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In the title compound, C12H16N4O3, all bond lengths and angles are within normal ranges. An O—H...N and an N—H...O intra­molecular hydrogen bond contribute to the approximately planar mol­ecular conformation. In the crystal structure, inter­molecular N—H...O and N—H...N hydrogen bonds link the mol­ecules into ribbons parallel to the [1\overline{1}0] direction.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807043383/cv2296sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807043383/cv2296Isup2.hkl
Contains datablock I

CCDC reference: 654090

Key indicators

  • Single-crystal X-ray study
  • T = 302 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.058
  • wR factor = 0.172
  • Data-to-parameter ratio = 14.9

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 200 Deg. PLAT230_ALERT_2_C Hirshfeld Test Diff for C4 - C7 .. 5.29 su PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.04 PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C4 - C7 ... 1.42 Ang.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 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

Pyridine derivatives are important compounds because of their presence in numerous natural products. For example, nicotine is found in a wide variety of plants, playing an important role in metabolism and possessing a wide spectrum of biological activities (Yildiz, 2004). We report here the crystal structure of the title compound, (I).

In (I), all bond lengths and angles are within normal ranges (Allen et al., 1987). Two intramolecular hydrogen bonds - O—H···N and N—H···O (Table 1), respectively, contribute to the approximately planar molecular conformation. In the crystal, intermolecular N—H···O and N—H···N hydrogen bonds (Table 1) link the molecules into ribbons parallel to direction [1–10] (Fig. 2).

Related literature top

For biological functions of nicotine, see: Yildiz (2004). For normal ranges of molecular bond lengths and angles in organic compounds, see: Allen et al. (1987).

Experimental top

2-[Amino-(2-hydroxy-ethylamino)-methylene]-malononitrile (1.52 g, 10 mmol) and ethyl acetoacetate (1.6 g, 12 mmol) were added to a solution of Zinc nitrate (3.56 g, 20 mmol) in ethanol (15 ml) at room temperature while stirring. The mixture was then refluxed for 12 h. The precipitate was filtered and washed with water, recrystallized from ethanol to give the title compound (yield 39%). Crystals of (I) suitable for X-ray structure analysis were grown from ethanol.

Refinement top

C-bound H atoms were placed in calculated positions, with C—H distances in the range 0.93–0.97 Å, and included in the final cycles of refinement using a riding-model approximation, with Uiso(H) = 1.2–1.5Ueq(C). The rest H atoms were located on a difference map, and refined with bond restraints O—H = 0.85 (2) Å, N—H = 0.85 (2) Å (for H4A) or 0.88 (2) Å (for H2A and H2B), with Uiso(H)=1.2Ueq(N) or 1.5Ueq(O).

Structure description top

Pyridine derivatives are important compounds because of their presence in numerous natural products. For example, nicotine is found in a wide variety of plants, playing an important role in metabolism and possessing a wide spectrum of biological activities (Yildiz, 2004). We report here the crystal structure of the title compound, (I).

In (I), all bond lengths and angles are within normal ranges (Allen et al., 1987). Two intramolecular hydrogen bonds - O—H···N and N—H···O (Table 1), respectively, contribute to the approximately planar molecular conformation. In the crystal, intermolecular N—H···O and N—H···N hydrogen bonds (Table 1) link the molecules into ribbons parallel to direction [1–10] (Fig. 2).

For biological functions of nicotine, see: Yildiz (2004). For normal ranges of molecular bond lengths and angles in organic compounds, see: Allen et al. (1987).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) showing 50% probability displacement ellipsoids and the atom-numbering scheme.
[Figure 2] Fig. 2. A portion of the crystal packing showing hydrogen bonds as dashed lines.
Ethyl 4-amino-5-cyano-6-[(2-hydroxyethyl)amino]-2-methylnicotinate top
Crystal data top
C12H16N4O3Z = 2
Mr = 264.29F(000) = 280
Triclinic, P1Dx = 1.352 Mg m3
Hall symbol: -p 1Mo Kα radiation, λ = 0.71073 Å
a = 7.8350 (7) ÅCell parameters from 1450 reflections
b = 9.1368 (9) Åθ = 3.2–20.8°
c = 10.3272 (10) ŵ = 0.10 mm1
α = 79.720 (2)°T = 302 K
β = 77.381 (2)°Block, colourless
γ = 64.657 (2)°0.35 × 0.20 × 0.10 mm
V = 648.97 (11) Å3
Data collection top
Bruker SMART CCD area detector
diffractometer
2767 independent reflections
Radiation source: fine-focus sealed tube1991 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.033
phi and ω scansθmax = 27.0°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
h = 1010
Tmin = 0.966, Tmax = 0.990k = 1111
4521 measured reflectionsl = 1113
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)] = 0.058Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.172H atoms treated by a mixture of independent and constrained refinement
S = 1.06 w = 1/[σ2(Fo2) + (0.0955P)2]
where P = (Fo2 + 2Fc2)/3
2767 reflections(Δ/σ)max < 0.001
186 parametersΔρmax = 0.27 e Å3
0 restraintsΔρmin = 0.29 e Å3
Crystal data top
C12H16N4O3γ = 64.657 (2)°
Mr = 264.29V = 648.97 (11) Å3
Triclinic, P1Z = 2
a = 7.8350 (7) ÅMo Kα radiation
b = 9.1368 (9) ŵ = 0.10 mm1
c = 10.3272 (10) ÅT = 302 K
α = 79.720 (2)°0.35 × 0.20 × 0.10 mm
β = 77.381 (2)°
Data collection top
Bruker SMART CCD area detector
diffractometer
2767 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
1991 reflections with I > 2σ(I)
Tmin = 0.966, Tmax = 0.990Rint = 0.033
4521 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0580 restraints
wR(F2) = 0.172H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.27 e Å3
2767 reflectionsΔρmin = 0.29 e Å3
186 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
C10.4786 (3)0.2753 (2)0.45970 (17)0.0404 (4)
C20.6483 (2)0.1345 (2)0.43570 (17)0.0372 (4)
C30.7156 (2)0.0230 (2)0.54871 (17)0.0359 (4)
C40.6070 (2)0.0620 (2)0.67547 (17)0.0377 (4)
C50.4355 (2)0.2018 (2)0.68772 (17)0.0362 (4)
C60.3927 (3)0.4091 (3)0.3547 (2)0.0642 (7)
H6A0.35360.36710.29300.096*
H6B0.48610.44980.30800.096*
H6C0.28370.49560.39630.096*
C70.6634 (3)0.0413 (2)0.79306 (18)0.0416 (5)
C80.7589 (3)0.0936 (2)0.30234 (18)0.0419 (5)
C90.7834 (3)0.1527 (2)0.06883 (18)0.0508 (5)
H9A0.79460.04720.05320.061*
H9B0.91110.14860.06060.061*
C100.6766 (3)0.2811 (3)0.0303 (2)0.0607 (6)
H10A0.54830.28840.01810.091*
H10B0.73950.25360.11880.091*
H10C0.67340.38390.01760.091*
C110.1222 (3)0.3504 (2)0.8233 (2)0.0510 (5)
H11A0.05910.32190.90960.061*
H11B0.06340.33610.75580.061*
C120.0869 (4)0.5254 (3)0.8139 (2)0.0636 (6)
H12A0.04310.58530.85610.076*
H12B0.17250.53580.86340.076*
N10.3761 (2)0.30703 (18)0.58156 (14)0.0422 (4)
N20.8725 (2)0.11440 (19)0.53691 (17)0.0473 (4)
H2B0.928 (3)0.122 (2)0.4515 (16)0.057*
H2A0.900 (3)0.174 (2)0.6103 (17)0.057*
N30.7004 (3)0.1181 (2)0.89125 (17)0.0560 (5)
N40.3234 (2)0.23730 (19)0.80702 (16)0.0461 (4)
H4A0.372 (3)0.164 (3)0.866 (2)0.055*
O10.9108 (2)0.02184 (18)0.28168 (15)0.0628 (5)
O20.67814 (19)0.19305 (16)0.20107 (12)0.0496 (4)
O30.1129 (3)0.59692 (18)0.68257 (16)0.0728 (5)
H3A0.111 (5)0.532 (3)0.633 (3)0.109*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0431 (10)0.0397 (9)0.0313 (10)0.0113 (8)0.0064 (8)0.0004 (7)
C20.0384 (10)0.0388 (9)0.0303 (9)0.0129 (8)0.0036 (7)0.0026 (7)
C30.0368 (9)0.0315 (8)0.0367 (10)0.0112 (7)0.0068 (7)0.0023 (7)
C40.0415 (10)0.0340 (9)0.0330 (10)0.0117 (8)0.0089 (8)0.0019 (7)
C50.0379 (9)0.0355 (9)0.0310 (9)0.0115 (7)0.0052 (7)0.0018 (7)
C60.0650 (14)0.0540 (12)0.0347 (11)0.0083 (11)0.0050 (10)0.0024 (9)
C70.0395 (10)0.0347 (9)0.0383 (10)0.0056 (8)0.0027 (8)0.0018 (8)
C80.0452 (11)0.0421 (10)0.0360 (10)0.0155 (9)0.0056 (8)0.0050 (8)
C90.0582 (13)0.0539 (12)0.0309 (10)0.0174 (10)0.0040 (9)0.0084 (9)
C100.0656 (15)0.0747 (15)0.0353 (11)0.0241 (12)0.0067 (10)0.0024 (10)
C110.0446 (11)0.0516 (11)0.0409 (11)0.0098 (9)0.0026 (8)0.0024 (9)
C120.0740 (15)0.0466 (11)0.0450 (13)0.0019 (10)0.0076 (11)0.0041 (9)
N10.0429 (9)0.0391 (8)0.0318 (8)0.0065 (7)0.0040 (7)0.0007 (6)
N20.0499 (10)0.0387 (8)0.0378 (9)0.0058 (7)0.0049 (8)0.0002 (7)
N30.0602 (11)0.0499 (10)0.0359 (9)0.0054 (8)0.0073 (8)0.0056 (8)
N40.0455 (10)0.0412 (9)0.0321 (9)0.0025 (7)0.0042 (7)0.0027 (7)
O10.0578 (9)0.0564 (9)0.0436 (8)0.0027 (7)0.0005 (7)0.0081 (7)
O20.0509 (8)0.0531 (8)0.0286 (7)0.0074 (6)0.0020 (6)0.0051 (6)
O30.0843 (12)0.0443 (8)0.0532 (10)0.0013 (8)0.0004 (8)0.0061 (7)
Geometric parameters (Å, º) top
C1—N11.342 (2)C9—C101.493 (3)
C1—C21.410 (2)C9—H9A0.9700
C1—C61.504 (2)C9—H9B0.9700
C2—C31.436 (2)C10—H10A0.9600
C2—C81.474 (2)C10—H10B0.9600
C3—N21.330 (2)C10—H10C0.9600
C3—C41.409 (2)C11—N41.461 (2)
C4—C51.403 (2)C11—C121.490 (3)
C4—C71.424 (2)C11—H11A0.9700
C5—N11.344 (2)C11—H11B0.9700
C5—N41.349 (2)C12—O31.409 (3)
C6—H6A0.9600C12—H12A0.9700
C6—H6B0.9600C12—H12B0.9700
C6—H6C0.9600N2—H2B0.895 (15)
C7—N31.142 (2)N2—H2A0.859 (15)
C8—O11.212 (2)N4—H4A0.84 (2)
C8—O21.333 (2)O3—H3A0.861 (17)
C9—O21.452 (2)
N1—C1—C2123.25 (16)C10—C9—H9B110.1
N1—C1—C6111.78 (16)H9A—C9—H9B108.4
C2—C1—C6124.95 (16)C9—C10—H10A109.5
C1—C2—C3117.65 (15)C9—C10—H10B109.5
C1—C2—C8124.27 (16)H10A—C10—H10B109.5
C3—C2—C8118.08 (16)C9—C10—H10C109.5
N2—C3—C4119.91 (16)H10A—C10—H10C109.5
N2—C3—C2122.47 (16)H10B—C10—H10C109.5
C4—C3—C2117.61 (15)N4—C11—C12115.13 (18)
C5—C4—C3120.14 (15)N4—C11—H11A108.5
C5—C4—C7118.39 (15)C12—C11—H11A108.5
C3—C4—C7121.43 (15)N4—C11—H11B108.5
N1—C5—N4117.00 (15)C12—C11—H11B108.5
N1—C5—C4121.62 (15)H11A—C11—H11B107.5
N4—C5—C4121.38 (16)O3—C12—C11114.25 (18)
C1—C6—H6A109.5O3—C12—H12A108.7
C1—C6—H6B109.5C11—C12—H12A108.7
H6A—C6—H6B109.5O3—C12—H12B108.7
C1—C6—H6C109.5C11—C12—H12B108.7
H6A—C6—H6C109.5H12A—C12—H12B107.6
H6B—C6—H6C109.5C1—N1—C5119.62 (15)
N3—C7—C4176.31 (18)C3—N2—H2B110.1 (13)
O1—C8—O2120.50 (17)C3—N2—H2A115.4 (15)
O1—C8—C2124.55 (18)H2B—N2—H2A134 (2)
O2—C8—C2114.94 (16)C5—N4—C11123.93 (15)
O2—C9—C10107.96 (16)C5—N4—H4A109.6 (16)
O2—C9—H9A110.1C11—N4—H4A123.3 (16)
C10—C9—H9A110.1C8—O2—C9115.70 (15)
O2—C9—H9B110.1C12—O3—H3A105 (2)
N1—C1—C2—C31.8 (3)C1—C2—C8—O1175.22 (19)
C6—C1—C2—C3176.79 (18)C3—C2—C8—O15.7 (3)
N1—C1—C2—C8177.27 (16)C1—C2—C8—O25.8 (3)
C6—C1—C2—C84.2 (3)C3—C2—C8—O2173.23 (14)
C1—C2—C3—N2179.06 (17)N4—C11—C12—O378.5 (3)
C8—C2—C3—N20.1 (3)C2—C1—N1—C50.4 (3)
C1—C2—C3—C40.2 (2)C6—C1—N1—C5178.30 (17)
C8—C2—C3—C4178.96 (15)N4—C5—N1—C1177.88 (16)
N2—C3—C4—C5176.27 (17)C4—C5—N1—C12.6 (3)
C2—C3—C4—C52.7 (2)N1—C5—N4—C1118.9 (3)
N2—C3—C4—C71.3 (3)C4—C5—N4—C11161.55 (17)
C2—C3—C4—C7179.74 (15)C12—C11—N4—C583.0 (2)
C3—C4—C5—N14.2 (3)O1—C8—O2—C90.1 (3)
C7—C4—C5—N1178.16 (15)C2—C8—O2—C9178.88 (15)
C3—C4—C5—N4176.30 (16)C10—C9—O2—C8177.24 (15)
C7—C4—C5—N41.4 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3A···N10.86 (2)2.25 (3)2.780 (2)120 (3)
N2—H2B···O10.90 (2)1.83 (2)2.613 (2)145 (2)
N4—H4A···N3i0.84 (2)2.45 (2)3.105 (2)136.1 (19)
N2—H2A···O3ii0.86 (2)2.18 (2)2.887 (2)140 (2)
C12—H12A···N3iii0.972.623.442 (3)142
Symmetry codes: (i) x+1, y, z+2; (ii) x+1, y1, z; (iii) x1, y+1, z.

Experimental details

Crystal data
Chemical formulaC12H16N4O3
Mr264.29
Crystal system, space groupTriclinic, P1
Temperature (K)302
a, b, c (Å)7.8350 (7), 9.1368 (9), 10.3272 (10)
α, β, γ (°)79.720 (2), 77.381 (2), 64.657 (2)
V3)648.97 (11)
Z2
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.35 × 0.20 × 0.10
Data collection
DiffractometerBruker SMART CCD area detector
Absorption correctionMulti-scan
(SADABS; Bruker, 2000)
Tmin, Tmax0.966, 0.990
No. of measured, independent and
observed [I > 2σ(I)] reflections
4521, 2767, 1991
Rint0.033
(sin θ/λ)max1)0.639
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.058, 0.172, 1.06
No. of reflections2767
No. of parameters186
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.27, 0.29

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2000).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3A···N10.861 (17)2.25 (3)2.780 (2)120 (3)
N2—H2B···O10.895 (15)1.832 (17)2.613 (2)144.6 (19)
N4—H4A···N3i0.84 (2)2.45 (2)3.105 (2)136.1 (19)
N2—H2A···O3ii0.859 (15)2.175 (18)2.887 (2)140 (2)
Symmetry codes: (i) x+1, y, z+2; (ii) x+1, y1, z.
 

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