N′-(4-Bromo­benzyl­idene)isonicotino­hydrazide

The title compound, C₁₃H₁₀BrN₃O, was prepared by the reaction of isonicotinohydrazide and 4-bromo­benzaldehyde. The dihedral angle between the benzene and pyridine rings is 8.60 (12)°. The crystal packing is stabilized by inter­molecular C—H...O and N—H...O hydogen-bonding inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 273 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.036
• wR factor = 0.094
• Data-to-parameter ratio = 18.2

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT057_ALERT_3_B Correction for Absorption Required   RT(exp) ...       1.21

Alert level C
ABSTM02_ALERT_3_C  The ratio of Tmax/Tmin expected RT(exp) is > 1.10
            Absorption corrections should be applied.
            Tmin and Tmax expected:      0.459     0.549
            RT(exp) =      1.195
            Value of measurement temperature given =   273.000
            Value of melting point given =     0.000
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.97
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          1
              C13 H10 Br N3 O

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   3 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
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 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 have received considerable attention in the literature. They are attractive from several points of view, such as the possibility of analytical application (Cimerman et al., 1997). As part of our search for new schiff base compounds we synthesized the title compound (I), and herein we report the crstal structure of (I).

In (I) (Fig. 1),

As seen in Fig. 1, the C12—N3 bond length of 1.276 (3)Å is comparable with C—N double bond [1.284 (2) Å] reported (Chiu et al., 1998). In the title molecule, the benzene ring (C6–C10) is essentialy planar with a maximum deviation of 0.009 (2) Å for C6 and C9, while the pyridine ring is planar, with a maximum deviation of 0.012 (2) Å for C3. The dihedral angle between the benzene and pyridine rings is 8.60 (12)°.

The crystal packing is stabilized by intermolecular C—H···O and N—H···O hydogen-bonding interactions.

Related literature

For background on Schiff bases, see: Chiu et al. (1998). For comparative bond-length data, see: Cimerman et al. (1997).

S2. Experimental

A mixture of the isonicotinohydrazide (0.1 mol), and 4-bromobenzaldehyde (0.1 mol) was stirred in refluxing ethanol (20 mL) for 4 h to afford the title compound (0.082 mol, yield 82%). Single crystals suitable for X-ray measurements were obtained by recrystallization from ethanol at room temperature.

S3. Refinement

H atoms were fixed geometrically and allowed to ride on their attached atoms, with N—H = 0.86 Å and C—H = 0.93 Å, and with U_iso=1.2–U_eq(C,N).

All H atoms were placed in idealized positions and refined with riding constraints, with N—H = 0.86 Å and C—H = 0.93 Å and with U_iso(H) = 1.2U_eq(C,N).

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

Fig. 1. An ORTEP view of the title compound (I), showing 30% probability displacement ellipsoids and the atom-numbering scheme.

N'-(4-Bromobenzylidene)isonicotinohydrazide

Crystal data

C13H10BrN3O	F(000) = 608
Mr = 304.15	Dx = 1.643 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2167 reflections
a = 18.715 (9) Å	θ = 3.3–24.3°
b = 6.517 (3) Å	µ = 3.33 mm^−1
c = 10.126 (5) Å	T = 273 K
β = 95.512 (9)°	Block, yellow
V = 1229.3 (11) Å^3	0.25 × 0.20 × 0.18 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	1914 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.034
Graphite monochromator	θmax = 28.4°, θmin = 2.2°
ϕ and ω scans	h = −18→25
7721 measured reflections	k = −7→8
2992 independent reflections	l = −13→13

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.036	H-atom parameters constrained
wR(F^2) = 0.094	w = 1/[σ^2(Fo^2) + (0.0429P)^2 + 0.1134P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max < 0.001
2992 reflections	Δρmax = 0.39 e Å^−3
164 parameters	Δρmin = −0.55 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0072 (10)

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	0.038461 (17)	0.64201 (4)	0.85386 (4)	0.08031 (18)
N3	0.25010 (10)	1.5120 (3)	0.93706 (17)	0.0390 (4)
N2	0.29511 (10)	1.6713 (3)	0.90925 (18)	0.0386 (4)
H2A	0.3079	1.6847	0.8304	0.046*
O1	0.30311 (10)	1.7983 (3)	1.11880 (16)	0.0529 (4)
C7	0.10215 (13)	0.8680 (3)	0.8543 (3)	0.0457 (6)
C10	0.19040 (12)	1.2072 (3)	0.8503 (2)	0.0369 (5)
N1	0.46415 (11)	2.2729 (3)	0.8926 (2)	0.0545 (6)
C4	0.36913 (11)	1.9665 (3)	0.9610 (2)	0.0349 (5)
C13	0.31906 (12)	1.8058 (3)	1.0047 (2)	0.0362 (5)
C9	0.19163 (13)	1.0539 (4)	0.7549 (2)	0.0446 (6)
H9A	0.2229	1.0656	0.6893	0.054*
C12	0.23656 (13)	1.3861 (3)	0.8414 (2)	0.0417 (5)
H12A	0.2570	1.4094	0.7626	0.050*
C3	0.37459 (13)	2.1531 (3)	1.0273 (2)	0.0448 (6)
H3B	0.3471	2.1787	1.0972	0.054*
C5	0.41305 (13)	1.9365 (4)	0.8605 (2)	0.0455 (6)
H5A	0.4115	1.8140	0.8133	0.055*
C11	0.14423 (13)	1.1841 (4)	0.9499 (2)	0.0438 (6)
H11A	0.1429	1.2844	1.0150	0.053*
C8	0.14730 (14)	0.8850 (3)	0.7560 (3)	0.0488 (6)
H8A	0.1480	0.7843	0.6911	0.059*
C6	0.10088 (13)	1.0151 (4)	0.9526 (2)	0.0473 (6)
H6A	0.0708	0.9994	1.0199	0.057*
C2	0.42134 (14)	2.3003 (4)	0.9882 (3)	0.0515 (6)
H2B	0.4229	2.4263	1.0315	0.062*
C1	0.45933 (14)	2.0919 (4)	0.8314 (3)	0.0552 (7)
H1B	0.4891	2.0684	0.7646	0.066*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br	0.0729 (3)	0.04607 (19)	0.1216 (4)	−0.01855 (14)	0.0075 (2)	−0.00034 (16)
N3	0.0430 (11)	0.0399 (10)	0.0350 (10)	−0.0045 (8)	0.0083 (8)	0.0038 (9)
N2	0.0456 (11)	0.0415 (10)	0.0301 (10)	−0.0063 (8)	0.0103 (8)	0.0034 (8)
O1	0.0674 (12)	0.0593 (10)	0.0341 (9)	−0.0110 (9)	0.0160 (8)	−0.0036 (8)
C7	0.0409 (13)	0.0333 (12)	0.0618 (16)	0.0013 (9)	−0.0016 (12)	0.0032 (11)
C10	0.0383 (12)	0.0367 (11)	0.0352 (12)	0.0003 (9)	0.0013 (10)	0.0032 (10)
N1	0.0568 (14)	0.0567 (14)	0.0492 (13)	−0.0143 (11)	0.0019 (11)	0.0077 (11)
C4	0.0363 (12)	0.0387 (12)	0.0294 (11)	0.0036 (9)	0.0022 (9)	0.0023 (9)
C13	0.0380 (13)	0.0390 (11)	0.0321 (12)	0.0051 (9)	0.0055 (10)	0.0024 (10)
C9	0.0509 (14)	0.0462 (13)	0.0375 (13)	0.0051 (11)	0.0081 (11)	−0.0005 (11)
C12	0.0469 (14)	0.0440 (13)	0.0355 (12)	−0.0016 (10)	0.0102 (11)	0.0037 (11)
C3	0.0457 (14)	0.0457 (14)	0.0437 (13)	0.0035 (10)	0.0086 (11)	−0.0041 (11)
C5	0.0482 (14)	0.0493 (13)	0.0400 (13)	−0.0052 (11)	0.0097 (11)	−0.0050 (11)
C11	0.0472 (14)	0.0443 (13)	0.0403 (13)	−0.0005 (10)	0.0060 (11)	−0.0057 (10)
C8	0.0571 (16)	0.0396 (13)	0.0487 (15)	0.0076 (11)	0.0005 (13)	−0.0090 (11)
C6	0.0431 (14)	0.0510 (14)	0.0489 (14)	−0.0025 (11)	0.0103 (11)	0.0065 (12)
C2	0.0532 (16)	0.0402 (13)	0.0596 (16)	−0.0022 (11)	−0.0029 (14)	−0.0006 (12)
C1	0.0541 (16)	0.0706 (18)	0.0428 (14)	−0.0117 (13)	0.0139 (12)	0.0010 (13)

Geometric parameters (Å, º)

Br—C7	1.894 (2)	C4—C13	1.500 (3)
N3—C12	1.276 (3)	C9—C8	1.379 (3)
N3—N2	1.383 (2)	C9—H9A	0.9300
N2—C13	1.349 (3)	C12—H12A	0.9300
N2—H2A	0.8600	C3—C2	1.382 (3)
O1—C13	1.222 (3)	C3—H3B	0.9300
C7—C8	1.371 (4)	C5—C1	1.382 (3)
C7—C6	1.384 (3)	C5—H5A	0.9300
C10—C9	1.391 (3)	C11—C6	1.370 (3)
C10—C11	1.398 (3)	C11—H11A	0.9300
C10—C12	1.459 (3)	C8—H8A	0.9300
N1—C2	1.326 (3)	C6—H6A	0.9300
N1—C1	1.331 (3)	C2—H2B	0.9300
C4—C5	1.382 (3)	C1—H1B	0.9300
C4—C3	1.388 (3)
C12—N3—N2	114.10 (18)	C10—C12—H12A	118.6
C13—N2—N3	120.59 (18)	C4—C3—C2	119.3 (2)
C13—N2—H2A	119.7	C4—C3—H3B	120.4
N3—N2—H2A	119.7	C2—C3—H3B	120.4
C8—C7—C6	121.4 (2)	C4—C5—C1	118.9 (2)
C8—C7—Br	119.52 (19)	C4—C5—H5A	120.6
C6—C7—Br	119.09 (19)	C1—C5—H5A	120.6
C9—C10—C11	118.4 (2)	C6—C11—C10	120.6 (2)
C9—C10—C12	118.8 (2)	C6—C11—H11A	119.7
C11—C10—C12	122.8 (2)	C10—C11—H11A	119.7
C2—N1—C1	116.1 (2)	C7—C8—C9	118.9 (2)
C5—C4—C3	117.3 (2)	C7—C8—H8A	120.5
C5—C4—C13	123.5 (2)	C9—C8—H8A	120.5
C3—C4—C13	119.2 (2)	C11—C6—C7	119.5 (2)
O1—C13—N2	123.8 (2)	C11—C6—H6A	120.3
O1—C13—C4	121.6 (2)	C7—C6—H6A	120.3
N2—C13—C4	114.59 (18)	N1—C2—C3	124.0 (2)
C8—C9—C10	121.2 (2)	N1—C2—H2B	118.0
C8—C9—H9A	119.4	C3—C2—H2B	118.0
C10—C9—H9A	119.4	N1—C1—C5	124.4 (2)
N3—C12—C10	122.9 (2)	N1—C1—H1B	117.8
N3—C12—H12A	118.6	C5—C1—H1B	117.8

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1^i	0.86	2.14	2.966 (3)	161
C12—H12A···O1^i	0.93	2.60	3.377 (3)	142

Symmetry code: (i) x, −y+7/2, z−1/2.