Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803005312/ob6221sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803005312/ob6221Isup2.hkl |
CCDC reference: 209952
Key indicators
- Single-crystal X-ray study
- T = 93 K
- Mean (C-C) = 0.004 Å
- R factor = 0.048
- wR factor = 0.107
- Data-to-parameter ratio = 13.0
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
REFLT_03 From the CIF: _diffrn_reflns_theta_max 68.25 From the CIF: _reflns_number_total 2243 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 2407 Completeness (_total/calc) 93.19% Alert C: < 95% complete
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
The title compound, (I), was prepared according to the method described in the literature (Zambounis et al., 1994). Single crystals of (I) were grown from an acetonitrile solution.
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: TEXSAN (Molecular Structure Corporation, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: TEXSAN; molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: TEXSAN.
Fig. 1. A view of the molecular structure of (I), showing ellipsoids at the 50% probability level for non-H atoms. |
C30H32N2O6 | F(000) = 548 |
Mr = 516.59 | Dx = 1.305 Mg m−3 |
Monoclinic, P21/n | Cu Kα radiation, λ = 1.5418 Å |
a = 7.148 (1) Å | Cell parameters from 5184 reflections |
b = 14.148 (3) Å | θ = 4.6–68.2° |
c = 13.065 (2) Å | µ = 0.75 mm−1 |
β = 95.729 (8)° | T = 93 K |
V = 1314.7 (4) Å3 | Block, colorless |
Z = 2 | 0.30 × 0.10 × 0.10 mm |
Rigaku R-AXIS RAPID Imaging Plate diffractometer | 1226 reflections with F2 > 2σ(F2) |
Detector resolution: 10.00 pixels mm-1 | Rint = 0.051 |
48 frames, delta ω = 15 deg scans | θmax = 68.3° |
Absorption correction: multi-scan (Higashi, 1995) | h = −7→7 |
Tmin = 0.841, Tmax = 0.928 | k = −16→17 |
12159 measured reflections | l = −15→15 |
2243 independent reflections |
Refinement on F2 | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.048 | w = 1/[σ2(Fo2) + (0.05P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.107 | (Δ/σ)max = 0.005 |
S = 0.87 | Δρmax = 0.57 e Å−3 |
2241 reflections | Δρmin = −0.33 e Å−3 |
172 parameters |
C30H32N2O6 | V = 1314.7 (4) Å3 |
Mr = 516.59 | Z = 2 |
Monoclinic, P21/n | Cu Kα radiation |
a = 7.148 (1) Å | µ = 0.75 mm−1 |
b = 14.148 (3) Å | T = 93 K |
c = 13.065 (2) Å | 0.30 × 0.10 × 0.10 mm |
β = 95.729 (8)° |
Rigaku R-AXIS RAPID Imaging Plate diffractometer | 2243 independent reflections |
Absorption correction: multi-scan (Higashi, 1995) | 1226 reflections with F2 > 2σ(F2) |
Tmin = 0.841, Tmax = 0.928 | Rint = 0.051 |
12159 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 172 parameters |
wR(F2) = 0.107 | H-atom parameters constrained |
S = 0.87 | Δρmax = 0.57 e Å−3 |
2241 reflections | Δρmin = −0.33 e Å−3 |
Refinement. Refinement using reflections with F2 > −10.0 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). |
x | y | z | Uiso*/Ueq | ||
O1 | 0.5113 (2) | 0.6072 (1) | 0.3071 (1) | 0.0368 (6) | |
O2 | 0.2681 (2) | 0.4883 (1) | 0.1822 (1) | 0.0410 (6) | |
O3 | 0.0431 (2) | 0.4415 (1) | 0.2832 (1) | 0.0311 (5) | |
N1 | 0.3296 (3) | 0.4789 (1) | 0.3582 (1) | 0.0285 (6) | |
C1 | 0.4748 (3) | 0.5508 (2) | 0.3722 (2) | 0.0320 (8) | |
C2 | 0.3152 (3) | 0.4277 (2) | 0.4515 (2) | 0.0282 (8) | |
C3 | 0.4485 (3) | 0.4633 (2) | 0.5214 (2) | 0.0286 (8) | |
C4 | 0.1805 (4) | 0.3506 (2) | 0.4632 (2) | 0.0337 (8) | |
C5 | 0.1886 (4) | 0.2654 (2) | 0.4109 (2) | 0.0361 (9) | |
C6 | 0.0587 (4) | 0.1932 (2) | 0.4297 (2) | 0.0381 (9) | |
C7 | −0.0718 (4) | 0.2090 (2) | 0.4976 (2) | 0.0415 (9) | |
C8 | −0.0807 (4) | 0.2940 (2) | 0.5504 (2) | 0.0444 (10) | |
C9 | 0.0461 (4) | 0.3640 (2) | 0.5350 (2) | 0.0424 (9) | |
C10 | 0.3378 (4) | 0.2478 (2) | 0.3438 (2) | 0.0443 (9) | |
C11 | 0.2117 (4) | 0.4703 (2) | 0.2638 (2) | 0.0335 (8) | |
C12 | −0.1026 (4) | 0.4160 (2) | 0.1978 (2) | 0.0321 (8) | |
C13 | −0.1674 (4) | 0.5058 (2) | 0.1412 (2) | 0.0419 (9) | |
C14 | −0.0268 (4) | 0.3432 (2) | 0.1283 (2) | 0.0414 (9) | |
C15 | −0.2543 (4) | 0.3740 (2) | 0.2560 (2) | 0.0416 (9) | |
H1 | 0.0611 | 0.1338 | 0.3959 | 0.0472* | |
H2 | −0.1598 | 0.1611 | 0.5084 | 0.0505* | |
H3 | −0.1729 | 0.3025 | 0.5965 | 0.0539* | |
H4 | 0.0430 | 0.4211 | 0.5730 | 0.0513* | |
H5 | −0.0635 | 0.5352 | 0.1147 | 0.0529* | |
H6 | −0.2609 | 0.4912 | 0.0873 | 0.0529* | |
H7 | −0.2186 | 0.5482 | 0.1884 | 0.0529* | |
H8 | 0.0100 | 0.2882 | 0.1670 | 0.0512* | |
H9 | −0.1201 | 0.3274 | 0.0746 | 0.0512* | |
H10 | 0.0803 | 0.3687 | 0.0998 | 0.0512* | |
H11 | −0.2976 | 0.4201 | 0.3012 | 0.0514* | |
H12 | −0.3574 | 0.3547 | 0.2083 | 0.0514* | |
H13 | −0.2069 | 0.3210 | 0.2943 | 0.0514* | |
H14 | 0.3237 | 0.1860 | 0.3121 | 0.0525* | |
H15 | 0.3333 | 0.2933 | 0.2884 | 0.0525* | |
H16 | 0.4594 | 0.2508 | 0.3805 | 0.0525* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.036 (1) | 0.040 (1) | 0.034 (1) | −0.0100 (9) | 0.0006 (9) | 0.0040 (9) |
O2 | 0.034 (1) | 0.057 (1) | 0.033 (1) | −0.0120 (10) | 0.0044 (9) | 0.000 (1) |
O3 | 0.021 (1) | 0.038 (1) | 0.034 (1) | −0.0042 (8) | 0.0000 (8) | 0.0002 (8) |
N1 | 0.021 (1) | 0.037 (1) | 0.026 (1) | −0.006 (1) | 0.0001 (9) | 0.001 (1) |
C1 | 0.025 (2) | 0.035 (2) | 0.037 (2) | −0.004 (1) | 0.003 (1) | −0.002 (1) |
C2 | 0.021 (2) | 0.035 (2) | 0.029 (1) | 0.001 (1) | 0.005 (1) | 0.000 (1) |
C3 | 0.020 (2) | 0.036 (2) | 0.029 (2) | −0.003 (1) | −0.001 (1) | 0.000 (1) |
C4 | 0.028 (2) | 0.036 (2) | 0.035 (2) | −0.003 (1) | −0.009 (1) | 0.000 (1) |
C5 | 0.024 (2) | 0.046 (2) | 0.037 (2) | 0.004 (1) | −0.006 (1) | 0.000 (1) |
C6 | 0.029 (2) | 0.044 (2) | 0.040 (2) | −0.007 (1) | −0.005 (1) | 0.001 (1) |
C7 | 0.043 (2) | 0.038 (2) | 0.043 (2) | −0.003 (1) | 0.005 (1) | 0.001 (1) |
C8 | 0.040 (2) | 0.051 (2) | 0.044 (2) | −0.007 (2) | 0.008 (1) | 0.003 (2) |
C9 | 0.029 (2) | 0.049 (2) | 0.048 (2) | −0.010 (1) | −0.003 (1) | 0.004 (2) |
C10 | 0.036 (2) | 0.047 (2) | 0.049 (2) | −0.004 (2) | −0.002 (1) | 0.001 (2) |
C11 | 0.026 (2) | 0.034 (2) | 0.040 (2) | −0.004 (1) | 0.002 (1) | −0.003 (1) |
C12 | 0.021 (2) | 0.039 (2) | 0.034 (2) | −0.001 (1) | −0.005 (1) | 0.000 (1) |
C13 | 0.034 (2) | 0.046 (2) | 0.043 (2) | 0.000 (1) | −0.008 (1) | 0.005 (1) |
C14 | 0.034 (2) | 0.047 (2) | 0.042 (2) | −0.006 (1) | −0.004 (1) | −0.008 (1) |
C15 | 0.025 (2) | 0.052 (2) | 0.047 (2) | −0.003 (1) | −0.004 (1) | 0.000 (1) |
O1—C1 | 1.214 (3) | C8—C9 | 1.370 (4) |
O2—C11 | 1.205 (3) | C8—H3 | 0.944 |
O3—C11 | 1.320 (3) | C9—H4 | 0.950 |
O3—C12 | 1.492 (3) | C10—H14 | 0.968 |
N1—C1 | 1.452 (3) | C10—H15 | 0.967 |
N1—C2 | 1.430 (3) | C10—H16 | 0.951 |
N1—C11 | 1.428 (3) | C12—C13 | 1.518 (4) |
C1—C3i | 1.456 (4) | C12—C14 | 1.510 (4) |
C2—C3 | 1.350 (3) | C12—C15 | 1.507 (4) |
C2—C4 | 1.473 (4) | C13—H5 | 0.947 |
C3—C3i | 1.420 (5) | C13—H6 | 0.944 |
C4—C5 | 1.390 (4) | C13—H7 | 0.959 |
C4—C9 | 1.421 (4) | C14—H8 | 0.951 |
C5—C6 | 1.419 (4) | C14—H9 | 0.946 |
C5—C10 | 1.468 (4) | C14—H10 | 0.954 |
C6—C7 | 1.368 (4) | C15—H11 | 0.952 |
C6—H1 | 0.951 | C15—H12 | 0.956 |
C7—C8 | 1.391 (4) | C15—H13 | 0.946 |
C7—H2 | 0.945 | ||
O1···C6ii | 3.315 (3) | O2···C6ii | 3.526 (3) |
O1···C14ii | 3.443 (4) | C1···C15iii | 3.592 (4) |
C11—O3—C12 | 120.9 (2) | C5—C10—H15 | 111.2 |
C1—N1—C2 | 111.0 (2) | C5—C10—H16 | 111.9 |
C1—N1—C11 | 121.4 (2) | H14—C10—H15 | 106.6 |
C2—N1—C11 | 127.3 (2) | H14—C10—H16 | 107.9 |
O1—C1—N1 | 125.0 (2) | H15—C10—H16 | 108.0 |
O1—C1—C3i | 132.3 (2) | O2—C11—O3 | 128.9 (2) |
N1—C1—C3i | 102.7 (2) | O2—C11—N1 | 121.7 (2) |
N1—C2—C3 | 106.4 (2) | O3—C11—N1 | 109.4 (2) |
N1—C2—C4 | 124.5 (2) | O3—C12—C13 | 108.6 (2) |
C3—C2—C4 | 129.1 (2) | O3—C12—C14 | 110.4 (2) |
C1i—C3—C2 | 140.2 (2) | O3—C12—C15 | 101.7 (2) |
C1i—C3—C3i | 108.4 (3) | C13—C12—C14 | 112.8 (2) |
C2—C3—C3i | 111.4 (3) | C13—C12—C15 | 112.0 (2) |
C2—C4—C5 | 122.1 (2) | C14—C12—C15 | 110.7 (2) |
C2—C4—C9 | 117.5 (2) | C12—C13—H5 | 109.5 |
C5—C4—C9 | 120.3 (3) | C12—C13—H6 | 109.9 |
C4—C5—C6 | 118.7 (3) | C12—C13—H7 | 109.1 |
C4—C5—C10 | 120.6 (3) | H5—C13—H6 | 110.2 |
C6—C5—C10 | 120.5 (3) | H5—C13—H7 | 108.9 |
C5—C6—C7 | 119.6 (3) | H6—C13—H7 | 109.2 |
C5—C6—H1 | 121.0 | C12—C14—H8 | 109.6 |
C7—C6—H1 | 119.4 | C12—C14—H9 | 109.8 |
C6—C7—C8 | 122.1 (3) | C12—C14—H10 | 109.1 |
C6—C7—H2 | 119.1 | H8—C14—H9 | 109.8 |
C8—C7—H2 | 118.8 | H8—C14—H10 | 109.1 |
C7—C8—C9 | 119.2 (3) | H9—C14—H10 | 109.5 |
C7—C8—H3 | 119.7 | C12—C15—H11 | 109.7 |
C9—C8—H3 | 121.1 | C12—C15—H12 | 109.3 |
C4—C9—C8 | 120.1 (3) | C12—C15—H13 | 109.9 |
C4—C9—H4 | 120.7 | H11—C15—H12 | 108.8 |
C8—C9—H4 | 119.2 | H11—C15—H13 | 109.7 |
C5—C10—H14 | 111.0 | H12—C15—H13 | 109.3 |
O1—C1—N1—C2 | −176.6 (2) | C2—C3—C3i—C2i | −180.0000 (2) |
O1—C1—N1—C11 | −1.5 (4) | C2—C4—C5—C6 | 177.3 (2) |
O1—C1—C3i—C2i | −1.4 (6) | C2—C4—C5—C10 | 2.1 (4) |
O1—C1—C3i—C3 | 176.6 (3) | C2—C4—C9—C8 | −178.9 (2) |
O2—C11—O3—C12 | 7.2 (4) | C3—C1i—N1i—C11i | −177.4 (2) |
O2—C11—N1—C1 | 32.9 (4) | C3—C2—N1—C11 | −176.3 (2) |
O2—C11—N1—C2 | −152.9 (3) | C3—C2—C4—C5 | −113.3 (3) |
O3—C11—N1—C1 | −146.8 (2) | C3—C2—C4—C9 | 63.3 (4) |
O3—C11—N1—C2 | 27.4 (3) | C3—C3i—C2i—C4i | −179.0 (3) |
N1—C1—C3i—C2i | 179.8 (3) | C4—C2—N1—C11 | 4.8 (4) |
N1—C1—C3i—C3 | −2.2 (3) | C4—C5—C6—C7 | 0.6 (4) |
N1—C2—C3—C1i | −177.9 (3) | C4—C9—C8—C7 | 2.1 (4) |
N1—C2—C3—C3i | 0.2 (3) | C5—C4—C9—C8 | −2.3 (4) |
N1—C2—C4—C5 | 65.3 (4) | C5—C6—C7—C8 | −0.8 (4) |
N1—C2—C4—C9 | −118.1 (3) | C6—C5—C4—C9 | 0.9 (4) |
N1—C11—O3—C12 | −173.0 (2) | C6—C7—C8—C9 | −0.6 (4) |
C1—N1—C2—C3 | −1.6 (3) | C7—C6—C5—C10 | 175.8 (2) |
C1—N1—C2—C4 | 179.5 (2) | C9—C4—C5—C10 | −174.3 (2) |
C1—C3i—C2i—C4i | −0.9 (5) | C11—O3—C12—C13 | −70.2 (3) |
C1—C3i—C3—C1i | 180.0 | C11—O3—C12—C14 | 53.9 (3) |
C1—C3i—C3—C2 | 1.3 (4) | C11—O3—C12—C15 | 171.5 (2) |
C2—N1—C1—C3i | 2.3 (3) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1/2, y+1/2, −z+1/2; (iii) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C30H32N2O6 |
Mr | 516.59 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 93 |
a, b, c (Å) | 7.148 (1), 14.148 (3), 13.065 (2) |
β (°) | 95.729 (8) |
V (Å3) | 1314.7 (4) |
Z | 2 |
Radiation type | Cu Kα |
µ (mm−1) | 0.75 |
Crystal size (mm) | 0.30 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID Imaging Plate diffractometer |
Absorption correction | Multi-scan (Higashi, 1995) |
Tmin, Tmax | 0.841, 0.928 |
No. of measured, independent and observed [F2 > 2σ(F2)] reflections | 12159, 2243, 1226 |
Rint | 0.051 |
(sin θ/λ)max (Å−1) | 0.602 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.107, 0.87 |
No. of reflections | 2241 |
No. of parameters | 172 |
No. of restraints | ? |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.57, −0.33 |
Computer programs: PROCESS-AUTO (Rigaku, 1998), PROCESS-AUTO, TEXSAN (Molecular Structure Corporation, 2001), SHELXS97 (Sheldrick, 1997), TEXSAN, ORTEPIII (Burnett & Johnson, 1996).
O1—C1 | 1.214 (3) | N1—C11 | 1.428 (3) |
O2—C11 | 1.205 (3) | C1—C3i | 1.456 (4) |
O3—C11 | 1.320 (3) | C2—C3 | 1.350 (3) |
O3—C12 | 1.492 (3) | C2—C4 | 1.473 (4) |
N1—C1 | 1.452 (3) | C3—C3i | 1.420 (5) |
N1—C2 | 1.430 (3) | ||
O2—C11—N1—C1 | 32.9 (4) | N1—C2—C4—C5 | 65.3 (4) |
O2—C11—N1—C2 | −152.9 (3) | N1—C2—C4—C9 | −118.1 (3) |
O3—C11—N1—C1 | −146.8 (2) | C3—C2—C4—C5 | −113.3 (3) |
O3—C11—N1—C2 | 27.4 (3) | C3—C2—C4—C9 | 63.3 (4) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
The title compound, (I), is a soluble yellow precursor (`latent pigment') (Zambounis et al., 1994, 1997) of diketopyrrolopyrrole pigments (DPP) (Herbst & Hunger, 1997) that are known as industrially important red pigments. The soluble precursor is prepared by replacing the H atom of the NH group with a tert-butoxycarbonyl (t-BOC) group, hereafter called t-BOC DPP. The insoluble parent DPP can then be regenerated by thermochemical treatment of the precursor. The present `latent pigment technology' is a versatile and promising technique for the preparation of nano pigment particles, as well as transparent pigmented thin films, etc. We have previously reported the crystal structures of the α- and β-forms of unsubstituted DPP (Mizuguchi, 2003a,b). The present paper deals with the crystal structure of o-methylphenyl derivative, (I).
The title compound crystallizes in space group P21/c and the molecule belongs to the molecular symmetry of Ci (Fig. 1). The phenyl rings are symmetrically deviated from the heterocyclic system by 64.5 (1)° [N1/C1/C2/C3/C3i and C4–C9; symmetry code: (i) 1 − x, 1 − y, 1 − z]. The t-BOC groups attached to the N atom of the heterocyclic ring are also symmetrically twisted to the heterocyclic system by 30.7 (1)° (N1/C1/C2/C3/C3i and N1/C11/O2/O3). The heterocyclic ring system is entirely planar. The molecules are stacked along the a axis.