Literature DB >> 21203248

(E)-Methyl N'-(4-bromo-benzyl-idene)-hydrazinecarboxyl-ate at 123 K.

Rong Sun1, Xiang-Wei Cheng.   

Abstract

The title compound, C(9)H(9)BrN(2)O(2), crystallizes with two independent but essentially identical mol-ecules in the asymmetric unit. Each mol-ecule adopts a trans configuration with respect to the C=N bond. In one of the mol-ecules, the dihedral angle between the benzene ring and the hydrazinecarboxylic acid plane is 24.9 (2)°, and that in the other mol-ecule is 16.1 (2)°. The mol-ecules are linked into a three-dimensional network via inter-molecular N-H⋯O, C-H⋯O, C-H⋯N and C-H⋯Br hydrogen bonds. An intramolecular N-H⋯O hydrogen bond is also present.

Entities:  

Year:  2008        PMID： 21203248      PMCID： PMC2962168          DOI： 10.1107/S1600536808021983

Source DB:  PubMed          Journal:  Acta Crystallogr Sect E Struct Rep Online        ISSN： 1600-5368


Related literature

For general background, see: Parashar et al. (1988 ▶); Hadjoudis et al. (1987 ▶); Borg et al. (1999 ▶). For a related structure, see: Cheng (2008 ▶).

Experimental

Crystal data

C9H9BrN2O2 M = 257.09 Monoclinic, a = 13.8585 (10) Å b = 9.5257 (7) Å c = 15.5871 (11) Å β = 95.967 (3)° V = 2046.5 (3) Å3 Z = 8 Mo Kα radiation μ = 3.99 mm−1 T = 123 (2) K 0.30 × 0.26 × 0.25 mm

Data collection

Bruker SMART CCD area-detector diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2002 ▶) T min = 0.320, T max = 0.367 20978 measured reflections 3610 independent reflections 2615 reflections with I > 2σ(I) R int = 0.056

Refinement

R[F 2 > 2σ(F 2)] = 0.036 wR(F 2) = 0.099 S = 1.05 3610 reflections 254 parameters H-atom parameters constrained Δρmax = 0.76 e Å−3 Δρmin = −0.49 e Å−3 Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; 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. Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808021983/ci2632sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S1600536808021983/ci2632Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report
C9H9BrN2O2F000 = 1024
Mr = 257.09Dx = 1.669 Mg m−3
Monoclinic, P21/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3610 reflections
a = 13.8585 (10) Åθ = 1.5–25.0º
b = 9.5257 (7) ŵ = 3.99 mm−1
c = 15.5871 (11) ÅT = 123 (2) K
β = 95.967 (3)ºBlock, colourless
V = 2046.5 (3) Å30.30 × 0.26 × 0.25 mm
Z = 8
Bruker SMART CCD area-detector diffractometer3610 independent reflections
Radiation source: fine-focus sealed tube2615 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.056
T = 123(2) Kθmax = 25.0º
φ and ω scansθmin = 1.5º
Absorption correction: multi-scan(SADABS; Bruker, 2002)h = −16→16
Tmin = 0.320, Tmax = 0.368k = −11→9
20978 measured reflectionsl = −18→18
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.036  w = 1/[σ2(Fo2) + (0.048P)2 + 0.8965P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.099(Δ/σ)max = 0.001
S = 1.05Δρmax = 0.76 e Å−3
3610 reflectionsΔρmin = −0.49 e Å−3
254 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0078 (6)
Secondary atom site location: difference Fourier map
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.
xyzUiso*/Ueq
Br20.54645 (3)0.79291 (5)0.97542 (3)0.07171 (19)
Br10.53903 (3)0.13944 (5)0.80455 (3)0.0767 (2)
O2−0.13460 (16)0.5200 (3)0.56109 (14)0.0519 (6)
O1−0.05639 (17)0.5733 (3)0.69189 (14)0.0545 (6)
O3−0.01087 (16)0.2800 (3)0.95955 (15)0.0562 (6)
O4−0.12520 (16)0.3158 (3)0.84755 (15)0.0558 (6)
N2−0.00584 (19)0.3978 (3)0.60735 (17)0.0473 (7)
H2A−0.02240.34310.56280.057*
N40.0057 (2)0.4480 (3)0.85778 (17)0.0484 (7)
H4A−0.02230.49150.81200.058*
N30.09646 (19)0.4870 (3)0.89337 (16)0.0473 (7)
N10.07984 (19)0.3755 (3)0.65906 (16)0.0447 (7)
C8−0.0638 (2)0.5048 (4)0.6263 (2)0.0423 (7)
C60.2240 (2)0.2373 (3)0.6832 (2)0.0420 (7)
C70.1282 (2)0.2684 (4)0.6391 (2)0.0443 (8)
H70.10120.20750.59460.053*
C160.1337 (2)0.5923 (4)0.8575 (2)0.0473 (8)
H160.09770.63920.81090.057*
C140.2665 (3)0.7650 (4)0.8564 (2)0.0527 (9)
H140.22650.81830.81540.063*
C30.2686 (3)0.1104 (4)0.6674 (2)0.0519 (9)
H30.23500.04340.63040.062*
C17−0.0398 (2)0.3416 (4)0.8945 (2)0.0435 (8)
C150.2313 (2)0.6402 (3)0.8879 (2)0.0449 (8)
C18−0.1841 (3)0.2064 (4)0.8805 (3)0.0655 (10)
H18A−0.24420.19550.84210.098*
H18B−0.19980.23210.93840.098*
H18C−0.14810.11770.88350.098*
C40.3665 (2)0.3015 (4)0.7766 (2)0.0519 (9)
H40.40040.36640.81500.062*
C20.3607 (3)0.0802 (4)0.7048 (2)0.0566 (9)
H20.3904−0.00690.69370.068*
C50.2746 (3)0.3315 (4)0.7396 (2)0.0508 (9)
H50.24500.41780.75260.061*
C130.2918 (3)0.5639 (4)0.9480 (2)0.0552 (9)
H130.26910.47850.97030.066*
C100.3585 (3)0.8122 (4)0.8839 (2)0.0562 (9)
H100.38150.89790.86250.067*
C110.4167 (2)0.7338 (4)0.9426 (2)0.0521 (9)
C10.4090 (2)0.1767 (4)0.7578 (2)0.0484 (8)
C9−0.2049 (3)0.6282 (4)0.5732 (3)0.0651 (10)
H9A−0.25340.63140.52280.098*
H9B−0.17210.71920.58020.098*
H9C−0.23710.60730.62480.098*
C120.3837 (3)0.6103 (4)0.9756 (2)0.0575 (9)
H120.42410.55781.01680.069*
U11U22U33U12U13U23
Br20.0498 (2)0.0817 (3)0.0820 (3)−0.0070 (2)−0.00095 (19)−0.0060 (2)
Br10.0418 (2)0.1006 (4)0.0865 (3)0.0154 (2)0.00182 (18)0.0141 (2)
O20.0420 (12)0.0612 (15)0.0504 (13)0.0084 (11)−0.0059 (10)−0.0043 (11)
O10.0605 (15)0.0590 (15)0.0427 (13)0.0140 (12)−0.0011 (11)−0.0030 (12)
O30.0524 (14)0.0644 (17)0.0493 (14)0.0002 (12)−0.0066 (11)0.0131 (12)
O40.0439 (13)0.0578 (15)0.0625 (14)−0.0003 (11)−0.0102 (11)0.0068 (12)
N20.0409 (15)0.0501 (17)0.0487 (15)0.0057 (13)−0.0060 (12)−0.0100 (13)
N40.0487 (16)0.0476 (18)0.0459 (15)0.0009 (13)−0.0096 (12)0.0090 (13)
N30.0452 (16)0.0499 (18)0.0453 (15)0.0034 (13)−0.0025 (12)−0.0006 (13)
N10.0415 (15)0.0497 (18)0.0420 (14)0.0004 (13)−0.0005 (11)0.0008 (12)
C80.0357 (16)0.049 (2)0.0417 (18)−0.0013 (15)0.0014 (13)0.0047 (16)
C60.0416 (17)0.0395 (19)0.0449 (17)0.0017 (15)0.0045 (13)0.0022 (14)
C70.0448 (18)0.040 (2)0.0470 (18)−0.0026 (15)0.0012 (14)−0.0019 (15)
C160.052 (2)0.045 (2)0.0430 (18)0.0084 (16)0.0009 (15)−0.0022 (16)
C140.057 (2)0.048 (2)0.052 (2)0.0085 (17)−0.0007 (16)0.0052 (17)
C30.055 (2)0.043 (2)0.057 (2)−0.0030 (17)0.0008 (16)−0.0047 (16)
C170.0405 (17)0.045 (2)0.0437 (18)0.0097 (15)−0.0005 (14)−0.0026 (15)
C150.0474 (18)0.043 (2)0.0436 (17)0.0068 (16)0.0022 (14)−0.0030 (15)
C180.048 (2)0.070 (3)0.078 (3)−0.005 (2)−0.0002 (18)0.001 (2)
C40.0491 (19)0.048 (2)0.056 (2)−0.0009 (17)−0.0036 (16)−0.0030 (16)
C20.055 (2)0.049 (2)0.068 (2)0.0130 (18)0.0124 (18)0.0032 (18)
C50.053 (2)0.043 (2)0.055 (2)0.0035 (16)−0.0003 (16)−0.0064 (16)
C130.061 (2)0.045 (2)0.058 (2)0.0010 (18)0.0006 (17)0.0061 (17)
C100.059 (2)0.052 (2)0.058 (2)−0.0010 (18)0.0059 (17)0.0058 (17)
C110.0416 (18)0.057 (2)0.057 (2)0.0005 (17)0.0024 (15)−0.0102 (17)
C10.0379 (17)0.054 (2)0.0537 (19)0.0032 (16)0.0041 (15)0.0096 (17)
C90.0423 (19)0.072 (3)0.078 (3)0.0148 (19)−0.0051 (18)0.004 (2)
C120.054 (2)0.053 (2)0.062 (2)0.0061 (18)−0.0060 (17)0.0071 (18)
Br2—C111.903 (3)C14—C151.394 (5)
Br1—C11.906 (3)C14—H140.95
O2—C81.345 (4)C3—C21.377 (5)
O2—C91.445 (4)C3—H30.95
O1—C81.208 (4)C15—C131.394 (5)
O3—C171.204 (4)C18—H18A0.98
O4—C171.348 (4)C18—H18B0.98
O4—C181.450 (5)C18—H18C0.98
N2—C81.349 (4)C4—C11.371 (5)
N2—N11.380 (3)C4—C51.374 (5)
N2—H2A0.88C4—H40.95
N4—C171.352 (4)C2—C11.364 (5)
N4—N31.372 (4)C2—H20.95
N4—H4A0.88C5—H50.95
N3—C161.283 (4)C13—C121.375 (5)
N1—C71.277 (4)C13—H130.95
C6—C51.393 (4)C10—C111.376 (5)
C6—C31.392 (5)C10—H100.95
C6—C71.460 (4)C11—C121.380 (5)
C7—H70.95C9—H9A0.98
C16—C151.458 (5)C9—H9B0.98
C16—H160.95C9—H9C0.98
C14—C101.377 (5)C12—H120.95
C8—O2—C9115.3 (3)O4—C18—H18B109.5
C17—O4—C18115.7 (3)H18A—C18—H18B109.5
C8—N2—N1118.9 (3)O4—C18—H18C109.5
C8—N2—H2A120.5H18A—C18—H18C109.5
N1—N2—H2A120.5H18B—C18—H18C109.5
C17—N4—N3118.7 (3)C1—C4—C5119.4 (3)
C17—N4—H4A120.7C1—C4—H4120.3
N3—N4—H4A120.7C5—C4—H4120.3
C16—N3—N4115.4 (3)C1—C2—C3119.4 (3)
C7—N1—N2115.0 (3)C1—C2—H2120.3
O1—C8—O2124.9 (3)C3—C2—H2120.3
O1—C8—N2126.4 (3)C4—C5—C6121.0 (3)
O2—C8—N2108.6 (3)C4—C5—H5119.5
C5—C6—C3117.9 (3)C6—C5—H5119.5
C5—C6—C7122.7 (3)C12—C13—C15121.0 (3)
C3—C6—C7119.5 (3)C12—C13—H13119.5
N1—C7—C6121.4 (3)C15—C13—H13119.5
N1—C7—H7119.3C14—C10—C11119.3 (3)
C6—C7—H7119.3C14—C10—H10120.4
N3—C16—C15120.3 (3)C11—C10—H10120.4
N3—C16—H16119.9C10—C11—C12121.1 (3)
C15—C16—H16119.9C10—C11—Br2119.3 (3)
C10—C14—C15121.1 (3)C12—C11—Br2119.5 (3)
C10—C14—H14119.5C2—C1—C4121.3 (3)
C15—C14—H14119.5C2—C1—Br1119.4 (3)
C2—C3—C6121.1 (3)C4—C1—Br1119.3 (3)
C2—C3—H3119.5O2—C9—H9A109.5
C6—C3—H3119.5O2—C9—H9B109.5
O3—C17—O4124.4 (3)H9A—C9—H9B109.5
O3—C17—N4126.4 (3)O2—C9—H9C109.5
O4—C17—N4109.2 (3)H9A—C9—H9C109.5
C13—C15—C14118.2 (3)H9B—C9—H9C109.5
C13—C15—C16121.8 (3)C13—C12—C11119.3 (3)
C14—C15—C16120.0 (3)C13—C12—H12120.3
O4—C18—H18A109.5C11—C12—H12120.3
C17—N4—N3—C16−177.3 (3)N3—C16—C15—C138.7 (5)
C8—N2—N1—C7176.9 (3)N3—C16—C15—C14−171.7 (3)
C9—O2—C8—O10.5 (5)C6—C3—C2—C1−0.2 (5)
C9—O2—C8—N2178.0 (3)C1—C4—C5—C60.0 (5)
N1—N2—C8—O1−11.7 (5)C3—C6—C5—C41.7 (5)
N1—N2—C8—O2170.8 (3)C7—C6—C5—C4−176.8 (3)
N2—N1—C7—C6174.9 (3)C14—C15—C13—C120.0 (5)
C5—C6—C7—N1−9.9 (5)C16—C15—C13—C12179.6 (3)
C3—C6—C7—N1171.6 (3)C15—C14—C10—C110.7 (5)
N4—N3—C16—C15−177.9 (3)C14—C10—C11—C12−1.2 (6)
C5—C6—C3—C2−1.6 (5)C14—C10—C11—Br2176.3 (3)
C7—C6—C3—C2177.0 (3)C3—C2—C1—C42.0 (5)
C18—O4—C17—O30.5 (5)C3—C2—C1—Br1−176.7 (3)
C18—O4—C17—N4−178.2 (3)C5—C4—C1—C2−1.8 (5)
N3—N4—C17—O34.3 (5)C5—C4—C1—Br1176.8 (3)
N3—N4—C17—O4−177.0 (3)C15—C13—C12—C11−0.5 (6)
C10—C14—C15—C13−0.1 (5)C10—C11—C12—C131.1 (6)
C10—C14—C15—C16−179.7 (3)Br2—C11—C12—C13−176.4 (3)
D—H···AD—HH···AD···AD—H···A
N2—H2A···O3i0.882.012.854 (4)160
N4—H4A···O10.882.042.896 (3)165
C7—H7···O3i0.952.493.261 (4)139
C9—H9A···Br2ii0.982.893.697 (3)141
C18—H18C···N1iii0.982.603.548 (5)162
Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯AD—HH⋯AD⋯AD—H⋯A
N2—H2A⋯O3i0.882.012.854 (4)160
N4—H4A⋯O10.882.042.896 (3)165
C7—H7⋯O3i0.952.493.261 (4)139
C9—H9A⋯Br2ii0.982.893.697 (3)141
C18—H18C⋯N1iii0.982.603.548 (5)162

Symmetry codes: (i) ; (ii) ; (iii) .

  3 in total

1.  A short history of SHELX.

Authors:  George M Sheldrick
Journal:  Acta Crystallogr A       Date:  2007-12-21       Impact factor: 2.290

2.  Design, synthesis, and evaluation of Phe-Gly mimetics: heterocyclic building blocks for pseudopeptides.

Authors:  S Borg; R C Vollinga; M Labarre; K Payza; L Terenius; K Luthman
Journal:  J Med Chem       Date:  1999-10-21       Impact factor: 7.446

3.  Ethyl N'-[(E)-4-hydroxy-benzyl-idene]hydrazinecarboxyl-ate at 123 K.

Authors:  Xiang-Wei Cheng
Journal:  Acta Crystallogr Sect E Struct Rep Online       Date:  2008-07-05
  3 in total

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