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The title compound, C12H15Br2N3O, is a hydrazone in which 3,5-dibromo-2-hydroxy­benzaldehyde has reacted with 1-amino-4-methyl­piperazine to form a product containing a C=N double bond. The piperazine ring adopts a chair conformation. The dihedral angle between the benzene ring and the C=N—N plane is 6.0 (5)°. Intra­molecular O—H...N hydrogen bonding generates an S(6) ring motif, while short inter­molecular Br...Br and Br...N contacts [3.5846 (10) and 3.379 (4) Å, respectively] link the mol­ecules to form a three-dimensional network.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807055705/su2017sup1.cif
Contains datablocks I, publication_text

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807055705/su2017Isup2.hkl
Contains datablock I

CCDC reference: 672893

Key indicators

  • Single-crystal X-ray study
  • T = 294 K
  • Mean [sigma](C-C) = 0.008 Å
  • R factor = 0.045
  • wR factor = 0.134
  • Data-to-parameter ratio = 15.1

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 8 PLAT431_ALERT_2_C Short Inter HL..A Contact Br1 .. Br2 .. 3.58 Ang. PLAT431_ALERT_2_C Short Inter HL..A Contact Br2 .. N3 .. 3.38 Ang.
0 ALERT level A = In general: serious problem 0 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 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

Salicylaldehyde, piperazine and their derivatives are important in diverse fields of chemistry and biochemistry. Thus, the chemists are prompted to generate the derivatives by introducing different substituents into the existing skeleton of the molecule (Özek et al., 2007; Guo, 2007; Xu & Liu, 2006). Here, we report the structure of the title compound, (I), Fig. 1, a new hydrazone, which was prepared by reaction of 3,5-dibromo-2-hydroxybenzaldehyde with 1-amino-4-methylpiperazine.

In the structure of the title compound, the aromatic substituent and methylpiperazine group lie trans to the CN double bond. The C7 N1 double bond is effectively coplanar with the benzene ring [N1—C7—C6—C1 = 1.5 (7)°]. The piperazine ring has a chair conformation. The bond distances and angles are normal, within experimental error (Allen et al., 1987).

Atom H1 is involved in a strong intramolecular O1—H1···N1 hydrogen bond (Brown, 1976). The molecules are loosely aggregated into a three-dimensional framework via some short intermolecular Br1···Br2i and Br2···N3ii contacts (d[Br1···Br2]=3.5846 (10) Å, d[Br2···N3]=3.379 (4) Å; symmetry codes: (i) 1 - x,-1/2 + y,-1/2 - z; (ii) -1 + x,1/2 - y,-1/2 + z). A packing diagram for (I) is shown in Fig. 2.

Related literature top

For related structures, see: Özek et al., (2007); Guo (2007); Xu & Liu (2006). For normal ranges of molecular bond lengths and angles, see: Allen et al. (1987). For related literature, see: Brown (1976).

Experimental top

The title compound, (I), was prepared by reaction of 3,5-dibromo-2-hydroxybenzaldehyde (1.4 g, 5 mmol) with 1-amino-4-methylpiperazine (0.7 g 6 mmol) in 20 ml of 95% ethanol. The mixture was stirred and heated in air at reflux temperature for 30 min, after which 10 ml distilled water was added, the resulting product was separated by filtration (1.6 g, yield 84.2%). The pure product (0.5 g) was heated and dissolved in 20 ml of 95% ethanol. Single crystals were obtained from this solution by slow evaporation over a period of 3 days at room temperature.

Refinement top

The OH H-atom was located from a difference Fourier map, however, during refinement the O—H distance was fixed at 0.82 Å and Uiso set to 1.5Ueq (O). The other H atoms were included in calculated positions and treated as riding atoms, with C—H = 0.93–0.97 Å and Uiso(H)= 1.2Ueq(C) [1.5Ueq(C) for methyl].

Computing details top

Data collection: SMART (Bruker 1997); cell refinement: SAINT (Bruker 1997); data reduction: SAINT (Bruker 1997); program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL (Bruker, 2001); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL (Bruker, 2001).

Figures top
[Figure 1] Fig. 1. A view of the molecular structure of (I), showing the atom-numbering scheme and the O1—H1···N1 hydrogen bond (dashed line); displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. Crystal packing diagram of (I) viewed down the a axis, showing the hydrogen bonds and short intermolecular contacts as dashed lines.
2,4-Dibromo-6-[(4-methylpiperazin-1-yl)iminomethyl]phenol top
Crystal data top
C12H15Br2N3OF(000) = 744
Mr = 377.09Dx = 1.770 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2492 reflections
a = 9.5733 (13) Åθ = 2.5–26.0°
b = 9.5493 (13) ŵ = 5.72 mm1
c = 16.039 (2) ÅT = 294 K
β = 105.236 (2)°Block, colourless
V = 1414.8 (3) Å30.28 × 0.22 × 0.10 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer
2493 independent reflections
Radiation source: fine-focus sealed tube1846 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.033
ϕ and ω scansθmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1110
Tmin = 0.243, Tmax = 0.565k = 1111
6952 measured reflectionsl = 1911
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.134H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0698P)2 + 2.1718P]
where P = (Fo2 + 2Fc2)/3
2493 reflections(Δ/σ)max = 0.002
165 parametersΔρmax = 0.93 e Å3
0 restraintsΔρmin = 0.66 e Å3
Crystal data top
C12H15Br2N3OV = 1414.8 (3) Å3
Mr = 377.09Z = 4
Monoclinic, P21/cMo Kα radiation
a = 9.5733 (13) ŵ = 5.72 mm1
b = 9.5493 (13) ÅT = 294 K
c = 16.039 (2) Å0.28 × 0.22 × 0.10 mm
β = 105.236 (2)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
2493 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
1846 reflections with I > 2σ(I)
Tmin = 0.243, Tmax = 0.565Rint = 0.033
6952 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.134H-atom parameters constrained
S = 1.04Δρmax = 0.93 e Å3
2493 reflectionsΔρmin = 0.66 e Å3
165 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
xyzUiso*/Ueq
O10.7537 (4)0.0040 (4)0.0332 (3)0.0509 (10)
H10.77140.02770.01590.076*
Br10.65266 (7)0.08480 (6)0.22008 (4)0.0576 (2)
Br20.27011 (6)0.42615 (6)0.09443 (4)0.0539 (2)
C10.6499 (5)0.1018 (5)0.0435 (4)0.0402 (13)
C20.5886 (5)0.1544 (5)0.1266 (3)0.0389 (12)
C30.4798 (5)0.2531 (5)0.1417 (3)0.0400 (12)
H30.44100.28800.19710.048*
C40.4290 (5)0.2996 (5)0.0733 (3)0.0395 (12)
C50.4873 (5)0.2501 (5)0.0091 (3)0.0398 (12)
H50.45240.28280.05440.048*
C60.5984 (5)0.1511 (5)0.0251 (3)0.0386 (12)
C70.6533 (5)0.0983 (5)0.1133 (4)0.0416 (13)
H70.61510.13190.15710.050*
C80.7700 (6)0.0154 (6)0.2849 (4)0.0484 (14)
H8A0.66730.03600.27230.058*
H8B0.82250.10330.29610.058*
C90.8139 (6)0.0777 (6)0.3645 (4)0.0507 (15)
H9A0.79870.02800.41420.061*
H9B0.75400.16110.35570.061*
C101.0082 (7)0.2029 (7)0.4601 (4)0.0661 (18)
H10A1.11100.21760.47500.099*
H10B0.95950.29170.45020.099*
H10C0.98220.15530.50660.099*
C110.9862 (6)0.1933 (6)0.3076 (4)0.0512 (14)
H11A0.92510.27590.29780.061*
H11B1.08620.22370.31960.061*
C120.9499 (6)0.1026 (6)0.2270 (4)0.0471 (14)
H12A1.01570.02350.23470.056*
H12B0.96050.15660.17780.056*
N10.7538 (4)0.0059 (5)0.1303 (3)0.0427 (11)
N20.8007 (4)0.0527 (4)0.2115 (3)0.0409 (10)
N30.9649 (4)0.1172 (5)0.3810 (3)0.0441 (11)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.046 (2)0.053 (2)0.055 (3)0.0105 (18)0.014 (2)0.0020 (19)
Br10.0601 (4)0.0621 (4)0.0590 (4)0.0025 (3)0.0307 (3)0.0079 (3)
Br20.0549 (4)0.0579 (4)0.0504 (4)0.0162 (3)0.0164 (3)0.0064 (3)
C10.028 (2)0.035 (3)0.057 (4)0.007 (2)0.010 (2)0.003 (2)
C20.038 (3)0.040 (3)0.040 (3)0.011 (2)0.014 (2)0.008 (2)
C30.035 (3)0.040 (3)0.044 (3)0.004 (2)0.008 (2)0.004 (2)
C40.035 (3)0.039 (3)0.043 (3)0.000 (2)0.009 (2)0.000 (2)
C50.036 (3)0.043 (3)0.041 (3)0.003 (2)0.010 (2)0.005 (2)
C60.033 (3)0.040 (3)0.040 (3)0.009 (2)0.006 (2)0.006 (2)
C70.032 (3)0.048 (3)0.044 (3)0.003 (2)0.008 (2)0.008 (2)
C80.035 (3)0.062 (4)0.049 (3)0.015 (2)0.011 (3)0.008 (3)
C90.035 (3)0.065 (4)0.054 (4)0.007 (3)0.014 (3)0.010 (3)
C100.054 (4)0.081 (5)0.060 (4)0.013 (3)0.009 (3)0.018 (3)
C110.043 (3)0.047 (3)0.062 (4)0.010 (2)0.010 (3)0.006 (3)
C120.037 (3)0.049 (3)0.055 (4)0.012 (2)0.011 (3)0.001 (3)
N10.031 (2)0.045 (3)0.049 (3)0.0034 (19)0.004 (2)0.000 (2)
N20.031 (2)0.043 (2)0.047 (3)0.0023 (18)0.006 (2)0.002 (2)
N30.037 (2)0.044 (2)0.048 (3)0.0064 (19)0.006 (2)0.006 (2)
Geometric parameters (Å, º) top
O1—C11.342 (6)C8—H8A0.9700
O1—H10.8200C8—H8B0.9700
Br1—C21.884 (5)C9—N31.450 (7)
Br2—C41.902 (5)C9—H9A0.9700
C1—C61.400 (8)C9—H9B0.9700
C1—C21.401 (7)C10—N31.475 (7)
C2—C31.378 (7)C10—H10A0.9600
C3—C41.384 (7)C10—H10B0.9600
C3—H30.9300C10—H10C0.9600
C4—C51.376 (7)C11—N31.443 (7)
C5—C61.396 (7)C11—C121.518 (8)
C5—H50.9300C11—H11A0.9700
C6—C71.463 (7)C11—H11B0.9700
C7—N11.281 (6)C12—N21.464 (6)
C7—H70.9300C12—H12A0.9700
C8—N21.441 (7)C12—H12B0.9700
C8—C91.522 (8)N1—N21.380 (6)
C1—O1—H1109.5C8—C9—H9A109.6
O1—C1—C6122.7 (5)N3—C9—H9B109.6
O1—C1—C2118.5 (5)C8—C9—H9B109.6
C6—C1—C2118.8 (5)H9A—C9—H9B108.1
C3—C2—C1121.3 (5)N3—C10—H10A109.5
C3—C2—Br1119.4 (4)N3—C10—H10B109.5
C1—C2—Br1119.2 (4)H10A—C10—H10B109.5
C2—C3—C4119.2 (5)N3—C10—H10C109.5
C2—C3—H3120.4H10A—C10—H10C109.5
C4—C3—H3120.4H10B—C10—H10C109.5
C5—C4—C3120.8 (5)N3—C11—C12111.0 (4)
C5—C4—Br2119.5 (4)N3—C11—H11A109.4
C3—C4—Br2119.6 (4)C12—C11—H11A109.4
C4—C5—C6120.5 (5)N3—C11—H11B109.4
C4—C5—H5119.8C12—C11—H11B109.4
C6—C5—H5119.8H11A—C11—H11B108.0
C5—C6—C1119.4 (5)N2—C12—C11108.9 (5)
C5—C6—C7118.3 (5)N2—C12—H12A109.9
C1—C6—C7122.2 (5)C11—C12—H12A109.9
N1—C7—C6120.2 (5)N2—C12—H12B109.9
N1—C7—H7119.9C11—C12—H12B109.9
C6—C7—H7119.9H12A—C12—H12B108.3
N2—C8—C9110.5 (5)C7—N1—N2121.4 (5)
N2—C8—H8A109.5N1—N2—C8120.1 (4)
C9—C8—H8A109.5N1—N2—C12110.7 (4)
N2—C8—H8B109.5C8—N2—C12114.1 (4)
C9—C8—H8B109.5C11—N3—C9109.3 (4)
H8A—C8—H8B108.1C11—N3—C10110.8 (4)
N3—C9—C8110.3 (5)C9—N3—C10110.0 (5)
N3—C9—H9A109.6
O1—C1—C2—C3178.8 (4)C5—C6—C7—N1179.0 (5)
C6—C1—C2—C30.1 (7)C1—C6—C7—N11.5 (7)
O1—C1—C2—Br10.6 (6)N2—C8—C9—N355.4 (6)
C6—C1—C2—Br1178.1 (3)N3—C11—C12—N256.9 (6)
C1—C2—C3—C40.9 (7)C6—C7—N1—N2175.5 (4)
Br1—C2—C3—C4177.3 (4)C7—N1—N2—C818.3 (7)
C2—C3—C4—C51.0 (7)C7—N1—N2—C12154.6 (5)
C2—C3—C4—Br2175.8 (4)C9—C8—N2—N1172.3 (4)
C3—C4—C5—C60.4 (7)C9—C8—N2—C1252.8 (6)
Br2—C4—C5—C6176.4 (4)C11—C12—N2—N1167.9 (4)
C4—C5—C6—C10.4 (7)C11—C12—N2—C853.0 (6)
C4—C5—C6—C7177.9 (4)C12—C11—N3—C961.8 (6)
O1—C1—C6—C5178.2 (4)C12—C11—N3—C10176.8 (5)
C2—C1—C6—C50.5 (7)C8—C9—N3—C1160.3 (6)
O1—C1—C6—C70.7 (7)C8—C9—N3—C10177.9 (5)
C2—C1—C6—C7178.0 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N10.821.912.624 (6)144

Experimental details

Crystal data
Chemical formulaC12H15Br2N3O
Mr377.09
Crystal system, space groupMonoclinic, P21/c
Temperature (K)294
a, b, c (Å)9.5733 (13), 9.5493 (13), 16.039 (2)
β (°) 105.236 (2)
V3)1414.8 (3)
Z4
Radiation typeMo Kα
µ (mm1)5.72
Crystal size (mm)0.28 × 0.22 × 0.10
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.243, 0.565
No. of measured, independent and
observed [I > 2σ(I)] reflections
6952, 2493, 1846
Rint0.033
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.045, 0.134, 1.04
No. of reflections2493
No. of parameters165
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.93, 0.66

Computer programs: SMART (Bruker 1997), SAINT (Bruker 1997), SHELXTL (Bruker, 2001).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N10.821.912.624 (6)144.4
 

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