N2-(4-Meth­oxy­salicyl­idene)arginine hemihydrate

Sethuram, M.; Bhargavi, G.; Dhandapani, M.; Amirthaganesan, G.; NizamMohideen, M.

doi:10.1107/S1600536813019727

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 69| Part 8| August 2013| Pages o1301-o1302

doi:10.1107/S1600536813019727

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N²-(4-Methoxysalicylidene)arginine hemihydrate

M. Sethuram,^a G. Bhargavi,^b M. Dhandapani,^a G. Amirthaganesan ^a and M. NizamMohideen ^c ^*

^aDepartment of Chemistry, Sri Ramakrishna Mission Vidyalaya College of Arts and Science, Coimbatore 641020, Tamil Nadu, India, ^bSchool of Chemistry, University of Hyderabad, Hyderabad 500 046, Andhra Pradesh, India, and ^cDepartment of Physics, The New College (Autonomous), Chennai 600 014, TamilNadu, India
^*Correspondence e-mail: mnizam_new@yahoo.in

(Received 19 June 2013; accepted 16 July 2013; online 24 July 2013)

The title compound, C₁₄H₂₀N₄O₄·0.5H₂O [systematic name: (2S)-5-{[amino(iminiumyl)methyl]amino}-2-{[(1Z)-4-methoxy-2-oxidobenzylidene]azaniumyl}pentanoate hemihydrate], has been synthesized by the reaction of L-arginine and 4-methoxysalicylaldehyde and crystallizes with two independent substituted L-arginine molecules and one water molecule of solvation in the asymmetric unit. Each molecule exists as a zwitterion and adopts a Z configuration about the central C=N. The molecular conformation is stabilized by strong intramolecular N—H⋯O hydrogen bonds that generate S(6) and S(10) ring motifs. Intermolecular N—H⋯O and O—H⋯O hydrogen bonds involving also the water molecule and weak intermolecular C—H⋯O_water interactions link the molecules into an infinite one-dimensional ribbon structure extending along the b axis. The known (2S) absolute configuration for L-arginine was invoked. Weak intermolecular C—H⋯π interactions are also present.

Related literature

For the synthesis of similar compounds, see: Srinivasan et al. (1986 ); Moutet & Ourari (1997 ). For general background on Schiff bases, see: von Konig et al. (1982 ); Lewis et al. (2009 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ). For related structures, see: Oueslati et al. (2007 ).

Experimental

Crystal data

C₁₄H₂₀N₄O₄·0.5H₂O
M_r = 317.35
Monoclinic, P 2₁
a = 10.1828 (11) Å
b = 10.3414 (11) Å
c = 15.5542 (16) Å
β = 102.688 (2)°
V = 1597.9 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.30 × 0.30 × 0.25 mm

Data collection

Bruker Kappa APEXII CCD-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.971, T_max = 0.976
18648 measured reflections
7483 independent reflections
5859 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.072
wR(F²) = 0.167
S = 1.10
7483 reflections
452 parameters
14 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2	0.89 (1)	1.94 (3)	2.638 (4)	134 (3)
N4—H4A⋯O4	0.90 (1)	2.06 (1)	2.935 (4)	165 (3)
N5—H5⋯O6	0.90 (1)	1.90 (3)	2.600 (4)	134 (3)
N8—H8A⋯O7	0.90 (1)	2.03 (1)	2.914 (4)	166 (3)
N2—H2⋯O2ⁱ	0.86	1.92	2.758 (4)	166
N3—H3A⋯O3ⁱ	0.89 (1)	2.58 (3)	3.333 (4)	142 (3)
N3—H3B⋯O4ⁱⁱ	0.89 (1)	1.93 (1)	2.817 (4)	175 (4)
N4—H4B⋯O3ⁱⁱ	0.89 (1)	2.03 (1)	2.912 (4)	171 (3)
N6—H6⋯O6ⁱⁱⁱ	0.86	1.89	2.705 (4)	158
N7—H7A⋯O8ⁱⁱⁱ	0.89 (1)	2.50 (3)	3.202 (4)	135 (3)
N7—H7B⋯O7^iv	0.90 (1)	1.91 (1)	2.800 (4)	173 (3)
N8—H8B⋯O8^iv	0.89 (1)	2.05 (2)	2.911 (4)	161 (3)
O1W—H2W⋯O3^v	0.94 (1)	1.98 (2)	2.881 (5)	159 (6)
C15—H15C⋯O1Wⁱ	0.96	2.56	3.451 (7)	155
C22—H22⋯O1W	0.93	2.53	3.359 (6)	149
C1—H1C⋯Cg1^vi	0.96	2.96	3.669 (4)	132
C15—H15C⋯Cg2^vii	0.96	2.98	3.762 (5)	139
Symmetry codes: (i) x, y-1, z; (ii) $[-x, y-{\script{1\over 2}}, -z]$ ; (iii) x, y+1, z; (iv) $[-x+1, y+{\script{1\over 2}}, -z+1]$ ; (v) x+1, y, z; (vi) $[-x, y-{\script{1\over 2}}, -z+1]$ ; (vii) $[-x+1, y+{\script{1\over 2}}, -z]$ .

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ) and Mercury (Macrae et al., 2008 ); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813019727/zs2267sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813019727/zs2267Isup2.hkl

checkCIF report

Comment top

The Schiff base ligands derived from salicylaldehyde derivatives have been found to be excellent chelating agents for most applications in coordination chemistry such as in catalysis (Srinivasan et al., 1986) and electrocatalysis (Moutet & Ourari, 1997). Schiff bases of the general type p-R'-C₆H₄—CH═N—C₆H₄—R"-p are well known reagents that find their practical application in various areas, e.g. photography (von Konig et al., 1982) and medicinal and pharmaceutical chemistry (Lewis et al., 2009). Here, we report the synthesis of the title compound, C₁₄H₂₀N₄O₄. 0.5H₂O [systematic name: (2S)-5- {[amino(iminio)methyl]amino}-2-{[(1Z)-(4-methoxy-2-oxidophenyl) methylene]ammonio}pentanoate hemihydrate] and the structure is reported herein.

This compound crystallizes with two independent substituted L-arginine molecules (A and B), together with one water molecule of solvation in the asymmetric unit (Fig. 1). Each molecule exists as a zwitterion and adopts a Z configuration about the central iminium C═N functional group which is coplanar with the adjacent benzene ring. The known (2S) absolute configuration for L-arginine was invoked for the trivially named chiral centres at C9 and C23. The C—N bond distances of the NH₂ groups(N3—C14, N4—C14, N7—C28 and N8—C28) are 1.332 (6), 1.319 (6), 1.328 (6) and 1.322 (5) Å, respectively, which is short for a C—N single bond, but still not quite as contracted as one would expect for a fully established C═N. These bond length features are consistent with an imino resonance form as is commonly found for C—N single bonds involving sp² hybridized C and N atoms (Oueslati et al., 2007). The bond distances C6—O2, C10—O3, C10—O4, C20—O6, C24—O7 and C24—O8 [1.284 (5), 1.248 (6), 1.239 (5), 1.285 (5), 1.253 (5) and 1.237 (5) Å, respectively], clearly indicate the presence of C═O double bonds, including those also generated through resonance. The H atoms attached to the phenolic groups (O2 and O6) are transferred to the basic centres N1 and N5 respectively, generating the iminium groups. Also, the carboxylic H-atoms on O4 and O7 have been transferred to N4 and N8, respectively, to generate the common amino acid zwitterions.

In both molecules A and B, all nitrogen H-atoms are involved in hydrogen bonding (Table 1). In each, intramolecular N—H···O hydrogen bonds lead to the formation of a six- and a ten-membered ring motif [S(6) and S(10), respectively (Bernstein et al., 1995)] (Fig.1). Intermolecular N—H···O and O—H···O hydrogen bonds involving also the water molecule and weak intermolecular C—H···O_water interactions link the molecules into an infinite one-dimensional ribbon structure extending along the b axis (Fig. 2). Present also are weak intermolecular C—H..π interactions.

Related literature top

For the synthesis of similar compounds, see: Srinivasan et al. (1986); Moutet & Ourari (1997). For general background on Schiff bases, see: von Konig et al. (1982); Lewis et al. (2009). For hydrogen-bond motifs, see: Bernstein et al. (1995). For related structures, see: Oueslati et al. (2007).

Experimental top

L-Arginine and 4-methoxy salicylaldehyde (E-Merck- analar grades) were mixed in 1:1 stoichiometric proportions and dissolved in a triply distilled water–ethanol mixture using a mechanical stirrer for about four hours. The raw reaction product was removed by filtration, then re-dissolved in a water–ethanol solvent mixture and kept aside to allow crystal growth at ambient temperature. Bright yellowish crystals formed in 3 days and on removal were recrystallized several times to obtain the crystal specimen used in the X-ray analysis.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

Figures top

	Fig. 1. Molecular configuration and atom numbering scheme for the two independent substituted L-arginine molecules and the water molecule of solvation in the asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 30% probability level and intramolecular hydrogen bonds are shown as dashed lines.
	Fig. 2. Packing diagram of the title compound viewed down the a axis. Dashed lines indicate intra and intermolecular N—H···O and O—H···O hydrogen bonds and weak C—H···O intermolecular interactions.

(2S)-5-{[Amino(iminiumyl)methyl]amino}-2-{[(1Z)-4-methoxy-2-oxidobenzylidene]azaniumyl}pentanoate hemihydrate top

Crystal data top

C₁₄H₂₀N₄O₄·0.5H₂O	F(000) = 676
M_r = 317.35	D_x = 1.319 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 3158 reflections
a = 10.1828 (11) Å	θ = 2.5–31.2°
b = 10.3414 (11) Å	µ = 0.10 mm⁻¹
c = 15.5542 (16) Å	T = 293 K
β = 102.688 (2)°	Block, yellow
V = 1597.9 (3) Å³	0.30 × 0.30 × 0.25 mm
Z = 4

Data collection top

Bruker Kappa APEXII CCD-detector diffractometer	7483 independent reflections
Radiation source: fine-focus sealed tube	5859 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
ω and ϕ scans	θ_max = 28.4°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −13→13
T_min = 0.971, T_max = 0.976	k = −13→13
18648 measured reflections	l = −20→20

Refinement top

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)] = 0.072	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.167	w = 1/[σ²(F_o²) + (0.0716P)² + 0.2262P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max < 0.001
7483 reflections	Δρ_max = 0.25 e Å⁻³
452 parameters	Δρ_min = −0.21 e Å⁻³
14 restraints	Absolute structure: Flack (1983), 3448 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.1 (14)

Crystal data top

C₁₄H₂₀N₄O₄·0.5H₂O	V = 1597.9 (3) Å³
M_r = 317.35	Z = 4
Monoclinic, P2₁	Mo Kα radiation
a = 10.1828 (11) Å	µ = 0.10 mm⁻¹
b = 10.3414 (11) Å	T = 293 K
c = 15.5542 (16) Å	0.30 × 0.30 × 0.25 mm
β = 102.688 (2)°

Data collection top

Bruker Kappa APEXII CCD-detector diffractometer	7483 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	5859 reflections with I > 2σ(I)
T_min = 0.971, T_max = 0.976	R_int = 0.036
18648 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.072	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.167	Δρ_max = 0.25 e Å⁻³
S = 1.10	Δρ_min = −0.21 e Å⁻³
7483 reflections	Absolute structure: Flack (1983), 3448 Friedel pairs
452 parameters	Absolute structure parameter: 0.1 (14)
14 restraints

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
C1	0.1564 (4)	1.2584 (4)	0.5422 (3)	0.0774 (13)
H1A	0.1669	1.3231	0.5874	0.116*
H1B	0.0660	1.2607	0.5074	0.116*
H1C	0.2185	1.2750	0.5051	0.116*
C2	0.1744 (3)	1.0292 (4)	0.5285 (2)	0.0536 (8)
C3	0.2238 (4)	0.9149 (4)	0.5704 (2)	0.0566 (9)
H3	0.2572	0.9129	0.6310	0.068*
C4	0.2224 (3)	0.8064 (4)	0.5214 (2)	0.0515 (8)
H4	0.2571	0.7303	0.5492	0.062*
C5	0.1703 (3)	0.8047 (3)	0.4296 (2)	0.0444 (7)
C6	0.1152 (4)	0.9209 (3)	0.3871 (2)	0.0487 (8)
C7	0.1196 (4)	1.0328 (4)	0.4389 (2)	0.0559 (9)
H7	0.0853	1.1101	0.4127	0.067*
C8	0.1721 (3)	0.6905 (3)	0.3831 (2)	0.0471 (7)
H8	0.2109	0.6185	0.4146	0.057*
C9	0.1152 (3)	0.5543 (3)	0.2513 (2)	0.0462 (7)
H9	0.2055	0.5167	0.2598	0.055*
C10	0.0613 (4)	0.5805 (3)	0.1526 (2)	0.0499 (8)
C11	0.0248 (4)	0.4611 (3)	0.2890 (2)	0.0521 (8)
H11A	0.0645	0.4484	0.3510	0.063*
H11B	−0.0618	0.5025	0.2849	0.063*
C12	0.0006 (4)	0.3291 (3)	0.2457 (2)	0.0496 (8)
H12A	−0.0534	0.2779	0.2773	0.059*
H12B	−0.0510	0.3401	0.1859	0.059*
C13	0.1279 (4)	0.2552 (3)	0.2433 (2)	0.0524 (8)
H13A	0.1827	0.3057	0.2120	0.063*
H13B	0.1792	0.2420	0.3030	0.063*
C14	0.0664 (3)	0.1157 (3)	0.1148 (2)	0.0474 (7)
C15	0.6713 (5)	−0.0130 (4)	0.0132 (3)	0.0757 (12)
H15A	0.6971	−0.0757	−0.0255	0.114*
H15B	0.5757	−0.0169	0.0082	0.114*
H15C	0.7165	−0.0313	0.0728	0.114*
C16	0.6801 (4)	0.2145 (4)	0.0364 (2)	0.0574 (9)
C17	0.7369 (4)	0.3301 (4)	0.0165 (2)	0.0575 (9)
H17	0.7866	0.3324	−0.0270	0.069*
C18	0.7196 (4)	0.4378 (4)	0.0602 (2)	0.0551 (8)
H18	0.7587	0.5146	0.0472	0.066*
C19	0.6423 (3)	0.4371 (3)	0.1264 (2)	0.0494 (8)
C20	0.5796 (4)	0.3217 (3)	0.1448 (2)	0.0573 (9)
C21	0.6024 (4)	0.2094 (4)	0.0976 (2)	0.0631 (10)
H21	0.5639	0.1313	0.1086	0.076*
C22	0.6243 (3)	0.5520 (3)	0.1693 (2)	0.0480 (7)
H22	0.6677	0.6254	0.1550	0.058*
C23	0.5306 (4)	0.6853 (3)	0.2695 (2)	0.0463 (7)
H23	0.6141	0.7357	0.2800	0.056*
C24	0.4951 (3)	0.6572 (3)	0.3579 (2)	0.0470 (8)
C25	0.4207 (4)	0.7613 (3)	0.2061 (2)	0.0532 (8)
H25A	0.4490	0.7738	0.1510	0.064*
H25B	0.3392	0.7097	0.1935	0.064*
C26	0.3882 (4)	0.8927 (3)	0.2403 (2)	0.0550 (9)
H26A	0.3201	0.9348	0.1956	0.066*
H26B	0.3509	0.8803	0.2920	0.066*
C27	0.5096 (4)	0.9796 (3)	0.2639 (2)	0.0582 (9)
H27A	0.5780	0.9366	0.3078	0.070*
H27B	0.5460	0.9925	0.2119	0.070*
C28	0.4773 (3)	1.1249 (3)	0.3797 (2)	0.0456 (7)
N1	0.1241 (3)	0.6759 (3)	0.29926 (18)	0.0476 (6)
N2	0.0979 (3)	0.1312 (3)	0.20033 (17)	0.0545 (7)
H2	0.1009	0.0637	0.2330	0.065*
N3	0.0323 (4)	−0.0009 (3)	0.0810 (2)	0.0585 (8)
N4	0.0709 (3)	0.2127 (3)	0.06010 (18)	0.0525 (7)
N5	0.5525 (3)	0.5643 (3)	0.22704 (17)	0.0482 (6)
N6	0.4817 (4)	1.1051 (3)	0.29785 (19)	0.0597 (8)
H6	0.4674	1.1695	0.2620	0.072*
N7	0.4545 (3)	1.2428 (3)	0.40673 (19)	0.0524 (7)
N8	0.4954 (4)	1.0294 (3)	0.43757 (19)	0.0575 (8)
O1	0.1831 (3)	1.1333 (3)	0.58193 (18)	0.0720 (8)
O2	0.0628 (3)	0.9232 (2)	0.30397 (14)	0.0621 (7)
O3	0.0088 (3)	0.6877 (3)	0.13073 (16)	0.0692 (8)
O4	0.0710 (3)	0.4893 (2)	0.10247 (15)	0.0584 (6)
O5	0.7073 (3)	0.1124 (3)	−0.01041 (17)	0.0733 (8)
O6	0.5054 (3)	0.3186 (3)	0.20185 (19)	0.0779 (9)
O7	0.5093 (3)	0.7516 (3)	0.40963 (15)	0.0587 (6)
O8	0.4554 (3)	0.5477 (2)	0.37124 (16)	0.0586 (6)
O1W	0.8113 (4)	0.8224 (5)	0.2043 (3)	0.1180 (13)
H1W	0.834 (6)	0.892 (5)	0.244 (4)	0.177*
H2W	0.889 (4)	0.783 (6)	0.194 (5)	0.177*
H4A	0.081 (3)	0.2932 (15)	0.082 (2)	0.044 (9)*
H7A	0.459 (4)	1.306 (3)	0.3681 (19)	0.058 (11)*
H4B	0.056 (4)	0.205 (4)	0.0015 (7)	0.060 (11)*
H7B	0.461 (3)	1.251 (3)	0.4649 (8)	0.047 (9)*
H8A	0.492 (4)	0.9466 (15)	0.420 (2)	0.055 (10)*
H8B	0.492 (4)	1.045 (4)	0.4935 (10)	0.056 (10)*
H3A	0.021 (4)	−0.064 (3)	0.118 (2)	0.065 (12)*
H3B	0.003 (3)	−0.009 (4)	0.0228 (8)	0.054 (10)*
H5	0.513 (3)	0.493 (2)	0.241 (2)	0.053 (10)*
H1	0.083 (3)	0.744 (2)	0.271 (2)	0.049 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.063 (2)	0.064 (3)	0.102 (3)	0.002 (2)	0.011 (2)	−0.035 (3)
C2	0.0496 (19)	0.061 (2)	0.0531 (19)	−0.0094 (17)	0.0164 (15)	−0.0168 (17)
C3	0.055 (2)	0.069 (2)	0.0425 (17)	−0.0028 (18)	0.0048 (15)	−0.0087 (18)
C4	0.0464 (18)	0.055 (2)	0.0472 (18)	−0.0038 (15)	−0.0021 (14)	−0.0025 (16)
C5	0.0464 (17)	0.0452 (17)	0.0428 (16)	−0.0023 (14)	0.0126 (14)	−0.0029 (14)
C6	0.0536 (19)	0.0472 (19)	0.0475 (18)	−0.0096 (15)	0.0158 (15)	−0.0057 (15)
C7	0.065 (2)	0.0477 (19)	0.056 (2)	−0.0052 (17)	0.0158 (17)	−0.0047 (16)
C8	0.0481 (18)	0.0470 (17)	0.0459 (17)	−0.0023 (15)	0.0097 (14)	0.0040 (15)
C9	0.0590 (19)	0.0395 (17)	0.0390 (16)	−0.0023 (15)	0.0085 (14)	−0.0018 (13)
C10	0.062 (2)	0.048 (2)	0.0410 (17)	−0.0091 (16)	0.0149 (15)	−0.0017 (15)
C11	0.075 (2)	0.0420 (18)	0.0416 (17)	−0.0030 (16)	0.0188 (16)	0.0003 (14)
C12	0.067 (2)	0.0421 (17)	0.0416 (16)	−0.0115 (16)	0.0158 (15)	−0.0018 (14)
C13	0.072 (2)	0.0427 (17)	0.0383 (16)	−0.0027 (17)	0.0039 (15)	−0.0006 (14)
C14	0.0542 (19)	0.0400 (17)	0.0479 (18)	0.0086 (15)	0.0110 (15)	−0.0007 (15)
C15	0.092 (3)	0.056 (2)	0.077 (3)	0.007 (2)	0.016 (2)	−0.017 (2)
C16	0.074 (2)	0.057 (2)	0.0395 (17)	0.0196 (18)	0.0091 (16)	0.0011 (15)
C17	0.062 (2)	0.070 (2)	0.0436 (18)	0.0046 (19)	0.0186 (16)	−0.0002 (17)
C18	0.058 (2)	0.058 (2)	0.0509 (19)	−0.0003 (17)	0.0150 (16)	0.0013 (17)
C19	0.0538 (19)	0.0484 (19)	0.0457 (17)	0.0080 (15)	0.0103 (14)	0.0053 (15)
C20	0.085 (3)	0.0418 (18)	0.0497 (19)	0.0124 (18)	0.0257 (18)	0.0095 (16)
C21	0.098 (3)	0.0403 (18)	0.057 (2)	0.0063 (19)	0.030 (2)	0.0084 (16)
C22	0.0561 (19)	0.0436 (17)	0.0435 (16)	0.0008 (15)	0.0090 (14)	0.0040 (14)
C23	0.062 (2)	0.0387 (16)	0.0384 (16)	0.0033 (15)	0.0125 (14)	0.0014 (13)
C24	0.0542 (19)	0.0458 (19)	0.0395 (17)	0.0143 (15)	0.0068 (14)	0.0091 (14)
C25	0.071 (2)	0.0432 (17)	0.0397 (17)	0.0071 (17)	0.0006 (15)	0.0000 (14)
C26	0.077 (2)	0.0447 (18)	0.0380 (17)	0.0116 (17)	0.0017 (16)	0.0011 (14)
C27	0.091 (3)	0.0456 (18)	0.0443 (18)	0.0001 (19)	0.0285 (18)	0.0043 (15)
C28	0.0564 (19)	0.0407 (17)	0.0414 (17)	−0.0062 (15)	0.0144 (14)	0.0009 (14)
N1	0.0623 (18)	0.0359 (14)	0.0433 (15)	0.0001 (13)	0.0085 (13)	0.0033 (12)
N2	0.086 (2)	0.0386 (14)	0.0359 (14)	0.0072 (14)	0.0062 (14)	0.0056 (12)
N3	0.090 (2)	0.0406 (16)	0.0440 (17)	−0.0011 (15)	0.0131 (16)	−0.0001 (14)
N4	0.082 (2)	0.0396 (15)	0.0363 (14)	−0.0004 (14)	0.0131 (14)	0.0004 (12)
N5	0.0685 (18)	0.0377 (14)	0.0424 (14)	0.0028 (13)	0.0205 (13)	0.0037 (11)
N6	0.104 (2)	0.0340 (14)	0.0457 (16)	0.0022 (15)	0.0258 (16)	0.0065 (12)
N7	0.0753 (19)	0.0424 (16)	0.0406 (15)	−0.0044 (14)	0.0153 (14)	−0.0013 (13)
N8	0.093 (2)	0.0435 (17)	0.0388 (15)	−0.0007 (16)	0.0215 (15)	0.0025 (13)
O1	0.083 (2)	0.0680 (18)	0.0646 (16)	−0.0093 (15)	0.0160 (14)	−0.0276 (14)
O2	0.0966 (19)	0.0432 (13)	0.0405 (13)	−0.0050 (13)	0.0020 (12)	0.0025 (11)
O3	0.108 (2)	0.0544 (16)	0.0412 (13)	0.0161 (15)	0.0071 (13)	0.0039 (12)
O4	0.0903 (19)	0.0466 (13)	0.0413 (12)	−0.0059 (13)	0.0210 (12)	−0.0030 (11)
O5	0.107 (2)	0.0646 (17)	0.0525 (15)	0.0202 (16)	0.0257 (15)	−0.0042 (13)
O6	0.133 (3)	0.0394 (13)	0.0811 (19)	0.0060 (16)	0.0668 (19)	0.0087 (14)
O7	0.0839 (18)	0.0523 (14)	0.0415 (12)	0.0089 (13)	0.0170 (12)	0.0003 (11)
O8	0.0798 (17)	0.0455 (14)	0.0527 (14)	0.0036 (13)	0.0189 (12)	0.0084 (11)
O1W	0.097 (3)	0.116 (3)	0.136 (4)	0.000 (2)	0.015 (2)	0.010 (3)

Geometric parameters (Å, º) top

C1—O1	1.434 (5)	C17—C18	1.336 (5)
C1—H1A	0.9600	C17—H17	0.9300
C1—H1B	0.9600	C18—C19	1.428 (5)
C1—H1C	0.9600	C18—H18	0.9300
C2—O1	1.351 (4)	C19—C22	1.394 (5)
C2—C7	1.383 (5)	C19—C20	1.412 (5)
C2—C3	1.390 (5)	C20—O6	1.286 (4)
C3—C4	1.355 (5)	C20—C21	1.420 (5)
C3—H3	0.9300	C21—H21	0.9300
C4—C5	1.409 (4)	C22—N5	1.282 (4)
C4—H4	0.9300	C22—H22	0.9300
C5—C8	1.388 (5)	C23—N5	1.454 (4)
C5—C6	1.426 (5)	C23—C24	1.525 (4)
C6—O2	1.286 (4)	C23—C25	1.535 (5)
C6—C7	1.405 (5)	C23—H23	0.9800
C7—H7	0.9300	C24—O8	1.235 (4)
C8—N1	1.297 (4)	C24—O7	1.253 (4)
C8—H8	0.9300	C25—C26	1.523 (5)
C9—N1	1.455 (4)	C25—H25A	0.9700
C9—C11	1.535 (5)	C25—H25B	0.9700
C9—C10	1.537 (4)	C26—C27	1.507 (6)
C9—H9	0.9800	C26—H26A	0.9700
C10—O4	1.241 (4)	C26—H26B	0.9700
C10—O3	1.245 (4)	C27—N6	1.452 (4)
C11—C12	1.518 (5)	C27—H27A	0.9700
C11—H11A	0.9700	C27—H27B	0.9700
C11—H11B	0.9700	C28—N6	1.300 (4)
C12—C13	1.512 (5)	C28—N8	1.321 (4)
C12—H12A	0.9700	C28—N7	1.326 (4)
C12—H12B	0.9700	N1—H1	0.891 (10)
C13—N2	1.448 (4)	N2—H2	0.8600
C13—H13A	0.9700	N3—H3A	0.894 (10)
C13—H13B	0.9700	N3—H3B	0.892 (10)
C14—N2	1.309 (4)	N4—H4A	0.898 (10)
C14—N4	1.323 (4)	N4—H4B	0.894 (10)
C14—N3	1.330 (4)	N5—H5	0.896 (10)
C15—O5	1.418 (5)	N6—H6	0.8600
C15—H15A	0.9600	N7—H7A	0.893 (10)
C15—H15B	0.9600	N7—H7B	0.896 (10)
C15—H15C	0.9600	N8—H8A	0.898 (10)
C16—O5	1.346 (4)	N8—H8B	0.893 (10)
C16—C21	1.366 (5)	O1W—H1W	0.940 (10)
C16—C17	1.393 (6)	O1W—H2W	0.937 (10)

O1—C1—H1A	109.5	C19—C18—H18	119.4
O1—C1—H1B	109.5	C22—C19—C20	120.7 (3)
H1A—C1—H1B	109.5	C22—C19—C18	119.5 (3)
O1—C1—H1C	109.5	C20—C19—C18	119.7 (3)
H1A—C1—H1C	109.5	O6—C20—C19	121.4 (3)
H1B—C1—H1C	109.5	O6—C20—C21	121.5 (3)
O1—C2—C7	123.8 (4)	C19—C20—C21	117.1 (3)
O1—C2—C3	114.9 (3)	C16—C21—C20	120.9 (4)
C7—C2—C3	121.3 (3)	C16—C21—H21	119.5
C4—C3—C2	118.8 (3)	C20—C21—H21	119.5
C4—C3—H3	120.6	N5—C22—C19	125.1 (3)
C2—C3—H3	120.6	N5—C22—H22	117.5
C3—C4—C5	122.4 (3)	C19—C22—H22	117.5
C3—C4—H4	118.8	N5—C23—C24	109.6 (3)
C5—C4—H4	118.8	N5—C23—C25	108.2 (3)
C8—C5—C4	119.6 (3)	C24—C23—C25	113.1 (3)
C8—C5—C6	121.6 (3)	N5—C23—H23	108.6
C4—C5—C6	118.8 (3)	C24—C23—H23	108.6
O2—C6—C7	121.0 (3)	C25—C23—H23	108.6
O2—C6—C5	121.1 (3)	O8—C24—O7	127.0 (3)
C7—C6—C5	117.9 (3)	O8—C24—C23	118.6 (3)
C2—C7—C6	120.8 (4)	O7—C24—C23	114.5 (3)
C2—C7—H7	119.6	C26—C25—C23	114.6 (3)
C6—C7—H7	119.6	C26—C25—H25A	108.6
N1—C8—C5	125.3 (3)	C23—C25—H25A	108.6
N1—C8—H8	117.3	C26—C25—H25B	108.6
C5—C8—H8	117.3	C23—C25—H25B	108.6
N1—C9—C11	108.8 (3)	H25A—C25—H25B	107.6
N1—C9—C10	109.1 (3)	C27—C26—C25	112.8 (3)
C11—C9—C10	112.3 (3)	C27—C26—H26A	109.0
N1—C9—H9	108.8	C25—C26—H26A	109.0
C11—C9—H9	108.8	C27—C26—H26B	109.0
C10—C9—H9	108.8	C25—C26—H26B	109.0
O4—C10—O3	126.4 (3)	H26A—C26—H26B	107.8
O4—C10—C9	115.6 (3)	N6—C27—C26	114.0 (3)
O3—C10—C9	117.9 (3)	N6—C27—H27A	108.8
C12—C11—C9	116.7 (3)	C26—C27—H27A	108.8
C12—C11—H11A	108.1	N6—C27—H27B	108.8
C9—C11—H11A	108.1	C26—C27—H27B	108.8
C12—C11—H11B	108.1	H27A—C27—H27B	107.7
C9—C11—H11B	108.1	N6—C28—N8	121.3 (3)
H11A—C11—H11B	107.3	N6—C28—N7	120.1 (3)
C13—C12—C11	114.1 (3)	N8—C28—N7	118.6 (3)
C13—C12—H12A	108.7	C8—N1—C9	125.7 (3)
C11—C12—H12A	108.7	C8—N1—H1	116 (2)
C13—C12—H12B	108.7	C9—N1—H1	118 (2)
C11—C12—H12B	108.7	C14—N2—C13	123.9 (3)
H12A—C12—H12B	107.6	C14—N2—H2	118.0
N2—C13—C12	111.3 (3)	C13—N2—H2	118.0
N2—C13—H13A	109.4	C14—N3—H3A	118 (3)
C12—C13—H13A	109.4	C14—N3—H3B	119 (2)
N2—C13—H13B	109.4	H3A—N3—H3B	122 (4)
C12—C13—H13B	109.4	C14—N4—H4A	118 (2)
H13A—C13—H13B	108.0	C14—N4—H4B	125 (3)
N2—C14—N4	121.7 (3)	H4A—N4—H4B	117 (3)
N2—C14—N3	119.8 (3)	C22—N5—C23	124.8 (3)
N4—C14—N3	118.4 (3)	C22—N5—H5	117 (2)
O5—C15—H15A	109.5	C23—N5—H5	118 (2)
O5—C15—H15B	109.5	C28—N6—C27	123.2 (3)
H15A—C15—H15B	109.5	C28—N6—H6	118.4
O5—C15—H15C	109.5	C27—N6—H6	118.4
H15A—C15—H15C	109.5	C28—N7—H7A	115 (2)
H15B—C15—H15C	109.5	C28—N7—H7B	115 (2)
O5—C16—C21	124.5 (4)	H7A—N7—H7B	127 (3)
O5—C16—C17	114.1 (3)	C28—N8—H8A	121 (2)
C21—C16—C17	121.4 (3)	C28—N8—H8B	120 (2)
C18—C17—C16	119.6 (3)	H8A—N8—H8B	118 (3)
C18—C17—H17	120.2	C2—O1—C1	118.2 (3)
C16—C17—H17	120.2	C16—O5—C15	118.8 (3)
C17—C18—C19	121.2 (3)	H1W—O1W—H2W	110.4 (17)
C17—C18—H18	119.4

O1—C2—C3—C4	−178.2 (3)	C18—C19—C20—C21	2.6 (5)
C7—C2—C3—C4	2.5 (5)	O5—C16—C21—C20	179.4 (4)
C2—C3—C4—C5	−1.2 (5)	C17—C16—C21—C20	−1.6 (6)
C3—C4—C5—C8	179.9 (3)	O6—C20—C21—C16	179.2 (4)
C3—C4—C5—C6	−1.0 (5)	C19—C20—C21—C16	−1.0 (6)
C8—C5—C6—O2	1.2 (5)	C20—C19—C22—N5	0.0 (5)
C4—C5—C6—O2	−177.9 (3)	C18—C19—C22—N5	176.9 (3)
C8—C5—C6—C7	−178.9 (3)	N5—C23—C24—O8	−18.7 (4)
C4—C5—C6—C7	2.0 (4)	C25—C23—C24—O8	102.2 (4)
O1—C2—C7—C6	179.3 (3)	N5—C23—C24—O7	161.9 (3)
C3—C2—C7—C6	−1.5 (5)	C25—C23—C24—O7	−77.3 (4)
O2—C6—C7—C2	179.1 (3)	N5—C23—C25—C26	−178.7 (3)
C5—C6—C7—C2	−0.8 (5)	C24—C23—C25—C26	59.7 (4)
C4—C5—C8—N1	178.1 (3)	C23—C25—C26—C27	57.0 (4)
C6—C5—C8—N1	−1.1 (5)	C25—C26—C27—N6	−179.2 (3)
N1—C9—C10—O4	167.8 (3)	C5—C8—N1—C9	−174.4 (3)
C11—C9—C10—O4	−71.5 (4)	C11—C9—N1—C8	60.9 (4)
N1—C9—C10—O3	−14.6 (4)	C10—C9—N1—C8	−176.2 (3)
C11—C9—C10—O3	106.2 (4)	N4—C14—N2—C13	6.0 (5)
N1—C9—C11—C12	178.7 (3)	N3—C14—N2—C13	−175.9 (3)
C10—C9—C11—C12	57.7 (4)	C12—C13—N2—C14	79.9 (4)
C9—C11—C12—C13	55.3 (4)	C19—C22—N5—C23	−177.9 (3)
C11—C12—C13—N2	−179.3 (3)	C24—C23—N5—C22	−155.8 (3)
O5—C16—C17—C18	−178.4 (3)	C25—C23—N5—C22	80.4 (4)
C21—C16—C17—C18	2.5 (6)	N8—C28—N6—C27	−1.6 (6)
C16—C17—C18—C19	−0.8 (6)	N7—C28—N6—C27	178.4 (3)
C17—C18—C19—C22	−178.7 (3)	C26—C27—N6—C28	83.0 (5)
C17—C18—C19—C20	−1.8 (5)	C7—C2—O1—C1	−11.4 (5)
C22—C19—C20—O6	−0.7 (5)	C3—C2—O1—C1	169.3 (3)
C18—C19—C20—O6	−177.6 (4)	C21—C16—O5—C15	−9.9 (6)
C22—C19—C20—C21	179.5 (3)	C17—C16—O5—C15	171.0 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.89 (1)	1.94 (3)	2.638 (4)	134 (3)
N4—H4A···O4	0.90 (1)	2.06 (1)	2.935 (4)	165 (3)
N5—H5···O6	0.90 (1)	1.90 (3)	2.600 (4)	134 (3)
N8—H8A···O7	0.90 (1)	2.03 (1)	2.914 (4)	166 (3)
N2—H2···O2ⁱ	0.86	1.92	2.758 (4)	166
N3—H3A···O3ⁱ	0.89 (1)	2.58 (3)	3.333 (4)	142 (3)
N3—H3B···O4ⁱⁱ	0.89 (1)	1.93 (1)	2.817 (4)	175 (4)
N4—H4B···O3ⁱⁱ	0.89 (1)	2.03 (1)	2.912 (4)	171 (3)
N6—H6···O6ⁱⁱⁱ	0.86	1.89	2.705 (4)	158
N7—H7A···O8ⁱⁱⁱ	0.89 (1)	2.50 (3)	3.202 (4)	135 (3)
N7—H7B···O7^iv	0.90 (1)	1.91 (1)	2.800 (4)	173 (3)
N8—H8B···O8^iv	0.89 (1)	2.05 (2)	2.911 (4)	161 (3)
O1W—H1W···O2^v	0.94 (1)	2.33 (6)	2.882 (5)	117 (4)
O1W—H2W···O3^v	0.94 (1)	1.98 (2)	2.881 (5)	159 (6)
C15—H15C···O1Wⁱ	0.96	2.56	3.451 (7)	155
C22—H22···O1W	0.93	2.53	3.359 (6)	149
C1—H1C···Cg1^vi	0.96	2.96	3.669 (4)	132
C15—H15C···Cg2^vii	0.96	2.98	3.762 (5)	139

Symmetry codes: (i) x, y−1, z; (ii) −x, y−1/2, −z; (iii) x, y+1, z; (iv) −x+1, y+1/2, −z+1; (v) x+1, y, z; (vi) −x, y−1/2, −z+1; (vii) −x+1, y+1/2, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.891 (10)	1.94 (3)	2.638 (4)	134 (3)
N4—H4A···O4	0.898 (10)	2.059 (14)	2.935 (4)	165 (3)
N5—H5···O6	0.896 (10)	1.90 (3)	2.600 (4)	134 (3)
N8—H8A···O7	0.898 (10)	2.034 (14)	2.914 (4)	166 (3)
N2—H2···O2ⁱ	0.86	1.92	2.758 (4)	166.1
N3—H3A···O3ⁱ	0.894 (10)	2.58 (3)	3.333 (4)	142 (3)
N3—H3B···O4ⁱⁱ	0.892 (10)	1.928 (12)	2.817 (4)	175 (4)
N4—H4B···O3ⁱⁱ	0.894 (10)	2.025 (12)	2.912 (4)	171 (3)
N6—H6···O6ⁱⁱⁱ	0.86	1.89	2.705 (4)	158.4
N7—H7A···O8ⁱⁱⁱ	0.893 (10)	2.50 (3)	3.202 (4)	135 (3)
N7—H7B···O7^iv	0.896 (10)	1.909 (12)	2.800 (4)	173 (3)
N8—H8B···O8^iv	0.893 (10)	2.054 (16)	2.911 (4)	161 (3)
O1W—H2W···O3^v	0.937 (10)	1.98 (2)	2.881 (5)	159 (6)
C15—H15C···O1Wⁱ	0.96	2.56	3.451 (7)	155.0
C22—H22···O1W	0.93	2.53	3.359 (6)	149.2
C1—H1C···Cg1^vi	0.96	2.96	3.669 (4)	132
C15—H15C···Cg2^vii	0.96	2.98	3.762 (5)	139

Symmetry codes: (i) x, y−1, z; (ii) −x, y−1/2, −z; (iii) x, y+1, z; (iv) −x+1, y+1/2, −z+1; (v) x+1, y, z; (vi) −x, y−1/2, −z+1; (vii) −x+1, y+1/2, −z.

Acknowledgements

MS thanks the UGC Networking Centre, School of Chemistry, University of Hyderabad, India, for the award of a Visiting Research Fellowship to use the facilities at the School. The authors also thank for access to the X-ray diffraction equipment.

References

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2004). APEX2, SAINT, XPREP and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Konig, A. von, Moll, F. & Rosenhahn, L. (1982). US Patent 4358531. Google Scholar
Lewis, J., Matteucci, M., Chen, T. & Jiao, H. (2009). WO Patent 2009140553 A2. Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CrossRef CAS IUCr Journals Google Scholar
Moutet, J. C. & Ourari, A. (1997). Electrochim. Acta, 42, 2525–2531. CrossRef CAS Web of Science Google Scholar
Oueslati, A., Kefi, R., Ben Nasr, C. & Lefebvre, F. (2007). J. Mol. Struct. 871, 49–58. 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
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Srinivasan, K., Michaud, P. & Kochi, J. K. (1986). J. Am. Chem. Soc. 108, 2309–2320. CSD CrossRef CAS PubMed Web of Science Google Scholar