3′,6′-Bis(ethyl­amino)-2′,7′-dimethyl-2-{2-(E)-[(thio­phen-2-yl)methyl­idene­amino]­eth­yl}spiro­[isoindoline-1,9′-xanthen]-3-one methanol monosolvate

Li, Q.; Guo, R.; Xu, Z.

doi:10.1107/S1600536812018181

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 5| May 2012| Page o1556

doi:10.1107/S1600536812018181

Open

access

3′,6′-Bis(ethylamino)-2′,7′-dimethyl-2-{2-(E)-[(thiophen-2-yl)methylideneamino]ethyl}spiro[isoindoline-1,9′-xanthen]-3-one methanol monosolvate

Qing-yu Li,^a Rui Guo ^b and Zhi-hong Xu ^b ^*

^aCollege of Urban Planning and Environmental Science, Xuchang University, Xuchang, Henan Province 461000, People's Republic of China, and ^bSchool of Chemistry and Chemical Engineering, Xuchang University, Xuchang, Henan Province 461000, People's Republic of China
^*Correspondence e-mail: xuzhihong1980@yahoo.com

(Received 10 April 2012; accepted 23 April 2012; online 28 April 2012)

The title compound, C₃₃H₃₄N₄O₂S·CH₃OH, was prepared as a spirolactam ring formation of rhodamine 6 G dye for comparison with a ring-opened form. The xanthene and spirolactam rings are approximately planar [r.m.s. deviations from planarity = 0.122 (3) and 0.072 (6) Å, respectively]. The dihedral angles formed by the spirolactam and thiophene rings with the xanthene ring system are 89.7 (6) and 86.5 (2)°, respectively. The crystal structure features N—H⋯O and C—H⋯O hydrogen bonds.

Related literature

For rhodamine derivatives bearing a lactam moiety, see: Tian & Peng (2008 ); Wu et al. (2007 ); Xi et al. (2011 ); Xu et al. (2009 , 2011 ); Xu, Guo et al. (2010 ); Xu, Zhang et al. (2010 ); Zhang et al. (2008 ).

Experimental

Crystal data

C₃₃H₃₄N₄O₂S·CH₄O
M_r = 582.74
Monoclinic, P 2₁ /c
a = 9.287 (2) Å
b = 9.493 (2) Å
c = 35.754 (8) Å
β = 95.683 (4)°
V = 3136.8 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.14 mm⁻¹
T = 296 K
0.25 × 0.23 × 0.18 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.965, T_max = 0.975
15561 measured reflections
5610 independent reflections
3564 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.077
wR(F²) = 0.250
S = 1.03
5610 reflections
385 parameters
35 restraints
H-atom parameters constrained
Δρ_max = 1.10 e Å⁻³
Δρ_min = −0.56 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O3ⁱ	0.86	2.27	3.108	166
C5—H5⋯O2ⁱⁱ	0.93	2.44	3.360	170
Symmetry codes: (i) x+1, y, z; (ii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812018181/zj2071sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812018181/zj2071Isup2.hkl

checkCIF report

Comment top

Among many fluorescent compounds, rhodamine dyes are known to have excellent photophysical properties, and they are one of the most widely used fluorophores for labeling and sensing biomolecules. There are a few single-crystal reports about rhodamine derivatives bearing a lactam moiety (Xu et al., 2009; Xi et al., 2011; Xu et al., 2011; Wu et al., 2007; Xu, Zhang et al., 2010; Xu, Guo et al., 2010; Zhang et al., 2008; Tian et al., 2008;). Detailed information on their molecular and crystal structures is necessary to understand their photophysical and photochemical properties.

In agreement with other reported models, (Xu et al., 2009; Wu et al., 2007; Zhang et al., 2008; Tian et al., 2008; Xi et al., 2011;) the main skeleton of the molecule is formed by the xanthene ring and the spirolactam-ring. As shown in Figure 1, The atoms of the xanthene ring or the spirolactam-ring are both nearly planar and are almost perpendicular to each other. The dihedral angle between the xanthene mean planes and the spirolactam ring fragment is 89.7 (6)°. The dihedral angle between the xanthene mean planes and the thiophene ring is 86.5 (2)°.

Related literature top

For rhodamine derivatives bearing a lactam moiety, see: Tian & Peng (2008); Wu et al. (2007); Xi et al. (2011); Xu et al. (2009, 2011); Xu, Guo et al. (2010); Xu, Zhang et al. (2010); Zhang et al. (2008).

Experimental top

A portion of N-(rhodamine-6 G)lactam-ethylenediamine (228 mg, 0.5 mmol) and thiophenecarboxaldehyde (57.7 mg, 0.6 mmol) were combined in fresh distilled acetonitrile (50 ml). The reaction solution was refluxed for 24 h under N2 atmosphere. After that, the solution was cooled (concentrated to 10 ml) and allowed to stand at room temperature overnight. The precipitate which appeared next day was filtered and the crude product was purified by recrystallization from acetonitrile to give 247.6 mg of the title compound in 90% yield. Single crystals suitable for X-ray measurements were obtained from reaction mother liquid by slow evaporation at room temperature.

Computing details top

Data collection: SMART (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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).

Figures top

	Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at 30% probability level.
	Fig. 2. The packing diagram of the compound and the solvent methanol molecular view down a-axis.

3',6'-Bis(ethylamino)-2',7'-dimethyl-2-{2-(E)-[(thiophen-2- yl)methylideneamino]ethyl}spiro[isoindoline-1,9'-xanthen]-3-one methanol monosolvate top

Crystal data top

C₃₃H₃₄N₄O₂S·CH₄O	F(000) = 1240
M_r = 582.74	D_x = 1.234 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.287 (2) Å	Cell parameters from 3316 reflections
b = 9.493 (2) Å	µ = 0.14 mm⁻¹
c = 35.754 (8) Å	T = 296 K
β = 95.683 (4)°	Block, colorless
V = 3136.8 (12) Å³	0.25 × 0.23 × 0.18 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	5610 independent reflections
Radiation source: fine-focus sealed tube	3564 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
phi and ω scans	θ_max = 25.2°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −11→11
T_min = 0.965, T_max = 0.975	k = −11→11
15561 measured reflections	l = −42→24

Refinement top

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)] = 0.077	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.250	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.1391P)² + 1.4198P] where P = (F_o² + 2F_c²)/3
5610 reflections	(Δ/σ)_max < 0.001
385 parameters	Δρ_max = 1.10 e Å⁻³
35 restraints	Δρ_min = −0.56 e Å⁻³

Crystal data top

C₃₃H₃₄N₄O₂S·CH₄O	V = 3136.8 (12) Å³
M_r = 582.74	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.287 (2) Å	µ = 0.14 mm⁻¹
b = 9.493 (2) Å	T = 296 K
c = 35.754 (8) Å	0.25 × 0.23 × 0.18 mm
β = 95.683 (4)°

Data collection top

Bruker SMART CCD area-detector diffractometer	5610 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	3564 reflections with I > 2σ(I)
T_min = 0.965, T_max = 0.975	R_int = 0.035
15561 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.077	35 restraints
wR(F²) = 0.250	H-atom parameters constrained
S = 1.03	Δρ_max = 1.10 e Å⁻³
5610 reflections	Δρ_min = −0.56 e Å⁻³
385 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N3	0.3532 (3)	0.0575 (4)	0.04285 (10)	0.0731 (9)
H3	0.2884	−0.0001	0.0492	0.088*
C21	0.3228 (4)	0.1405 (5)	0.01026 (12)	0.0769 (12)
H21A	0.3916	0.1190	−0.0076	0.092*
H21B	0.3326	0.2395	0.0168	0.092*
C22	0.1706 (5)	0.1118 (6)	−0.00738 (14)	0.1012 (17)
H22A	0.1629	0.0151	−0.0152	0.152*
H22B	0.1495	0.1720	−0.0288	0.152*
H22C	0.1030	0.1300	0.0107	0.152*
N2	1.2815 (3)	0.4693 (3)	0.07386 (9)	0.0700 (9)
H2	1.3620	0.4874	0.0870	0.084*
C28	1.2508 (6)	0.5386 (6)	0.03806 (16)	0.0947 (15)
H28A	1.3418	0.5698	0.0297	0.114*
H28B	1.2103	0.4692	0.0201	0.114*
C29	1.1596 (11)	0.6506 (11)	0.0368 (3)	0.181 (3)
H29A	1.0626	0.6183	0.0386	0.272*
H29B	1.1637	0.6999	0.0134	0.272*
H29C	1.1881	0.7130	0.0573	0.272*
S1	0.50637 (16)	0.71838 (15)	0.19815 (4)	0.1033 (5)
O1	0.8277 (3)	0.2390 (3)	0.06317 (7)	0.0677 (8)
C16	0.7508 (3)	0.0775 (3)	0.10973 (9)	0.0468 (8)
C33	0.9946 (3)	0.1860 (3)	0.11752 (8)	0.0448 (7)
C14	0.9616 (3)	−0.0529 (3)	0.14470 (9)	0.0437 (7)
C25	0.9593 (3)	0.2555 (3)	0.08435 (9)	0.0493 (8)
C30	1.2295 (3)	0.3048 (4)	0.12193 (9)	0.0508 (8)
N4	0.8638 (3)	0.1385 (3)	0.17287 (7)	0.0463 (6)
C20	0.4841 (4)	0.0657 (4)	0.06497 (10)	0.0577 (9)
C27	1.1875 (3)	0.3756 (3)	0.08784 (9)	0.0516 (8)
C17	0.6351 (4)	−0.0026 (4)	0.11972 (10)	0.0573 (9)
H17	0.6481	−0.0545	0.1419	0.069*
C9	0.9808 (3)	−0.0692 (3)	0.18313 (9)	0.0477 (8)
O2	0.9118 (3)	0.0733 (3)	0.23449 (7)	0.0712 (7)
C23	0.5967 (4)	0.1470 (4)	0.05452 (10)	0.0589 (9)
H23	0.5848	0.1982	0.0322	0.071*
C8	0.9173 (3)	0.0521 (4)	0.20091 (9)	0.0511 (8)
C24	0.7267 (3)	0.1532 (4)	0.07680 (9)	0.0515 (8)
C26	1.0530 (4)	0.3494 (4)	0.06969 (10)	0.0579 (9)
H26	1.0243	0.3954	0.0472	0.070*
C15	0.8912 (3)	0.0887 (3)	0.13460 (8)	0.0436 (7)
C32	1.1319 (3)	0.2136 (3)	0.13547 (9)	0.0502 (8)
H32	1.1592	0.1675	0.1580	0.060*
C12	1.0738 (4)	−0.2726 (4)	0.13768 (12)	0.0616 (10)
H12	1.1052	−0.3431	0.1224	0.074*
C13	1.0076 (3)	−0.1542 (4)	0.12131 (10)	0.0540 (8)
H13	0.9947	−0.1437	0.0953	0.065*
C7	0.7759 (4)	0.2598 (4)	0.17917 (11)	0.0559 (9)
H7A	0.7385	0.2495	0.2034	0.067*
H7B	0.6938	0.2609	0.1602	0.067*
N1	0.7468 (3)	0.5095 (3)	0.18310 (9)	0.0635 (8)
C11	1.0941 (4)	−0.2885 (4)	0.17591 (13)	0.0669 (10)
H11	1.1398	−0.3689	0.1862	0.080*
C5	0.7711 (4)	0.5849 (4)	0.21151 (12)	0.0659 (10)
H5	0.8553	0.5697	0.2273	0.079*
C10	1.0479 (4)	−0.1873 (4)	0.19906 (11)	0.0621 (10)
H10	1.0615	−0.1978	0.2250	0.074*
C3	0.7036 (6)	0.7954 (6)	0.25073 (17)	0.1065 (18)
H3A	0.7857	0.7988	0.2679	0.128*
C4	0.6718 (5)	0.6968 (4)	0.22100 (12)	0.0725 (11)
C6	0.8522 (4)	0.3990 (4)	0.17837 (12)	0.0641 (10)
H6A	0.9303	0.4035	0.1985	0.077*
H6B	0.8930	0.4108	0.1546	0.077*
C1	0.4698 (8)	0.8549 (7)	0.2229 (2)	0.121 (2)
H1	0.3823	0.9031	0.2198	0.145*
C2	0.5783 (10)	0.8903 (7)	0.2483 (2)	0.142 (3)
H2A	0.5750	0.9697	0.2634	0.170*
O3	0.5909 (4)	0.5509 (5)	0.10809 (10)	0.1090 (12)
H3B	0.6220	0.5510	0.1304	0.164*
C34	0.6938 (7)	0.6016 (7)	0.08725 (18)	0.126 (2)
H34A	0.6659	0.6935	0.0779	0.188*
H34B	0.7038	0.5394	0.0665	0.188*
H34C	0.7844	0.6078	0.1026	0.188*
C18	0.5032 (4)	−0.0097 (4)	0.09893 (11)	0.0629 (10)
C19	0.3811 (5)	−0.0949 (6)	0.11157 (15)	0.0973 (16)
H19A	0.4152	−0.1482	0.1335	0.146*
H19B	0.3453	−0.1581	0.0918	0.146*
H19C	0.3048	−0.0331	0.1175	0.146*
C31	1.3756 (4)	0.3270 (5)	0.14240 (12)	0.0770 (12)
H31A	1.3874	0.2660	0.1639	0.116*
H31B	1.3851	0.4233	0.1505	0.116*
H31C	1.4485	0.3060	0.1260	0.116*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N3	0.0471 (17)	0.087 (2)	0.080 (2)	−0.0115 (16)	−0.0174 (15)	−0.0034 (19)
C21	0.057 (2)	0.093 (3)	0.075 (3)	0.004 (2)	−0.020 (2)	−0.011 (2)
C22	0.058 (3)	0.143 (5)	0.095 (3)	0.007 (3)	−0.027 (2)	−0.024 (3)
N2	0.0590 (18)	0.079 (2)	0.071 (2)	−0.0209 (16)	0.0008 (15)	0.0240 (17)
C28	0.081 (3)	0.088 (3)	0.114 (4)	−0.021 (3)	0.004 (3)	0.040 (3)
C29	0.193 (9)	0.179 (8)	0.170 (8)	−0.020 (7)	0.005 (7)	0.007 (7)
S1	0.1007 (10)	0.0925 (9)	0.1156 (11)	0.0222 (7)	0.0048 (8)	0.0020 (8)
O1	0.0522 (14)	0.0884 (18)	0.0585 (14)	−0.0218 (13)	−0.0145 (11)	0.0252 (13)
C16	0.0396 (16)	0.0493 (18)	0.0501 (18)	−0.0038 (14)	−0.0019 (13)	0.0029 (15)
C33	0.0427 (17)	0.0447 (17)	0.0462 (17)	−0.0008 (13)	0.0002 (13)	0.0029 (14)
C14	0.0352 (15)	0.0459 (17)	0.0492 (18)	−0.0076 (13)	0.0003 (13)	0.0038 (14)
C25	0.0438 (17)	0.0559 (19)	0.0467 (18)	−0.0054 (14)	−0.0028 (14)	0.0044 (15)
C30	0.0428 (17)	0.0556 (19)	0.0527 (19)	−0.0068 (15)	−0.0022 (14)	0.0047 (15)
N4	0.0449 (14)	0.0462 (15)	0.0472 (14)	−0.0008 (12)	0.0013 (11)	0.0020 (12)
C20	0.0448 (18)	0.063 (2)	0.062 (2)	−0.0004 (16)	−0.0102 (15)	−0.0086 (18)
C27	0.0465 (18)	0.0512 (19)	0.058 (2)	−0.0066 (15)	0.0075 (15)	0.0026 (16)
C17	0.0484 (19)	0.061 (2)	0.061 (2)	−0.0095 (16)	−0.0030 (16)	0.0100 (17)
C9	0.0455 (17)	0.0466 (18)	0.0491 (18)	−0.0084 (14)	−0.0049 (14)	0.0044 (15)
O2	0.0900 (19)	0.0758 (17)	0.0470 (14)	−0.0010 (15)	0.0027 (13)	−0.0039 (13)
C23	0.0492 (19)	0.070 (2)	0.055 (2)	−0.0055 (17)	−0.0098 (16)	0.0029 (17)
C8	0.0501 (18)	0.0543 (19)	0.0473 (19)	−0.0087 (15)	−0.0027 (14)	0.0006 (16)
C24	0.0426 (17)	0.061 (2)	0.0496 (18)	−0.0058 (15)	−0.0009 (14)	−0.0006 (16)
C26	0.058 (2)	0.063 (2)	0.0512 (19)	−0.0083 (17)	−0.0012 (16)	0.0146 (17)
C15	0.0397 (16)	0.0460 (17)	0.0442 (16)	−0.0030 (13)	−0.0010 (13)	0.0025 (14)
C32	0.0427 (17)	0.056 (2)	0.0505 (18)	−0.0038 (15)	−0.0026 (14)	0.0101 (15)
C12	0.050 (2)	0.050 (2)	0.085 (3)	0.0005 (16)	0.0104 (19)	−0.0049 (19)
C13	0.0457 (18)	0.056 (2)	0.060 (2)	−0.0050 (15)	0.0064 (15)	−0.0048 (17)
C7	0.0488 (19)	0.053 (2)	0.065 (2)	0.0001 (15)	0.0029 (16)	−0.0059 (16)
N1	0.0647 (19)	0.0474 (16)	0.077 (2)	0.0011 (14)	−0.0005 (16)	−0.0065 (16)
C11	0.057 (2)	0.050 (2)	0.093 (3)	0.0025 (17)	0.004 (2)	0.014 (2)
C5	0.060 (2)	0.063 (2)	0.075 (3)	−0.0038 (18)	0.0062 (19)	0.005 (2)
C10	0.061 (2)	0.058 (2)	0.065 (2)	−0.0041 (18)	−0.0041 (18)	0.0150 (19)
C3	0.093 (3)	0.103 (4)	0.125 (4)	−0.001 (3)	0.018 (3)	−0.066 (3)
C4	0.080 (3)	0.063 (2)	0.077 (3)	−0.003 (2)	0.021 (2)	−0.004 (2)
C6	0.057 (2)	0.053 (2)	0.082 (3)	−0.0007 (17)	0.0056 (18)	−0.0047 (19)
C1	0.120 (5)	0.108 (5)	0.140 (5)	0.032 (4)	0.040 (4)	−0.004 (4)
C2	0.159 (7)	0.115 (5)	0.159 (6)	0.019 (5)	0.053 (5)	−0.055 (5)
O3	0.078 (2)	0.149 (3)	0.097 (2)	−0.047 (2)	−0.0066 (18)	0.023 (2)
C34	0.099 (4)	0.158 (6)	0.121 (5)	−0.034 (4)	0.015 (3)	0.023 (4)
C18	0.0433 (19)	0.067 (2)	0.077 (3)	−0.0107 (17)	−0.0006 (17)	0.003 (2)
C19	0.059 (3)	0.127 (4)	0.103 (3)	−0.034 (3)	−0.007 (2)	0.022 (3)
C31	0.054 (2)	0.097 (3)	0.077 (3)	−0.025 (2)	−0.0080 (19)	0.022 (2)

Geometric parameters (Å, º) top

N3—C20	1.385 (4)	C17—H17	0.9300
N3—C21	1.412 (5)	C9—C10	1.379 (5)
N3—H3	0.8600	C9—C8	1.466 (5)
C21—C22	1.515 (5)	O2—C8	1.223 (4)
C21—H21A	0.9700	C23—C24	1.381 (4)
C21—H21B	0.9700	C23—H23	0.9300
C22—H22A	0.9600	C26—H26	0.9300
C22—H22B	0.9600	C32—H32	0.9300
C22—H22C	0.9600	C12—C11	1.370 (6)
N2—C27	1.375 (4)	C12—C13	1.383 (5)
N2—C28	1.442 (5)	C12—H12	0.9300
N2—H2	0.8600	C13—H13	0.9300
C28—C29	1.357 (10)	C7—C6	1.502 (5)
C28—H28A	0.9700	C7—H7A	0.9700
C28—H28B	0.9700	C7—H7B	0.9700
C29—H29A	0.9600	N1—C5	1.245 (5)
C29—H29B	0.9600	N1—C6	1.456 (5)
C29—H29C	0.9600	C11—C10	1.365 (5)
S1—C1	1.625 (7)	C11—H11	0.9300
S1—C4	1.680 (5)	C5—C4	1.468 (6)
O1—C24	1.368 (4)	C5—H5	0.9300
O1—C25	1.381 (4)	C10—H10	0.9300
C16—C24	1.379 (4)	C3—C4	1.425 (6)
C16—C17	1.392 (4)	C3—C2	1.468 (9)
C16—C15	1.507 (4)	C3—H3A	0.9300
C33—C25	1.368 (4)	C6—H6A	0.9700
C33—C32	1.394 (4)	C6—H6B	0.9700
C33—C15	1.505 (4)	C1—C2	1.330 (9)
C14—C13	1.370 (5)	C1—H1	0.9300
C14—C9	1.377 (4)	C2—H2A	0.9300
C14—C15	1.522 (4)	O3—C34	1.357 (6)
C25—C26	1.384 (5)	O3—H3B	0.8200
C30—C32	1.376 (4)	C34—H34A	0.9600
C30—C27	1.413 (5)	C34—H34B	0.9600
C30—C31	1.492 (5)	C34—H34C	0.9600
N4—C8	1.351 (4)	C18—C19	1.498 (5)
N4—C7	1.442 (4)	C19—H19A	0.9600
N4—C15	1.493 (4)	C19—H19B	0.9600
C20—C23	1.381 (5)	C19—H19C	0.9600
C20—C18	1.405 (5)	C31—H31A	0.9600
C27—C26	1.372 (5)	C31—H31B	0.9600
C17—C18	1.370 (5)	C31—H31C	0.9600

C20—N3—C21	122.1 (3)	C25—C26—H26	119.5
C20—N3—H3	118.9	N4—C15—C33	110.5 (2)
C21—N3—H3	118.9	N4—C15—C16	110.3 (2)
N3—C21—C22	110.2 (4)	C33—C15—C16	110.7 (2)
N3—C21—H21A	109.6	N4—C15—C14	99.8 (2)
C22—C21—H21A	109.6	C33—C15—C14	111.2 (2)
N3—C21—H21B	109.6	C16—C15—C14	113.8 (2)
C22—C21—H21B	109.6	C30—C32—C33	124.1 (3)
H21A—C21—H21B	108.1	C30—C32—H32	117.9
C21—C22—H22A	109.5	C33—C32—H32	117.9
C21—C22—H22B	109.5	C11—C12—C13	121.6 (4)
H22A—C22—H22B	109.5	C11—C12—H12	119.2
C21—C22—H22C	109.5	C13—C12—H12	119.2
H22A—C22—H22C	109.5	C14—C13—C12	117.7 (3)
H22B—C22—H22C	109.5	C14—C13—H13	121.2
C27—N2—C28	122.7 (3)	C12—C13—H13	121.2
C27—N2—H2	118.6	N4—C7—C6	115.1 (3)
C28—N2—H2	118.6	N4—C7—H7A	108.5
C29—C28—N2	117.1 (6)	C6—C7—H7A	108.5
C29—C28—H28A	108.0	N4—C7—H7B	108.5
N2—C28—H28A	108.0	C6—C7—H7B	108.5
C29—C28—H28B	108.0	H7A—C7—H7B	107.5
N2—C28—H28B	108.0	C5—N1—C6	116.0 (3)
H28A—C28—H28B	107.3	C10—C11—C12	120.4 (3)
C28—C29—H29A	109.5	C10—C11—H11	119.8
C28—C29—H29B	109.5	C12—C11—H11	119.8
H29A—C29—H29B	109.5	N1—C5—C4	122.5 (4)
C28—C29—H29C	109.5	N1—C5—H5	118.7
H29A—C29—H29C	109.5	C4—C5—H5	118.7
H29B—C29—H29C	109.5	C11—C10—C9	118.6 (3)
C1—S1—C4	93.6 (3)	C11—C10—H10	120.7
C24—O1—C25	118.2 (2)	C9—C10—H10	120.7
C24—C16—C17	116.1 (3)	C4—C3—C2	104.7 (5)
C24—C16—C15	121.6 (3)	C4—C3—H3A	127.6
C17—C16—C15	122.1 (3)	C2—C3—H3A	127.6
C25—C33—C32	116.0 (3)	C3—C4—C5	124.0 (4)
C25—C33—C15	122.7 (3)	C3—C4—S1	113.3 (4)
C32—C33—C15	121.3 (3)	C5—C4—S1	122.8 (3)
C13—C14—C9	120.9 (3)	N1—C6—C7	107.9 (3)
C13—C14—C15	128.9 (3)	N1—C6—H6A	110.1
C9—C14—C15	110.3 (3)	C7—C6—H6A	110.1
C33—C25—O1	122.9 (3)	N1—C6—H6B	110.1
C33—C25—C26	122.2 (3)	C7—C6—H6B	110.1
O1—C25—C26	114.9 (3)	H6A—C6—H6B	108.4
C32—C30—C27	117.9 (3)	C2—C1—S1	112.8 (5)
C32—C30—C31	121.0 (3)	C2—C1—H1	123.6
C27—C30—C31	121.1 (3)	S1—C1—H1	123.6
C8—N4—C7	122.8 (3)	C1—C2—C3	115.3 (6)
C8—N4—C15	113.9 (3)	C1—C2—H2A	122.3
C7—N4—C15	123.1 (3)	C3—C2—H2A	122.3
C23—C20—N3	121.5 (3)	C34—O3—H3B	109.5
C23—C20—C18	119.0 (3)	O3—C34—H34A	109.5
N3—C20—C18	119.5 (3)	O3—C34—H34B	109.5
C26—C27—N2	121.8 (3)	H34A—C34—H34B	109.5
C26—C27—C30	118.8 (3)	O3—C34—H34C	109.5
N2—C27—C30	119.4 (3)	H34A—C34—H34C	109.5
C18—C17—C16	124.0 (3)	H34B—C34—H34C	109.5
C18—C17—H17	118.0	C17—C18—C20	118.2 (3)
C16—C17—H17	118.0	C17—C18—C19	121.7 (4)
C14—C9—C10	120.8 (3)	C20—C18—C19	120.1 (3)
C14—C9—C8	109.1 (3)	C18—C19—H19A	109.5
C10—C9—C8	130.1 (3)	C18—C19—H19B	109.5
C20—C23—C24	120.7 (3)	H19A—C19—H19B	109.5
C20—C23—H23	119.7	C18—C19—H19C	109.5
C24—C23—H23	119.7	H19A—C19—H19C	109.5
O2—C8—N4	125.5 (3)	H19B—C19—H19C	109.5
O2—C8—C9	127.7 (3)	C30—C31—H31A	109.5
N4—C8—C9	106.8 (3)	C30—C31—H31B	109.5
O1—C24—C16	123.8 (3)	H31A—C31—H31B	109.5
O1—C24—C23	114.3 (3)	C30—C31—H31C	109.5
C16—C24—C23	122.0 (3)	H31A—C31—H31C	109.5
C27—C26—C25	121.0 (3)	H31B—C31—H31C	109.5
C27—C26—H26	119.5

C20—N3—C21—C22	−178.4 (4)	C25—C33—C15—N4	−120.9 (3)
C27—N2—C28—C29	79.0 (7)	C32—C33—C15—N4	57.2 (4)
C32—C33—C25—O1	179.7 (3)	C25—C33—C15—C16	1.7 (4)
C15—C33—C25—O1	−2.1 (5)	C32—C33—C15—C16	179.8 (3)
C32—C33—C25—C26	−1.0 (5)	C25—C33—C15—C14	129.2 (3)
C15—C33—C25—C26	177.2 (3)	C32—C33—C15—C14	−52.7 (4)
C24—O1—C25—C33	2.5 (5)	C24—C16—C15—N4	120.7 (3)
C24—O1—C25—C26	−176.8 (3)	C17—C16—C15—N4	−55.2 (4)
C21—N3—C20—C23	−5.7 (6)	C24—C16—C15—C33	−2.0 (4)
C21—N3—C20—C18	174.1 (4)	C17—C16—C15—C33	−177.9 (3)
C28—N2—C27—C26	−4.7 (6)	C24—C16—C15—C14	−128.1 (3)
C28—N2—C27—C30	175.7 (4)	C17—C16—C15—C14	56.0 (4)
C32—C30—C27—C26	−0.7 (5)	C13—C14—C15—N4	177.2 (3)
C31—C30—C27—C26	178.6 (4)	C9—C14—C15—N4	−4.9 (3)
C32—C30—C27—N2	178.9 (3)	C13—C14—C15—C33	−66.1 (4)
C31—C30—C27—N2	−1.8 (5)	C9—C14—C15—C33	111.7 (3)
C24—C16—C17—C18	0.3 (5)	C13—C14—C15—C16	59.7 (4)
C15—C16—C17—C18	176.4 (3)	C9—C14—C15—C16	−122.4 (3)
C13—C14—C9—C10	0.6 (5)	C27—C30—C32—C33	0.4 (5)
C15—C14—C9—C10	−177.5 (3)	C31—C30—C32—C33	−178.9 (4)
C13—C14—C9—C8	−178.1 (3)	C25—C33—C32—C30	0.4 (5)
C15—C14—C9—C8	3.8 (3)	C15—C33—C32—C30	−177.9 (3)
N3—C20—C23—C24	−179.6 (3)	C9—C14—C13—C12	−0.1 (4)
C18—C20—C23—C24	0.7 (6)	C15—C14—C13—C12	177.6 (3)
C7—N4—C8—O2	−8.3 (5)	C11—C12—C13—C14	−0.5 (5)
C15—N4—C8—O2	177.7 (3)	C8—N4—C7—C6	103.6 (4)
C7—N4—C8—C9	171.4 (3)	C15—N4—C7—C6	−82.9 (4)
C15—N4—C8—C9	−2.6 (3)	C13—C12—C11—C10	0.6 (5)
C14—C9—C8—O2	178.9 (3)	C6—N1—C5—C4	−177.4 (3)
C10—C9—C8—O2	0.3 (6)	C12—C11—C10—C9	−0.1 (5)
C14—C9—C8—N4	−0.8 (3)	C14—C9—C10—C11	−0.5 (5)
C10—C9—C8—N4	−179.4 (3)	C8—C9—C10—C11	177.9 (3)
C25—O1—C24—C16	−2.9 (5)	C2—C3—C4—C5	177.0 (5)
C25—O1—C24—C23	177.7 (3)	C2—C3—C4—S1	−4.4 (6)
C17—C16—C24—O1	178.9 (3)	N1—C5—C4—C3	−172.5 (5)
C15—C16—C24—O1	2.8 (5)	N1—C5—C4—S1	9.0 (6)
C17—C16—C24—C23	−1.7 (5)	C1—S1—C4—C3	2.2 (4)
C15—C16—C24—C23	−177.8 (3)	C1—S1—C4—C5	−179.1 (4)
C20—C23—C24—O1	−179.3 (3)	C5—N1—C6—C7	118.2 (4)
C20—C23—C24—C16	1.2 (6)	N4—C7—C6—N1	176.9 (3)
N2—C27—C26—C25	−179.5 (3)	C4—S1—C1—C2	1.0 (6)
C30—C27—C26—C25	0.1 (5)	S1—C1—C2—C3	−4.0 (9)
C33—C25—C26—C27	0.8 (6)	C4—C3—C2—C1	5.3 (8)
O1—C25—C26—C27	−179.9 (3)	C16—C17—C18—C20	1.5 (6)
C8—N4—C15—C33	−112.6 (3)	C16—C17—C18—C19	−178.4 (4)
C7—N4—C15—C33	73.4 (3)	C23—C20—C18—C17	−2.0 (5)
C8—N4—C15—C16	124.6 (3)	N3—C20—C18—C17	178.2 (3)
C7—N4—C15—C16	−49.4 (4)	C23—C20—C18—C19	178.0 (4)
C8—N4—C15—C14	4.6 (3)	N3—C20—C18—C19	−1.8 (6)
C7—N4—C15—C14	−169.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O3ⁱ	0.86	2.27	3.108	166
C5—H5···O2ⁱⁱ	0.93	2.44	3.360	170

Symmetry codes: (i) x+1, y, z; (ii) −x+2, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₃₃H₃₄N₄O₂S·CH₄O
M_r	582.74
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	9.287 (2), 9.493 (2), 35.754 (8)
β (°)	95.683 (4)
V (Å³)	3136.8 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.14
Crystal size (mm)	0.25 × 0.23 × 0.18

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.965, 0.975
No. of measured, independent and observed [I > 2σ(I)] reflections	15561, 5610, 3564
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.077, 0.250, 1.03
No. of reflections	5610
No. of parameters	385
No. of restraints	35
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.10, −0.56

Computer programs: SMART (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O3ⁱ	0.860	2.270	3.108	166
C5—H5···O2ⁱⁱ	0.930	2.440	3.360	170

Symmetry codes: (i) x+1, y, z; (ii) −x+2, y+1/2, −z+1/2.

Acknowledgements

The authors thank the Foundation for Key Youth Teachers of Henan Province, the Foundation for Key Youth Teachers of Xuchang University, Henan Province Science and Technology project (122300410005) and the Natural Science Foundation of the Education Department of Henan Province (12 A150029) for financial support.

References

Bruker (2005). SMART, 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
Tian, M.-Z. & Peng, X.-J. (2008). Acta Cryst. E64, o1645. Web of Science CSD CrossRef IUCr Journals Google Scholar
Wu, D., Huang, W., Duan, C.-Y., Lin, Z.-H. & Meng, Q.-J. (2007). Inorg. Chem. 46, 1538–1540. Web of Science CSD CrossRef PubMed CAS Google Scholar
Xi, P., Huang, L., Xie, G., Chen, F., Xu, Z., Bai, D. & Zeng, Z. (2011). Dalton Trans. 40, 6382–6384. Web of Science CSD CrossRef CAS PubMed Google Scholar
Xu, Z., Guo, W., Su, B., Shen, X.-K. & Yang, F. (2010). Acta Cryst. E66, o1500. Web of Science CSD CrossRef IUCr Journals Google Scholar
Xu, Z.-H., Wang, H.-S., Tao, L.-T. & Wang, H.-W. (2009). Acta Cryst. E65, o1876. Web of Science CSD CrossRef IUCr Journals Google Scholar
Xu, Z., Zhang, L., Guo, R., Xiang, T., Wu, C., Zheng, Z. & Yang, F. (2011). Sens. Actuator B Chem. 156, 546–552. Web of Science CSD CrossRef CAS Google Scholar
Xu, Z.-H., Zhang, Y.-L., Zhao, Y.-R. & Yang, F.-L. (2010). Acta Cryst. E66, o1504. Web of Science CSD CrossRef IUCr Journals Google Scholar
Zhang, L.-Z., Peng, X.-J., Gao, S. & Fan, J.-L. (2008). Acta Cryst. E64, o403. Web of Science CSD CrossRef IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 5| May 2012| Page o1556

doi:10.1107/S1600536812018181

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

3′,6′-Bis(ethyl­amino)-2′,7′-di­methyl-2-{2-(E)-[(thio­phen-2-yl)methyl­­idene­amino]­eth­yl}spiro­[isoindoline-1,9′-xanthen]-3-one methanol monosolvate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

3′,6′-Bis(ethylamino)-2′,7′-dimethyl-2-{2-(E)-[(thiophen-2-yl)methylideneamino]ethyl}spiro[isoindoline-1,9′-xanthen]-3-one methanol monosolvate