supplementary materials


Acta Cryst. (2007). E63, o3739    [ doi:10.1107/S1600536807038512 ]

6-Bromo-2'-[4-(dimethylamino)benzylidene]nicotinohydrazide monohydrate

D.-S. Yang

Abstract top

The asymmetric unit of the title compound, C15H15BrN4O·H2O, consists of a roughly planar Schiff base molecule and a solvent water molecule. The Schiff base molecule displays a trans configuration with respect to the C=N double bond. The dihedral angle between the benzene and pyridine rings is 4.6 (2)°. In the crystal structure, molecules are linked through intermolecular O-H...O and O-H...N hydrogen bonds.

Comment top

Schiff base compounds have been of great interest for a long time. These compounds play an important role in the development of coordination chemistry (Musie et al., 2001; Bernardo et al., 1996; Paul et al., 2002). Recently, we have reported a few Schiff base compounds (Yang, 2006a,b,c,d,e, 2007; Yang & Guo, 2006). As a further investigation of this work, the crystal structure of the title compound is reported here.

The title compound, C15H15BrN4O·H2O, consists of a roughly planar Schiff base molecule and a lattice water molecule (Fig. 1). The Schiff base molecule displays a trans configuration with respect to the CN double bond. All the bond lengths are within normal ranges (Allen et al., 1987). The C7N3 bond length of 1.279 (3) Å conforms to the value for a double bond. The bond length of 1.338 (3) Å between atoms C6 and N2 is intermediate between an N—N single bond and an NN double bond, because of conjugation effects in the molecule. The dihedral angle between the benzene ring and the pyridine ring is 4.6 (2)°. In the crystal structure, molecules are linked through intermolecular O—H···O and O—H···N hydrogen bonds, forming tetrammers (Fig. 2).

Related literature top

For related structures, see Yang (2006a,b,c,d,e, 2007); Yang & Guo (2006). For related literature, see: Allen et al. (1987); Bernardo et al. (1996); Musie et al. (2001); Paul et al. (2002).

Experimental top

4-Dimethylaminobenzaldehyde (0.1 mmol, 15.0 mg) and 5-bromonicotinic acid hydrazide (0.1 mmol, 21.6 mg) were dissolved in MeOH (10 ml). The mixture was stirred at room temperature to give a clear colorless solution. Crystals of the title compound were formed by gradual evaporation of the solvent over a period of 3 days at room temperature.

Refinement top

Atoms H2A, H2B and H2C were located in a difference Fourier map and refined isotropically, with O—H distances restrained to 0.85 (1) Å, N—H distance restrained to 0.90 (1) Å, H···H distance restrained to 1.37 (2) Å. Other H atoms were placed in idealized positions and constrained to ride on their parent atoms, with C—H distances of 0.93–0.96 Å, and with Uiso(H) = 1.2Ueq(C) and 1.5Ueq(methyl C).

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; 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: SHELXL97.

Figures top
[Figure 1] Fig. 1. The structure of the title compound showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. Molecular packing as viewed along the b axis. Hydrogen bonds are shown as dashed lines.
6-Bromo-2'-[4-(dimethylamino)benzylidene]nicotinohydrazide monohydrate top
Crystal data top
C15H15BrN4O1·H2O1F000 = 744
Mr = 365.24Dx = 1.538 Mg m3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
a = 10.535 (6) ÅCell parameters from 2425 reflections
b = 12.363 (7) Åθ = 2.5–24.3º
c = 12.889 (7) ŵ = 2.62 mm1
β = 110.067 (6)ºT = 298 (2) K
V = 1576.8 (15) Å3Block, colourless
Z = 40.23 × 0.22 × 0.20 mm
Data collection top
Bruker SMART CCD
diffractometer
3572 independent reflections
Radiation source: fine-focus sealed tube2312 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.032
T = 298(2) Kθmax = 27.5º
ω scansθmin = 2.2º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 12→13
Tmin = 0.584, Tmax = 0.622k = 10→15
9266 measured reflectionsl = 16→16
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.035H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.086  w = 1/[σ2(Fo2) + (0.0367P)2 + 0.2692P]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max < 0.001
3572 reflectionsΔρmax = 0.23 e Å3
210 parametersΔρmin = 0.32 e Å3
4 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
C15H15BrN4O1·H2O1V = 1576.8 (15) Å3
Mr = 365.24Z = 4
Monoclinic, P21/nMo Kα
a = 10.535 (6) ŵ = 2.62 mm1
b = 12.363 (7) ÅT = 298 (2) K
c = 12.889 (7) Å0.23 × 0.22 × 0.20 mm
β = 110.067 (6)º
Data collection top
Bruker SMART CCD
diffractometer
3572 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
2312 reflections with I > 2σ(I)
Tmin = 0.584, Tmax = 0.622Rint = 0.032
9266 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0354 restraints
wR(F2) = 0.086H atoms treated by a mixture of
independent and constrained refinement
S = 1.01Δρmax = 0.23 e Å3
3572 reflectionsΔρmin = 0.32 e Å3
210 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 > 2sigma(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*/Ueq
Br10.47397 (3)0.42451 (2)0.16814 (2)0.06254 (13)
O10.6679 (2)0.43639 (13)0.61464 (15)0.0656 (6)
O20.64188 (19)0.03201 (13)0.68079 (17)0.0555 (5)
N10.5521 (2)0.14776 (17)0.35409 (18)0.0521 (6)
N20.6671 (2)0.26731 (15)0.68069 (16)0.0420 (5)
N30.7079 (2)0.30497 (16)0.78919 (16)0.0424 (5)
N40.8832 (2)0.31198 (18)1.32054 (18)0.0597 (6)
C10.6001 (2)0.29484 (18)0.48329 (19)0.0373 (5)
C20.5636 (2)0.36808 (19)0.3968 (2)0.0414 (6)
H20.56570.44200.41040.050*
C30.5239 (2)0.32913 (19)0.28971 (19)0.0409 (6)
C40.5194 (2)0.2193 (2)0.2719 (2)0.0481 (6)
H40.49230.19400.19960.058*
C50.5927 (2)0.18524 (19)0.4576 (2)0.0457 (6)
H50.61720.13560.51530.055*
C60.6478 (2)0.3389 (2)0.5989 (2)0.0422 (6)
C70.7264 (2)0.2307 (2)0.8620 (2)0.0434 (6)
H70.71380.15890.83920.052*
C80.7665 (2)0.25483 (18)0.97939 (19)0.0393 (5)
C90.7856 (2)0.35918 (19)1.0216 (2)0.0437 (6)
H90.77310.41740.97340.052*
C100.8223 (2)0.3783 (2)1.1329 (2)0.0457 (6)
H100.83300.44931.15840.055*
C110.8443 (2)0.2932 (2)1.20932 (19)0.0427 (6)
C120.8246 (3)0.1880 (2)1.1664 (2)0.0481 (6)
H120.83720.12941.21420.058*
C130.7868 (3)0.17021 (19)1.0544 (2)0.0474 (6)
H130.77440.09951.02810.057*
C140.9084 (3)0.2233 (3)1.3982 (2)0.0659 (8)
H14A0.82650.18311.38540.099*
H14B0.93900.25141.47220.099*
H14C0.97650.17681.38860.099*
C150.9053 (4)0.4204 (2)1.3647 (3)0.0746 (9)
H15A0.97860.45291.34780.112*
H15B0.92720.41781.44340.112*
H15C0.82480.46261.33230.112*
H2A0.648 (3)0.1969 (10)0.671 (2)0.080*
H2B0.7067 (18)0.006 (2)0.720 (2)0.080*
H2C0.5687 (15)0.002 (2)0.667 (3)0.080*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0862 (2)0.05148 (19)0.04669 (17)0.00208 (16)0.01863 (15)0.00658 (13)
O10.1116 (16)0.0305 (10)0.0472 (11)0.0100 (10)0.0175 (11)0.0051 (8)
O20.0598 (12)0.0307 (9)0.0676 (13)0.0010 (9)0.0110 (11)0.0033 (9)
N10.0674 (15)0.0320 (11)0.0513 (14)0.0002 (10)0.0134 (11)0.0068 (10)
N20.0529 (13)0.0318 (10)0.0420 (12)0.0031 (10)0.0172 (10)0.0042 (9)
N30.0514 (13)0.0379 (11)0.0389 (11)0.0020 (9)0.0168 (10)0.0056 (9)
N40.0813 (17)0.0547 (14)0.0408 (13)0.0002 (13)0.0181 (12)0.0024 (11)
C10.0397 (13)0.0300 (12)0.0440 (13)0.0039 (10)0.0166 (11)0.0041 (10)
C20.0464 (15)0.0295 (12)0.0489 (15)0.0009 (11)0.0171 (12)0.0045 (11)
C30.0422 (14)0.0391 (14)0.0412 (13)0.0008 (11)0.0142 (11)0.0018 (11)
C40.0557 (16)0.0424 (15)0.0433 (15)0.0006 (13)0.0131 (12)0.0094 (12)
C50.0551 (16)0.0354 (14)0.0448 (14)0.0013 (12)0.0147 (12)0.0022 (11)
C60.0486 (15)0.0347 (14)0.0436 (14)0.0022 (11)0.0161 (12)0.0030 (11)
C70.0456 (14)0.0369 (14)0.0492 (15)0.0025 (11)0.0183 (12)0.0044 (12)
C80.0413 (13)0.0370 (13)0.0405 (13)0.0008 (11)0.0153 (11)0.0002 (10)
C90.0538 (15)0.0333 (13)0.0448 (14)0.0003 (12)0.0176 (12)0.0049 (11)
C100.0555 (16)0.0324 (13)0.0503 (15)0.0013 (12)0.0194 (13)0.0044 (11)
C110.0412 (14)0.0441 (14)0.0428 (14)0.0009 (11)0.0144 (11)0.0003 (11)
C120.0602 (17)0.0350 (14)0.0474 (15)0.0014 (12)0.0163 (13)0.0083 (11)
C130.0589 (16)0.0297 (13)0.0517 (16)0.0028 (12)0.0168 (13)0.0021 (11)
C140.069 (2)0.083 (2)0.0444 (16)0.0051 (17)0.0179 (14)0.0074 (15)
C150.099 (2)0.068 (2)0.0534 (18)0.0004 (18)0.0211 (17)0.0172 (15)
Geometric parameters (Å, °) top
Br1—C31.886 (2)C5—H50.9300
O1—C61.229 (3)C7—C81.455 (3)
O2—H2B0.837 (10)C7—H70.9300
O2—H2C0.841 (10)C8—C91.388 (3)
N1—C41.331 (3)C8—C131.390 (3)
N1—C51.337 (3)C9—C101.372 (3)
N2—C61.338 (3)C9—H90.9300
N2—N31.394 (3)C10—C111.405 (3)
N2—H2A0.893 (10)C10—H100.9300
N3—C71.279 (3)C11—C121.401 (4)
N4—C111.369 (3)C12—C131.378 (3)
N4—C151.444 (3)C12—H120.9300
N4—C141.446 (3)C13—H130.9300
C1—C21.384 (3)C14—H14A0.9600
C1—C51.391 (3)C14—H14B0.9600
C1—C61.501 (3)C14—H14C0.9600
C2—C31.384 (3)C15—H15A0.9600
C2—H20.9300C15—H15B0.9600
C3—C41.376 (3)C15—H15C0.9600
C4—H40.9300
H2B—O2—H2C111 (2)C9—C8—C13117.4 (2)
C4—N1—C5118.1 (2)C9—C8—C7123.3 (2)
C6—N2—N3118.75 (19)C13—C8—C7119.3 (2)
C6—N2—H2A124.3 (19)C10—C9—C8121.4 (2)
N3—N2—H2A116.7 (19)C10—C9—H9119.3
C7—N3—N2114.4 (2)C8—C9—H9119.3
C11—N4—C15121.3 (2)C9—C10—C11121.6 (2)
C11—N4—C14121.0 (2)C9—C10—H10119.2
C15—N4—C14117.7 (2)C11—C10—H10119.2
C2—C1—C5117.9 (2)N4—C11—C12121.4 (2)
C2—C1—C6117.9 (2)N4—C11—C10121.7 (2)
C5—C1—C6124.2 (2)C12—C11—C10116.9 (2)
C1—C2—C3118.7 (2)C13—C12—C11120.8 (2)
C1—C2—H2120.6C13—C12—H12119.6
C3—C2—H2120.6C11—C12—H12119.6
C4—C3—C2119.4 (2)C12—C13—C8121.9 (2)
C4—C3—Br1119.66 (19)C12—C13—H13119.0
C2—C3—Br1120.92 (18)C8—C13—H13119.0
N1—C4—C3122.6 (2)N4—C14—H14A109.5
N1—C4—H4118.7N4—C14—H14B109.5
C3—C4—H4118.7H14A—C14—H14B109.5
N1—C5—C1123.2 (2)N4—C14—H14C109.5
N1—C5—H5118.4H14A—C14—H14C109.5
C1—C5—H5118.4H14B—C14—H14C109.5
O1—C6—N2123.2 (2)N4—C15—H15A109.5
O1—C6—C1120.0 (2)N4—C15—H15B109.5
N2—C6—C1116.8 (2)H15A—C15—H15B109.5
N3—C7—C8122.1 (2)N4—C15—H15C109.5
N3—C7—H7118.9H15A—C15—H15C109.5
C8—C7—H7118.9H15B—C15—H15C109.5
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O2—H2C···N1i0.841 (10)2.171 (17)2.948 (3)154 (3)
O2—H2B···N3ii0.837 (10)2.52 (2)3.180 (3)136 (3)
O2—H2B···O1ii0.837 (10)2.209 (19)2.956 (3)149 (3)
N2—H2A···O20.893 (10)2.045 (12)2.921 (3)167 (3)
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+3/2, y−1/2, −z+3/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O2—H2C···N1i0.841 (10)2.171 (17)2.948 (3)154 (3)
O2—H2B···N3ii0.837 (10)2.52 (2)3.180 (3)136 (3)
O2—H2B···O1ii0.837 (10)2.209 (19)2.956 (3)149 (3)
N2—H2A···O20.893 (10)2.045 (12)2.921 (3)167 (3)
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+3/2, y−1/2, −z+3/2.
Acknowledgements top

The author acknowledges Key Laboratory Construction Support from the Education Office of Shanxi Province (Project No. 05JS43).

references
References top

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