N-[(E)-Morpholin-4-yl-methyl-idene]-1-phenyl-1H-1,2,4-triazole-3,5-diamine monohydrate.

In the title compound, C(13)H(16)N(6)O·H(2)O, the mean planes of the benzene and 1,2,4-triazole rings form a dihedral angle of 54.80 (5)°. The N atom of the amino group adopts a trigonal-pyramidal configuration. Conjugation in the amidine N=C-N fragment results in sufficient shortening of the formal single bond. In the crystal, inter-molecular N-H⋯O and O-H⋯N hydrogen bonds link mol-ecules into double layers parallel to the bc plane.

Related literature

The title compound was synthesized according to Astakhov & Chernyshev (2010 ▶). The synthesis of <span class="Chemical">3,5-diamino-1-phenyl-1,2,4-triazolen> is described by Steck et al. (1958 ▶). Intra­molecular reactions of N-substituted amino­methyl­ene malonates accompanied by nucleophilic substitution of <span class="Chemical">malonic ester were described by Sunder & Peet (1980 ▶); Yamazaki et al. (1988 ▶); Selic et al. (1998 ▶, 2000 ▶); Tkachev et al. (2007 ▶). Analogous inter­molecular reaction affording substituted <span class="Chemical">formamidines was described by Rajappa et al. (1970 ▶); Bao et al. (2008 ▶). For examples of the use of the triazolyl-substituted amidines in the synthesis of annulated heterocycles, see: Dolzhenko et al. (2007 ▶, 2008 ▶). For crystal structures of substituted 3,5-diamino-1,2,4-triazoles, see: Ried et al. (1983 ▶); Dunstan et al. (1998 ▶); Chernyshev et al. (2006 ▶, 2007 ▶, 2009 ▶). For crystal structures of hetaryl substituted amidines, see: Ryng & Glowiak (1998 ▶); Kurbatov et al. (2006 ▶); Xie et al. (2007 ▶); Lyakhov et al. (2008 ▶); Quiroga et al. (2010 ▶). The synthesis of mesoionic [1,2,4]triazolo[4,3-a]pyrimidines from N-(5-amino-1-R-1,2,4-triazol-3-yl)-substituted enamino­esters was described by Chernyshev et al. (2010 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶). For values of bond lengths in organic compounds, see: Allen et al. (1987 ▶). For the correlation of bond lengths with bond orders between sp 2 hybridized C and N atoms, see: Burke-Laing & Laing (1976 ▶).

Experimental

Crystal data

<span class="Chemical">C13H16n class="Chemical">N6O·<spn>an class="Chemical">H2O

M = 290.33

Triclinic,

a = 8.7886 (7) Å

b = 9.0100 (7) Å

c = 9.4373 (7) Å

α = 99.938 (1)°

β = 105.933 (1)°

γ = 95.331 (1)°

V = 700.00 (9) Å3

Z = 2

Mo Kα radiation

μ = 0.10 mm−1

T = 100 K

0.55 × 0.30 × 0.25 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.948, T max = 0.976

5231 measured reflections

2724 independent reflections

2510 reflections with I > 2σ(I)

R int = 0.015

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.088

S = 1.00

2724 reflections

206 parameters

<span class="Disease">H atomsn> treated by a mixture of independent and constrained refinement

Δρmax = 0.18 e Å−3

Δρmin = −0.29 e Å−3

Data collection: <span class="Gene">APEX2n> (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶), publCIF (Westrip, 2010 ▶) and PLATON (<span class="Chemical">Spek, 2009 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681004729X/cv2798sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681004729X/cv2798Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C13H16N6O·H2O	Z = 2
Mr = 290.33	F(000) = 308
Triclinic, P1	Dx = 1.377 Mg m−3
Hall symbol: -P 1	Melting point: 208 K
a = 8.7886 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.0100 (7) Å	Cell parameters from 334 reflections
c = 9.4373 (7) Å	θ = 3–26°
α = 99.938 (1)°	µ = 0.10 mm−1
β = 105.933 (1)°	T = 100 K
γ = 95.331 (1)°	Plate, colourless
V = 700.00 (9) Å3	0.55 × 0.30 × 0.25 mm

Bruker APEXII CCD area-detector diffractometer	2724 independent reflections
Radiation source: fine-focus sealed tube	2510 reflections with I > 2σ(I)
graphite	Rint = 0.015
ω scans	θmax = 26.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −10→10
Tmin = 0.948, Tmax = 0.976	k = −11→11
5231 measured reflections	l = −11→11

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)] = 0.034	Hydrogen site location: difference Fourier map
wR(F2) = 0.088	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ2(Fo2) + (0.0447P)2 + 0.3407P] where P = (Fo2 + 2Fc2)/3
2724 reflections	(Δ/σ)max < 0.001
206 parameters	Δρmax = 0.18 e Å−3
0 restraints	Δρmin = −0.28 e Å−3

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.

	x	y	z	Uiso*/Ueq
O1	0.71171 (11)	0.75346 (9)	0.92066 (9)	0.0197 (2)
N1	0.75642 (11)	0.22365 (11)	0.11933 (11)	0.0140 (2)
N2	0.73939 (12)	0.36780 (11)	0.19018 (11)	0.0149 (2)
N4	0.82835 (11)	0.22141 (11)	0.36142 (11)	0.0140 (2)
N5	0.83821 (12)	−0.00456 (11)	0.19122 (12)	0.0163 (2)
H5A	0.7927 (19)	−0.0581 (18)	0.0975 (19)	0.025 (4)*
H5B	0.8474 (19)	−0.0575 (18)	0.2638 (19)	0.027 (4)*
N3	0.77750 (11)	0.48235 (11)	0.44096 (11)	0.0146 (2)
N6	0.79432 (12)	0.56639 (11)	0.69189 (11)	0.0154 (2)
C5	0.80778 (13)	0.13965 (13)	0.22417 (12)	0.0132 (2)
C3	0.78422 (13)	0.35886 (13)	0.33343 (13)	0.0131 (2)
C1	0.81153 (13)	0.46393 (13)	0.57891 (13)	0.0139 (2)
H1	0.8498	0.3750	0.6003	0.017*
C6	0.85744 (15)	0.55214 (13)	0.84809 (13)	0.0179 (3)
H6A	0.9620	0.6136	0.8926	0.021*
H6B	0.8697	0.4468	0.8515	0.021*
C7	0.74577 (17)	0.60386 (14)	0.93772 (14)	0.0225 (3)
H7A	0.6468	0.5329	0.9031	0.027*
H7B	0.7949	0.6046	1.0433	0.027*
C8	0.63106 (14)	0.74989 (14)	0.76612 (13)	0.0173 (2)
H8A	0.5986	0.8484	0.7557	0.021*
H8B	0.5356	0.6743	0.7322	0.021*
C9	0.73945 (15)	0.71137 (13)	0.66976 (13)	0.0179 (3)
H9A	0.6819	0.7038	0.5646	0.021*
H9B	0.8306	0.7912	0.6975	0.021*
C10	0.71449 (14)	0.18521 (13)	−0.04071 (12)	0.0141 (2)
C11	0.56426 (14)	0.20692 (14)	−0.12420 (13)	0.0179 (3)
H11	0.4903	0.2391	−0.0761	0.021*
C12	0.52581 (15)	0.18009 (14)	−0.27987 (14)	0.0206 (3)
H12	0.4252	0.1937	−0.3365	0.025*
C13	0.63660 (15)	0.13300 (14)	−0.35193 (13)	0.0188 (3)
H13	0.6114	0.1180	−0.4562	0.023*
C14	0.78489 (14)	0.10853 (13)	−0.26786 (13)	0.0167 (2)
H14	0.8581	0.0749	−0.3162	0.020*
C15	0.82470 (14)	0.13401 (13)	−0.11178 (13)	0.0154 (2)
H15	0.9239	0.1170	−0.0555	0.019*
O2	0.88944 (11)	0.77890 (11)	0.38883 (10)	0.0217 (2)
H2A	0.840 (2)	0.688 (2)	0.389 (2)	0.041 (5)*
H2B	0.979 (2)	0.788 (2)	0.467 (2)	0.048 (5)*

	U11	U22	U33	U12	U13	U23
O1	0.0301 (5)	0.0169 (4)	0.0141 (4)	0.0069 (4)	0.0092 (4)	0.0025 (3)
N1	0.0184 (5)	0.0133 (5)	0.0105 (5)	0.0043 (4)	0.0048 (4)	0.0016 (4)
N2	0.0192 (5)	0.0134 (5)	0.0131 (5)	0.0043 (4)	0.0063 (4)	0.0015 (4)
N4	0.0147 (5)	0.0149 (5)	0.0122 (5)	0.0028 (4)	0.0039 (4)	0.0027 (4)
N5	0.0218 (5)	0.0148 (5)	0.0120 (5)	0.0049 (4)	0.0037 (4)	0.0027 (4)
N3	0.0166 (5)	0.0150 (5)	0.0128 (5)	0.0035 (4)	0.0055 (4)	0.0018 (4)
N6	0.0205 (5)	0.0156 (5)	0.0114 (5)	0.0062 (4)	0.0052 (4)	0.0034 (4)
C5	0.0108 (5)	0.0158 (5)	0.0132 (5)	0.0012 (4)	0.0037 (4)	0.0036 (4)
C3	0.0117 (5)	0.0147 (5)	0.0135 (5)	0.0018 (4)	0.0047 (4)	0.0029 (4)
C1	0.0140 (5)	0.0134 (5)	0.0147 (5)	0.0023 (4)	0.0047 (4)	0.0025 (4)
C6	0.0241 (6)	0.0168 (6)	0.0121 (6)	0.0059 (5)	0.0032 (5)	0.0037 (4)
C7	0.0373 (7)	0.0187 (6)	0.0164 (6)	0.0082 (5)	0.0133 (5)	0.0061 (5)
C8	0.0177 (6)	0.0177 (6)	0.0163 (6)	0.0041 (4)	0.0054 (5)	0.0021 (4)
C9	0.0252 (6)	0.0171 (6)	0.0146 (6)	0.0087 (5)	0.0082 (5)	0.0053 (4)
C10	0.0181 (6)	0.0128 (5)	0.0112 (5)	0.0011 (4)	0.0044 (4)	0.0029 (4)
C11	0.0161 (6)	0.0215 (6)	0.0172 (6)	0.0039 (5)	0.0064 (5)	0.0039 (5)
C12	0.0176 (6)	0.0266 (6)	0.0160 (6)	0.0031 (5)	0.0014 (5)	0.0060 (5)
C13	0.0243 (6)	0.0190 (6)	0.0113 (5)	−0.0017 (5)	0.0043 (5)	0.0025 (4)
C14	0.0211 (6)	0.0143 (5)	0.0164 (6)	0.0012 (4)	0.0099 (5)	0.0016 (4)
C15	0.0161 (5)	0.0136 (5)	0.0168 (6)	0.0024 (4)	0.0047 (4)	0.0036 (4)
O2	0.0204 (5)	0.0227 (5)	0.0224 (5)	0.0028 (4)	0.0027 (4)	0.0121 (4)

O1—C8	1.4292 (14)	C7—H7A	0.9700
O1—C7	1.4338 (15)	C7—H7B	0.9700
N1—C5	1.3536 (15)	C8—C9	1.5109 (16)
N1—N2	1.3956 (13)	C8—H8A	0.9700
N1—C10	1.4238 (14)	C8—H8B	0.9700
N2—C3	1.3193 (15)	C9—H9A	0.9700
N4—C5	1.3305 (15)	C9—H9B	0.9700
N4—C3	1.3783 (15)	C10—C11	1.3900 (16)
N5—C5	1.3517 (15)	C10—C15	1.3906 (16)
N5—H5A	0.893 (17)	C11—C12	1.3858 (17)
N5—H5B	0.890 (17)	C11—H11	0.9300
N3—C1	1.2968 (15)	C12—C13	1.3897 (18)
N3—C3	1.3880 (15)	C12—H12	0.9300
N6—C1	1.3367 (15)	C13—C14	1.3866 (17)
N6—C6	1.4584 (14)	C13—H13	0.9300
N6—C9	1.4623 (15)	C14—C15	1.3893 (16)
C1—H1	0.9300	C14—H14	0.9300
C6—C7	1.5167 (17)	C15—H15	0.9300
C6—H6A	0.9700	O2—H2A	0.89 (2)
C6—H6B	0.9700	O2—H2B	0.91 (2)
C8—O1—C7	109.34 (9)	H7A—C7—H7B	108.1
C5—N1—N2	109.50 (9)	O1—C8—C9	110.45 (9)
C5—N1—C10	130.86 (10)	O1—C8—H8A	109.6
N2—N1—C10	119.58 (9)	C9—C8—H8A	109.6
C3—N2—N1	101.95 (9)	O1—C8—H8B	109.6
C5—N4—C3	103.04 (9)	C9—C8—H8B	109.6
C5—N5—H5A	117.9 (10)	H8A—C8—H8B	108.1
C5—N5—H5B	116.4 (10)	N6—C9—C8	109.22 (9)
H5A—N5—H5B	115.6 (14)	N6—C9—H9A	109.8
C1—N3—C3	116.52 (10)	C8—C9—H9A	109.8
C1—N6—C6	121.12 (10)	N6—C9—H9B	109.8
C1—N6—C9	122.19 (10)	C8—C9—H9B	109.8
C6—N6—C9	115.74 (9)	H9A—C9—H9B	108.3
N4—C5—N5	126.03 (10)	C11—C10—C15	120.75 (10)
N4—C5—N1	110.18 (10)	C11—C10—N1	118.68 (10)
N5—C5—N1	123.76 (10)	C15—C10—N1	120.49 (10)
N2—C3—N4	115.33 (10)	C12—C11—C10	119.35 (11)
N2—C3—N3	118.89 (10)	C12—C11—H11	120.3
N4—C3—N3	125.73 (10)	C10—C11—H11	120.3
N3—C1—N6	123.28 (11)	C11—C12—C13	120.41 (11)
N3—C1—H1	118.4	C11—C12—H12	119.8
N6—C1—H1	118.4	C13—C12—H12	119.8
N6—C6—C7	110.52 (10)	C14—C13—C12	119.80 (11)
N6—C6—H6A	109.5	C14—C13—H13	120.1
C7—C6—H6A	109.5	C12—C13—H13	120.1
N6—C6—H6B	109.5	C13—C14—C15	120.40 (11)
C7—C6—H6B	109.5	C13—C14—H14	119.8
H6A—C6—H6B	108.1	C15—C14—H14	119.8
O1—C7—C6	110.56 (10)	C14—C15—C10	119.25 (11)
O1—C7—H7A	109.5	C14—C15—H15	120.4
C6—C7—H7A	109.5	C10—C15—H15	120.4
O1—C7—H7B	109.5	H2A—O2—H2B	101.2 (16)
C6—C7—H7B	109.5
C5—N1—N2—C3	0.70 (11)	C8—O1—C7—C6	62.51 (13)
C10—N1—N2—C3	178.22 (9)	N6—C6—C7—O1	−52.83 (13)
C3—N4—C5—N5	178.66 (11)	C7—O1—C8—C9	−64.75 (12)
C3—N4—C5—N1	0.87 (12)	C1—N6—C9—C8	142.14 (11)
N2—N1—C5—N4	−1.03 (12)	C6—N6—C9—C8	−48.90 (13)
C10—N1—C5—N4	−178.18 (10)	O1—C8—C9—N6	56.40 (13)
N2—N1—C5—N5	−178.89 (10)	C5—N1—C10—C11	124.87 (13)
C10—N1—C5—N5	3.96 (19)	N2—N1—C10—C11	−52.04 (14)
N1—N2—C3—N4	−0.16 (12)	C5—N1—C10—C15	−58.21 (16)
N1—N2—C3—N3	−177.65 (9)	N2—N1—C10—C15	124.87 (11)
C5—N4—C3—N2	−0.43 (12)	C15—C10—C11—C12	−1.36 (18)
C5—N4—C3—N3	176.86 (10)	N1—C10—C11—C12	175.55 (10)
C1—N3—C3—N2	175.10 (10)	C10—C11—C12—C13	−0.46 (18)
C1—N3—C3—N4	−2.11 (16)	C11—C12—C13—C14	1.84 (18)
C3—N3—C1—N6	−172.89 (10)	C12—C13—C14—C15	−1.42 (18)
C6—N6—C1—N3	−170.20 (11)	C13—C14—C15—C10	−0.37 (17)
C9—N6—C1—N3	−1.83 (17)	C11—C10—C15—C14	1.77 (17)
C1—N6—C6—C7	−143.44 (11)	N1—C10—C15—C14	−175.08 (10)
C9—N6—C6—C7	47.47 (14)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5A···O1i	0.89 (2)	2.08 (2)	2.929 (2)	159 (1)
N5—H5B···O2ii	0.89 (2)	2.04 (2)	2.906 (2)	164 (1)
O2—H2A···N3	0.89 (2)	2.07 (2)	2.929 (2)	164 (1)
O2—H2B···N4iii	0.91 (2)	2.01 (2)	2.916 (2)	172 (1)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5A⋯O1i	0.89 (2)	2.08 (2)	2.929 (2)	159 (1)
N5—H5B⋯O2ii	0.89 (2)	2.04 (2)	2.906 (2)	164 (1)
O2—H2A⋯N3	0.89 (2)	2.07 (2)	2.929 (2)	164 (1)
O2—H2B⋯N4iii	0.91 (2)	2.01 (2)	2.916 (2)	172 (1)

Symmetry codes: (i) ; (ii) ; (iii) .