1,5-Bis[(1E)-3,4-dimethoxy­benzyl­idene]thio­carbonohydrazide tetra­hydrate

Sarojini, B.K.; Yathirajan, H.S.; Narayana, B.; Sunil, K.; Bolte, M.

doi:10.1107/S1600536807034265

1,5-Bis[(1E)-3,4-dimethoxybenzylidene]thiocarbonohydrazide tetrahydrate

B. K. Sarojini, H. S. Yathirajan, B. Narayana, K. Sunil and M. Bolte

Geometric parameters of the title compound, C₁₉H₂₂N₄O₄S·4H₂O, are in the usual ranges. Both C=N double bonds are trans configured, while only one of the C—N single bonds shows a trans configuration (with the other one being cis configured). The crystal packing is stabilized by N—H

S, N—H

O, O—H

S and O—H

O hydrogen bonds.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807034265/at2339sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807034265/at2339Isup2.hkl Contains datablock I

CCDC reference: 657786

checkCIF report

Key indicators

Single-crystal X-ray study
T = 173 K
Mean (C-C) = 0.006 Å
R factor = 0.042
wR factor = 0.108
Data-to-parameter ratio = 13.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          6
PLAT417_ALERT_2_C Short Inter D-H..H-D       H3WB   ..  H4WB    ..       2.12 Ang.
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          8
PLAT731_ALERT_1_C Bond    Calc     0.84(5), Rep     0.84(2) ......       2.50 su-Ra
              O2W  -H2WA    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.84(6), Rep     0.84(2) ......       3.00 su-Ra
              O2W  -H2WB    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.87(5), Rep     0.87(2) ......       2.50 su-Ra
              O3W  -H3WA    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.86(5), Rep     0.85(2) ......       2.50 su-Ra
              O4W  -H4WA    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.85(5), Rep     0.85(2) ......       2.50 su-Ra
              O4W  -H4WB    1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.84(5), Rep     0.84(2) ......       2.50 su-Ra
              O2W  -H3#     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.84(6), Rep     0.84(2) ......       3.00 su-Ra
              O2W  -H4#     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.87(5), Rep     0.87(2) ......       2.50 su-Ra
              O3W  -H5#     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.86(5), Rep     0.85(2) ......       2.50 su-Ra
              O4W  -H7#     1.555   1.555
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          2
              H2 O

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         12

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
  14 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

  10 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

Schiff bases are used as substrates in the preparation of number of industrial and biologically active compounds via ring closure, cycloaddition and replacement reactions. Some Schiff base derivatives were reported to possess antimicrobial, anti-inflammatory and central nervous system activities. Moreover, Schiff bases are also known to have biological activities such as antimicrobial, antifungal, antitumor, and as herbicides. A new Schiff base of thiocarbohydrazide with 3,4-dimethoxy benzaldehyde was synthesized and its crystal structure is reported here.

Geometric parameters of the title compound (Fig. 1) are in the usual ranges. Both C═N double bonds are trans configured, but only one of the C—N single bond shows a trans configuration whereas the other one is cis configured. The crystal packing is stabilized by N—H···S, N—H···O, O—H···S and O—H···O hydrogen bonds.

Related literature top

For related structures, see: Braibanti et al. (1969); Fang et al. (2006); Chantrapromma et al. (2001); Sarojini et al. (2007).

For related literature, see: Hodnett & Dunn (1970); Wiles & Suprunchuk (1970); Misra et al. (1981); Agarwal et al. (1983); Varma et al. (1986); Singh & Dash (1988).

Experimental top

A mixture of 3,4-dimethoxybenzaldehyde (1.66 g, 0.01 mol) and thiocarbohydrazide (0.53 g, 0.005 mol) in 15 ml of absolute ethanol containing 2 drops of dilute sulfuric acid was refluxed for about 4 h. On cooling, the solid separated was filtered and recrystallized from (2:8) DMF and ethanol mixture (m.p.: 468–470 K). Analysis for C₁₉H₂₂N₄O₄S.4H₂O: Found (Calculated): C 47.96 (48.05); H 6.27 (6.32); N 11.74 (11.80); S 6.68% (6.74%).

Structure description top

For related structures, see: Braibanti et al. (1969); Fang et al. (2006); Chantrapromma et al. (2001); Sarojini et al. (2007).

For related literature, see: Hodnett & Dunn (1970); Wiles & Suprunchuk (1970); Misra et al. (1981); Agarwal et al. (1983); Varma et al. (1986); Singh & Dash (1988).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 1991); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003).

Figures top

	Fig. 1. Perspective view of the title compound with the atom numbering; displacement ellipsoids are at the 50% probability level.
	Fig. 2. Preparation of the title compound.

1,5-Bis[(1E)-3,4-dimethoxybenzylidene]thiocarbonohydrazide tetrahydrate top

Crystal data top

C₁₉H₂₂N₄O₄S·4H₂O	F(000) = 1008
M_r = 474.53	D_x = 1.355 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 17322 reflections
a = 15.9418 (11) Å	θ = 3.6–25.7°
b = 8.7714 (7) Å	µ = 0.19 mm⁻¹
c = 16.6510 (11) Å	T = 173 K
β = 92.815 (5)°	Block, red-brown
V = 2325.5 (3) Å³	0.33 × 0.32 × 0.28 mm
Z = 4

Data collection top

Stoe IPDSII two-circle diffractometer	4349 independent reflections
Radiation source: fine-focus sealed tube	3712 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
ω scans	θ_max = 25.6°, θ_min = 3.5°
Absorption correction: multi-scan (MULABS; Spek, 2003; Blessing, 1995)	h = −19→19
T_min = 0.937, T_max = 0.951	k = −10→10
18188 measured reflections	l = −20→19

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0583P)² + 1.0873P] where P = (F_o² + 2F_c²)/3
4349 reflections	(Δ/σ)_max < 0.001
325 parameters	Δρ_max = 0.54 e Å⁻³
12 restraints	Δρ_min = −0.40 e Å⁻³

Crystal data top

C₁₉H₂₂N₄O₄S·4H₂O	V = 2325.5 (3) Å³
M_r = 474.53	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 15.9418 (11) Å	µ = 0.19 mm⁻¹
b = 8.7714 (7) Å	T = 173 K
c = 16.6510 (11) Å	0.33 × 0.32 × 0.28 mm
β = 92.815 (5)°

Data collection top

Stoe IPDSII two-circle diffractometer	4349 independent reflections
Absorption correction: multi-scan (MULABS; Spek, 2003; Blessing, 1995)	3712 reflections with I > 2σ(I)
T_min = 0.937, T_max = 0.951	R_int = 0.044
18188 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	12 restraints
wR(F²) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.54 e Å⁻³
4349 reflections	Δρ_min = −0.40 e Å⁻³
325 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
S1	0.62197 (6)	0.59999 (11)	0.48744 (7)	0.0229 (3)
N1	0.6007 (2)	0.1935 (4)	0.5838 (2)	0.0194 (7)
N2	0.5838 (2)	0.3291 (4)	0.5438 (2)	0.0206 (7)
H2	0.533 (4)	0.346 (7)	0.524 (4)	0.048 (17)*
N3	0.7878 (2)	0.4980 (4)	0.5639 (2)	0.0212 (7)
N4	0.7202 (2)	0.4006 (4)	0.5727 (2)	0.0204 (7)
H4	0.728 (3)	0.309 (7)	0.590 (3)	0.034 (14)*
O1	1.02971 (18)	0.8313 (3)	0.46858 (19)	0.0284 (7)
O2	1.15681 (17)	0.7740 (3)	0.56386 (19)	0.0264 (7)
O3	0.70084 (17)	−0.3072 (3)	0.72897 (18)	0.0237 (7)
O4	0.56812 (18)	−0.4716 (3)	0.73882 (19)	0.0267 (7)
C1	0.5380 (2)	0.1016 (4)	0.5873 (2)	0.0197 (8)
H1	0.4850	0.1314	0.5637	0.024*
C2	0.8533 (2)	0.4659 (5)	0.6089 (2)	0.0208 (8)
H2A	0.8509	0.3859	0.6472	0.025*
C3	0.6448 (2)	0.4356 (4)	0.5375 (2)	0.0181 (8)
C11	0.5458 (2)	−0.0475 (4)	0.6265 (2)	0.0191 (8)
C12	0.6238 (2)	−0.1012 (4)	0.6591 (2)	0.0184 (8)
H12	0.6727	−0.0401	0.6561	0.022*
C13	0.6288 (2)	−0.2430 (4)	0.6954 (2)	0.0184 (8)
C14	0.5556 (3)	−0.3341 (4)	0.7008 (2)	0.0208 (8)
C15	0.4790 (3)	−0.2810 (5)	0.6688 (3)	0.0240 (9)
H15	0.4299	−0.3418	0.6720	0.029*
C16	0.4742 (3)	−0.1377 (5)	0.6319 (3)	0.0236 (9)
H16	0.4217	−0.1015	0.6103	0.028*
C17	0.4996 (3)	−0.5796 (5)	0.7329 (3)	0.0297 (10)
H17A	0.4509	−0.5372	0.7588	0.045*
H17B	0.5168	−0.6749	0.7596	0.045*
H17C	0.4846	−0.6000	0.6761	0.045*
C18	0.7780 (2)	−0.2235 (5)	0.7209 (3)	0.0258 (9)
H18A	0.7878	−0.2090	0.6638	0.039*
H18B	0.8249	−0.2809	0.7464	0.039*
H18C	0.7737	−0.1239	0.7470	0.039*
C21	0.9316 (2)	0.5514 (4)	0.6017 (2)	0.0198 (8)
C22	0.9387 (2)	0.6590 (5)	0.5394 (3)	0.0211 (8)
H22	0.8913	0.6827	0.5048	0.025*
C23	1.0145 (2)	0.7296 (4)	0.5290 (3)	0.0211 (8)
C24	1.0852 (2)	0.6970 (4)	0.5814 (3)	0.0208 (8)
C25	1.0777 (2)	0.5930 (5)	0.6435 (3)	0.0228 (9)
H25	1.1246	0.5714	0.6791	0.027*
C26	1.0006 (2)	0.5200 (5)	0.6532 (2)	0.0215 (8)
H26	0.9955	0.4483	0.6955	0.026*
C27	0.9587 (3)	0.8724 (6)	0.4161 (3)	0.0325 (10)
H27A	0.9398	0.7830	0.3848	0.049*
H27B	0.9750	0.9533	0.3794	0.049*
H27C	0.9129	0.9087	0.4483	0.049*
C28	1.2329 (3)	0.7296 (6)	0.6074 (3)	0.0301 (10)
H28A	1.2280	0.7515	0.6647	0.045*
H28B	1.2802	0.7870	0.5873	0.045*
H28C	1.2424	0.6202	0.6001	0.045*
O1W	1.18874 (19)	0.9053 (4)	0.4019 (2)	0.0301 (7)
H1WA	1.147 (2)	0.882 (6)	0.430 (2)	0.036*
H1WB	1.171 (3)	0.922 (6)	0.3536 (15)	0.036*
O2W	0.2300 (3)	0.5813 (5)	0.9698 (2)	0.0592 (12)
H2WA	0.214 (4)	0.666 (5)	0.987 (4)	0.071*
H2WB	0.252 (4)	0.535 (7)	1.010 (3)	0.071*
O3W	0.2901 (3)	0.5995 (5)	0.8110 (3)	0.0601 (12)
H3WA	0.274 (4)	0.529 (6)	0.777 (3)	0.072*
H3WB	0.268 (4)	0.576 (7)	0.856 (2)	0.072*
O4W	0.2830 (4)	0.3797 (5)	0.6932 (3)	0.0706 (15)
H4WA	0.300 (5)	0.396 (8)	0.646 (2)	0.085*
H4WB	0.259 (5)	0.293 (5)	0.695 (4)	0.085*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0204 (5)	0.0187 (5)	0.0295 (6)	−0.0011 (4)	0.0002 (4)	0.0063 (4)
N1	0.0198 (16)	0.0167 (16)	0.0216 (18)	0.0005 (13)	−0.0002 (13)	0.0034 (13)
N2	0.0174 (17)	0.0184 (16)	0.0258 (19)	−0.0014 (13)	−0.0022 (14)	0.0059 (14)
N3	0.0178 (16)	0.0210 (16)	0.0248 (19)	−0.0034 (13)	0.0015 (13)	0.0012 (14)
N4	0.0182 (16)	0.0182 (17)	0.0246 (19)	−0.0030 (13)	−0.0008 (13)	0.0037 (14)
O1	0.0248 (15)	0.0308 (16)	0.0296 (17)	−0.0023 (13)	0.0008 (12)	0.0128 (13)
O2	0.0184 (14)	0.0300 (16)	0.0309 (17)	−0.0056 (12)	0.0016 (12)	0.0045 (13)
O3	0.0198 (14)	0.0216 (14)	0.0295 (17)	−0.0001 (11)	−0.0011 (12)	0.0069 (12)
O4	0.0272 (15)	0.0186 (14)	0.0344 (18)	−0.0040 (12)	0.0023 (13)	0.0083 (13)
C1	0.0183 (18)	0.0195 (19)	0.021 (2)	0.0001 (15)	−0.0013 (15)	0.0007 (16)
C2	0.022 (2)	0.0205 (19)	0.020 (2)	−0.0022 (16)	0.0024 (15)	0.0010 (16)
C3	0.0198 (19)	0.0183 (18)	0.0164 (19)	−0.0016 (15)	0.0019 (14)	−0.0009 (15)
C11	0.0208 (19)	0.0191 (19)	0.017 (2)	−0.0017 (15)	0.0007 (15)	−0.0001 (16)
C12	0.0185 (18)	0.0185 (19)	0.018 (2)	−0.0033 (15)	0.0018 (15)	−0.0012 (15)
C13	0.0202 (19)	0.0197 (19)	0.015 (2)	−0.0001 (15)	0.0005 (14)	−0.0017 (15)
C14	0.026 (2)	0.0171 (18)	0.019 (2)	−0.0019 (16)	0.0033 (16)	0.0013 (16)
C15	0.022 (2)	0.023 (2)	0.027 (2)	−0.0072 (16)	0.0016 (16)	0.0008 (17)
C16	0.020 (2)	0.024 (2)	0.026 (2)	−0.0031 (16)	−0.0036 (16)	0.0008 (17)
C17	0.036 (2)	0.021 (2)	0.033 (3)	−0.0096 (18)	0.0076 (19)	0.0022 (18)
C18	0.0183 (19)	0.026 (2)	0.033 (2)	−0.0009 (16)	−0.0003 (16)	0.0051 (18)
C21	0.0193 (19)	0.0185 (18)	0.022 (2)	−0.0006 (15)	0.0028 (15)	−0.0022 (16)
C22	0.0188 (19)	0.0223 (19)	0.022 (2)	0.0008 (15)	−0.0005 (15)	0.0000 (16)
C23	0.023 (2)	0.0187 (19)	0.021 (2)	0.0003 (16)	0.0034 (16)	0.0020 (16)
C24	0.0186 (19)	0.0198 (19)	0.024 (2)	−0.0016 (15)	0.0044 (15)	−0.0025 (16)
C25	0.0199 (19)	0.026 (2)	0.022 (2)	0.0003 (16)	−0.0011 (15)	−0.0002 (17)
C26	0.024 (2)	0.0207 (19)	0.020 (2)	−0.0006 (16)	0.0018 (16)	0.0024 (16)
C27	0.033 (2)	0.035 (2)	0.029 (3)	0.0017 (19)	−0.0029 (19)	0.012 (2)
C28	0.018 (2)	0.039 (3)	0.033 (3)	−0.0034 (18)	−0.0018 (17)	0.001 (2)
O1W	0.0291 (16)	0.0345 (17)	0.0270 (18)	−0.0094 (14)	0.0026 (13)	0.0030 (14)
O2W	0.094 (3)	0.051 (2)	0.033 (2)	0.043 (2)	0.008 (2)	0.0042 (18)
O3W	0.090 (3)	0.050 (2)	0.041 (2)	0.002 (2)	0.006 (2)	0.000 (2)
O4W	0.127 (5)	0.047 (3)	0.039 (2)	−0.019 (3)	0.026 (3)	−0.004 (2)

Geometric parameters (Å, º) top

S1—C3	1.696 (4)	C17—H17A	0.9800
N1—C1	1.289 (5)	C17—H17B	0.9800
N1—N2	1.384 (5)	C17—H17C	0.9800
N2—C3	1.355 (5)	C18—H18A	0.9800
N2—H2	0.87 (6)	C18—H18B	0.9800
N3—C2	1.285 (5)	C18—H18C	0.9800
N3—N4	1.388 (5)	C21—C26	1.389 (6)
N4—C3	1.347 (5)	C21—C22	1.411 (6)
N4—H4	0.86 (6)	C22—C23	1.377 (6)
O1—C23	1.375 (5)	C22—H22	0.9500
O1—C27	1.442 (5)	C23—C24	1.420 (6)
O2—C24	1.370 (5)	C24—C25	1.387 (6)
O2—C28	1.436 (5)	C25—C26	1.403 (6)
O3—C13	1.374 (5)	C25—H25	0.9500
O3—C18	1.445 (5)	C26—H26	0.9500
O4—C14	1.372 (5)	C27—H27A	0.9800
O4—C17	1.446 (5)	C27—H27B	0.9800
C1—C11	1.464 (5)	C27—H27C	0.9800
C1—H1	0.9500	C28—H28A	0.9800
C2—C21	1.466 (5)	C28—H28B	0.9800
C2—H2A	0.9500	C28—H28C	0.9800
C11—C16	1.395 (5)	O1W—H1WA	0.85 (2)
C11—C12	1.413 (5)	O1W—H1WB	0.85 (2)
C12—C13	1.383 (5)	O2W—H2WA	0.84 (2)
C12—H12	0.9500	O2W—H2WB	0.84 (2)
C13—C14	1.420 (5)	O3W—H3WA	0.87 (2)
C14—C15	1.389 (6)	O3W—H3WB	0.87 (2)
C15—C16	1.399 (6)	O4W—H4WA	0.85 (2)
C15—H15	0.9500	O4W—H4WB	0.85 (2)
C16—H16	0.9500

C1—N1—N2	115.2 (3)	H17A—C17—H17C	109.5
C3—N2—N1	120.4 (3)	H17B—C17—H17C	109.5
C3—N2—H2	120 (4)	O3—C18—H18A	109.5
N1—N2—H2	119 (4)	O3—C18—H18B	109.5
C2—N3—N4	114.6 (3)	H18A—C18—H18B	109.5
C3—N4—N3	119.7 (3)	O3—C18—H18C	109.5
C3—N4—H4	118 (3)	H18A—C18—H18C	109.5
N3—N4—H4	121 (3)	H18B—C18—H18C	109.5
C23—O1—C27	116.4 (3)	C26—C21—C22	119.8 (4)
C24—O2—C28	116.8 (3)	C26—C21—C2	120.0 (4)
C13—O3—C18	116.9 (3)	C22—C21—C2	120.1 (4)
C14—O4—C17	116.9 (3)	C23—C22—C21	119.7 (4)
N1—C1—C11	122.0 (3)	C23—C22—H22	120.1
N1—C1—H1	119.0	C21—C22—H22	120.1
C11—C1—H1	119.0	O1—C23—C22	124.8 (4)
N3—C2—C21	120.8 (4)	O1—C23—C24	114.7 (3)
N3—C2—H2A	119.6	C22—C23—C24	120.5 (4)
C21—C2—H2A	119.6	O2—C24—C25	125.8 (4)
N4—C3—N2	116.0 (3)	O2—C24—C23	114.4 (4)
N4—C3—S1	124.9 (3)	C25—C24—C23	119.7 (4)
N2—C3—S1	119.1 (3)	C24—C25—C26	119.6 (4)
C16—C11—C12	119.5 (4)	C24—C25—H25	120.2
C16—C11—C1	118.9 (3)	C26—C25—H25	120.2
C12—C11—C1	121.6 (3)	C21—C26—C25	120.7 (4)
C13—C12—C11	119.9 (3)	C21—C26—H26	119.7
C13—C12—H12	120.1	C25—C26—H26	119.7
C11—C12—H12	120.1	O1—C27—H27A	109.5
O3—C13—C12	125.1 (3)	O1—C27—H27B	109.5
O3—C13—C14	114.6 (3)	H27A—C27—H27B	109.5
C12—C13—C14	120.3 (4)	O1—C27—H27C	109.5
O4—C14—C15	125.2 (4)	H27A—C27—H27C	109.5
O4—C14—C13	115.0 (3)	H27B—C27—H27C	109.5
C15—C14—C13	119.8 (4)	O2—C28—H28A	109.5
C14—C15—C16	119.8 (4)	O2—C28—H28B	109.5
C14—C15—H15	120.1	H28A—C28—H28B	109.5
C16—C15—H15	120.1	O2—C28—H28C	109.5
C11—C16—C15	120.8 (4)	H28A—C28—H28C	109.5
C11—C16—H16	119.6	H28B—C28—H28C	109.5
C15—C16—H16	119.6	H1WA—O1W—H1WB	109 (3)
O4—C17—H17A	109.5	H2WA—O2W—H2WB	106 (7)
O4—C17—H17B	109.5	H3WA—O3W—H3WB	106 (3)
H17A—C17—H17B	109.5	H4WA—O4W—H4WB	110 (4)
O4—C17—H17C	109.5

C1—N1—N2—C3	178.9 (4)	C13—C14—C15—C16	−0.4 (6)
C2—N3—N4—C3	170.5 (4)	C12—C11—C16—C15	−0.3 (6)
N2—N1—C1—C11	179.2 (3)	C1—C11—C16—C15	179.9 (4)
N4—N3—C2—C21	175.3 (3)	C14—C15—C16—C11	0.3 (6)
N3—N4—C3—N2	175.1 (3)	N3—C2—C21—C26	177.1 (4)
N3—N4—C3—S1	−5.1 (5)	N3—C2—C21—C22	−6.8 (6)
N1—N2—C3—N4	−0.6 (5)	C26—C21—C22—C23	1.5 (6)
N1—N2—C3—S1	179.5 (3)	C2—C21—C22—C23	−174.6 (4)
N1—C1—C11—C16	176.6 (4)	C27—O1—C23—C22	4.1 (6)
N1—C1—C11—C12	−3.2 (6)	C27—O1—C23—C24	−177.5 (4)
C16—C11—C12—C13	0.5 (6)	C21—C22—C23—O1	177.2 (4)
C1—C11—C12—C13	−179.7 (4)	C21—C22—C23—C24	−1.2 (6)
C18—O3—C13—C12	−4.1 (6)	C28—O2—C24—C25	7.8 (6)
C18—O3—C13—C14	176.4 (3)	C28—O2—C24—C23	−171.4 (4)
C11—C12—C13—O3	179.9 (4)	O1—C23—C24—O2	0.9 (5)
C11—C12—C13—C14	−0.7 (6)	C22—C23—C24—O2	179.4 (4)
C17—O4—C14—C15	11.1 (6)	O1—C23—C24—C25	−178.4 (4)
C17—O4—C14—C13	−168.9 (4)	C22—C23—C24—C25	0.1 (6)
O3—C13—C14—O4	0.1 (5)	O2—C24—C25—C26	−178.5 (4)
C12—C13—C14—O4	−179.3 (4)	C23—C24—C25—C26	0.6 (6)
O3—C13—C14—C15	−179.9 (4)	C22—C21—C26—C25	−0.7 (6)
C12—C13—C14—C15	0.6 (6)	C2—C21—C26—C25	175.4 (4)
O4—C14—C15—C16	179.5 (4)	C24—C25—C26—C21	−0.4 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···S1ⁱ	0.87 (6)	2.52 (6)	3.355 (4)	161 (5)
N4—H4···O1Wⁱⁱ	0.86 (6)	2.31 (6)	3.070 (5)	148 (5)
O1W—H1WA···O1	0.85 (2)	2.06 (3)	2.891 (4)	165 (4)
O1W—H1WB···O3ⁱⁱⁱ	0.85 (2)	2.37 (4)	3.021 (4)	133 (4)
O2W—H2WA···S1^iv	0.84 (2)	2.52 (4)	3.305 (4)	155 (7)
O2W—H2WB···O1W^v	0.84 (2)	2.05 (3)	2.890 (5)	173 (7)
O3W—H3WB···O2W	0.87 (2)	2.02 (3)	2.861 (6)	163 (6)
O3W—H3WA···O4W	0.87 (2)	1.92 (3)	2.749 (6)	158 (6)
O4W—H4WA···S1ⁱ	0.85 (2)	2.60 (3)	3.438 (5)	167 (7)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y+1, −z+1; (iii) x+1/2, −y+1/2, z−1/2; (iv) x−1/2, −y+3/2, z+1/2; (v) −x+3/2, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₉H₂₂N₄O₄S·4H₂O
M_r	474.53
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	173
a, b, c (Å)	15.9418 (11), 8.7714 (7), 16.6510 (11)
β (°)	92.815 (5)
V (Å³)	2325.5 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.19
Crystal size (mm)	0.33 × 0.32 × 0.28

Data collection
Diffractometer	Stoe IPDSII two-circle
Absorption correction	Multi-scan (MULABS; Spek, 2003; Blessing, 1995)
T_min, T_max	0.937, 0.951
No. of measured, independent and observed [I > 2σ(I)] reflections	18188, 4349, 3712
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.608

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.108, 1.05
No. of reflections	4349
No. of parameters	325
No. of restraints	12
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.54, −0.40

Computer programs: X-AREA (Stoe & Cie, 2001), X-AREA, SHELXS86 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP in SHELXTL-Plus (Sheldrick, 1991), SHELXL97 and PLATON (Spek, 2003).