dashed lines.
5,5'-Dibromo-2,2'-bis[4-(methylsulfanyl)phenyl]-4,4'-bipyridine top
Crystal data top
C24H18Br2N2S2F(000) = 1112
Mr = 558.34Dx = 1.713 Mg m3
Monoclinic, C2/cCu Kα radiation, λ = 1.54180 Å
Hall symbol: -C 2ycCell parameters from 18560 reflections
a = 21.4175 (2) Åθ = 4.3–76.3°
b = 5.9779 (1) ŵ = 6.66 mm1
c = 17.6539 (2) ÅT = 110 K
β = 106.648 (1)°Plate, colourless
V = 2165.52 (5) Å30.25 × 0.16 × 0.06 mm
Z = 4
Data collection top
Oxford SuperNova dual
diffractometer with Atlas detector
2281 independent reflections
Radiation source: SuperNova (Cu) X-ray Source2255 reflections with I > 2σ(I)
Mirror monochromatorRint = 0.019
Detector resolution: 10.4508 pixels mm-1θmax = 76.5°, θmin = 4.3°
ω scansh = 2626
Absorption correction: analytical
[CrysAlis PRO (Oxford Diffraction, 2009), using a multifaceted crystal model (Clark & Reid, 1995)]
k = 77
Tmin = 0.338, Tmax = 0.706l = 2222
21521 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.017H-atom parameters constrained
wR(F2) = 0.044 w = 1/[σ2(Fo2) + (0.0218P)2 + 2.9248P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.002
2281 reflectionsΔρmax = 0.35 e Å3
138 parametersΔρmin = 0.33 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.00063 (3)
Crystal data top
C24H18Br2N2S2V = 2165.52 (5) Å3
Mr = 558.34Z = 4
Monoclinic, C2/cCu Kα radiation
a = 21.4175 (2) ŵ = 6.66 mm1
b = 5.9779 (1) ÅT = 110 K
c = 17.6539 (2) Å0.25 × 0.16 × 0.06 mm
β = 106.648 (1)°
Data collection top
Oxford SuperNova dual
diffractometer with Atlas detector
2281 independent reflections
Absorption correction: analytical
[CrysAlis PRO (Oxford Diffraction, 2009), using a multifaceted crystal model (Clark & Reid, 1995)]
2255 reflections with I > 2σ(I)
Tmin = 0.338, Tmax = 0.706Rint = 0.019
21521 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0170 restraints
wR(F2) = 0.044H-atom parameters constrained
S = 1.05Δρmax = 0.35 e Å3
2281 reflectionsΔρmin = 0.33 e Å3
138 parameters
Special details top

Experimental. CrysAlisPro, Oxford Diffraction Ltd., Analytical numeric absorption correction using a multifaceted crystal model (Clark & Reid, 1995).

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
Br10.595232 (7)0.56859 (2)0.734066 (7)0.02061 (7)
S130.23991 (2)0.44165 (8)0.33466 (2)0.03432 (11)
N10.47754 (5)0.2387 (2)0.54280 (6)0.0185 (2)
C40.49639 (6)0.2248 (2)0.70670 (7)0.0157 (2)
C50.53126 (6)0.3711 (2)0.67269 (7)0.0165 (2)
C60.52022 (6)0.3733 (2)0.59134 (8)0.0190 (3)
H60.54420.47550.56930.023*
C30.45305 (6)0.0802 (2)0.65571 (8)0.0173 (3)
H30.42910.02570.67630.021*
C90.32858 (7)0.1140 (3)0.38355 (8)0.0251 (3)
H90.31440.06850.32980.030*
C70.39745 (6)0.0535 (2)0.51702 (8)0.0175 (3)
C110.32537 (7)0.3749 (3)0.48577 (8)0.0247 (3)
H110.30890.50780.50250.030*
C80.37526 (7)0.0102 (3)0.43742 (8)0.0220 (3)
H80.39260.14060.42020.026*
C120.37268 (7)0.2499 (2)0.53968 (8)0.0217 (3)
H120.38840.29940.59290.026*
C100.30209 (7)0.3051 (3)0.40725 (8)0.0238 (3)
C140.21852 (8)0.6727 (3)0.38739 (11)0.0352 (4)
H14B0.25710.76580.40960.053*
H14A0.18460.76250.35110.053*
H14C0.20220.61590.43020.053*
C20.44471 (6)0.0905 (2)0.57414 (8)0.0165 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.02500 (9)0.02205 (9)0.01358 (9)0.00558 (5)0.00360 (6)0.00206 (5)
S130.02770 (19)0.0499 (3)0.02063 (18)0.00968 (16)0.00059 (15)0.01331 (16)
N10.0219 (5)0.0219 (6)0.0111 (5)0.0003 (4)0.0038 (4)0.0012 (4)
C40.0179 (6)0.0180 (6)0.0107 (6)0.0030 (5)0.0032 (4)0.0010 (5)
C50.0182 (6)0.0180 (6)0.0125 (6)0.0004 (5)0.0027 (5)0.0013 (5)
C60.0231 (6)0.0207 (6)0.0136 (6)0.0010 (5)0.0058 (5)0.0017 (5)
C30.0198 (6)0.0198 (6)0.0121 (6)0.0007 (5)0.0042 (5)0.0010 (5)
C90.0264 (7)0.0342 (8)0.0113 (6)0.0022 (6)0.0001 (5)0.0014 (6)
C70.0180 (6)0.0223 (7)0.0115 (6)0.0009 (5)0.0031 (5)0.0023 (5)
C110.0269 (7)0.0275 (7)0.0190 (7)0.0065 (6)0.0052 (6)0.0034 (6)
C80.0249 (7)0.0264 (7)0.0132 (6)0.0001 (6)0.0031 (5)0.0000 (5)
C120.0255 (6)0.0256 (7)0.0124 (6)0.0022 (6)0.0027 (5)0.0008 (5)
C100.0196 (6)0.0326 (8)0.0169 (6)0.0005 (6)0.0016 (5)0.0095 (6)
C140.0234 (7)0.0317 (8)0.0452 (10)0.0031 (6)0.0012 (7)0.0133 (7)
C20.0178 (6)0.0196 (6)0.0114 (6)0.0023 (5)0.0028 (5)0.0002 (5)
Geometric parameters (Å, º) top
Br1—C51.8958 (13)C9—C101.392 (2)
S13—C101.7618 (14)C9—H90.9500
S13—C141.7969 (19)C7—C121.393 (2)
N1—C61.3298 (18)C7—C81.4010 (18)
N1—C21.3449 (17)C7—C21.4824 (18)
C4—C51.3931 (18)C11—C121.3921 (19)
C4—C31.3931 (18)C11—C101.396 (2)
C4—C4i1.492 (2)C11—H110.9500
C5—C61.3871 (18)C8—H80.9500
C6—H60.9500C12—H120.9500
C3—C21.4008 (18)C14—H14B0.9800
C3—H30.9500C14—H14A0.9800
C9—C81.382 (2)C14—H14C0.9800
C10—S13—C14103.36 (8)C12—C11—H11119.9
C6—N1—C2118.52 (11)C10—C11—H11119.9
C5—C4—C3116.84 (11)C9—C8—C7120.99 (14)
C5—C4—C4i122.06 (11)C9—C8—H8119.5
C3—C4—C4i121.09 (11)C7—C8—H8119.5
C6—C5—C4119.92 (12)C11—C12—C7121.21 (13)
C6—C5—Br1117.83 (10)C11—C12—H12119.4
C4—C5—Br1122.25 (9)C7—C12—H12119.4
N1—C6—C5122.91 (13)C9—C10—C11118.89 (13)
N1—C6—H6118.5C9—C10—S13116.74 (11)
C5—C6—H6118.5C11—C10—S13124.37 (12)
C4—C3—C2120.13 (12)S13—C14—H14B109.5
C4—C3—H3119.9S13—C14—H14A109.5
C2—C3—H3119.9H14B—C14—H14A109.5
C8—C9—C10120.72 (13)S13—C14—H14C109.5
C8—C9—H9119.6H14B—C14—H14C109.5
C10—C9—H9119.6H14A—C14—H14C109.5
C12—C7—C8117.99 (13)N1—C2—C3121.62 (12)
C12—C7—C2122.40 (12)N1—C2—C7115.99 (11)
C8—C7—C2119.60 (13)C3—C2—C7122.34 (12)
C12—C11—C10120.11 (14)
C3—C4—C5—C62.26 (19)C2—C7—C12—C11176.05 (13)
C4i—C4—C5—C6176.42 (12)C8—C9—C10—C112.6 (2)
C3—C4—C5—Br1176.87 (9)C8—C9—C10—S13176.74 (12)
C4i—C4—C5—Br14.46 (18)C12—C11—C10—C92.2 (2)
C3ii—Br1—C5—C676.64 (11)C12—C11—C10—S13177.08 (12)
C3ii—Br1—C5—C4104.22 (11)C14—S13—C10—C9179.45 (12)
C2—N1—C6—C51.6 (2)C14—S13—C10—C110.12 (15)
C4—C5—C6—N10.6 (2)C6—N1—C2—C32.02 (19)
Br1—C5—C6—N1178.55 (10)C6—N1—C2—C7179.51 (12)
C5—C4—C3—C21.81 (19)C4—C3—C2—N10.3 (2)
C4i—C4—C3—C2176.87 (12)C4—C3—C2—C7177.64 (12)
C10—C9—C8—C70.4 (2)C12—C7—C2—N1162.92 (13)
C12—C7—C8—C92.2 (2)C8—C7—C2—N118.51 (18)
C2—C7—C8—C9176.47 (13)C12—C7—C2—C319.6 (2)
C10—C11—C12—C70.4 (2)C8—C7—C2—C3158.96 (13)
C8—C7—C12—C112.5 (2)
Symmetry codes: (i) x+1, y, z+3/2; (ii) x, y+1, z.

Experimental details

Crystal data
Chemical formulaC24H18Br2N2S2
Mr558.34
Crystal system, space groupMonoclinic, C2/c
Temperature (K)110
a, b, c (Å)21.4175 (2), 5.9779 (1), 17.6539 (2)
β (°) 106.648 (1)
V3)2165.52 (5)
Z4
Radiation typeCu Kα
µ (mm1)6.66
Crystal size (mm)0.25 × 0.16 × 0.06
Data collection
DiffractometerOxford SuperNova dual
diffractometer with Atlas detector
Absorption correctionAnalytical
[CrysAlis PRO (Oxford Diffraction, 2009), using a multifaceted crystal model (Clark & Reid, 1995)]
Tmin, Tmax0.338, 0.706
No. of measured, independent and
observed [I > 2σ(I)] reflections
21521, 2281, 2255
Rint0.019
(sin θ/λ)max1)0.631
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.017, 0.044, 1.05
No. of reflections2281
No. of parameters138
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.35, 0.33

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2008), publCIF (Westrip, 2010).

Intermolecular interaction energies within pairs of molecules top
The reference molecule is built from (x, y, z) and (-x + 1, y, -z + 3/2) symmetry codes; `Symm' gives the symmetries to be applied to the reference molecule in order to obtain the required molecular pair and N is the number of such interactions per molecule. `Cont' lists the number and type of identified interatomic contacts within each molecular dimer. d is the distance between molecular mass centres (Å). `Coul.', `Pol.', `Disp.' and `Rep.' are Coulombic, polarization, dispersion and repulsion contributions to the total interaction energy (Tot.). Energies are in kJ mol-1.
No.NCont.dSymmCoul.Pol.Disp.Rep.Tot.
122 ππ; 2 H···Br; 2 H···π5.978x, y - 1, z; -x + 1, y - 1, -z + 3/2-22.1-11.1-77.850.9-60
221 ππ; 2 H···Br; 2 H···π12.442x - 1/2, -y - 1/2, z - 1/2; -x + 1/2, -y - 1/2, -z + 1-22.8-9.2-56.446.2-42.2
322 ππ8.89-x + 1, -y, -z + 1; x, -y, z - 1/2-6.0-5.1-52.837.3-26.6
422 H···N10.105-x + 1, -y + 1, -z + 1; x, -y + 1, z - 1/2-15.7-6.3-32.030.4-23.7
522 Br···S11.923x + 1/2, -y + 1/2, z + 1/2; -x + 3/2, -y + 1/2, -z + 2-7.4-3.0-13.69.8-14.2
641 S···H18.082-x + 1/2, y + 1/2, -z + 1/2; x - 1/2, y + 1/2, z - 1-3.9-3.1-10.09.8-7.2
722 H···methyl15.457-x + 1/2, -y - 3/2, -z + 1; x - 1/2, -y - 3/2, z - 1/21.3-2.4-17.711.9-6.9
82No contact11.288x, -y - 1, z - 1/2; -x + 1, -y - 1, -z + 1-2.5-0.2-2.70.0-5.4
92No contact11.956x, y - 2, z; -x + 1, y - 2, -z + 3/2-0.50.0-0.80.0-1.4
ππ interactions top
Cg1 and Cg2 are the centroids of N1/C2–C6 and C7–C12 rings, respectively. No. is the corresponding entry number in Table 1. CCD is the distance between ring centroids, SA is the angle subtended by the centroid-to-centroid vector and each of the plane normals (i.e. slippage angle) and IPD is the distance from one plane to the neighbouring centroid.
Group 1/Group 2No.CCD (Å)SA (°)IPD (Å)
Cg2/Cg1i14.9384 (11)52.0–32.24.1809 (8)–3.0381 (7)
Cg2/Cg2ii24.9236 (11)42.4–42.43.6380 (8)–3.6380 (8)
Cg1/Cg2iii34.1855 (11)45.8–29.23.6528 (7)–2.9191 (8)
Symmetry codes: (i) x, y - 1, z; (ii) -x + 1/2, -y - 1/2, -z + 1; (iii) -x + 1, -y, -z + 1.
Hydrogen-bond geometry (Å, °) top
No. is the corresponding entry number in Table 1.
D—H···ANo.D—HH···AD···AD—H···A
C3—H3···Br1iv10.953.023.919 (2)158
C6—H6···N1v40.952.563.324 (2)138
C9—H9···S13vi60.952.903.850 (2)175
Symmetry codes: (iv) -x + 1, y - 1, -z + 3/2; (v) -x + 1, -y + 1, -z + 1; (vi) -x + 1/2, y + 1/2, -z + 1/2.
 

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