2-Amino-1-(2-carboxyl­atoeth­yl)pyrimidin-1-ium monohydrate

Sparrow, C.R.; Walker Jr, E.H.; Fronczek, F.R.

doi:10.1107/S1600536810045332

organic compounds

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ISSN: 2056-9890

Volume 66| Part 12| December 2010| Pages o3156-o3157

https://doi.org/10.1107/S1600536810045332

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2-Amino-1-(2-carboxylatoethyl)pyrimidin-1-ium monohydrate

Christopher R. Sparrow,^a Edwin H. Walker Jr ^a and Frank R. Fronczek ^b ^*

^aDepartment of Chemistry, Southern University, Baton Rouge, LA 70813, USA, and ^bDepartment of Chemistry, Louisiana State University, Baton Rouge, LA 70803-1804, USA
^*Correspondence e-mail: ffroncz@lsu.edu

(Received 21 October 2010; accepted 4 November 2010; online 13 November 2010)

In the title structure, C₇H₉N₃O₂·H₂O, there are two formula units in the asymmetric unit. The molecule is a zwitterion, containing a quaternary N atom and a deprotonated carboxyl group, with C—O distances in the range 1.256 (2)–1.266 (3) Å. The two independent molecules form a hydrogen-bonded R₂²(16) dimer about an approximate inversion center via N—H⋯O hydrogen bonds, with N⋯O distances of 2.766 (2) and 2.888 (2) Å. O—H⋯O hydrogen bonds involving the water molecules and additional N—H⋯O hydrogen bonds link these dimers, forming double chains.

Related literature

For background information on deep eutectic solvents, see: Abbott et al. (2003 , 2004 ); Reddy (2006 ); Santos et al. (2007 ); Walker et al. (2004 ). For graph sets, see: Etter (1990 ). For a description of the Cambridge Structural Database, see: Allen (2002 ). For related structures, see: Holy et al. (1999 ); Slouf et al. (2002 ).

Experimental

Crystal data

C₇H₉N₃O₂·H₂O
M_r = 185.19
Monoclinic, P 2₁ /c
a = 10.075 (2) Å
b = 15.576 (5) Å
c = 10.810 (3) Å
β = 107.741 (16)°
V = 1615.7 (8) Å³
Z = 8
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 90 K
0.17 × 0.12 × 0.05 mm

Data collection

Nonius KappaCCD diffractometer with Oxford Cryostream cooler
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997 ) T_min = 0.980, T_max = 0.994
10202 measured reflections
3518 independent reflections
2418 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.119
S = 1.02
3518 reflections
260 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H31N⋯O4ⁱ	0.85 (3)	2.05 (3)	2.882 (3)	170 (2)
N3—H32N⋯O3	0.91 (2)	1.99 (2)	2.888 (2)	166 (2)
N6—H61N⋯O2ⁱⁱ	0.85 (3)	2.12 (3)	2.960 (3)	170 (2)
N6—H62N⋯O1	0.90 (2)	1.88 (2)	2.766 (2)	169 (2)
O1W—H11W⋯O3	0.89 (3)	1.93 (3)	2.794 (2)	165 (3)
O1W—H12W⋯O2ⁱⁱⁱ	0.84 (3)	2.04 (3)	2.867 (2)	170 (3)
O2W—H21W⋯O1	0.90 (3)	2.00 (3)	2.863 (2)	159 (2)
O2W—H22W⋯O4^iv	0.86 (3)	2.10 (3)	2.923 (2)	159 (3)
Symmetry codes: (i) -x, -y+1, -z+1; (ii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iv) -x, -y+1, -z.

Data collection: COLLECT (Nonius, 2000 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810045332/pv2345sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810045332/pv2345Isup2.hkl

checkCIF report

Comment top

With the growing environmental awareness of the global economy, there has been an increased interest in "green" solvents. Since ionic liquids or ionic solvents are considered nonvolatile substances with negligible vapor pressure, they can be utilized in establishing novel "green" synthetic routes (Santos et al., 2007). Deep eutectic solvents (DES) are considered a designated group within the broad range of ionic solvents, more specifically, they are a type of ionic solvent with special properties composed of a mixture that forms a eutectic with a melting point much lower than either of the individual components. The first generation eutectic solvents were based on mixtures of quaternary ammonium salts with hydrogen donors such as amines and carboxylic acids. The deep eutectic solvent concept was first described by Abbot et al. (2003, 2004) for a mixture of choline chloride and urea. The mixture resulted in a eutectic that melts at 285 K.

DES are capable of dissolving many metal salts. Since the solvents are conductive, DES have a potential application as battery electrolytes. Compared to ionic liquids, deep eutectic solvents are cheaper to make, much less toxic, and are sometimes biodegradable. Production of 3-(2-aminopyrimidin-1-yl) propanoate by quaternerization of the amine within the aromatic system presents a new molecular construct for deep eutectic solvents. DES can be modified in order to control factors such as conductivity, viscosity, and surface tension (Reddy, 2006). The synthesis of of 3-(2-aminopyrimidin-1-yl) propanoate takes advantage of the self-initiating condensation of 2-aminopyrimidine with the vinyl group of the αβ-unsaturated acrylic acid via anti-Markovnikov addition, which is similar to chemistry involved in the synthesis of the novel 3,3',3"-nitrilotripropionic acid precursor gel, that we have recently developed (Walker et al., 2004).

The asymmetric unit of the title compound, consisting of two 2-aminopyrimidinium carboxylate molecules and two water molecules, is shown in Fig. 1. The two main molecules form a hydrogen-bonded dimer of graph set (Etter, 1990) R²₂(16) about an approximate inversion center located near 0.186, 0.632, 0.281. The carboxyl group is deprotonated, as evidenced by all C—O distances falling within a narrow range 1.256 (2) - 1.266 (3) Å. The propionate side chains are extended, with N—C—C—C torsion angles 179.52 (17)° about C5—C6 and -175.40 (17)° about C12—C13. The 18-membered hydrogen-bonded rings are linked by centrosymmetric R⁴₄(12) rings involving both H atoms on N3 and both O atoms O3 and O4 of the same carboxylate, as can been seen in the unit-cell diagram, Figure 2. Both water molecules link the 18-membered rings via O—H···O hydrogen bonds, forming double chains in which N6—H···O2 (at x, 3/2 - y, z - 1/2) are also involved, as illustrated in Fig. 3.

We find no previous examples of 2-aminopyrimidine with a C atom on a ring N in the Cambridge Structural Database (Allen, 2002, version 5.31, Nov. 2009), although there are a few examples of N—-C substituted 2,4-diaminopyrimidine structures (Holy et al., 1999; Slouf et al., 2002).

Related literature top

For background information, see: Abbott et al. (2003, 2004); Reddy (2006); Santos et al. (2007); Walker et al. (2004). For graph sets, see: Etter (1990). For a description of the Cambridge Structural Database, see: Allen (2002). For related structures, see: Holy et al. (1999); Slouf et al. (2002).

Experimental top

2-Aminopyrimidine (1.001 g, 10.52 mmol) was dissolved in 10 ml deionized water. The solution was charged with acrylic acid (1.5 ml, 21.9 mmol) and refluxed at 343–348 K for 2 h. After heating, the mixture was stirred continuously until the temperature gradually cooled to room temperature (299 K). A light yellow aqueous slurry was obtained. In a 125 ml separatory funnel, the aqueous slurry was combined with 15 ml of benzene and shaken for several minutes. The aqueous layer was isolated and filtered. The resulting white crystalline material product was isolated by gravimetric filtration, washed with three 20 ml aliquots of cold ethanol, and allowed to air-dry overnight, yielding 1.217 g (69.36%) of white solid material.

Structure description top

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit, with ellipsoids at the 50% level and H atoms having arbitrary radius. Dotted lines are hydrogen bonds.
	Fig. 2. The unit cell.
	Fig. 3. A portion of the hydrogen-bonded double chain.

2-Amino-1-(2-carboxylatoethyl)pyrimidin-1-ium monohydrate top

Crystal data top

C₇H₉N₃O₂·H₂O	F(000) = 784
M_r = 185.19	D_x = 1.523 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3071 reflections
a = 10.075 (2) Å	θ = 2.5–27.1°
b = 15.576 (5) Å	µ = 0.12 mm⁻¹
c = 10.810 (3) Å	T = 90 K
β = 107.741 (16)°	Plate, colorless
V = 1615.7 (8) Å³	0.17 × 0.12 × 0.05 mm
Z = 8

Data collection top

Nonius KappaCCD diffractometer with Oxford Cryostream cooler	3518 independent reflections
Radiation source: fine-focus sealed tube	2418 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ω and φ scans	θ_max = 27.1°, θ_min = 2.7°
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	h = −12→12
T_min = 0.980, T_max = 0.994	k = −19→16
10202 measured reflections	l = −13→13

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)] = 0.050	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.119	w = 1/[σ²(F_o²) + (0.0416P)² + 1.0034P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
3518 reflections	Δρ_max = 0.26 e Å⁻³
260 parameters	Δρ_min = −0.34 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0052 (10)

Crystal data top

C₇H₉N₃O₂·H₂O	V = 1615.7 (8) Å³
M_r = 185.19	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.075 (2) Å	µ = 0.12 mm⁻¹
b = 15.576 (5) Å	T = 90 K
c = 10.810 (3) Å	0.17 × 0.12 × 0.05 mm
β = 107.741 (16)°

Data collection top

Nonius KappaCCD diffractometer with Oxford Cryostream cooler	3518 independent reflections
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	2418 reflections with I > 2σ(I)
T_min = 0.980, T_max = 0.994	R_int = 0.031
10202 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.26 e Å⁻³
3518 reflections	Δρ_min = −0.34 e Å⁻³
260 parameters

Special details top

Experimental. ¹H (D₂O): δ(p.p.m.) 2.72 (t, 2H, J = 6.14 Hz), 4.33 (t, 2H, J = 6.14 Hz), 7.01 (t, 1H, J = 5.6 Hz), 8.32 (d, 1H, J = 5.6 Hz), and 8.69 (d, 1H, J = 5.6 Hz). ¹³C (D₂O): δ(p.p.m.) 34.2, 51.9, 111.3, 150.5, 155.8, 166.2, and 177.5. IR (thin film, KBr plates, cm^-1): 3428.76 (m, br), 3093.35 (br), 2363.8 (m), 1675.0 (m), 1386.82 (s), 1262.48 (s), 1193.82 (w, sh), 1094.27 (w), 1024.62 (w), and 931.94 (w, sh).

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
O1	0.16601 (14)	0.69376 (10)	0.15055 (14)	0.0176 (4)
O2	0.30612 (14)	0.78552 (10)	0.28952 (15)	0.0188 (4)
N1	−0.14185 (16)	0.70633 (11)	0.33727 (16)	0.0135 (4)
N2	−0.23793 (17)	0.66797 (12)	0.50401 (18)	0.0161 (4)
N3	−0.02988 (18)	0.60908 (12)	0.50172 (19)	0.0159 (4)
H31N	−0.036 (2)	0.5803 (16)	0.566 (2)	0.019*
H32N	0.038 (2)	0.5978 (15)	0.464 (2)	0.019*
C1	−0.1350 (2)	0.66116 (13)	0.4473 (2)	0.0134 (4)
C2	−0.3421 (2)	0.72143 (14)	0.4525 (2)	0.0152 (5)
H2	−0.4151	0.7250	0.4909	0.018*
C3	−0.3504 (2)	0.77295 (14)	0.3446 (2)	0.0159 (5)
H3	−0.4249	0.8122	0.3112	0.019*
C4	−0.2464 (2)	0.76392 (14)	0.2900 (2)	0.0161 (5)
H4	−0.2467	0.7985	0.2175	0.019*
C5	−0.0369 (2)	0.69512 (14)	0.2672 (2)	0.0143 (5)
H5A	−0.0817	0.7058	0.1734	0.017*
H5B	−0.0029	0.6351	0.2774	0.017*
C6	0.0857 (2)	0.75559 (14)	0.3174 (2)	0.0164 (5)
H6A	0.1298	0.7452	0.4113	0.020*
H6B	0.0516	0.8156	0.3065	0.020*
C7	0.1944 (2)	0.74413 (14)	0.2470 (2)	0.0142 (5)
O3	0.20974 (14)	0.56176 (10)	0.42323 (14)	0.0169 (3)
O4	0.07476 (14)	0.47312 (10)	0.27549 (14)	0.0175 (4)
N4	0.51826 (16)	0.56177 (11)	0.22871 (16)	0.0132 (4)
N5	0.58362 (17)	0.58906 (12)	0.03946 (17)	0.0159 (4)
N6	0.37231 (18)	0.63627 (12)	0.05084 (19)	0.0161 (4)
H61N	0.362 (2)	0.6558 (16)	−0.025 (3)	0.019*
H62N	0.313 (2)	0.6537 (15)	0.094 (2)	0.019*
C8	0.4900 (2)	0.59599 (13)	0.1067 (2)	0.0137 (4)
C9	0.7023 (2)	0.54856 (14)	0.0946 (2)	0.0164 (5)
H9	0.7685	0.5450	0.0483	0.020*
C10	0.7352 (2)	0.51078 (14)	0.2174 (2)	0.0172 (5)
H10	0.8202	0.4807	0.2535	0.021*
C11	0.6406 (2)	0.51888 (14)	0.2830 (2)	0.0169 (5)
H11	0.6595	0.4946	0.3672	0.020*
C12	0.4179 (2)	0.56957 (14)	0.3045 (2)	0.0140 (5)
H12A	0.3793	0.6285	0.2953	0.017*
H12B	0.4672	0.5594	0.3976	0.017*
C13	0.2994 (2)	0.50517 (14)	0.2575 (2)	0.0171 (5)
H13A	0.3384	0.4464	0.2729	0.021*
H13B	0.2565	0.5123	0.1627	0.021*
C14	0.1859 (2)	0.51433 (14)	0.3239 (2)	0.0144 (5)
O1W	0.42213 (16)	0.65900 (11)	0.59146 (17)	0.0215 (4)
H11W	0.359 (3)	0.6329 (17)	0.527 (3)	0.032*
H12W	0.384 (3)	0.6801 (18)	0.643 (3)	0.032*
O2W	−0.06112 (17)	0.60258 (12)	−0.02453 (18)	0.0270 (4)
H21W	0.023 (3)	0.6207 (18)	0.026 (3)	0.040*
H22W	−0.043 (3)	0.5764 (19)	−0.088 (3)	0.040*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0148 (7)	0.0222 (9)	0.0171 (8)	0.0004 (6)	0.0067 (6)	−0.0044 (7)
O2	0.0152 (7)	0.0226 (9)	0.0200 (9)	−0.0030 (6)	0.0072 (6)	−0.0027 (7)
N1	0.0126 (8)	0.0152 (9)	0.0133 (10)	0.0016 (7)	0.0050 (7)	0.0000 (8)
N2	0.0147 (8)	0.0181 (10)	0.0170 (10)	−0.0001 (7)	0.0070 (7)	−0.0013 (8)
N3	0.0152 (9)	0.0178 (10)	0.0164 (10)	0.0020 (8)	0.0073 (8)	0.0037 (8)
C1	0.0138 (9)	0.0130 (11)	0.0136 (11)	−0.0026 (8)	0.0044 (8)	−0.0024 (9)
C2	0.0116 (9)	0.0182 (12)	0.0169 (12)	−0.0017 (9)	0.0061 (9)	−0.0049 (9)
C3	0.0129 (10)	0.0168 (12)	0.0177 (12)	0.0018 (8)	0.0042 (9)	0.0004 (9)
C4	0.0167 (10)	0.0168 (12)	0.0137 (12)	0.0002 (9)	0.0030 (9)	−0.0010 (9)
C5	0.0145 (10)	0.0168 (11)	0.0138 (11)	0.0016 (9)	0.0073 (8)	0.0005 (9)
C6	0.0153 (10)	0.0163 (12)	0.0186 (12)	−0.0011 (9)	0.0065 (9)	−0.0016 (9)
C7	0.0158 (10)	0.0150 (11)	0.0127 (11)	0.0019 (9)	0.0056 (9)	0.0047 (9)
O3	0.0154 (7)	0.0205 (8)	0.0159 (8)	0.0005 (6)	0.0063 (6)	−0.0019 (7)
O4	0.0141 (7)	0.0216 (9)	0.0168 (8)	−0.0026 (6)	0.0050 (6)	0.0005 (7)
N4	0.0123 (8)	0.0142 (9)	0.0143 (9)	0.0001 (7)	0.0057 (7)	0.0010 (7)
N5	0.0156 (8)	0.0172 (10)	0.0167 (10)	−0.0018 (7)	0.0077 (7)	−0.0012 (8)
N6	0.0170 (9)	0.0196 (10)	0.0135 (10)	0.0025 (8)	0.0074 (8)	0.0011 (8)
C8	0.0138 (9)	0.0118 (11)	0.0163 (11)	−0.0029 (8)	0.0059 (8)	−0.0019 (9)
C9	0.0134 (10)	0.0187 (12)	0.0183 (12)	−0.0029 (9)	0.0068 (9)	−0.0050 (10)
C10	0.0134 (10)	0.0169 (12)	0.0202 (12)	0.0003 (9)	0.0037 (9)	−0.0025 (9)
C11	0.0149 (10)	0.0168 (12)	0.0180 (12)	−0.0019 (9)	0.0035 (9)	−0.0010 (9)
C12	0.0146 (10)	0.0174 (12)	0.0116 (11)	0.0001 (8)	0.0064 (8)	−0.0013 (9)
C13	0.0178 (10)	0.0161 (11)	0.0190 (12)	−0.0009 (9)	0.0080 (9)	−0.0032 (9)
C14	0.0141 (10)	0.0168 (12)	0.0132 (11)	0.0020 (9)	0.0055 (8)	0.0040 (9)
O1W	0.0201 (8)	0.0266 (10)	0.0194 (9)	−0.0030 (7)	0.0083 (7)	−0.0066 (7)
O2W	0.0221 (8)	0.0396 (11)	0.0215 (10)	−0.0092 (8)	0.0100 (7)	−0.0071 (8)

Geometric parameters (Å, º) top

O1—C7	1.266 (3)	N4—C11	1.367 (3)
O2—C7	1.256 (2)	N4—C8	1.370 (3)
N1—C4	1.359 (3)	N4—C12	1.487 (2)
N1—C1	1.365 (3)	N5—C9	1.322 (3)
N1—C5	1.487 (3)	N5—C8	1.359 (3)
N2—C2	1.322 (3)	N6—C8	1.315 (3)
N2—C1	1.360 (3)	N6—H61N	0.85 (3)
N3—C1	1.322 (3)	N6—H62N	0.90 (2)
N3—H31N	0.85 (3)	C9—C10	1.397 (3)
N3—H32N	0.91 (2)	C9—H9	0.9500
C2—C3	1.397 (3)	C10—C11	1.356 (3)
C2—H2	0.9500	C10—H10	0.9500
C3—C4	1.358 (3)	C11—H11	0.9500
C3—H3	0.9500	C12—C13	1.523 (3)
C4—H4	0.9500	C12—H12A	0.9900
C5—C6	1.516 (3)	C12—H12B	0.9900
C5—H5A	0.9900	C13—C14	1.531 (3)
C5—H5B	0.9900	C13—H13A	0.9900
C6—C7	1.522 (3)	C13—H13B	0.9900
C6—H6A	0.9900	O1W—H11W	0.89 (3)
C6—H6B	0.9900	O1W—H12W	0.84 (3)
O3—C14	1.265 (3)	O2W—H21W	0.90 (3)
O4—C14	1.258 (2)	O2W—H22W	0.86 (3)

C4—N1—C1	119.69 (17)	C11—N4—C12	118.61 (17)
C4—N1—C5	118.41 (17)	C8—N4—C12	121.46 (16)
C1—N1—C5	121.90 (17)	C9—N5—C8	118.44 (19)
C2—N2—C1	118.38 (19)	C8—N6—H61N	116.1 (16)
C1—N3—H31N	116.4 (16)	C8—N6—H62N	123.7 (15)
C1—N3—H32N	121.7 (15)	H61N—N6—H62N	119 (2)
H31N—N3—H32N	121 (2)	N6—C8—N5	117.9 (2)
N3—C1—N2	117.7 (2)	N6—C8—N4	121.43 (18)
N3—C1—N1	121.68 (18)	N5—C8—N4	120.66 (18)
N2—C1—N1	120.64 (18)	N5—C9—C10	123.34 (19)
N2—C2—C3	123.45 (19)	N5—C9—H9	118.3
N2—C2—H2	118.3	C10—C9—H9	118.3
C3—C2—H2	118.3	C11—C10—C9	117.2 (2)
C4—C3—C2	116.5 (2)	C11—C10—H10	121.4
C4—C3—H3	121.8	C9—C10—H10	121.4
C2—C3—H3	121.8	C10—C11—N4	120.4 (2)
C3—C4—N1	121.1 (2)	C10—C11—H11	119.8
C3—C4—H4	119.4	N4—C11—H11	119.8
N1—C4—H4	119.4	N4—C12—C13	110.99 (17)
N1—C5—C6	111.90 (17)	N4—C12—H12A	109.4
N1—C5—H5A	109.2	C13—C12—H12A	109.4
C6—C5—H5A	109.2	N4—C12—H12B	109.4
N1—C5—H5B	109.2	C13—C12—H12B	109.4
C6—C5—H5B	109.2	H12A—C12—H12B	108.0
H5A—C5—H5B	107.9	C12—C13—C14	113.84 (18)
C5—C6—C7	112.33 (18)	C12—C13—H13A	108.8
C5—C6—H6A	109.1	C14—C13—H13A	108.8
C7—C6—H6A	109.1	C12—C13—H13B	108.8
C5—C6—H6B	109.1	C14—C13—H13B	108.8
C7—C6—H6B	109.1	H13A—C13—H13B	107.7
H6A—C6—H6B	107.9	O4—C14—O3	124.47 (19)
O2—C7—O1	124.89 (19)	O4—C14—C13	117.05 (19)
O2—C7—C6	117.22 (19)	O3—C14—C13	118.48 (18)
O1—C7—C6	117.88 (18)	H11W—O1W—H12W	110 (2)
C11—N4—C8	119.92 (17)	H21W—O2W—H22W	104 (2)

C2—N2—C1—N3	178.36 (19)	C9—N5—C8—N6	−179.88 (19)
C2—N2—C1—N1	−2.2 (3)	C9—N5—C8—N4	0.0 (3)
C4—N1—C1—N3	−175.13 (19)	C11—N4—C8—N6	178.78 (19)
C5—N1—C1—N3	4.3 (3)	C12—N4—C8—N6	−0.8 (3)
C4—N1—C1—N2	5.4 (3)	C11—N4—C8—N5	−1.1 (3)
C5—N1—C1—N2	−175.12 (18)	C12—N4—C8—N5	179.27 (18)
C1—N2—C2—C3	−1.6 (3)	C8—N5—C9—C10	1.5 (3)
N2—C2—C3—C4	2.1 (3)	N5—C9—C10—C11	−1.8 (3)
C2—C3—C4—N1	1.2 (3)	C9—C10—C11—N4	0.6 (3)
C1—N1—C4—C3	−4.9 (3)	C8—N4—C11—C10	0.8 (3)
C5—N1—C4—C3	175.6 (2)	C12—N4—C11—C10	−179.63 (19)
C4—N1—C5—C6	90.1 (2)	C11—N4—C12—C13	−101.4 (2)
C1—N1—C5—C6	−89.4 (2)	C8—N4—C12—C13	78.2 (2)
N1—C5—C6—C7	179.52 (17)	N4—C12—C13—C14	−175.40 (17)
C5—C6—C7—O2	−173.50 (18)	C12—C13—C14—O4	168.71 (18)
C5—C6—C7—O1	6.4 (3)	C12—C13—C14—O3	−11.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H31N···O4ⁱ	0.85 (3)	2.05 (3)	2.882 (3)	170 (2)
N3—H32N···O3	0.91 (2)	1.99 (2)	2.888 (2)	166 (2)
N6—H61N···O2ⁱⁱ	0.85 (3)	2.12 (3)	2.960 (3)	170 (2)
N6—H62N···O1	0.90 (2)	1.88 (2)	2.766 (2)	169 (2)
O1W—H11W···O3	0.89 (3)	1.93 (3)	2.794 (2)	165 (3)
O1W—H12W···O2ⁱⁱⁱ	0.84 (3)	2.04 (3)	2.867 (2)	170 (3)
O2W—H21W···O1	0.90 (3)	2.00 (3)	2.863 (2)	159 (2)
O2W—H22W···O4^iv	0.86 (3)	2.10 (3)	2.923 (2)	159 (3)

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

Experimental details

Crystal data
Chemical formula	C₇H₉N₃O₂·H₂O
M_r	185.19
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	90
a, b, c (Å)	10.075 (2), 15.576 (5), 10.810 (3)
β (°)	107.741 (16)
V (Å³)	1615.7 (8)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.17 × 0.12 × 0.05

Data collection
Diffractometer	Nonius KappaCCD diffractometer with Oxford Cryostream cooler
Absorption correction	Multi-scan (SCALEPACK; Otwinowski & Minor, 1997)
T_min, T_max	0.980, 0.994
No. of measured, independent and observed [I > 2σ(I)] reflections	10202, 3518, 2418
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.641

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.119, 1.02
No. of reflections	3518
No. of parameters	260
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.34

Computer programs: COLLECT (Nonius, 2000), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H31N···O4ⁱ	0.85 (3)	2.05 (3)	2.882 (3)	170 (2)
N3—H32N···O3	0.91 (2)	1.99 (2)	2.888 (2)	166 (2)
N6—H61N···O2ⁱⁱ	0.85 (3)	2.12 (3)	2.960 (3)	170 (2)
N6—H62N···O1	0.90 (2)	1.88 (2)	2.766 (2)	169 (2)
O1W—H11W···O3	0.89 (3)	1.93 (3)	2.794 (2)	165 (3)
O1W—H12W···O2ⁱⁱⁱ	0.84 (3)	2.04 (3)	2.867 (2)	170 (3)
O2W—H21W···O1	0.90 (3)	2.00 (3)	2.863 (2)	159 (2)
O2W—H22W···O4^iv	0.86 (3)	2.10 (3)	2.923 (2)	159 (3)

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

Acknowledgements

This research was made possible by a grant supplied by the National Science Foundation's Early CAREER program (Cooperative Agreement DMR-0449886) at Southern University. The purchase of the NMR was made possible by the National Science Foundation's Major Research Instrument program (Cooperative Agreement CHE-0321591) at Southern University. The purchase of the FTIR was made possible by grant No. LEQSF(2005–2007)-ENH-TR-65, and the purchase of the diffractometer at LSU was made possible by grant No. LEQSF (1999–2000)-ENH-TR-13, both administered by the Louisiana Board of Regents.

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Volume 66| Part 12| December 2010| Pages o3156-o3157

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