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In the title compound, C14H11BrN2O2, which has the oxime group in an E conformation, molecules are linked by strong O—H...O and N—H...O hydrogen bonds into chains of edge-fused rings, unlike closely related compounds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105009868/ga1096sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270105009868/ga1096Isup2.hkl
Contains datablock I

CCDC reference: 273077

Comment top

The oxime group (CN—OH) possesses stronger hydrogen-bonding capabilities than alcohols, phenols and carboxylic acids (Marsman et al., 1999). Intermolecular hydrogen bonding has received considerable attention among the range of directional non-covalent intermolecular interactions, which combine moderate strength and directionally, in the design of compounds with supramolecular structures (Karle et al., 1996). The hydrogen-bonding geometry of molecules containing the oxime group and the nature of the supramolecular interactions have been studied (Glidewell et al., 2004). The crystal structure determination of the title compound, (I), was carried out to determine the strength of the hydrogen-bonding capabilities of the oxime group, in order to establish the molecular arrangements and to compare the geometry of the oxime moiety with those found in the related compounds N1-(2,6-dimethylphenyl)-N2-hydroxy-α-oxo-α-phenylacetamidine, (II) (Soylu, Taş, Batı et al., 2004 or Soylu, Taş, Saraçoĝlu et al., 2004), N-(3-chloro-4-metoxyphenyl)-N'-hydroxy-2-oxo-2-phenylacetamidine,(III) (Soylu et al., 2003), 2-[benzoyl(hydroxyimino) methylamino]benzoic acid, (IV) (Soylu, Taş, Batı et al., 2004 or Soylu, Taş, Saraçoĝlu et al., 2004), N-hydroxy-2-oxo-2,N'-diphenylacetamidine, (V) (Büyükgüngör et al., 2003), N-hydroxy-N'-(1-naphthyl)- 2-phenylacetamidin-2-one, (VI) (Hökelek et al., 2004a), and N-(3-chloro-4-methylphenyl)-N'-hydroxy-2-oxo-2-phenylacetamidine,(VII) (Hökelek et al., 2004b).

Compound (I) consist of two aromatic rings linked through a monoxime group (Fig.1 and Table 1). The 4-bromophenyl group shows orientional disorder with a final C10A—C14A,Br1A/C10B—C14B,Br1B ratio of 49.1:50.9 (3)% and an interplanar angle of 27.6 (2)°. The molecule has an E configuration at the CN bond, with a C2—C1N1—O1 torsion angle of 172.54 (19)°, which deviates slightly from the values reported in (II)–(VII) (169–174°). Other steric effects of the oxime group may influence the differences; here, atom O1 of the oxime group behaves as a donor, resulting in the formation of a nearly linear O1—H1···O2 hydrogen bond (see Table 2). This intermolecular hydrogen bond forms a C(6) graph-set chain (Bernstein et al., 1995), viz. O1—H1···O2—C2—C1—N1, running along the [001] direction with glide-plane symmetry (x, 1 − y, 1/2 + z) (Fig. 2). Additionally, atom N2 of the amine forms as a donor an intermolecular hydrogen bond with atom O1 of an adjacent oxime moiety. This interaction links the molecules into N—H···O hydrogen-bonded dimers that have a graph-set motif of R22(10) (Fig. 2). Propagation by translation of the R22(10) motif linking parallel C(6) chains then generates a polymeric chain of edge-fused rings, with R22(10) and R44(14) motifs, along the c axis (Fig. 2).

The results obtained in this study indicate that there are significant differences between the molecular packing of (I) and of the other related oxime groups (II)–(VII). In these latter structures, the crystal packing is mainly stabilized by intermolecular hydrogen bonds in which the whole hydrogen-bonding pattern of the oxime moiety has a centre of symmetry and can be described according to graph-set notation as R22(6) (Bernstein et al., 1995). In (I), the molecules form polymers with a chain of edge-fused rings as noted above, and there is also one C—H···π interaction involved in the molecular packing (Cg3 in Table 2 is the centre of the C9—C14A phenyl ring).

There is also a weak intramolecular N—H···O hydrogen bond [N2—H2···O1; Table 2]. This interaction has been reported in the related structures (II)–(VII).

Experimental top

The title compound was prepared from a mixture of ω-chloroisonitrosoacetophenone (2.75 g, 0.015 mol) and 4-bromophenylamine (1.82 g, 0,015 mol) in ethanol (20 ml). The mixture was stirred for 1 h, filtered, stirred for a further 4 h and then dissolved in water (10 ml). The crystallized product was filtered off, washed with ethanol and dried.

Refinement top

All H atoms bonded to C atoms were refined using a riding model, with C—H distances of 0.93 Å. The positions of all other H atoms were refined fully. For all H atoms, Uiso(H) values were set at 1.2Ueq(parent atom). The 4-bromophenyl group shows two-position orientational disorder, the final site-occupancy factors for C10A—C14A,Br1A and C10B—C14B,Br1B being 49 (3) and 51 (3)%, respectively.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); 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) drawing of (I), with displacement ellipsoids shown at the 50% probability level.
[Figure 2] Fig. 2. : A view of the chain of edge-fused R22(10) and R44(14) rings in (I), down the a axis. For clarity, only one chain is shown, and H atoms bonded to C atoms and the second disordered phenyl ring have been omitted. [Symmetry codes: (i) x, 1 − y, 1/2 + z; (ii) −x, y, 3/2 − z.]
N1-(4-Bromophenyl)-N2-hydroxy-2-oxo-2-phenylacetamidine top
Crystal data top
C14H11BrN2O2F(000) = 1280
Mr = 319.16Dx = 1.624 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71069 Å
Hall symbol: -C 2ycCell parameters from 8747 reflections
a = 21.593 (5) Åθ = 1.8–28.3°
b = 13.328 (5) ŵ = 3.15 mm1
c = 9.352 (5) ÅT = 293 K
β = 104.008 (5)°Prism, yellow
V = 2611.4 (18) Å30.30 × 0.28 × 0.26 mm
Z = 8
Data collection top
Stoe IPDS-II
diffractometer
3210 independent reflections
Radiation source: fine-focus sealed tube2023 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.054
Detector resolution: 6.67 pixels mm-1θmax = 28.3°, θmin = 1.8°
ω scansh = 1928
Absorption correction: integration
(X-RED 32; Stoe & Cie, 2002)
k = 1717
Tmin = 0.452, Tmax = 0.495l = 1212
8727 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)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.089H atoms treated by a mixture of independent and constrained refinement
S = 0.99 w = 1/[σ2(Fo2) + (0.0384P)2]
where P = (Fo2 + 2Fc2)/3
3210 reflections(Δ/σ)max = 0.001
234 parametersΔρmax = 0.41 e Å3
203 restraintsΔρmin = 0.37 e Å3
Crystal data top
C14H11BrN2O2V = 2611.4 (18) Å3
Mr = 319.16Z = 8
Monoclinic, C2/cMo Kα radiation
a = 21.593 (5) ŵ = 3.15 mm1
b = 13.328 (5) ÅT = 293 K
c = 9.352 (5) Å0.30 × 0.28 × 0.26 mm
β = 104.008 (5)°
Data collection top
Stoe IPDS-II
diffractometer
3210 independent reflections
Absorption correction: integration
(X-RED 32; Stoe & Cie, 2002)
2023 reflections with I > 2σ(I)
Tmin = 0.452, Tmax = 0.495Rint = 0.054
8727 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.041203 restraints
wR(F2) = 0.089H atoms treated by a mixture of independent and constrained refinement
S = 0.99Δρmax = 0.41 e Å3
3210 reflectionsΔρmin = 0.37 e Å3
234 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*/UeqOcc. (<1)
O10.07518 (9)0.50667 (12)0.8416 (2)0.0262 (4)
H10.094 (2)0.549 (3)0.898 (4)0.061 (12)*
O20.15096 (9)0.34321 (13)0.5191 (2)0.0304 (4)
N10.12255 (10)0.44234 (14)0.8083 (2)0.0237 (4)
N20.03559 (11)0.38690 (15)0.6179 (2)0.0248 (5)
H20.0149 (15)0.431 (2)0.636 (3)0.030*
C10.09702 (12)0.38486 (16)0.6992 (3)0.0216 (5)
C20.14505 (12)0.32310 (16)0.6430 (3)0.0235 (5)
C30.18155 (12)0.24376 (17)0.7359 (3)0.0253 (5)
C40.16961 (13)0.21725 (17)0.8705 (3)0.0259 (5)
H40.13940.25250.90650.031*
C50.20254 (14)0.13868 (18)0.9508 (3)0.0307 (6)
H50.19420.12081.04040.037*
C60.24764 (14)0.08679 (19)0.8989 (3)0.0338 (6)
H60.27000.03450.95420.041*
C70.25990 (15)0.1120 (2)0.7651 (3)0.0397 (7)
H70.29030.07640.73030.048*
C80.22719 (15)0.1898 (2)0.6832 (3)0.0357 (6)
H80.23540.20650.59300.043*
C90.00317 (11)0.30735 (17)0.5329 (3)0.0240 (4)
Br1A0.10515 (8)0.06085 (13)0.2153 (2)0.0493 (4)0.491 (3)
C10A0.0109 (2)0.2110 (4)0.5889 (6)0.0248 (4)0.491 (3)
H10A0.03960.19900.67880.030*0.491 (3)
C11A0.0238 (2)0.1321 (3)0.5127 (6)0.0254 (4)0.491 (3)
H11A0.01830.06750.55130.030*0.491 (3)
C12A0.0661 (2)0.1493 (4)0.3807 (6)0.0253 (4)0.491 (3)
C13A0.0748 (3)0.2447 (4)0.3222 (7)0.0253 (4)0.491 (3)
H13A0.10360.25590.23220.030*0.491 (3)
C14A0.0398 (2)0.3244 (4)0.3990 (6)0.0246 (4)0.491 (3)
H14A0.04550.38900.36020.029*0.491 (3)
Br1B0.11050 (8)0.04174 (10)0.26719 (19)0.0406 (3)0.509 (3)
C10B0.0282 (2)0.2082 (3)0.5400 (5)0.0255 (4)0.509 (3)
H10B0.06560.19200.60900.031*0.509 (3)
C11B0.0037 (2)0.1362 (3)0.4436 (5)0.0256 (4)0.509 (3)
H11B0.01220.07110.44700.031*0.509 (3)
C12B0.0588 (2)0.1615 (4)0.3426 (5)0.0252 (4)0.509 (3)
C13B0.0845 (3)0.2586 (4)0.3333 (7)0.0252 (4)0.509 (3)
H13B0.12200.27440.26410.030*0.509 (3)
C14B0.0524 (3)0.3296 (4)0.4297 (5)0.0238 (4)0.509 (3)
H14B0.06860.39450.42530.029*0.509 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0248 (10)0.0243 (8)0.0314 (10)0.0014 (7)0.0104 (8)0.0091 (7)
O20.0351 (11)0.0345 (9)0.0246 (10)0.0092 (8)0.0130 (9)0.0066 (7)
N10.0241 (11)0.0226 (9)0.0251 (11)0.0007 (8)0.0076 (9)0.0018 (8)
N20.0205 (11)0.0234 (10)0.0301 (12)0.0003 (8)0.0054 (10)0.0075 (8)
C10.0226 (13)0.0210 (10)0.0209 (12)0.0019 (9)0.0050 (10)0.0024 (9)
C20.0242 (13)0.0242 (11)0.0225 (13)0.0026 (9)0.0065 (11)0.0005 (9)
C30.0240 (13)0.0267 (11)0.0255 (13)0.0002 (10)0.0065 (11)0.0017 (9)
C40.0287 (14)0.0263 (12)0.0230 (13)0.0019 (10)0.0067 (12)0.0007 (9)
C50.0355 (16)0.0294 (12)0.0250 (14)0.0024 (11)0.0031 (12)0.0023 (10)
C60.0301 (15)0.0282 (12)0.0363 (16)0.0005 (11)0.0051 (13)0.0047 (11)
C70.0329 (16)0.0397 (14)0.0478 (19)0.0128 (13)0.0121 (15)0.0054 (13)
C80.0360 (16)0.0405 (14)0.0349 (16)0.0112 (13)0.0168 (14)0.0072 (12)
C90.0245 (8)0.0245 (6)0.0242 (8)0.0023 (6)0.0083 (6)0.0019 (6)
Br1A0.0458 (5)0.0455 (6)0.0542 (8)0.0139 (4)0.0074 (6)0.0279 (6)
C10A0.0253 (9)0.0246 (7)0.0254 (9)0.0022 (7)0.0081 (7)0.0017 (7)
C11A0.0259 (9)0.0249 (7)0.0264 (9)0.0028 (7)0.0086 (7)0.0016 (7)
C12A0.0259 (9)0.0256 (6)0.0255 (9)0.0035 (7)0.0082 (7)0.0026 (6)
C13A0.0254 (9)0.0263 (6)0.0250 (9)0.0027 (7)0.0077 (7)0.0022 (6)
C14A0.0249 (9)0.0254 (7)0.0245 (9)0.0025 (7)0.0080 (7)0.0014 (7)
Br1B0.0424 (4)0.0346 (4)0.0429 (7)0.0138 (3)0.0064 (5)0.0147 (4)
C10B0.0258 (9)0.0251 (7)0.0261 (9)0.0023 (7)0.0075 (7)0.0018 (7)
C11B0.0261 (9)0.0251 (7)0.0264 (9)0.0028 (6)0.0079 (7)0.0023 (7)
C12B0.0257 (9)0.0254 (6)0.0255 (9)0.0037 (6)0.0082 (7)0.0027 (7)
C13B0.0253 (9)0.0262 (6)0.0250 (9)0.0026 (6)0.0078 (7)0.0022 (7)
C14B0.0241 (9)0.0251 (7)0.0239 (9)0.0022 (7)0.0090 (7)0.0020 (7)
Geometric parameters (Å, º) top
O1—N11.426 (3)C3—C81.402 (4)
O1—H10.81 (4)C4—C51.381 (4)
O2—C21.225 (3)C4—H40.9300
N1—C11.288 (3)C5—C61.375 (4)
N2—C11.360 (3)C5—H50.9300
N2—C91.406 (3)C6—C71.382 (4)
N2—H20.78 (3)C6—H60.9300
C1—C21.515 (3)C7—C81.378 (4)
C2—C31.471 (3)C7—H70.9300
C3—C41.390 (4)C8—H80.9300
N1—O1—H1107 (3)C5—C4—H4120.0
C1—N1—O1109.8 (2)C3—C4—H4120.0
C1—N2—C9125.9 (2)C6—C5—C4120.4 (3)
C1—N2—H2115 (2)C6—C5—H5119.8
C9—N2—H2117 (2)C4—C5—H5119.8
N1—C1—N2127.1 (2)C5—C6—C7120.3 (3)
N1—C1—C2113.6 (2)C5—C6—H6119.9
N2—C1—C2118.3 (2)C7—C6—H6119.9
O2—C2—C3123.5 (2)C8—C7—C6120.1 (3)
O2—C2—C1116.5 (2)C8—C7—H7119.9
C3—C2—C1120.0 (2)C6—C7—H7119.9
C4—C3—C8119.2 (2)C7—C8—C3120.0 (3)
C4—C3—C2121.8 (2)C7—C8—H8120.0
C8—C3—C2118.9 (2)C3—C8—H8120.0
C5—C4—C3120.0 (2)
O1—N1—C1—N24.3 (3)O2—C2—C3—C82.1 (4)
O1—N1—C1—C2172.54 (18)C1—C2—C3—C8178.0 (2)
C9—N2—C1—N1158.6 (2)C8—C3—C4—C50.1 (4)
C9—N2—C1—C233.6 (3)C2—C3—C4—C5176.5 (2)
N1—C1—C2—O2112.8 (3)C3—C4—C5—C60.6 (4)
N2—C1—C2—O256.6 (3)C4—C5—C6—C70.8 (4)
N1—C1—C2—C367.3 (3)C5—C6—C7—C80.4 (4)
N2—C1—C2—C3123.3 (2)C6—C7—C8—C30.3 (5)
O2—C2—C3—C4174.3 (2)C4—C3—C8—C70.5 (4)
C1—C2—C3—C45.6 (4)C2—C3—C8—C7177.0 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O2i0.81 (4)2.05 (4)2.850 (3)171 (4)
N2—H2···O1ii0.78 (3)2.24 (3)2.975 (3)156 (3)
N2—H2···O10.78 (3)2.28 (3)2.605 (3)106 (3)
C4—H4···Cg3ii0.932.933.722 (4)143
Symmetry codes: (i) x, y+1, z+1/2; (ii) x, y, z+3/2.

Experimental details

Crystal data
Chemical formulaC14H11BrN2O2
Mr319.16
Crystal system, space groupMonoclinic, C2/c
Temperature (K)293
a, b, c (Å)21.593 (5), 13.328 (5), 9.352 (5)
β (°) 104.008 (5)
V3)2611.4 (18)
Z8
Radiation typeMo Kα
µ (mm1)3.15
Crystal size (mm)0.30 × 0.28 × 0.26
Data collection
DiffractometerStoe IPDS-II
diffractometer
Absorption correctionIntegration
(X-RED 32; Stoe & Cie, 2002)
Tmin, Tmax0.452, 0.495
No. of measured, independent and
observed [I > 2σ(I)] reflections
8727, 3210, 2023
Rint0.054
(sin θ/λ)max1)0.667
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.089, 0.99
No. of reflections3210
No. of parameters234
No. of restraints203
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.41, 0.37

Computer programs: X-AREA (Stoe & Cie, 2002), X-RED32 (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top
O1—N11.426 (3)N2—C11.360 (3)
N1—C11.288 (3)C1—C21.515 (3)
N1—O1—H1107 (3)C1—N2—C9125.9 (2)
C1—N1—O1109.8 (2)C3—C2—C1120.0 (2)
O1—N1—C1—N24.3 (3)N1—C1—C2—O2112.8 (3)
C9—N2—C1—N1158.6 (2)N2—C1—C2—O256.6 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O2i0.81 (4)2.05 (4)2.850 (3)171 (4)
N2—H2···O1ii0.78 (3)2.24 (3)2.975 (3)156 (3)
N2—H2···O10.78 (3)2.28 (3)2.605 (3)106 (3)
C4—H4···Cg3ii0.932.933.722 (4)143
Symmetry codes: (i) x, y+1, z+1/2; (ii) x, y, z+3/2.
 

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