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Structure analyses of 4,4'-bis(4-hydroxy­butyl)-2,2'-bi­pyridine, C18H24N2O2, (I), and 4,4'-bis(4-bromo­butyl)-2,2'-bi­pyridine, C18H22Br2N2, (II), reveal intermolecular hydrogen bonding in both compounds. For (I), O-H...N intermolecular hydrogen bonding leads to the formation of an infinite two-dimensional polymer, and [pi] stacking interactions are also observed. For (II), C-H...N intermolecular hydrogen bonding leads to the formation of a zigzag polymer. The two compounds crystallize in different crystal systems, but both mol­ecules possess Ci symmetry, with one half mol­ecule in the asymmetric unit.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105006438/sk1818sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270105006438/sk1818Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270105006438/sk1818IIsup3.hkl
Contains datablock II

CCDC references: 252257; 252258

Comment top

Compounds containing 2,2'-bipyridine (bpy), substituted at the 4,4'-positions with alkyl chains of different lengths, are interesting precursors for functionalization with thiols, carboxylic acids, disulfides or other anchoring groups. Compounds with such terminating groups have displayed the potential to form a self-assembled monolayer on metallic or semiconducting surfaces (Bain, Troughton et al., 1989; Haga et al., 2000; Bain, Biebuyck & Whitesides, 1989; Vogelson et al., 2003). Interestingly, alkyl-substituted bpy at the 4,4'-positions has been used as a covalent link in porphyrin–RuO2 clusters and the influence of the linking alkyl chain length on the photoinduced intramolecular electron transfer in such clusters has also been studied (Resch & Fox, 1991). Derivatives of [Ru(bpy)3]2+ with different alkyl substituents (e.g. tert-butyl and dinonyl) on the bipyridyl ligands have been prepared and, due to their enhanced solubility, processed for the construction of electroluminescent devices (Rudmann et al., 2002).

4,4'-Alkyl-substituted 2,2'-bpy-based compounds have also been used to synthesize macrocyclic compounds (Chambron & Sauvage, 1986, 1987). Owing to the chelating nature of bpy, metal complexes with alkyl-substituted bipyridine have been prepared and their behaviour as versatile solvatochromic probes that form metalloaggregates in water-rich media has been investigated (Gameiro et al., 2001). Ruthenium(II) complexes of 2,2'-bpy derivatives, [Ru(bpy)3]2+ [Rbpy is 4,4'-bis(alkylaminocarbonyl)-2,2'-bipyridine, where the alkyl is propyl, hexyl or adamantyl], have been synthesized and the kinetics of the photo-induced electron transfer (ET) reaction between these complexes and methyl viologen (MV2+) has been investigated (Hamada et al., 2003). Compounds derived from the alkylation of 4,4'-dimethyl-2,2'-bpy have also been screened for fungicidal activity against nine plant diseases (Kelly Basetti et al., 1995).

The different synthetic strategies to prepare the 4,4'-substituted derivatives of 2,2'-bpy have been critically discussed and evaluated by Newkome et al. (2004). Our interest in alkyl-substituted bpy stems from the possibility of preparing prototype molecules with appropriate end-groups that could form self-assembled monolayers when brought into contact with substrates such as gold, ITO, platinum or silver. We report here the crystal structure analyses of the important precursors 4,4'-bis(hydroxybutyl)-2,2'-bipyridine, (I), and 4,4'-bis(bromobutyl)-2,2'-bipyridine, (II), which will lead us to the final prototype compounds.

The centrosymmetric molecular structure of (I) is shown in Fig. 1. The bond distances and angles are normal, and the bipyridine moiety is planar. Atoms C5, C2, C2A and C5A are collinear, and the N1—C2—C2A—C3A torsion angle is equal to −0.84 (16)° [symmetry code: (a) −x, 1 − y, −z].

Analysis of the crystal packing diagram (Fig. 2) reveals interesting features at the supramolecular level. Intermolecular hydrogen bonding occurs between the lone pair on the N atoms of the bipyridine group and the H atom of the hydroxy group [O1—H1···N1i = 1.91 (2) Å; for details and symmetry code see Table 1]. As a result, the diol molecules lie one behind each other, as in a tandem arrangement, giving rise to well ordered double-stranded chains forming a two-dimensional polymeric sheet structure parallel to (10–1). These chains are aligned parallel to one another in the ac plane. Another notable feature of the crystal structure is that the diol molecules lying in different planes are interconnected through ππ contacts established between the bipyridine moieties, with an interplanar distance of 3.296 (1) Å and a centroid–centroid offset (or ring slippage) of about 1.25 Å (Fig. 2).

Halogenation (Chambron & Sauvage, 1987) of (I) yielded an interesting precursor in the form of the corresponding dibromide, 4,4'-bis(bromobutyl)-2,2'-bipyridine, (II). The molecular structure of (II) is depicted in Fig. 3. Again the molecule is centrosymmetric and the bond distances and angles are normal. The four C atoms of the bipyridine moiety, C5, C2, C2A and C5A, are collinear, and the N1—C2—C2A—N3A torsion angle is 1.1 (4)° [symmetry code: (a) 2 − x, 1 − y, 2 − z].

Part of the crystal structure of (II) is illustrated in Fig. 4. It can be seen that a zigzag polymeric chain is formed as a result of intermolecular hydrogen bonding between the lone pair on the N atom of the aromatic rings and the H atoms of the C atom attached to the bromo group in the alkyl chain (Table 2). The inherent fashion of hydrogen bonding in this molecule makes it nearly impossible to establish ππ interactions, as was observed in the case of the diol (I).

The dibromo derivative can, very efficiently, be complexed with different types of metal ions upon rotation of the pyridine ring in order to obtain a cis conformation of the heteroaromatic rings. Furthermore, both the free ligand and the corresponding metal complex can undergo a very facile substitution of the bromo group with thioacetate (Gryko et al., 1999, 2000; Zheng et al., 1999). Such thioacetate functionalized molecules are extremely good candidates for immobilization on the surface of metals such as gold, silver and copper. The nanostructures thus created on such metallic surfaces can be characterized by a series of analytical techniques, for instance, scanning tunelling microscopy (STM), atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS), to elicit a great deal of information concerning the arrangement and packing of molecules on the surface, as well as their electrical and optical behaviour.

Experimental top

Compound (I) was synthesized from 4,4'-dimethyl-2,2'-bipyridine in accordance with the protocol described by Chambron & Sauvage (1987). Suitable crystals of (I) were obtained as colourless rods by slow concentration of a solution in chloroform. Halogenation of (I) (Chambron & Sauvage, 1987) yielded the corresponding dibromide, (II). Crystals were grown from a solution in chloroform. 1H NMR and elemental analyses for (I) and (II) have been reported previously (Chambron & Sauvage, 1987). For (I): dC (400 MHz, CD3OD, p.p.m.): 157.2, 154.9, 150.07, 125.5, 123.03, 62.58, 36.09, 33.12, 27.77; ESI–MS (MeOH): m/z 301 ([M+H]+, 100%). For (II): dC (400 MHz, CDCl3, p.p.m.): 155.10, 153.01, 148.74, 124.39, 121.94, 34.73, 33.33, 32.26, 28.83; ESI–MS (CHCl3/MeOH): m/z 427 ([M+H]+, 100%).

Refinement top

For (I), H atoms were located in difference Fourier maps and refined isotropically [C—H = 0.944 (16)–1.025 (18) Å]. For (II), H atoms were included in calculated positions and treated as riding atoms [C—H = 0.95–0.99 Å, with Uiso(H) = 1.2Ueq(C)].

Computing details top

For both compounds, data collection: X-AREA (Stoe & Cie, 2004); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with displacement ellipsoids at the 50% probability level. [Symmetry operation: (A) −x, 1 − y, −z.]
[Figure 2] Fig. 2. The crystal structure of (I), showing the formation of double-stranded hydrogen-bonded (dashed lines) two-dimensional sheets parallel to (10–1).
[Figure 3] Fig. 3. The molecular structure of (II), with displacement ellipsoids at the 50% probability level. [Symmetry operation: (A) 2 − x, 1 − y, 2 − z.]
[Figure 4] Fig. 4. Part of the crystal structure of (II), showing the formation of the hydrogen-bonded (dashed lines) C—H···N zigzag polymer chain. [Symmetry code: (i) 3/2 − x, 1/2 + y, z.]
(I) 4,4'-bis(4-hydroxybutyl)-2,2'-bipyridine top
Crystal data top
C18H24N2O2F(000) = 648
Mr = 300.39Dx = 1.221 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 4949 reflections
a = 22.878 (3) Åθ = 2.0–29.5°
b = 4.7657 (5) ŵ = 0.08 mm1
c = 16.789 (2) ÅT = 173 K
β = 116.759 (9)°Rod, colourless
V = 1634.5 (4) Å30.50 × 0.17 × 0.10 mm
Z = 4
Data collection top
STOE IPDS
diffractometer
1733 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.048
Graphite monochromatorθmax = 29.2°, θmin = 2.0°
Detector resolution: 0.81Å pixels mm-1h = 3030
ϕ oscillation scansk = 66
11138 measured reflectionsl = 2322
2210 independent 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)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.118All H-atom parameters refined
S = 1.05 w = 1/[σ2(Fo2) + (0.0673P)2 + 0.3603P]
where P = (Fo2 + 2Fc2)/3
2210 reflections(Δ/σ)max < 0.001
148 parametersΔρmax = 0.32 e Å3
0 restraintsΔρmin = 0.16 e Å3
Crystal data top
C18H24N2O2V = 1634.5 (4) Å3
Mr = 300.39Z = 4
Monoclinic, C2/cMo Kα radiation
a = 22.878 (3) ŵ = 0.08 mm1
b = 4.7657 (5) ÅT = 173 K
c = 16.789 (2) Å0.50 × 0.17 × 0.10 mm
β = 116.759 (9)°
Data collection top
STOE IPDS
diffractometer
1733 reflections with I > 2σ(I)
11138 measured reflectionsRint = 0.048
2210 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0410 restraints
wR(F2) = 0.118All H-atom parameters refined
S = 1.05Δρmax = 0.32 e Å3
2210 reflectionsΔρmin = 0.16 e Å3
148 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
O10.38863 (5)0.1556 (2)0.23801 (7)0.0430 (3)
H10.4194 (9)0.068 (4)0.2911 (13)0.062 (5)*
N10.02394 (4)0.3477 (2)0.10911 (6)0.0245 (2)
C20.01218 (5)0.3912 (2)0.02070 (6)0.0206 (2)
C30.06885 (5)0.2382 (2)0.02965 (7)0.0228 (2)
H30.0927 (7)0.264 (3)0.0928 (9)0.029 (3)*
C40.09052 (5)0.0360 (2)0.01106 (7)0.0242 (2)
C50.05314 (5)0.0074 (2)0.10196 (7)0.0280 (2)
H50.0644 (8)0.144 (3)0.1336 (10)0.040 (4)*
C60.00341 (5)0.1495 (3)0.14721 (7)0.0287 (3)
H60.0312 (7)0.124 (3)0.2102 (10)0.033 (4)*
C70.15147 (5)0.1321 (2)0.04344 (8)0.0297 (3)
H7A0.1565 (9)0.269 (4)0.0056 (12)0.049 (5)*
H7B0.1457 (8)0.220 (4)0.0922 (11)0.045 (4)*
C80.21374 (5)0.0427 (3)0.08786 (8)0.0312 (3)
H8A0.2202 (9)0.150 (4)0.0396 (12)0.054 (5)*
H8B0.2073 (8)0.189 (4)0.1239 (11)0.048 (4)*
C90.27345 (6)0.1367 (3)0.14334 (9)0.0326 (3)
H9A0.2672 (9)0.243 (4)0.1900 (12)0.057 (5)*
H9B0.2785 (9)0.278 (4)0.1036 (12)0.057 (5)*
C100.33580 (6)0.0300 (3)0.19055 (9)0.0386 (3)
H10A0.3435 (9)0.138 (4)0.1449 (13)0.060 (5)*
H10B0.3327 (9)0.161 (4)0.2366 (12)0.050 (5)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0292 (5)0.0427 (6)0.0383 (5)0.0083 (4)0.0014 (4)0.0077 (4)
N10.0226 (4)0.0284 (5)0.0210 (4)0.0009 (3)0.0085 (3)0.0008 (3)
C20.0185 (4)0.0220 (5)0.0215 (4)0.0032 (4)0.0092 (4)0.0004 (4)
C30.0193 (4)0.0237 (5)0.0229 (4)0.0024 (4)0.0074 (4)0.0011 (4)
C40.0201 (5)0.0221 (5)0.0310 (5)0.0026 (4)0.0118 (4)0.0006 (4)
C50.0289 (5)0.0279 (6)0.0306 (5)0.0015 (4)0.0165 (4)0.0045 (4)
C60.0283 (5)0.0347 (6)0.0227 (5)0.0010 (4)0.0113 (4)0.0040 (4)
C70.0228 (5)0.0245 (5)0.0387 (6)0.0013 (4)0.0110 (4)0.0007 (5)
C80.0233 (5)0.0273 (6)0.0374 (6)0.0002 (4)0.0085 (4)0.0011 (5)
C90.0251 (5)0.0301 (6)0.0369 (6)0.0020 (4)0.0090 (5)0.0006 (5)
C100.0254 (6)0.0349 (7)0.0404 (7)0.0008 (5)0.0015 (5)0.0011 (5)
Geometric parameters (Å, º) top
O1—C101.4181 (15)C6—H60.965 (15)
O1—H10.95 (2)C7—C81.5242 (16)
N1—C61.3387 (14)C7—H7A0.953 (18)
N1—C21.3509 (12)C7—H7B0.978 (17)
C2—C31.3931 (14)C8—C91.5227 (16)
C2—C2i1.4890 (19)C8—H8A1.025 (18)
C3—C41.3951 (15)C8—H8B0.978 (18)
C3—H30.957 (13)C9—C101.5085 (17)
C4—C51.3885 (16)C9—H9A0.997 (19)
C4—C71.5081 (15)C9—H9B0.99 (2)
C5—C61.3876 (16)C10—H10A1.00 (2)
C5—H50.944 (16)C10—H10B1.020 (17)
C10—O1—H1109.8 (12)C8—C7—H7B105.8 (10)
C6—N1—C2117.43 (9)H7A—C7—H7B111.7 (14)
N1—C2—C3121.88 (9)C9—C8—C7112.08 (10)
N1—C2—C2i116.58 (11)C9—C8—H8A110.8 (10)
C3—C2—C2i121.54 (11)C7—C8—H8A108.8 (10)
C2—C3—C4120.22 (9)C9—C8—H8B111.5 (10)
C2—C3—H3121.0 (8)C7—C8—H8B108.9 (10)
C4—C3—H3118.7 (8)H8A—C8—H8B104.4 (13)
C5—C4—C3117.54 (10)C10—C9—C8113.66 (10)
C5—C4—C7122.10 (10)C10—C9—H9A107.0 (11)
C3—C4—C7120.34 (10)C8—C9—H9A111.1 (11)
C6—C5—C4118.86 (10)C10—C9—H9B110.0 (11)
C6—C5—H5119.1 (9)C8—C9—H9B108.4 (11)
C4—C5—H5122.1 (9)H9A—C9—H9B106.5 (16)
N1—C6—C5124.05 (10)O1—C10—C9109.38 (11)
N1—C6—H6114.4 (9)O1—C10—H10A110.5 (11)
C5—C6—H6121.6 (9)C9—C10—H10A108.6 (11)
C4—C7—C8114.31 (9)O1—C10—H10B106.7 (10)
C4—C7—H7A108.4 (11)C9—C10—H10B110.4 (10)
C8—C7—H7A109.4 (10)H10A—C10—H10B111.3 (14)
C4—C7—H7B107.3 (10)
C6—N1—C2—C30.25 (14)C2—N1—C6—C51.62 (16)
C6—N1—C2—C2i178.87 (11)C4—C5—C6—N11.68 (17)
N1—C2—C3—C41.03 (15)C5—C4—C7—C8119.31 (12)
C2i—C2—C3—C4179.90 (11)C3—C4—C7—C862.34 (14)
C2—C3—C4—C50.95 (15)C4—C7—C8—C9178.92 (10)
C2—C3—C4—C7179.37 (9)C7—C8—C9—C10178.35 (11)
C3—C4—C5—C60.31 (16)C8—C9—C10—O1178.28 (11)
C7—C4—C5—C6178.08 (10)
Symmetry code: (i) x, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N1ii0.95 (2)1.91 (2)2.8495 (14)172.5 (18)
Symmetry code: (ii) x+1/2, y+1/2, z+1/2.
(II) 4,4'-bis(4-bromobutyl)-2,2'-bipyridine top
Crystal data top
C18H22Br2N2F(000) = 856
Mr = 426.20Dx = 1.609 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 4377 reflections
a = 8.3566 (12) Åθ = 1.4–25.6°
b = 14.246 (2) ŵ = 4.61 mm1
c = 14.779 (2) ÅT = 173 K
V = 1759.4 (4) Å3Plate, colourless
Z = 40.30 × 0.20 × 0.10 mm
Data collection top
STOE IPDS-II
diffractometer
1560 independent reflections
Radiation source: fine-focus sealed tube1064 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.055
rotation method scansθmax = 25.1°, θmin = 2.9°
Absorption correction: refdelF
DELrefABS in PLATON (Spek, 2003)
h = 99
Tmin = 0.267, Tmax = 0.631k = 1616
7834 measured reflectionsl = 1714
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)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.091H-atom parameters constrained
S = 0.96 w = 1/[σ2(Fo2) + (0.0503P)2]
where P = (Fo2 + 2Fc2)/3
1560 reflections(Δ/σ)max < 0.001
100 parametersΔρmax = 0.41 e Å3
0 restraintsΔρmin = 0.65 e Å3
Crystal data top
C18H22Br2N2V = 1759.4 (4) Å3
Mr = 426.20Z = 4
Orthorhombic, PbcaMo Kα radiation
a = 8.3566 (12) ŵ = 4.61 mm1
b = 14.246 (2) ÅT = 173 K
c = 14.779 (2) Å0.30 × 0.20 × 0.10 mm
Data collection top
STOE IPDS-II
diffractometer
1560 independent reflections
Absorption correction: refdelF
DELrefABS in PLATON (Spek, 2003)
1064 reflections with I > 2σ(I)
Tmin = 0.267, Tmax = 0.631Rint = 0.055
7834 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0370 restraints
wR(F2) = 0.091H-atom parameters constrained
S = 0.96Δρmax = 0.41 e Å3
1560 reflectionsΔρmin = 0.65 e Å3
100 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
Br10.03706 (4)0.74683 (3)0.37863 (3)0.04190 (17)
N11.0144 (3)0.4109 (2)0.41392 (19)0.0277 (6)
C20.9514 (3)0.4823 (2)0.4614 (2)0.0240 (7)
C30.8025 (4)0.5208 (2)0.4414 (2)0.0273 (7)
H80.76200.57090.47720.033*
C40.7129 (4)0.4866 (2)0.3699 (2)0.0283 (8)
C50.7792 (4)0.4121 (2)0.3209 (2)0.0276 (8)
H50.72280.38560.27130.033*
C60.9255 (4)0.3780 (2)0.3449 (3)0.0301 (8)
H30.96770.32740.31050.036*
C70.5509 (4)0.5241 (3)0.3431 (3)0.0347 (8)
H2A0.47300.47190.34660.042*
H2B0.55650.54410.27910.042*
C80.4859 (4)0.6056 (2)0.3985 (3)0.0323 (8)
H11A0.55990.65970.39380.039*
H11B0.47910.58710.46290.039*
C90.3199 (4)0.6346 (2)0.3646 (3)0.0316 (8)
H7A0.32870.65860.30200.038*
H7B0.24900.57890.36370.038*
C100.2476 (4)0.7085 (2)0.4235 (3)0.0299 (8)
H10A0.31930.76380.42540.036*
H10B0.23680.68410.48600.036*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0373 (2)0.0474 (3)0.0410 (3)0.01093 (17)0.00046 (15)0.00705 (19)
N10.0270 (14)0.0269 (15)0.0292 (15)0.0002 (12)0.0002 (12)0.0009 (13)
C20.0243 (16)0.0223 (16)0.0253 (18)0.0026 (12)0.0024 (12)0.0012 (14)
C30.0291 (16)0.0243 (16)0.028 (2)0.0022 (14)0.0003 (14)0.0044 (15)
C40.0271 (17)0.0263 (17)0.031 (2)0.0036 (13)0.0006 (13)0.0041 (16)
C50.0288 (17)0.0288 (18)0.0253 (19)0.0049 (14)0.0022 (13)0.0028 (15)
C60.0329 (17)0.0301 (18)0.0272 (19)0.0041 (14)0.0055 (15)0.0032 (15)
C70.0311 (18)0.0364 (19)0.037 (2)0.0023 (15)0.0053 (15)0.0061 (18)
C80.0298 (18)0.0325 (19)0.035 (2)0.0016 (15)0.0047 (15)0.0009 (16)
C90.0280 (16)0.0338 (18)0.033 (2)0.0034 (14)0.0013 (15)0.0047 (17)
C100.0261 (15)0.0276 (18)0.036 (2)0.0021 (15)0.0038 (15)0.0043 (16)
Geometric parameters (Å, º) top
Br1—C101.958 (3)C7—C81.521 (5)
N1—C21.344 (4)C7—H2A0.9900
N1—C61.346 (5)C7—H2B0.9900
C2—C31.392 (4)C8—C91.531 (5)
C2—C2i1.488 (6)C8—H11A0.9900
C3—C41.383 (5)C8—H11B0.9900
C3—H80.9500C9—C101.494 (5)
C4—C51.400 (5)C9—H7A0.9900
C4—C71.508 (4)C9—H7B0.9900
C5—C61.363 (5)C10—H10A0.9900
C5—H50.9500C10—H10B0.9900
C6—H30.9500
C2—N1—C6116.3 (3)C8—C7—H2B108.1
N1—C2—C3122.5 (3)H2A—C7—H2B107.3
N1—C2—C2i116.3 (3)C7—C8—C9110.7 (3)
C3—C2—C2i121.2 (4)C7—C8—H11A109.5
C4—C3—C2120.5 (3)C9—C8—H11A109.5
C4—C3—H8119.8C7—C8—H11B109.5
C2—C3—H8119.8C9—C8—H11B109.5
C3—C4—C5116.6 (3)H11A—C8—H11B108.1
C3—C4—C7124.2 (3)C10—C9—C8111.5 (3)
C5—C4—C7119.2 (3)C10—C9—H7A109.3
C6—C5—C4119.4 (3)C8—C9—H7A109.3
C6—C5—H5120.3C10—C9—H7B109.3
C4—C5—H5120.3C8—C9—H7B109.3
N1—C6—C5124.7 (3)H7A—C9—H7B108.0
N1—C6—H3117.7C9—C10—Br1111.2 (2)
C5—C6—H3117.7C9—C10—H10A109.4
C4—C7—C8116.7 (3)Br1—C10—H10A109.4
C4—C7—H2A108.1C9—C10—H10B109.4
C8—C7—H2A108.1Br1—C10—H10B109.4
C4—C7—H2B108.1H10A—C10—H10B108.0
C6—N1—C2—C30.2 (5)C2—N1—C6—C50.1 (5)
C6—N1—C2—C2i179.1 (3)C4—C5—C6—N10.0 (5)
N1—C2—C3—C40.6 (5)C3—C4—C7—C81.0 (5)
C2i—C2—C3—C4179.5 (4)C5—C4—C7—C8179.5 (3)
C2—C3—C4—C50.7 (5)C4—C7—C8—C9178.9 (3)
C2—C3—C4—C7179.8 (3)C7—C8—C9—C10174.7 (3)
C3—C4—C5—C60.4 (5)C8—C9—C10—Br1178.9 (2)
C7—C4—C5—C6179.9 (3)
Symmetry code: (i) x+2, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C10—H10A···N1ii0.992.523.506 (4)173
Symmetry code: (ii) x+3/2, y+1/2, z.

Experimental details

(I)(II)
Crystal data
Chemical formulaC18H24N2O2C18H22Br2N2
Mr300.39426.20
Crystal system, space groupMonoclinic, C2/cOrthorhombic, Pbca
Temperature (K)173173
a, b, c (Å)22.878 (3), 4.7657 (5), 16.789 (2)8.3566 (12), 14.246 (2), 14.779 (2)
α, β, γ (°)90, 116.759 (9), 9090, 90, 90
V3)1634.5 (4)1759.4 (4)
Z44
Radiation typeMo KαMo Kα
µ (mm1)0.084.61
Crystal size (mm)0.50 × 0.17 × 0.100.30 × 0.20 × 0.10
Data collection
DiffractometerSTOE IPDS
diffractometer
STOE IPDS-II
diffractometer
Absorption correctionRefdelF
DELrefABS in PLATON (Spek, 2003)
Tmin, Tmax0.267, 0.631
No. of measured, independent and
observed [I > 2σ(I)] reflections
11138, 2210, 1733 7834, 1560, 1064
Rint0.0480.055
(sin θ/λ)max1)0.6870.596
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.118, 1.05 0.037, 0.091, 0.96
No. of reflections22101560
No. of parameters148100
H-atom treatmentAll H-atom parameters refinedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.32, 0.160.41, 0.65

Computer programs: X-AREA (Stoe & Cie, 2004), X-AREA, X-RED32 (Stoe & Cie, 2004), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97.

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N1i0.95 (2)1.91 (2)2.8495 (14)172.5 (18)
Symmetry code: (i) x+1/2, y+1/2, z+1/2.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
C10—H10A···N1i0.992.523.506 (4)173
Symmetry code: (i) x+3/2, y+1/2, z.
 

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