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In the title compound, C
9H
10N
2O
2, the amide groups are rotated out of the C(ONH
2)-C(HPh)-C(ONH
2) plane by
ca 25-47° and the phenyl ring is almost perpendicular to this plane. The crystal structure is stabilized by intra- and intermolecular N-H
O hydrogen bonds.
Supporting information
CCDC reference: 152682
A suspension of diethyl phenylmalonate and NH3 solution was refluxed for 1 week with vigorous stirring. The crystals of (I) used in the X-ray measurement were obtained by slow evaporation of an ethanol solution.
All the H atoms were located from the difference Fourier map and were refined isotropically. The C—H range is 0.94 (2)–1.02 (2) Å and the N—H range is 0.85 (2)–0.94 (2) Å.
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1990); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation & Rigaku Corporation, 1999); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: TEXSAN; software used to prepare material for publication: TEXSAN.
Crystal data top
| C9H10N2O2 | Dx = 1.367 Mg m−3 |
| Mr = 178.19 | Mo Kα radiation, λ = 0.7107 Å |
| Monoclinic, P21/n | Cell parameters from 25 reflections |
| a = 9.079 (2) Å | θ = 14.6–15.0° |
| b = 7.555 (2) Å | µ = 0.10 mm−1 |
| c = 13.015 (2) Å | T = 296 K |
| β = 104.10 (1)° | Prismatic, colorless |
| V = 865.8 (3) Å3 | 0.20 × 0.20 × 0.10 mm |
| Z = 4 | |
Data collection top
Rigaku AFC-5R
diffractometer | θmax = 27.5° |
| ω–2θ scans | h = 0→11 |
| 2275 measured reflections | k = −9→0 |
| 1994 independent reflections | l = −16→16 |
| 1347 reflections with I > 2σ(I) | 3 standard reflections every 150 reflections |
| Rint = 0.016 | intensity decay: 2.0% |
Refinement top
| Refinement on F2 | All H-atom parameters refined |
| R[F2 > 2σ(F2)] = 0.038 | w = 1/[σ2(Fo2) + {0.050[Max(Fo2,0) + 2Fc2]/3}2] |
| wR(F2) = 0.104 | (Δ/σ)max = 0.004 |
| S = 1.23 | Δρmax = 0.54 e Å−3 |
| 1658 reflections | Δρmin = −0.22 e Å−3 |
| 158 parameters | |
Crystal data top
| C9H10N2O2 | V = 865.8 (3) Å3 |
| Mr = 178.19 | Z = 4 |
| Monoclinic, P21/n | Mo Kα radiation |
| a = 9.079 (2) Å | µ = 0.10 mm−1 |
| b = 7.555 (2) Å | T = 296 K |
| c = 13.015 (2) Å | 0.20 × 0.20 × 0.10 mm |
| β = 104.10 (1)° | |
Data collection top
Rigaku AFC-5R
diffractometer | Rint = 0.016 |
| 2275 measured reflections | 3 standard reflections every 150 reflections |
| 1994 independent reflections | intensity decay: 2.0% |
| 1347 reflections with I > 2σ(I) | |
Refinement top
| R[F2 > 2σ(F2)] = 0.038 | 158 parameters |
| wR(F2) = 0.104 | All H-atom parameters refined |
| S = 1.23 | Δρmax = 0.54 e Å−3 |
| 1658 reflections | Δρmin = −0.22 e Å−3 |
Special details top
Refinement. Refinement using reflections with F2 > 0.5 σ(F2). The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top| | x | y | z | Uiso*/Ueq | |
| O(1) | −0.3987 (1) | −0.0458 (2) | 0.14484 (9) | 0.0421 (3) | |
| O(2) | −0.0650 (1) | −0.2840 (2) | 0.01448 (8) | 0.0380 (3) | |
| N(1) | −0.3087 (2) | −0.0668 (2) | −0.0008 (1) | 0.0449 (4) | |
| N(2) | −0.0672 (2) | −0.4955 (2) | 0.1354 (1) | 0.0386 (4) | |
| C(1) | −0.3028 (2) | −0.0996 (2) | 0.0998 (1) | 0.0294 (4) | |
| C(2) | −0.1680 (2) | −0.2077 (2) | 0.1634 (1) | 0.0276 (4) | |
| C(3) | −0.0958 (2) | −0.3331 (2) | 0.0975 (1) | 0.0289 (4) | |
| C(4) | −0.0465 (2) | −0.0843 (2) | 0.2279 (1) | 0.0294 (4) | |
| C(5) | −0.0096 (2) | −0.0941 (3) | 0.3374 (1) | 0.0403 (5) | |
| C(6) | 0.1028 (2) | 0.0151 (3) | 0.3968 (1) | 0.0495 (5) | |
| C(7) | 0.1798 (2) | 0.1326 (3) | 0.3481 (2) | 0.0484 (5) | |
| C(8) | 0.1430 (2) | 0.1433 (3) | 0.2385 (2) | 0.0473 (5) | |
| C(9) | 0.0297 (2) | 0.0362 (2) | 0.1790 (1) | 0.0396 (5) | |
| H(1) | −0.063 (2) | −0.183 (3) | 0.372 (1) | 0.046 (5)* | |
| H(2) | 0.130 (3) | 0.006 (3) | 0.472 (2) | 0.058 (6)* | |
| H(3) | 0.262 (3) | 0.208 (3) | 0.393 (2) | 0.069 (7)* | |
| H(4) | 0.201 (2) | 0.228 (3) | 0.202 (2) | 0.060 (6)* | |
| H(5) | 0.004 (2) | 0.044 (3) | 0.100 (2) | 0.055 (6)* | |
| H(6) | −0.241 (3) | −0.112 (3) | −0.030 (2) | 0.067 (7)* | |
| H(7) | −0.388 (3) | −0.018 (3) | −0.039 (2) | 0.059 (6)* | |
| H(8) | −0.023 (2) | −0.573 (3) | 0.098 (2) | 0.047 (5)* | |
| H(9) | −0.084 (2) | −0.529 (2) | 0.202 (2) | 0.046 (5)* | |
| H(10) | −0.208 (2) | −0.276 (2) | 0.210 (1) | 0.026 (4)* | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| O(1) | 0.0352 (6) | 0.0552 (8) | 0.0371 (7) | 0.0153 (5) | 0.0111 (5) | −0.0019 (6) |
| O(2) | 0.0473 (7) | 0.0384 (6) | 0.0331 (6) | 0.0114 (5) | 0.0192 (5) | 0.0053 (5) |
| N(1) | 0.0384 (8) | 0.065 (1) | 0.0320 (8) | 0.0231 (8) | 0.0094 (6) | 0.0101 (7) |
| N(2) | 0.0502 (9) | 0.0326 (8) | 0.0368 (8) | 0.0116 (6) | 0.0179 (7) | 0.0051 (6) |
| C(1) | 0.0274 (7) | 0.0295 (8) | 0.0308 (8) | 0.0017 (6) | 0.0063 (6) | −0.0030 (6) |
| C(2) | 0.0300 (7) | 0.0293 (8) | 0.0252 (7) | 0.0039 (6) | 0.0100 (6) | 0.0025 (6) |
| C(3) | 0.0271 (7) | 0.0322 (8) | 0.0273 (7) | 0.0026 (6) | 0.0064 (5) | −0.0006 (6) |
| C(4) | 0.0280 (7) | 0.0304 (8) | 0.0287 (8) | 0.0063 (6) | 0.0050 (6) | −0.0017 (6) |
| C(5) | 0.0418 (9) | 0.046 (1) | 0.0318 (8) | 0.0012 (8) | 0.0072 (7) | 0.0011 (7) |
| C(6) | 0.049 (1) | 0.064 (1) | 0.0301 (9) | 0.0019 (9) | −0.0009 (8) | −0.0064 (9) |
| C(7) | 0.0353 (9) | 0.050 (1) | 0.054 (1) | 0.0000 (8) | 0.0006 (8) | −0.0117 (10) |
| C(8) | 0.0430 (10) | 0.044 (1) | 0.055 (1) | −0.0060 (8) | 0.0117 (8) | −0.0002 (9) |
| C(9) | 0.0420 (9) | 0.0417 (10) | 0.0343 (9) | −0.0035 (7) | 0.0079 (7) | 0.0016 (7) |
Geometric parameters (Å, º) top
| O(1)—C(1) | 1.230 (2) | C(4)—C(5) | 1.384 (2) |
| O(2)—C(3) | 1.237 (2) | C(4)—C(9) | 1.388 (2) |
| N(1)—C(1) | 1.321 (2) | C(5)—C(6) | 1.391 (3) |
| N(1)—H(6) | 0.87 (2) | C(5)—H(1) | 1.00 (2) |
| N(1)—H(7) | 0.85 (2) | C(6)—C(7) | 1.376 (3) |
| N(2)—C(3) | 1.324 (2) | C(6)—H(2) | 0.96 (2) |
| N(2)—H(8) | 0.91 (2) | C(7)—C(8) | 1.385 (3) |
| N(2)—H(9) | 0.94 (2) | C(7)—H(3) | 1.00 (2) |
| C(1)—C(2) | 1.535 (2) | C(8)—C(9) | 1.388 (3) |
| C(2)—C(3) | 1.528 (2) | C(8)—H(4) | 1.02 (2) |
| C(2)—C(4) | 1.530 (2) | C(9)—H(5) | 1.00 (2) |
| C(2)—H(10) | 0.94 (2) | | |
| | | |
| O(1)···H(1)i | 2.76 (2) | C(5)···H(7)xi | 3.40 (2) |
| O(1)···H(10)i | 2.79 (2) | C(5)···H(6)xi | 3.44 (2) |
| O(1)···N(2)i | 2.975 (2) | C(5)···H(10)i | 3.46 (2) |
| O(1)···N(1)ii | 2.978 (2) | C(6)···H(2)x | 3.03 (2) |
| O(1)···H(6)ii | 3.46 (2) | C(6)···H(4)iv | 3.26 (2) |
| O(1)···C(2)i | 3.520 (2) | C(6)···H(1)x | 3.37 (2) |
| O(1)···C(5)i | 3.534 (2) | C(6)···H(6)xi | 3.40 (2) |
| O(1)···C(7)iii | 3.541 (2) | C(7)···H(4)iv | 3.36 (2) |
| O(1)···H(8)i | 3.59 (2) | C(7)···H(7)xii | 3.38 (2) |
| O(2)···H(3)iv | 2.72 (2) | C(7)···H(8)xiii | 3.40 (2) |
| O(2)···H(4)v | 2.82 (2) | C(8)···H(8)xiv | 2.98 (2) |
| O(2)···N(2)vi | 3.027 (2) | C(8)···H(6)v | 3.07 (2) |
| O(2)···H(2)vii | 3.17 (2) | C(8)···H(9)xiv | 3.18 (2) |
| O(2)···C(9)v | 3.216 (2) | C(8)···H(4)iv | 3.45 (2) |
| O(2)···C(8)v | 3.367 (2) | C(9)···H(6)v | 3.10 (2) |
| O(2)···C(6)vii | 3.498 (2) | C(9)···H(8)xiv | 3.13 (2) |
| O(2)···O(2)vi | 3.522 (2) | C(9)···H(3)iv | 3.39 (2) |
| O(2)···C(7)iv | 3.575 (2) | C(9)···H(4)iv | 3.46 (2) |
| N(1)···H(7)ii | 3.00 (2) | C(9)···H(9)xiv | 3.48 (2) |
| N(1)···H(1)vii | 3.13 (2) | H(1)···H(2)x | 2.62 (3) |
| N(1)···H(3)viii | 3.18 (2) | H(1)···H(7)xi | 2.84 (3) |
| N(1)···H(4)v | 3.24 (2) | H(1)···H(6)xi | 3.28 (3) |
| N(1)···H(5)v | 3.33 (2) | H(1)···H(9)i | 3.32 (3) |
| N(1)···H(2)vii | 3.37 (2) | H(1)···H(7)iii | 3.44 (3) |
| N(1)···C(5)vii | 3.529 (3) | H(2)···H(2)x | 2.63 (4) |
| N(2)···H(2)vii | 3.04 (2) | H(2)···H(6)xi | 3.20 (3) |
| N(2)···H(4)ix | 3.17 (2) | H(2)···H(8)xi | 3.21 (3) |
| N(2)···H(3)iv | 3.27 (2) | H(2)···H(9)xi | 3.45 (3) |
| N(2)···H(8)vi | 3.38 (2) | H(2)···H(10)xi | 3.54 (3) |
| N(2)···C(8)ix | 3.412 (3) | H(3)···H(7)xii | 2.95 (3) |
| N(2)···H(3)vii | 3.54 (2) | H(3)···H(8)xi | 3.08 (3) |
| N(2)···H(5)ix | 3.59 (2) | H(3)···H(8)xiii | 3.16 (3) |
| C(1)···H(7)ii | 2.87 (2) | H(3)···H(6)xii | 3.21 (3) |
| C(1)···H(9)i | 3.05 (2) | H(3)···H(5)xiii | 3.30 (3) |
| C(1)···H(1)i | 3.42 (2) | H(3)···H(5)xii | 3.57 (3) |
| C(1)···H(10)i | 3.46 (2) | H(4)···H(6)v | 2.51 (3) |
| C(1)···H(2)vii | 3.47 (2) | H(4)···H(8)xiv | 2.63 (3) |
| C(2)···H(9)i | 3.45 (2) | H(4)···H(9)xiv | 3.17 (3) |
| C(2)···H(2)vii | 3.52 (2) | H(4)···H(7)v | 3.40 (3) |
| C(3)···H(2)vii | 2.93 (2) | H(5)···H(6)v | 2.59 (3) |
| C(3)···H(3)iv | 3.02 (2) | H(5)···H(5)v | 2.68 (4) |
| C(3)···H(8)vi | 3.09 (2) | H(5)···H(8)xiv | 2.90 (3) |
| C(3)···C(6)vii | 3.567 (2) | H(7)···H(7)ii | 2.51 (5) |
| C(4)···H(4)iv | 3.36 (2) | H(7)···H(9)vii | 3.43 (3) |
| C(4)···H(10)i | 3.45 (2) | H(8)···H(8)vi | 2.91 (4) |
| C(5)···H(2)x | 3.02 (2) | H(9)···H(10)iii | 3.07 (3) |
| C(5)···H(4)iv | 3.25 (2) | | |
| | | |
| C(1)—N(1)—H(6) | 119 (1) | C(2)—C(4)—C(5) | 119.6 (1) |
| C(1)—N(1)—H(7) | 119 (1) | C(2)—C(4)—C(9) | 121.4 (1) |
| H(6)—N(1)—H(7) | 119 (2) | C(5)—C(4)—C(9) | 119.0 (2) |
| C(3)—N(2)—H(8) | 118 (1) | C(4)—C(5)—C(6) | 120.1 (2) |
| C(3)—N(2)—H(9) | 121 (1) | C(4)—C(5)—H(1) | 118 (1) |
| H(8)—N(2)—H(9) | 119 (1) | C(6)—C(5)—H(1) | 121 (1) |
| O(1)—C(1)—N(1) | 123.2 (1) | C(5)—C(6)—C(7) | 120.9 (2) |
| O(1)—C(1)—C(2) | 118.9 (1) | C(5)—C(6)—H(2) | 120 (1) |
| N(1)—C(1)—C(2) | 117.9 (1) | C(7)—C(6)—H(2) | 119 (1) |
| C(1)—C(2)—C(3) | 115.0 (1) | C(6)—C(7)—C(8) | 119.3 (2) |
| C(1)—C(2)—C(4) | 110.2 (1) | C(6)—C(7)—H(3) | 119 (1) |
| C(1)—C(2)—H(10) | 104.9 (9) | C(8)—C(7)—H(3) | 121 (1) |
| C(3)—C(2)—C(4) | 109.6 (1) | C(7)—C(8)—C(9) | 120.1 (2) |
| C(3)—C(2)—H(10) | 108.2 (10) | C(7)—C(8)—H(4) | 119 (1) |
| C(4)—C(2)—H(10) | 108.7 (9) | C(9)—C(8)—H(4) | 120 (1) |
| O(2)—C(3)—N(2) | 122.5 (1) | C(4)—C(9)—C(8) | 120.7 (2) |
| O(2)—C(3)—C(2) | 121.6 (1) | C(4)—C(9)—H(5) | 119 (1) |
| N(2)—C(3)—C(2) | 115.9 (1) | C(8)—C(9)—H(5) | 119 (1) |
| | | |
| O(1)—C(1)—C(2)—C(3) | 154.6 (1) | C(2)—C(4)—C(5)—C(6) | 178.7 (2) |
| O(1)—C(1)—C(2)—C(4) | −80.9 (2) | C(2)—C(4)—C(9)—C(8) | −178.0 (2) |
| O(2)—C(3)—C(2)—C(1) | 46.6 (2) | C(3)—C(2)—C(4)—C(5) | −115.3 (1) |
| O(2)—C(3)—C(2)—C(4) | −78.2 (2) | C(3)—C(2)—C(4)—C(9) | 63.8 (2) |
| N(1)—C(1)—C(2)—C(3) | −26.2 (2) | C(4)—C(5)—C(6)—C(7) | −0.6 (3) |
| N(1)—C(1)—C(2)—C(4) | 98.2 (2) | C(4)—C(9)—C(8)—C(7) | −0.9 (3) |
| N(2)—C(3)—C(2)—C(1) | −134.1 (1) | C(5)—C(4)—C(9)—C(8) | 1.1 (3) |
| N(2)—C(3)—C(2)—C(4) | 101.1 (2) | C(5)—C(6)—C(7)—C(8) | 0.8 (3) |
| C(1)—C(2)—C(4)—C(5) | 117.3 (2) | C(6)—C(5)—C(4)—C(9) | −0.3 (2) |
| C(1)—C(2)—C(4)—C(9) | −63.7 (2) | C(6)—C(7)—C(8)—C(9) | 0.0 (3) |
| Symmetry codes: (i) −x−1/2, y+1/2, −z+1/2; (ii) −x−1, −y, −z; (iii) −x−1/2, y−1/2, −z+1/2; (iv) −x+1/2, y−1/2, −z+1/2; (v) −x, −y, −z; (vi) −x, −y−1, −z; (vii) x−1/2, −y−1/2, z−1/2; (viii) x−1/2, −y+1/2, z−1/2; (ix) x, y−1, z; (x) −x, −y, −z+1; (xi) x+1/2, −y−1/2, z+1/2; (xii) x+1/2, −y+1/2, z+1/2; (xiii) −x+1/2, y+1/2, −z+1/2; (xiv) x, y+1, z. |
Hydrogen-bond geometry (Å, º) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H6···O2 | 0.87 (3) | 2.03 (3) | 2.723 (2) | 136 (2) |
| N1—H7···O1ii | 0.85 (3) | 2.14 (3) | 2.978 (2) | 167 (2) |
| N2—H8···O2vi | 0.91 (2) | 2.13 (2) | 3.027 (2) | 168 (2) |
| N2—H9···O1iii | 0.95 (2) | 2.04 (2) | 2.9753 (19) | 167 (2) |
| Symmetry codes: (ii) −x−1, −y, −z; (iii) −x−1/2, y−1/2, −z+1/2; (vi) −x, −y−1, −z. |
Experimental details
| Crystal data |
| Chemical formula | C9H10N2O2 |
| Mr | 178.19 |
| Crystal system, space group | Monoclinic, P21/n |
| Temperature (K) | 296 |
| a, b, c (Å) | 9.079 (2), 7.555 (2), 13.015 (2) |
| β (°) | 104.10 (1) |
| V (Å3) | 865.8 (3) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.10 |
| Crystal size (mm) | 0.20 × 0.20 × 0.10 |
| |
| Data collection |
| Diffractometer | Rigaku AFC-5R
diffractometer |
| Absorption correction | – |
No. of measured, independent and
observed [I > 2σ(I)] reflections | 2275, 1994, 1347 |
| Rint | 0.016 |
| (sin θ/λ)max (Å−1) | 0.650 |
| |
| Refinement |
| R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.104, 1.23 |
| No. of reflections | 1658 |
| No. of parameters | 158 |
| No. of restraints | ? |
| H-atom treatment | All H-atom parameters refined |
| Δρmax, Δρmin (e Å−3) | 0.54, −0.22 |
Selected geometric parameters (Å, º) top| O(1)—C(1) | 1.230 (2) | C(1)—C(2) | 1.535 (2) |
| O(2)—C(3) | 1.237 (2) | C(2)—C(3) | 1.528 (2) |
| N(1)—C(1) | 1.321 (2) | C(2)—C(4) | 1.530 (2) |
| N(2)—C(3) | 1.324 (2) | | |
| | | |
| C(1)—C(2)—C(3) | 115.0 (1) | | |
Hydrogen-bond geometry (Å, º) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H6···O2 | 0.87 (3) | 2.03 (3) | 2.723 (2) | 136 (2) |
| N1—H7···O1i | 0.85 (3) | 2.14 (3) | 2.978 (2) | 167 (2) |
| N2—H8···O2ii | 0.91 (2) | 2.13 (2) | 3.027 (2) | 168 (2) |
| N2—H9···O1iii | 0.95 (2) | 2.04 (2) | 2.9753 (19) | 167.1 (15) |
| Symmetry codes: (i) −x−1, −y, −z; (ii) −x, −y−1, −z; (iii) −x−1/2, y−1/2, −z+1/2. |
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Subscribe to Acta Crystallographica Section C: Structural Chemistry
The malonamides have the stronger extracting capacity than other diamides, which is due to the larger electron delocalization and the higher chelating abilities of malonamides (Siddall et al., 1967). The title malonamide derivative, (I), had been synthesized with the aim of studying its lipophilic suitability as an extractant.
In the crystal, the amide N atoms are involved in intramolecular and intermolecular hydrogen bonds (Table 2). These hydrogen bonds form eight-membered [R22(8)] and 16-membered [R86(16)] hydrogen-bonded rings. These rings link the molecules into an infinite three-dimensional network.