8-Bromo­naphthalene-1-carbaldehyde (4-methyl­phenyl­sulfon­yl)hydrazone

Novak, I.; Li, W.; Harrison, L.J.

doi:10.1107/S1600536807019113

8-Bromonaphthalene-1-carbaldehyde (4-methylphenylsulfonyl)hydrazone

The title compound, C₁₈H₁₅BrN₂O₂S, was obtained as a by-product during the synthesis of dihalonaphthalenes. The hydrazone and naphthyl units are twisted away from each other by 35 (1)°. The bromine substituent and the C center attached to the hydrazone group are twisted out of the plane of the naphthalene system by 6 (1) and 7 (1)°, respectively. Intermolecular hydrogen bonding and π–π stacking hold the molecules together. The average distance between stacked naphthyl ring planes is 3.7 (1) Å.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807019113/kp2101sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807019113/kp2101Isup2.hkl Contains datablock I

CCDC reference: 647610

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Key indicators

Single-crystal X-ray study
T = 223 K
Mean (C-C) = 0.005 Å
R factor = 0.055
wR factor = 0.151
Data-to-parameter ratio = 17.8

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Alert level C
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C2

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
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Comment top

The crystal structure of (I) is nonplanar with the planes of phenyl and naphthyl moieties inclined at 71° angle (Fig.1). The bromine substituent and C11 center are twisted out of the naphthalene plane by 5(1)°, presumably due to the steric repulsion between bromine and hydrogen situated at C11. (I) exhibits eclipsed anti conformation along N1—N2—S1—O2 linkage with the torsional angle of 177.3 (3)°.

The two S—O bond lengths differ by only 0.007Å which suggests that there is no delocalization of N2 lone pair into the sulfonyl group; the two moieties being in gauche conformation with respect to each other. This is different from the cyclopentanone tosylhydrazone where such delocalization had been proposed (Ojala & Gleason, 1998). The phenyl ring is in the gauche conformation at 20 (2)° versus the SO₂ group.

The crystal packing of (I) is dominated by two kinds of intermolecular interactions: NH···O hydrogen bonding and aryl (naphthalene) ring stacking (Fig. 2). The interplanar distance pertinent to π···π stacking is 3.619 (8) Å. The length of hydrogen bonding which is 2.16 (4)Å suggests that π···π stacking is more important of the two. This is similar to the results obtained for cyclohexanone tosylhydrazone (Ojala & Gleason, 1998) where hydrogen bond length is 2.17 (2) Å.

Related literature top

Sulfonylhydrazone (tosyl) derivatives of the general formula p-CH₃Ph—SO₂—NH—N=CH—R have been used to probe the structural features of R-substituents, especially of their less stable conformers. Thus for instance, the conformations of carbocyclic acids and silacyclic ring substituents (Boss et al. 1998; Ojala & Gleason, 1998; Ojala et al. 1998; Sim 1990; Negron et al. 1993) and intramolecular hydrogen bonding (Maas & Hoge, 1980) in tosylates have been studied. For details of the synthesis, see: Bailey et al. (1983).

Experimental top

The synthesis of (I) was performed according to the procedure reported perviously by Bailey et al. (1983). The single crystals were grown from the methanol solution.

Structure description top

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.

Figures top

	Fig. 1. The molecular structure of (I), with atom labels and 50% probability displacement ellipsoids for non-H atoms.
	Fig. 2. The packing of (I), viewed down the a axis. H atoms have been omitted.

8-Bromonaphthalene-1-carbaldehyde (4-methylphenylsulfonyl)hydrazone top

Crystal data top

C₁₈H₁₅BrN₂O₂S	F(000) = 816
M_r = 403.29	D_x = 1.558 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P2ybc	Cell parameters from 2105 reflections
a = 12.2464 (8) Å	θ = 2.2–22.9°
b = 18.7781 (12) Å	µ = 2.52 mm⁻¹
c = 7.4984 (5) Å	T = 223 K
β = 94.241 (2)°	Needle, colourless
V = 1719.64 (19) Å³	0.46 × 0.10 × 0.08 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	3941 independent reflections
Radiation source: fine-focus sealed tube	2581 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
ω scans	θ_max = 27.5°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −15→14
T_min = 0.390, T_max = 0.824	k = −23→24
11977 measured reflections	l = −9→9

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.151	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.062P)² + 1.172P] where P = (F_o² + 2F_c²)/3
3941 reflections	(Δ/σ)_max < 0.001
221 parameters	Δρ_max = 0.87 e Å⁻³
0 restraints	Δρ_min = −1.08 e Å⁻³

Crystal data top

C₁₈H₁₅BrN₂O₂S	V = 1719.64 (19) Å³
M_r = 403.29	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.2464 (8) Å	µ = 2.52 mm⁻¹
b = 18.7781 (12) Å	T = 223 K
c = 7.4984 (5) Å	0.46 × 0.10 × 0.08 mm
β = 94.241 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3941 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	2581 reflections with I > 2σ(I)
T_min = 0.390, T_max = 0.824	R_int = 0.033
11977 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.151	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.87 e Å⁻³
3941 reflections	Δρ_min = −1.08 e Å⁻³
221 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

	x	y	z	U_iso*/U_eq
Br1	0.40011 (4)	0.08029 (3)	0.73517 (11)	0.1087 (3)
S1	0.07404 (7)	0.31733 (5)	0.78451 (12)	0.0485 (2)
O1	0.1068 (2)	0.34964 (14)	0.9527 (3)	0.0593 (7)
O2	−0.0310 (2)	0.28498 (15)	0.7576 (4)	0.0655 (7)
N1	0.2709 (2)	0.27425 (15)	0.7687 (4)	0.0460 (6)
N2	0.1611 (2)	0.25271 (16)	0.7556 (4)	0.0470 (7)
H2	0.144 (3)	0.226 (2)	0.664 (5)	0.049 (11)*
C1	0.5391 (3)	0.20422 (19)	0.6797 (4)	0.0478 (8)
C2	0.5315 (3)	0.1286 (2)	0.6893 (5)	0.0567 (9)
C3	0.6192 (4)	0.0852 (2)	0.6796 (6)	0.0734 (12)
H3	0.6100	0.0356	0.6864	0.088*
C4	0.7231 (4)	0.1134 (3)	0.6596 (6)	0.0776 (13)
H4	0.7831	0.0828	0.6495	0.093*
C5	0.7369 (3)	0.1844 (3)	0.6547 (6)	0.0736 (12)
H5	0.8074	0.2032	0.6446	0.088*
C6	0.6471 (3)	0.2313 (2)	0.6646 (5)	0.0565 (9)
C7	0.6657 (4)	0.3053 (2)	0.6644 (6)	0.0692 (11)
H7	0.7371	0.3227	0.6559	0.083*
C8	0.5826 (4)	0.3513 (2)	0.6763 (7)	0.0759 (12)
H8	0.5962	0.4006	0.6776	0.091*
C9	0.4761 (3)	0.3262 (2)	0.6868 (6)	0.0623 (10)
H9	0.4190	0.3593	0.6942	0.075*
C10	0.4517 (3)	0.25488 (18)	0.6868 (4)	0.0463 (8)
C11	0.3349 (3)	0.23599 (18)	0.6834 (4)	0.0460 (8)
H11	0.3080	0.1960	0.6188	0.055*
C12	0.0890 (3)	0.38028 (18)	0.6158 (4)	0.0449 (8)
C13	0.0225 (3)	0.37623 (19)	0.4594 (5)	0.0507 (8)
H13	−0.0334	0.3419	0.4466	0.061*
C14	0.0386 (3)	0.42278 (19)	0.3226 (5)	0.0533 (9)
H14	−0.0068	0.4201	0.2161	0.064*
C15	0.1207 (3)	0.47362 (19)	0.3389 (5)	0.0512 (9)
C16	0.1855 (3)	0.4770 (2)	0.4967 (5)	0.0571 (9)
H16	0.2410	0.5115	0.5097	0.069*
C17	0.1711 (3)	0.43105 (19)	0.6358 (5)	0.0524 (9)
H17	0.2162	0.4340	0.7425	0.063*
C18	0.1399 (4)	0.5224 (2)	0.1843 (6)	0.0698 (11)
H18A	0.1564	0.4942	0.0813	0.105*
H18B	0.2010	0.5538	0.2174	0.105*
H18C	0.0747	0.5506	0.1548	0.105*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0653 (3)	0.0562 (3)	0.2042 (8)	−0.0074 (2)	0.0086 (4)	0.0218 (3)
S1	0.0445 (5)	0.0489 (5)	0.0527 (5)	0.0059 (4)	0.0085 (4)	0.0051 (4)
O1	0.0676 (16)	0.0624 (16)	0.0491 (14)	0.0143 (13)	0.0116 (13)	−0.0017 (12)
O2	0.0465 (14)	0.0670 (17)	0.0839 (19)	−0.0001 (13)	0.0111 (13)	0.0162 (15)
N1	0.0450 (15)	0.0448 (15)	0.0482 (16)	0.0024 (13)	0.0026 (13)	0.0006 (12)
N2	0.0440 (16)	0.0430 (16)	0.0538 (18)	0.0019 (12)	0.0026 (14)	−0.0014 (14)
C1	0.0463 (18)	0.052 (2)	0.0445 (18)	0.0037 (15)	0.0017 (15)	−0.0029 (15)
C2	0.047 (2)	0.054 (2)	0.068 (2)	0.0006 (17)	0.0014 (18)	−0.0038 (18)
C3	0.069 (3)	0.060 (3)	0.090 (3)	0.016 (2)	−0.001 (2)	−0.011 (2)
C4	0.057 (3)	0.088 (3)	0.088 (3)	0.020 (2)	0.006 (2)	−0.011 (3)
C5	0.040 (2)	0.094 (4)	0.086 (3)	0.001 (2)	0.004 (2)	−0.009 (3)
C6	0.047 (2)	0.065 (2)	0.057 (2)	−0.0039 (18)	−0.0004 (17)	−0.0044 (19)
C7	0.054 (2)	0.073 (3)	0.081 (3)	−0.013 (2)	0.003 (2)	0.002 (2)
C8	0.074 (3)	0.053 (2)	0.101 (3)	−0.017 (2)	0.006 (3)	−0.002 (2)
C9	0.060 (2)	0.050 (2)	0.077 (3)	0.0027 (18)	0.007 (2)	−0.0004 (19)
C10	0.0472 (18)	0.0459 (18)	0.0457 (18)	0.0010 (15)	0.0021 (15)	−0.0062 (15)
C11	0.0492 (19)	0.0438 (18)	0.0444 (18)	0.0052 (15)	−0.0008 (15)	0.0000 (15)
C12	0.0434 (17)	0.0424 (18)	0.0493 (19)	0.0066 (14)	0.0064 (15)	0.0023 (15)
C13	0.0452 (18)	0.050 (2)	0.057 (2)	0.0012 (15)	0.0037 (17)	0.0016 (17)
C14	0.054 (2)	0.058 (2)	0.0473 (19)	0.0097 (17)	−0.0017 (17)	−0.0019 (17)
C15	0.056 (2)	0.0447 (19)	0.055 (2)	0.0145 (16)	0.0134 (18)	0.0029 (16)
C16	0.055 (2)	0.048 (2)	0.069 (2)	−0.0052 (17)	0.007 (2)	−0.0007 (18)
C17	0.052 (2)	0.050 (2)	0.055 (2)	−0.0005 (16)	−0.0038 (17)	−0.0019 (16)
C18	0.078 (3)	0.061 (3)	0.072 (3)	0.010 (2)	0.016 (2)	0.016 (2)

Geometric parameters (Å, º) top

Br1—C2	1.900 (4)	C8—C9	1.394 (6)
S1—O2	1.423 (3)	C8—H8	0.9400
S1—O1	1.430 (3)	C9—C10	1.372 (5)
S1—N2	1.640 (3)	C9—H9	0.9400
S1—C12	1.751 (3)	C10—C11	1.472 (5)
N1—C11	1.271 (4)	C11—H11	0.9400
N1—N2	1.400 (4)	C12—C13	1.380 (5)
N2—H2	0.86 (4)	C12—C17	1.386 (5)
C1—C2	1.425 (5)	C13—C14	1.373 (5)
C1—C6	1.430 (5)	C13—H13	0.9400
C1—C10	1.436 (5)	C14—C15	1.385 (5)
C2—C3	1.355 (5)	C14—H14	0.9400
C3—C4	1.396 (6)	C15—C16	1.377 (5)
C3—H3	0.9400	C15—C18	1.509 (5)
C4—C5	1.345 (7)	C16—C17	1.374 (5)
C4—H4	0.9400	C16—H16	0.9400
C5—C6	1.416 (6)	C17—H17	0.9400
C5—H5	0.9400	C18—H18A	0.9700
C6—C7	1.408 (6)	C18—H18B	0.9700
C7—C8	1.343 (6)	C18—H18C	0.9700
C7—H7	0.9400

O2—S1—O1	119.83 (17)	C10—C9—C8	122.3 (4)
O2—S1—N2	104.79 (16)	C10—C9—H9	118.8
O1—S1—N2	106.73 (16)	C8—C9—H9	118.8
O2—S1—C12	109.13 (17)	C9—C10—C1	119.0 (3)
O1—S1—C12	108.24 (16)	C9—C10—C11	116.5 (3)
N2—S1—C12	107.47 (15)	C1—C10—C11	124.4 (3)
C11—N1—N2	115.3 (3)	N1—C11—C10	119.4 (3)
N1—N2—S1	114.0 (2)	N1—C11—H11	120.3
N1—N2—H2	114 (2)	C10—C11—H11	120.3
S1—N2—H2	114 (2)	C13—C12—C17	120.5 (3)
C2—C1—C6	115.1 (3)	C13—C12—S1	119.4 (3)
C2—C1—C10	127.3 (3)	C17—C12—S1	120.0 (3)
C6—C1—C10	117.6 (3)	C14—C13—C12	119.5 (3)
C3—C2—C1	122.8 (4)	C14—C13—H13	120.3
C3—C2—Br1	114.1 (3)	C12—C13—H13	120.3
C1—C2—Br1	123.0 (3)	C13—C14—C15	121.1 (4)
C2—C3—C4	120.6 (4)	C13—C14—H14	119.5
C2—C3—H3	119.7	C15—C14—H14	119.5
C4—C3—H3	119.7	C16—C15—C14	118.4 (3)
C5—C4—C3	119.8 (4)	C16—C15—C18	121.3 (4)
C5—C4—H4	120.1	C14—C15—C18	120.3 (4)
C3—C4—H4	120.1	C17—C16—C15	121.7 (4)
C4—C5—C6	121.1 (4)	C17—C16—H16	119.2
C4—C5—H5	119.5	C15—C16—H16	119.2
C6—C5—H5	119.5	C16—C17—C12	118.9 (4)
C7—C6—C5	119.2 (4)	C16—C17—H17	120.6
C7—C6—C1	120.2 (4)	C12—C17—H17	120.6
C5—C6—C1	120.6 (4)	C15—C18—H18A	109.5
C8—C7—C6	120.7 (4)	C15—C18—H18B	109.5
C8—C7—H7	119.6	H18A—C18—H18B	109.5
C6—C7—H7	119.6	C15—C18—H18C	109.5
C7—C8—C9	120.2 (4)	H18A—C18—H18C	109.5
C7—C8—H8	119.9	H18B—C18—H18C	109.5
C9—C8—H8	119.9

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1ⁱ	0.86 (4)	2.15 (4)	3.012 (4)	174 (3)

Symmetry code: (i) x, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₈H₁₅BrN₂O₂S
M_r	403.29
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	223
a, b, c (Å)	12.2464 (8), 18.7781 (12), 7.4984 (5)
β (°)	94.241 (2)
V (Å³)	1719.64 (19)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.52
Crystal size (mm)	0.46 × 0.10 × 0.08

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 2001)
T_min, T_max	0.390, 0.824
No. of measured, independent and observed [I > 2σ(I)] reflections	11977, 3941, 2581
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.151, 1.06
No. of reflections	3941
No. of parameters	221
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.87, −1.08

Computer programs: SMART (Bruker, 1997), SMART, SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL.

Selected geometric parameters (Å, º) top

Br1—C2	1.900 (4)	S1—N2	1.640 (3)
S1—O2	1.423 (3)	N1—N2	1.400 (4)

O2—S1—O1	119.83 (17)	N1—N2—S1	114.0 (2)
C11—N1—N2	115.3 (3)