l-2-Nitrimino-1,3-diazepane-4-carboxylic acid monohydrate

Karapetyan, H.A.

doi:10.1107/S1600536808015146

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 7| July 2008| Page o1222

doi:10.1107/S1600536808015146

Open

access

L-2-Nitrimino-1,3-diazepane-4-carboxylic acid monohydrate

Harutyun A. Karapetyan ^a ^*

^aMolecular Structure Research Center, National Academy of Sciences RA, Azatutyan Ave. 26, 375014 Yerevan, Republic of Armenia
^*Correspondence e-mail: harkar@nfsat.am

(Received 9 May 2008; accepted 19 May 2008; online 7 June 2008)

The title compound, C₆H₁₀N₄O₄·H₂O, crystallizes with two independent formula units in the asymmetric unit, their geometric parameters being quite similar. The conformations of the 1,3-diazepane rings are also similar and close to a twist-boat. All ten O- and N-bound H atoms are involved in hydrogen bonds, two of which are intra- and eight intermolecular linking crystallographically independent molecules, into a three-dimensional hydrogen-bonded network.

Related literature

For the crystal structures of some analogues of the title compound, see: Apreyan et al. (2008a , 2008b ); Karapetyan et al. (2007 ); Petrosyan et al. (2005 ); Karapetyan (2008 ). For related literature, see: Paul et al. (1961 ); Apreyan & Petrosyan (2008 ).

Experimental

Crystal data

C₆H₁₀N₄O₄·H₂O
M_r = 220.20
Orthorhombic, P 2₁ 2₁ 2₁
a = 9.0115 (18) Å
b = 14.729 (3) Å
c = 15.257 (3) Å
V = 2025.0 (7) Å³
Z = 8
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 293 (2) K
0.22 × 0.17 × 0.12 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: none
6714 measured reflections
2512 independent reflections
1583 reflections with I > 2σ(I)
R_int = 0.040
3 standard reflections every 400 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.132
S = 1.02
2512 reflections
286 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N3ⁱ	0.82	1.90	2.716 (4)	173
N1—H3⋯O3	0.86	2.02	2.586 (4)	123
N2—H10⋯O2ⁱⁱ	0.86	2.05	2.889 (4)	163
O5—H11⋯O9ⁱⁱⁱ	0.82	1.69	2.510 (5)	174
N5—H13⋯O7	0.86	2.04	2.584 (5)	121
N6—H20⋯O6^iv	0.86	2.16	2.937 (5)	150
O9—H21⋯N7	0.83 (4)	2.11 (3)	2.902 (6)	160 (7)
O9—H22⋯O10	0.84 (4)	1.86 (3)	2.662 (7)	159 (7)
O10—H23⋯O7^v	0.86 (4)	2.04 (4)	2.869 (6)	163 (6)
O10—H24⋯O3	0.86 (4)	2.41 (8)	2.856 (6)	113 (5)
Symmetry codes: (i) $[-x+2, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (v) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+2]$ .

Data collection: DATCOL in CAD-4 Manual (Enraf–Nonius, 1988 ); cell refinement: LS in CAD-4 Manual (Enraf–Nonius, 1988); data reduction: HELENA (Spek, 1997 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808015146/bg2187sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808015146/bg2187Isup2.hkl

checkCIF report

Comment top

The L-nitroarginine and its crystaline salts have been investigated as a promising line of non-linear optical materials [Apreyan et al.(2008a) and Apreyan et al.(2008b)]. The cyclic form of L-nitroarginine was reported for the first time in Paul et al., 1961, where it was suggested to be 2-nitro-4-carboxy-1,3-diazacycloheptane. Recently, on the basis of the crystal structure of the cyclic form of L-nitroarginine [Karapetyan, 2008] it was shown to be L-2-nitrimino-1,3-diazepane-4-carboxylic acid (L-NIDCA).

We present herein a structural study of the L-NIDCA monohydrate, C₆H₁₀N₄O₄ × H₂O (I), which crystallizes with two independent formulas in the asymmetric unit, shown in Fig. 1. The metric parameters of independent L-NIDCA molecules are in agreement with commonly accepted values and their conformations are the same, being close to that of a 7-membered ring twist-boat . All ten active H atoms in the crystal are involved in hydrogen bonding (Table 1), two of them being intra- and eight inter-molecular, linking crystallographically independent units and by way of which a tree-dimensional H bonded network results (Fig. 2).

Related literature top

For the crystal structures of some analogues of the title compound, see: Apreyan et al. (2008a, 2008b); Karapetyan et al. (2007); Petrosyan et al. (2005); Karapetyan (2008). For related literature, see: Paul et al. (1961); Apreyan & Petrosyan (2008).

Experimental top

By the reaction of L-nitroarginine with KOH the potassium salt was obtained. By the interaction of this potassium salt with HBF4 and further separation of the poorly soluble KBF4 salt, single crystals of (I) were obtained by slow evaporation below room temperature. Details of the obtainment of L-NIDCA and L-NIDCA^.H₂O, as well as vibrational spectra, thermal properties and SHG will be reported soon separately [Apreyan and Petrosyan, 2008].

Computing details top

Data collection: DATCOL in CAD-4 Manual (Enraf–Nonius, 1988); cell refinement: LS in CAD4 Manual (Enraf–Nonius, 1988); data reduction: HELENA (Spek, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. View of the asymmetric unit of (I) showing atomic numbering and displacement ellipsoids at the 50% probability. Only active H atoms are presented for clarity. H-bonds drawn in broken lines.
	Fig. 2. Packing view of the structure ( non-active H atoms not shown). H-bonds drawn in broken lines. Symmetry codes: (i) -x + 2, y - 1/2, -z + 3/2; (ii) -x + 2, y + 1/2, -z + 3/2; (iii) -x + 1, y - 1/2, -z + 3/2; (iv) -x + 1, y + 1/2, -z + 3/2.

L-2-Nitrimino-1,3-diazepane-4-carboxylic acid monohydrate top

Crystal data top

C₆H₁₀N₄O₄·H₂O	F(000) = 928
M_r = 220.20	D_x = 1.445 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 24 reflections
a = 9.0115 (18) Å	θ = 14–16°
b = 14.729 (3) Å	µ = 0.13 mm⁻¹
c = 15.257 (3) Å	T = 293 K
V = 2025.0 (7) Å³	Prismatic, yellow
Z = 8	0.22 × 0.17 × 0.12 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.040
Radiation source: fine-focus sealed tube	θ_max = 27.0°, θ_min = 2.6°
Graphite monochromator	h = 0→11
ω/2θ scans	k = −17→18
6714 measured reflections	l = −19→19
2512 independent reflections	3 standard reflections every 400 reflections
1583 reflections with I > 2σ(I)	intensity decay: none

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.132	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0704P)² + 0.3433P] where P = (F_o² + 2F_c²)/3
2512 reflections	(Δ/σ)_max = 0.014
286 parameters	Δρ_max = 0.44 e Å⁻³
6 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₆H₁₀N₄O₄·H₂O	V = 2025.0 (7) Å³
M_r = 220.20	Z = 8
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 9.0115 (18) Å	µ = 0.13 mm⁻¹
b = 14.729 (3) Å	T = 293 K
c = 15.257 (3) Å	0.22 × 0.17 × 0.12 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.040
6714 measured reflections	3 standard reflections every 400 reflections
2512 independent reflections	intensity decay: none
1583 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.046	6 restraints
wR(F²) = 0.132	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.44 e Å⁻³
2512 reflections	Δρ_min = −0.27 e Å⁻³
286 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
O1	0.8550 (4)	0.81385 (17)	0.6510 (2)	0.0559 (8)
H1	0.8648	0.7605	0.6653	0.084*
O2	1.0592 (4)	0.83261 (16)	0.7324 (2)	0.0556 (8)
O3	1.2651 (4)	1.00838 (17)	0.83155 (19)	0.0592 (8)
O4	1.2868 (4)	1.1299 (2)	0.90927 (18)	0.0591 (8)
N1	1.0627 (4)	1.00945 (18)	0.7113 (2)	0.0421 (7)
H3	1.1404	0.9789	0.7256	0.051*
N2	0.9663 (4)	1.1533 (2)	0.6923 (2)	0.0507 (9)
H10	0.9437	1.2018	0.7207	0.061*
N3	1.1385 (4)	1.13746 (18)	0.7971 (2)	0.0407 (7)
N4	1.2311 (4)	1.0889 (2)	0.8470 (2)	0.0431 (8)
C1	0.9593 (5)	0.8623 (2)	0.6876 (2)	0.0399 (9)
C2	0.9446 (5)	0.9624 (2)	0.6654 (2)	0.0409 (9)
H2	0.8492	0.9843	0.6879	0.049*
C3	0.9495 (6)	0.9789 (3)	0.5664 (2)	0.0561 (11)
H4	1.0283	0.9428	0.5406	0.067*
H5	0.8563	0.9601	0.5403	0.067*
C4	0.9765 (8)	1.0790 (3)	0.5471 (3)	0.0733 (16)
H6	1.0822	1.0907	0.5512	0.088*
H7	0.9467	1.0911	0.4872	0.088*
C5	0.8980 (6)	1.1435 (3)	0.6055 (3)	0.0688 (15)
H9	0.8951	1.2026	0.5774	0.083*
H8	0.7964	1.1231	0.6129	0.083*
C6	1.0582 (5)	1.0969 (2)	0.7326 (2)	0.0382 (8)
O5	0.2203 (4)	0.6209 (2)	0.6113 (2)	0.0681 (9)
H11	0.1992	0.5667	0.6112	0.102*
O6	0.3842 (4)	0.5793 (2)	0.7134 (2)	0.0702 (9)
O7	0.6264 (5)	0.6721 (2)	0.8634 (2)	0.0816 (12)
O8	0.7679 (5)	0.7592 (2)	0.9383 (2)	0.0785 (11)
N5	0.5019 (4)	0.7416 (2)	0.7264 (2)	0.0474 (8)
H13	0.5467	0.6920	0.7399	0.057*
N6	0.5183 (5)	0.8983 (2)	0.7299 (2)	0.0581 (10)
H20	0.5327	0.9434	0.7646	0.070*
N7	0.6483 (5)	0.8224 (2)	0.8311 (2)	0.0564 (10)
N8	0.6787 (5)	0.7483 (3)	0.8780 (2)	0.0594 (10)
C7	0.3282 (5)	0.6353 (3)	0.6665 (3)	0.0518 (10)
C8	0.3764 (5)	0.7345 (2)	0.6670 (3)	0.0479 (10)
H12	0.2949	0.7710	0.6908	0.057*
C9	0.4115 (6)	0.7691 (3)	0.5742 (3)	0.0577 (12)
H14	0.4718	0.7244	0.5441	0.069*
H15	0.3195	0.7757	0.5419	0.069*
C10	0.4921 (8)	0.8586 (4)	0.5744 (3)	0.0860 (17)
H16	0.5977	0.8462	0.5761	0.103*
H17	0.4717	0.8888	0.5191	0.103*
C11	0.4585 (9)	0.9205 (3)	0.6433 (3)	0.0859 (19)
H18	0.3515	0.9250	0.6482	0.103*
H19	0.4953	0.9799	0.6267	0.103*
C12	0.5530 (5)	0.8170 (2)	0.7613 (2)	0.0453 (9)
O9	0.8626 (5)	0.9582 (3)	0.8857 (4)	0.0980 (13)
H21	0.799 (5)	0.918 (3)	0.883 (4)	0.118*
H22	0.927 (6)	0.944 (4)	0.923 (4)	0.118*
O10	1.1127 (6)	0.9147 (4)	0.9685 (4)	0.134 (2)
H23	1.132 (9)	0.882 (5)	1.014 (3)	0.161*
H24	1.170 (9)	0.893 (6)	0.929 (4)	0.161*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.063 (2)	0.0304 (13)	0.0741 (19)	−0.0079 (14)	−0.0175 (17)	0.0017 (13)
O2	0.0548 (17)	0.0305 (13)	0.081 (2)	0.0015 (13)	−0.0159 (18)	0.0023 (14)
O3	0.0668 (19)	0.0344 (13)	0.0765 (18)	0.0104 (14)	−0.0205 (18)	−0.0031 (13)
O4	0.070 (2)	0.0534 (16)	0.0541 (16)	0.0008 (17)	−0.0194 (16)	−0.0042 (14)
N1	0.0486 (19)	0.0241 (13)	0.0536 (17)	0.0017 (14)	−0.0098 (16)	−0.0009 (13)
N2	0.065 (2)	0.0289 (15)	0.058 (2)	0.0053 (16)	−0.0198 (19)	−0.0017 (14)
N3	0.0478 (19)	0.0276 (14)	0.0467 (16)	0.0026 (15)	−0.0085 (16)	−0.0011 (13)
N4	0.051 (2)	0.0338 (15)	0.0446 (16)	−0.0019 (16)	−0.0056 (17)	0.0014 (13)
C1	0.042 (2)	0.0301 (16)	0.047 (2)	0.0002 (18)	0.0023 (19)	−0.0020 (16)
C2	0.048 (2)	0.0291 (17)	0.0456 (19)	−0.0018 (17)	−0.008 (2)	−0.0025 (15)
C3	0.082 (3)	0.042 (2)	0.045 (2)	−0.008 (2)	−0.006 (2)	−0.0004 (17)
C4	0.117 (5)	0.057 (3)	0.047 (2)	−0.008 (3)	−0.011 (3)	0.008 (2)
C5	0.099 (4)	0.040 (2)	0.068 (3)	0.006 (3)	−0.031 (3)	0.007 (2)
C6	0.046 (2)	0.0289 (16)	0.0402 (18)	−0.0023 (17)	0.0028 (18)	−0.0001 (15)
O5	0.072 (2)	0.0556 (18)	0.077 (2)	−0.0083 (17)	−0.010 (2)	0.0005 (17)
O6	0.086 (2)	0.0405 (15)	0.085 (2)	0.0007 (16)	−0.015 (2)	0.0082 (16)
O7	0.123 (3)	0.0527 (19)	0.069 (2)	−0.007 (2)	−0.022 (2)	0.0136 (16)
O8	0.111 (3)	0.074 (2)	0.0512 (16)	0.024 (2)	−0.021 (2)	−0.0030 (15)
N5	0.060 (2)	0.0358 (15)	0.0461 (18)	0.0087 (16)	−0.0062 (19)	−0.0002 (14)
N6	0.082 (3)	0.0379 (17)	0.055 (2)	0.0094 (18)	−0.006 (2)	−0.0026 (15)
N7	0.081 (3)	0.0446 (18)	0.0435 (17)	0.0112 (19)	−0.010 (2)	−0.0004 (15)
N8	0.082 (3)	0.057 (2)	0.0387 (17)	0.018 (2)	−0.003 (2)	−0.0031 (17)
C7	0.053 (3)	0.047 (2)	0.056 (2)	0.005 (2)	0.000 (2)	−0.003 (2)
C8	0.050 (2)	0.039 (2)	0.055 (2)	0.0087 (19)	0.001 (2)	−0.0025 (18)
C9	0.069 (3)	0.055 (3)	0.049 (2)	0.000 (2)	−0.011 (2)	0.0107 (19)
C10	0.114 (5)	0.084 (4)	0.059 (3)	−0.012 (4)	−0.005 (3)	0.017 (3)
C11	0.140 (6)	0.040 (2)	0.078 (3)	0.008 (3)	−0.035 (4)	0.013 (2)
C12	0.059 (2)	0.0377 (19)	0.0396 (19)	0.009 (2)	0.006 (2)	0.0003 (16)
O9	0.082 (3)	0.059 (2)	0.152 (4)	0.013 (2)	−0.013 (3)	0.009 (2)
O10	0.110 (4)	0.172 (5)	0.120 (4)	0.017 (4)	−0.016 (3)	0.082 (4)

Geometric parameters (Å, º) top

O1—C1	1.306 (5)	O6—C7	1.203 (5)
O1—H1	0.8200	O7—N8	1.238 (5)
O2—C1	1.212 (5)	O8—N8	1.232 (5)
O3—N4	1.247 (4)	N5—C12	1.316 (5)
O4—N4	1.232 (4)	N5—C8	1.453 (5)
N1—C6	1.329 (4)	N5—H13	0.8600
N1—C2	1.450 (5)	N6—C12	1.326 (5)
N1—H3	0.8600	N6—C11	1.463 (6)
N2—C6	1.324 (5)	N6—H20	0.8600
N2—C5	1.467 (5)	N7—N8	1.334 (5)
N2—H10	0.8600	N7—C12	1.371 (6)
N3—N4	1.338 (4)	C7—C8	1.525 (6)
N3—C6	1.359 (5)	C8—C9	1.536 (6)
C1—C2	1.518 (5)	C8—H12	0.9800
C2—C3	1.531 (5)	C9—C10	1.505 (7)
C2—H2	0.9800	C9—H14	0.9700
C3—C4	1.523 (6)	C9—H15	0.9700
C3—H4	0.9700	C10—C11	1.424 (7)
C3—H5	0.9700	C10—H16	0.9700
C4—C5	1.482 (7)	C10—H17	0.9700
C4—H6	0.9700	C11—H18	0.9700
C4—H7	0.9700	C11—H19	0.9700
C5—H9	0.9700	O9—H21	0.83 (4)
C5—H8	0.9700	O9—H22	0.84 (4)
O5—C7	1.304 (5)	O10—H23	0.86 (4)
O5—H11	0.8200	O10—H24	0.86 (4)

C1—O1—H1	109.5	C12—N5—C8	125.8 (3)
C6—N1—C2	124.0 (3)	C12—N5—H13	117.1
C6—N1—H3	118.0	C8—N5—H13	117.1
C2—N1—H3	118.0	C12—N6—C11	127.9 (3)
C6—N2—C5	128.3 (3)	C12—N6—H20	116.1
C6—N2—H10	115.9	C11—N6—H20	116.1
C5—N2—H10	115.9	N8—N7—C12	119.9 (3)
N4—N3—C6	120.6 (3)	O8—N8—O7	120.1 (4)
O4—N4—O3	120.8 (3)	O8—N8—N7	115.3 (4)
O4—N4—N3	115.5 (3)	O7—N8—N7	124.6 (4)
O3—N4—N3	123.6 (3)	O6—C7—O5	125.8 (4)
O2—C1—O1	125.4 (3)	O6—C7—C8	122.4 (4)
O2—C1—C2	122.7 (4)	O5—C7—C8	111.8 (4)
O1—C1—C2	111.9 (3)	N5—C8—C7	107.0 (3)
N1—C2—C1	107.0 (3)	N5—C8—C9	113.0 (3)
N1—C2—C3	112.3 (3)	C7—C8—C9	111.9 (3)
C1—C2—C3	111.8 (3)	N5—C8—H12	108.3
N1—C2—H2	108.5	C7—C8—H12	108.3
C1—C2—H2	108.5	C9—C8—H12	108.3
C3—C2—H2	108.5	C10—C9—C8	112.9 (4)
C4—C3—C2	110.4 (3)	C10—C9—H14	109.0
C4—C3—H4	109.6	C8—C9—H14	109.0
C2—C3—H4	109.6	C10—C9—H15	109.0
C4—C3—H5	109.6	C8—C9—H15	109.0
C2—C3—H5	109.6	H14—C9—H15	107.8
H4—C3—H5	108.1	C11—C10—C9	117.3 (5)
C5—C4—C3	115.4 (4)	C11—C10—H16	108.0
C5—C4—H6	108.4	C9—C10—H16	108.0
C3—C4—H6	108.4	C11—C10—H17	108.0
C5—C4—H7	108.4	C9—C10—H17	108.0
C3—C4—H7	108.4	H16—C10—H17	107.2
H6—C4—H7	107.5	C10—C11—N6	116.5 (4)
N2—C5—C4	113.9 (4)	C10—C11—H18	108.2
N2—C5—H9	108.8	N6—C11—H18	108.2
C4—C5—H9	108.8	C10—C11—H19	108.2
N2—C5—H8	108.8	N6—C11—H19	108.2
C4—C5—H8	108.8	H18—C11—H19	107.3
H9—C5—H8	107.7	N5—C12—N6	122.2 (4)
N2—C6—N1	120.9 (4)	N5—C12—N7	125.7 (3)
N2—C6—N3	113.2 (3)	N6—C12—N7	112.1 (3)
N1—C6—N3	125.9 (3)	H21—O9—H22	109 (5)
C7—O5—H11	109.5	H23—O10—H24	104 (5)

C6—N3—N4—O4	−172.7 (4)	C12—N7—N8—O8	178.5 (4)
C6—N3—N4—O3	9.7 (6)	C12—N7—N8—O7	0.0 (7)
C6—N1—C2—C1	−156.2 (3)	C12—N5—C8—C7	−162.6 (4)
C6—N1—C2—C3	80.7 (5)	C12—N5—C8—C9	73.8 (5)
O2—C1—C2—N1	−3.2 (5)	O6—C7—C8—N5	4.4 (6)
O1—C1—C2—N1	178.4 (3)	O5—C7—C8—N5	−176.7 (3)
O2—C1—C2—C3	120.1 (4)	O6—C7—C8—C9	128.7 (5)
O1—C1—C2—C3	−58.3 (5)	O5—C7—C8—C9	−52.4 (5)
N1—C2—C3—C4	−44.5 (6)	N5—C8—C9—C10	−45.9 (5)
C1—C2—C3—C4	−164.7 (4)	C7—C8—C9—C10	−166.7 (4)
C2—C3—C4—C5	−39.4 (7)	C8—C9—C10—C11	−32.6 (7)
C6—N2—C5—C4	−20.4 (7)	C9—C10—C11—N6	73.8 (8)
C3—C4—C5—N2	77.0 (6)	C12—N6—C11—C10	−26.1 (9)
C5—N2—C6—N1	−22.8 (7)	C8—N5—C12—N6	−16.8 (7)
C5—N2—C6—N3	159.5 (4)	C8—N5—C12—N7	164.7 (4)
C2—N1—C6—N2	−19.6 (6)	C11—N6—C12—N5	−18.4 (8)
C2—N1—C6—N3	157.9 (4)	C11—N6—C12—N7	160.3 (5)
N4—N3—C6—N2	176.6 (3)	N8—N7—C12—N5	−10.4 (6)
N4—N3—C6—N1	−1.0 (6)	N8—N7—C12—N6	170.9 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N3ⁱ	0.82	1.90	2.716 (4)	173
N1—H3···O3	0.86	2.02	2.586 (4)	123
N2—H10···O2ⁱⁱ	0.86	2.05	2.889 (4)	163
O5—H11···O9ⁱⁱⁱ	0.82	1.69	2.510 (5)	174
N5—H13···O7	0.86	2.04	2.584 (5)	121
N6—H20···O6^iv	0.86	2.16	2.937 (5)	150
O9—H21···N7	0.83 (4)	2.11 (3)	2.902 (6)	160 (7)
O9—H22···O10	0.84 (4)	1.86 (3)	2.662 (7)	159 (7)
O10—H23···O7^v	0.86 (4)	2.04 (4)	2.869 (6)	163 (6)
O10—H24···O3	0.86 (4)	2.41 (8)	2.856 (6)	113 (5)

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

Experimental details

Crystal data
Chemical formula	C₆H₁₀N₄O₄·H₂O
M_r	220.20
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	9.0115 (18), 14.729 (3), 15.257 (3)
V (Å³)	2025.0 (7)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.22 × 0.17 × 0.12

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	6714, 2512, 1583
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.132, 1.02
No. of reflections	2512
No. of parameters	286
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.27

Computer programs: DATCOL in CAD-4 Manual (Enraf–Nonius, 1988), LS in CAD4 Manual (Enraf–Nonius, 1988), HELENA (Spek, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N3ⁱ	0.82	1.90	2.716 (4)	172.7
N1—H3···O3	0.86	2.02	2.586 (4)	123.0
N2—H10···O2ⁱⁱ	0.86	2.05	2.889 (4)	163.2
O5—H11···O9ⁱⁱⁱ	0.82	1.69	2.510 (5)	173.9
N5—H13···O7	0.86	2.04	2.584 (5)	120.7
N6—H20···O6^iv	0.86	2.16	2.937 (5)	149.6
O9—H21···N7	0.83 (4)	2.11 (3)	2.902 (6)	160 (7)
O9—H22···O10	0.84 (4)	1.86 (3)	2.662 (7)	159 (7)
O10—H23···O7^v	0.86 (4)	2.04 (4)	2.869 (6)	163 (6)
O10—H24···O3	0.86 (4)	2.41 (8)	2.856 (6)	113 (5)

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

Acknowledgements

The author thanks Dr R. A. Apreyan and Dr A. M. Petrosyan for providing the crystals and Dr R. A. Tamazyan for valuable discussion of the results.

References

Apreyan, R. A., Karapetyan, H. A. & Petrosyan, A. M. (2008a). J. Mol. Struct. 874, 187–193. Web of Science CSD CrossRef CAS Google Scholar
Apreyan, R. A., Karapetyan, H. A. & Petrosyan, A. M. (2008b). J. Mol. Struct. 875, 272–281. Web of Science CSD CrossRef CAS Google Scholar
Apreyan, R. A. & Petrosyan, A. M. (2008). In preparation. Google Scholar
Enraf–Nonius (1988). CAD-4 Manual. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Karapetyan, H. A. (2008). Acta Cryst. E64, o943. Web of Science CSD CrossRef IUCr Journals Google Scholar
Karapetyan, H. A., Antipin, M. Yu., Sukiasyan, R. P. & Petrosyan, A. M. (2007). J. Mol. Struct. 831, 90–96. Web of Science CSD CrossRef CAS Google Scholar
Paul, R., Anderson, G. W. & Callahan, F. M. (1961). J. Org. Chem. 26, 3347–3350. CrossRef Web of Science Google Scholar
Petrosyan, A. M., Sukiasyan, R. P., Karapetyan, H. A., Antipin, M. Yu. & Apreyan, R. A. (2005). J. Cryst. Growth, 275, e1927–e1933. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (1997). HELENA. University of Utrecht, The Netherlands. Google Scholar