N¹-(4-Bromo­phen­yl)-N²-hydr­oxy-2-oxo-2-phenyl­acetamidine

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.

S1. Comment

The oxime group (C═N—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 C═N bond, with a C2—C1═N1—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).

S2. Experimental

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.

S3. Refinement

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, U_iso(H) values were set at 1.2U_eq(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

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

	Fig. 1. : An ORTEP-3 (Farrugia, 1997) drawing of (I), with displacement ellipsoids shown at the 50% probability level.
	Fig. 2. : A view of the chain of edge-fused R^22(10) and R^44(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

Crystal data

C14H11BrN2O2	F(000) = 1280
Mr = 319.16	Dx = 1.624 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -C 2yc	Cell parameters from 8747 reflections
a = 21.593 (5) Å	θ = 1.8–28.3°
b = 13.328 (5) Å	µ = 3.15 mm^−1
c = 9.352 (5) Å	T = 293 K
β = 104.008 (5)°	Prism, yellow
V = 2611.4 (18) Å^3	0.30 × 0.28 × 0.26 mm
Z = 8

Data collection

Stoe IPDS-II diffractometer	3210 independent reflections
Radiation source: fine-focus sealed tube	2023 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.054
Detector resolution: 6.67 pixels mm^-1	θmax = 28.3°, θmin = 1.8°
ω scans	h = −19→28
Absorption correction: integration (X-RED 32; Stoe & Cie, 2002)	k = −17→17
Tmin = 0.452, Tmax = 0.495	l = −12→12
8727 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.089	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	w = 1/[σ^2(Fo^2) + (0.0384P)^2] where P = (Fo^2 + 2Fc^2)/3
3210 reflections	(Δ/σ)max = 0.001
234 parameters	Δρmax = 0.41 e Å^−3
203 restraints	Δρmin = −0.37 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.07518 (9)	0.50667 (12)	0.8416 (2)	0.0262 (4)
H1	0.094 (2)	0.549 (3)	0.898 (4)	0.061 (12)*
O2	0.15096 (9)	0.34321 (13)	0.5191 (2)	0.0304 (4)
N1	0.12255 (10)	0.44234 (14)	0.8083 (2)	0.0237 (4)
N2	0.03559 (11)	0.38690 (15)	0.6179 (2)	0.0248 (5)
H2	0.0149 (15)	0.431 (2)	0.636 (3)	0.030*
C1	0.09702 (12)	0.38486 (16)	0.6992 (3)	0.0216 (5)
C2	0.14505 (12)	0.32310 (16)	0.6430 (3)	0.0235 (5)
C3	0.18155 (12)	0.24376 (17)	0.7359 (3)	0.0253 (5)
C4	0.16961 (13)	0.21725 (17)	0.8705 (3)	0.0259 (5)
H4	0.1394	0.2525	0.9065	0.031*
C5	0.20254 (14)	0.13868 (18)	0.9508 (3)	0.0307 (6)
H5	0.1942	0.1208	1.0404	0.037*
C6	0.24764 (14)	0.08679 (19)	0.8989 (3)	0.0338 (6)
H6	0.2700	0.0345	0.9542	0.041*
C7	0.25990 (15)	0.1120 (2)	0.7651 (3)	0.0397 (7)
H7	0.2903	0.0764	0.7303	0.048*
C8	0.22719 (15)	0.1898 (2)	0.6832 (3)	0.0357 (6)
H8	0.2354	0.2065	0.5930	0.043*
C9	0.00317 (11)	0.30735 (17)	0.5329 (3)	0.0240 (4)
Br1A	−0.10515 (8)	0.06085 (13)	0.2153 (2)	0.0493 (4)	0.491 (3)
C10A	0.0109 (2)	0.2110 (4)	0.5889 (6)	0.0248 (4)	0.491 (3)
H10A	0.0396	0.1990	0.6788	0.030*	0.491 (3)
C11A	−0.0238 (2)	0.1321 (3)	0.5127 (6)	0.0254 (4)	0.491 (3)
H11A	−0.0183	0.0675	0.5513	0.030*	0.491 (3)
C12A	−0.0661 (2)	0.1493 (4)	0.3807 (6)	0.0253 (4)	0.491 (3)
C13A	−0.0748 (3)	0.2447 (4)	0.3222 (7)	0.0253 (4)	0.491 (3)
H13A	−0.1036	0.2559	0.2322	0.030*	0.491 (3)
C14A	−0.0398 (2)	0.3244 (4)	0.3990 (6)	0.0246 (4)	0.491 (3)
H14A	−0.0455	0.3890	0.3602	0.029*	0.491 (3)
Br1B	−0.11050 (8)	0.04174 (10)	0.26719 (19)	0.0406 (3)	0.509 (3)
C10B	0.0282 (2)	0.2082 (3)	0.5400 (5)	0.0255 (4)	0.509 (3)
H10B	0.0656	0.1920	0.6090	0.031*	0.509 (3)
C11B	−0.0037 (2)	0.1362 (3)	0.4436 (5)	0.0256 (4)	0.509 (3)
H11B	0.0122	0.0711	0.4470	0.031*	0.509 (3)
C12B	−0.0588 (2)	0.1615 (4)	0.3426 (5)	0.0252 (4)	0.509 (3)
C13B	−0.0845 (3)	0.2586 (4)	0.3333 (7)	0.0252 (4)	0.509 (3)
H13B	−0.1220	0.2744	0.2641	0.030*	0.509 (3)
C14B	−0.0524 (3)	0.3296 (4)	0.4297 (5)	0.0238 (4)	0.509 (3)
H14B	−0.0686	0.3945	0.4253	0.029*	0.509 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0248 (10)	0.0243 (8)	0.0314 (10)	−0.0014 (7)	0.0104 (8)	−0.0091 (7)
O2	0.0351 (11)	0.0345 (9)	0.0246 (10)	0.0092 (8)	0.0130 (9)	0.0066 (7)
N1	0.0241 (11)	0.0226 (9)	0.0251 (11)	−0.0007 (8)	0.0076 (9)	−0.0018 (8)
N2	0.0205 (11)	0.0234 (10)	0.0301 (12)	0.0003 (8)	0.0054 (10)	−0.0075 (8)
C1	0.0226 (13)	0.0210 (10)	0.0209 (12)	−0.0019 (9)	0.0050 (10)	0.0024 (9)
C2	0.0242 (13)	0.0242 (11)	0.0225 (13)	−0.0026 (9)	0.0065 (11)	−0.0005 (9)
C3	0.0240 (13)	0.0267 (11)	0.0255 (13)	0.0002 (10)	0.0065 (11)	0.0017 (9)
C4	0.0287 (14)	0.0263 (12)	0.0230 (13)	−0.0019 (10)	0.0067 (12)	−0.0007 (9)
C5	0.0355 (16)	0.0294 (12)	0.0250 (14)	−0.0024 (11)	0.0031 (12)	0.0023 (10)
C6	0.0301 (15)	0.0282 (12)	0.0363 (16)	−0.0005 (11)	−0.0051 (13)	0.0047 (11)
C7	0.0329 (16)	0.0397 (14)	0.0478 (19)	0.0128 (13)	0.0121 (15)	0.0054 (13)
C8	0.0360 (16)	0.0405 (14)	0.0349 (16)	0.0112 (13)	0.0168 (14)	0.0072 (12)
C9	0.0245 (8)	0.0245 (6)	0.0242 (8)	−0.0023 (6)	0.0083 (6)	−0.0019 (6)
Br1A	0.0458 (5)	0.0455 (6)	0.0542 (8)	−0.0139 (4)	0.0074 (6)	−0.0279 (6)
C10A	0.0253 (9)	0.0246 (7)	0.0254 (9)	−0.0022 (7)	0.0081 (7)	−0.0017 (7)
C11A	0.0259 (9)	0.0249 (7)	0.0264 (9)	−0.0028 (7)	0.0086 (7)	−0.0016 (7)
C12A	0.0259 (9)	0.0256 (6)	0.0255 (9)	−0.0035 (7)	0.0082 (7)	−0.0026 (6)
C13A	0.0254 (9)	0.0263 (6)	0.0250 (9)	−0.0027 (7)	0.0077 (7)	−0.0022 (6)
C14A	0.0249 (9)	0.0254 (7)	0.0245 (9)	−0.0025 (7)	0.0080 (7)	−0.0014 (7)
Br1B	0.0424 (4)	0.0346 (4)	0.0429 (7)	−0.0138 (3)	0.0064 (5)	−0.0147 (4)
C10B	0.0258 (9)	0.0251 (7)	0.0261 (9)	−0.0023 (7)	0.0075 (7)	−0.0018 (7)
C11B	0.0261 (9)	0.0251 (7)	0.0264 (9)	−0.0028 (6)	0.0079 (7)	−0.0023 (7)
C12B	0.0257 (9)	0.0254 (6)	0.0255 (9)	−0.0037 (6)	0.0082 (7)	−0.0027 (7)
C13B	0.0253 (9)	0.0262 (6)	0.0250 (9)	−0.0026 (6)	0.0078 (7)	−0.0022 (7)
C14B	0.0241 (9)	0.0251 (7)	0.0239 (9)	−0.0022 (7)	0.0090 (7)	−0.0020 (7)

Geometric parameters (Å, º)

O1—N1	1.426 (3)	C3—C8	1.402 (4)
O1—H1	0.81 (4)	C4—C5	1.381 (4)
O2—C2	1.225 (3)	C4—H4	0.9300
N1—C1	1.288 (3)	C5—C6	1.375 (4)
N2—C1	1.360 (3)	C5—H5	0.9300
N2—C9	1.406 (3)	C6—C7	1.382 (4)
N2—H2	0.78 (3)	C6—H6	0.9300
C1—C2	1.515 (3)	C7—C8	1.378 (4)
C2—C3	1.471 (3)	C7—H7	0.9300
C3—C4	1.390 (4)	C8—H8	0.9300
N1—O1—H1	107 (3)	C5—C4—H4	120.0
C1—N1—O1	109.8 (2)	C3—C4—H4	120.0
C1—N2—C9	125.9 (2)	C6—C5—C4	120.4 (3)
C1—N2—H2	115 (2)	C6—C5—H5	119.8
C9—N2—H2	117 (2)	C4—C5—H5	119.8
N1—C1—N2	127.1 (2)	C5—C6—C7	120.3 (3)
N1—C1—C2	113.6 (2)	C5—C6—H6	119.9
N2—C1—C2	118.3 (2)	C7—C6—H6	119.9
O2—C2—C3	123.5 (2)	C8—C7—C6	120.1 (3)
O2—C2—C1	116.5 (2)	C8—C7—H7	119.9
C3—C2—C1	120.0 (2)	C6—C7—H7	119.9
C4—C3—C8	119.2 (2)	C7—C8—C3	120.0 (3)
C4—C3—C2	121.8 (2)	C7—C8—H8	120.0
C8—C3—C2	118.9 (2)	C3—C8—H8	120.0
C5—C4—C3	120.0 (2)
O1—N1—C1—N2	4.3 (3)	O2—C2—C3—C8	2.1 (4)
O1—N1—C1—C2	172.54 (18)	C1—C2—C3—C8	−178.0 (2)
C9—N2—C1—N1	−158.6 (2)	C8—C3—C4—C5	0.1 (4)
C9—N2—C1—C2	33.6 (3)	C2—C3—C4—C5	176.5 (2)
N1—C1—C2—O2	−112.8 (3)	C3—C4—C5—C6	0.6 (4)
N2—C1—C2—O2	56.6 (3)	C4—C5—C6—C7	−0.8 (4)
N1—C1—C2—C3	67.3 (3)	C5—C6—C7—C8	0.4 (4)
N2—C1—C2—C3	−123.3 (2)	C6—C7—C8—C3	0.3 (5)
O2—C2—C3—C4	−174.3 (2)	C4—C3—C8—C7	−0.5 (4)
C1—C2—C3—C4	5.6 (4)	C2—C3—C8—C7	−177.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2^i	0.81 (4)	2.05 (4)	2.850 (3)	171 (4)
N2—H2···O1^ii	0.78 (3)	2.24 (3)	2.975 (3)	156 (3)
N2—H2···O1	0.78 (3)	2.28 (3)	2.605 (3)	106 (3)
C4—H4···Cg3^ii	0.93	2.93	3.722 (4)	143

Symmetry codes: (i) x, −y+1, z+1/2; (ii) −x, y, −z+3/2.