Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807055705/su2017sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807055705/su2017Isup2.hkl |
CCDC reference: 672893
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (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
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).
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.
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].
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).
C12H15Br2N3O | F(000) = 744 |
Mr = 377.09 | Dx = 1.770 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2492 reflections |
a = 9.5733 (13) Å | θ = 2.5–26.0° |
b = 9.5493 (13) Å | µ = 5.72 mm−1 |
c = 16.039 (2) Å | T = 294 K |
β = 105.236 (2)° | Block, colourless |
V = 1414.8 (3) Å3 | 0.28 × 0.22 × 0.10 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 2493 independent reflections |
Radiation source: fine-focus sealed tube | 1846 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −11→10 |
Tmin = 0.243, Tmax = 0.565 | k = −11→11 |
6952 measured reflections | l = −19→11 |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.134 | H-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 parameters | Δρmax = 0.93 e Å−3 |
0 restraints | Δρmin = −0.66 e Å−3 |
C12H15Br2N3O | V = 1414.8 (3) Å3 |
Mr = 377.09 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.5733 (13) Å | µ = 5.72 mm−1 |
b = 9.5493 (13) Å | T = 294 K |
c = 16.039 (2) Å | 0.28 × 0.22 × 0.10 mm |
β = 105.236 (2)° |
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 = 0.565 | Rint = 0.033 |
6952 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.134 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.93 e Å−3 |
2493 reflections | Δρmin = −0.66 e Å−3 |
165 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.7537 (4) | 0.0040 (4) | −0.0332 (3) | 0.0509 (10) | |
H1 | 0.7714 | −0.0277 | 0.0159 | 0.076* | |
Br1 | 0.65266 (7) | 0.08480 (6) | −0.22008 (4) | 0.0576 (2) | |
Br2 | 0.27011 (6) | 0.42615 (6) | −0.09443 (4) | 0.0539 (2) | |
C1 | 0.6499 (5) | 0.1018 (5) | −0.0435 (4) | 0.0402 (13) | |
C2 | 0.5886 (5) | 0.1544 (5) | −0.1266 (3) | 0.0389 (12) | |
C3 | 0.4798 (5) | 0.2531 (5) | −0.1417 (3) | 0.0400 (12) | |
H3 | 0.4410 | 0.2880 | −0.1971 | 0.048* | |
C4 | 0.4290 (5) | 0.2996 (5) | −0.0733 (3) | 0.0395 (12) | |
C5 | 0.4873 (5) | 0.2501 (5) | 0.0091 (3) | 0.0398 (12) | |
H5 | 0.4524 | 0.2828 | 0.0544 | 0.048* | |
C6 | 0.5984 (5) | 0.1511 (5) | 0.0251 (3) | 0.0386 (12) | |
C7 | 0.6533 (5) | 0.0983 (5) | 0.1133 (4) | 0.0416 (13) | |
H7 | 0.6151 | 0.1319 | 0.1571 | 0.050* | |
C8 | 0.7700 (6) | 0.0154 (6) | 0.2849 (4) | 0.0484 (14) | |
H8A | 0.6673 | 0.0360 | 0.2723 | 0.058* | |
H8B | 0.8225 | 0.1033 | 0.2961 | 0.058* | |
C9 | 0.8139 (6) | −0.0777 (6) | 0.3645 (4) | 0.0507 (15) | |
H9A | 0.7987 | −0.0280 | 0.4142 | 0.061* | |
H9B | 0.7540 | −0.1611 | 0.3557 | 0.061* | |
C10 | 1.0082 (7) | −0.2029 (7) | 0.4601 (4) | 0.0661 (18) | |
H10A | 1.1110 | −0.2176 | 0.4750 | 0.099* | |
H10B | 0.9595 | −0.2917 | 0.4502 | 0.099* | |
H10C | 0.9822 | −0.1553 | 0.5066 | 0.099* | |
C11 | 0.9862 (6) | −0.1933 (6) | 0.3076 (4) | 0.0512 (14) | |
H11A | 0.9251 | −0.2759 | 0.2978 | 0.061* | |
H11B | 1.0862 | −0.2237 | 0.3196 | 0.061* | |
C12 | 0.9499 (6) | −0.1026 (6) | 0.2270 (4) | 0.0471 (14) | |
H12A | 1.0157 | −0.0235 | 0.2347 | 0.056* | |
H12B | 0.9605 | −0.1566 | 0.1778 | 0.056* | |
N1 | 0.7538 (4) | 0.0059 (5) | 0.1303 (3) | 0.0427 (11) | |
N2 | 0.8007 (4) | −0.0527 (4) | 0.2115 (3) | 0.0409 (10) | |
N3 | 0.9649 (4) | −0.1172 (5) | 0.3810 (3) | 0.0441 (11) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.046 (2) | 0.053 (2) | 0.055 (3) | 0.0105 (18) | 0.014 (2) | −0.0020 (19) |
Br1 | 0.0601 (4) | 0.0621 (4) | 0.0590 (4) | −0.0025 (3) | 0.0307 (3) | −0.0079 (3) |
Br2 | 0.0549 (4) | 0.0579 (4) | 0.0504 (4) | 0.0162 (3) | 0.0164 (3) | 0.0064 (3) |
C1 | 0.028 (2) | 0.035 (3) | 0.057 (4) | −0.007 (2) | 0.010 (2) | −0.003 (2) |
C2 | 0.038 (3) | 0.040 (3) | 0.040 (3) | −0.011 (2) | 0.014 (2) | −0.008 (2) |
C3 | 0.035 (3) | 0.040 (3) | 0.044 (3) | −0.004 (2) | 0.008 (2) | 0.004 (2) |
C4 | 0.035 (3) | 0.039 (3) | 0.043 (3) | 0.000 (2) | 0.009 (2) | 0.000 (2) |
C5 | 0.036 (3) | 0.043 (3) | 0.041 (3) | −0.003 (2) | 0.010 (2) | −0.005 (2) |
C6 | 0.033 (3) | 0.040 (3) | 0.040 (3) | −0.009 (2) | 0.006 (2) | −0.006 (2) |
C7 | 0.032 (3) | 0.048 (3) | 0.044 (3) | −0.003 (2) | 0.008 (2) | −0.008 (2) |
C8 | 0.035 (3) | 0.062 (4) | 0.049 (3) | 0.015 (2) | 0.011 (3) | 0.008 (3) |
C9 | 0.035 (3) | 0.065 (4) | 0.054 (4) | 0.007 (3) | 0.014 (3) | 0.010 (3) |
C10 | 0.054 (4) | 0.081 (5) | 0.060 (4) | 0.013 (3) | 0.009 (3) | 0.018 (3) |
C11 | 0.043 (3) | 0.047 (3) | 0.062 (4) | 0.010 (2) | 0.010 (3) | 0.006 (3) |
C12 | 0.037 (3) | 0.049 (3) | 0.055 (4) | 0.012 (2) | 0.011 (3) | −0.001 (3) |
N1 | 0.031 (2) | 0.045 (3) | 0.049 (3) | −0.0034 (19) | 0.004 (2) | 0.000 (2) |
N2 | 0.031 (2) | 0.043 (2) | 0.047 (3) | 0.0023 (18) | 0.006 (2) | 0.002 (2) |
N3 | 0.037 (2) | 0.044 (2) | 0.048 (3) | 0.0064 (19) | 0.006 (2) | 0.006 (2) |
O1—C1 | 1.342 (6) | C8—H8A | 0.9700 |
O1—H1 | 0.8200 | C8—H8B | 0.9700 |
Br1—C2 | 1.884 (5) | C9—N3 | 1.450 (7) |
Br2—C4 | 1.902 (5) | C9—H9A | 0.9700 |
C1—C6 | 1.400 (8) | C9—H9B | 0.9700 |
C1—C2 | 1.401 (7) | C10—N3 | 1.475 (7) |
C2—C3 | 1.378 (7) | C10—H10A | 0.9600 |
C3—C4 | 1.384 (7) | C10—H10B | 0.9600 |
C3—H3 | 0.9300 | C10—H10C | 0.9600 |
C4—C5 | 1.376 (7) | C11—N3 | 1.443 (7) |
C5—C6 | 1.396 (7) | C11—C12 | 1.518 (8) |
C5—H5 | 0.9300 | C11—H11A | 0.9700 |
C6—C7 | 1.463 (7) | C11—H11B | 0.9700 |
C7—N1 | 1.281 (6) | C12—N2 | 1.464 (6) |
C7—H7 | 0.9300 | C12—H12A | 0.9700 |
C8—N2 | 1.441 (7) | C12—H12B | 0.9700 |
C8—C9 | 1.522 (8) | N1—N2 | 1.380 (6) |
C1—O1—H1 | 109.5 | C8—C9—H9A | 109.6 |
O1—C1—C6 | 122.7 (5) | N3—C9—H9B | 109.6 |
O1—C1—C2 | 118.5 (5) | C8—C9—H9B | 109.6 |
C6—C1—C2 | 118.8 (5) | H9A—C9—H9B | 108.1 |
C3—C2—C1 | 121.3 (5) | N3—C10—H10A | 109.5 |
C3—C2—Br1 | 119.4 (4) | N3—C10—H10B | 109.5 |
C1—C2—Br1 | 119.2 (4) | H10A—C10—H10B | 109.5 |
C2—C3—C4 | 119.2 (5) | N3—C10—H10C | 109.5 |
C2—C3—H3 | 120.4 | H10A—C10—H10C | 109.5 |
C4—C3—H3 | 120.4 | H10B—C10—H10C | 109.5 |
C5—C4—C3 | 120.8 (5) | N3—C11—C12 | 111.0 (4) |
C5—C4—Br2 | 119.5 (4) | N3—C11—H11A | 109.4 |
C3—C4—Br2 | 119.6 (4) | C12—C11—H11A | 109.4 |
C4—C5—C6 | 120.5 (5) | N3—C11—H11B | 109.4 |
C4—C5—H5 | 119.8 | C12—C11—H11B | 109.4 |
C6—C5—H5 | 119.8 | H11A—C11—H11B | 108.0 |
C5—C6—C1 | 119.4 (5) | N2—C12—C11 | 108.9 (5) |
C5—C6—C7 | 118.3 (5) | N2—C12—H12A | 109.9 |
C1—C6—C7 | 122.2 (5) | C11—C12—H12A | 109.9 |
N1—C7—C6 | 120.2 (5) | N2—C12—H12B | 109.9 |
N1—C7—H7 | 119.9 | C11—C12—H12B | 109.9 |
C6—C7—H7 | 119.9 | H12A—C12—H12B | 108.3 |
N2—C8—C9 | 110.5 (5) | C7—N1—N2 | 121.4 (5) |
N2—C8—H8A | 109.5 | N1—N2—C8 | 120.1 (4) |
C9—C8—H8A | 109.5 | N1—N2—C12 | 110.7 (4) |
N2—C8—H8B | 109.5 | C8—N2—C12 | 114.1 (4) |
C9—C8—H8B | 109.5 | C11—N3—C9 | 109.3 (4) |
H8A—C8—H8B | 108.1 | C11—N3—C10 | 110.8 (4) |
N3—C9—C8 | 110.3 (5) | C9—N3—C10 | 110.0 (5) |
N3—C9—H9A | 109.6 | ||
O1—C1—C2—C3 | 178.8 (4) | C5—C6—C7—N1 | 179.0 (5) |
C6—C1—C2—C3 | 0.1 (7) | C1—C6—C7—N1 | 1.5 (7) |
O1—C1—C2—Br1 | 0.6 (6) | N2—C8—C9—N3 | 55.4 (6) |
C6—C1—C2—Br1 | −178.1 (3) | N3—C11—C12—N2 | −56.9 (6) |
C1—C2—C3—C4 | −0.9 (7) | C6—C7—N1—N2 | −175.5 (4) |
Br1—C2—C3—C4 | 177.3 (4) | C7—N1—N2—C8 | −18.3 (7) |
C2—C3—C4—C5 | 1.0 (7) | C7—N1—N2—C12 | −154.6 (5) |
C2—C3—C4—Br2 | −175.8 (4) | C9—C8—N2—N1 | 172.3 (4) |
C3—C4—C5—C6 | −0.4 (7) | C9—C8—N2—C12 | −52.8 (6) |
Br2—C4—C5—C6 | 176.4 (4) | C11—C12—N2—N1 | −167.9 (4) |
C4—C5—C6—C1 | −0.4 (7) | C11—C12—N2—C8 | 53.0 (6) |
C4—C5—C6—C7 | −177.9 (4) | C12—C11—N3—C9 | 61.8 (6) |
O1—C1—C6—C5 | −178.2 (4) | C12—C11—N3—C10 | −176.8 (5) |
C2—C1—C6—C5 | 0.5 (7) | C8—C9—N3—C11 | −60.3 (6) |
O1—C1—C6—C7 | −0.7 (7) | C8—C9—N3—C10 | 177.9 (5) |
C2—C1—C6—C7 | 178.0 (4) |
Experimental details
Crystal data | |
Chemical formula | C12H15Br2N3O |
Mr | 377.09 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 294 |
a, b, c (Å) | 9.5733 (13), 9.5493 (13), 16.039 (2) |
β (°) | 105.236 (2) |
V (Å3) | 1414.8 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 5.72 |
Crystal size (mm) | 0.28 × 0.22 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.243, 0.565 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6952, 2493, 1846 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.134, 1.04 |
No. of reflections | 2493 |
No. of parameters | 165 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.93, −0.66 |
Computer programs: SMART (Bruker 1997), SAINT (Bruker 1997), SHELXTL (Bruker, 2001).
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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 C═N 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.