organic compounds
(Z)-3′,6′-Bis(diethylamino)-2-(4-oxopent-2-en-2-ylamino)spiro[isoindoline-1,9′-xanthen]-3-one
aDepartment of Chemistry, Capital Normal University, Beijing 100048, People's Republic of China
*Correspondence e-mail: changbin.guo@gmail.com
In the title compound, C33H38N4O3, the mean planes of the 9H-xanthene unit and spirolactam (nine-atom) core are almost mutually perpendicular at 87.26 (6)°. Intramolecular N—H⋯O and C—H⋯N interactions influence the 4-oxopent-2-en-2-ylamino conformation. In the crystal, weak C—H⋯O hydrogen bonds link the molecules into chains along [001].
Related literature
For the use of Rhodamine B derivatives as fluorescent chemosensors, see: Zhang et al. (2007); Soh et al. (2007). For a related structure, see: Xiang et al. (2006).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2007); cell APEX2 and SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009).
Supporting information
https://doi.org/10.1107/S1600536812027602/gg2084sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812027602/gg2084Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536812027602/gg2084Isup3.cml
To a solution of 2-amino-3',6'-bis(diethylamino)spiro [isoindoline-1,9'-xanthen]-3-one (0.50 g, 1.09 mmol) in 3 mL absolute anhydrous ethanol was added 0.5 mL pentane-2,4-dione and CAN (5% mol), then the resulting mixture was stirred at room temperature for 6 h. The reaction mixture was dissolved in 20 mL CH2Cl2, washed twice with water and dried over Na2SO4, filtered, and the filtrate was concentrated under reduced pressure. The residue was purified by
(EA:PE=1:1, v/v) to yield the title compound as a white powder (0.47 g, 80.1%). Crystals suitable for X-ray analysis were obtained by slow evaporation of a solution of the title compound in ethanol at room temperature in four days.All the H atoms were discernible in the difference electro density maps with C—H = 0.93 and 0.96Å for aryl and methyl, respectively. Uiso(H)=1.2Ueq(C).
Rhodamine B derivatives are known to have excellent photophysical properties, such as the long absorption and emission wavelengths elongated to the visible region. Therefore, they have been extensively used as fluorescent chemosensors for heavy and transition metal ions, such as Cu(II) (Zhang et al., 2007) and Hg(II) chemical sensor (Soh et al., 2007). Herein, we report the synthesis and
of a new Rhodamine B derivative, namely (Z)-3',6'-bis(diethylamino)-2-(4-oxopent-2-en-2-ylamino)spiroisoindoline- [1,9'-xanthen]-3-one.In the title compound C33H38N4O3, the mean plane of the 9H-xanthene moiety and that of the spirolactam moiety are almost perpendicular to each other (Fig. 1). Two N,N-diethylamino groups bond to the 9H-xanthene moiety at C5 and C15, respectivly, while a 4-oxopent-2-en-2-ylamino links to the spirolactam moiety at N2 position (Fig. 1). The 9H-xanthene fragment exhibits a butterfly-like conformation with two benzene rings (C12-C13-C14-C15-C16-C17 and C1-C2-C3-C4-C5-C6, respectively) exhibiting a dihedral angle of 160.06 (4)°. For the 4-oxopent-2-en-2-ylamino group, the double bond between C29 and C30 shows a Z-configuration. The structure of the title compound is similar to that of other reported Rhodamine B derivatives (Xiang et al. 2006). The molecular packing is stabilized by an intermolecular interaction (C7—H7B···O3i, C7O3i = 3.334 (3) Å, C7—H7B···O3i = 133 °).
For the use of Rhodamine B derivatives as fluorescent chemosensors, see: Zhang et al. (2007); Soh et al. (2007). For a related structure, see: Xiang et al. (2006).
Data collection: APEX2 (Bruker, 2007); cell
APEX2 and SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).Fig. 1. The structure of (I) with 35% probability displacement ellipsoids and the atom numbering scheme. | |
Fig. 2. The crystal structure packing structure of (I). |
C33H38N4O3 | F(000) = 1152 |
Mr = 538.67 | Dx = 1.210 Mg m−3 Dm = 1.210 Mg m−3 Dm measured by not measured |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 7869 reflections |
a = 17.4255 (3) Å | θ = 2.5–28.8° |
b = 15.0965 (3) Å | µ = 0.08 mm−1 |
c = 11.5354 (2) Å | T = 296 K |
β = 103.008 (1)° | Block, colorless |
V = 2956.68 (9) Å3 | 0.26 × 0.26 × 0.24 mm |
Z = 4 |
Bruker APEXII CCD area-detector diffractometer | 7000 independent reflections |
Radiation source: fine-focus sealed tube | 4223 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
ω scans | θmax = 28.0°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Bruker, 2007) | h = −22→22 |
Tmin = 0.666, Tmax = 0.746 | k = −19→19 |
24441 measured reflections | l = −15→15 |
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)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.165 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0751P)2 + 0.4182P] where P = (Fo2 + 2Fc2)/3 |
7000 reflections | (Δ/σ)max < 0.001 |
365 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
C33H38N4O3 | V = 2956.68 (9) Å3 |
Mr = 538.67 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 17.4255 (3) Å | µ = 0.08 mm−1 |
b = 15.0965 (3) Å | T = 296 K |
c = 11.5354 (2) Å | 0.26 × 0.26 × 0.24 mm |
β = 103.008 (1)° |
Bruker APEXII CCD area-detector diffractometer | 7000 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2007) | 4223 reflections with I > 2σ(I) |
Tmin = 0.666, Tmax = 0.746 | Rint = 0.038 |
24441 measured reflections |
R[F2 > 2σ(F2)] = 0.055 | 0 restraints |
wR(F2) = 0.165 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.31 e Å−3 |
7000 reflections | Δρmin = −0.23 e Å−3 |
365 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 | ||
C1 | 0.72483 (9) | 0.55285 (12) | 0.35969 (17) | 0.0411 (4) | |
C2 | 0.79924 (9) | 0.58683 (11) | 0.40887 (16) | 0.0391 (4) | |
C3 | 0.85265 (10) | 0.58468 (13) | 0.33574 (18) | 0.0480 (5) | |
H3A | 0.9032 | 0.6065 | 0.3652 | 0.058* | |
C4 | 0.83408 (11) | 0.55181 (14) | 0.22229 (18) | 0.0516 (5) | |
H4A | 0.8721 | 0.5512 | 0.1773 | 0.062* | |
C5 | 0.75792 (10) | 0.51884 (13) | 0.17260 (17) | 0.0464 (4) | |
C6 | 0.70398 (10) | 0.51974 (12) | 0.24555 (17) | 0.0461 (4) | |
H6A | 0.6534 | 0.4978 | 0.2168 | 0.055* | |
C7 | 0.79176 (13) | 0.50105 (16) | −0.0224 (2) | 0.0622 (6) | |
H7A | 0.8178 | 0.5578 | −0.0046 | 0.075* | |
H7B | 0.7609 | 0.5034 | −0.1036 | 0.075* | |
C8 | 0.85292 (16) | 0.43034 (19) | −0.0135 (3) | 0.0839 (8) | |
H8A | 0.8857 | 0.4430 | −0.0681 | 0.126* | |
H8B | 0.8276 | 0.3741 | −0.0330 | 0.126* | |
H8C | 0.8846 | 0.4286 | 0.0661 | 0.126* | |
C9 | 0.65814 (12) | 0.46323 (16) | 0.0011 (2) | 0.0661 (6) | |
H9A | 0.6348 | 0.4319 | 0.0580 | 0.079* | |
H9B | 0.6592 | 0.4230 | −0.0641 | 0.079* | |
C10 | 0.60719 (17) | 0.5411 (2) | −0.0460 (3) | 0.1075 (11) | |
H10A | 0.5551 | 0.5209 | −0.0825 | 0.161* | |
H10B | 0.6291 | 0.5717 | −0.1040 | 0.161* | |
H10C | 0.6047 | 0.5807 | 0.0182 | 0.161* | |
C11 | 0.81924 (9) | 0.61870 (11) | 0.53530 (16) | 0.0393 (4) | |
C12 | 0.74476 (9) | 0.64566 (12) | 0.57294 (17) | 0.0417 (4) | |
C13 | 0.74226 (11) | 0.70387 (13) | 0.66550 (18) | 0.0523 (5) | |
H13A | 0.7879 | 0.7342 | 0.7011 | 0.063* | |
C14 | 0.67532 (11) | 0.71844 (14) | 0.70650 (19) | 0.0555 (5) | |
H14A | 0.6761 | 0.7598 | 0.7665 | 0.067* | |
C15 | 0.60520 (10) | 0.67139 (13) | 0.65862 (17) | 0.0479 (5) | |
C16 | 0.60620 (10) | 0.61550 (12) | 0.56295 (18) | 0.0473 (5) | |
H16A | 0.5607 | 0.5851 | 0.5268 | 0.057* | |
C17 | 0.67389 (10) | 0.60457 (12) | 0.52103 (17) | 0.0423 (4) | |
C18 | 0.46914 (11) | 0.62613 (16) | 0.6584 (2) | 0.0612 (6) | |
H18A | 0.4395 | 0.6212 | 0.7199 | 0.073* | |
H18B | 0.4863 | 0.5670 | 0.6431 | 0.073* | |
C19 | 0.41471 (14) | 0.6596 (2) | 0.5467 (3) | 0.0848 (8) | |
H19A | 0.3709 | 0.6198 | 0.5239 | 0.127* | |
H19B | 0.4427 | 0.6630 | 0.4841 | 0.127* | |
H19C | 0.3958 | 0.7174 | 0.5610 | 0.127* | |
C20 | 0.53268 (13) | 0.74897 (16) | 0.7899 (2) | 0.0663 (6) | |
H20A | 0.5831 | 0.7544 | 0.8459 | 0.080* | |
H20B | 0.4942 | 0.7309 | 0.8342 | 0.080* | |
C21 | 0.50958 (18) | 0.83815 (19) | 0.7354 (3) | 0.0957 (9) | |
H21A | 0.5069 | 0.8800 | 0.7970 | 0.144* | |
H21B | 0.4590 | 0.8340 | 0.6814 | 0.144* | |
H21C | 0.5481 | 0.8575 | 0.6930 | 0.144* | |
C28 | 0.92523 (10) | 0.57242 (13) | 0.69867 (18) | 0.0491 (5) | |
C27 | 0.94264 (10) | 0.66190 (12) | 0.65927 (17) | 0.0464 (5) | |
C26 | 1.00665 (11) | 0.71638 (15) | 0.7041 (2) | 0.0592 (6) | |
H26A | 1.0454 | 0.6993 | 0.7697 | 0.071* | |
C25 | 1.01124 (11) | 0.79624 (15) | 0.6490 (2) | 0.0605 (6) | |
H25A | 1.0532 | 0.8341 | 0.6783 | 0.073* | |
C24 | 0.95405 (11) | 0.82103 (14) | 0.5504 (2) | 0.0569 (5) | |
H24A | 0.9591 | 0.8745 | 0.5127 | 0.068* | |
C23 | 0.88946 (10) | 0.76746 (13) | 0.50691 (19) | 0.0506 (5) | |
H23A | 0.8507 | 0.7848 | 0.4414 | 0.061* | |
C22 | 0.88396 (9) | 0.68792 (12) | 0.56306 (17) | 0.0417 (4) | |
C29 | 0.83791 (10) | 0.39074 (12) | 0.59552 (18) | 0.0469 (5) | |
C33 | 0.90031 (14) | 0.38742 (16) | 0.5252 (3) | 0.0764 (7) | |
H33A | 0.9179 | 0.4464 | 0.5140 | 0.115* | |
H33B | 0.8791 | 0.3609 | 0.4490 | 0.115* | |
H33C | 0.9440 | 0.3528 | 0.5673 | 0.115* | |
C30 | 0.80224 (11) | 0.31622 (13) | 0.6247 (2) | 0.0559 (5) | |
H30A | 0.8153 | 0.2625 | 0.5946 | 0.067* | |
C31 | 0.74681 (12) | 0.31462 (15) | 0.6976 (2) | 0.0601 (6) | |
C32 | 0.72173 (19) | 0.22546 (19) | 0.7353 (3) | 0.1099 (11) | |
H32A | 0.6843 | 0.2336 | 0.7840 | 0.165* | |
H32B | 0.7669 | 0.1944 | 0.7798 | 0.165* | |
H32C | 0.6980 | 0.1916 | 0.6660 | 0.165* | |
N1 | 0.73857 (9) | 0.48717 (13) | 0.05820 (15) | 0.0580 (5) | |
N2 | 0.85909 (8) | 0.54639 (10) | 0.61756 (14) | 0.0445 (4) | |
N3 | 0.81807 (9) | 0.47045 (10) | 0.63140 (15) | 0.0463 (4) | |
N4 | 0.53859 (9) | 0.67999 (12) | 0.70403 (16) | 0.0569 (5) | |
O1 | 0.66609 (7) | 0.55024 (9) | 0.42302 (12) | 0.0517 (4) | |
O2 | 0.96133 (9) | 0.52827 (11) | 0.78133 (15) | 0.0744 (5) | |
O3 | 0.71972 (9) | 0.38277 (11) | 0.73323 (15) | 0.0710 (5) | |
H1 | 0.7807 (13) | 0.4688 (15) | 0.671 (2) | 0.070 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0388 (8) | 0.0427 (9) | 0.0429 (11) | −0.0010 (7) | 0.0111 (8) | −0.0032 (9) |
C2 | 0.0391 (8) | 0.0402 (9) | 0.0368 (10) | −0.0009 (7) | 0.0060 (7) | −0.0023 (8) |
C3 | 0.0387 (8) | 0.0578 (11) | 0.0466 (12) | −0.0077 (8) | 0.0078 (8) | −0.0049 (10) |
C4 | 0.0479 (10) | 0.0644 (12) | 0.0455 (12) | −0.0067 (9) | 0.0172 (9) | −0.0065 (10) |
C5 | 0.0504 (10) | 0.0489 (10) | 0.0399 (11) | −0.0005 (8) | 0.0100 (9) | −0.0055 (9) |
C6 | 0.0417 (9) | 0.0512 (11) | 0.0442 (12) | −0.0061 (8) | 0.0072 (8) | −0.0094 (9) |
C7 | 0.0704 (13) | 0.0709 (14) | 0.0463 (13) | −0.0035 (11) | 0.0156 (10) | −0.0087 (11) |
C8 | 0.0891 (17) | 0.0923 (19) | 0.0758 (19) | 0.0133 (14) | 0.0305 (15) | −0.0065 (15) |
C9 | 0.0631 (12) | 0.0859 (17) | 0.0471 (13) | −0.0102 (11) | 0.0073 (11) | −0.0177 (12) |
C10 | 0.0870 (18) | 0.146 (3) | 0.081 (2) | 0.0269 (19) | 0.0007 (16) | 0.011 (2) |
C11 | 0.0376 (8) | 0.0405 (9) | 0.0380 (10) | −0.0016 (7) | 0.0047 (7) | −0.0005 (8) |
C12 | 0.0394 (8) | 0.0442 (10) | 0.0407 (11) | −0.0020 (7) | 0.0073 (8) | −0.0033 (9) |
C13 | 0.0481 (10) | 0.0574 (12) | 0.0509 (13) | −0.0086 (8) | 0.0101 (9) | −0.0171 (10) |
C14 | 0.0564 (11) | 0.0600 (12) | 0.0521 (13) | −0.0046 (9) | 0.0167 (10) | −0.0203 (11) |
C15 | 0.0461 (9) | 0.0549 (11) | 0.0430 (12) | 0.0032 (8) | 0.0108 (8) | −0.0039 (10) |
C16 | 0.0407 (8) | 0.0547 (11) | 0.0461 (12) | −0.0053 (8) | 0.0090 (8) | −0.0097 (10) |
C17 | 0.0444 (9) | 0.0441 (10) | 0.0384 (11) | −0.0029 (7) | 0.0092 (8) | −0.0081 (9) |
C18 | 0.0515 (10) | 0.0751 (15) | 0.0618 (15) | −0.0025 (10) | 0.0229 (11) | −0.0047 (12) |
C19 | 0.0626 (13) | 0.108 (2) | 0.0784 (19) | −0.0008 (13) | 0.0049 (13) | −0.0022 (17) |
C20 | 0.0628 (12) | 0.0779 (15) | 0.0641 (15) | 0.0054 (11) | 0.0270 (11) | −0.0147 (13) |
C21 | 0.106 (2) | 0.0736 (18) | 0.105 (2) | 0.0087 (15) | 0.0189 (18) | −0.0119 (17) |
C28 | 0.0422 (9) | 0.0573 (12) | 0.0446 (12) | −0.0013 (8) | 0.0029 (9) | 0.0054 (10) |
C27 | 0.0408 (8) | 0.0536 (11) | 0.0434 (11) | −0.0055 (8) | 0.0066 (8) | −0.0021 (9) |
C26 | 0.0455 (10) | 0.0753 (15) | 0.0516 (13) | −0.0125 (9) | −0.0001 (9) | −0.0002 (12) |
C25 | 0.0480 (10) | 0.0632 (13) | 0.0693 (16) | −0.0180 (9) | 0.0113 (11) | −0.0093 (12) |
C24 | 0.0572 (11) | 0.0474 (11) | 0.0680 (15) | −0.0082 (9) | 0.0182 (11) | −0.0020 (11) |
C23 | 0.0487 (10) | 0.0474 (11) | 0.0532 (13) | −0.0014 (8) | 0.0062 (9) | 0.0025 (10) |
C22 | 0.0384 (8) | 0.0458 (10) | 0.0397 (11) | −0.0030 (7) | 0.0064 (8) | −0.0049 (9) |
C29 | 0.0438 (9) | 0.0476 (11) | 0.0469 (12) | 0.0064 (8) | 0.0049 (8) | −0.0012 (9) |
C33 | 0.0751 (14) | 0.0654 (14) | 0.099 (2) | 0.0142 (11) | 0.0411 (14) | −0.0054 (14) |
C30 | 0.0557 (11) | 0.0431 (11) | 0.0652 (15) | 0.0015 (8) | 0.0058 (10) | −0.0049 (10) |
C31 | 0.0600 (11) | 0.0571 (13) | 0.0596 (15) | −0.0134 (10) | 0.0058 (11) | −0.0025 (12) |
C32 | 0.126 (2) | 0.0762 (18) | 0.134 (3) | −0.0367 (17) | 0.043 (2) | 0.007 (2) |
N1 | 0.0552 (9) | 0.0793 (12) | 0.0401 (10) | −0.0082 (8) | 0.0122 (8) | −0.0151 (9) |
N2 | 0.0445 (7) | 0.0429 (8) | 0.0433 (9) | −0.0051 (6) | 0.0039 (7) | 0.0028 (7) |
N3 | 0.0479 (8) | 0.0430 (9) | 0.0508 (10) | −0.0037 (7) | 0.0166 (8) | −0.0003 (8) |
N4 | 0.0488 (8) | 0.0699 (11) | 0.0556 (11) | 0.0002 (8) | 0.0190 (8) | −0.0136 (9) |
O1 | 0.0432 (6) | 0.0642 (8) | 0.0505 (8) | −0.0143 (6) | 0.0164 (6) | −0.0221 (7) |
O2 | 0.0680 (9) | 0.0804 (11) | 0.0629 (11) | −0.0071 (8) | −0.0106 (8) | 0.0246 (9) |
O3 | 0.0750 (9) | 0.0730 (11) | 0.0710 (12) | −0.0168 (8) | 0.0293 (9) | −0.0126 (9) |
C1—C6 | 1.378 (3) | C18—C19 | 1.505 (3) |
C1—O1 | 1.386 (2) | C18—H18A | 0.9700 |
C1—C2 | 1.391 (2) | C18—H18B | 0.9700 |
C2—C3 | 1.390 (2) | C19—H19A | 0.9600 |
C2—C11 | 1.500 (3) | C19—H19B | 0.9600 |
C3—C4 | 1.369 (3) | C19—H19C | 0.9600 |
C3—H3A | 0.9300 | C20—N4 | 1.456 (3) |
C4—C5 | 1.412 (3) | C20—C21 | 1.502 (4) |
C4—H4A | 0.9300 | C20—H20A | 0.9700 |
C5—N1 | 1.372 (2) | C20—H20B | 0.9700 |
C5—C6 | 1.396 (2) | C21—H21A | 0.9600 |
C6—H6A | 0.9300 | C21—H21B | 0.9600 |
C7—N1 | 1.468 (3) | C21—H21C | 0.9600 |
C7—C8 | 1.496 (3) | C28—O2 | 1.216 (2) |
C7—H7A | 0.9700 | C28—N2 | 1.368 (2) |
C7—H7B | 0.9700 | C28—C27 | 1.478 (3) |
C8—H8A | 0.9600 | C27—C22 | 1.386 (3) |
C8—H8B | 0.9600 | C27—C26 | 1.389 (3) |
C8—H8C | 0.9600 | C26—C25 | 1.374 (3) |
C9—N1 | 1.454 (3) | C26—H26A | 0.9300 |
C9—C10 | 1.500 (4) | C25—C24 | 1.385 (3) |
C9—H9A | 0.9700 | C25—H25A | 0.9300 |
C9—H9B | 0.9700 | C24—C23 | 1.385 (3) |
C10—H10A | 0.9600 | C24—H24A | 0.9300 |
C10—H10B | 0.9600 | C23—C22 | 1.378 (3) |
C10—H10C | 0.9600 | C23—H23A | 0.9300 |
C11—N2 | 1.509 (2) | C29—N3 | 1.343 (2) |
C11—C12 | 1.514 (2) | C29—C30 | 1.364 (3) |
C11—C22 | 1.518 (2) | C29—C33 | 1.497 (3) |
C12—C13 | 1.391 (3) | C33—H33A | 0.9600 |
C12—C17 | 1.391 (2) | C33—H33B | 0.9600 |
C13—C14 | 1.371 (3) | C33—H33C | 0.9600 |
C13—H13A | 0.9300 | C30—C31 | 1.416 (3) |
C14—C15 | 1.414 (3) | C30—H30A | 0.9300 |
C14—H14A | 0.9300 | C31—O3 | 1.240 (3) |
C15—N4 | 1.383 (2) | C31—C32 | 1.509 (3) |
C15—C16 | 1.392 (3) | C32—H32A | 0.9600 |
C16—C17 | 1.382 (2) | C32—H32B | 0.9600 |
C16—H16A | 0.9300 | C32—H32C | 0.9600 |
C17—O1 | 1.379 (2) | N2—N3 | 1.379 (2) |
C18—N4 | 1.455 (3) | N3—H1 | 0.88 (2) |
C6—C1—O1 | 115.22 (14) | C18—C19—H19B | 109.5 |
C6—C1—C2 | 122.99 (16) | H19A—C19—H19B | 109.5 |
O1—C1—C2 | 121.79 (16) | C18—C19—H19C | 109.5 |
C3—C2—C1 | 115.71 (16) | H19A—C19—H19C | 109.5 |
C3—C2—C11 | 123.82 (14) | H19B—C19—H19C | 109.5 |
C1—C2—C11 | 120.39 (15) | N4—C20—C21 | 114.2 (2) |
C4—C3—C2 | 122.84 (16) | N4—C20—H20A | 108.7 |
C4—C3—H3A | 118.6 | C21—C20—H20A | 108.7 |
C2—C3—H3A | 118.6 | N4—C20—H20B | 108.7 |
C3—C4—C5 | 120.94 (17) | C21—C20—H20B | 108.7 |
C3—C4—H4A | 119.5 | H20A—C20—H20B | 107.6 |
C5—C4—H4A | 119.5 | C20—C21—H21A | 109.5 |
N1—C5—C6 | 122.01 (16) | C20—C21—H21B | 109.5 |
N1—C5—C4 | 121.20 (16) | H21A—C21—H21B | 109.5 |
C6—C5—C4 | 116.79 (17) | C20—C21—H21C | 109.5 |
C1—C6—C5 | 120.72 (16) | H21A—C21—H21C | 109.5 |
C1—C6—H6A | 119.6 | H21B—C21—H21C | 109.5 |
C5—C6—H6A | 119.6 | O2—C28—N2 | 125.88 (18) |
N1—C7—C8 | 113.3 (2) | O2—C28—C27 | 129.50 (18) |
N1—C7—H7A | 108.9 | N2—C28—C27 | 104.58 (16) |
C8—C7—H7A | 108.9 | C22—C27—C26 | 121.10 (18) |
N1—C7—H7B | 108.9 | C22—C27—C28 | 109.86 (15) |
C8—C7—H7B | 108.9 | C26—C27—C28 | 129.03 (18) |
H7A—C7—H7B | 107.7 | C25—C26—C27 | 118.22 (19) |
C7—C8—H8A | 109.5 | C25—C26—H26A | 120.9 |
C7—C8—H8B | 109.5 | C27—C26—H26A | 120.9 |
H8A—C8—H8B | 109.5 | C26—C25—C24 | 120.76 (18) |
C7—C8—H8C | 109.5 | C26—C25—H25A | 119.6 |
H8A—C8—H8C | 109.5 | C24—C25—H25A | 119.6 |
H8B—C8—H8C | 109.5 | C23—C24—C25 | 121.02 (19) |
N1—C9—C10 | 113.6 (2) | C23—C24—H24A | 119.5 |
N1—C9—H9A | 108.8 | C25—C24—H24A | 119.5 |
C10—C9—H9A | 108.8 | C22—C23—C24 | 118.40 (18) |
N1—C9—H9B | 108.8 | C22—C23—H23A | 120.8 |
C10—C9—H9B | 108.8 | C24—C23—H23A | 120.8 |
H9A—C9—H9B | 107.7 | C23—C22—C27 | 120.44 (16) |
C9—C10—H10A | 109.5 | C23—C22—C11 | 128.89 (16) |
C9—C10—H10B | 109.5 | C27—C22—C11 | 110.67 (15) |
H10A—C10—H10B | 109.5 | N3—C29—C30 | 119.99 (17) |
C9—C10—H10C | 109.5 | N3—C29—C33 | 117.77 (17) |
H10A—C10—H10C | 109.5 | C30—C29—C33 | 122.24 (18) |
H10B—C10—H10C | 109.5 | C29—C33—H33A | 109.5 |
C2—C11—N2 | 110.65 (14) | C29—C33—H33B | 109.5 |
C2—C11—C12 | 109.78 (13) | H33A—C33—H33B | 109.5 |
N2—C11—C12 | 108.48 (14) | C29—C33—H33C | 109.5 |
C2—C11—C22 | 115.13 (15) | H33A—C33—H33C | 109.5 |
N2—C11—C22 | 98.65 (13) | H33B—C33—H33C | 109.5 |
C12—C11—C22 | 113.49 (14) | C29—C30—C31 | 124.77 (19) |
C13—C12—C17 | 115.72 (16) | C29—C30—H30A | 117.6 |
C13—C12—C11 | 124.54 (15) | C31—C30—H30A | 117.6 |
C17—C12—C11 | 119.46 (16) | O3—C31—C30 | 122.95 (19) |
C14—C13—C12 | 122.82 (17) | O3—C31—C32 | 119.2 (2) |
C14—C13—H13A | 118.6 | C30—C31—C32 | 117.8 (2) |
C12—C13—H13A | 118.6 | C31—C32—H32A | 109.5 |
C13—C14—C15 | 120.80 (18) | C31—C32—H32B | 109.5 |
C13—C14—H14A | 119.6 | H32A—C32—H32B | 109.5 |
C15—C14—H14A | 119.6 | C31—C32—H32C | 109.5 |
N4—C15—C16 | 121.23 (16) | H32A—C32—H32C | 109.5 |
N4—C15—C14 | 122.02 (17) | H32B—C32—H32C | 109.5 |
C16—C15—C14 | 116.75 (16) | C5—N1—C9 | 121.71 (16) |
C17—C16—C15 | 120.92 (16) | C5—N1—C7 | 120.39 (16) |
C17—C16—H16A | 119.5 | C9—N1—C7 | 115.47 (17) |
C15—C16—H16A | 119.5 | C28—N2—N3 | 122.57 (16) |
O1—C17—C16 | 115.08 (15) | C28—N2—C11 | 114.82 (14) |
O1—C17—C12 | 122.17 (15) | N3—N2—C11 | 119.79 (13) |
C16—C17—C12 | 122.76 (17) | C29—N3—N2 | 122.22 (16) |
N4—C18—C19 | 115.8 (2) | C29—N3—H1 | 114.1 (15) |
N4—C18—H18A | 108.3 | N2—N3—H1 | 123.3 (15) |
C19—C18—H18A | 108.3 | C15—N4—C18 | 120.76 (16) |
N4—C18—H18B | 108.3 | C15—N4—C20 | 121.22 (17) |
C19—C18—H18B | 108.3 | C18—N4—C20 | 117.73 (16) |
H18A—C18—H18B | 107.4 | C17—O1—C1 | 117.87 (13) |
C18—C19—H19A | 109.5 | ||
C6—C1—C2—C3 | −0.7 (3) | C26—C27—C22—C23 | 2.4 (3) |
O1—C1—C2—C3 | 179.48 (16) | C28—C27—C22—C23 | −176.69 (17) |
C6—C1—C2—C11 | −177.65 (17) | C26—C27—C22—C11 | −177.41 (17) |
O1—C1—C2—C11 | 2.5 (3) | C28—C27—C22—C11 | 3.5 (2) |
C1—C2—C3—C4 | 0.3 (3) | C2—C11—C22—C23 | 53.6 (2) |
C11—C2—C3—C4 | 177.12 (18) | N2—C11—C22—C23 | 171.29 (18) |
C2—C3—C4—C5 | 0.8 (3) | C12—C11—C22—C23 | −74.1 (2) |
C3—C4—C5—N1 | 178.90 (19) | C2—C11—C22—C27 | −126.66 (17) |
C3—C4—C5—C6 | −1.4 (3) | N2—C11—C22—C27 | −8.93 (18) |
O1—C1—C6—C5 | 179.87 (17) | C12—C11—C22—C27 | 105.64 (18) |
C2—C1—C6—C5 | 0.0 (3) | N3—C29—C30—C31 | −3.6 (3) |
N1—C5—C6—C1 | −179.30 (19) | C33—C29—C30—C31 | 175.6 (2) |
C4—C5—C6—C1 | 1.0 (3) | C29—C30—C31—O3 | 7.0 (4) |
C3—C2—C11—N2 | −82.0 (2) | C29—C30—C31—C32 | −171.5 (2) |
C1—C2—C11—N2 | 94.69 (18) | C6—C5—N1—C9 | 8.0 (3) |
C3—C2—C11—C12 | 158.27 (17) | C4—C5—N1—C9 | −172.3 (2) |
C1—C2—C11—C12 | −25.0 (2) | C6—C5—N1—C7 | 169.48 (19) |
C3—C2—C11—C22 | 28.7 (2) | C4—C5—N1—C7 | −10.9 (3) |
C1—C2—C11—C22 | −154.56 (16) | C10—C9—N1—C5 | 79.8 (3) |
C2—C11—C12—C13 | −157.51 (18) | C10—C9—N1—C7 | −82.5 (3) |
N2—C11—C12—C13 | 81.5 (2) | C8—C7—N1—C5 | 87.5 (3) |
C22—C11—C12—C13 | −27.1 (3) | C8—C7—N1—C9 | −109.9 (2) |
C2—C11—C12—C17 | 28.9 (2) | O2—C28—N2—N3 | 10.4 (3) |
N2—C11—C12—C17 | −92.1 (2) | C27—C28—N2—N3 | −171.76 (15) |
C22—C11—C12—C17 | 159.33 (17) | O2—C28—N2—C11 | 171.30 (19) |
C17—C12—C13—C14 | 2.0 (3) | C27—C28—N2—C11 | −10.9 (2) |
C11—C12—C13—C14 | −171.81 (19) | C2—C11—N2—C28 | 133.47 (16) |
C12—C13—C14—C15 | 2.5 (3) | C12—C11—N2—C28 | −106.05 (17) |
C13—C14—C15—N4 | 175.21 (19) | C22—C11—N2—C28 | 12.38 (19) |
C13—C14—C15—C16 | −4.7 (3) | C2—C11—N2—N3 | −65.08 (19) |
N4—C15—C16—C17 | −177.43 (18) | C12—C11—N2—N3 | 55.4 (2) |
C14—C15—C16—C17 | 2.5 (3) | C22—C11—N2—N3 | 173.83 (15) |
C15—C16—C17—O1 | −177.51 (18) | C30—C29—N3—N2 | 171.54 (17) |
C15—C16—C17—C12 | 2.0 (3) | C33—C29—N3—N2 | −7.6 (3) |
C13—C12—C17—O1 | 175.24 (18) | C28—N2—N3—C29 | −85.6 (2) |
C11—C12—C17—O1 | −10.6 (3) | C11—N2—N3—C29 | 114.41 (19) |
C13—C12—C17—C16 | −4.3 (3) | C16—C15—N4—C18 | 4.3 (3) |
C11—C12—C17—C16 | 169.85 (17) | C14—C15—N4—C18 | −175.7 (2) |
O2—C28—C27—C22 | −178.0 (2) | C16—C15—N4—C20 | −169.4 (2) |
N2—C28—C27—C22 | 4.3 (2) | C14—C15—N4—C20 | 10.7 (3) |
O2—C28—C27—C26 | 3.0 (4) | C19—C18—N4—C15 | −83.0 (3) |
N2—C28—C27—C26 | −174.7 (2) | C19—C18—N4—C20 | 90.9 (2) |
C22—C27—C26—C25 | −1.3 (3) | C21—C20—N4—C15 | 81.3 (3) |
C28—C27—C26—C25 | 177.6 (2) | C21—C20—N4—C18 | −92.6 (3) |
C27—C26—C25—C24 | −0.9 (3) | C16—C17—O1—C1 | 164.94 (16) |
C26—C25—C24—C23 | 2.1 (3) | C12—C17—O1—C1 | −14.6 (3) |
C25—C24—C23—C22 | −1.1 (3) | C6—C1—O1—C17 | −160.98 (17) |
C24—C23—C22—C27 | −1.2 (3) | C2—C1—O1—C17 | 18.9 (2) |
C24—C23—C22—C11 | 178.60 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H1···O3 | 0.88 (2) | 1.92 (2) | 2.641 (2) | 139 (2) |
C33—H33A···N2 | 0.96 | 2.30 | 2.785 (3) | 110 |
C7—H7B···O3i | 0.97 | 2.60 | 3.334 (3) | 133 |
Symmetry code: (i) x, y, z−1. |
Experimental details
Crystal data | |
Chemical formula | C33H38N4O3 |
Mr | 538.67 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 17.4255 (3), 15.0965 (3), 11.5354 (2) |
β (°) | 103.008 (1) |
V (Å3) | 2956.68 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.26 × 0.26 × 0.24 |
Data collection | |
Diffractometer | Bruker APEXII CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2007) |
Tmin, Tmax | 0.666, 0.746 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 24441, 7000, 4223 |
Rint | 0.038 |
(sin θ/λ)max (Å−1) | 0.659 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.165, 1.04 |
No. of reflections | 7000 |
No. of parameters | 365 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.31, −0.23 |
Computer programs: APEX2 (Bruker, 2007), APEX2 and SAINT (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H1···O3 | 0.88 (2) | 1.92 (2) | 2.641 (2) | 139 (2) |
C33—H33A···N2 | 0.96 | 2.30 | 2.785 (3) | 110 |
C7—H7B···O3i | 0.97 | 2.60 | 3.334 (3) | 133 |
Symmetry code: (i) x, y, z−1. |
Acknowledgements
This work was supported by the National Natural Science Foundation of China (project No. 30873140), the Program for Excellent Talents of Beijing City (project No. 20071D0501600227) and the Beijing Municipal Commission of Education (project No. KM201010028011).
References
Bruker (2007). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Soh, J. H., Swamy, K. M. K., Kim, S. K., Kim, S., Lee, S. H. & Yoon, J. (2007). Tetrahedron Lett. 48, 5966–5969. Web of Science CrossRef CAS Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Xiang, Y., Tong, A. J., Jin, P. Y. & Ju, Y. (2006). Org. Lett. 8, 2863–2866. Web of Science CrossRef PubMed CAS Google Scholar
Zhang, X., Shiraishi, Y. & Hirai, T. (2007). Org. Lett. 9, 5039–5042. Web of Science CrossRef PubMed CAS Google Scholar
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Rhodamine B derivatives are known to have excellent photophysical properties, such as the long absorption and emission wavelengths elongated to the visible region. Therefore, they have been extensively used as fluorescent chemosensors for heavy and transition metal ions, such as Cu(II) (Zhang et al., 2007) and Hg(II) chemical sensor (Soh et al., 2007). Herein, we report the synthesis and crystal structure of a new Rhodamine B derivative, namely (Z)-3',6'-bis(diethylamino)-2-(4-oxopent-2-en-2-ylamino)spiroisoindoline- [1,9'-xanthen]-3-one.
In the title compound C33H38N4O3, the mean plane of the 9H-xanthene moiety and that of the spirolactam moiety are almost perpendicular to each other (Fig. 1). Two N,N-diethylamino groups bond to the 9H-xanthene moiety at C5 and C15, respectivly, while a 4-oxopent-2-en-2-ylamino links to the spirolactam moiety at N2 position (Fig. 1). The 9H-xanthene fragment exhibits a butterfly-like conformation with two benzene rings (C12-C13-C14-C15-C16-C17 and C1-C2-C3-C4-C5-C6, respectively) exhibiting a dihedral angle of 160.06 (4)°. For the 4-oxopent-2-en-2-ylamino group, the double bond between C29 and C30 shows a Z-configuration. The structure of the title compound is similar to that of other reported Rhodamine B derivatives (Xiang et al. 2006). The molecular packing is stabilized by an intermolecular interaction (C7—H7B···O3i, C7O3i = 3.334 (3) Å, C7—H7B···O3i = 133 °).