Neutral 4-phenyl-1-[phen­yl(pyridin-2-yl)methyl­idene]semicarbazide and its salt forms with inorganic anions

Semicarbazones can exist in two tautomeric forms. In the solid state, they are found in the keto form. This work presents the synthesis, structures and spec­troscopic characterization (IR and NMR spectroscopy) of four such com­pounds, namely the neutral mol­ecule 4-phenyl-1-[phen­yl(pyridin-2-yl)methyl­idene]semicarbazide, C₁₉H₁₆N₄O, (I), abbreviated as HBzPyS, and three different hydrated salts, namely the chloride dihydrate, C₁₉H₁₇N₄O⁺·Cl⁻·2H₂O, (II), the nitrate dihydrate, C₁₉H₁₇N₄O⁺·NO₃⁻·2H₂O, (III), and the thio­cyanate 2.5-hydrate, C₁₉H₁₇N₄O⁺·SCN⁻·2.5H₂O, (IV), of 2-[phen­yl({[(phenyl­carbamo­yl)amino]­imino})meth­yl]pyridinium, abbreviated as [H₂BzPyS]⁺·X⁻·nH₂O, with X = Cl⁻ and n = 2 for (II), X = NO₃⁻ and n = 2 for (III), and X = SCN⁻ and n = 2.5 for (IV), showing the influence of the anionic form in the inter­molecular inter­actions. Water mol­ecules and counter-ions (chloride or nitrate) are involved in the formation of a two-dimensional arrangement by the establishment of hydrogen bonds with the N—H groups of the cation, stabilizing the E isomers in the solid state. The neutral HBzPyS mol­ecule crystallized as the E isomer due to the existence of weak π–π inter­actions between pairs of mol­ecules. The calculated IR spectrum of the hydrated [H₂BzPyS]⁺ cation is in good agreement with the experimental results.

Computing details

For all structures, data collection: APEX3 (Bruker, 2015); cell refinement: SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).

4-Phenyl-1-[phenyl(pyridin-2-yl)methylidene]semicarbazide (I)

Crystal data

C19H16N4O	F(000) = 664
Mr = 316.36	Dx = 1.365 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9971 reflections
a = 5.6126 (3) Å	θ = 2.5–30.5°
b = 10.0683 (4) Å	µ = 0.09 mm^−1
c = 27.2349 (12) Å	T = 100 K
β = 90.095 (2)°	Block, colourless
V = 1539.02 (12) Å^3	0.31 × 0.13 × 0.07 mm
Z = 4

Data collection

Bruker D8 Venture Photon 100 diffractometer	3813 reflections with I > 2σ(I)
Radiation source: microfocus X ray tube	Rint = 0.039
φ and ω scans	θmax = 30.5°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2015)	h = −8→8
Tmin = 0.715, Tmax = 0.746	k = −14→14
37458 measured reflections	l = −38→38
4693 independent reflections

Refinement

Refinement on F^2	0 constraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.048	H-atom parameters constrained
wR(F^2) = 0.130	w = 1/[σ^2(Fo^2) + (0.0685P)^2 + 0.7078P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.001
4693 reflections	Δρmax = 0.43 e Å^−3
217 parameters	Δρmin = −0.24 e Å^−3
0 restraints

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	1.05213 (17)	0.05900 (9)	0.62708 (3)	0.0231 (2)
N1	0.09296 (18)	0.44896 (10)	0.55743 (4)	0.0173 (2)
N2	0.58312 (18)	0.28384 (10)	0.61287 (3)	0.0152 (2)
N3	0.73938 (19)	0.18385 (10)	0.60314 (4)	0.0182 (2)
H3A	0.7275	0.14	0.5753	0.022*
N4	0.91577 (18)	0.22644 (10)	0.67747 (4)	0.0173 (2)
H4A	0.7922	0.2792	0.6812	0.021*
C1	−0.0760 (2)	0.53746 (13)	0.56891 (4)	0.0199 (2)
H1	−0.1889	0.5609	0.5444	0.024*
C2	−0.0950 (2)	0.59682 (12)	0.61466 (4)	0.0196 (2)
H2	−0.2206	0.6573	0.6216	0.023*
C3	0.0740 (2)	0.56568 (12)	0.65015 (4)	0.0200 (2)
H3	0.0673	0.6056	0.6817	0.024*
C4	0.2517 (2)	0.47617 (12)	0.63895 (4)	0.0181 (2)
H4	0.3705	0.4545	0.6625	0.022*
C5	0.2540 (2)	0.41762 (11)	0.59223 (4)	0.0135 (2)
C6	0.4318 (2)	0.31515 (11)	0.57900 (4)	0.0136 (2)
C7	0.4285 (2)	0.25270 (11)	0.52920 (4)	0.0135 (2)
C8	0.2388 (2)	0.17334 (12)	0.51455 (4)	0.0185 (2)
H8	0.1083	0.1594	0.5361	0.022*
C9	0.2392 (2)	0.11422 (12)	0.46839 (5)	0.0204 (2)
H9	0.1087	0.0605	0.4585	0.024*
C10	0.4293 (2)	0.13349 (12)	0.43688 (4)	0.0191 (2)
H10	0.4298	0.0923	0.4055	0.023*
C11	0.6184 (2)	0.21273 (14)	0.45113 (4)	0.0215 (3)
H11	0.7484	0.2264	0.4294	0.026*
C12	0.6188 (2)	0.27252 (13)	0.49728 (4)	0.0189 (2)
H12	0.749	0.3269	0.507	0.023*
C13	0.9165 (2)	0.15002 (11)	0.63625 (4)	0.0158 (2)
C14	1.0893 (2)	0.23100 (12)	0.71477 (4)	0.0154 (2)
C15	1.2864 (2)	0.14683 (13)	0.71683 (4)	0.0183 (2)
H15	1.3078	0.0797	0.6927	0.022*
C16	1.4520 (2)	0.16245 (13)	0.75474 (4)	0.0213 (3)
H16	1.5862	0.1051	0.7563	0.026*
C17	1.4241 (2)	0.26024 (14)	0.79021 (4)	0.0227 (3)
H17	1.5396	0.271	0.8154	0.027*
C18	1.2252 (2)	0.34212 (13)	0.78834 (4)	0.0218 (3)
H18	1.2029	0.4082	0.8128	0.026*
C19	1.0589 (2)	0.32794 (12)	0.75103 (4)	0.0188 (2)
H19	0.9234	0.3844	0.7501	0.023*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0272 (5)	0.0230 (4)	0.0191 (4)	0.0077 (4)	−0.0042 (3)	−0.0028 (3)
N1	0.0197 (5)	0.0177 (5)	0.0144 (4)	−0.0005 (4)	−0.0046 (4)	−0.0013 (4)
N2	0.0171 (5)	0.0149 (4)	0.0137 (4)	−0.0004 (4)	−0.0020 (3)	0.0009 (3)
N3	0.0223 (5)	0.0183 (5)	0.0138 (4)	0.0031 (4)	−0.0044 (4)	−0.0035 (4)
N4	0.0169 (5)	0.0201 (5)	0.0149 (4)	0.0040 (4)	−0.0028 (4)	−0.0023 (4)
C1	0.0205 (6)	0.0214 (6)	0.0180 (5)	0.0009 (5)	−0.0049 (4)	−0.0012 (4)
C2	0.0211 (6)	0.0176 (5)	0.0199 (5)	0.0009 (4)	0.0003 (4)	−0.0016 (4)
C3	0.0257 (6)	0.0208 (6)	0.0135 (5)	−0.0007 (5)	−0.0006 (4)	−0.0028 (4)
C4	0.0214 (6)	0.0209 (5)	0.0120 (5)	−0.0014 (5)	−0.0036 (4)	−0.0003 (4)
C5	0.0155 (5)	0.0133 (5)	0.0118 (4)	−0.0034 (4)	−0.0018 (4)	0.0012 (4)
C6	0.0157 (5)	0.0133 (5)	0.0120 (4)	−0.0038 (4)	−0.0010 (4)	0.0009 (4)
C7	0.0158 (5)	0.0129 (5)	0.0118 (4)	−0.0003 (4)	−0.0021 (4)	0.0003 (4)
C8	0.0172 (5)	0.0197 (5)	0.0186 (5)	−0.0055 (4)	0.0019 (4)	−0.0029 (4)
C9	0.0207 (6)	0.0191 (5)	0.0213 (5)	−0.0056 (5)	−0.0016 (4)	−0.0048 (4)
C10	0.0254 (6)	0.0178 (5)	0.0142 (5)	−0.0014 (5)	−0.0015 (4)	−0.0023 (4)
C11	0.0211 (6)	0.0284 (6)	0.0150 (5)	−0.0046 (5)	0.0026 (4)	−0.0013 (5)
C12	0.0163 (5)	0.0243 (6)	0.0160 (5)	−0.0061 (5)	−0.0011 (4)	−0.0010 (4)
C13	0.0197 (5)	0.0155 (5)	0.0124 (5)	−0.0016 (4)	−0.0003 (4)	0.0016 (4)
C14	0.0161 (5)	0.0176 (5)	0.0124 (5)	−0.0008 (4)	−0.0013 (4)	0.0027 (4)
C15	0.0175 (5)	0.0221 (6)	0.0154 (5)	0.0023 (4)	−0.0001 (4)	0.0014 (4)
C16	0.0169 (5)	0.0286 (6)	0.0182 (5)	0.0035 (5)	−0.0014 (4)	0.0033 (5)
C17	0.0220 (6)	0.0304 (7)	0.0157 (5)	−0.0030 (5)	−0.0036 (4)	0.0012 (5)
C18	0.0272 (6)	0.0224 (6)	0.0159 (5)	−0.0020 (5)	−0.0018 (4)	−0.0019 (4)
C19	0.0211 (6)	0.0189 (5)	0.0164 (5)	0.0017 (4)	−0.0016 (4)	0.0005 (4)

Geometric parameters (Å, º)

O1—C13	1.2173 (15)	C7—C12	1.3926 (16)
N1—C1	1.3385 (16)	C8—C9	1.3911 (16)
N1—C5	1.3462 (14)	C8—H8	0.95
N2—C6	1.2919 (14)	C9—C10	1.3839 (18)
N2—N3	1.3615 (14)	C9—H9	0.95
N3—C13	1.3839 (15)	C10—C11	1.3829 (18)
N3—H3A	0.88	C10—H10	0.95
N4—C13	1.3610 (15)	C11—C12	1.3936 (16)
N4—C14	1.4066 (14)	C11—H11	0.95
N4—H4A	0.88	C12—H12	0.95
C1—C2	1.3864 (17)	C14—C15	1.3949 (16)
C1—H1	0.95	C14—C19	1.3990 (16)
C2—C3	1.3891 (17)	C15—C16	1.3968 (16)
C2—H2	0.95	C15—H15	0.95
C3—C4	1.3785 (18)	C16—C17	1.3883 (18)
C3—H3	0.95	C16—H16	0.95
C4—C5	1.4024 (15)	C17—C18	1.3888 (19)
C4—H4	0.95	C17—H17	0.95
C5—C6	1.4804 (16)	C18—C19	1.3858 (16)
C6—C7	1.4949 (15)	C18—H18	0.95
C7—C8	1.3894 (16)	C19—H19	0.95
C1—N1—C5	117.81 (10)	C10—C9—H9	119.9
C6—N2—N3	117.67 (9)	C8—C9—H9	119.9
N2—N3—C13	121.17 (9)	C11—C10—C9	119.92 (11)
N2—N3—H3A	119.4	C11—C10—H10	120
C13—N3—H3A	119.4	C9—C10—H10	120
C13—N4—C14	127.66 (10)	C10—C11—C12	120.16 (11)
C13—N4—H4A	116.2	C10—C11—H11	119.9
C14—N4—H4A	116.2	C12—C11—H11	119.9
N1—C1—C2	123.55 (11)	C7—C12—C11	120.07 (11)
N1—C1—H1	118.2	C7—C12—H12	120
C2—C1—H1	118.2	C11—C12—H12	120
C1—C2—C3	118.32 (11)	O1—C13—N4	126.70 (11)
C1—C2—H2	120.8	O1—C13—N3	120.02 (10)
C3—C2—H2	120.8	N4—C13—N3	113.28 (10)
C4—C3—C2	119.15 (11)	C15—C14—C19	119.53 (11)
C4—C3—H3	120.4	C15—C14—N4	123.87 (10)
C2—C3—H3	120.4	C19—C14—N4	116.59 (10)
C3—C4—C5	118.90 (10)	C14—C15—C16	119.22 (11)
C3—C4—H4	120.5	C14—C15—H15	120.4
C5—C4—H4	120.5	C16—C15—H15	120.4
N1—C5—C4	122.21 (11)	C17—C16—C15	121.23 (12)
N1—C5—C6	116.36 (10)	C17—C16—H16	119.4
C4—C5—C6	121.41 (10)	C15—C16—H16	119.4
N2—C6—C5	116.03 (10)	C16—C17—C18	119.14 (11)
N2—C6—C7	123.52 (10)	C16—C17—H17	120.4
C5—C6—C7	120.45 (9)	C18—C17—H17	120.4
C8—C7—C12	119.43 (10)	C19—C18—C17	120.40 (12)
C8—C7—C6	120.71 (10)	C19—C18—H18	119.8
C12—C7—C6	119.86 (10)	C17—C18—H18	119.8
C7—C8—C9	120.21 (11)	C18—C19—C14	120.45 (11)
C7—C8—H8	119.9	C18—C19—H19	119.8
C9—C8—H8	119.9	C14—C19—H19	119.8
C10—C9—C8	120.20 (11)
C6—N2—N3—C13	175.88 (11)	C7—C8—C9—C10	0.36 (19)
C5—N1—C1—C2	−0.80 (19)	C8—C9—C10—C11	−0.59 (19)
N1—C1—C2—C3	1.8 (2)	C9—C10—C11—C12	0.42 (19)
C1—C2—C3—C4	−0.86 (19)	C8—C7—C12—C11	−0.19 (18)
C2—C3—C4—C5	−0.99 (18)	C6—C7—C12—C11	178.94 (11)
C1—N1—C5—C4	−1.21 (17)	C10—C11—C12—C7	−0.03 (19)
C1—N1—C5—C6	177.43 (10)	C14—N4—C13—O1	10.2 (2)
C3—C4—C5—N1	2.11 (18)	C14—N4—C13—N3	−170.32 (11)
C3—C4—C5—C6	−176.45 (11)	N2—N3—C13—O1	178.95 (11)
N3—N2—C6—C5	175.80 (10)	N2—N3—C13—N4	−0.52 (16)
N3—N2—C6—C7	−3.42 (16)	C13—N4—C14—C15	−5.38 (19)
N1—C5—C6—N2	−178.80 (10)	C13—N4—C14—C19	173.74 (11)
C4—C5—C6—N2	−0.15 (16)	C19—C14—C15—C16	−0.99 (18)
N1—C5—C6—C7	0.45 (15)	N4—C14—C15—C16	178.09 (11)
C4—C5—C6—C7	179.09 (10)	C14—C15—C16—C17	−0.18 (19)
N2—C6—C7—C8	113.46 (13)	C15—C16—C17—C18	1.3 (2)
C5—C6—C7—C8	−65.72 (15)	C16—C17—C18—C19	−1.2 (2)
N2—C6—C7—C12	−65.65 (15)	C17—C18—C19—C14	0.00 (19)
C5—C6—C7—C12	115.16 (12)	C15—C14—C19—C18	1.09 (18)
C12—C7—C8—C9	0.03 (18)	N4—C14—C19—C18	−178.07 (11)
C6—C7—C8—C9	−179.09 (11)

2-[Phenyl({[(phenylcarbamoyl)amino]imino})methyl]pyridinium chloride dihydrate (II)

Crystal data

C19H17N4O^+·Cl^−·2H2O	F(000) = 816
Mr = 388.85	Dx = 1.367 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9932 reflections
a = 9.4452 (19) Å	θ = 2.9–30.5°
b = 9.5489 (19) Å	µ = 0.23 mm^−1
c = 21.039 (4) Å	T = 100 K
β = 95.26 (3)°	Block, yellow
V = 1889.5 (7) Å^3	0.28 × 0.23 × 0.13 mm
Z = 4

Data collection

Bruker D8 Venture Photon 100 diffractometer	4889 reflections with I > 2σ(I)
Radiation source: microfocus X ray tube	Rint = 0.119
φ and ω scans	θmax = 30.6°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2015)	h = −13→13
Tmin = 0.724, Tmax = 0.745	k = −13→13
66072 measured reflections	l = −30→30
5794 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: structure-invariant direct methods
R[F^2 > 2σ(F^2)] = 0.041	Hydrogen site location: mixed
wR(F^2) = 0.112	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0553P)^2 + 0.9098P] where P = (Fo^2 + 2Fc^2)/3
5794 reflections	(Δ/σ)max = 0.001
256 parameters	Δρmax = 0.42 e Å^−3
0 restraints	Δρmin = −0.39 e Å^−3
0 constraints

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.06783 (3)	0.09797 (4)	0.22145 (2)	0.02280 (9)
O1	−0.17520 (9)	0.40910 (9)	0.50096 (4)	0.01606 (18)
N1	0.10125 (10)	0.07050 (10)	0.43270 (4)	0.01254 (18)
H1A	0.0284	0.1283	0.4307	0.015*
N2	0.05449 (10)	0.24698 (10)	0.52436 (4)	0.01189 (18)
N3	0.01723 (10)	0.33890 (10)	0.56830 (4)	0.01274 (19)
H3A	0.0691	0.3502	0.6049	0.015*
N4	−0.13882 (10)	0.49480 (11)	0.60335 (5)	0.01421 (19)
H4A	−0.081	0.4876	0.6384	0.017*
C1	0.11352 (13)	−0.01729 (13)	0.38390 (5)	0.0155 (2)
H1	0.0446	−0.0152	0.3481	0.019*
C2	0.22502 (13)	−0.11075 (13)	0.38504 (6)	0.0164 (2)
H2	0.2337	−0.1734	0.3505	0.02*
C3	0.32428 (13)	−0.11085 (13)	0.43795 (6)	0.0169 (2)
H3	0.4021	−0.1742	0.44	0.02*
C4	0.30990 (12)	−0.01824 (13)	0.48798 (5)	0.0153 (2)
H4	0.378	−0.0184	0.5241	0.018*
C5	0.19622 (12)	0.07440 (12)	0.48516 (5)	0.0116 (2)
C6	0.17085 (12)	0.17684 (12)	0.53552 (5)	0.0116 (2)
C7	0.27603 (12)	0.19470 (12)	0.59235 (5)	0.0125 (2)
C8	0.30414 (13)	0.08615 (13)	0.63600 (6)	0.0165 (2)
H8	0.2542	0	0.6305	0.02*
C9	0.40567 (14)	0.10438 (14)	0.68769 (6)	0.0204 (3)
H9	0.4248	0.0305	0.7175	0.024*
C10	0.47906 (13)	0.22994 (15)	0.69591 (6)	0.0201 (3)
H10	0.5501	0.2408	0.7305	0.024*
C11	0.44861 (13)	0.33944 (14)	0.65360 (6)	0.0191 (2)
H11	0.4973	0.4261	0.6598	0.023*
C12	0.34667 (12)	0.32249 (13)	0.60189 (5)	0.0153 (2)
H12	0.3253	0.3979	0.5732	0.018*
C13	−0.10673 (12)	0.41545 (12)	0.55349 (5)	0.0118 (2)
C14	−0.25407 (12)	0.58765 (12)	0.60569 (5)	0.0115 (2)
C15	−0.24406 (12)	0.68459 (12)	0.65562 (5)	0.0139 (2)
H15	−0.161	0.6875	0.6847	0.017*
C16	−0.35501 (13)	0.77650 (12)	0.66282 (5)	0.0154 (2)
H16	−0.3471	0.8433	0.6964	0.018*
C17	−0.47787 (13)	0.77128 (13)	0.62103 (6)	0.0169 (2)
H17	−0.5545	0.8333	0.6264	0.02*
C18	−0.48763 (13)	0.67484 (13)	0.57150 (6)	0.0168 (2)
H18	−0.5714	0.6714	0.5429	0.02*
C19	−0.37619 (12)	0.58294 (12)	0.56314 (5)	0.0140 (2)
H19	−0.3834	0.5178	0.5289	0.017*
O2	−0.13582 (10)	0.21563 (10)	0.40474 (4)	0.01835 (18)
H1W	−0.144 (2)	0.278 (2)	0.4289 (9)	0.028*
H2W	−0.154 (2)	0.2521 (19)	0.3676 (10)	0.028*
O3	−0.17336 (12)	0.28318 (13)	0.27789 (5)	0.0287 (2)
H3W	−0.152 (2)	0.377 (2)	0.2752 (10)	0.043*
H4W	−0.110 (2)	0.232 (2)	0.2630 (11)	0.043*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.02539 (17)	0.02989 (17)	0.01209 (14)	−0.00797 (12)	−0.00386 (11)	−0.00191 (11)
O1	0.0156 (4)	0.0207 (4)	0.0110 (4)	0.0054 (3)	−0.0033 (3)	−0.0029 (3)
N1	0.0126 (4)	0.0153 (4)	0.0097 (4)	0.0016 (3)	0.0009 (3)	0.0000 (3)
N2	0.0118 (4)	0.0132 (4)	0.0107 (4)	0.0017 (3)	0.0013 (3)	−0.0013 (3)
N3	0.0120 (4)	0.0165 (5)	0.0093 (4)	0.0041 (3)	−0.0016 (3)	−0.0029 (3)
N4	0.0124 (4)	0.0190 (5)	0.0104 (4)	0.0058 (4)	−0.0033 (3)	−0.0034 (3)
C1	0.0179 (5)	0.0188 (5)	0.0098 (5)	−0.0007 (4)	0.0007 (4)	−0.0010 (4)
C2	0.0186 (6)	0.0188 (6)	0.0123 (5)	0.0001 (4)	0.0036 (4)	−0.0028 (4)
C3	0.0158 (5)	0.0192 (6)	0.0161 (5)	0.0041 (4)	0.0032 (4)	−0.0026 (4)
C4	0.0133 (5)	0.0201 (6)	0.0125 (5)	0.0030 (4)	0.0005 (4)	−0.0027 (4)
C5	0.0115 (5)	0.0143 (5)	0.0092 (4)	−0.0004 (4)	0.0015 (4)	−0.0003 (4)
C6	0.0112 (5)	0.0137 (5)	0.0097 (4)	0.0013 (4)	0.0008 (4)	−0.0003 (4)
C7	0.0093 (5)	0.0175 (5)	0.0106 (5)	0.0034 (4)	0.0005 (4)	−0.0027 (4)
C8	0.0183 (5)	0.0169 (5)	0.0139 (5)	0.0052 (4)	−0.0005 (4)	−0.0020 (4)
C9	0.0235 (6)	0.0235 (6)	0.0133 (5)	0.0101 (5)	−0.0029 (4)	−0.0015 (4)
C10	0.0149 (5)	0.0319 (7)	0.0127 (5)	0.0060 (5)	−0.0024 (4)	−0.0074 (5)
C11	0.0144 (5)	0.0277 (6)	0.0153 (5)	−0.0027 (5)	0.0017 (4)	−0.0068 (5)
C12	0.0136 (5)	0.0202 (6)	0.0123 (5)	−0.0001 (4)	0.0015 (4)	−0.0015 (4)
C13	0.0110 (5)	0.0127 (5)	0.0118 (5)	0.0015 (4)	0.0007 (4)	−0.0002 (4)
C14	0.0112 (5)	0.0132 (5)	0.0100 (4)	0.0022 (4)	0.0009 (4)	0.0001 (4)
C15	0.0128 (5)	0.0177 (5)	0.0109 (5)	−0.0002 (4)	−0.0003 (4)	−0.0025 (4)
C16	0.0175 (5)	0.0160 (5)	0.0130 (5)	0.0010 (4)	0.0032 (4)	−0.0042 (4)
C17	0.0162 (5)	0.0166 (5)	0.0178 (5)	0.0057 (4)	0.0015 (4)	−0.0019 (4)
C18	0.0145 (5)	0.0190 (6)	0.0160 (5)	0.0049 (4)	−0.0035 (4)	−0.0020 (4)
C19	0.0141 (5)	0.0154 (5)	0.0119 (5)	0.0029 (4)	−0.0023 (4)	−0.0026 (4)
O2	0.0207 (4)	0.0202 (4)	0.0132 (4)	0.0053 (3)	−0.0034 (3)	−0.0023 (3)
O3	0.0287 (5)	0.0355 (6)	0.0213 (5)	0.0013 (5)	−0.0020 (4)	0.0026 (4)

Geometric parameters (Å, º)

O1—C13	1.2298 (14)	C8—H8	0.95
N1—C1	1.3387 (15)	C9—C10	1.388 (2)
N1—C5	1.3575 (15)	C9—H9	0.95
N1—H1A	0.88	C10—C11	1.3863 (19)
N2—C6	1.2901 (14)	C10—H10	0.95
N2—N3	1.3448 (13)	C11—C12	1.3946 (17)
N3—C13	1.3912 (14)	C11—H11	0.95
N3—H3A	0.88	C12—H12	0.95
N4—C13	1.3507 (14)	C14—C19	1.3946 (16)
N4—C14	1.4083 (14)	C14—C15	1.3968 (15)
N4—H4A	0.88	C15—C16	1.3858 (16)
C1—C2	1.3790 (17)	C15—H15	0.95
C1—H1	0.95	C16—C17	1.3911 (17)
C2—C3	1.3881 (17)	C16—H16	0.95
C2—H2	0.95	C17—C18	1.3874 (17)
C3—C4	1.3910 (16)	C17—H17	0.95
C3—H3	0.95	C18—C19	1.3939 (16)
C4—C5	1.3883 (16)	C18—H18	0.95
C4—H4	0.95	C19—H19	0.95
C5—C6	1.4777 (15)	O2—H1W	0.79 (2)
C6—C7	1.4926 (16)	O2—H2W	0.86 (2)
C7—C8	1.3942 (16)	O3—H3W	0.92 (2)
C7—C12	1.3963 (17)	O3—H4W	0.85 (2)
C8—C9	1.3935 (17)
C1—N1—C5	122.92 (10)	C10—C9—H9	119.8
C1—N1—H1A	118.5	C8—C9—H9	119.8
C5—N1—H1A	118.5	C11—C10—C9	119.99 (11)
C6—N2—N3	119.08 (10)	C11—C10—H10	120
N2—N3—C13	117.18 (9)	C9—C10—H10	120
N2—N3—H3A	121.4	C10—C11—C12	120.08 (12)
C13—N3—H3A	121.4	C10—C11—H11	120
C13—N4—C14	127.56 (10)	C12—C11—H11	120
C13—N4—H4A	116.2	C11—C12—C7	120.02 (11)
C14—N4—H4A	116.2	C11—C12—H12	120
N1—C1—C2	120.77 (11)	C7—C12—H12	120
N1—C1—H1	119.6	O1—C13—N4	126.06 (10)
C2—C1—H1	119.6	O1—C13—N3	122.54 (10)
C1—C2—C3	118.23 (11)	N4—C13—N3	111.40 (10)
C1—C2—H2	120.9	C19—C14—C15	119.95 (10)
C3—C2—H2	120.9	C19—C14—N4	123.62 (10)
C2—C3—C4	120.06 (11)	C15—C14—N4	116.38 (10)
C2—C3—H3	120	C16—C15—C14	120.14 (11)
C4—C3—H3	120	C16—C15—H15	119.9
C5—C4—C3	120.10 (11)	C14—C15—H15	119.9
C5—C4—H4	120	C15—C16—C17	120.24 (11)
C3—C4—H4	120	C15—C16—H16	119.9
N1—C5—C4	117.92 (10)	C17—C16—H16	119.9
N1—C5—C6	117.56 (10)	C18—C17—C16	119.52 (11)
C4—C5—C6	124.52 (10)	C18—C17—H17	120.2
N2—C6—C5	113.87 (10)	C16—C17—H17	120.2
N2—C6—C7	125.44 (10)	C17—C18—C19	120.91 (11)
C5—C6—C7	120.68 (10)	C17—C18—H18	119.5
C8—C7—C12	119.69 (11)	C19—C18—H18	119.5
C8—C7—C6	121.02 (11)	C18—C19—C14	119.24 (10)
C12—C7—C6	119.29 (10)	C18—C19—H19	120.4
C9—C8—C7	119.81 (12)	C14—C19—H19	120.4
C9—C8—H8	120.1	H1W—O2—H2W	104.9 (18)
C7—C8—H8	120.1	H3W—O3—H4W	111 (2)
C10—C9—C8	120.35 (12)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1W···O1	0.79 (2)	2.01 (2)	2.7906 (13)	169.6 (19)
N3—H3A···Cl1^i	0.88	2.5	3.2698 (12)	146
O3—H3W···Cl1^ii	0.92 (2)	2.25 (2)	3.1665 (14)	171.1 (19)
N1—H1A···O2	0.88	1.8	2.6531 (14)	162
N4—H4A···Cl1^i	0.88	2.29	3.1432 (13)	163
O3—H4W···Cl1	0.85 (2)	2.35 (2)	3.1973 (14)	178 (2)
O2—H2W···O3	0.86 (2)	1.90 (2)	2.7370 (15)	163.8 (18)

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

2-[Phenyl({[(phenylcarbamoyl)amino]imino})methyl]pyridinium nitrate dihydrate (III)

Crystal data

C19H17N4O^+·NO3^−·2H2O	F(000) = 872
Mr = 415.41	Dx = 1.401 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8565 reflections
a = 9.5556 (4) Å	θ = 2.7–27.9°
b = 9.3050 (4) Å	µ = 0.11 mm^−1
c = 22.2715 (10) Å	T = 100 K
β = 96.048 (2)°	Block, colourless
V = 1969.24 (15) Å^3	0.21 × 0.10 × 0.08 mm
Z = 4

Data collection

Bruker D8 Venture Photon 100 diffractometer	3810 reflections with I > 2σ(I)
Radiation source: microfocus X ray tube	Rint = 0.068
φ and ω scans	θmax = 30.6°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2015)	h = −10→13
Tmin = 0.683, Tmax = 0.746	k = −11→13
42340 measured reflections	l = −31→31
6023 independent reflections

Refinement

Refinement on F^2	0 constraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.058	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.140	w = 1/[σ^2(Fo^2) + (0.055P)^2 + 0.9729P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.001
6023 reflections	Δρmax = 0.37 e Å^−3
293 parameters	Δρmin = −0.54 e Å^−3
0 restraints

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.32424 (12)	0.59204 (13)	0.50656 (5)	0.0272 (3)
N1	0.61087 (14)	0.92847 (15)	0.44107 (6)	0.0235 (3)
H1A	0.538	0.8701	0.438	0.028*
N2	0.55957 (14)	0.74698 (14)	0.52725 (6)	0.0222 (3)
N3	0.52299 (14)	0.65225 (15)	0.56847 (6)	0.0231 (3)
H3A	0.5761	0.6381	0.6027	0.028*
N4	0.36940 (14)	0.49149 (15)	0.60069 (6)	0.0257 (3)
H4A	0.434	0.4888	0.6319	0.031*
C1	0.62604 (18)	1.01918 (19)	0.39554 (8)	0.0276 (4)
H1	0.5586	1.0192	0.361	0.033*
C2	0.73808 (19)	1.11222 (19)	0.39826 (8)	0.0287 (4)
H2	0.7494	1.1762	0.3659	0.034*
C3	0.83374 (18)	1.11048 (19)	0.44915 (8)	0.0298 (4)
H3	0.9118	1.1742	0.4522	0.036*
C4	0.81631 (17)	1.01591 (19)	0.49601 (8)	0.0278 (4)
H4	0.8822	1.0152	0.5311	0.033*
C5	0.70294 (16)	0.92278 (17)	0.49155 (7)	0.0220 (3)
C6	0.67558 (16)	0.81803 (17)	0.53874 (7)	0.0222 (3)
C7	0.77787 (16)	0.80131 (18)	0.59359 (7)	0.0232 (3)
C8	0.79217 (19)	0.90835 (19)	0.63769 (8)	0.0283 (4)
H8	0.7356	0.9924	0.6332	0.034*
C9	0.8892 (2)	0.8918 (2)	0.68806 (8)	0.0341 (4)
H9	0.898	0.9643	0.7183	0.041*
C10	0.97306 (19)	0.7707 (2)	0.69468 (8)	0.0323 (4)
H10	1.0416	0.7615	0.7286	0.039*
C11	0.95692 (18)	0.6625 (2)	0.65172 (8)	0.0313 (4)
H11	1.013	0.5782	0.6567	0.038*
C12	0.85883 (18)	0.6771 (2)	0.60138 (8)	0.0281 (4)
H12	0.8471	0.6023	0.5723	0.034*
C13	0.39750 (17)	0.57767 (17)	0.55469 (7)	0.0228 (3)
C14	0.24971 (17)	0.40541 (17)	0.60497 (7)	0.0240 (3)
C15	0.25362 (19)	0.31422 (19)	0.65482 (8)	0.0304 (4)
H15	0.3352	0.311	0.6831	0.036*
C16	0.1394 (2)	0.2286 (2)	0.66323 (9)	0.0344 (4)
H16	0.1436	0.1656	0.6969	0.041*
C17	0.0190 (2)	0.2338 (2)	0.62299 (9)	0.0353 (4)
H17	−0.0598	0.1755	0.6292	0.042*
C18	0.0146 (2)	0.32443 (19)	0.57376 (8)	0.0337 (4)
H18	−0.068	0.3281	0.5461	0.04*
C19	0.12930 (18)	0.41061 (18)	0.56400 (8)	0.0277 (4)
H19	0.1254	0.4721	0.5298	0.033*
N5	0.35984 (18)	0.7937 (2)	0.26526 (7)	0.0420 (4)
O3	0.27741 (16)	0.73306 (18)	0.29534 (6)	0.0475 (4)
O4	0.4492 (2)	0.8758 (3)	0.28338 (8)	0.0799 (7)
O5A	0.3005 (3)	0.8518 (4)	0.21244 (13)	0.0435 (11)	0.448 (4)
O5B	0.4115 (4)	0.7187 (4)	0.22044 (14)	0.0774 (15)	0.552 (4)
O2	0.36998 (14)	0.78603 (15)	0.41599 (6)	0.0318 (3)
H1W	0.359 (2)	0.721 (3)	0.4424 (11)	0.048*
H2W	0.342 (2)	0.755 (3)	0.3815 (12)	0.048*
O6	0.60636 (15)	0.95394 (19)	0.18834 (6)	0.0431 (4)
H3W	0.563 (3)	0.907 (3)	0.2169 (12)	0.065*
H4W	0.656 (3)	1.044 (3)	0.2014 (12)	0.065*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0320 (6)	0.0274 (6)	0.0225 (6)	−0.0074 (5)	0.0041 (5)	0.0012 (5)
N1	0.0258 (7)	0.0223 (7)	0.0234 (7)	−0.0013 (6)	0.0079 (5)	−0.0009 (5)
N2	0.0244 (7)	0.0218 (7)	0.0217 (6)	0.0005 (6)	0.0084 (5)	0.0006 (5)
N3	0.0235 (7)	0.0262 (7)	0.0201 (6)	−0.0013 (6)	0.0047 (5)	0.0039 (5)
N4	0.0228 (7)	0.0290 (7)	0.0259 (7)	−0.0008 (6)	0.0055 (5)	0.0053 (6)
C1	0.0330 (9)	0.0281 (9)	0.0230 (8)	0.0029 (7)	0.0091 (7)	0.0030 (7)
C2	0.0355 (9)	0.0257 (8)	0.0278 (8)	0.0033 (7)	0.0162 (7)	0.0043 (7)
C3	0.0290 (9)	0.0285 (9)	0.0341 (9)	−0.0042 (7)	0.0136 (7)	0.0009 (7)
C4	0.0247 (8)	0.0320 (9)	0.0276 (8)	−0.0027 (7)	0.0075 (7)	0.0005 (7)
C5	0.0235 (8)	0.0231 (8)	0.0209 (7)	0.0018 (6)	0.0086 (6)	−0.0016 (6)
C6	0.0223 (8)	0.0241 (8)	0.0214 (7)	0.0024 (6)	0.0079 (6)	−0.0007 (6)
C7	0.0211 (7)	0.0272 (8)	0.0227 (8)	−0.0025 (7)	0.0084 (6)	0.0020 (6)
C8	0.0330 (9)	0.0245 (8)	0.0279 (8)	−0.0027 (7)	0.0055 (7)	0.0019 (7)
C9	0.0424 (11)	0.0338 (10)	0.0261 (9)	−0.0081 (8)	0.0026 (8)	−0.0011 (7)
C10	0.0272 (9)	0.0462 (11)	0.0239 (8)	−0.0064 (8)	0.0044 (7)	0.0073 (8)
C11	0.0272 (8)	0.0415 (10)	0.0265 (9)	0.0067 (8)	0.0087 (7)	0.0058 (8)
C12	0.0277 (8)	0.0340 (9)	0.0238 (8)	0.0035 (7)	0.0082 (7)	−0.0011 (7)
C13	0.0261 (8)	0.0200 (8)	0.0237 (8)	0.0010 (6)	0.0084 (6)	−0.0015 (6)
C14	0.0283 (8)	0.0191 (7)	0.0267 (8)	0.0006 (6)	0.0134 (7)	−0.0015 (6)
C15	0.0315 (9)	0.0308 (9)	0.0308 (9)	0.0049 (8)	0.0126 (7)	0.0065 (7)
C16	0.0429 (11)	0.0273 (9)	0.0367 (10)	0.0009 (8)	0.0208 (8)	0.0051 (8)
C17	0.0423 (11)	0.0262 (9)	0.0399 (10)	−0.0122 (8)	0.0166 (9)	−0.0042 (8)
C18	0.0398 (10)	0.0280 (9)	0.0336 (10)	−0.0127 (8)	0.0056 (8)	−0.0054 (7)
C19	0.0360 (9)	0.0221 (8)	0.0259 (8)	−0.0072 (7)	0.0073 (7)	−0.0038 (7)
N5	0.0413 (9)	0.0690 (12)	0.0153 (7)	−0.0250 (9)	0.0002 (6)	−0.0117 (7)
O3	0.0451 (8)	0.0632 (10)	0.0341 (7)	−0.0108 (7)	0.0034 (6)	0.0024 (7)
O4	0.0730 (12)	0.1290 (18)	0.0398 (9)	−0.0472 (13)	0.0160 (8)	−0.0220 (11)
O5A	0.0423 (19)	0.060 (2)	0.0261 (16)	−0.0135 (16)	−0.0057 (13)	0.0111 (14)
O5B	0.109 (3)	0.082 (3)	0.0463 (19)	−0.036 (2)	0.0351 (19)	−0.0313 (17)
O2	0.0369 (7)	0.0350 (7)	0.0232 (6)	−0.0070 (6)	0.0023 (5)	0.0055 (5)
O6	0.0371 (8)	0.0598 (10)	0.0333 (8)	−0.0059 (7)	0.0082 (6)	−0.0129 (7)

Geometric parameters (Å, º)

O1—C13	1.224 (2)	C9—H9	0.95
N1—C1	1.339 (2)	C10—C11	1.386 (3)
N1—C5	1.354 (2)	C10—H10	0.95
N1—H1A	0.88	C11—C12	1.390 (2)
N2—C6	1.293 (2)	C11—H11	0.95
N2—N3	1.3451 (18)	C12—H12	0.95
N3—C13	1.391 (2)	C14—C19	1.392 (2)
N3—H3A	0.88	C14—C15	1.395 (2)
N4—C13	1.350 (2)	C15—C16	1.380 (3)
N4—C14	1.408 (2)	C15—H15	0.95
N4—H4A	0.88	C16—C17	1.383 (3)
C1—C2	1.373 (2)	C16—H16	0.95
C1—H1	0.95	C17—C18	1.381 (3)
C2—C3	1.379 (3)	C17—H17	0.95
C2—H2	0.95	C18—C19	1.393 (2)
C3—C4	1.389 (2)	C18—H18	0.95
C3—H3	0.95	C19—H19	0.95
C4—C5	1.383 (2)	N5—O4	1.185 (2)
C4—H4	0.95	N5—O3	1.224 (2)
C5—C6	1.477 (2)	N5—O5B	1.353 (3)
C6—C7	1.490 (2)	N5—O5A	1.363 (3)
C7—C12	1.391 (2)	O2—H1W	0.86 (3)
C7—C8	1.395 (2)	O2—H2W	0.84 (3)
C8—C9	1.386 (2)	O6—H3W	0.91 (3)
C8—H8	0.95	O6—H4W	0.99 (3)
C9—C10	1.382 (3)
C1—N1—C5	122.74 (15)	C9—C10—C11	119.83 (17)
C1—N1—H1A	118.6	C9—C10—H10	120.1
C5—N1—H1A	118.6	C11—C10—H10	120.1
C6—N2—N3	118.62 (14)	C10—C11—C12	120.15 (17)
N2—N3—C13	117.15 (13)	C10—C11—H11	119.9
N2—N3—H3A	121.4	C12—C11—H11	119.9
C13—N3—H3A	121.4	C11—C12—C7	120.04 (17)
C13—N4—C14	128.13 (14)	C11—C12—H12	120
C13—N4—H4A	115.9	C7—C12—H12	120
C14—N4—H4A	115.9	O1—C13—N4	126.03 (15)
N1—C1—C2	120.68 (16)	O1—C13—N3	122.58 (14)
N1—C1—H1	119.7	N4—C13—N3	111.39 (14)
C2—C1—H1	119.7	C19—C14—C15	119.60 (16)
C1—C2—C3	118.35 (16)	C19—C14—N4	123.86 (15)
C1—C2—H2	120.8	C15—C14—N4	116.51 (15)
C3—C2—H2	120.8	C16—C15—C14	120.28 (17)
C2—C3—C4	120.23 (16)	C16—C15—H15	119.9
C2—C3—H3	119.9	C14—C15—H15	119.9
C4—C3—H3	119.9	C15—C16—C17	120.53 (17)
C5—C4—C3	119.88 (16)	C15—C16—H16	119.7
C5—C4—H4	120.1	C17—C16—H16	119.7
C3—C4—H4	120.1	C18—C17—C16	119.32 (17)
N1—C5—C4	118.10 (15)	C18—C17—H17	120.3
N1—C5—C6	117.94 (14)	C16—C17—H17	120.3
C4—C5—C6	123.96 (15)	C17—C18—C19	121.13 (18)
N2—C6—C5	114.14 (14)	C17—C18—H18	119.4
N2—C6—C7	125.70 (14)	C19—C18—H18	119.4
C5—C6—C7	120.16 (14)	C14—C19—C18	119.15 (16)
C12—C7—C8	119.55 (16)	C14—C19—H19	120.4
C12—C7—C6	119.81 (15)	C18—C19—H19	120.4
C8—C7—C6	120.64 (15)	O4—N5—O3	126.39 (16)
C9—C8—C7	119.86 (17)	O4—N5—O5B	106.1 (2)
C9—C8—H8	120.1	O3—N5—O5B	118.2 (2)
C7—C8—H8	120.1	O4—N5—O5A	104.9 (2)
C10—C9—C8	120.50 (17)	O3—N5—O5A	114.96 (19)
C10—C9—H9	119.7	H1W—O2—H2W	109 (2)
C8—C9—H9	119.7	H3W—O6—H4W	116 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2	0.88	1.81	2.6639 (19)	164
N3—H3A···O6^i	0.88	2.08	2.8794 (19)	150
N4—H4A···O6^i	0.88	2.03	2.875 (2)	159
O2—H1W···O1	0.86 (3)	1.92 (3)	2.7756 (17)	174 (2)
O2—H2W···O3	0.84 (3)	1.96 (3)	2.783 (2)	165 (2)
O6—H3W···O4	0.91 (3)	1.95 (3)	2.816 (2)	159 (2)
O6—H3W···O5A	0.91 (3)	2.55 (3)	3.172 (3)	126 (2)
O6—H3W···O5B	0.91 (3)	2.28 (3)	3.008 (4)	137 (2)
O6—H4W···O3^ii	0.99 (3)	1.87 (3)	2.833 (2)	163 (2)
O6—H4W···O5B^ii	0.99 (3)	2.51 (3)	3.210 (4)	127.0 (19)

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

2-[Phenyl({[(phenylcarbamoyl)amino]imino})methyl]pyridinium thiocyanate 2.5-hydrate (IV)

Crystal data

C19H17N4O^+·NCS^−·2.5H2O	F(000) = 884
Mr = 420.48	Dx = 1.387 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 9596 reflections
a = 13.0053 (4) Å	θ = 2.8–30.4°
b = 7.7965 (2) Å	µ = 0.20 mm^−1
c = 20.8703 (7) Å	T = 100 K
β = 107.887 (1)°	Block, colourless
V = 2013.87 (11) Å^3	0.24 × 0.10 × 0.05 mm
Z = 4

Data collection

Bruker D8 Venture Photon 100 diffractometer	4590 reflections with I > 2σ(I)
Radiation source: microfocus X ray tube	Rint = 0.040
φ and ω scans	θmax = 30.6°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2015)	h = −18→18
Tmin = 0.707, Tmax = 0.746	k = −9→11
31447 measured reflections	l = −29→29
6146 independent reflections

Refinement

Refinement on F^2	0 constraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.049	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.131	w = 1/[σ^2(Fo^2) + (0.0561P)^2 + 1.2977P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max < 0.001
6146 reflections	Δρmax = 0.4 e Å^−3
326 parameters	Δρmin = −0.41 e Å^−3
6 restraints

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.47184 (8)	0.41475 (14)	0.59764 (5)	0.0210 (2)
N1	0.61991 (9)	0.14483 (15)	0.45619 (6)	0.0149 (2)
H1A	0.6215	0.203	0.4926	0.018*
N2	0.44095 (9)	0.23927 (15)	0.48298 (6)	0.0152 (2)
N3	0.35678 (9)	0.30584 (16)	0.49958 (6)	0.0177 (2)
H3A	0.29	0.2947	0.4729	0.021*
N4	0.28807 (9)	0.44702 (15)	0.57257 (6)	0.0174 (2)
H4A	0.2267	0.42	0.5421	0.021*
C1	0.71372 (11)	0.09103 (18)	0.44878 (7)	0.0180 (3)
H1	0.7798	0.1174	0.4824	0.022*
C2	0.71496 (11)	−0.00216 (19)	0.39290 (7)	0.0197 (3)
H2	0.7811	−0.0414	0.3877	0.024*
C3	0.61693 (12)	−0.03710 (19)	0.34444 (8)	0.0209 (3)
H3	0.6155	−0.1005	0.3053	0.025*
C4	0.52099 (11)	0.02051 (18)	0.35314 (7)	0.0182 (3)
H4	0.454	−0.0039	0.32	0.022*
C5	0.52304 (10)	0.11323 (17)	0.40989 (7)	0.0141 (3)
C6	0.42486 (10)	0.17971 (17)	0.42306 (7)	0.0143 (2)
C7	0.32143 (10)	0.17993 (17)	0.36716 (7)	0.0149 (3)
C8	0.31493 (11)	0.27020 (19)	0.30834 (7)	0.0197 (3)
H8	0.376	0.3318	0.3048	0.024*
C9	0.21989 (12)	0.2705 (2)	0.25502 (8)	0.0219 (3)
H9	0.2161	0.3321	0.2151	0.026*
C10	0.13050 (12)	0.18130 (19)	0.25987 (8)	0.0209 (3)
H10	0.0656	0.1813	0.2232	0.025*
C11	0.13570 (11)	0.09185 (19)	0.31826 (8)	0.0209 (3)
H11	0.0741	0.0316	0.3216	0.025*
C12	0.23077 (11)	0.09030 (18)	0.37174 (7)	0.0179 (3)
H12	0.2343	0.0282	0.4115	0.022*
C13	0.37967 (11)	0.39275 (17)	0.56052 (7)	0.0162 (3)
C14	0.28004 (11)	0.54163 (17)	0.62831 (7)	0.0163 (3)
C15	0.17552 (12)	0.5914 (2)	0.62653 (8)	0.0218 (3)
H15	0.1152	0.5589	0.5896	0.026*
C16	0.16016 (13)	0.6876 (2)	0.67847 (8)	0.0252 (3)
H16	0.0892	0.7209	0.677	0.03*
C17	0.24754 (13)	0.7358 (2)	0.73280 (8)	0.0243 (3)
H17	0.2369	0.8039	0.768	0.029*
C18	0.35041 (13)	0.68370 (19)	0.73511 (8)	0.0231 (3)
H18	0.4103	0.7143	0.7727	0.028*
C19	0.36737 (11)	0.58715 (18)	0.68315 (7)	0.0188 (3)
H19	0.4384	0.5526	0.6852	0.023*
S1A	0.89347 (17)	0.4590 (5)	0.6458 (2)	0.0352 (6)	0.571 (10)
C20A	0.9293 (4)	0.3324 (9)	0.5930 (3)	0.0380 (13)	0.571 (10)
N5A	0.9541 (3)	0.2489 (9)	0.5538 (3)	0.0572 (18)	0.571 (10)
O3A	0.1094 (3)	0.2788 (8)	0.4800 (2)	0.0432 (12)	0.571 (10)
H3WA	0.068 (3)	0.319 (6)	0.4430 (14)	0.065*	0.571 (10)
H4WA	0.077 (3)	0.204 (5)	0.496 (2)	0.065*	0.571 (10)
S1B	0.9023 (2)	0.4113 (5)	0.6645 (2)	0.0313 (5)	0.429 (10)
C20B	0.9362 (5)	0.2778 (9)	0.6152 (4)	0.0328 (13)	0.429 (10)
N5B	0.9595 (5)	0.1776 (7)	0.5811 (3)	0.0436 (13)	0.429 (10)
O3B	0.1309 (4)	0.3389 (7)	0.4610 (3)	0.0346 (11)	0.429 (10)
H3WB	0.110 (4)	0.407 (5)	0.4269 (17)	0.052*	0.429 (10)
H4WB	0.098 (5)	0.243 (4)	0.453 (3)	0.052*	0.429 (10)
O2	0.65756 (10)	0.29775 (19)	0.57474 (6)	0.0339 (3)
H1W	0.604 (2)	0.340 (3)	0.5815 (12)	0.051*
H2W	0.714 (2)	0.346 (3)	0.5973 (13)	0.051*
O4	−0.0067 (3)	0.0865 (5)	0.46176 (17)	0.0568 (8)	0.5
H5W	−0.0156	0.0898	0.5085	0.085*	0.5
H6W	0.0065	−0.036	0.4523	0.085*	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0158 (5)	0.0269 (5)	0.0219 (5)	0.0016 (4)	0.0084 (4)	−0.0045 (4)
N1	0.0160 (5)	0.0168 (5)	0.0135 (5)	0.0018 (4)	0.0068 (4)	0.0022 (4)
N2	0.0157 (5)	0.0156 (5)	0.0172 (6)	0.0024 (4)	0.0092 (4)	0.0026 (4)
N3	0.0139 (5)	0.0215 (6)	0.0195 (6)	0.0027 (4)	0.0080 (4)	−0.0014 (5)
N4	0.0146 (5)	0.0208 (6)	0.0185 (6)	0.0025 (4)	0.0078 (4)	−0.0007 (5)
C1	0.0149 (6)	0.0207 (7)	0.0195 (7)	0.0034 (5)	0.0071 (5)	0.0073 (5)
C2	0.0191 (6)	0.0208 (7)	0.0229 (7)	0.0054 (5)	0.0122 (6)	0.0063 (6)
C3	0.0252 (7)	0.0202 (7)	0.0219 (7)	0.0026 (5)	0.0139 (6)	−0.0008 (6)
C4	0.0185 (6)	0.0187 (6)	0.0189 (7)	0.0002 (5)	0.0080 (5)	−0.0005 (5)
C5	0.0150 (6)	0.0131 (6)	0.0158 (6)	0.0012 (5)	0.0069 (5)	0.0036 (5)
C6	0.0138 (6)	0.0140 (6)	0.0167 (6)	0.0006 (5)	0.0068 (5)	0.0031 (5)
C7	0.0145 (6)	0.0148 (6)	0.0163 (6)	0.0014 (5)	0.0063 (5)	−0.0002 (5)
C8	0.0163 (6)	0.0220 (7)	0.0219 (7)	0.0007 (5)	0.0073 (5)	0.0053 (6)
C9	0.0220 (7)	0.0238 (7)	0.0192 (7)	0.0037 (6)	0.0052 (6)	0.0065 (6)
C10	0.0186 (6)	0.0199 (7)	0.0211 (7)	0.0024 (5)	0.0017 (5)	−0.0004 (5)
C11	0.0178 (6)	0.0194 (7)	0.0260 (8)	−0.0030 (5)	0.0076 (6)	−0.0019 (6)
C12	0.0193 (6)	0.0177 (6)	0.0183 (7)	−0.0006 (5)	0.0080 (5)	0.0012 (5)
C13	0.0185 (6)	0.0153 (6)	0.0179 (7)	0.0018 (5)	0.0102 (5)	0.0020 (5)
C14	0.0201 (6)	0.0144 (6)	0.0184 (7)	0.0022 (5)	0.0119 (5)	0.0032 (5)
C15	0.0185 (6)	0.0259 (7)	0.0243 (8)	0.0026 (6)	0.0114 (6)	0.0020 (6)
C16	0.0242 (7)	0.0273 (8)	0.0314 (8)	0.0043 (6)	0.0195 (6)	0.0019 (6)
C17	0.0327 (8)	0.0204 (7)	0.0279 (8)	−0.0004 (6)	0.0214 (7)	−0.0014 (6)
C18	0.0274 (7)	0.0204 (7)	0.0249 (8)	−0.0022 (6)	0.0132 (6)	−0.0019 (6)
C19	0.0202 (6)	0.0166 (6)	0.0228 (7)	0.0014 (5)	0.0111 (6)	0.0015 (5)
S1A	0.0246 (5)	0.0454 (12)	0.0383 (11)	−0.0050 (6)	0.0136 (6)	−0.0152 (8)
C20A	0.0224 (16)	0.054 (3)	0.039 (3)	−0.0089 (19)	0.0109 (18)	−0.016 (2)
N5A	0.0403 (19)	0.076 (4)	0.058 (3)	−0.007 (2)	0.0193 (19)	−0.033 (3)
O3A	0.0255 (14)	0.064 (3)	0.033 (2)	0.0072 (15)	−0.0012 (12)	−0.0149 (17)
S1B	0.0217 (6)	0.0371 (11)	0.0338 (11)	−0.0032 (6)	0.0068 (7)	−0.0009 (8)
C20B	0.036 (3)	0.032 (3)	0.031 (3)	−0.009 (2)	0.012 (2)	0.006 (2)
N5B	0.063 (3)	0.036 (3)	0.038 (3)	−0.004 (2)	0.025 (2)	0.009 (2)
O3B	0.0267 (19)	0.044 (3)	0.031 (2)	0.0023 (16)	0.0051 (15)	−0.0012 (17)
O2	0.0160 (5)	0.0557 (8)	0.0280 (6)	0.0060 (5)	0.0041 (5)	−0.0176 (6)
O4	0.066 (2)	0.055 (2)	0.055 (2)	−0.0040 (17)	0.0280 (17)	−0.0048 (16)

Geometric parameters (Å, º)

O1—C13	1.2232 (17)	C10—H10	0.95
N1—C1	1.3431 (17)	C11—C12	1.388 (2)
N1—C5	1.3542 (17)	C11—H11	0.95
N1—H1A	0.88	C12—H12	0.95
N2—C6	1.2895 (18)	C14—C19	1.388 (2)
N2—N3	1.3492 (15)	C14—C15	1.4030 (19)
N3—C13	1.3902 (18)	C15—C16	1.382 (2)
N3—H3A	0.88	C15—H15	0.95
N4—C13	1.3585 (17)	C16—C17	1.388 (2)
N4—C14	1.4081 (18)	C16—H16	0.95
N4—H4A	0.88	C17—C18	1.385 (2)
C1—C2	1.378 (2)	C17—H17	0.95
C1—H1	0.95	C18—C19	1.392 (2)
C2—C3	1.389 (2)	C18—H18	0.95
C2—H2	0.95	C19—H19	0.95
C3—C4	1.3894 (19)	S1A—C20A	1.650 (5)
C3—H3	0.95	C20A—N5A	1.166 (6)
C4—C5	1.3809 (19)	O3A—H3WA	0.855 (10)
C4—H4	0.95	O3A—H4WA	0.850 (10)
C5—C6	1.4798 (18)	S1B—C20B	1.616 (8)
C6—C7	1.4855 (18)	C20B—N5B	1.159 (8)
C7—C8	1.3950 (19)	O3B—H3WB	0.863 (10)
C7—C12	1.3988 (19)	O3B—H4WB	0.856 (10)
C8—C9	1.386 (2)	O2—H1W	0.82 (3)
C8—H8	0.95	O2—H2W	0.83 (3)
C9—C10	1.385 (2)	O4—H5W	1.016
C9—H9	0.95	O4—H6W	1.0012
C10—C11	1.388 (2)
C1—N1—C5	122.68 (12)	C9—C10—C11	120.07 (13)
C1—N1—H1A	118.7	C9—C10—H10	120
C5—N1—H1A	118.7	C11—C10—H10	120
C6—N2—N3	119.00 (12)	C10—C11—C12	120.10 (13)
N2—N3—C13	117.37 (11)	C10—C11—H11	119.9
N2—N3—H3A	121.3	C12—C11—H11	119.9
C13—N3—H3A	121.3	C11—C12—C7	120.14 (13)
C13—N4—C14	127.43 (12)	C11—C12—H12	119.9
C13—N4—H4A	116.3	C7—C12—H12	119.9
C14—N4—H4A	116.3	O1—C13—N4	125.70 (13)
N1—C1—C2	120.60 (13)	O1—C13—N3	122.73 (12)
N1—C1—H1	119.7	N4—C13—N3	111.57 (12)
C2—C1—H1	119.7	C19—C14—C15	119.45 (13)
C1—C2—C3	118.20 (13)	C19—C14—N4	124.44 (12)
C1—C2—H2	120.9	C15—C14—N4	116.10 (13)
C3—C2—H2	120.9	C16—C15—C14	120.10 (14)
C2—C3—C4	120.11 (13)	C16—C15—H15	119.9
C2—C3—H3	119.9	C14—C15—H15	119.9
C4—C3—H3	119.9	C15—C16—C17	120.55 (14)
C5—C4—C3	119.98 (13)	C15—C16—H16	119.7
C5—C4—H4	120	C17—C16—H16	119.7
C3—C4—H4	120	C18—C17—C16	119.26 (14)
N1—C5—C4	118.41 (12)	C18—C17—H17	120.4
N1—C5—C6	118.07 (12)	C16—C17—H17	120.4
C4—C5—C6	123.52 (12)	C17—C18—C19	120.93 (15)
N2—C6—C5	114.46 (12)	C17—C18—H18	119.5
N2—C6—C7	126.82 (12)	C19—C18—H18	119.5
C5—C6—C7	118.65 (12)	C14—C19—C18	119.68 (13)
C8—C7—C12	119.19 (13)	C14—C19—H19	120.2
C8—C7—C6	119.16 (12)	C18—C19—H19	120.2
C12—C7—C6	121.65 (12)	N5A—C20A—S1A	177.1 (5)
C9—C8—C7	120.36 (13)	H3WA—O3A—H4WA	111 (3)
C9—C8—H8	119.8	N5B—C20B—S1B	177.7 (5)
C7—C8—H8	119.8	H3WB—O3B—H4WB	111 (3)
C10—C9—C8	120.14 (14)	H1W—O2—H2W	112 (2)
C10—C9—H9	119.9	H5W—O4—H6W	106.9
C8—C9—H9	119.9

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2	0.88	1.79	2.6531 (17)	166
N3—H3A···O3A	0.88	2.4	3.123 (5)	139
N3—H3A···O3B	0.88	2.04	2.809 (5)	146
N4—H4A···O3A	0.88	2	2.845 (4)	160
N4—H4A···O3B	0.88	1.88	2.718 (4)	160
O2—H1W···O1	0.82 (3)	1.94 (3)	2.7575 (15)	174 (2)
O2—H2W···S1A	0.83 (3)	2.40 (3)	3.225 (2)	168 (2)
O2—H2W···S1B	0.83 (3)	2.47 (3)	3.280 (3)	164 (2)
O3A—H3WA···S1A^i	0.86 (1)	2.69 (3)	3.319 (5)	131 (4)
O3B—H3WB···S1B^i	0.86 (1)	2.34 (2)	3.185 (5)	166 (5)

Symmetry code: (i) −x+1, −y+1, −z+1.