The skeleton, without hydrogen atoms, of the title molecule, C
10H
9BrN
2O
3, is planar, and intramolecular N—H
O and O—H
O hydrogen bonds contribute to this planarity. The molecules exist in the stereoisomeric
Z form.
Supporting information
CCDC reference: 202360
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.011 Å
- R factor = 0.071
- wR factor = 0.186
- Data-to-parameter ratio = 13.0
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level B:
CHEMS_01 Alert B The sum formula contains elements in the wrong order.
Br precedes C
Sequence must be C, H, then alphabetical.
PLAT_031 Alert B Refined Extinction Parameter within Range .... 1.64 Sigma
Alert Level C:
ABSTM_02 Alert C The ratio of expected to reported Tmax/Tmin(RR) is > 1.10
Tmin and Tmax reported: 0.756 0.989
Tmin and Tmax expected: 0.355 0.526
RR = 1.133
Please check that your absorption correction is appropriate.
REFLT_03
From the CIF: _diffrn_reflns_theta_max 69.88
From the CIF: _reflns_number_total 1912
TEST2: Reflns within _diffrn_reflns_theta_max
Count of symmetry unique reflns 2064
Completeness (_total/calc) 92.64%
Alert C: < 95% complete
General Notes
ABSTM_02 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 0.532
Tmax scaled 0.526 Tmin scaled 0.402
REFLT_03
From the CIF: _diffrn_reflns_theta_max 69.88
From the CIF: _reflns_number_total 1912
From the CIF: _diffrn_reflns_limit_ max hkl 8. 8. 11.
From the CIF: _diffrn_reflns_limit_ min hkl 0. -8. -11.
TEST1: Expected hkl limits for theta max
Calculated maximum hkl 8. 8. 13.
Calculated minimum hkl -8. -8. -13.
ALERT: Expected hkl max differ from CIF values
0 Alert Level A = Potentially serious problem
2 Alert Level B = Potential problem
2 Alert Level C = Please check
The title compound, (I), was prepared by the partial hydrolysis of ethyl 2-(2-bromophenylhydrazono)-3-oxobutyrate by the action of strong acids (Prasad et al., 1994) and was recrystallized from methanol at room temperature.
After checking their presence in the difference map, all the H atoms were placed at calculated positions and were allowed to ride on their respective parent atoms.
Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: MolEN (Fair, 1990); 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: SHELXL97.
2-(
p-Bromophenylhydrazono)-3-oxobutanoic acid
top
Crystal data top
C10H9BrN2O3 | Z = 2 |
Mr = 285.10 | F(000) = 284 |
Triclinic, P1 | Dx = 1.743 Mg m−3 |
Hall symbol: -P 1 | Cu Kα radiation, λ = 1.54180 Å |
a = 7.058 (4) Å | Cell parameters from 25 reflections |
b = 7.126 (3) Å | θ = 17.7–39.9° |
c = 11.311 (6) Å | µ = 5.14 mm−1 |
α = 77.05 (3)° | T = 293 K |
β = 86.35 (4)° | Elongated plate, light yellow |
γ = 78.47 (5)° | 0.25 × 0.19 × 0.13 mm |
V = 543.1 (5) Å3 | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | 1171 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.026 |
Graphite monochromator | θmax = 69.9°, θmin = 4.0° |
ω–2θ scans | h = 0→8 |
Absorption correction: ψ scan (North at el., 1968) | k = −8→8 |
Tmin = 0.756, Tmax = 0.989 | l = −11→11 |
2079 measured reflections | 3 standard reflections every 1 hr min |
1912 independent reflections | intensity decay: 0.0% |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.071 | H-atom parameters constrained |
wR(F2) = 0.186 | w = 1/[σ2(Fo2) + (0.1211P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.90 | (Δ/σ)max = 0.001 |
1912 reflections | Δρmax = 1.11 e Å−3 |
147 parameters | Δρmin = −0.91 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0018 (11) |
Crystal data top
C10H9BrN2O3 | γ = 78.47 (5)° |
Mr = 285.10 | V = 543.1 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.058 (4) Å | Cu Kα radiation |
b = 7.126 (3) Å | µ = 5.14 mm−1 |
c = 11.311 (6) Å | T = 293 K |
α = 77.05 (3)° | 0.25 × 0.19 × 0.13 mm |
β = 86.35 (4)° | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | 1171 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North at el., 1968) | Rint = 0.026 |
Tmin = 0.756, Tmax = 0.989 | 3 standard reflections every 1 hr min |
2079 measured reflections | intensity decay: 0.0% |
1912 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.071 | 0 restraints |
wR(F2) = 0.186 | H-atom parameters constrained |
S = 0.90 | Δρmax = 1.11 e Å−3 |
1912 reflections | Δρmin = −0.91 e Å−3 |
147 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 | x | y | z | Uiso*/Ueq | |
Br | 0.92940 (15) | 0.12344 (13) | 0.13951 (8) | 0.0729 (5) | |
O1 | −0.0291 (8) | 0.4290 (8) | 0.8160 (5) | 0.0663 (14) | |
H1O | 0.0430 | 0.4131 | 0.8729 | 0.080* | |
O2 | −0.0050 (8) | 0.3976 (8) | 0.6254 (5) | 0.0690 (15) | |
O3 | 0.2778 (9) | 0.3219 (9) | 0.9413 (5) | 0.0757 (16) | |
N1 | 0.3493 (10) | 0.3007 (8) | 0.5359 (5) | 0.0552 (15) | |
H1N | 0.2291 | 0.3418 | 0.5189 | 0.083* | |
N2 | 0.4070 (10) | 0.2778 (8) | 0.6462 (5) | 0.0566 (16) | |
C1 | 0.4867 (12) | 0.2573 (9) | 0.4446 (6) | 0.0512 (18) | |
C2 | 0.4237 (13) | 0.2738 (10) | 0.3306 (6) | 0.061 (2) | |
H2 | 0.2925 | 0.3119 | 0.3143 | 0.073* | |
C3 | 0.5549 (12) | 0.2340 (10) | 0.2396 (7) | 0.060 (2) | |
H3 | 0.5125 | 0.2447 | 0.1617 | 0.072* | |
C4 | 0.7473 (12) | 0.1788 (9) | 0.2643 (6) | 0.0529 (18) | |
C5 | 0.8127 (13) | 0.1655 (11) | 0.3788 (6) | 0.062 (2) | |
H5 | 0.9442 | 0.1292 | 0.3947 | 0.074* | |
C6 | 0.6808 (13) | 0.2066 (10) | 0.4696 (6) | 0.058 (2) | |
H6 | 0.7229 | 0.1999 | 0.5470 | 0.069* | |
C7 | 0.2884 (12) | 0.3141 (9) | 0.7348 (6) | 0.0521 (18) | |
C8 | 0.0739 (13) | 0.3820 (10) | 0.7206 (7) | 0.060 (2) | |
C9 | 0.3764 (13) | 0.2826 (11) | 0.8530 (7) | 0.062 (2) | |
C10 | 0.5880 (13) | 0.2057 (14) | 0.8624 (8) | 0.081 (3) | |
H10A | 0.6363 | 0.2423 | 0.9297 | 0.122* | |
H10B | 0.6521 | 0.2597 | 0.7890 | 0.122* | |
H10C | 0.6124 | 0.0653 | 0.8748 | 0.122* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br | 0.0948 (8) | 0.0673 (6) | 0.0556 (6) | −0.0121 (4) | 0.0116 (4) | −0.0181 (4) |
O1 | 0.070 (4) | 0.084 (4) | 0.046 (3) | −0.014 (3) | 0.001 (3) | −0.014 (3) |
O2 | 0.079 (4) | 0.087 (4) | 0.041 (3) | −0.017 (3) | −0.010 (3) | −0.010 (2) |
O3 | 0.099 (5) | 0.092 (4) | 0.040 (3) | −0.026 (3) | 0.001 (3) | −0.016 (3) |
N1 | 0.077 (4) | 0.052 (3) | 0.041 (4) | −0.018 (3) | 0.002 (3) | −0.013 (2) |
N2 | 0.088 (5) | 0.047 (3) | 0.036 (4) | −0.019 (3) | 0.003 (3) | −0.006 (2) |
C1 | 0.075 (5) | 0.034 (3) | 0.046 (4) | −0.016 (3) | 0.004 (4) | −0.008 (3) |
C2 | 0.087 (6) | 0.059 (4) | 0.040 (4) | −0.017 (4) | −0.007 (4) | −0.014 (3) |
C3 | 0.084 (6) | 0.056 (4) | 0.041 (4) | −0.008 (4) | −0.004 (4) | −0.016 (3) |
C4 | 0.074 (5) | 0.037 (3) | 0.046 (4) | −0.002 (3) | 0.008 (3) | −0.014 (3) |
C5 | 0.083 (6) | 0.060 (4) | 0.040 (4) | −0.004 (4) | −0.012 (4) | −0.010 (3) |
C6 | 0.088 (6) | 0.059 (4) | 0.027 (4) | −0.021 (4) | −0.012 (4) | −0.005 (3) |
C7 | 0.086 (6) | 0.043 (3) | 0.030 (4) | −0.022 (4) | −0.005 (3) | −0.004 (3) |
C8 | 0.081 (6) | 0.051 (4) | 0.047 (4) | −0.019 (4) | −0.004 (4) | −0.004 (3) |
C9 | 0.087 (6) | 0.062 (4) | 0.039 (4) | −0.024 (4) | −0.005 (4) | −0.004 (3) |
C10 | 0.079 (7) | 0.099 (7) | 0.060 (6) | −0.016 (5) | −0.017 (5) | −0.002 (5) |
Geometric parameters (Å, º) top
Br—C4 | 1.901 (7) | C3—C4 | 1.365 (11) |
O1—C8 | 1.330 (9) | C3—H3 | 0.9300 |
O1—H1O | 0.8200 | C4—C5 | 1.379 (10) |
O2—C8 | 1.217 (9) | C5—C6 | 1.383 (11) |
O3—C9 | 1.233 (9) | C5—H5 | 0.9300 |
N1—N2 | 1.302 (8) | C6—H6 | 0.9300 |
N1—C1 | 1.414 (9) | C7—C9 | 1.462 (10) |
N1—H1N | 0.8600 | C7—C8 | 1.502 (12) |
N2—C7 | 1.302 (9) | C9—C10 | 1.487 (12) |
C1—C2 | 1.362 (10) | C10—H10A | 0.9600 |
C1—C6 | 1.376 (11) | C10—H10B | 0.9600 |
C2—C3 | 1.380 (10) | C10—H10C | 0.9600 |
C2—H2 | 0.9300 | | |
| | | |
Br···O1i | 3.547 (6) | N1···C6i | 3.461 (9) |
Br···O3ii | 3.513 (7) | N2···C1i | 3.459 (9) |
O1···C2iii | 3.413 (10) | N2···C4v | 3.550 (9) |
O1···C10iv | 3.358 (11) | C3···C9i | 3.491 (11) |
O2···O2iii | 2.888 (8) | C4···C7v | 3.569 (10) |
O2···C2iii | 3.469 (10) | C5···C8i | 3.406 (11) |
O2···C6iv | 3.558 (10) | | |
| | | |
C8—O1—H1O | 109.5 | C6—C5—H5 | 120.3 |
N2—N1—C1 | 119.2 (7) | C1—C6—C5 | 119.4 (7) |
N2—N1—H1N | 120.4 | C1—C6—H6 | 120.3 |
C1—N1—H1N | 120.4 | C5—C6—H6 | 120.3 |
C7—N2—N1 | 122.5 (7) | N2—C7—C9 | 115.8 (8) |
C2—C1—C6 | 120.8 (7) | N2—C7—C8 | 123.6 (6) |
C2—C1—N1 | 118.8 (8) | C9—C7—C8 | 120.6 (7) |
C6—C1—N1 | 120.4 (7) | O2—C8—O1 | 120.3 (8) |
C1—C2—C3 | 119.9 (8) | O2—C8—C7 | 122.1 (7) |
C1—C2—H2 | 120.0 | O1—C8—C7 | 117.6 (7) |
C3—C2—H2 | 120.0 | O3—C9—C7 | 120.7 (8) |
C4—C3—C2 | 119.7 (7) | O3—C9—C10 | 121.3 (7) |
C4—C3—H3 | 120.2 | C7—C9—C10 | 118.0 (8) |
C2—C3—H3 | 120.2 | C9—C10—H10A | 109.5 |
C3—C4—C5 | 120.8 (7) | C9—C10—H10B | 109.5 |
C3—C4—Br | 120.0 (5) | H10A—C10—H10B | 109.5 |
C5—C4—Br | 119.2 (6) | C9—C10—H10C | 109.5 |
C4—C5—C6 | 119.3 (8) | H10A—C10—H10C | 109.5 |
C4—C5—H5 | 120.3 | H10B—C10—H10C | 109.5 |
| | | |
C1—N1—N2—C7 | −179.7 (6) | C4—C5—C6—C1 | 0.9 (11) |
N2—N1—C1—C2 | 177.3 (6) | N1—N2—C7—C9 | −179.5 (6) |
N2—N1—C1—C6 | −5.2 (9) | N1—N2—C7—C8 | 1.2 (10) |
C6—C1—C2—C3 | 1.9 (11) | N2—C7—C8—O2 | 4.0 (11) |
N1—C1—C2—C3 | 179.4 (6) | C9—C7—C8—O2 | −175.3 (7) |
C1—C2—C3—C4 | −0.2 (11) | N2—C7—C8—O1 | −174.7 (6) |
C2—C3—C4—C5 | −1.1 (11) | C9—C7—C8—O1 | 6.0 (10) |
C2—C3—C4—Br | 180.0 (5) | N2—C7—C9—O3 | 176.4 (6) |
C3—C4—C5—C6 | 0.7 (11) | C8—C7—C9—O3 | −4.2 (11) |
Br—C4—C5—C6 | 179.7 (5) | N2—C7—C9—C10 | −2.4 (10) |
C2—C1—C6—C5 | −2.2 (10) | C8—C7—C9—C10 | 176.9 (7) |
N1—C1—C6—C5 | −179.7 (6) | | |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1, y, z−1; (iii) −x, −y+1, −z+1; (iv) x−1, y, z; (v) −x+1, −y, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O2 | 0.86 | 2.01 | 2.656 (9) | 131 |
N1—H1N···O2iii | 0.86 | 2.53 | 3.252 (9) | 142 |
O1—H1O···O3 | 0.82 | 1.81 | 2.555 (8) | 150 |
Symmetry code: (iii) −x, −y+1, −z+1. |
Experimental details
Crystal data |
Chemical formula | C10H9BrN2O3 |
Mr | 285.10 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 7.058 (4), 7.126 (3), 11.311 (6) |
α, β, γ (°) | 77.05 (3), 86.35 (4), 78.47 (5) |
V (Å3) | 543.1 (5) |
Z | 2 |
Radiation type | Cu Kα |
µ (mm−1) | 5.14 |
Crystal size (mm) | 0.25 × 0.19 × 0.13 |
|
Data collection |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North at el., 1968) |
Tmin, Tmax | 0.756, 0.989 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2079, 1912, 1171 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.609 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.071, 0.186, 0.90 |
No. of reflections | 1912 |
No. of parameters | 147 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.11, −0.91 |
Selected geometric parameters (Å, º) topBr—C4 | 1.901 (7) | N1—C1 | 1.414 (9) |
O1—C8 | 1.330 (9) | N2—C7 | 1.302 (9) |
O2—C8 | 1.217 (9) | C7—C9 | 1.462 (10) |
O3—C9 | 1.233 (9) | C7—C8 | 1.502 (12) |
N1—N2 | 1.302 (8) | C9—C10 | 1.487 (12) |
| | | |
Br···O1i | 3.547 (6) | N1···C6i | 3.461 (9) |
Br···O3ii | 3.513 (7) | N2···C1i | 3.459 (9) |
O1···C2iii | 3.413 (10) | N2···C4v | 3.550 (9) |
O1···C10iv | 3.358 (11) | C3···C9i | 3.491 (11) |
O2···O2iii | 2.888 (8) | C4···C7v | 3.569 (10) |
O2···C2iii | 3.469 (10) | C5···C8i | 3.406 (11) |
O2···C6iv | 3.558 (10) | | |
| | | |
N2—N1—C1 | 119.2 (7) | C9—C7—C8 | 120.6 (7) |
C7—N2—N1 | 122.5 (7) | O2—C8—O1 | 120.3 (8) |
C2—C1—N1 | 118.8 (8) | O2—C8—C7 | 122.1 (7) |
C6—C1—N1 | 120.4 (7) | O1—C8—C7 | 117.6 (7) |
C3—C4—Br | 120.0 (5) | O3—C9—C7 | 120.7 (8) |
C5—C4—Br | 119.2 (6) | O3—C9—C10 | 121.3 (7) |
N2—C7—C9 | 115.8 (8) | C7—C9—C10 | 118.0 (8) |
N2—C7—C8 | 123.6 (6) | | |
| | | |
C1—N1—N2—C7 | −179.7 (6) | N2—C7—C8—O2 | 4.0 (11) |
N2—N1—C1—C2 | 177.3 (6) | C9—C7—C8—O2 | −175.3 (7) |
N2—N1—C1—C6 | −5.2 (9) | N2—C7—C8—O1 | −174.7 (6) |
N1—C1—C2—C3 | 179.4 (6) | N2—C7—C9—O3 | 176.4 (6) |
N1—C1—C6—C5 | −179.7 (6) | N2—C7—C9—C10 | −2.4 (10) |
N1—N2—C7—C9 | −179.5 (6) | C8—C7—C9—C10 | 176.9 (7) |
N1—N2—C7—C8 | 1.2 (10) | | |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1, y, z−1; (iii) −x, −y+1, −z+1; (iv) x−1, y, z; (v) −x+1, −y, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O2 | 0.86 | 2.01 | 2.656 (9) | 131.2 |
N1—H1N···O2iii | 0.86 | 2.53 | 3.252 (9) | 141.9 |
O1—H1O···O3 | 0.82 | 1.81 | 2.555 (8) | 150.4 |
Symmetry code: (iii) −x, −y+1, −z+1. |
As a part of our project to study the crystal structures of a series of phenylhydrazones and their stereochemistry, the crystal structure of the title compound, (I), has been determined. Earlier, this laboratory has reported two related structures, viz. 2-(2-methoxyphenylhydrazono)-3-oxobutanoic acid (Rani et al., 2002a) and 3-oxo-2-(phenylhydrazono)butanoic acid (Rani et al., 2002b), compound (I) being a Br derivative of the latter. The replacement of a H atom by a Br atom has effectively increased the volume of the cell by 24.92 Å3 per Br atom. The bond lengths and angles in (I) show normal values and are comparable with those observed in the two reported structures. The molecule is nearly planar, with atoms O1 and C10 displaced from the mean least-squares plane by −0.108 (5) and 0.127 (10) Å, respectively (on opposite sides). The planarity of the molecule is facilitated by the intramolecular hydrogen bonds. The N1—H1N bond is involved in the formation of a bifurcated hydrogen bond, the shorter interaction, called the major component (Steiner, 2002), is an intramolecular N1—H1N···O2 hydrogen bond with the carbonyl O atom of the carboxyl group, whereas the longer one, the minor component, is an intermolecular N1—H1N···O2(-x, 1 − y, 1 − z) hydrogen bond, which links two molecules via hydrogen-bond dimers across a centre of symmetry (Table 3). The carbonyl O atom of the carbomethoxy group is also involved in an intramolecular O1—H1O···O3 hydrogen bond with the carboxyl group (Fig. 1). Along the b-cell direction, the molecules related by inversion are stacked alternatively 3.419 (5) and 3.490 (5) Å apart, optimum distances for π–π stacking interactions. The short contacts observed in the structure are listed in Table 2. The distance O2···O2(-x, 1 − y, 1 − z) of 2.888 (8) Å is less than the sum of the van der Waals radii, but since the C8—O2 bond length is 1.217 (9) Å, O2 is the double-bonded carbonyl O atom, hence the O2···O2 contact must be regarded as a strong van der Waals interaction.