Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807054554/dn2257sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807054554/dn2257Isup2.hkl |
CCDC reference: 672811
Ethoxymethylenecyanoacetate (1.7 g, 0.01 mol) was added in small portion to a solution of 2-hydrazino-5-bromo-pyrimidine (1.9.0 g, 0.01 mol) in ethanol (17 ml). The reaction mass was refluxed for 1 h on a water bath, the completion of the reaction was monitored by TLC. The contents were cooled to room temperature and distilled mineral water (17 ml) was added, stirred for 2 h, the solid obtained was filtered, washed with DM water and dried. Recrystallization from ethyl acetate gave the title compound as pinkish crystals, yield (2.0 g, 64%).
Amino hydrogen atoms were located from a difference Fourier map and refined isotropically. Remaining H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.95 to 0.99 Å and Uiso=1.2–1.5 times Ueq(C).
Data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis RED (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); 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: PLATON (Spek, 2003).
C10H10BrN5O2 | F(000) = 624 |
Mr = 312.13 | Dx = 1.731 Mg m−3 |
Monoclinic, P21/n | Melting point: 484(1) K |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.7107 Å |
a = 6.3433 (3) Å | Cell parameters from 4274 reflections |
b = 28.9030 (8) Å | θ = 4.7–32.4° |
c = 6.9439 (3) Å | µ = 3.44 mm−1 |
β = 109.821 (5)° | T = 200 K |
V = 1197.68 (9) Å3 | Rectangular-plate, colourless |
Z = 4 | 0.52 × 0.39 × 0.14 mm |
Oxford Diffraction Gemini diffractometer | 3933 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 2361 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
Detector resolution: 10.5081 pixels mm-1 | θmax = 32.4°, θmin = 4.7° |
ϕ and ω scans | h = −9→8 |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007) | k = −42→41 |
Tmin = 0.221, Tmax = 0.633 | l = −10→10 |
12255 measured reflections |
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)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.077 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0342P)2] where P = (Fo2 + 2Fc2)/3 |
3933 reflections | (Δ/σ)max < 0.001 |
172 parameters | Δρmax = 0.37 e Å−3 |
0 restraints | Δρmin = −0.48 e Å−3 |
C10H10BrN5O2 | V = 1197.68 (9) Å3 |
Mr = 312.13 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 6.3433 (3) Å | µ = 3.44 mm−1 |
b = 28.9030 (8) Å | T = 200 K |
c = 6.9439 (3) Å | 0.52 × 0.39 × 0.14 mm |
β = 109.821 (5)° |
Oxford Diffraction Gemini diffractometer | 3933 independent reflections |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007) | 2361 reflections with I > 2σ(I) |
Tmin = 0.221, Tmax = 0.633 | Rint = 0.030 |
12255 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.077 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.37 e Å−3 |
3933 reflections | Δρmin = −0.48 e Å−3 |
172 parameters |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
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 | ||
Br1 | 1.22590 (4) | −0.15293 (1) | 0.84262 (3) | 0.0432 (1) | |
O41 | 0.4802 (2) | 0.14654 (5) | 0.5849 (2) | 0.0374 (5) | |
O42 | 0.7778 (2) | 0.19419 (5) | 0.6487 (2) | 0.0294 (4) | |
N1 | 1.0031 (2) | 0.04632 (5) | 0.7293 (2) | 0.0222 (5) | |
N2 | 1.1764 (3) | 0.07781 (5) | 0.7447 (3) | 0.0282 (5) | |
N5 | 0.6064 (3) | 0.04722 (6) | 0.6635 (3) | 0.0309 (6) | |
N12 | 0.8851 (3) | −0.02943 (5) | 0.7405 (3) | 0.0308 (5) | |
N16 | 1.2688 (3) | −0.01193 (6) | 0.8024 (3) | 0.0338 (5) | |
C3 | 1.0773 (3) | 0.11816 (7) | 0.7149 (3) | 0.0263 (6) | |
C4 | 0.8460 (3) | 0.11555 (7) | 0.6794 (3) | 0.0233 (5) | |
C5 | 0.7997 (3) | 0.06879 (6) | 0.6884 (3) | 0.0213 (5) | |
C11 | 1.0544 (3) | −0.00088 (6) | 0.7589 (3) | 0.0228 (5) | |
C13 | 0.9366 (3) | −0.07441 (7) | 0.7638 (3) | 0.0331 (6) | |
C14 | 1.1527 (3) | −0.08978 (7) | 0.8098 (3) | 0.0290 (6) | |
C15 | 1.3162 (4) | −0.05673 (7) | 0.8309 (3) | 0.0366 (7) | |
C41 | 0.6802 (3) | 0.15228 (6) | 0.6332 (3) | 0.0240 (5) | |
C43 | 0.6324 (4) | 0.23428 (7) | 0.6071 (3) | 0.0373 (7) | |
C44 | 0.7478 (4) | 0.27217 (8) | 0.5359 (4) | 0.0509 (8) | |
H3 | 1.15424 | 0.14647 | 0.71703 | 0.0316* | |
H5A | 0.498 (4) | 0.0619 (7) | 0.668 (3) | 0.028 (6)* | |
H5B | 0.603 (3) | 0.0169 (8) | 0.685 (3) | 0.034 (6)* | |
H13 | 0.82039 | −0.09633 | 0.74809 | 0.0397* | |
H15 | 1.46789 | −0.06636 | 0.86713 | 0.0439* | |
H43A | 0.60326 | 0.24388 | 0.73262 | 0.0448* | |
H43B | 0.48727 | 0.22693 | 0.50016 | 0.0448* | |
H44A | 0.77406 | 0.26244 | 0.41075 | 0.0764* | |
H44B | 0.65362 | 0.29995 | 0.50771 | 0.0764* | |
H44C | 0.89149 | 0.27902 | 0.64250 | 0.0764* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0682 (2) | 0.0255 (1) | 0.0432 (1) | 0.0145 (1) | 0.0284 (1) | 0.0065 (1) |
O41 | 0.0204 (7) | 0.0319 (9) | 0.0607 (10) | 0.0011 (6) | 0.0149 (7) | 0.0077 (7) |
O42 | 0.0253 (7) | 0.0196 (7) | 0.0429 (8) | 0.0022 (5) | 0.0110 (6) | 0.0031 (6) |
N1 | 0.0182 (8) | 0.0186 (8) | 0.0315 (8) | −0.0016 (6) | 0.0108 (6) | −0.0030 (6) |
N2 | 0.0215 (8) | 0.0208 (8) | 0.0443 (9) | −0.0053 (7) | 0.0138 (7) | −0.0045 (7) |
N5 | 0.0184 (9) | 0.0236 (10) | 0.0535 (11) | −0.0001 (7) | 0.0160 (8) | 0.0010 (8) |
N12 | 0.0238 (8) | 0.0218 (9) | 0.0472 (10) | −0.0022 (7) | 0.0124 (7) | −0.0002 (8) |
N16 | 0.0223 (8) | 0.0278 (9) | 0.0508 (10) | 0.0024 (7) | 0.0117 (8) | 0.0043 (8) |
C3 | 0.0232 (10) | 0.0213 (10) | 0.0356 (10) | −0.0053 (7) | 0.0115 (8) | −0.0042 (8) |
C4 | 0.0215 (9) | 0.0246 (10) | 0.0255 (9) | −0.0013 (7) | 0.0104 (8) | −0.0001 (8) |
C5 | 0.0190 (9) | 0.0237 (9) | 0.0230 (9) | 0.0003 (7) | 0.0095 (7) | −0.0030 (7) |
C11 | 0.0237 (9) | 0.0229 (10) | 0.0222 (9) | 0.0009 (7) | 0.0083 (7) | −0.0019 (7) |
C13 | 0.0343 (11) | 0.0204 (10) | 0.0460 (12) | −0.0034 (8) | 0.0154 (10) | −0.0019 (9) |
C14 | 0.0385 (11) | 0.0238 (10) | 0.0268 (10) | 0.0038 (8) | 0.0138 (9) | 0.0000 (8) |
C15 | 0.0280 (11) | 0.0310 (12) | 0.0512 (13) | 0.0102 (9) | 0.0140 (10) | 0.0071 (10) |
C41 | 0.0250 (9) | 0.0229 (9) | 0.0268 (9) | 0.0023 (8) | 0.0124 (7) | 0.0020 (8) |
C43 | 0.0345 (11) | 0.0254 (11) | 0.0517 (13) | 0.0074 (9) | 0.0144 (10) | 0.0055 (10) |
C44 | 0.0477 (14) | 0.0328 (13) | 0.0672 (16) | 0.0024 (11) | 0.0131 (12) | 0.0200 (12) |
Br1—C14 | 1.878 (2) | C3—C4 | 1.405 (3) |
O41—C41 | 1.209 (2) | C4—C41 | 1.452 (3) |
O42—C41 | 1.348 (2) | C4—C5 | 1.389 (3) |
O42—C43 | 1.448 (3) | C13—C14 | 1.372 (3) |
N1—N2 | 1.403 (2) | C14—C15 | 1.381 (3) |
N1—C5 | 1.385 (2) | C43—C44 | 1.492 (3) |
N1—C11 | 1.401 (2) | C3—H3 | 0.9500 |
N2—C3 | 1.308 (3) | C13—H13 | 0.9500 |
N5—C5 | 1.334 (3) | C15—H15 | 0.9500 |
N12—C11 | 1.326 (3) | C43—H43A | 0.9900 |
N12—C13 | 1.337 (3) | C43—H43B | 0.9900 |
N16—C11 | 1.328 (3) | C44—H44A | 0.9800 |
N16—C15 | 1.329 (3) | C44—H44B | 0.9800 |
N5—H5B | 0.89 (2) | C44—H44C | 0.9800 |
N5—H5A | 0.82 (2) | ||
Br1···C4i | 3.663 (2) | C11···C11ii | 3.424 (3) |
Br1···C41ii | 3.551 (2) | C13···C3ii | 3.530 (3) |
Br1···C4ii | 3.660 (2) | C13···N2ii | 3.358 (3) |
Br1···C41i | 3.483 (2) | C14···C3ii | 3.532 (3) |
Br1···H44Biii | 3.2300 | C14···C5i | 3.448 (3) |
Br1···H44Civ | 3.1000 | C14···C4ii | 3.480 (3) |
O41···N2v | 3.216 (2) | C15···C5ii | 3.445 (3) |
O41···N5 | 2.980 (2) | C15···N5i | 3.387 (3) |
O41···C3v | 3.096 (2) | C41···Br1ii | 3.551 (2) |
O42···C44vi | 3.410 (3) | C41···Br1i | 3.483 (2) |
O41···H3v | 2.5300 | C44···O42x | 3.410 (3) |
O41···H5A | 2.51 (2) | C3···H44Bvi | 3.0500 |
O41···H13vii | 2.8500 | C11···H5B | 2.78 (2) |
O41···H43B | 2.4000 | C41···H5A | 2.90 (2) |
O42···H3 | 2.6600 | C43···H43Bvi | 3.1000 |
O42···H44Bvi | 2.8100 | C43···H44Cx | 3.0900 |
N2···O41viii | 3.216 (2) | C44···H43Bvi | 3.0600 |
N2···N5viii | 3.096 (3) | H3···O41viii | 2.5300 |
N2···N16 | 2.659 (2) | H3···O42 | 2.6600 |
N2···C13ii | 3.358 (3) | H3···H44Bvi | 2.5500 |
N5···C15i | 3.387 (3) | H5A···O41 | 2.51 (2) |
N5···N12 | 2.771 (2) | H5A···N2v | 2.32 (3) |
N5···O41 | 2.980 (2) | H5A···N16v | 2.91 (2) |
N5···N2v | 3.096 (3) | H5A···C41 | 2.90 (2) |
N5···N16v | 3.137 (3) | H5B···N12 | 2.16 (2) |
N12···N5 | 2.771 (2) | H5B···N16v | 2.65 (2) |
N16···N2 | 2.659 (2) | H5B···C11 | 2.78 (2) |
N16···N5viii | 3.137 (3) | H13···O41vii | 2.8500 |
N2···H5Aviii | 2.32 (3) | H15···N2ix | 2.8900 |
N2···H15ix | 2.8900 | H43B···O41 | 2.4000 |
N12···H5B | 2.16 (2) | H43B···C43x | 3.1000 |
N16···H5Aviii | 2.91 (2) | H43B···C44x | 3.0600 |
N16···H5Bviii | 2.65 (2) | H43B···H44Cx | 2.3500 |
C3···O41viii | 3.096 (2) | H44B···Br1xi | 3.2300 |
C3···C13ii | 3.530 (3) | H44B···O42x | 2.8100 |
C3···C14ii | 3.532 (3) | H44B···C3x | 3.0500 |
C4···C14ii | 3.480 (3) | H44B···H3x | 2.5500 |
C4···Br1ii | 3.660 (2) | H44C···Br1xii | 3.1000 |
C4···Br1i | 3.663 (2) | H44C···C43vi | 3.0900 |
C5···C14i | 3.448 (3) | H44C···H43Bvi | 2.3500 |
C5···C15ii | 3.445 (3) | ||
C41—O42—C43 | 117.32 (16) | C13—C14—C15 | 117.13 (19) |
N2—N1—C5 | 111.27 (14) | N16—C15—C14 | 122.3 (2) |
N2—N1—C11 | 118.90 (14) | O41—C41—O42 | 123.78 (17) |
C5—N1—C11 | 129.82 (15) | O41—C41—C4 | 125.07 (17) |
N1—N2—C3 | 104.14 (17) | O42—C41—C4 | 111.15 (17) |
C11—N12—C13 | 115.91 (19) | O42—C43—C44 | 107.6 (2) |
C11—N16—C15 | 115.51 (19) | N2—C3—H3 | 123.00 |
H5A—N5—H5B | 116 (2) | C4—C3—H3 | 123.00 |
C5—N5—H5A | 120.1 (16) | N12—C13—H13 | 119.00 |
C5—N5—H5B | 120.8 (13) | C14—C13—H13 | 119.00 |
N2—C3—C4 | 113.41 (19) | N16—C15—H15 | 119.00 |
C3—C4—C5 | 105.58 (18) | C14—C15—H15 | 119.00 |
C3—C4—C41 | 129.40 (18) | O42—C43—H43A | 110.00 |
C5—C4—C41 | 124.97 (18) | O42—C43—H43B | 110.00 |
N5—C5—C4 | 130.41 (19) | C44—C43—H43A | 110.00 |
N1—C5—N5 | 123.99 (16) | C44—C43—H43B | 110.00 |
N1—C5—C4 | 105.60 (17) | H43A—C43—H43B | 108.00 |
N1—C11—N16 | 115.87 (16) | C43—C44—H44A | 109.00 |
N1—C11—N12 | 116.85 (17) | C43—C44—H44B | 109.00 |
N12—C11—N16 | 127.28 (17) | C43—C44—H44C | 109.00 |
N12—C13—C14 | 121.81 (19) | H44A—C44—H44B | 109.00 |
Br1—C14—C13 | 121.97 (15) | H44A—C44—H44C | 109.00 |
Br1—C14—C15 | 120.90 (16) | H44B—C44—H44C | 109.00 |
C43—O42—C41—O41 | 0.8 (3) | C15—N16—C11—N1 | 179.79 (17) |
C43—O42—C41—C4 | −179.89 (16) | C15—N16—C11—N12 | −0.3 (3) |
C41—O42—C43—C44 | −153.54 (18) | C11—N16—C15—C14 | 2.2 (3) |
N2—N1—C5—C4 | −0.5 (2) | N2—C3—C4—C41 | −177.5 (2) |
C11—N1—C5—N5 | −2.1 (3) | N2—C3—C4—C5 | −0.1 (2) |
C11—N1—C5—C4 | 178.32 (17) | C3—C4—C5—N5 | −179.2 (2) |
N2—N1—C11—N12 | −179.22 (17) | C3—C4—C41—O41 | 172.3 (2) |
N2—N1—C11—N16 | 0.8 (2) | C41—C4—C5—N1 | 177.91 (18) |
C5—N1—C11—N12 | 2.1 (3) | C41—C4—C5—N5 | −1.6 (4) |
C5—N1—C11—N16 | −177.97 (18) | C3—C4—C5—N1 | 0.3 (2) |
C11—N1—N2—C3 | −178.50 (16) | C5—C4—C41—O42 | 176.03 (18) |
N2—N1—C5—N5 | 179.11 (19) | C3—C4—C41—O42 | −7.0 (3) |
C5—N1—N2—C3 | 0.4 (2) | C5—C4—C41—O41 | −4.7 (3) |
N1—N2—C3—C4 | −0.2 (2) | N12—C13—C14—Br1 | −180.00 (17) |
C13—N12—C11—N16 | −1.7 (3) | N12—C13—C14—C15 | −0.1 (3) |
C13—N12—C11—N1 | 178.25 (17) | Br1—C14—C15—N16 | 177.87 (16) |
C11—N12—C13—C14 | 1.8 (3) | C13—C14—C15—N16 | −2.0 (3) |
Symmetry codes: (i) −x+2, −y, −z+2; (ii) −x+2, −y, −z+1; (iii) −x+3/2, y−1/2, −z+3/2; (iv) −x+5/2, y−1/2, −z+3/2; (v) x−1, y, z; (vi) x+1/2, −y+1/2, z+1/2; (vii) −x+1, −y, −z+1; (viii) x+1, y, z; (ix) −x+3, −y, −z+2; (x) x−1/2, −y+1/2, z−1/2; (xi) −x+3/2, y+1/2, −z+3/2; (xii) −x+5/2, y+1/2, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5A···O41 | 0.82 (2) | 2.51 (2) | 2.980 (2) | 118 (2) |
N5—H5A···N2v | 0.82 (2) | 2.32 (3) | 3.096 (3) | 158.0 (19) |
N5—H5B···N12 | 0.89 (2) | 2.16 (2) | 2.771 (2) | 125.0 (17) |
C3—H3···O41viii | 0.95 | 2.53 | 3.096 (2) | 118.0 |
Symmetry codes: (v) x−1, y, z; (viii) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C10H10BrN5O2 |
Mr | 312.13 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 200 |
a, b, c (Å) | 6.3433 (3), 28.9030 (8), 6.9439 (3) |
β (°) | 109.821 (5) |
V (Å3) | 1197.68 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 3.44 |
Crystal size (mm) | 0.52 × 0.39 × 0.14 |
Data collection | |
Diffractometer | Oxford Diffraction Gemini diffractometer |
Absorption correction | Multi-scan (CrysAlis RED; Oxford Diffraction, 2007) |
Tmin, Tmax | 0.221, 0.633 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12255, 3933, 2361 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.754 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.077, 1.03 |
No. of reflections | 3933 |
No. of parameters | 172 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.37, −0.48 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2007), CrysAlis RED (Oxford Diffraction, 2007), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), PLATON (Spek, 2003).
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5A···O41 | 0.82 (2) | 2.51 (2) | 2.980 (2) | 118 (2) |
N5—H5A···N2i | 0.82 (2) | 2.32 (3) | 3.096 (3) | 158.0 (19) |
N5—H5B···N12 | 0.89 (2) | 2.16 (2) | 2.771 (2) | 125.0 (17) |
C3—H3···O41ii | 0.95 | 2.53 | 3.096 (2) | 118.0 |
Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z. |
Thiruvalluvar et al., (2007a,b,c) have reported the crystal structures of pyrimidine derivatives. The title compound, C10H10BrN5O2, is planar, except the amino and carboxylate group (Fig. 1). The molecules are linked by intermolecular C—H···O and N—H···N hydrogen bonds forming ribbons parallel to the a axis (Fig. 2, Table 1). These ribbons are further interconnected through weak slippest π-π stacking between the N1—N2—C3—C4—C5 and the symmetry related (2 - x, -y, 1 - z) N12—C11—N16—C15—C14—C13 rings(centroid-to-centroid distance of 3.512 (1) Å, interplanar distance of 3.391 Å and offset angle of 15.1°). Intramolecular N—H···N and N—H···O hydrogen bonds (Table 1) stabilize the planar conformation