Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680200613X/cf6166sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680200613X/cf6166Isup2.hkl |
CCDC reference: 185786
Key indicators
- Single-crystal X-ray study
- T = 110 K
- Mean (C-C) = 0.002 Å
- R factor = 0.044
- wR factor = 0.114
- Data-to-parameter ratio = 13.1
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
PLAT_420 Alert C D-H Without Acceptor N(3) - H(3) ?
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
A solution of p-nitrobenzaldehyde (0.906 g, 6 mmol) in pyrrole (16.8 ml, 240 mmol) was degassed by bubbling with argon for 10 min. Then trifluoroacetic acid (0.05 ml, 0.06 mmol) was added to the reaction mixture and it was stirred for 30 min at room temperature. The reaction mixture was diluted with 200 ml of CH2Cl2, washed successively with 0.1 N aq. NaOH and water, and dried with anhydrous Na2SO4. The solvent was removed under pressure, and then the unreacted pyrrole was removed by vacuum distillation. The black–green semi-solid thus obtained was treated with n-hexane to give a solid compound. This solid was dissolved in methanol (a small amount remained undissolved) and decolorized by charcoal powder. Slow evaporation of the methanol solution afforded yellow crystals of (I), which were suitable for X-ray analysis. Yield 0.721 g (45%). 1H NMR (200 MHz, CDCl3, TMS): δ 8.17 (d, J = 6 Hz, 2H), 7.90 (bs, 4H, 2H), 7.35 (d, J = 6 Hz, 2H), 6.76 (q, 2H), 5.89 (m, 2H), 5.58 (s, 1H, meso-H).
Data collection: COLLECT (Nonius, 1999); cell refinement: DENZO (Otwinowski, 1985); data reduction: DENZO; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97.
C15H13N3O2 | F(000) = 560 |
Mr = 267.28 | Dx = 1.371 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 10.1940 (2) Å | Cell parameters from 2204 reflections |
b = 11.4380 (3) Å | θ = 2.6–27.9° |
c = 11.3180 (3) Å | µ = 0.09 mm−1 |
β = 101.1840 (11)° | T = 110 K |
V = 1294.61 (5) Å3 | Prism, yellow |
Z = 4 | 0.25 × 0.20 × 0.20 mm |
Nonius KappaCCD diffractometer | 2204 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.030 |
Graphite monochromator | θmax = 27.9°, θmin = 2.6° |
Detector resolution: 56 microns pixels mm-1 | h = −13→13 |
ϕ scans | k = −13→15 |
5274 measured reflections | l = −14→14 |
3061 independent 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)] = 0.044 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.114 | All H-atom parameters refined |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0491P)2 + 0.4783P] where P = (Fo2 + 2Fc2)/3 |
3061 reflections | (Δ/σ)max < 0.001 |
233 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.32 e Å−3 |
C15H13N3O2 | V = 1294.61 (5) Å3 |
Mr = 267.28 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.1940 (2) Å | µ = 0.09 mm−1 |
b = 11.4380 (3) Å | T = 110 K |
c = 11.3180 (3) Å | 0.25 × 0.20 × 0.20 mm |
β = 101.1840 (11)° |
Nonius KappaCCD diffractometer | 2204 reflections with I > 2σ(I) |
5274 measured reflections | Rint = 0.030 |
3061 independent reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.114 | All H-atom parameters refined |
S = 1.00 | Δρmax = 0.23 e Å−3 |
3061 reflections | Δρmin = −0.32 e Å−3 |
233 parameters |
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. All H-atoms were refined as free parameters. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.71718 (15) | 0.24320 (13) | 0.46676 (13) | 0.0170 (3) | |
H1 | 0.6903 (16) | 0.2895 (15) | 0.5327 (15) | 0.019 (4)* | |
C2 | 0.73658 (15) | 0.11850 (13) | 0.51152 (13) | 0.0180 (3) | |
N3 | 0.64868 (13) | 0.06777 (12) | 0.57390 (12) | 0.0219 (3) | |
H3 | 0.576 (2) | 0.1025 (17) | 0.5957 (17) | 0.032 (5)* | |
C4 | 0.68709 (18) | −0.04556 (15) | 0.60190 (16) | 0.0264 (4) | |
H4 | 0.6387 (19) | −0.0936 (17) | 0.6465 (18) | 0.037 (5)* | |
C5 | 0.79928 (17) | −0.06728 (14) | 0.55633 (16) | 0.0256 (4) | |
H5 | 0.8481 (19) | −0.1380 (18) | 0.5644 (18) | 0.033 (5)* | |
C6 | 0.83019 (16) | 0.03651 (14) | 0.49864 (15) | 0.0223 (4) | |
H6 | 0.9047 (19) | 0.0500 (16) | 0.4568 (17) | 0.029 (5)* | |
C7 | 0.60386 (15) | 0.25283 (13) | 0.35952 (13) | 0.0187 (3) | |
N8 | 0.58732 (14) | 0.17396 (12) | 0.26644 (12) | 0.0216 (3) | |
H8 | 0.640 (2) | 0.1097 (19) | 0.2610 (19) | 0.044 (6)* | |
C9 | 0.47908 (16) | 0.20564 (16) | 0.17972 (15) | 0.0248 (4) | |
H9 | 0.4528 (19) | 0.1562 (18) | 0.1103 (19) | 0.035 (5)* | |
C10 | 0.42647 (17) | 0.30507 (16) | 0.21796 (15) | 0.0247 (4) | |
H10 | 0.355 (2) | 0.3456 (16) | 0.1776 (17) | 0.028 (5)* | |
C11 | 0.50562 (16) | 0.33531 (15) | 0.33154 (15) | 0.0216 (3) | |
H11 | 0.4942 (18) | 0.4020 (16) | 0.3787 (16) | 0.025 (5)* | |
C12 | 0.84894 (15) | 0.29540 (13) | 0.44531 (13) | 0.0169 (3) | |
C13 | 0.95693 (15) | 0.30651 (13) | 0.54247 (14) | 0.0186 (3) | |
H13 | 0.9480 (16) | 0.2790 (15) | 0.6227 (16) | 0.020 (4)* | |
C14 | 1.07547 (16) | 0.35851 (13) | 0.52783 (14) | 0.0191 (3) | |
H14 | 1.1474 (18) | 0.3695 (15) | 0.5959 (16) | 0.022 (4)* | |
C15 | 1.08470 (15) | 0.39904 (13) | 0.41442 (14) | 0.0174 (3) | |
C16 | 0.98115 (16) | 0.38888 (14) | 0.31622 (14) | 0.0204 (3) | |
H16 | 0.9890 (18) | 0.4192 (15) | 0.2382 (18) | 0.026 (5)* | |
C17 | 0.86333 (16) | 0.33571 (14) | 0.33279 (14) | 0.0207 (3) | |
H17 | 0.7869 (19) | 0.3308 (16) | 0.2644 (17) | 0.028 (5)* | |
N18 | 1.20583 (13) | 0.46113 (11) | 0.39800 (12) | 0.0212 (3) | |
O19 | 1.29820 (11) | 0.47170 (10) | 0.48469 (11) | 0.0265 (3) | |
O20 | 1.20881 (12) | 0.50178 (12) | 0.29768 (11) | 0.0337 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0155 (7) | 0.0185 (7) | 0.0170 (7) | 0.0006 (6) | 0.0034 (6) | −0.0017 (6) |
C2 | 0.0159 (7) | 0.0205 (7) | 0.0173 (7) | −0.0018 (6) | 0.0028 (6) | 0.0000 (6) |
N3 | 0.0184 (7) | 0.0241 (7) | 0.0244 (7) | −0.0009 (6) | 0.0075 (6) | 0.0010 (6) |
C4 | 0.0271 (9) | 0.0238 (8) | 0.0275 (9) | −0.0073 (7) | 0.0031 (7) | 0.0034 (7) |
C5 | 0.0278 (9) | 0.0178 (8) | 0.0293 (9) | 0.0012 (7) | 0.0006 (7) | −0.0013 (7) |
C6 | 0.0196 (8) | 0.0241 (8) | 0.0233 (8) | 0.0007 (6) | 0.0042 (6) | −0.0007 (7) |
C7 | 0.0169 (8) | 0.0204 (7) | 0.0195 (8) | −0.0016 (6) | 0.0053 (6) | −0.0004 (6) |
N8 | 0.0198 (7) | 0.0220 (7) | 0.0234 (7) | 0.0000 (5) | 0.0052 (5) | −0.0028 (6) |
C9 | 0.0209 (8) | 0.0335 (9) | 0.0197 (8) | −0.0076 (7) | 0.0037 (6) | −0.0012 (7) |
C10 | 0.0162 (8) | 0.0335 (9) | 0.0235 (8) | 0.0014 (7) | 0.0020 (6) | 0.0081 (7) |
C11 | 0.0208 (8) | 0.0227 (8) | 0.0223 (8) | 0.0013 (6) | 0.0066 (6) | 0.0002 (7) |
C12 | 0.0169 (8) | 0.0144 (7) | 0.0196 (7) | 0.0015 (6) | 0.0041 (6) | −0.0006 (6) |
C13 | 0.0204 (8) | 0.0185 (7) | 0.0163 (7) | 0.0007 (6) | 0.0023 (6) | 0.0017 (6) |
C14 | 0.0181 (8) | 0.0177 (7) | 0.0202 (7) | 0.0019 (6) | 0.0007 (6) | −0.0009 (6) |
C15 | 0.0152 (7) | 0.0144 (7) | 0.0234 (8) | −0.0001 (5) | 0.0054 (6) | −0.0006 (6) |
C16 | 0.0222 (8) | 0.0223 (8) | 0.0178 (7) | −0.0011 (6) | 0.0062 (6) | 0.0011 (7) |
C17 | 0.0193 (8) | 0.0237 (8) | 0.0178 (7) | −0.0020 (6) | 0.0004 (6) | −0.0006 (6) |
N18 | 0.0182 (7) | 0.0181 (7) | 0.0283 (7) | 0.0003 (5) | 0.0073 (6) | −0.0017 (6) |
O19 | 0.0170 (6) | 0.0269 (6) | 0.0341 (7) | −0.0020 (5) | 0.0009 (5) | −0.0022 (5) |
O20 | 0.0312 (7) | 0.0416 (7) | 0.0299 (7) | −0.0089 (6) | 0.0101 (5) | 0.0091 (6) |
C1—C7 | 1.509 (2) | C9—H9 | 0.96 (2) |
C1—C2 | 1.514 (2) | C10—C11 | 1.422 (2) |
C1—C12 | 1.532 (2) | C10—H10 | 0.910 (19) |
C1—H1 | 0.996 (17) | C11—H11 | 0.951 (19) |
C2—C6 | 1.366 (2) | C12—C17 | 1.389 (2) |
C2—N3 | 1.372 (2) | C12—C13 | 1.403 (2) |
N3—C4 | 1.373 (2) | C13—C14 | 1.385 (2) |
N3—H3 | 0.92 (2) | C13—H13 | 0.981 (18) |
C4—C5 | 1.365 (3) | C14—C15 | 1.385 (2) |
C4—H4 | 0.95 (2) | C14—H14 | 0.963 (18) |
C5—C6 | 1.419 (2) | C15—C16 | 1.381 (2) |
C5—H5 | 0.94 (2) | C15—N18 | 1.4673 (19) |
C6—H6 | 0.982 (19) | C16—C17 | 1.391 (2) |
C7—C11 | 1.368 (2) | C16—H16 | 0.97 (2) |
C7—N8 | 1.372 (2) | C17—H17 | 0.988 (19) |
N8—C9 | 1.375 (2) | N18—O19 | 1.2269 (17) |
N8—H8 | 0.92 (2) | N18—O20 | 1.2327 (17) |
C9—C10 | 1.363 (3) | ||
C7—C1—C2 | 111.59 (12) | N8—C9—H9 | 119.0 (12) |
C7—C1—C12 | 113.72 (12) | C9—C10—C11 | 107.51 (15) |
C2—C1—C12 | 111.02 (12) | C9—C10—H10 | 126.3 (12) |
C7—C1—H1 | 106.6 (9) | C11—C10—H10 | 126.1 (12) |
C2—C1—H1 | 106.7 (10) | C7—C11—C10 | 107.66 (15) |
C12—C1—H1 | 106.8 (9) | C7—C11—H11 | 126.0 (11) |
C6—C2—N3 | 107.70 (14) | C10—C11—H11 | 126.3 (11) |
C6—C2—C1 | 131.29 (14) | C17—C12—C13 | 118.84 (14) |
N3—C2—C1 | 120.97 (13) | C17—C12—C1 | 121.78 (13) |
C2—N3—C4 | 109.41 (14) | C13—C12—C1 | 119.35 (13) |
C2—N3—H3 | 126.7 (12) | C14—C13—C12 | 121.02 (14) |
C4—N3—H3 | 123.9 (12) | C14—C13—H13 | 119.2 (10) |
C5—C4—N3 | 107.87 (15) | C12—C13—H13 | 119.8 (10) |
C5—C4—H4 | 131.1 (12) | C15—C14—C13 | 118.18 (14) |
N3—C4—H4 | 121.1 (12) | C15—C14—H14 | 121.3 (11) |
C4—C5—C6 | 107.37 (15) | C13—C14—H14 | 120.4 (11) |
C4—C5—H5 | 125.7 (12) | C16—C15—C14 | 122.61 (14) |
C6—C5—H5 | 126.9 (12) | C16—C15—N18 | 117.99 (13) |
C2—C6—C5 | 107.64 (15) | C14—C15—N18 | 119.31 (14) |
C2—C6—H6 | 124.4 (11) | C15—C16—C17 | 118.25 (14) |
C5—C6—H6 | 127.9 (11) | C15—C16—H16 | 121.3 (11) |
C11—C7—N8 | 107.47 (14) | C17—C16—H16 | 120.4 (11) |
C11—C7—C1 | 130.44 (14) | C12—C17—C16 | 121.09 (14) |
N8—C7—C1 | 122.05 (14) | C12—C17—H17 | 119.5 (11) |
C9—N8—C7 | 109.68 (14) | C16—C17—H17 | 119.3 (11) |
C9—N8—H8 | 124.1 (14) | O19—N18—O20 | 123.18 (14) |
C7—N8—H8 | 126.3 (14) | O19—N18—C15 | 118.72 (13) |
C10—C9—N8 | 107.69 (15) | O20—N18—C15 | 118.10 (13) |
C10—C9—H9 | 133.2 (12) | ||
C7—C1—C2—C6 | 103.51 (19) | C1—C7—C11—C10 | 178.16 (15) |
C12—C1—C2—C6 | −24.5 (2) | C9—C10—C11—C7 | −0.35 (19) |
C7—C1—C2—N3 | −74.05 (18) | C7—C1—C12—C17 | −6.5 (2) |
C12—C1—C2—N3 | 157.96 (13) | C2—C1—C12—C17 | 120.33 (16) |
C6—C2—N3—C4 | 0.73 (18) | C7—C1—C12—C13 | 171.38 (13) |
C1—C2—N3—C4 | 178.81 (13) | C2—C1—C12—C13 | −61.80 (17) |
C2—N3—C4—C5 | −0.46 (19) | C17—C12—C13—C14 | 1.1 (2) |
N3—C4—C5—C6 | 0.02 (19) | C1—C12—C13—C14 | −176.80 (13) |
N3—C2—C6—C5 | −0.70 (18) | C12—C13—C14—C15 | −0.2 (2) |
C1—C2—C6—C5 | −178.51 (15) | C13—C14—C15—C16 | −0.4 (2) |
C4—C5—C6—C2 | 0.43 (19) | C13—C14—C15—N18 | 176.13 (13) |
C2—C1—C7—C11 | 138.64 (17) | C14—C15—C16—C17 | 0.0 (2) |
C12—C1—C7—C11 | −94.8 (2) | N18—C15—C16—C17 | −176.57 (13) |
C2—C1—C7—N8 | −43.78 (19) | C13—C12—C17—C16 | −1.5 (2) |
C12—C1—C7—N8 | 82.75 (17) | C1—C12—C17—C16 | 176.34 (14) |
C11—C7—N8—C9 | −0.15 (18) | C15—C16—C17—C12 | 1.0 (2) |
C1—C7—N8—C9 | −178.23 (14) | C16—C15—N18—O19 | 179.40 (14) |
C7—N8—C9—C10 | −0.07 (18) | C14—C15—N18—O19 | 2.7 (2) |
N8—C9—C10—C11 | 0.26 (19) | C16—C15—N18—O20 | 0.5 (2) |
N8—C7—C11—C10 | 0.31 (18) | C14—C15—N18—O20 | −176.22 (14) |
Experimental details
Crystal data | |
Chemical formula | C15H13N3O2 |
Mr | 267.28 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 110 |
a, b, c (Å) | 10.1940 (2), 11.4380 (3), 11.3180 (3) |
β (°) | 101.1840 (11) |
V (Å3) | 1294.61 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.25 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5274, 3061, 2204 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.658 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.114, 1.00 |
No. of reflections | 3061 |
No. of parameters | 233 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.23, −0.32 |
Computer programs: COLLECT (Nonius, 1999), DENZO (Otwinowski, 1985), DENZO, SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996), SHELXL97.
Dipyrromethane derivatives are useful building blocks in the synthesis of porphyrin model systems, with direct approaches to trans-substituted porphyrins by condensation of dipyrromethanes with aldehydes (Lee & Lindsey, 1994). Acidolysis of the dipyrromethane is negligible under the conditions of the porphyrin-forming reaction. Most of the dipyrromethanes are indefinitely stable in the purified form when stored at 273 K in the absence of light. Only a few crystal structures of dipyrromethane derivatives have been reported (Lin et al., 1996; Bennis & Gallagher, 1998; Gallagher & Moriarty, 1999). Herein we describe the synthesis and the structure of the title compound, (I), at ca 110 K. In the crystal, molecules related by a screw axis form weak N—H8···O20(2 - x, y - 1/2, 1/2 - z) hydrogen bonds, with N—H = 0.92 (2) Å, N···O = 3.051 (2) Å, H···O = 2.18 (2) Å, and N—H···O = 158.5 (15)°.