




Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536808000548/gg3141sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536808000548/gg3141Isup2.hkl |
CCDC reference: 677636
Key indicators
- Single-crystal X-ray study
- T = 119 K
- Mean
(C-C) = 0.009 Å
- R factor = 0.079
- wR factor = 0.203
- Data-to-parameter ratio = 26.2
checkCIF/PLATON results
No syntax errors found
Alert level A REFLT03_ALERT_3_A Reflection count > 15% excess reflns - sys abs data present? From the CIF: _diffrn_reflns_theta_max 25.00 From the CIF: _diffrn_reflns_theta_full 25.00 From the CIF: _reflns_number_total 11128 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 6035 Completeness (_total/calc) 184.39%
Author Response: Data is in twinned data format (HKLF 5) with contribution to each of two twins. |
PLAT029_ALERT_3_A _diffrn_measured_fraction_theta_full Low ....... 0.92
Author Response: Not all reciprocal space was sampled but sufficient data to determine the structure was collected. |
Alert level B ABSTM02_ALERT_3_B The ratio of expected to reported Tmax/Tmin(RR') is < 0.75 Tmin and Tmax reported: 0.733 1.000 Tmin(prime) and Tmax expected: 0.972 0.993 RR(prime) = 0.749 Please check that your absorption correction is appropriate. REFLT01_ALERT_1_B The number of symmetry-independent reflections cannot exceed the total number of reflections measured Number of symmetry-independent reflections = 11128 Total number of reflections = 11106 PLAT021_ALERT_1_B Ratio Unique / Expected Reflections too High ... 1.84 PLAT061_ALERT_3_B Tmax/Tmin Range Test RR' too Large ............. 0.75 PLAT201_ALERT_2_B Isotropic non-H Atoms in Main Residue(s) ....... 3
Alert level C PLAT030_ALERT_1_C _diffrn_reflns_number .LE. _reflns_number_total ? PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 9 PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C1 - C2 ... 1.45 Ang. PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C1' - C2' ... 1.42 Ang. PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 6
Alert level G ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.993 Tmax scaled 0.993 Tmin scaled 0.728
2 ALERT level A = In general: serious problem 5 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 3 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 6 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
To a solution of 5.8 mmole of {4-(4-Acetanilido-trans-1,3-butadienyl)-3-cyano-5,5-dimethyl-2(5H)-furanylidene} propanedinitrile (compound 11b, Kay et al., 2004) in 30 ml of ethanol was added an equimolar quantity of piperidine. The solution was refluxed 1 h, cooled and the product collected by filtration and washed with ethanol. Final crystallization was from ethanol.
The measured crystal was a pseudo-merohedral twin. The twin operation was a 2-fold rotation about (1 0 - 2), with twin matrix (-1 0 - 1/0 - 1 0/-0.001 0 1) as indicated by the PLATON/TwinRotMat (Spek, 2003) utility that also produced an HKLF5 file for twin refinement with SHELXL97. The twin fraction refined to 0.5124 (16). Data was restricted to 2θ ≤ 50° (see _refine_special_details for other statistics of the dataset used).
All H atoms bound to carbon were constrained to their expected geometries (C—H 0.98, 0.99 Å). All methyl and tertiary H atoms were refined with Uiso 1.5 & 1.2 times respectively that of the Ueq of their parent atom. All non-hydrogen atoms were refined with anisotropic thermal parameters.
Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005) and SADABS (Sheldrick, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2003).
C19H20N4O | F(000) = 1360 |
Mr = 320.39 | Dx = 1.241 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4176 reflections |
a = 15.094 (4) Å | θ = 2.7–30.2° |
b = 18.994 (5) Å | µ = 0.08 mm−1 |
c = 13.332 (4) Å | T = 119 K |
β = 116.193 (8)° | Plate, red |
V = 3429.7 (16) Å3 | 0.35 × 0.25 × 0.09 mm |
Z = 8 |
Bruker–Nonius APEXII CCD area-detector diffractometer | 11128 independent reflections |
Radiation source: fine-focus sealed tube | 5766 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.088 |
Detector resolution: 8.192 pixels mm-1 | θmax = 25.0°, θmin = 2.0° |
/f and /w scans | h = −16→17 |
Absorption correction: multi-scan (Blessing, 1995) | k = −22→22 |
Tmin = 0.733, Tmax = 1.0 | l = −15→15 |
18712 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.079 | H-atom parameters constrained |
wR(F2) = 0.203 | w = 1/[σ2(Fo2) + (0.041P)2 + 5.943P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max < 0.001 |
11128 reflections | Δρmax = 0.46 e Å−3 |
424 parameters | Δρmin = −0.36 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0014 (2) |
C19H20N4O | V = 3429.7 (16) Å3 |
Mr = 320.39 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 15.094 (4) Å | µ = 0.08 mm−1 |
b = 18.994 (5) Å | T = 119 K |
c = 13.332 (4) Å | 0.35 × 0.25 × 0.09 mm |
β = 116.193 (8)° |
Bruker–Nonius APEXII CCD area-detector diffractometer | 11128 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 5766 reflections with I > 2σ(I) |
Tmin = 0.733, Tmax = 1.0 | Rint = 0.088 |
18712 measured reflections |
R[F2 > 2σ(F2)] = 0.079 | 0 restraints |
wR(F2) = 0.203 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.46 e Å−3 |
11128 reflections | Δρmin = −0.36 e Å−3 |
424 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. An extinction parameter was refined. Data above 2θ 50° were excluded on the basis of low intensity/error ratio. A total of 477 reflections were either not recorded or affected by the backstop within this θ limit (of 6035 expected). A further 13 reflections (and their Friedel opposites) were omitted from the refinement on the basis of being clearly outliers (with Fo<<Fc). 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 | ||
O1 | 0.7393 (3) | 0.8303 (2) | 0.4515 (3) | 0.0343 (10) | |
N1 | 0.9567 (4) | 0.7590 (3) | 0.2970 (5) | 0.0422 (15) | |
N2 | 0.8344 (4) | 0.9570 (3) | 0.3440 (4) | 0.0489 (15) | |
N3 | 0.8724 (4) | 0.6091 (3) | 0.4162 (5) | 0.0473 (15) | |
N4 | 0.5250 (3) | 0.5399 (2) | 0.7252 (4) | 0.0326 (12) | |
C1 | 0.9063 (4) | 0.7849 (3) | 0.3282 (5) | 0.0356 (16) | |
C2 | 0.8470 (4) | 0.8229 (3) | 0.3707 (5) | 0.0321 (14) | |
C3 | 0.8397 (4) | 0.8966 (4) | 0.3552 (5) | 0.0362 (15) | |
C4 | 0.7276 (4) | 0.7135 (3) | 0.5029 (5) | 0.0289 (15) | |
C5 | 0.6857 (4) | 0.7869 (3) | 0.4989 (5) | 0.0311 (15) | |
C6 | 0.7962 (4) | 0.7888 (3) | 0.4209 (5) | 0.0305 (14) | |
C7 | 0.7908 (4) | 0.7191 (3) | 0.4492 (5) | 0.0283 (14)* | |
C8 | 0.5770 (4) | 0.7903 (3) | 0.4147 (5) | 0.0395 (16) | |
H8A | 0.5545 | 0.8394 | 0.4055 | 0.059* | |
H8B | 0.5378 | 0.7621 | 0.4420 | 0.059* | |
H8C | 0.5690 | 0.7718 | 0.3426 | 0.059* | |
C9 | 0.7073 (4) | 0.8205 (3) | 0.6121 (5) | 0.0400 (17) | |
H9A | 0.6905 | 0.8707 | 0.6015 | 0.060* | |
H9B | 0.7776 | 0.8151 | 0.6630 | 0.060* | |
H9C | 0.6677 | 0.7971 | 0.6440 | 0.060* | |
C10 | 0.8375 (4) | 0.6601 (3) | 0.4304 (5) | 0.0336 (15) | |
C11 | 0.7080 (4) | 0.6540 (3) | 0.5476 (5) | 0.0344 (16) | |
H11 | 0.7436 | 0.6126 | 0.5486 | 0.041* | |
C12 | 0.6398 (4) | 0.6493 (3) | 0.5920 (4) | 0.0297 (14) | |
H12 | 0.6046 | 0.6906 | 0.5925 | 0.036* | |
C13 | 0.6206 (4) | 0.5883 (3) | 0.6352 (5) | 0.0323 (15) | |
H13 | 0.6557 | 0.5462 | 0.6387 | 0.039* | |
C14 | 0.5483 (4) | 0.5901 (3) | 0.6736 (5) | 0.0362 (16) | |
H14 | 0.5117 | 0.6327 | 0.6610 | 0.043* | |
C15 | 0.4434 (4) | 0.5482 (3) | 0.7556 (5) | 0.0389 (16) | |
H15A | 0.4120 | 0.5948 | 0.7305 | 0.047* | |
H15B | 0.4690 | 0.5458 | 0.8379 | 0.047* | |
C16 | 0.3684 (4) | 0.4911 (3) | 0.7020 (5) | 0.0438 (17)* | |
H16A | 0.3393 | 0.4959 | 0.6197 | 0.053* | |
H16B | 0.3147 | 0.4958 | 0.7250 | 0.053* | |
C17 | 0.4162 (4) | 0.4197 (3) | 0.7361 (5) | 0.0448 (17) | |
H17A | 0.3667 | 0.3824 | 0.6982 | 0.054* | |
H17B | 0.4412 | 0.4135 | 0.8178 | 0.054* | |
C18 | 0.5018 (4) | 0.4130 (3) | 0.7040 (6) | 0.0430 (17)* | |
H18A | 0.5355 | 0.3673 | 0.7307 | 0.052* | |
H18B | 0.4756 | 0.4143 | 0.6216 | 0.052* | |
C19 | 0.5750 (4) | 0.4721 (3) | 0.7545 (5) | 0.0391 (16) | |
H19A | 0.6084 | 0.4669 | 0.8368 | 0.047* | |
H19B | 0.6259 | 0.4697 | 0.7267 | 0.047* | |
O1' | 0.2394 (3) | 0.8340 (2) | 0.2535 (3) | 0.0340 (10) | |
N1' | 0.4636 (4) | 0.7639 (3) | 0.6209 (5) | 0.0443 (15) | |
N2' | 0.3455 (4) | 0.9652 (3) | 0.4508 (4) | 0.0480 (15) | |
N3' | 0.3582 (4) | 0.6149 (3) | 0.4407 (4) | 0.0443 (15) | |
N4' | 0.0597 (3) | 0.5220 (2) | −0.2095 (4) | 0.0313 (12) | |
C1' | 0.4113 (4) | 0.7928 (3) | 0.5417 (5) | 0.0347 (15) | |
C2' | 0.3478 (4) | 0.8300 (3) | 0.4436 (5) | 0.0288 (14) | |
C3' | 0.3455 (4) | 0.9041 (4) | 0.4475 (5) | 0.0334 (15) | |
C4' | 0.2259 (4) | 0.7152 (3) | 0.1981 (5) | 0.0269 (14) | |
C5' | 0.1910 (4) | 0.7881 (3) | 0.1521 (5) | 0.0320 (15) | |
C6' | 0.2942 (4) | 0.7932 (3) | 0.3443 (5) | 0.0311 (15) | |
C7' | 0.2857 (4) | 0.7224 (3) | 0.3153 (5) | 0.0295 (15) | |
C8' | 0.0811 (4) | 0.7979 (3) | 0.1116 (5) | 0.0465 (18) | |
H8'A | 0.0653 | 0.8482 | 0.1026 | 0.070* | |
H8'B | 0.0613 | 0.7778 | 0.1663 | 0.070* | |
H8'C | 0.0456 | 0.7740 | 0.0396 | 0.070* | |
C9' | 0.2278 (4) | 0.8151 (3) | 0.0713 (5) | 0.0422 (17) | |
H9'A | 0.2170 | 0.8660 | 0.0622 | 0.063* | |
H9'B | 0.1918 | 0.7918 | −0.0011 | 0.063* | |
H9'C | 0.2984 | 0.8050 | 0.1002 | 0.063* | |
C10' | 0.3282 (4) | 0.6651 (3) | 0.3876 (5) | 0.0315 (15) | |
C11' | 0.2043 (4) | 0.6539 (3) | 0.1390 (5) | 0.0303 (14) | |
H11' | 0.2299 | 0.6119 | 0.1804 | 0.036* | |
C12' | 0.1479 (4) | 0.6464 (3) | 0.0229 (5) | 0.0296 (14) | |
H12' | 0.1188 | 0.6872 | −0.0203 | 0.035* | |
C13' | 0.1330 (4) | 0.5823 (3) | −0.0312 (5) | 0.0318 (15) | |
H13' | 0.1608 | 0.5407 | 0.0103 | 0.038* | |
C14' | 0.0770 (4) | 0.5789 (3) | −0.1468 (5) | 0.0330 (15) | |
H14' | 0.0486 | 0.6217 | −0.1841 | 0.040* | |
C15' | −0.0091 (4) | 0.5216 (3) | −0.3290 (5) | 0.0425 (18) | |
H15C | 0.0259 | 0.5050 | −0.3723 | 0.051* | |
H15D | −0.0324 | 0.5702 | −0.3534 | 0.051* | |
C16' | −0.0964 (4) | 0.4748 (3) | −0.3530 (5) | 0.0440 (17) | |
H16C | −0.1387 | 0.4728 | −0.4346 | 0.053* | |
H16D | −0.1362 | 0.4944 | −0.3172 | 0.053* | |
C17' | −0.0618 (4) | 0.4010 (3) | −0.3085 (5) | 0.0444 (18) | |
H17C | −0.0300 | 0.3789 | −0.3516 | 0.053* | |
H17D | −0.1194 | 0.3718 | −0.3183 | 0.053* | |
C18' | 0.0114 (4) | 0.4035 (3) | −0.1846 (5) | 0.0419 (18) | |
H18C | −0.0224 | 0.4209 | −0.1406 | 0.050* | |
H18D | 0.0362 | 0.3554 | −0.1583 | 0.050* | |
C19' | 0.0967 (4) | 0.4509 (3) | −0.1666 (5) | 0.0374 (15) | |
H19C | 0.1422 | 0.4535 | −0.0858 | 0.045* | |
H19D | 0.1337 | 0.4317 | −0.2060 | 0.045* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.041 (3) | 0.032 (2) | 0.036 (3) | 0.000 (2) | 0.023 (2) | 0.003 (2) |
N1 | 0.037 (3) | 0.047 (4) | 0.047 (4) | 0.001 (3) | 0.023 (3) | 0.002 (3) |
N2 | 0.066 (4) | 0.047 (4) | 0.037 (4) | −0.002 (3) | 0.026 (3) | −0.004 (3) |
N3 | 0.051 (4) | 0.047 (4) | 0.053 (4) | 0.002 (3) | 0.031 (3) | 0.005 (3) |
N4 | 0.028 (3) | 0.036 (3) | 0.034 (3) | 0.000 (3) | 0.014 (2) | 0.002 (3) |
C1 | 0.024 (4) | 0.039 (4) | 0.035 (4) | −0.001 (3) | 0.005 (3) | 0.002 (3) |
C2 | 0.033 (3) | 0.034 (4) | 0.032 (4) | −0.004 (3) | 0.016 (3) | −0.002 (3) |
C3 | 0.036 (4) | 0.044 (4) | 0.028 (4) | −0.006 (4) | 0.014 (3) | −0.004 (3) |
C4 | 0.024 (3) | 0.030 (4) | 0.030 (4) | −0.008 (3) | 0.010 (3) | −0.004 (3) |
C5 | 0.037 (4) | 0.029 (4) | 0.035 (4) | −0.007 (3) | 0.023 (3) | −0.002 (3) |
C6 | 0.025 (3) | 0.043 (4) | 0.024 (3) | −0.001 (3) | 0.012 (3) | −0.001 (3) |
C8 | 0.033 (4) | 0.047 (4) | 0.040 (4) | 0.005 (3) | 0.017 (3) | 0.005 (3) |
C9 | 0.053 (4) | 0.044 (4) | 0.027 (4) | −0.004 (3) | 0.021 (3) | −0.010 (3) |
C10 | 0.030 (4) | 0.042 (4) | 0.027 (3) | −0.003 (3) | 0.011 (3) | 0.008 (3) |
C11 | 0.028 (3) | 0.041 (4) | 0.034 (4) | −0.006 (3) | 0.014 (3) | 0.000 (3) |
C12 | 0.023 (3) | 0.035 (4) | 0.027 (3) | −0.004 (3) | 0.007 (3) | 0.000 (3) |
C13 | 0.030 (4) | 0.031 (4) | 0.035 (4) | −0.003 (3) | 0.013 (3) | −0.001 (3) |
C14 | 0.029 (4) | 0.039 (4) | 0.036 (4) | −0.006 (3) | 0.010 (3) | 0.002 (3) |
C15 | 0.036 (4) | 0.043 (4) | 0.045 (4) | −0.007 (3) | 0.024 (3) | 0.001 (3) |
C17 | 0.043 (4) | 0.046 (4) | 0.047 (4) | −0.013 (4) | 0.020 (3) | −0.005 (4) |
C19 | 0.034 (4) | 0.047 (4) | 0.039 (4) | 0.008 (3) | 0.018 (3) | 0.010 (3) |
O1' | 0.038 (3) | 0.037 (3) | 0.022 (2) | 0.001 (2) | 0.0086 (19) | −0.005 (2) |
N1' | 0.045 (4) | 0.045 (4) | 0.034 (4) | 0.003 (3) | 0.010 (3) | −0.007 (3) |
N2' | 0.060 (4) | 0.049 (4) | 0.037 (4) | −0.004 (3) | 0.023 (3) | −0.004 (3) |
N3' | 0.042 (3) | 0.051 (4) | 0.035 (3) | 0.006 (3) | 0.012 (3) | 0.003 (3) |
N4' | 0.035 (3) | 0.024 (3) | 0.028 (3) | −0.001 (2) | 0.008 (2) | −0.003 (2) |
C1' | 0.027 (4) | 0.043 (4) | 0.029 (4) | −0.004 (3) | 0.007 (3) | −0.008 (3) |
C2' | 0.022 (3) | 0.034 (4) | 0.028 (3) | −0.001 (3) | 0.009 (3) | −0.001 (3) |
C3' | 0.035 (4) | 0.047 (4) | 0.020 (3) | −0.004 (4) | 0.014 (3) | −0.006 (3) |
C4' | 0.020 (3) | 0.033 (4) | 0.027 (3) | −0.001 (3) | 0.009 (2) | −0.005 (3) |
C5' | 0.031 (4) | 0.043 (4) | 0.015 (3) | −0.005 (3) | 0.004 (2) | −0.006 (3) |
C6' | 0.020 (3) | 0.046 (4) | 0.024 (3) | −0.001 (3) | 0.008 (3) | −0.003 (3) |
C7' | 0.021 (3) | 0.035 (4) | 0.028 (4) | 0.002 (3) | 0.007 (3) | 0.000 (3) |
C8' | 0.046 (4) | 0.055 (4) | 0.034 (4) | 0.009 (4) | 0.013 (3) | −0.001 (3) |
C9' | 0.059 (4) | 0.039 (4) | 0.030 (4) | 0.002 (3) | 0.020 (3) | 0.006 (3) |
C10' | 0.026 (4) | 0.037 (4) | 0.030 (4) | −0.001 (3) | 0.010 (3) | −0.006 (3) |
C11' | 0.024 (3) | 0.036 (4) | 0.026 (3) | 0.004 (3) | 0.007 (3) | 0.000 (3) |
C12' | 0.031 (3) | 0.028 (3) | 0.031 (4) | 0.003 (3) | 0.015 (3) | 0.000 (3) |
C13' | 0.026 (3) | 0.038 (4) | 0.028 (4) | −0.001 (3) | 0.009 (3) | −0.002 (3) |
C14' | 0.034 (4) | 0.028 (4) | 0.036 (4) | −0.002 (3) | 0.015 (3) | −0.006 (3) |
C15' | 0.051 (4) | 0.045 (4) | 0.021 (3) | 0.008 (4) | 0.007 (3) | 0.000 (3) |
C16' | 0.036 (4) | 0.054 (5) | 0.035 (4) | 0.000 (4) | 0.009 (3) | −0.004 (3) |
C17' | 0.034 (4) | 0.052 (5) | 0.043 (4) | −0.007 (4) | 0.014 (3) | −0.010 (3) |
C18' | 0.050 (4) | 0.041 (4) | 0.034 (4) | −0.005 (3) | 0.017 (3) | −0.005 (3) |
C19' | 0.037 (4) | 0.033 (4) | 0.037 (4) | 0.010 (3) | 0.012 (3) | 0.000 (3) |
O1—C6 | 1.355 (6) | O1'—C6' | 1.365 (6) |
O1—C5 | 1.478 (6) | O1'—C5' | 1.500 (6) |
N1—C1 | 1.128 (7) | N1'—C1' | 1.141 (7) |
N2—C3 | 1.156 (7) | N2'—C3' | 1.161 (7) |
N3—C10 | 1.157 (7) | N3'—C10' | 1.154 (7) |
N4—C14 | 1.310 (7) | N4'—C14' | 1.320 (6) |
N4—C19 | 1.458 (6) | N4'—C15' | 1.468 (6) |
N4—C15 | 1.466 (7) | N4'—C19' | 1.477 (6) |
C1—C2 | 1.446 (8) | C1'—C2' | 1.422 (8) |
C2—C6 | 1.381 (8) | C2'—C6' | 1.396 (7) |
C2—C3 | 1.412 (8) | C2'—C3' | 1.410 (8) |
C4—C11 | 1.370 (7) | C4'—C11' | 1.362 (7) |
C4—C7 | 1.426 (8) | C4'—C7' | 1.425 (7) |
C4—C5 | 1.523 (8) | C4'—C5' | 1.511 (7) |
C5—C8 | 1.527 (7) | C5'—C9' | 1.503 (8) |
C5—C9 | 1.534 (8) | C5'—C8' | 1.512 (7) |
C6—C7 | 1.390 (7) | C6'—C7' | 1.390 (7) |
C7—C10 | 1.404 (8) | C7'—C10' | 1.407 (8) |
C8—H8A | 0.9800 | C8'—H8'A | 0.9800 |
C8—H8B | 0.9800 | C8'—H8'B | 0.9800 |
C8—H8C | 0.9800 | C8'—H8'C | 0.9800 |
C9—H9A | 0.9800 | C9'—H9'A | 0.9800 |
C9—H9B | 0.9800 | C9'—H9'B | 0.9800 |
C9—H9C | 0.9800 | C9'—H9'C | 0.9800 |
C11—C12 | 1.398 (7) | C11'—C12' | 1.405 (8) |
C11—H11 | 0.9500 | C11'—H11' | 0.9500 |
C12—C13 | 1.380 (7) | C12'—C13' | 1.382 (7) |
C12—H12 | 0.9500 | C12'—H12' | 0.9500 |
C13—C14 | 1.396 (8) | C13'—C14' | 1.395 (7) |
C13—H13 | 0.9500 | C13'—H13' | 0.9500 |
C14—H14 | 0.9500 | C14'—H14' | 0.9500 |
C15—C16 | 1.501 (7) | C15'—C16' | 1.503 (8) |
C15—H15A | 0.9900 | C15'—H15C | 0.9900 |
C15—H15B | 0.9900 | C15'—H15D | 0.9900 |
C16—C17 | 1.509 (7) | C16'—C17' | 1.522 (8) |
C16—H16A | 0.9900 | C16'—H16C | 0.9900 |
C16—H16B | 0.9900 | C16'—H16D | 0.9900 |
C17—C18 | 1.536 (8) | C17'—C18' | 1.530 (7) |
C17—H17A | 0.9900 | C17'—H17C | 0.9900 |
C17—H17B | 0.9900 | C17'—H17D | 0.9900 |
C18—C19 | 1.508 (7) | C18'—C19' | 1.501 (7) |
C18—H18A | 0.9900 | C18'—H18C | 0.9900 |
C18—H18B | 0.9900 | C18'—H18D | 0.9900 |
C19—H19A | 0.9900 | C19'—H19C | 0.9900 |
C19—H19B | 0.9900 | C19'—H19D | 0.9900 |
C6—O1—C5 | 110.2 (4) | C6'—O1'—C5' | 109.4 (4) |
C14—N4—C19 | 123.9 (5) | C14'—N4'—C15' | 122.6 (5) |
C14—N4—C15 | 121.3 (5) | C14'—N4'—C19' | 124.6 (5) |
C19—N4—C15 | 114.8 (5) | C15'—N4'—C19' | 112.4 (4) |
N1—C1—C2 | 175.4 (7) | N1'—C1'—C2' | 178.8 (7) |
C6—C2—C3 | 120.7 (6) | C6'—C2'—C3' | 121.4 (5) |
C6—C2—C1 | 121.9 (5) | C6'—C2'—C1' | 119.8 (5) |
C3—C2—C1 | 117.4 (6) | C3'—C2'—C1' | 118.7 (5) |
N2—C3—C2 | 179.1 (8) | N2'—C3'—C2' | 178.7 (7) |
C11—C4—C7 | 126.9 (6) | C11'—C4'—C7' | 126.2 (5) |
C11—C4—C5 | 127.2 (5) | C11'—C4'—C5' | 126.6 (5) |
C7—C4—C5 | 105.9 (5) | C7'—C4'—C5' | 107.2 (5) |
O1—C5—C4 | 103.2 (4) | O1'—C5'—C9' | 105.1 (4) |
O1—C5—C8 | 106.0 (5) | O1'—C5'—C4' | 102.9 (4) |
C4—C5—C8 | 111.1 (5) | C9'—C5'—C4' | 115.5 (5) |
O1—C5—C9 | 105.7 (4) | O1'—C5'—C8' | 105.8 (5) |
C4—C5—C9 | 116.2 (5) | C9'—C5'—C8' | 113.3 (5) |
C8—C5—C9 | 113.5 (5) | C4'—C5'—C8' | 112.8 (5) |
O1—C6—C2 | 115.8 (5) | O1'—C6'—C7' | 110.9 (5) |
O1—C6—C7 | 110.5 (5) | O1'—C6'—C2' | 115.4 (5) |
C2—C6—C7 | 133.7 (6) | C7'—C6'—C2' | 133.7 (6) |
C6—C7—C10 | 128.1 (5) | C6'—C7'—C10' | 126.9 (5) |
C6—C7—C4 | 109.9 (5) | C6'—C7'—C4' | 109.5 (5) |
C10—C7—C4 | 122.0 (5) | C10'—C7'—C4' | 123.6 (5) |
C5—C8—H8A | 109.5 | C5'—C8'—H8'A | 109.5 |
C5—C8—H8B | 109.5 | C5'—C8'—H8'B | 109.5 |
H8A—C8—H8B | 109.5 | H8'A—C8'—H8'B | 109.5 |
C5—C8—H8C | 109.5 | C5'—C8'—H8'C | 109.5 |
H8A—C8—H8C | 109.5 | H8'A—C8'—H8'C | 109.5 |
H8B—C8—H8C | 109.5 | H8'B—C8'—H8'C | 109.5 |
C5—C9—H9A | 109.5 | C5'—C9'—H9'A | 109.5 |
C5—C9—H9B | 109.5 | C5'—C9'—H9'B | 109.5 |
H9A—C9—H9B | 109.5 | H9'A—C9'—H9'B | 109.5 |
C5—C9—H9C | 109.5 | C5'—C9'—H9'C | 109.5 |
H9A—C9—H9C | 109.5 | H9'A—C9'—H9'C | 109.5 |
H9B—C9—H9C | 109.5 | H9'B—C9'—H9'C | 109.5 |
N3—C10—C7 | 176.2 (6) | N3'—C10'—C7' | 174.9 (6) |
C4—C11—C12 | 125.3 (6) | C4'—C11'—C12' | 126.7 (6) |
C4—C11—H11 | 117.3 | C4'—C11'—H11' | 116.7 |
C12—C11—H11 | 117.3 | C12'—C11'—H11' | 116.7 |
C13—C12—C11 | 124.1 (6) | C13'—C12'—C11' | 122.9 (6) |
C13—C12—H12 | 118.0 | C13'—C12'—H12' | 118.5 |
C11—C12—H12 | 118.0 | C11'—C12'—H12' | 118.5 |
C12—C13—C14 | 118.4 (6) | C12'—C13'—C14' | 119.8 (6) |
C12—C13—H13 | 120.8 | C12'—C13'—H13' | 120.1 |
C14—C13—H13 | 120.8 | C14'—C13'—H13' | 120.1 |
N4—C14—C13 | 127.5 (6) | N4'—C14'—C13' | 126.3 (6) |
N4—C14—H14 | 116.3 | N4'—C14'—H14' | 116.9 |
C13—C14—H14 | 116.3 | C13'—C14'—H14' | 116.9 |
N4—C15—C16 | 109.8 (5) | N4'—C15'—C16' | 111.6 (5) |
N4—C15—H15A | 109.7 | N4'—C15'—H15C | 109.3 |
C16—C15—H15A | 109.7 | C16'—C15'—H15C | 109.3 |
N4—C15—H15B | 109.7 | N4'—C15'—H15D | 109.3 |
C16—C15—H15B | 109.7 | C16'—C15'—H15D | 109.3 |
H15A—C15—H15B | 108.2 | H15C—C15'—H15D | 108.0 |
C15—C16—C17 | 110.3 (5) | C15'—C16'—C17' | 110.2 (5) |
C15—C16—H16A | 109.6 | C15'—C16'—H16C | 109.6 |
C17—C16—H16A | 109.6 | C17'—C16'—H16C | 109.6 |
C15—C16—H16B | 109.6 | C15'—C16'—H16D | 109.6 |
C17—C16—H16B | 109.6 | C17'—C16'—H16D | 109.6 |
H16A—C16—H16B | 108.1 | H16C—C16'—H16D | 108.1 |
C16—C17—C18 | 109.8 (5) | C16'—C17'—C18' | 110.6 (5) |
C16—C17—H17A | 109.7 | C16'—C17'—H17C | 109.5 |
C18—C17—H17A | 109.7 | C18'—C17'—H17C | 109.5 |
C16—C17—H17B | 109.7 | C16'—C17'—H17D | 109.5 |
C18—C17—H17B | 109.7 | C18'—C17'—H17D | 109.5 |
H17A—C17—H17B | 108.2 | H17C—C17'—H17D | 108.1 |
C19—C18—C17 | 110.8 (5) | C19'—C18'—C17' | 110.6 (5) |
C19—C18—H18A | 109.5 | C19'—C18'—H18C | 109.5 |
C17—C18—H18A | 109.5 | C17'—C18'—H18C | 109.5 |
C19—C18—H18B | 109.5 | C19'—C18'—H18D | 109.5 |
C17—C18—H18B | 109.5 | C17'—C18'—H18D | 109.5 |
H18A—C18—H18B | 108.1 | H18C—C18'—H18D | 108.1 |
N4—C19—C18 | 110.3 (5) | N4'—C19'—C18' | 109.6 (4) |
N4—C19—H19A | 109.6 | N4'—C19'—H19C | 109.8 |
C18—C19—H19A | 109.6 | C18'—C19'—H19C | 109.8 |
N4—C19—H19B | 109.6 | N4'—C19'—H19D | 109.8 |
C18—C19—H19B | 109.6 | C18'—C19'—H19D | 109.8 |
H19A—C19—H19B | 108.1 | H19C—C19'—H19D | 108.2 |
C6—O1—C5—C4 | 5.6 (5) | C6'—O1'—C5'—C9' | −121.2 (5) |
C6—O1—C5—C8 | −111.2 (5) | C6'—O1'—C5'—C4' | 0.1 (6) |
C6—O1—C5—C9 | 128.1 (5) | C6'—O1'—C5'—C8' | 118.7 (5) |
C11—C4—C5—O1 | 174.9 (5) | C11'—C4'—C5'—O1' | −178.6 (5) |
C7—C4—C5—O1 | −5.7 (6) | C7'—C4'—C5'—O1' | 1.6 (6) |
C11—C4—C5—C8 | −71.9 (7) | C11'—C4'—C5'—C9' | −64.7 (8) |
C7—C4—C5—C8 | 107.4 (5) | C7'—C4'—C5'—C9' | 115.5 (5) |
C11—C4—C5—C9 | 59.8 (7) | C11'—C4'—C5'—C8' | 67.9 (8) |
C7—C4—C5—C9 | −120.8 (5) | C7'—C4'—C5'—C8' | −112.0 (5) |
C5—O1—C6—C2 | 177.3 (5) | C5'—O1'—C6'—C7' | −1.7 (7) |
C5—O1—C6—C7 | −3.3 (6) | C5'—O1'—C6'—C2' | 176.7 (5) |
C3—C2—C6—O1 | 0.9 (8) | C3'—C2'—C6'—O1' | −0.9 (8) |
C1—C2—C6—O1 | −176.6 (5) | C1'—C2'—C6'—O1' | −176.6 (5) |
C3—C2—C6—C7 | −178.2 (6) | C3'—C2'—C6'—C7' | 177.0 (7) |
C1—C2—C6—C7 | 4.3 (11) | C1'—C2'—C6'—C7' | 1.3 (11) |
O1—C6—C7—C10 | 179.1 (5) | O1'—C6'—C7'—C10' | −177.2 (5) |
C2—C6—C7—C10 | −1.7 (11) | C2'—C6'—C7'—C10' | 4.8 (11) |
O1—C6—C7—C4 | −0.6 (7) | O1'—C6'—C7'—C4' | 2.8 (7) |
C2—C6—C7—C4 | 178.5 (6) | C2'—C6'—C7'—C4' | −175.2 (6) |
C11—C4—C7—C6 | −176.5 (5) | C11'—C4'—C7'—C6' | 177.5 (6) |
C5—C4—C7—C6 | 4.1 (7) | C5'—C4'—C7'—C6' | −2.7 (6) |
C11—C4—C7—C10 | 3.8 (10) | C11'—C4'—C7'—C10' | −2.5 (10) |
C5—C4—C7—C10 | −175.6 (5) | C5'—C4'—C7'—C10' | 177.3 (5) |
C7—C4—C11—C12 | −174.8 (6) | C7'—C4'—C11'—C12' | −177.9 (6) |
C5—C4—C11—C12 | 4.4 (10) | C5'—C4'—C11'—C12' | 2.3 (10) |
C4—C11—C12—C13 | 179.1 (5) | C4'—C11'—C12'—C13' | 177.1 (6) |
C11—C12—C13—C14 | −177.9 (6) | C11'—C12'—C13'—C14' | −179.4 (5) |
C19—N4—C14—C13 | 1.9 (10) | C15'—N4'—C14'—C13' | 173.0 (6) |
C15—N4—C14—C13 | −176.8 (6) | C19'—N4'—C14'—C13' | 0.6 (10) |
C12—C13—C14—N4 | −174.1 (5) | C12'—C13'—C14'—N4' | 177.6 (5) |
C14—N4—C15—C16 | 121.5 (6) | C14'—N4'—C15'—C16' | −115.0 (6) |
C19—N4—C15—C16 | −57.3 (6) | C19'—N4'—C15'—C16' | 58.3 (7) |
N4—C15—C16—C17 | 57.2 (7) | N4'—C15'—C16'—C17' | −55.0 (7) |
C15—C16—C17—C18 | −57.4 (7) | C15'—C16'—C17'—C18' | 53.9 (7) |
C16—C17—C18—C19 | 55.7 (7) | C16'—C17'—C18'—C19' | −55.8 (7) |
C14—N4—C19—C18 | −123.2 (6) | C14'—N4'—C19'—C18' | 114.3 (6) |
C15—N4—C19—C18 | 55.5 (7) | C15'—N4'—C19'—C18' | −58.9 (7) |
C17—C18—C19—N4 | −53.5 (7) | C17'—C18'—C19'—N4' | 57.2 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
C13′—H13′···N2i | 0.95 | 2.49 | 3.324 (8) | 147 |
C14—H14···N1′ | 0.95 | 2.58 | 3.498 (8) | 161 |
C14′—H14′···N1ii | 0.95 | 2.61 | 3.484 (8) | 153 |
C16′—H16D···N2ii | 0.99 | 2.55 | 3.477 (8) | 156 |
C19—H19A···N2′iii | 0.99 | 2.60 | 3.568 (8) | 166 |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x−1, −y+3/2, z−1/2; (iii) −x+1, y−1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | C19H20N4O |
Mr | 320.39 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 119 |
a, b, c (Å) | 15.094 (4), 18.994 (5), 13.332 (4) |
β (°) | 116.193 (8) |
V (Å3) | 3429.7 (16) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.35 × 0.25 × 0.09 |
Data collection | |
Diffractometer | Bruker–Nonius APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (Blessing, 1995) |
Tmin, Tmax | 0.733, 1.0 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18712, 11128, 5766 |
Rint | 0.088 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.079, 0.203, 1.02 |
No. of reflections | 11128 |
No. of parameters | 424 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.46, −0.36 |
Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005) and SADABS (Sheldrick, 2003), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2003).
D—H···A | D—H | H···A | D···A | D—H···A |
C13'—H13'···N2i | 0.95 | 2.49 | 3.324 (8) | 147 |
C14—H14···N1' | 0.95 | 2.58 | 3.498 (8) | 161 |
C14'—H14'···N1ii | 0.95 | 2.61 | 3.484 (8) | 153 |
C16'—H16D···N2ii | 0.99 | 2.55 | 3.477 (8) | 156 |
C19—H19A···N2'iii | 0.99 | 2.60 | 3.568 (8) | 166 |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x−1, −y+3/2, z−1/2; (iii) −x+1, y−1/2, −z+3/2. |
We have previously reported on the synthesis of a number of high figure of merit chromophores for nonlinear optics (Kay et al., 2004), and the X-ray crystallographic and structural properties of crucial dye precursors used (Gainsford et al., 2007, 2008). As part of our ongoing studies of the structure of these highly polar materials, we report here the crystallographic data of another of the chromophore precursors.
The asymmetric unit contents of the title compound (I) is shown in Figures 1 (unprimed & primed independent molecules hereafter A & B) with hydrogen bond data in Table 1. The structures are almost superimposable with a weighted r.m.s. fit between A & inverted B molecules of 0.61Å (Spek, 2003). The only notable difference in bond lengths concerns those involving atoms C11 & C11'. Minor differences in orientations may be attributed to the packing interactions (Table 1). For example the polyene chains C4, C11—C14 are tilted at 7.1 (5)° & 3.4 (6)° to the "CDFP" 5-membered ring planes (O1, C4—C8) in molecules A & B respectively. Similarly the dicyanomethylene groups (N1,N2, C1—C3) are at 3.5 (4) and 7.7 (4)° to the CDFP ring in A & B, respectively. The piperidin-1-yl rings adopt a chair conformation.
The polyene-C—H···N interactions with adjacent cyano N atoms (C13', C14, C14') are commonly observed for these molecules (Gainsford et al., 2008) as is the methylene-C19—H19A interaction with N2' (entry 5, Table 1). Only once before has it been reported when the adjacent polyene C hydrogen atoms (on C13' & C14') are both H bonded to cyano N atoms (NEQHAT01, Reck & Dahne, 2006) from the Cambridge Structural Database (Version 5.29 with November 2007 updates; Allen, 2002). There are few meta-C(C16')—H···N(cyano) interactions reported: two examples exist in the somewhat related compounds YAMXEP (Marder et al., 1993) and ZOSZAI (Bock et al., 1996) with H···N, C—H···N 2.69 & 2.64 Å, 148° & 147°, respectively.