5-Hy­droxy-2-nitro­benzaldehyde thio­semicarbazone (HNBATSC)

Reddy, M.S.; Sarala, Y.; Jagadeesh, M.; Das, S.K.; Ammireddy, V.R.

doi:10.1107/S1600536814015098

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 8| August 2014| Page o846

doi:10.1107/S1600536814015098

Open

access

5-Hydroxy-2-nitrobenzaldehyde thiosemicarbazone (HNBATSC)

M. Sivasankar Reddy,^a ^* Y. Sarala,^b M. Jagadeesh,^a Samar K. Das ^c and Varada Reddy Ammireddy ^a

^aDepartment of Chemistry, Sri Venkateswara University, Tirupati 517 502, India, ^bDepartment of Chemistry, Chaitanya Bharathi Institute of Technology, Gandipet, Hyderabad 500 075, India, and ^cSchool of Chemistry, University of Hyderabad, Hyderabad 500 046, India
^*Correspondence e-mail: ammireddyv@yahoo.co.in

(Received 23 April 2014; accepted 26 June 2014; online 2 July 2014)

The asymmetric unit of the title compound, C₈H₈N₄O₃S, consists of two independent molecules. Each molecule is approximately planar with dihedral angles of 8.71 (3) and 1.50 (2)° between the aromatic ring and the thiosemicarbazide moiety while the NO₂ group makes dihedral angles of 29.27 (3) and 17.78 (3)° with the benzene ring. In the crystal, the molecules are linked by N—H⋯S, O—H⋯O and N—H⋯O hydrogen bonds, forming two-dimensional networks parallel to (100).

Keywords: Thiosemicarbazone; Evolution of molecular structure; Crystallographic studies; Triclinic symmetry; crystal structure.

CCDC reference: 1010403

Related literature

For the crystal structures of similar Schiff base compounds see: Chattopadhyay et al. (1988 ). For the structure of 2-hydroxy-5-nitrobenzaldehyde thiosemicarbazone, see: Alhadi et al. (2008 ). For general background to the biological activity and anti-tumour activity of benzaldehyde thiosemicarbazone derivatives, see: Hamre et al. (1950 ); Brockman et al. (1956 ).

Experimental

Crystal data

C₈H₈N₄O₃S
M_r = 240.24
Triclinic, $[P \overline 1]$
a = 7.1328 (13) Å
b = 8.0738 (15) Å
c = 17.868 (3) Å
α = 102.142 (16)°
β = 94.325 (15)°
γ = 95.212 (15)°
V = 997.1 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 298 K
0.30 × 0.20 × 0.14 mm

Data collection

Agilent Xcalibur (Eos, Gemini) diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013 ) T_min = 0.796, T_max = 1.000
7083 measured reflections
4063 independent reflections
1973 reflections with I > 2σ(I)
R_int = 0.063

Refinement

R[F² > 2σ(F²)] = 0.065
wR(F²) = 0.137
S = 0.99
4063 reflections
321 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N8—H8B⋯S1ⁱ	0.80 (6)	2.59 (6)	3.323 (5)	153 (6)
N7—H7N⋯S1ⁱⁱ	1.07 (4)	2.22 (4)	3.264 (4)	162 (3)
N3—H3N⋯S2ⁱⁱⁱ	0.95 (4)	2.41 (4)	3.324 (4)	160 (4)
N4—H4B⋯S2^iv	0.86 (4)	2.51 (4)	3.373 (4)	180 (4)
O4—H4O⋯O5ⁱⁱⁱ	0.76 (5)	2.27 (6)	2.960 (5)	153 (7)
C3—H3⋯O9^v	0.93	2.57	3.491 (6)	168
C7—H7⋯O5^v	0.93	2.79	3.295 (5)	115
N4—H4A⋯O7ⁱⁱⁱ	0.87 (4)	2.48 (4)	3.066 (5)	125 (3)
O6—H6O⋯O4^vi	1.01 (5)	1.81 (5)	2.810 (5)	170 (4)
N8—H8A⋯O9ⁱⁱ	0.98 (5)	2.39 (4)	3.002 (5)	120 (3)
C13—H13⋯O10ⁱⁱ	0.93	2.67	3.506 (5)	150
Symmetry codes: (i) x, y+2, z; (ii) x, y+1, z; (iii) x, y-1, z; (iv) x, y-2, z; (v) -x+2, -y+1, -z+1; (vi) x, y+1, z-1.

Data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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: publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1010403

Crystal structure: contains datablock I. DOI: 10.1107/S1600536814015098/ds2241sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814015098/ds2241Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814015098/ds2241Isup3.cml

checkCIF report

Comment top

Benzaldehydethiosemicarbazone derivatives show in vitro anti-bacterial, anti-oxidant and anti-tubercular activities. Thiosemicarbazones have also been used as second line drugs in the chemotherapy of leprosy. Since then, several workers have reported the anti-microbial activity of thiosemicarbazones against selected plant pathogenic and saprophytic fungi. The anti-viral effect of thiosemicarbazones was first demonstrated (Hamre et al., 1950). They explained that p-aminobenzaldehyde-3-thiosemicarbazone and several of its derivatives were active against vaccinia virus in mice. Antitumor activity against leukemia in mice was first reported (Brockman et al., 1956).

We reported here the synthesis and structural characterization of a Schiff base, 5-hydroxy-2-nitrobenzaldehydethiosemicarbazone (Fig. 1). Due to the presence of potential hydrogen donor sites in the molecule, supramolecular hydrogen bonding interactions in the domain of thiosemicarbazones are observed. Intermolecular N—H···S interactions through R²₂(8) synthons result in the formation of 1D chains (Fig. 2). These 1D chains, with the aid of O—H···O interactions, form 2D corrugated sheets (Fig.3).

Experimental top

5-Hydroxy-2-nitrobenzaldehydethiosemicarbazone (0.33 g, 2 mmol) and thiosemicarbazide (0.18 g, 2 mmol) were separately dissolved in 20 ml of ethanol and subsequently they were mixed. The resulting mixture (40 ml) was refluxed for 5 hrs. The precipitate, formed during this time, was filtered and washed with a small amount of ethanol. The purity of the product HNBATSC was checked by TLC. Finally HNBATSC was dissolved in acetonitrile and then slowly it was evaporated for the removal of acetonitrile to obtain white crystals.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1.

Related literature top

For the crystal structures of similar Schiff base compounds see: Chattopadhyay et al. (1988). For the structure of 2-hydroxy-5-nitrobenzaldehyde thiosemicarbazone see: Alhadi et al. (2008). For general background to what?, see: Hamre et al. (1950); Brockman et al. (1956).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis PRO (Agilent, 2013); 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: publCIF (Westrip, 2010).

Figures top

	Fig. 1. ORTEP view of one of the independent molecules of the title compound. Thermal ellipsoids are at the 50% probability level.
	Fig. 2. one-dimensional chain formed due to N—H···S interactions.
	Fig. 3. Combination of O—H···O and N—H···S interactions leading to the formation of two-dimensional corrugated sheet.

5-Hydroxy-2-nitrobenzaldehyde thiosemicarbazone top

Crystal data top

C₈H₈N₄O₃S	Z = 4
M_r = 240.24	F(000) = 496
Triclinic, P1	D_x = 1.600 Mg m⁻³
Hall symbol: -P 1	Melting point: 538 K
a = 7.1328 (13) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.0738 (15) Å	Cell parameters from 858 reflections
c = 17.868 (3) Å	θ = 2.9–23.0°
α = 102.142 (16)°	µ = 0.32 mm⁻¹
β = 94.325 (15)°	T = 298 K
γ = 95.212 (15)°	Block, colorless
V = 997.1 (3) Å³	0.30 × 0.20 × 0.14 mm

Data collection top

Agilent Xcalibur (Eos, Gemini) diffractometer	1973 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.063
Graphite monochromator	θ_max = 26.4°, θ_min = 2.9°
ω scans	h = −8→5
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	k = −10→9
T_min = 0.796, T_max = 1.000	l = −22→21
7083 measured reflections	3904 standard reflections every 0 reflections
4063 independent reflections	intensity decay: none

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)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.137	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	w = 1/[σ²(F_o²) + (0.0237P)²] where P = (F_o² + 2F_c²)/3
4063 reflections	(Δ/σ)_max < 0.001
321 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

C₈H₈N₄O₃S	γ = 95.212 (15)°
M_r = 240.24	V = 997.1 (3) Å³
Triclinic, P1	Z = 4
a = 7.1328 (13) Å	Mo Kα radiation
b = 8.0738 (15) Å	µ = 0.32 mm⁻¹
c = 17.868 (3) Å	T = 298 K
α = 102.142 (16)°	0.30 × 0.20 × 0.14 mm
β = 94.325 (15)°

Data collection top

Agilent Xcalibur (Eos, Gemini) diffractometer	1973 reflections with I > 2σ(I)
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	R_int = 0.063
T_min = 0.796, T_max = 1.000	3904 standard reflections every 0 reflections
7083 measured reflections	intensity decay: none
4063 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.065	0 restraints
wR(F²) = 0.137	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	Δρ_max = 0.28 e Å⁻³
4063 reflections	Δρ_min = −0.33 e Å⁻³
321 parameters

Special details top

Experimental. Absorption correction: (CrysAlisPro, Agilent Technologies, 2013) Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET) (compiled Feb 1 2013,16:14:44) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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
S1	0.47754 (18)	−0.25982 (13)	0.26463 (6)	0.0460 (3)
S2	0.46264 (19)	1.26534 (13)	0.31459 (7)	0.0502 (4)
N3	0.6268 (5)	−0.0428 (4)	0.3896 (2)	0.0412 (10)
N2	0.7076 (5)	−0.0018 (4)	0.46366 (19)	0.0392 (9)
N6	0.6606 (5)	1.0485 (4)	0.1259 (2)	0.0437 (9)
N8	0.6172 (7)	1.3598 (5)	0.1978 (3)	0.0520 (12)
N4	0.6096 (6)	−0.3229 (5)	0.3963 (3)	0.0483 (11)
C7	0.7530 (6)	0.1563 (5)	0.4924 (2)	0.0413 (11)
H7	0.7302	0.2376	0.4639	0.050*
N7	0.5833 (5)	1.0750 (4)	0.1944 (2)	0.0451 (10)
C1	0.9021 (6)	0.3740 (5)	0.6117 (2)	0.0381 (11)
C6	0.8416 (6)	0.2067 (5)	0.5711 (2)	0.0388 (11)
C8	0.5768 (6)	−0.2103 (5)	0.3549 (2)	0.0363 (10)
C16	0.5603 (6)	1.2346 (5)	0.2306 (2)	0.0405 (11)
O4	0.9804 (6)	−0.0116 (5)	0.7225 (2)	0.0636 (12)
C5	0.8744 (6)	0.0787 (5)	0.6102 (2)	0.0426 (11)
H5	0.8391	−0.0344	0.5853	0.051*
C9	0.7661 (6)	0.6841 (5)	−0.0180 (2)	0.0405 (11)
N1	0.8718 (6)	0.5229 (5)	0.5792 (2)	0.0501 (11)
O5	0.9645 (5)	0.6588 (4)	0.6107 (2)	0.0773 (12)
C13	0.7647 (6)	0.9729 (5)	−0.0234 (2)	0.0428 (11)
H13	0.7424	1.0838	−0.0020	0.051*
C4	0.9566 (7)	0.1144 (6)	0.6837 (2)	0.0455 (12)
O6	0.8570 (5)	1.0706 (4)	−0.1298 (2)	0.0665 (11)
C14	0.7334 (6)	0.8488 (5)	0.0184 (2)	0.0397 (11)
C2	0.9894 (6)	0.4091 (6)	0.6850 (3)	0.0505 (12)
H2	1.0305	0.5213	0.7096	0.061*
C10	0.8258 (7)	0.6471 (6)	−0.0898 (3)	0.0521 (13)
H10	0.8436	0.5355	−0.1123	0.063*
O7	0.7578 (6)	0.5092 (4)	0.5244 (2)	0.0791 (13)
C12	0.8277 (7)	0.9384 (6)	−0.0954 (3)	0.0484 (12)
C11	0.8594 (7)	0.7740 (6)	−0.1289 (3)	0.0533 (13)
H11	0.9031	0.7499	−0.1773	0.064*
C15	0.6601 (7)	0.8923 (5)	0.0926 (2)	0.0474 (12)
H15	0.6129	0.8067	0.1159	0.057*
C3	1.0168 (6)	0.2796 (6)	0.7225 (3)	0.0500 (12)
H3	1.0744	0.3027	0.7726	0.060*
O10	0.7007 (7)	0.4005 (4)	−0.0180 (2)	0.0960 (15)
N5	0.7434 (6)	0.5429 (5)	0.0211 (3)	0.0558 (12)
O9	0.7659 (6)	0.5702 (4)	0.0907 (2)	0.0748 (12)
H4B	0.572 (6)	−0.428 (5)	0.376 (2)	0.054 (15)*
H3N	0.598 (6)	0.035 (5)	0.358 (2)	0.069 (15)*
H7N	0.534 (6)	0.983 (5)	0.226 (2)	0.081 (15)*
H8A	0.667 (7)	1.338 (6)	0.147 (3)	0.080 (18)*
H4A	0.659 (6)	−0.292 (5)	0.444 (2)	0.048 (15)*
H8B	0.617 (9)	1.453 (7)	0.224 (4)	0.13 (3)*
H6O	0.891 (7)	1.030 (6)	−0.184 (3)	0.082 (18)*
H4O	0.939 (9)	−0.096 (7)	0.697 (3)	0.10 (3)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0546 (9)	0.0391 (6)	0.0446 (8)	0.0091 (6)	0.0054 (6)	0.0076 (5)
S2	0.0669 (10)	0.0391 (6)	0.0465 (8)	0.0115 (6)	0.0140 (7)	0.0084 (5)
N3	0.050 (3)	0.035 (2)	0.039 (2)	0.0082 (19)	0.0018 (19)	0.0072 (18)
N2	0.042 (2)	0.039 (2)	0.036 (2)	0.0052 (18)	0.0036 (18)	0.0061 (17)
N6	0.048 (3)	0.043 (2)	0.040 (2)	0.0083 (19)	0.0091 (19)	0.0047 (18)
N8	0.074 (3)	0.034 (2)	0.048 (3)	0.004 (2)	0.016 (2)	0.006 (2)
N4	0.064 (3)	0.034 (2)	0.046 (3)	0.010 (2)	−0.002 (2)	0.007 (2)
C7	0.043 (3)	0.037 (2)	0.047 (3)	0.005 (2)	0.008 (2)	0.012 (2)
N7	0.057 (3)	0.0358 (19)	0.045 (2)	0.007 (2)	0.014 (2)	0.0111 (19)
C1	0.037 (3)	0.034 (2)	0.042 (3)	0.002 (2)	0.008 (2)	0.007 (2)
C6	0.032 (3)	0.041 (2)	0.043 (3)	0.003 (2)	0.007 (2)	0.008 (2)
C8	0.030 (3)	0.038 (2)	0.045 (3)	0.007 (2)	0.009 (2)	0.015 (2)
C16	0.047 (3)	0.038 (2)	0.038 (3)	0.005 (2)	0.001 (2)	0.012 (2)
O4	0.092 (3)	0.053 (2)	0.043 (2)	0.009 (2)	−0.010 (2)	0.0098 (19)
C5	0.048 (3)	0.035 (2)	0.044 (3)	0.005 (2)	0.006 (2)	0.006 (2)
C9	0.044 (3)	0.040 (2)	0.039 (3)	0.008 (2)	0.004 (2)	0.010 (2)
N1	0.062 (3)	0.036 (2)	0.054 (3)	0.009 (2)	0.024 (2)	0.008 (2)
O5	0.079 (3)	0.0408 (19)	0.109 (3)	−0.005 (2)	0.014 (2)	0.012 (2)
C13	0.043 (3)	0.039 (2)	0.048 (3)	0.007 (2)	0.005 (2)	0.012 (2)
C4	0.053 (3)	0.051 (3)	0.034 (3)	0.009 (3)	0.004 (2)	0.011 (2)
O6	0.085 (3)	0.067 (2)	0.052 (2)	0.003 (2)	0.018 (2)	0.023 (2)
C14	0.044 (3)	0.037 (2)	0.038 (3)	0.004 (2)	0.002 (2)	0.009 (2)
C2	0.044 (3)	0.044 (3)	0.057 (3)	−0.002 (2)	0.011 (3)	−0.004 (2)
C10	0.063 (4)	0.049 (3)	0.042 (3)	0.018 (3)	0.004 (3)	0.000 (2)
O7	0.122 (4)	0.056 (2)	0.059 (3)	0.019 (2)	−0.011 (2)	0.015 (2)
C12	0.043 (3)	0.060 (3)	0.045 (3)	0.006 (3)	0.006 (2)	0.018 (3)
C11	0.059 (4)	0.063 (3)	0.041 (3)	0.018 (3)	0.016 (3)	0.008 (2)
C15	0.061 (4)	0.038 (2)	0.044 (3)	0.004 (2)	0.007 (3)	0.011 (2)
C3	0.042 (3)	0.055 (3)	0.050 (3)	0.000 (3)	0.001 (2)	0.008 (3)
O10	0.147 (4)	0.0392 (19)	0.097 (3)	0.009 (2)	0.014 (3)	0.005 (2)
N5	0.073 (3)	0.038 (2)	0.055 (3)	0.011 (2)	0.007 (2)	0.005 (2)
O9	0.113 (4)	0.063 (2)	0.056 (2)	0.020 (2)	0.019 (2)	0.023 (2)

Geometric parameters (Å, º) top

S1—C8	1.664 (4)	C4—C3	1.381 (6)
S2—C16	1.682 (4)	O6—C12	1.347 (5)
N3—N2	1.364 (4)	C14—C15	1.448 (6)
N3—C8	1.366 (5)	C2—C3	1.376 (5)
N2—C7	1.274 (5)	C10—C11	1.370 (5)
N6—C15	1.276 (5)	C12—C11	1.382 (6)
N6—N7	1.365 (5)	O10—N5	1.212 (4)
N8—C16	1.321 (5)	N5—O9	1.212 (4)
N4—C8	1.312 (5)	N3—H3N	0.96 (4)
C7—C6	1.457 (5)	N8—H8A	0.98 (5)
N7—C16	1.345 (5)	N8—H8B	0.80 (6)
C1—C2	1.368 (5)	N4—H4B	0.86 (4)
C1—C6	1.403 (5)	N4—H4A	0.87 (4)
C1—N1	1.467 (5)	C7—H7	0.9300
C6—C5	1.390 (5)	N7—H7N	1.07 (4)
O4—C4	1.362 (5)	O4—H4O	0.76 (5)
C5—C4	1.359 (5)	C5—H5	0.9300
C9—C10	1.363 (5)	C13—H13	0.9300
C9—C14	1.401 (5)	O6—H6O	1.00 (5)
C9—N5	1.461 (5)	C2—H2	0.9300
N1—O7	1.204 (4)	C10—H10	0.9300
N1—O5	1.229 (4)	C11—H11	0.9300
C13—C12	1.377 (5)	C15—H15	0.9300
C13—C14	1.381 (5)	C3—H3	0.9300

N2—N3—C8	119.2 (3)	C13—C12—C11	119.9 (4)
C7—N2—N3	116.2 (3)	C10—C11—C12	119.2 (4)
C15—N6—N7	114.8 (4)	N6—C15—C14	119.7 (4)
N2—C7—C6	118.4 (4)	C2—C3—C4	118.1 (4)
C16—N7—N6	119.7 (3)	O9—N5—O10	122.0 (4)
C2—C1—C6	122.1 (4)	O9—N5—C9	120.0 (4)
C2—C1—N1	115.5 (4)	O10—N5—C9	118.0 (4)
C6—C1—N1	122.3 (4)	N2—N3—H3N	127 (3)
C5—C6—C1	116.0 (4)	C8—N3—H3N	114 (3)
C5—C6—C7	117.9 (4)	C16—N8—H8A	122 (3)
C1—C6—C7	126.2 (4)	C16—N8—H8B	114 (4)
N4—C8—N3	116.9 (4)	H8A—N8—H8B	124 (5)
N4—C8—S1	124.0 (4)	C8—N4—H4B	117 (3)
N3—C8—S1	119.0 (3)	C8—N4—H4A	122 (3)
N8—C16—N7	117.4 (4)	H4B—N4—H4A	121 (4)
N8—C16—S2	123.4 (3)	N2—C7—H7	120.8
N7—C16—S2	119.2 (3)	C6—C7—H7	120.8
C4—C5—C6	121.7 (4)	C16—N7—H7N	112 (2)
C10—C9—C14	122.7 (4)	N6—N7—H7N	129 (2)
C10—C9—N5	116.5 (4)	C4—O4—H4O	108 (4)
C14—C9—N5	120.8 (4)	C4—C5—H5	119.1
O7—N1—O5	122.7 (4)	C6—C5—H5	119.1
O7—N1—C1	119.9 (4)	C12—C13—H13	118.8
O5—N1—C1	117.4 (4)	C14—C13—H13	118.8
C12—C13—C14	122.5 (4)	C12—O6—H6O	110 (2)
C5—C4—O4	121.2 (4)	C1—C2—H2	119.8
C5—C4—C3	121.5 (4)	C3—C2—H2	119.8
O4—C4—C3	117.3 (4)	C9—C10—H10	120.0
C13—C14—C9	115.6 (4)	C11—C10—H10	120.0
C13—C14—C15	119.6 (4)	C10—C11—H11	120.4
C9—C14—C15	124.6 (4)	C12—C11—H11	120.4
C1—C2—C3	120.5 (4)	N6—C15—H15	120.1
C9—C10—C11	120.1 (4)	C14—C15—H15	120.1
O6—C12—C13	117.0 (4)	C2—C3—H3	120.9
O6—C12—C11	123.1 (5)	C4—C3—H3	120.9

C8—N3—N2—C7	179.2 (4)	C10—C9—C14—C13	0.2 (7)
N3—N2—C7—C6	−179.4 (4)	N5—C9—C14—C13	178.2 (4)
C15—N6—N7—C16	−173.7 (4)	C10—C9—C14—C15	176.4 (4)
C2—C1—C6—C5	0.5 (6)	N5—C9—C14—C15	−5.7 (7)
N1—C1—C6—C5	−177.9 (4)	C6—C1—C2—C3	−1.6 (7)
C2—C1—C6—C7	−178.0 (4)	N1—C1—C2—C3	176.9 (4)
N1—C1—C6—C7	3.6 (7)	C14—C9—C10—C11	1.2 (8)
N2—C7—C6—C5	1.0 (6)	N5—C9—C10—C11	−176.8 (4)
N2—C7—C6—C1	179.4 (4)	C14—C13—C12—O6	−178.6 (4)
N2—N3—C8—N4	0.4 (6)	C14—C13—C12—C11	0.9 (7)
N2—N3—C8—S1	179.8 (3)	C9—C10—C11—C12	−1.6 (7)
N6—N7—C16—N8	−0.8 (7)	O6—C12—C11—C10	−180.0 (4)
N6—N7—C16—S2	179.3 (3)	C13—C12—C11—C10	0.6 (8)
C1—C6—C5—C4	1.3 (6)	N7—N6—C15—C14	178.1 (4)
C7—C6—C5—C4	179.9 (4)	C13—C14—C15—N6	−14.0 (7)
C2—C1—N1—O7	−161.7 (4)	C9—C14—C15—N6	170.0 (4)
C6—C1—N1—O7	16.8 (7)	C1—C2—C3—C4	1.0 (7)
C2—C1—N1—O5	17.3 (6)	C5—C4—C3—C2	0.8 (7)
C6—C1—N1—O5	−164.2 (4)	O4—C4—C3—C2	−178.3 (4)
C6—C5—C4—O4	177.1 (4)	C10—C9—N5—O9	150.5 (5)
C6—C5—C4—C3	−2.0 (7)	C14—C9—N5—O9	−27.6 (7)
C12—C13—C14—C9	−1.3 (7)	C10—C9—N5—O10	−30.0 (7)
C12—C13—C14—C15	−177.6 (4)	C14—C9—N5—O10	152.0 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N8—H8B···S1ⁱ	0.80 (6)	2.59 (6)	3.323 (5)	153 (6)
N7—H7N···S1ⁱⁱ	1.07 (4)	2.22 (4)	3.264 (4)	162 (3)
N3—H3N···S2ⁱⁱⁱ	0.95 (4)	2.41 (4)	3.324 (4)	160 (4)
N4—H4B···S2^iv	0.86 (4)	2.51 (4)	3.373 (4)	180 (4)
O4—H4O···O5ⁱⁱⁱ	0.76 (5)	2.27 (6)	2.960 (5)	153 (7)
C3—H3···O9^v	0.93	2.57	3.491 (6)	168
C7—H7···O5^v	0.93	2.79	3.295 (5)	115
N4—H4A···O7ⁱⁱⁱ	0.87 (4)	2.48 (4)	3.066 (5)	125 (3)
O6—H6O···O4^vi	1.01 (5)	1.81 (5)	2.810 (5)	170 (4)
N8—H8A···O9ⁱⁱ	0.98 (5)	2.39 (4)	3.002 (5)	120 (3)
C13—H13···O10ⁱⁱ	0.93	2.67	3.506 (5)	150

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N8—H8B···S1ⁱ	0.80 (6)	2.59 (6)	3.323 (5)	153 (6)
N7—H7N···S1ⁱⁱ	1.07 (4)	2.22 (4)	3.264 (4)	162 (3)
N3—H3N···S2ⁱⁱⁱ	0.95 (4)	2.41 (4)	3.324 (4)	160 (4)
N4—H4B···S2^iv	0.86 (4)	2.51 (4)	3.373 (4)	180 (4)
O4—H4O···O5ⁱⁱⁱ	0.76 (5)	2.27 (6)	2.960 (5)	153 (7)
C3—H3···O9^v	0.93	2.57	3.491 (6)	168.4
C7—H7···O5^v	0.93	2.79	3.295 (5)	115.0
N4—H4A···O7ⁱⁱⁱ	0.87 (4)	2.48 (4)	3.066 (5)	125 (3)
O6—H6O···O4^vi	1.01 (5)	1.81 (5)	2.810 (5)	170 (4)
N8—H8A···O9ⁱⁱ	0.98 (5)	2.39 (4)	3.002 (5)	120 (3)
C13—H13···O10ⁱⁱ	0.93	2.67	3.506 (5)	149.6

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

Acknowledgements

MSR is grateful to the UGC, Government of India, New Delhi for financial assistance in the form of a meritorious research fellowship. The authors also thank the School of Chemistry, UGC Networking Resource centre, University of Hyderabad, for providing the single-crystal X-ray diffractometer facility. Special thanks are due to Dr Bharat Kumar Tripuramallu, School of Chemistry, University of Hyderabad, for his valuable suggestions and help in processing the data.

References

Agilent (2013). CrysAlis PRO. Agilent Technologies Ltd, Yarnton, England. Google Scholar
Alhadi, A. A., Ali, H. M., Puvaneswary, S., Robinson, W. T. & Ng, S. W. (2008). Acta Cryst. E64, o1606. Web of Science CSD CrossRef IUCr Journals Google Scholar
Brockman, R. W., Thomson, J. R., Bell, M. J. & Skipper, H. E. (1956). Cancer Res. 16, 167–170. PubMed CAS Web of Science Google Scholar
Chattopadhyay, D., Mazumdar, S. K., Banerjee, T., Ghosh, S. & Mak, T. C. W. (1988). Acta Cryst. C44, 1025–1028. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Hamre, D., Brownlee, K. & Donovick, R. (1950). J. Immunol. 67, 305–305. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. 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 70| Part 8| August 2014| Page o846

doi:10.1107/S1600536814015098

Open

access