A redetermination of 2-(6-diethyl­amino-3-diethyl­iminio-3H-xanthen-9-yl)benzoate–ethyl gallate (1/1) at room temperature

Mizuguchi, J.; Sato, K.

doi:10.1107/S160053680900751X

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 4| April 2009| Pages o701-o702

doi:10.1107/S160053680900751X

Open

access

A redetermination of 2-(6-diethylamino-3-diethyliminio-3H-xanthen-9-yl)benzoate–ethyl gallate (1/1) at room temperature

Jin Mizuguchi ^a ^* and Kazuyuki Sato ^a

^aDepartment of Applied Physics, Graduate School of Engineering, Yokohama National University, Tokiwadai 79-5, Hodogaya-ku, Yokohama 240-8501, Japan
^*Correspondence e-mail: mizu-j@ynu.ac.jp

(Received 26 February 2009; accepted 2 March 2009; online 6 March 2009)

The title compound, C₂₈H₃₀N₂O₃·C₉H₁₀O₅, is a well known red leuco complex of 2-(6-diethylamino-3-diethyliminio-3H-xanthene-9-yl)benzoate (rhodamine B base abbreviated to RBB: leuco dye) with ethyl gallate (EG: developer). The structure of the complex at room temperature has recently been reported by Sekiguchi, Takayama, Gotanda & Sano [(2007) Chem. Lett. 36, 1010–1011]. The RBB–EG complex forms a dimer (RBB⋯EG⋯EG⋯RBB) through intermolecular O—H⋯O hydrogen bonds. In a subsequent re-examination of the structure at room temperature, we found the RBB molecule to be disordered with a methyl group of one ethyl substituent of a diethylamino group at one extremity of the xanthene unit disordered over two positions [occupancies: 0.735 (5)/0.265 (5)]. Furthermore, at the other end of the xanthene residue, the entire diethylamino substituent (i.e. the N atom and the associated C and H atoms) was also disordered over two sites with occupancies 0.653 (7)/0.347 (7). This leads to four kinds of RBB conformations, which, in turn, results in the formation of 16 discrete RBB⋯EG⋯EG⋯RBB dimers in the crystal.

Related literature

For the previous determination of the structure of the 1:1 RBB/EG complex at room temperature, see: Sekiguchi et al. (2007 ) and for the structure of a second triclinic form of the same complex at 93 K, see: Mizuguchi (2008 ). For the related structure of n-propyl gallate, see: Iwata et al. (2005 ); Hitachi et al. (2005 ).

Experimental

Crystal data

C₂₈H₃₀N₂O₃·C₉H₁₀O₅
M_r = 640.71
Triclinic, $[P \overline 1]$
a = 11.4721 (3) Å
b = 11.8036 (3) Å
c = 12.4816 (3) Å
α = 85.805 (2)°
β = 87.202 (1)°
γ = 81.973 (1)°
V = 1667.84 (7) Å³
Z = 2
Cu Kα radiation
μ = 0.74 mm⁻¹
T = 296 K
0.20 × 0.20 × 0.20 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (Higashi, 1995 ) T_min = 0.851, T_max = 0.863
15046 measured reflections
5610 independent reflections
3355 reflections with F² > 2σ(F²)
R_int = 0.077

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.141
S = 0.93
5610 reflections
476 parameters
31 restraints
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4O⋯O7ⁱ	0.82	2.00	2.811 (2)	168
O5—H5O⋯O2	0.82	2.79	3.257 (2)	118
O5—H5O⋯O3	0.82	1.78	2.579 (2)	164
O6—H6O⋯O2	0.82	1.86	2.5991 (18)	148
O6—H6O⋯O3	0.82	2.78	3.3842 (19)	132
O6—H6O⋯O5	0.82	2.47	2.8758 (19)	112
Symmetry code: (i) -x, -y+2, -z+2.

Data collection: PROCESS-AUTO (Rigaku, 1998 ); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC & Rigaku, 2006 ); program(s) used to solve structure: SIR2004 (Burla et al., 2005 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ); software used to prepare material for publication: CrystalStructure.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680900751X/sj2586sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680900751X/sj2586Isup2.hkl

checkCIF report

Comment top

The title compound, C₂₈H₃₀N₂O₃.C₉H₁₀O₅, is a well known red leuco complex of 2-(6-diethylamino-3-diethyliminio-3H-xanthene-9-yl)benzoate with ethyl gallate (rhodamine B base abbreviated to RBB: leuco dye) with ethyl gallate (EG: developer). The structure of the RBB/EG complex at room temperature has recently been reported by Sekiguchi et al. (2007), where the RBB conformation is uniquely RBB-A as shown schematically in Fig. 1a. That is, the ethyl groups of the xanthene diethylamino substituents lie on the same side of the xanthene plane in RBB-A. Quite recently, we have also found a new triclinic phase with two discrete base/developer complexes (RBB-A/EG-A and RBB-B/EG-B: see Fig. 1a) at 93 K (Mizuguchi, 2008). In both phases, two RBBs are connected by a sub-dimer of EG through intermolecular O—H···O hydrogen bonds. However, close inspection of the supplementary CIF of the report of Sekiguchi et al. (2007) revealed that there was a residual electron density peak of about 1.35 e Å^-3. For this reason, a redetermination of the structure has been carried out at room temperature in the present investigation. This revealed that the RBB molecule is disordered as shown in Fig. 1b with the C28 methyl group of one ethyl substituent of the N1 diethylamino group at one extremity of the xanthene moiety as well as the entire diethylamino-substituent (i.e. N2 atom with the associated C and H atoms) at the other end of the xanthene unit disordered over two positions.

As shown in Fig. 1b, the RBB molecule is disordered at C28A/C28B together with their associated H atoms at one extremity of the xanthene moiety. The disordered structure is separated into the major (0.735 (5)) and minor (0.265 (5)) components which correspond to the RBB-A and RBB-B forms respectively, as shown in Fig. 1a. These are similar to those found at 93K, where the diethylamino-substituents lie either on the same side, or on opposite sides of the xanthene plane. Similarly, the disorder at the entire N2 diethylamino-substituents at the other end of the xanthene plane also leads to the presence of the two conformations described above: N2A group (diethylamino-substituents on the same side; occupancy 0.653 (7)) and N2B group (on opposite sides; occupancy 0.347 (7)). Figs. 2–5 show plots of the four possible structures of (I). Of these, the previous report (Sekiguchi et al., 2007) only identified the conformation shown in Fig. 2.

The lactone ring is opened to form a zwitterionic structure and the benzene ring with the carboxylate is twisted to be nearly perpendicular to the xanthene plane with a dihedral angle of 98.9 (1)° between the O1/C1—C13 plane of the xanthene and the C14—C19 plane of the benzene ring. The xanthene moiety is nearly flat (mean deviation from the least-squares plane, 0.0300 Å).

There are intra and intermolecular O—H···O hydrogen bonds leading to the formation of the RBB/EG complexes as shown in Fig. 6. For example, two major RBB/EG complexes are further connected by intermolecular O—H···O hydrogen bonds between two EGs to form a dimer as shown in Fig. 7. The existence of the four possible RBB conformations leads to the formation of 16 kinds of RBB···EG···EG···RBB dimers in the crystal. The formation of the EG dimer is similar to that found in n-propyl gallate (Iwata et al., 2005; Hitachi et al., 2005).

Related literature top

For the previous determination of the structure of the 1:1 RBB/EG complex at room temperature, see: Sekiguchi et al. (2007) and for the structure of a second triclinic form of the same complex at 93 K, see: Mizuguchi (2008). For the related structure of n-propyl gallate, see: Iwata et al. (2005); Hitachi et al. (2005).

Experimental top

Rhodamine B base and 4-hydroxybenzophenone were purchased from Sigma-Aldrich Corp. and Wako Pure Chemical Industries, Ltd., respectively. Single crystals of (I) were grown by recrystallization from a toluene solution which includes an equimolar quantity of both chemicals. After 24 h, a number of red crystals were obtained in the form of blocks.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC & Rigaku, 2006); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: CrystalStructure (Rigaku/MSC & Rigaku, 2006).

Figures top

	Fig. 1. (a) A schematic representation of the two independent conformations of RBB found at 93 K, where RBB-A illustrates the diethylamino substituents on the same side while in RBB-B they are on opposite sides, of the xanthene plane. (b) The disordered structure of the title molecule at room temperature, where the major and minor disorder components are depicted as solid and dotted lines, respectively.
	Fig. 2. Plot of one of the four possible disordered conformations of (I), showing 10% displacement ellipsoids. Hydrogen atoms except for those involved in the intermolecular hydrogen bonds are omitted for clarity. The "major/major" combination shown here corresponds to the RBB-A form found at 93K and shown in Fig. 1a.
	Fig. 3. Plot of one of the four possible disordered conformations of (I), showing 10% displacement ellipsoids. Hydrogen atoms except for those involved in the intermolecular hydrogen bonds are omitted for clarity.
	Fig. 4. Plot of one of the four possible disordered conformations of (I), showing 10% displacement ellipsoids. Hydrogen atoms except for those involved in the intermolecular hydrogen bonds are omitted for clarity.
	Fig. 5. Plot of one of the four possible disordered conformations of (I), showing 10% displacement ellipsoids. Hydrogen atoms except for those involved in the intermolecular hydrogen bonds are omitted for clarity. The "minor/minor" combination shown here corresponds to the RBB-B form found at 93K and shown in Fig. 1a.
	Fig. 6. Intra- and intermolecular O—H···O hydrogen bonds leading to the formation of the RBB/EG complex. For clarity, only the C14/C19 benzene ring and its substituents are shown for the RBB unit.
	Fig. 7. The hydrogen-bonded RBB (major)···EG···EG···RBB (major) dimer formed by linking two RBB/EG complexes through intermolecular O—H···O hydrogen bonds.

2-(6-diethylamino-3-diethyliminio-3H-xanthen-9-yl)benzoate–ethyl gallate (1/1) top

Crystal data top

C₂₈H₃₀N₂O₃·C₉H₁₀O₅	Z = 2
M_r = 640.71	F(000) = 680.00
Triclinic, P1	D_x = 1.276 Mg m⁻³
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54187 Å
a = 11.4721 (3) Å	Cell parameters from 10532 reflections
b = 11.8036 (3) Å	θ = 3.0–68.5°
c = 12.4816 (3) Å	µ = 0.74 mm⁻¹
α = 85.805 (2)°	T = 296 K
β = 87.202 (1)°	Block, red
γ = 81.973 (1)°	0.20 × 0.20 × 0.20 mm
V = 1667.84 (7) Å³

Data collection top

Rigaku R-AXIS RAPID diffractometer	3355 reflections with F² > 2σ(F²)
ω scans	R_int = 0.077
Absorption correction: multi-scan (Higashi, 1995)	θ_max = 68.2°
T_min = 0.851, T_max = 0.863	h = −13→13
15046 measured reflections	k = −13→14
5610 independent reflections	l = −14→15

Refinement top

Refinement on F²	31 restraints
R[F² > 2σ(F²)] = 0.050	H-atom parameters constrained
wR(F²) = 0.141	w = 1/[σ²(F_o²) + (0.0812P)²] where P = (F_o² + 2F_c²)/3
S = 0.93	(Δ/σ)_max < 0.001
5610 reflections	Δρ_max = 0.16 e Å⁻³
476 parameters	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₂₈H₃₀N₂O₃·C₉H₁₀O₅	γ = 81.973 (1)°
M_r = 640.71	V = 1667.84 (7) Å³
Triclinic, P1	Z = 2
a = 11.4721 (3) Å	Cu Kα radiation
b = 11.8036 (3) Å	µ = 0.74 mm⁻¹
c = 12.4816 (3) Å	T = 296 K
α = 85.805 (2)°	0.20 × 0.20 × 0.20 mm
β = 87.202 (1)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	5610 independent reflections
Absorption correction: multi-scan (Higashi, 1995)	3355 reflections with F² > 2σ(F²)
T_min = 0.851, T_max = 0.863	R_int = 0.077
15046 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	31 restraints
wR(F²) = 0.141	H-atom parameters constrained
S = 0.93	Δρ_max = 0.16 e Å⁻³
5610 reflections	Δρ_min = −0.19 e Å⁻³
476 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	Occ. (<1)
O1	0.62196 (11)	0.41220 (11)	0.45212 (10)	0.0516 (3)
O2	0.57084 (12)	0.69798 (13)	0.66780 (12)	0.0664 (4)
O3	0.60107 (12)	0.76396 (14)	0.82411 (12)	0.0728 (5)
O4	0.21545 (15)	0.78684 (15)	1.01780 (12)	0.0889 (6)
H4O	0.1650	0.8183	1.0587	0.107*
O5	0.38741 (12)	0.72981 (13)	0.87434 (12)	0.0768 (5)
H5O	0.4509	0.7531	0.8609	0.092*
O6	0.37281 (12)	0.83482 (12)	0.65926 (11)	0.0693 (5)
H6O	0.4205	0.7806	0.6808	0.083*
O7	−0.06957 (15)	1.09897 (17)	0.82505 (14)	0.1034 (7)
O8	0.01167 (13)	1.10673 (14)	0.66131 (13)	0.0808 (5)
N1	0.54396 (19)	0.14504 (17)	0.73818 (16)	0.0812 (6)
C1	0.58390 (19)	0.24391 (19)	0.70248 (18)	0.0604 (6)
C2	0.63447 (19)	0.30991 (18)	0.77375 (17)	0.0611 (6)
H2	0.6350	0.2872	0.8467	0.073*
C3	0.68183 (18)	0.40497 (18)	0.73815 (16)	0.0553 (5)
H3	0.7149	0.4456	0.7872	0.066*
C4	0.68265 (16)	0.44474 (16)	0.62802 (15)	0.0462 (5)
C5	0.62725 (16)	0.38095 (16)	0.55992 (15)	0.0463 (5)
C6	0.58048 (17)	0.28344 (18)	0.59322 (17)	0.0556 (5)
H6	0.5466	0.2435	0.5442	0.067*
C7	0.67239 (16)	0.50429 (16)	0.40937 (16)	0.0468 (5)
C8	0.66879 (18)	0.52327 (18)	0.29939 (16)	0.0559 (5)
H8	0.6337	0.4751	0.2590	0.067*
C9	0.7186 (2)	0.6162 (2)	0.24908 (18)	0.0715 (7)
C10	0.7693 (2)	0.6883 (2)	0.31501 (18)	0.0724 (7)
H10	0.7999	0.7523	0.2835	0.087*
C11	0.77389 (19)	0.66561 (19)	0.42244 (17)	0.0598 (6)
H11	0.8080	0.7143	0.4630	0.072*
C12	0.72836 (16)	0.57016 (16)	0.47512 (15)	0.0459 (5)
C13	0.73447 (15)	0.53923 (16)	0.58585 (15)	0.0442 (5)
C14	0.81034 (16)	0.59702 (16)	0.65346 (15)	0.0470 (5)
C15	0.93057 (18)	0.5612 (2)	0.64624 (18)	0.0638 (6)
H15	0.9598	0.5038	0.6009	0.077*
C16	1.0074 (2)	0.6089 (2)	0.7050 (2)	0.0762 (7)
H16	1.0877	0.5830	0.7000	0.091*
C17	0.9652 (2)	0.6951 (2)	0.7711 (2)	0.0738 (7)
H17	1.0170	0.7301	0.8085	0.089*
C18	0.84517 (19)	0.72899 (19)	0.78127 (18)	0.0610 (6)
H18	0.8165	0.7854	0.8278	0.073*
C19	0.76644 (16)	0.68071 (16)	0.72356 (15)	0.0456 (5)
C20	0.63599 (17)	0.71751 (16)	0.73885 (17)	0.0507 (5)
N2A	0.7055 (4)	0.6508 (4)	0.1419 (3)	0.0667 (12)	0.653 (7)
C21A	0.6481 (6)	0.5815 (5)	0.0733 (4)	0.0907 (19)	0.653 (7)
H21A	0.6120	0.6300	0.0144	0.109*	0.653 (7)
H21B	0.5865	0.5474	0.1147	0.109*	0.653 (7)
C22A	0.7368 (7)	0.4881 (7)	0.0290 (6)	0.121 (3)	0.653 (7)
H22A	0.6985	0.4446	−0.0173	0.181*	0.653 (7)
H22B	0.7701	0.4383	0.0872	0.181*	0.653 (7)
H22C	0.7982	0.5218	−0.0112	0.181*	0.653 (7)
C23A	0.7631 (5)	0.7444 (5)	0.0886 (5)	0.0845 (18)	0.653 (7)
H23A	0.7451	0.8113	0.1302	0.101*	0.653 (7)
H23B	0.7306	0.7641	0.0183	0.101*	0.653 (7)
C24A	0.8941 (6)	0.7159 (9)	0.0753 (6)	0.119 (3)	0.653 (7)
H24A	0.9263	0.7806	0.0405	0.179*	0.653 (7)
H24B	0.9128	0.6512	0.0322	0.179*	0.653 (7)
H24C	0.9273	0.6976	0.1446	0.179*	0.653 (7)
N2B	0.7578 (9)	0.6057 (7)	0.1399 (5)	0.067 (2)	0.347 (7)
C21B	0.7208 (8)	0.5243 (11)	0.0689 (8)	0.070 (3)	0.347 (7)
H21C	0.7341	0.4489	0.1063	0.084*	0.347 (7)
H21D	0.7742	0.5225	0.0062	0.084*	0.347 (7)
C22B	0.5970 (7)	0.5395 (8)	0.0285 (7)	0.083 (3)	0.347 (7)
H22D	0.5889	0.4783	−0.0160	0.124*	0.347 (7)
H22E	0.5821	0.6116	−0.0127	0.124*	0.347 (7)
H22F	0.5415	0.5383	0.0885	0.124*	0.347 (7)
C23B	0.8235 (11)	0.6926 (10)	0.0826 (10)	0.097 (4)	0.347 (7)
H23C	0.8078	0.7636	0.1186	0.116*	0.347 (7)
H23D	0.7968	0.7078	0.0097	0.116*	0.347 (7)
C24B	0.9536 (10)	0.6518 (13)	0.0797 (12)	0.119 (3)	0.347 (7)
H24D	0.9947	0.7101	0.0439	0.179*	0.347 (7)
H24E	0.9695	0.5832	0.0416	0.179*	0.347 (7)
H24F	0.9798	0.6360	0.1518	0.179*	0.347 (7)
C25	0.5100 (3)	0.0666 (2)	0.6627 (3)	0.0976 (9)
H25A	0.4601	0.1105	0.6096	0.117*
H25B	0.4642	0.0128	0.7018	0.117*
C26	0.6126 (3)	0.0012 (2)	0.6064 (2)	0.1088 (10)
H26A	0.5863	−0.0588	0.5697	0.163*
H26B	0.6693	−0.0318	0.6579	0.163*
H26C	0.6482	0.0519	0.5552	0.163*
C27	0.5405 (3)	0.1044 (3)	0.8530 (2)	0.1106 (11)
H27A	0.5321	0.1708	0.8956	0.133*	0.735 (5)
H27B	0.4704	0.0674	0.8674	0.133*	0.735 (5)
H27C	0.5688	0.0229	0.8592	0.133*	0.265 (5)
H27D	0.5939	0.1429	0.8907	0.133*	0.265 (5)
C28A	0.6391 (4)	0.0270 (3)	0.8895 (4)	0.1142 (17)	0.735 (5)
H28A	0.6298	0.0102	0.9656	0.171*	0.735 (5)
H28B	0.7098	0.0612	0.8741	0.171*	0.735 (5)
H28C	0.6443	−0.0427	0.8533	0.171*	0.735 (5)
C28B	0.4273 (9)	0.1232 (10)	0.9041 (10)	0.122 (4)	0.265 (5)
H28D	0.4288	0.0834	0.9740	0.183*	0.265 (5)
H28E	0.3713	0.0951	0.8616	0.183*	0.265 (5)
H28F	0.4050	0.2038	0.9113	0.183*	0.265 (5)
C29	0.11073 (17)	0.97922 (17)	0.78864 (17)	0.0535 (5)
C30	0.11491 (18)	0.92607 (19)	0.89144 (17)	0.0615 (6)
H30	0.0550	0.9460	0.9423	0.074*
C31	0.20825 (19)	0.84344 (19)	0.91795 (17)	0.0594 (6)
C32	0.29921 (17)	0.81247 (17)	0.84399 (17)	0.0535 (5)
C33	0.29226 (16)	0.86332 (17)	0.73917 (16)	0.0507 (5)
C34	0.19940 (16)	0.94763 (17)	0.71342 (16)	0.0533 (5)
H34	0.1967	0.9834	0.6445	0.064*
C35	0.00929 (19)	1.0669 (2)	0.76249 (19)	0.0658 (6)
C36	−0.0881 (2)	1.1878 (3)	0.6247 (2)	0.1044 (10)
H36A	−0.1612	1.1623	0.6524	0.125*
H36B	−0.0840	1.2626	0.6506	0.125*
C37	−0.0845 (3)	1.1951 (3)	0.5094 (3)	0.1308 (13)
H37A	−0.1495	1.2489	0.4839	0.196*
H37B	−0.0898	1.1210	0.4844	0.196*
H37C	−0.0119	1.2202	0.4826	0.196*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0572 (8)	0.0526 (8)	0.0461 (8)	−0.0103 (6)	−0.0067 (6)	−0.0016 (6)
O2	0.0483 (8)	0.0812 (11)	0.0693 (10)	0.0075 (7)	−0.0122 (7)	−0.0277 (8)
O3	0.0586 (9)	0.0995 (12)	0.0594 (10)	0.0023 (8)	0.0045 (7)	−0.0285 (9)
O4	0.0873 (11)	0.1121 (14)	0.0514 (10)	0.0240 (10)	0.0129 (8)	0.0185 (9)
O5	0.0579 (9)	0.0789 (11)	0.0819 (12)	0.0115 (8)	0.0084 (8)	0.0248 (9)
O6	0.0639 (9)	0.0755 (10)	0.0580 (9)	0.0156 (8)	0.0159 (7)	0.0057 (8)
O7	0.0816 (12)	0.1408 (17)	0.0679 (12)	0.0465 (11)	0.0147 (10)	−0.0040 (11)
O8	0.0677 (10)	0.0974 (12)	0.0635 (10)	0.0285 (9)	0.0027 (8)	0.0085 (9)
N1	0.1076 (16)	0.0714 (13)	0.0693 (14)	−0.0378 (12)	−0.0053 (12)	0.0142 (11)
C1	0.0624 (13)	0.0581 (14)	0.0593 (14)	−0.0089 (11)	0.0006 (11)	0.0053 (11)
C2	0.0745 (14)	0.0618 (14)	0.0446 (13)	−0.0062 (11)	−0.0027 (11)	0.0065 (11)
C3	0.0637 (13)	0.0564 (13)	0.0442 (12)	−0.0016 (10)	−0.0041 (10)	−0.0028 (10)
C4	0.0453 (10)	0.0487 (11)	0.0422 (11)	0.0017 (9)	−0.0034 (9)	−0.0007 (9)
C5	0.0455 (10)	0.0500 (12)	0.0407 (11)	0.0009 (9)	−0.0009 (8)	0.0000 (9)
C6	0.0595 (12)	0.0565 (13)	0.0514 (13)	−0.0103 (10)	−0.0053 (10)	−0.0006 (10)
C7	0.0456 (11)	0.0470 (11)	0.0462 (12)	−0.0011 (9)	−0.0038 (9)	−0.0017 (9)
C8	0.0634 (13)	0.0644 (14)	0.0414 (12)	−0.0134 (11)	−0.0086 (10)	−0.0015 (10)
C9	0.0893 (17)	0.0864 (17)	0.0431 (13)	−0.0308 (14)	−0.0096 (12)	0.0078 (12)
C10	0.0964 (18)	0.0740 (16)	0.0514 (14)	−0.0331 (14)	−0.0072 (13)	0.0085 (12)
C11	0.0689 (14)	0.0618 (14)	0.0512 (13)	−0.0166 (11)	−0.0084 (11)	−0.0010 (11)
C12	0.0472 (10)	0.0467 (11)	0.0435 (11)	−0.0035 (9)	−0.0044 (9)	−0.0046 (9)
C13	0.0432 (10)	0.0481 (11)	0.0386 (10)	0.0042 (8)	−0.0018 (8)	−0.0055 (9)
C14	0.0451 (11)	0.0527 (12)	0.0423 (11)	−0.0038 (9)	−0.0050 (9)	0.0002 (9)
C15	0.0498 (12)	0.0821 (16)	0.0573 (14)	0.0034 (11)	−0.0027 (10)	−0.0132 (12)
C16	0.0457 (12)	0.111 (2)	0.0716 (17)	−0.0057 (13)	−0.0079 (12)	−0.0113 (16)
C17	0.0582 (14)	0.103 (2)	0.0649 (15)	−0.0214 (13)	−0.0135 (12)	−0.0110 (15)
C18	0.0638 (14)	0.0689 (14)	0.0523 (13)	−0.0112 (11)	−0.0035 (11)	−0.0126 (11)
C19	0.0480 (11)	0.0495 (11)	0.0393 (10)	−0.0065 (9)	−0.0025 (9)	−0.0030 (9)
C20	0.0513 (12)	0.0477 (12)	0.0514 (12)	−0.0010 (9)	0.0001 (10)	−0.0042 (10)
N2A	0.087 (3)	0.074 (3)	0.0399 (19)	−0.015 (2)	−0.0150 (19)	0.0078 (18)
C21A	0.116 (5)	0.106 (4)	0.050 (3)	−0.020 (4)	−0.006 (3)	0.008 (3)
C22A	0.168 (6)	0.107 (6)	0.094 (6)	−0.040 (4)	0.016 (5)	−0.021 (4)
C23A	0.114 (4)	0.085 (4)	0.056 (3)	−0.028 (3)	−0.007 (3)	0.016 (3)
C24A	0.120 (7)	0.146 (9)	0.101 (3)	−0.052 (5)	0.003 (5)	−0.004 (5)
N2B	0.090 (6)	0.066 (5)	0.046 (4)	−0.022 (4)	−0.014 (4)	0.015 (4)
C21B	0.085 (7)	0.087 (10)	0.043 (6)	−0.032 (6)	0.006 (5)	−0.014 (5)
C22B	0.101 (6)	0.084 (6)	0.066 (5)	−0.021 (5)	−0.039 (5)	0.008 (4)
C23B	0.158 (16)	0.084 (8)	0.053 (5)	−0.037 (9)	−0.018 (9)	0.012 (6)
C24B	0.120 (7)	0.146 (9)	0.101 (3)	−0.052 (5)	0.003 (5)	−0.004 (5)
C25	0.124 (2)	0.0791 (19)	0.098 (2)	−0.0515 (19)	−0.0053 (19)	0.0119 (17)
C26	0.159 (3)	0.077 (2)	0.092 (2)	−0.027 (2)	−0.011 (2)	0.0052 (17)
C27	0.143 (3)	0.094 (2)	0.099 (2)	−0.049 (2)	−0.018 (2)	0.0329 (18)
C28A	0.146 (4)	0.089 (3)	0.110 (3)	−0.024 (3)	−0.024 (3)	0.005 (2)
C28B	0.161 (8)	0.109 (7)	0.098 (7)	−0.044 (7)	0.026 (6)	0.013 (6)
C29	0.0500 (11)	0.0600 (13)	0.0489 (12)	0.0002 (10)	0.0000 (9)	−0.0086 (10)
C30	0.0558 (12)	0.0769 (15)	0.0477 (12)	0.0038 (11)	0.0059 (10)	−0.0054 (11)
C31	0.0634 (13)	0.0677 (14)	0.0435 (12)	−0.0005 (11)	0.0020 (10)	0.0022 (11)
C32	0.0482 (11)	0.0532 (12)	0.0563 (13)	−0.0010 (9)	0.0014 (10)	0.0023 (10)
C33	0.0462 (11)	0.0538 (12)	0.0503 (12)	−0.0046 (9)	0.0071 (9)	−0.0020 (10)
C34	0.0518 (11)	0.0583 (13)	0.0468 (12)	0.0007 (10)	0.0009 (9)	−0.0010 (10)
C35	0.0577 (13)	0.0800 (16)	0.0551 (14)	0.0073 (12)	0.0006 (11)	−0.0075 (12)
C36	0.0872 (19)	0.120 (2)	0.088 (2)	0.0448 (17)	−0.0106 (16)	0.0104 (18)
C37	0.108 (2)	0.176 (3)	0.091 (2)	0.039 (2)	−0.019 (2)	0.011 (2)

Geometric parameters (Å, º) top

O1—C7	1.364 (2)	C22A—H22B	0.9600
O1—C5	1.371 (2)	C22A—H22C	0.9600
O2—C20	1.241 (2)	C23A—C24A	1.498 (6)
O3—C20	1.255 (2)	C23A—H23A	0.9700
O4—C31	1.371 (2)	C23A—H23B	0.9700
O4—H4O	0.8200	C24A—H24A	0.9600
O5—C32	1.352 (2)	C24A—H24B	0.9600
O5—H5O	0.8200	C24A—H24C	0.9600
O6—C33	1.354 (2)	N2B—C21B	1.471 (7)
O6—H6O	0.8200	N2B—C23B	1.478 (7)
O7—C35	1.204 (2)	C21B—C22B	1.513 (8)
O8—C35	1.315 (3)	C21B—H21C	0.9700
O8—C36	1.455 (3)	C21B—H21D	0.9700
N1—C1	1.350 (3)	C22B—H22D	0.9600
N1—C25	1.470 (3)	C22B—H22E	0.9600
N1—C27	1.479 (3)	C22B—H22F	0.9600
C1—C6	1.409 (3)	C23B—C24B	1.503 (9)
C1—C2	1.419 (3)	C23B—H23C	0.9700
C2—C3	1.351 (3)	C23B—H23D	0.9700
C2—H2	0.9300	C24B—H24D	0.9600
C3—C4	1.420 (3)	C24B—H24E	0.9600
C3—H3	0.9300	C24B—H24F	0.9600
C4—C13	1.394 (3)	C25—C26	1.490 (4)
C4—C5	1.405 (3)	C25—H25A	0.9700
C5—C6	1.366 (3)	C25—H25B	0.9700
C6—H6	0.9300	C26—H26A	0.9600
C7—C8	1.376 (3)	C26—H26B	0.9600
C7—C12	1.405 (3)	C26—H26C	0.9600
C8—C9	1.401 (3)	C27—C28B	1.415 (8)
C8—H8	0.9300	C27—C28A	1.422 (4)
C9—N2A	1.379 (4)	C27—H27A	0.9700
C9—N2B	1.423 (6)	C27—H27B	0.9700
C9—C10	1.424 (3)	C27—H27C	0.9700
C10—C11	1.350 (3)	C27—H27D	0.9700
C10—H10	0.9300	C28A—H28A	0.9600
C11—C12	1.413 (3)	C28A—H28B	0.9600
C11—H11	0.9300	C28A—H28C	0.9600
C12—C13	1.406 (3)	C28B—H28D	0.9600
C13—C14	1.502 (3)	C28B—H28E	0.9600
C14—C15	1.386 (3)	C28B—H28F	0.9600
C14—C19	1.393 (3)	C29—C34	1.381 (3)
C15—C16	1.376 (3)	C29—C30	1.386 (3)
C15—H15	0.9300	C29—C35	1.477 (3)
C16—C17	1.377 (3)	C30—C31	1.380 (3)
C16—H16	0.9300	C30—H30	0.9300
C17—C18	1.382 (3)	C31—C32	1.387 (3)
C17—H17	0.9300	C32—C33	1.400 (3)
C18—C19	1.388 (3)	C33—C34	1.385 (3)
C18—H18	0.9300	C34—H34	0.9300
C19—C20	1.506 (3)	C36—C37	1.435 (4)
N2A—C21A	1.465 (5)	C36—H36A	0.9700
N2A—C23A	1.467 (5)	C36—H36B	0.9700
C21A—C22A	1.509 (6)	C37—H37A	0.9600
C21A—H21A	0.9700	C37—H37B	0.9600
C21A—H21B	0.9700	C37—H37C	0.9600
C22A—H22A	0.9600

O2···O6	2.5991 (18)	N2A···C28Bⁱⁱ	2.914 (11)
O3···O5	2.579 (2)	C22B···C22Bⁱⁱⁱ	2.676 (12)
O4···O7ⁱ	2.811 (2)	C23A···C28Bⁱⁱ	2.504 (11)
O5···O3	2.579 (2)	C28B···N2Aⁱⁱ	2.914 (11)
O6···O2	2.5991 (18)	C28B···C23Aⁱⁱ	2.504 (11)
O7···O4ⁱ	2.811 (2)

C7—O1—C5	120.40 (16)	N2B—C21B—C22B	121.2 (12)
C31—O4—H4O	109.5	N2B—C21B—H21C	107.0
C32—O5—H5O	109.5	C22B—C21B—H21C	107.0
C33—O6—H6O	109.5	N2B—C21B—H21D	107.0
C35—O8—C36	117.74 (19)	C22B—C21B—H21D	107.0
C1—N1—C25	121.1 (2)	H21C—C21B—H21D	106.8
C1—N1—C27	122.9 (2)	C21B—C22B—H22D	109.5
C25—N1—C27	115.9 (2)	C21B—C22B—H22E	109.5
N1—C1—C6	121.6 (2)	H22D—C22B—H22E	109.5
N1—C1—C2	120.8 (2)	C21B—C22B—H22F	109.5
C6—C1—C2	117.6 (2)	H22D—C22B—H22F	109.5
C3—C2—C1	121.5 (2)	H22E—C22B—H22F	109.5
C3—C2—H2	119.2	N2B—C23B—C24B	110.8 (8)
C1—C2—H2	119.2	N2B—C23B—H23C	109.5
C2—C3—C4	121.9 (2)	C24B—C23B—H23C	109.5
C2—C3—H3	119.0	N2B—C23B—H23D	109.5
C4—C3—H3	119.0	C24B—C23B—H23D	109.5
C13—C4—C5	120.04 (17)	H23C—C23B—H23D	108.1
C13—C4—C3	124.57 (19)	C23B—C24B—H24D	109.5
C5—C4—C3	115.39 (18)	C23B—C24B—H24E	109.5
C6—C5—O1	115.64 (18)	H24D—C24B—H24E	109.5
C6—C5—C4	123.93 (18)	C23B—C24B—H24F	109.5
O1—C5—C4	120.37 (17)	H24D—C24B—H24F	109.5
C5—C6—C1	119.5 (2)	H24E—C24B—H24F	109.5
C5—C6—H6	120.3	N1—C25—C26	113.4 (2)
C1—C6—H6	120.3	N1—C25—H25A	108.9
O1—C7—C8	115.50 (18)	C26—C25—H25A	108.9
O1—C7—C12	120.75 (17)	N1—C25—H25B	108.9
C8—C7—C12	123.68 (19)	C26—C25—H25B	108.9
C7—C8—C9	119.1 (2)	H25A—C25—H25B	107.7
C7—C8—H8	120.4	C25—C26—H26A	109.5
C9—C8—H8	120.4	C25—C26—H26B	109.5
N2A—C9—C8	123.0 (3)	H26A—C26—H26B	109.5
C8—C9—N2B	116.2 (3)	C25—C26—H26C	109.5
N2A—C9—C10	118.2 (3)	H26A—C26—H26C	109.5
C8—C9—C10	118.1 (2)	H26B—C26—H26C	109.5
N2B—C9—C10	120.7 (4)	C28B—C27—C28A	127.0 (6)
C11—C10—C9	121.2 (2)	C28B—C27—N1	114.1 (6)
C11—C10—H10	119.4	C28A—C27—N1	116.6 (3)
C9—C10—H10	119.4	C28B—C27—H27A	68.6
C10—C11—C12	122.0 (2)	C28A—C27—H27A	108.1
C10—C11—H11	119.0	N1—C27—H27A	108.1
C12—C11—H11	119.0	C28A—C27—H27B	108.1
C7—C12—C13	119.51 (18)	N1—C27—H27B	108.1
C7—C12—C11	115.67 (18)	H27A—C27—H27B	107.3
C13—C12—C11	124.82 (19)	C28B—C27—H27C	108.7
C4—C13—C12	118.90 (18)	N1—C27—H27C	108.7
C4—C13—C14	120.76 (16)	H27A—C27—H27C	140.0
C12—C13—C14	119.77 (17)	H27B—C27—H27C	74.9
C15—C14—C19	119.29 (19)	C28B—C27—H27D	108.7
C15—C14—C13	116.78 (18)	C28A—C27—H27D	68.4
C19—C14—C13	123.91 (16)	N1—C27—H27D	108.7
C16—C15—C14	121.2 (2)	H27B—C27—H27D	139.7
C16—C15—H15	119.4	H27C—C27—H27D	107.6
C14—C15—H15	119.4	C27—C28A—H28A	109.5
C15—C16—C17	119.9 (2)	C27—C28A—H28B	109.5
C15—C16—H16	120.1	H28A—C28A—H28B	109.5
C17—C16—H16	120.1	C27—C28A—H28C	109.5
C16—C17—C18	119.3 (2)	H28A—C28A—H28C	109.5
C16—C17—H17	120.3	H28B—C28A—H28C	109.5
C18—C17—H17	120.3	C27—C28B—H28D	109.5
C17—C18—C19	121.4 (2)	C27—C28B—H28E	109.5
C17—C18—H18	119.3	H28D—C28B—H28E	109.5
C19—C18—H18	119.3	C27—C28B—H28F	109.5
C18—C19—C14	118.84 (18)	H28D—C28B—H28F	109.5
C18—C19—C20	119.97 (18)	H28E—C28B—H28F	109.5
C14—C19—C20	121.18 (18)	C34—C29—C30	119.53 (19)
O2—C20—O3	124.83 (19)	C34—C29—C35	122.0 (2)
O2—C20—C19	118.03 (18)	C30—C29—C35	118.48 (19)
O3—C20—C19	117.13 (19)	C31—C30—C29	119.74 (19)
C9—N2A—C21A	119.5 (4)	C31—C30—H30	120.1
C9—N2A—C23A	122.6 (4)	C29—C30—H30	120.1
C21A—N2A—C23A	117.2 (4)	O4—C31—C30	122.02 (19)
N2A—C21A—C22A	110.3 (7)	O4—C31—C32	116.56 (19)
N2A—C21A—H21A	109.6	C30—C31—C32	121.4 (2)
C22A—C21A—H21A	109.6	O5—C32—C31	118.64 (19)
N2A—C21A—H21B	109.6	O5—C32—C33	122.70 (18)
C22A—C21A—H21B	109.6	C31—C32—C33	118.55 (18)
H21A—C21A—H21B	108.1	O6—C33—C34	116.86 (18)
C21A—C22A—H22A	109.5	O6—C33—C32	123.40 (18)
C21A—C22A—H22B	109.5	C34—C33—C32	119.75 (18)
H22A—C22A—H22B	109.5	C29—C34—C33	120.9 (2)
C21A—C22A—H22C	109.5	C29—C34—H34	119.5
H22A—C22A—H22C	109.5	C33—C34—H34	119.5
H22B—C22A—H22C	109.5	O7—C35—O8	122.1 (2)
N2A—C23A—C24A	113.7 (5)	O7—C35—C29	124.9 (2)
N2A—C23A—H23A	108.8	O8—C35—C29	112.99 (19)
C24A—C23A—H23A	108.8	C37—C36—O8	108.5 (2)
N2A—C23A—H23B	108.8	C37—C36—H36A	110.0
C24A—C23A—H23B	108.8	O8—C36—H36A	110.0
H23A—C23A—H23B	107.7	C37—C36—H36B	110.0
C23A—C24A—H24A	109.5	O8—C36—H36B	110.0
C23A—C24A—H24B	109.5	H36A—C36—H36B	108.4
H24A—C24A—H24B	109.5	C36—C37—H37A	109.5
C23A—C24A—H24C	109.5	C36—C37—H37B	109.5
H24A—C24A—H24C	109.5	H37A—C37—H37B	109.5
H24B—C24A—H24C	109.5	C36—C37—H37C	109.5
C9—N2B—C21B	124.8 (7)	H37A—C37—H37C	109.5
C9—N2B—C23B	120.8 (7)	H37B—C37—H37C	109.5
C21B—N2B—C23B	113.6 (8)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4O···O7ⁱ	0.82	2.00	2.811 (2)	168
O5—H5O···O2	0.82	2.79	3.257 (2)	118
O5—H5O···O3	0.82	1.78	2.579 (2)	164
O6—H6O···O2	0.82	1.86	2.5991 (18)	148
O6—H6O···O3	0.82	2.78	3.3842 (19)	132
O6—H6O···O5	0.82	2.47	2.8758 (19)	112

Symmetry code: (i) −x, −y+2, −z+2.

Experimental details

Crystal data
Chemical formula	C₂₈H₃₀N₂O₃·C₉H₁₀O₅
M_r	640.71
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	11.4721 (3), 11.8036 (3), 12.4816 (3)
α, β, γ (°)	85.805 (2), 87.202 (1), 81.973 (1)
V (Å³)	1667.84 (7)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	0.74
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (Higashi, 1995)
T_min, T_max	0.851, 0.863
No. of measured, independent and observed [F² > 2σ(F²)] reflections	15046, 5610, 3355
R_int	0.077
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.141, 0.93
No. of reflections	5610
No. of parameters	476
No. of restraints	31
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.19

Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC & Rigaku, 2006), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996), CrystalStructure (Rigaku/MSC & Rigaku, 2006).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4O···O7ⁱ	0.820	2.000	2.811 (2)	168.4
O5—H5O···O2	0.820	2.789	3.257 (2)	118.1
O5—H5O···O3	0.820	1.780	2.579 (2)	164.3
O6—H6O···O2	0.820	1.860	2.5991 (18)	148.4
O6—H6O···O3	0.820	2.780	3.3842 (19)	132.1
O6—H6O···O5	0.820	2.4700	2.8758 (19)	111.7

Symmetry code: (i) −x, −y+2, −z+2.

Acknowledgements

The authors express their sincere thanks to Mr H. Shima for experimental assistance.

References

Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., De Caro, L., Giacovazzo, C., Polidori, G. & Spagna, R. (2005). J. Appl. Cryst. 38, 381-388. Web of Science CrossRef CAS IUCr Journals Google Scholar
Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory. Tennessee, USA. Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Hitachi, A., Makino, T., Iwata, S. & Mizuguchi, J. (2005). Acta Cryst. E61, o2590–o2592. Web of Science CSD CrossRef IUCr Journals Google Scholar
Iwata, S., Hitachi, A., Makino, T. & Mizuguchi, J. (2005). Acta Cryst. E61, o2587–o2589. Web of Science CSD CrossRef IUCr Journals Google Scholar
Mizuguchi, J. (2008). Acta Cryst. E64, o1238–o1239. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rigaku (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC & Rigaku (2006). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA, and Rigaku Corporation, Tokyo, Japan. Google Scholar
Sekiguchi, Y., Takayama, S., Gotanda, T. & Sano, K. (2007). Chem. Lett. 36, 1010–1011. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS 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 65| Part 4| April 2009| Pages o701-o702

doi:10.1107/S160053680900751X

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

A redetermination of 2-(6-di­ethyl­amino-3-di­ethyl­iminio-3H-xanthen-9-yl)benzoate–ethyl gallate (1/1) at room temperature

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

A redetermination of 2-(6-diethylamino-3-diethyliminio-3H-xanthen-9-yl)benzoate–ethyl gallate (1/1) at room temperature