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

The cyclic form of l-nitro-arginine, C(6)H(10)N(4)O(4), crystallizes with two independent mol-ecules in the asymmetric unit. According to the geometrical parameters, similar in both mol-ecules, the structure corresponds to that of l-2-nitrimino-1,3-diazepane-4-carboxylic acid; there are, however, conformational differences between the independent molecules, one of them being close to a twisted chair while the other might be described as a rather flattened boat. All six active H atoms in the two molecules are involved in hydrogen bonds, two of which are intra-molecular and four inter-molecular, forming an infinite chain of mol-ecules along the b axis.

Related literature

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

Experimental

Crystal data

C6H10N4O4

M = 202.18

Orthorhombic,

a = 6.9787 (14) Å

b = 15.233 (3) Å

c = 16.637 (3) Å

V = 1768.6 (6) Å3

Z = 8

Mo Kα radiation

μ = 0.13 mm−1

T = 293 (2) K

0.20 × 0.17 × 0.14 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: none

13278 measured reflections

2211 independent reflections

1509 reflections with I > 2σ(I)

R int = 0.046

3 standard reflections every 400 reflections intensity decay: none

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.114

S = 1.06

2211 reflections

255 parameters

H-atom parameters constraned

Δρmax = 0.25 e Å−3

Δρmin = −0.21 e Å−3

Data collection: CAD-4 Manual (Enraf–Nonius, 1988 ▶); cell refinement: CAD-4 Manual; 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.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808011835/bg2177sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808011835/bg2177Isup2.hkl

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

C6H10N4O4	F000 = 848
Mr = 202.18	Dx = 1.519 Mg m−3
Orthorhombic, P212121	Mo Kα radiation λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 24 reflections
a = 6.9787 (14) Å	θ = 14–16º
b = 15.233 (3) Å	µ = 0.13 mm−1
c = 16.637 (3) Å	T = 293 (2) K
V = 1768.6 (6) Å3	Block, colourless
Z = 8	0.20 × 0.17 × 0.14 mm

Enraf–Nonius CAD-4 diffractometer	Rint = 0.046
Radiation source: fine-focus sealed tube	θmax = 27.0º
Monochromator: graphite	θmin = 2.5º
T = 293(2) K	h = −7→8
ω/2θ scans	k = −19→19
Absorption correction: none	l = −21→21
13278 measured reflections	3 standard reflections
2211 independent reflections	every 400 reflections
1509 reflections with I > 2σ(I)	intensity decay: none

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)] = 0.041	H-atom parameters constrained
wR(F2) = 0.114	w = 1/[σ2(Fo2) + (0.0543P)2 + 0.5039P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max = 0.001
2211 reflections	Δρmax = 0.25 e Å−3
255 parameters	Δρmin = −0.21 e Å−3
Primary atom site location: structure-invariant direct methods

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	0.7754 (5)	0.88281 (14)	0.60814 (15)	0.0563 (8)
H1	0.7796	0.9337	0.5922	0.085*
O2	0.8669 (4)	0.85314 (15)	0.48298 (16)	0.0472 (7)
O3	0.8340 (4)	0.67954 (15)	0.34868 (15)	0.0530 (8)
O4	0.7646 (6)	0.55602 (18)	0.29427 (15)	0.0723 (10)
O5	0.8340 (6)	0.38278 (15)	0.38570 (16)	0.0659 (10)
H11	0.8210	0.4336	0.4009	0.099*
O6	0.8143 (4)	0.35371 (15)	0.51572 (15)	0.0442 (7)
O7	0.8020 (5)	0.17963 (15)	0.64914 (14)	0.0525 (8)
O8	0.7484 (6)	0.05314 (16)	0.70190 (15)	0.0632 (9)
N1	0.8515 (4)	0.68230 (16)	0.50423 (17)	0.0333 (7)
H3	0.9030	0.7103	0.4649	0.040*
N2	0.8213 (5)	0.54128 (18)	0.55682 (17)	0.0392 (8)
H10	0.7518	0.4952	0.5506	0.047*
N3	0.8130 (5)	0.55431 (18)	0.42317 (17)	0.0384 (8)
N4	0.8015 (5)	0.59993 (18)	0.35350 (18)	0.0426 (8)
N5	0.8587 (4)	0.18391 (17)	0.49647 (17)	0.0366 (7)
H13	0.8600	0.2132	0.5407	0.044*
N6	0.8668 (5)	0.04394 (18)	0.44140 (17)	0.0393 (7)
H20	0.8344	−0.0099	0.4491	0.047*
N7	0.8136 (4)	0.05420 (18)	0.57390 (16)	0.0356 (7)
N8	0.7869 (5)	0.09867 (18)	0.64405 (18)	0.0405 (7)
C1	0.8179 (5)	0.8301 (2)	0.5493 (2)	0.0348 (9)
C2	0.7977 (5)	0.73407 (19)	0.57448 (18)	0.0313 (8)
H2	0.6619	0.7230	0.5854	0.038*
C3	0.9090 (6)	0.7139 (2)	0.6508 (2)	0.0442 (9)
H5	1.0450	0.7133	0.6388	0.053*
H4	0.8857	0.7598	0.6900	0.053*
C4	0.8511 (6)	0.6259 (2)	0.6862 (2)	0.0429 (9)
H6	0.9056	0.6202	0.7396	0.052*
H7	0.7128	0.6236	0.6912	0.052*
C5	0.9179 (6)	0.5504 (2)	0.6348 (2)	0.0428 (9)
H8	1.0542	0.5571	0.6253	0.051*
H9	0.9000	0.4964	0.6649	0.051*
C6	0.8289 (5)	0.5961 (2)	0.4948 (2)	0.0313 (8)
C7	0.8343 (5)	0.3309 (2)	0.4473 (2)	0.0343 (8)
C8	0.8689 (5)	0.2356 (2)	0.42267 (19)	0.0336 (8)
H12	0.9992	0.2310	0.4011	0.040*
C9	0.7300 (6)	0.2026 (2)	0.3592 (2)	0.0455 (9)
H15	0.6101	0.1870	0.3849	0.055*
H14	0.7039	0.2496	0.3214	0.055*
C10	0.8042 (6)	0.1241 (2)	0.3135 (2)	0.0483 (10)
H17	0.6959	0.0893	0.2955	0.058*
H16	0.8716	0.1446	0.2661	0.058*
C11	0.9367 (6)	0.0661 (2)	0.36141 (19)	0.0437 (9)
H19	0.9578	0.0122	0.3317	0.052*
H18	1.0594	0.0955	0.3667	0.052*
C12	0.8479 (5)	0.09769 (19)	0.5036 (2)	0.0306 (8)

	U11	U22	U33	U12	U13	U23
O1	0.107 (2)	0.0200 (12)	0.0418 (15)	−0.0005 (15)	0.0200 (17)	−0.0027 (11)
O2	0.0777 (19)	0.0213 (11)	0.0427 (15)	−0.0003 (12)	0.0161 (14)	0.0023 (11)
O3	0.093 (2)	0.0271 (13)	0.0389 (15)	0.0039 (13)	0.0023 (15)	0.0058 (12)
O4	0.137 (3)	0.0472 (18)	0.0325 (15)	−0.009 (2)	−0.009 (2)	−0.0075 (14)
O5	0.137 (3)	0.0214 (13)	0.0387 (15)	0.0028 (16)	0.0074 (17)	0.0042 (11)
O6	0.0735 (18)	0.0234 (12)	0.0357 (13)	0.0021 (12)	0.0036 (13)	−0.0026 (11)
O7	0.096 (2)	0.0264 (12)	0.0353 (14)	−0.0023 (14)	0.0031 (15)	−0.0035 (12)
O8	0.115 (3)	0.0393 (15)	0.0347 (15)	−0.0006 (19)	0.0091 (18)	0.0087 (13)
N1	0.0498 (18)	0.0193 (13)	0.0307 (16)	−0.0017 (13)	0.0056 (14)	0.0026 (13)
N2	0.064 (2)	0.0215 (13)	0.0319 (15)	−0.0086 (13)	0.0034 (15)	0.0008 (13)
N3	0.062 (2)	0.0205 (14)	0.0325 (16)	−0.0005 (14)	0.0049 (15)	−0.0004 (13)
N4	0.067 (2)	0.0277 (14)	0.0334 (17)	0.0067 (15)	−0.0013 (17)	−0.0016 (15)
N5	0.063 (2)	0.0188 (13)	0.0278 (16)	−0.0042 (14)	0.0032 (15)	0.0005 (13)
N6	0.064 (2)	0.0198 (13)	0.0339 (16)	0.0009 (14)	0.0020 (15)	−0.0001 (13)
N7	0.0563 (19)	0.0212 (14)	0.0294 (15)	−0.0001 (13)	0.0012 (15)	−0.0011 (12)
N8	0.063 (2)	0.0258 (14)	0.0332 (17)	−0.0007 (14)	0.0005 (17)	0.0020 (14)
C1	0.042 (2)	0.0233 (18)	0.039 (2)	−0.0016 (14)	0.0035 (17)	−0.0020 (17)
C2	0.0437 (19)	0.0193 (14)	0.0310 (17)	−0.0004 (14)	0.0016 (16)	−0.0015 (13)
C3	0.063 (2)	0.0331 (16)	0.0363 (18)	−0.0035 (17)	−0.0063 (19)	−0.0031 (14)
C4	0.067 (2)	0.0336 (18)	0.0278 (18)	0.0030 (17)	−0.0058 (17)	0.0015 (15)
C5	0.061 (2)	0.0317 (17)	0.036 (2)	0.0055 (18)	−0.0003 (19)	0.0027 (15)
C6	0.037 (2)	0.0225 (16)	0.0344 (19)	−0.0017 (13)	0.0061 (15)	0.0002 (15)
C7	0.050 (2)	0.0197 (17)	0.0335 (19)	−0.0037 (14)	−0.0001 (16)	0.0014 (15)
C8	0.046 (2)	0.0205 (14)	0.0345 (18)	0.0019 (14)	0.0019 (16)	0.0002 (13)
C9	0.061 (2)	0.0350 (17)	0.0401 (19)	0.0117 (17)	−0.0133 (19)	−0.0061 (15)
C10	0.078 (3)	0.0290 (18)	0.038 (2)	0.0057 (18)	−0.006 (2)	−0.0030 (16)
C11	0.069 (3)	0.0296 (17)	0.0326 (19)	0.0080 (17)	0.0094 (19)	−0.0046 (15)
C12	0.041 (2)	0.0198 (15)	0.0309 (18)	0.0005 (13)	−0.0014 (15)	0.0023 (14)

O1—C1	1.300 (4)	N7—N8	1.362 (4)
O1—H1	0.8200	N7—C12	1.365 (4)
O2—C1	1.207 (4)	C1—C2	1.528 (4)
O3—N4	1.236 (3)	C2—C3	1.519 (4)
O4—N4	1.219 (4)	C2—H2	0.9800
O5—C7	1.294 (4)	C3—C4	1.519 (5)
O5—H11	0.8200	C3—H5	0.9700
O6—C7	1.199 (4)	C3—H4	0.9700
O7—N8	1.241 (3)	C4—C5	1.507 (5)
O8—N8	1.216 (3)	C4—H6	0.9700
N1—C6	1.332 (4)	C4—H7	0.9700
N1—C2	1.459 (4)	C5—H8	0.9700
N1—H3	0.8600	C5—H9	0.9700
N2—C6	1.328 (4)	C7—C8	1.527 (4)
N2—C5	1.469 (4)	C8—C9	1.520 (5)
N2—H10	0.8600	C8—H12	0.9800
N3—N4	1.354 (4)	C9—C10	1.508 (5)
N3—C6	1.356 (4)	C9—H15	0.9700
N5—C12	1.321 (4)	C9—H14	0.9700
N5—C8	1.460 (4)	C10—C11	1.506 (5)
N5—H13	0.8600	C10—H17	0.9700
N6—C12	1.327 (4)	C10—H16	0.9700
N6—C11	1.457 (4)	C11—H19	0.9700
N6—H20	0.8600	C11—H18	0.9700
C1—O1—H1	109.5	C3—C4—H7	109.2
C7—O5—H11	109.5	H6—C4—H7	107.9
C6—N1—C2	126.6 (3)	N2—C5—C4	115.5 (3)
C6—N1—H3	116.7	N2—C5—H8	108.4
C2—N1—H3	116.7	C4—C5—H8	108.4
C6—N2—C5	127.5 (3)	N2—C5—H9	108.4
C6—N2—H10	116.3	C4—C5—H9	108.4
C5—N2—H10	116.3	H8—C5—H9	107.5
N4—N3—C6	121.1 (3)	N2—C6—N1	122.2 (3)
O4—N4—O3	121.6 (3)	N2—C6—N3	112.6 (3)
O4—N4—N3	115.0 (3)	N1—C6—N3	125.2 (3)
O3—N4—N3	123.2 (3)	O6—C7—O5	125.1 (3)
C12—N5—C8	127.9 (3)	O6—C7—C8	123.3 (3)
C12—N5—H13	116.0	O5—C7—C8	111.6 (3)
C8—N5—H13	116.0	N5—C8—C9	112.0 (3)
C12—N6—C11	127.1 (3)	N5—C8—C7	106.2 (3)
C12—N6—H20	116.5	C9—C8—C7	113.6 (3)
C11—N6—H20	116.5	N5—C8—H12	108.3
N8—N7—C12	121.1 (3)	C9—C8—H12	108.3
O8—N8—O7	122.1 (3)	C7—C8—H12	108.3
O8—N8—N7	115.1 (3)	C10—C9—C8	113.2 (3)
O7—N8—N7	122.8 (3)	C10—C9—H15	108.9
O2—C1—O1	125.0 (3)	C8—C9—H15	108.9
O2—C1—C2	123.7 (3)	C10—C9—H14	108.9
O1—C1—C2	111.4 (3)	C8—C9—H14	108.9
N1—C2—C3	115.4 (3)	H15—C9—H14	107.8
N1—C2—C1	105.9 (3)	C11—C10—C9	114.1 (3)
C3—C2—C1	112.0 (3)	C11—C10—H17	108.7
N1—C2—H2	107.7	C9—C10—H17	108.7
C3—C2—H2	107.7	C11—C10—H16	108.7
C1—C2—H2	107.7	C9—C10—H16	108.7
C4—C3—C2	111.5 (3)	H17—C10—H16	107.6
C4—C3—H5	109.3	N6—C11—C10	114.5 (3)
C2—C3—H5	109.3	N6—C11—H19	108.6
C4—C3—H4	109.3	C10—C11—H19	108.6
C2—C3—H4	109.3	N6—C11—H18	108.6
H5—C3—H4	108.0	C10—C11—H18	108.6
C5—C4—C3	111.9 (3)	H19—C11—H18	107.6
C5—C4—H6	109.2	N5—C12—N6	122.5 (3)
C3—C4—H6	109.2	N5—C12—N7	124.8 (3)
C5—C4—H7	109.2	N6—C12—N7	112.7 (3)
C6—N3—N4—O4	−171.5 (4)	N4—N3—C6—N2	174.4 (3)
C6—N3—N4—O3	11.6 (6)	N4—N3—C6—N1	−6.2 (5)
C12—N7—N8—O8	176.6 (4)	C12—N5—C8—C9	43.1 (5)
C12—N7—N8—O7	−3.9 (6)	C12—N5—C8—C7	167.7 (4)
C6—N1—C2—C3	65.9 (5)	O6—C7—C8—N5	3.5 (5)
C6—N1—C2—C1	−169.6 (3)	O5—C7—C8—N5	−177.9 (3)
O2—C1—C2—N1	0.9 (5)	O6—C7—C8—C9	127.1 (4)
O1—C1—C2—N1	−179.2 (3)	O5—C7—C8—C9	−54.3 (4)
O2—C1—C2—C3	127.5 (4)	N5—C8—C9—C10	−80.9 (4)
O1—C1—C2—C3	−52.6 (4)	C7—C8—C9—C10	158.7 (3)
N1—C2—C3—C4	−72.3 (4)	C8—C9—C10—C11	30.0 (5)
C1—C2—C3—C4	166.4 (3)	C12—N6—C11—C10	−69.0 (5)
C2—C3—C4—C5	69.8 (4)	C9—C10—C11—N6	47.6 (5)
C6—N2—C5—C4	66.1 (5)	C8—N5—C12—N6	8.0 (6)
C3—C4—C5—N2	−69.2 (4)	C8—N5—C12—N7	−171.0 (3)
C5—N2—C6—N1	−30.9 (6)	C11—N6—C12—N5	12.6 (6)
C5—N2—C6—N3	148.5 (3)	C11—N6—C12—N7	−168.3 (3)
C2—N1—C6—N2	−25.9 (5)	N8—N7—C12—N5	0.1 (5)
C2—N1—C6—N3	154.8 (3)	N8—N7—C12—N6	−178.9 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H10···O6i	0.86	2.27	2.938 (4)	134
N6—H20···O2i	0.86	2.17	2.988 (4)	158
N1—H3···O2i	0.86	2.21	2.629 (3)	110
N1—H3···O3i	0.86	2.05	2.591 (4)	121
N5—H13···O6i	0.86	2.20	2.625 (4)	110
N5—H13···O7i	0.86	1.92	2.571 (4)	132
O5—H11···N3i	0.82	1.88	2.690 (4)	172
O5—H11···O4i	0.82	2.60	3.084 (4)	119
O1—H1···N7i	0.82	1.88	2.685 (3)	169
O1—H1···O8i	0.82	2.59	3.033 (3)	116

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H10⋯O6	0.86	2.27	2.938 (4)	134
N6—H20⋯O2i	0.86	2.17	2.988 (4)	158
N1—H3⋯O3	0.86	2.05	2.591 (4)	121
N5—H13⋯O7	0.86	1.92	2.571 (4)	132
O5—H11⋯N3	0.82	1.88	2.690 (4)	172
O1—H1⋯N7ii	0.82	1.88	2.685 (3)	169

Symmetry codes: (i) ; (ii) .