2-Bromo-N′-[(E)-4-chloro­benzyl­idene]-5-methoxy­benzohydrazide

In the title mol­ecule, C₁₅H₁₂BrClN₂O₂, the mean planes of the coplanar 4-chloro­phenyl and methyl­enehydrazide groups are twisted from that of the 2-bromo-5-methoxy­phenyl group by 52.3 (2)°. Crystal packing is stabilized by inter­molecular N—H...O hydrogen bonds between a hydrazide H atom and the carbonyl O atom, which link the mol­ecules into anti-parallel ribbons along the b axis of the unit cell.

Key indicators

• Single-crystal X-ray study
• T = 203 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.031
• wR factor = 0.081
• Data-to-parameter ratio = 26.2

checkCIF/PLATON results

No syntax errors found



Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR) is > 1.10
            Tmin and Tmax reported:      0.460     1.000
            Tmin and Tmax expected:      0.204     0.609
            RR =      1.376
            Please check that your absorption correction is appropriate.
PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low ....         44 Perc.
PLAT060_ALERT_3_C Ratio Tmax/Tmin (Exp-to-Rep) (too) Large .......       1.36
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.61
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C3     -   C4      ..       5.14 su

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.609
            Tmax scaled      0.609 Tmin scaled      0.280

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   1 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
   4 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Schiff bases are used as substrates in the preparation of number of industrial and biologically active compounds via ring closure, cycloaddition and replacement reactions. Some Schiff base derivatives were reported to possess antimicrobial, anti-inflammatory and central nervous system activities. Moreover, Schiff bases are also known to have biological activities such as antimicrobial, antifungal, antitumor, and as herbicides. A new Schiff base, C₁₅H₁₂BrClN₂O₂ was synthesized and its crystal structure is reported.

The mean planes of 4-chlorophenyl and methylene hydrazide groups are coplanar [N2–C8–C9–C10 dihedral angle = -3.0 (3)°] and twisted from that of the 2-bromo, 5-methoxybenzo group by 52.3 (2)°.

Intermolecular N—H···O hydrogen bonding interactions involving a hydrizide hydrogen (N1–H1A) and the methylene oxygen (O1) link the molecules into inverted parallel ribbons along the b axis of the unit cell.

Related literature

For related structures, see: Chen & Yu (2006a,b); Zhen & Han (2005a,b); Diao & Yu (2006); Qiu et al. (2006a,b); For related literature, see: Varma et al. (1986); Misra et al. (1981); Desai et al. (2001); Singh & Dash (1988); Hodnett & Dunn (1970); Yathirajan et al. (2007).

S2. Experimental

A mixture of 2-bromo-5-methoxybenzohydrazide (0.735 g, 0.003 mol) and 4-chlorobenzaldehyde (0.42 g, 0.003 mol) in 15 ml of absolute ethyl alcohol containing 2 drops of 4 M sulfuric acid was refluxed for about 3 h. On cooling, the solid separated was filtered and recrystallized from ethyl acetate (m.p.: 445–447 K). Analysis found: C 48.92, H 3.21, N 7.54%; C₁₅H₁₂BrClN₂O₂ requires: C 49.01, H 3.29, N 7.62%.

S3. Refinement

All H atoms were refined using a riding model with N—H = 0.87 Å and C—H = 0.94–0.97 Å, and with U_iso(H) = 1.18–1.49U_eq(C,N).

Computing details

Data collection: CrysAlis PRO (Oxford Diffraction, 2007); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. Molecular structure of the title compound, showing atom labelling and 50% probability displacement ellipsoids.
	Fig. 2. Packing diagram of the title compound, viewed down the a axis. Dashed lines indicate N—H···O hydrogen bonds.

2-Bromo-N'-[(E)-4-chlorobenzylidene]-5-methoxybenzohydrazide

Crystal data

C15H12BrClN2O2	F(000) = 736
Mr = 367.63	Dx = 1.625 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4592 reflections
a = 7.2921 (3) Å	θ = 4.7–32.5°
b = 21.7635 (9) Å	µ = 2.92 mm^−1
c = 9.5067 (4) Å	T = 203 K
β = 95.268 (4)°	Plate, yellow
V = 1502.36 (11) Å^3	0.57 × 0.49 × 0.17 mm
Z = 4

Data collection

Oxford Diffraction Gemini R diffractometer	4997 independent reflections
Radiation source: fine-focus sealed tube	2202 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.056
Detector resolution: 10.5081 pixels mm^-1	θmax = 32.6°, θmin = 4.7°
φ and ω scans	h = −10→10
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	k = −32→32
Tmin = 0.460, Tmax = 1.000	l = −14→13
17240 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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.081	H-atom parameters constrained
S = 0.95	w = 1/[σ^2(Fo^2) + (0.0305P)^2] where P = (Fo^2 + 2Fc^2)/3
4997 reflections	(Δ/σ)max = 0.001
191 parameters	Δρmax = 0.85 e Å^−3
0 restraints	Δρmin = −0.46 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
Br	0.69194 (3)	0.101993 (12)	0.41614 (3)	0.03808 (10)
Cl	0.90438 (10)	0.62116 (3)	0.30120 (8)	0.0506 (2)
O1	0.5198 (2)	0.22677 (7)	0.28481 (17)	0.0340 (4)
O2	0.0069 (2)	0.16145 (8)	0.6990 (2)	0.0420 (5)
N1	0.5265 (2)	0.28449 (9)	0.4846 (2)	0.0266 (5)
H1A	0.5063	0.2856	0.5733	0.032*
N2	0.5964 (2)	0.33582 (9)	0.4208 (2)	0.0270 (5)
C1	0.4697 (3)	0.12299 (11)	0.4942 (2)	0.0264 (5)
C2	0.3792 (3)	0.07815 (12)	0.5642 (3)	0.0311 (6)
H2A	0.4255	0.0378	0.5683	0.037*
C3	0.2230 (3)	0.09179 (12)	0.6277 (3)	0.0362 (6)
H3A	0.1595	0.0605	0.6712	0.043*
C4	0.1583 (3)	0.15199 (12)	0.6275 (3)	0.0293 (6)
C41	−0.0660 (4)	0.22188 (13)	0.7003 (3)	0.0549 (9)
H41A	−0.1768	0.2219	0.7495	0.082*
H41B	−0.0954	0.2359	0.6040	0.082*
H41C	0.0244	0.2492	0.7483	0.082*
C5	0.2471 (3)	0.19706 (11)	0.5575 (2)	0.0261 (5)
H5A	0.2019	0.2375	0.5557	0.031*
C6	0.4031 (3)	0.18314 (10)	0.4896 (2)	0.0229 (5)
C7	0.4899 (3)	0.23276 (11)	0.4082 (2)	0.0242 (5)
C8	0.6299 (3)	0.38136 (11)	0.5042 (3)	0.0258 (5)
H8A	0.6084	0.3776	0.5998	0.031*
C9	0.7011 (3)	0.43919 (11)	0.4533 (2)	0.0257 (6)
C10	0.7435 (3)	0.44632 (11)	0.3144 (3)	0.0284 (6)
H10A	0.7305	0.4128	0.2520	0.034*
C11	0.8042 (3)	0.50197 (12)	0.2673 (3)	0.0325 (6)
H11A	0.8315	0.5066	0.1732	0.039*
C12	0.8246 (3)	0.55101 (11)	0.3607 (3)	0.0298 (6)
C13	0.7867 (3)	0.54521 (11)	0.4987 (3)	0.0330 (6)
H13A	0.8026	0.5787	0.5611	0.040*
C14	0.7248 (3)	0.48933 (11)	0.5444 (3)	0.0305 (6)
H14A	0.6982	0.4850	0.6388	0.037*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br	0.04184 (16)	0.03696 (17)	0.03731 (17)	0.00850 (13)	0.01377 (11)	0.00091 (13)
Cl	0.0590 (4)	0.0315 (4)	0.0599 (5)	−0.0118 (3)	−0.0027 (4)	0.0166 (3)
O1	0.0519 (10)	0.0302 (10)	0.0215 (10)	−0.0067 (8)	0.0111 (8)	−0.0010 (8)
O2	0.0403 (10)	0.0351 (11)	0.0545 (13)	−0.0035 (9)	0.0257 (9)	0.0033 (9)
N1	0.0364 (11)	0.0238 (11)	0.0211 (11)	−0.0064 (9)	0.0106 (8)	0.0014 (8)
N2	0.0310 (10)	0.0223 (12)	0.0283 (12)	−0.0035 (10)	0.0068 (8)	0.0015 (9)
C1	0.0317 (12)	0.0258 (14)	0.0223 (14)	0.0005 (11)	0.0062 (10)	−0.0010 (10)
C2	0.0422 (14)	0.0227 (14)	0.0279 (15)	0.0023 (12)	−0.0001 (11)	0.0013 (11)
C3	0.0425 (14)	0.0349 (17)	0.0321 (16)	−0.0101 (13)	0.0075 (12)	0.0051 (12)
C4	0.0282 (12)	0.0303 (15)	0.0306 (15)	−0.0027 (12)	0.0099 (10)	0.0002 (11)
C41	0.0457 (16)	0.046 (2)	0.079 (3)	0.0093 (15)	0.0390 (16)	0.0093 (16)
C5	0.0297 (12)	0.0221 (13)	0.0266 (14)	−0.0019 (11)	0.0038 (10)	0.0008 (10)
C6	0.0269 (12)	0.0214 (13)	0.0204 (13)	−0.0057 (10)	0.0031 (9)	0.0005 (9)
C7	0.0259 (12)	0.0261 (14)	0.0207 (14)	0.0004 (10)	0.0034 (10)	−0.0003 (10)
C8	0.0311 (12)	0.0256 (14)	0.0210 (13)	−0.0003 (11)	0.0041 (10)	0.0017 (10)
C9	0.0229 (12)	0.0264 (14)	0.0278 (15)	−0.0002 (10)	0.0032 (10)	0.0007 (10)
C10	0.0291 (12)	0.0224 (14)	0.0340 (16)	−0.0010 (11)	0.0036 (11)	−0.0024 (11)
C11	0.0332 (14)	0.0343 (16)	0.0301 (15)	−0.0005 (12)	0.0036 (11)	0.0059 (12)
C12	0.0288 (12)	0.0216 (14)	0.0380 (17)	−0.0013 (11)	−0.0026 (11)	0.0077 (11)
C13	0.0350 (13)	0.0254 (15)	0.0378 (17)	−0.0001 (12)	−0.0009 (11)	−0.0053 (12)
C14	0.0364 (13)	0.0254 (14)	0.0306 (15)	−0.0009 (12)	0.0071 (11)	−0.0033 (11)

Geometric parameters (Å, º)

Br—C1	1.899 (2)	C41—H41B	0.9700
Cl—C12	1.746 (2)	C41—H41C	0.9700
O1—C7	1.220 (2)	C5—C6	1.392 (3)
O2—C4	1.365 (3)	C5—H5A	0.9400
O2—C41	1.419 (3)	C6—C7	1.502 (3)
N1—C7	1.353 (3)	C8—C9	1.461 (3)
N1—N2	1.390 (2)	C8—H8A	0.9400
N1—H1A	0.8700	C9—C10	1.392 (3)
N2—C8	1.279 (3)	C9—C14	1.394 (3)
C1—C2	1.383 (3)	C10—C11	1.379 (3)
C1—C6	1.396 (3)	C10—H10A	0.9400
C2—C3	1.369 (3)	C11—C12	1.388 (3)
C2—H2A	0.9400	C11—H11A	0.9400
C3—C4	1.392 (3)	C12—C13	1.370 (3)
C3—H3A	0.9400	C13—C14	1.381 (3)
C4—C5	1.380 (3)	C13—H13A	0.9400
C41—H41A	0.9700	C14—H14A	0.9400
C4—O2—C41	117.70 (19)	C5—C6—C7	118.9 (2)
C7—N1—N2	119.81 (19)	C1—C6—C7	121.92 (19)
C7—N1—H1A	120.1	O1—C7—N1	124.1 (2)
N2—N1—H1A	120.1	O1—C7—C6	122.7 (2)
C8—N2—N1	114.2 (2)	N1—C7—C6	113.18 (19)
C2—C1—C6	119.8 (2)	N2—C8—C9	121.1 (2)
C2—C1—Br	118.72 (19)	N2—C8—H8A	119.5
C6—C1—Br	121.37 (17)	C9—C8—H8A	119.5
C3—C2—C1	120.8 (2)	C10—C9—C14	118.5 (2)
C3—C2—H2A	119.6	C10—C9—C8	121.8 (2)
C1—C2—H2A	119.6	C14—C9—C8	119.7 (2)
C2—C3—C4	119.9 (2)	C11—C10—C9	120.8 (2)
C2—C3—H3A	120.0	C11—C10—H10A	119.6
C4—C3—H3A	120.0	C9—C10—H10A	119.6
O2—C4—C5	124.8 (2)	C10—C11—C12	119.1 (2)
O2—C4—C3	115.5 (2)	C10—C11—H11A	120.4
C5—C4—C3	119.7 (2)	C12—C11—H11A	120.4
O2—C41—H41A	109.5	C13—C12—C11	121.5 (2)
O2—C41—H41B	109.5	C13—C12—Cl	119.54 (19)
H41A—C41—H41B	109.5	C11—C12—Cl	119.0 (2)
O2—C41—H41C	109.5	C12—C13—C14	118.9 (2)
H41A—C41—H41C	109.5	C12—C13—H13A	120.6
H41B—C41—H41C	109.5	C14—C13—H13A	120.6
C4—C5—C6	120.6 (2)	C13—C14—C9	121.3 (2)
C4—C5—H5A	119.7	C13—C14—H14A	119.4
C6—C5—H5A	119.7	C9—C14—H14A	119.4
C5—C6—C1	119.1 (2)
C7—N1—N2—C8	−178.3 (2)	C5—C6—C7—O1	−126.1 (2)
C6—C1—C2—C3	1.0 (4)	C1—C6—C7—O1	51.1 (3)
Br—C1—C2—C3	177.07 (19)	C5—C6—C7—N1	52.4 (3)
C1—C2—C3—C4	−2.9 (4)	C1—C6—C7—N1	−130.3 (2)
C41—O2—C4—C5	0.7 (4)	N1—N2—C8—C9	−178.99 (18)
C41—O2—C4—C3	−179.1 (2)	N2—C8—C9—C10	−3.0 (3)
C2—C3—C4—O2	−177.1 (2)	N2—C8—C9—C14	175.8 (2)
C2—C3—C4—C5	3.1 (4)	C14—C9—C10—C11	−1.2 (3)
O2—C4—C5—C6	178.8 (2)	C8—C9—C10—C11	177.6 (2)
C3—C4—C5—C6	−1.4 (4)	C9—C10—C11—C12	0.6 (3)
C4—C5—C6—C1	−0.5 (4)	C10—C11—C12—C13	0.4 (4)
C4—C5—C6—C7	176.8 (2)	C10—C11—C12—Cl	179.21 (17)
C2—C1—C6—C5	0.8 (3)	C11—C12—C13—C14	−0.8 (3)
Br—C1—C6—C5	−175.25 (18)	Cl—C12—C13—C14	−179.60 (18)
C2—C1—C6—C7	−176.5 (2)	C12—C13—C14—C9	0.2 (4)
Br—C1—C6—C7	7.5 (3)	C10—C9—C14—C13	0.8 (3)
N2—N1—C7—O1	2.5 (3)	C8—C9—C14—C13	−178.1 (2)
N2—N1—C7—C6	−176.03 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1^i	0.87	2.02	2.870 (2)	165

Symmetry code: (i) x, −y+1/2, z+1/2.