X-ray studies on crystalline complexes involving amino acids and peptides. XLII. Adipic acid complexes of l- and dl-arginine and supramolecular association in arginine–dicarboxylic acid complexes

Roy, S.; Singh, D.D.; Vijayan, M.

doi:10.1107/S0108768104030010

X-ray studies on crystalline complexes involving amino acids and peptides. XLII. Adipic acid complexes of L- and DL-arginine and supramolecular association in arginine-dicarboxylic acid complexes

The adipic acid complexes of DL-arginine and L-arginine are made up of zwitterionic, singularly positively charged arginium ions and doubly negatively charged adipate ions, with a 2:1 stoichiometry. One of the two crystallographically independent arginium ions in the L-arginine complex has a conformation hitherto unobserved in crystal structures containing the amino acid. In the present study the structural data on arginine complexes of saturated dicarboxylic acids with 0-5 C atoms separating the two carboxyl functions are given. In terms of molecular aggregation, formic and acetic acid complexes behave in a similar way to those involving fairly long carboxylic acids such as adipic acid. By and large, the supramolecular assembly in complexes involving dicarboxylic acids with 3 or more C atoms separating the carboxyl groups (glutaric, adipic and pimelic acids), and those involving formic and acetic acids, have common features. The aggregation patterns in complexes involving oxalic, malonic and maleic acids do not share striking features among themselves (except for the mode of hydrogen-bonded dimerization of arginium ions) or with those involving larger dicarboxylic acids. Complexes of succinic acid, the shortest linear dicarboxylic acid, share features with those involving shorter as well as longer dicarboxylic acids. The difference in the behaviour of long and short dicarboxylic acids and the ambiguous behaviour of succinic acid can be broadly related to their lengths.

Keywords: amino acids; peptides; supramolecular association.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768104030010/de5013sup1.cif Contains datablocks global, dlarad_m, larad_m
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768104030010/de5013dlarad_msup2.fcf Contains datablock dl_arg
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768104030010/de5013larad_msup3.fcf Contains datablock largadi

CCDC references: 263171; 263172

Computing details top

For both compounds, data collection: Bruker SMART; cell refinement: Bruker SMART; data reduction: Bruker SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3; software used to prepare material for publication: PLATON (Spek, 1990).

Figures top

View of the title compound with the atom numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level.

(dlarad_m) top

Crystal data top

C₆H₁₅N₄O₂·0.5(C₆H₈O₄)·H₂O	F(000) = 572
M_r = 265.30	D_x = 1.376 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2581 reflections
a = 13.825 (4) Å	θ = 1.5–26.4°
b = 5.0531 (16) Å	µ = 0.11 mm⁻¹
c = 18.804 (6) Å	T = 298 K
β = 102.900 (6)°	Plate, colourless
V = 1280.5 (7) Å³	0.59 × 0.11 × 0.02 mm
Z = 4

Data collection top

Bruker SMART CCD area detector diffractometer	2581 independent reflections
Radiation source: fine-focus sealed tube	2150 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
phi and ω scans	θ_max = 26.4°, θ_min = 1.5°
Absorption correction: multi-scan SADABS,Sheldrick, 1997	h = −15→16
T_min = 0.937, T_max = 0.998	k = −6→6
9412 measured reflections	l = −23→23

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)] = 0.054	All H-atom parameters refined
wR(F²) = 0.128	w = 1/[σ²(F_o²) + (0.0354P)² + 0.8605P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
2581 reflections	Δρ_max = 0.28 e Å⁻³
247 parameters	Δρ_min = −0.17 e Å⁻³
0 restraints	Absolute structure: Flack H.D. (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: centrosymmetric

Crystal data top

C₆H₁₅N₄O₂·0.5(C₆H₈O₄)·H₂O	V = 1280.5 (7) Å³
M_r = 265.30	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.825 (4) Å	µ = 0.11 mm⁻¹
b = 5.0531 (16) Å	T = 298 K
c = 18.804 (6) Å	0.59 × 0.11 × 0.02 mm
β = 102.900 (6)°

Data collection top

Bruker SMART CCD area detector diffractometer	2581 independent reflections
Absorption correction: multi-scan SADABS,Sheldrick, 1997	2150 reflections with I > 2σ(I)
T_min = 0.937, T_max = 0.998	R_int = 0.031
9412 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	All H-atom parameters refined
wR(F²) = 0.128	Δρ_max = 0.28 e Å⁻³
S = 1.05	Δρ_min = −0.17 e Å⁻³
2581 reflections	Absolute structure: Flack H.D. (1983), Acta Cryst. A39, 876-881
247 parameters	Absolute structure parameter: centrosymmetric
0 restraints

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
N1	0.62752 (14)	0.6252 (4)	0.51182 (10)	0.0281 (4)
O2	0.53502 (11)	1.2185 (3)	0.41877 (8)	0.0346 (4)
O1	0.47059 (11)	0.8150 (3)	0.41053 (10)	0.0468 (5)
C1	0.53967 (15)	0.9713 (4)	0.42921 (10)	0.0253 (4)
C2	0.64106 (14)	0.8607 (4)	0.46758 (10)	0.0243 (4)
C3	0.69967 (16)	0.7768 (4)	0.41130 (11)	0.0278 (5)
C4	0.73618 (17)	1.0090 (4)	0.37272 (12)	0.0300 (5)
C5	0.80091 (17)	0.9200 (5)	0.32166 (12)	0.0322 (5)
N6	0.74420 (14)	0.7534 (4)	0.26397 (10)	0.0345 (5)
C7	0.78389 (15)	0.5899 (4)	0.22320 (11)	0.0298 (5)
N8	0.87995 (14)	0.5456 (4)	0.23660 (12)	0.0350 (5)
N9	0.72569 (17)	0.4649 (5)	0.16773 (12)	0.0453 (6)
O11	0.95427 (11)	0.1802 (3)	0.14957 (8)	0.0365 (4)
O12	0.80437 (11)	0.0837 (4)	0.08604 (10)	0.0509 (5)
C13	0.89578 (15)	0.0407 (4)	0.10453 (11)	0.0294 (5)
C14	0.93856 (18)	−0.1875 (5)	0.06947 (13)	0.0348 (5)
C15	1.01776 (18)	−0.1011 (5)	0.02977 (13)	0.0365 (5)
O16	0.53048 (13)	0.8619 (4)	0.22510 (11)	0.0437 (4)
H1A	0.689 (2)	0.569 (5)	0.5375 (14)	0.042 (7)*
H1B	0.584 (2)	0.671 (5)	0.5432 (14)	0.045 (7)*
H1C	0.5970 (17)	0.484 (5)	0.4806 (13)	0.035 (6)*
H2	0.6770 (15)	0.995 (4)	0.5028 (12)	0.025 (5)*
H3A	0.6547 (18)	0.658 (5)	0.3759 (13)	0.038 (6)*
H3B	0.7588 (18)	0.669 (4)	0.4382 (12)	0.034 (6)*
H4A	0.6783 (18)	1.109 (5)	0.3454 (12)	0.035 (6)*
H4B	0.7750 (19)	1.122 (5)	0.4091 (14)	0.045 (7)*
H5A	0.8568 (17)	0.816 (4)	0.3486 (12)	0.029 (6)*
H5B	0.8256 (18)	1.084 (5)	0.2994 (13)	0.039 (6)*
H6	0.683 (2)	0.782 (5)	0.2507 (13)	0.042 (7)*
H8A	0.9202 (19)	0.606 (5)	0.2703 (14)	0.037 (7)*
H8B	0.905 (2)	0.431 (5)	0.2078 (15)	0.050 (8)*
H9A	0.751 (2)	0.346 (6)	0.1439 (15)	0.048 (8)*
H9B	0.662 (2)	0.471 (5)	0.1588 (14)	0.048 (8)*
H14A	0.964 (2)	−0.308 (5)	0.1058 (15)	0.048 (7)*
H14B	0.8877 (18)	−0.285 (5)	0.0373 (13)	0.037 (6)*
H15A	1.0758 (19)	−0.026 (5)	0.0637 (14)	0.044 (7)*
H15B	1.0446 (18)	−0.262 (5)	0.0072 (13)	0.047 (7)*
H16A	0.518 (2)	1.015 (7)	0.2352 (18)	0.066 (11)*
H16B	0.510 (3)	0.847 (7)	0.182 (2)	0.076 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0232 (9)	0.0310 (10)	0.0292 (9)	0.0050 (8)	0.0041 (8)	0.0046 (8)
O2	0.0404 (9)	0.0259 (8)	0.0358 (8)	0.0079 (6)	0.0047 (7)	0.0019 (6)
O1	0.0246 (8)	0.0395 (9)	0.0678 (12)	−0.0008 (7)	−0.0076 (8)	0.0086 (8)
C1	0.0249 (11)	0.0302 (11)	0.0221 (9)	0.0055 (8)	0.0081 (8)	0.0010 (8)
C2	0.0214 (10)	0.0266 (10)	0.0236 (9)	0.0017 (8)	0.0027 (8)	0.0008 (8)
C3	0.0254 (11)	0.0302 (11)	0.0286 (10)	0.0036 (9)	0.0076 (9)	−0.0006 (9)
C4	0.0269 (11)	0.0319 (11)	0.0320 (11)	−0.0011 (9)	0.0086 (9)	−0.0040 (9)
C5	0.0305 (12)	0.0360 (12)	0.0315 (11)	−0.0036 (10)	0.0099 (9)	−0.0023 (10)
N6	0.0206 (10)	0.0516 (12)	0.0308 (10)	0.0055 (8)	0.0046 (8)	−0.0073 (8)
C7	0.0253 (11)	0.0396 (12)	0.0244 (10)	0.0004 (9)	0.0052 (8)	0.0013 (9)
N8	0.0208 (10)	0.0496 (12)	0.0336 (10)	0.0019 (8)	0.0036 (8)	−0.0135 (9)
N9	0.0248 (11)	0.0663 (15)	0.0419 (12)	0.0023 (10)	0.0012 (9)	−0.0222 (11)
O11	0.0254 (8)	0.0448 (9)	0.0359 (8)	0.0019 (7)	−0.0005 (6)	−0.0107 (7)
O12	0.0220 (9)	0.0632 (12)	0.0631 (12)	0.0012 (8)	−0.0002 (8)	−0.0308 (9)
C13	0.0258 (11)	0.0348 (11)	0.0282 (10)	−0.0008 (9)	0.0074 (9)	−0.0004 (9)
C14	0.0378 (13)	0.0293 (11)	0.0378 (12)	0.0006 (10)	0.0097 (10)	−0.0015 (10)
C15	0.0368 (13)	0.0346 (12)	0.0405 (13)	0.0063 (10)	0.0134 (11)	−0.0041 (10)
O16	0.0426 (10)	0.0497 (12)	0.0347 (10)	0.0037 (8)	−0.0001 (8)	−0.0018 (8)

Geometric parameters (Å, º) top

N1—C2	1.487 (3)	N6—H6	0.83 (3)
N1—H1A	0.92 (3)	C7—N8	1.315 (3)
N1—H1B	0.96 (3)	C7—N9	1.326 (3)
N1—H1C	0.96 (3)	N8—H8A	0.81 (3)
O2—C1	1.264 (2)	N8—H8B	0.91 (3)
O1—C1	1.229 (3)	N9—H9A	0.87 (3)
C1—C2	1.532 (3)	N9—H9B	0.87 (3)
C2—C3	1.529 (3)	O11—C13	1.250 (3)
C2—H2	1.00 (2)	O12—C13	1.253 (3)
C3—C4	1.524 (3)	C13—C14	1.513 (3)
C3—H3A	1.00 (2)	C14—C15	1.521 (3)
C3—H3B	1.02 (2)	C14—H14A	0.92 (3)
C4—C5	1.519 (3)	C14—H14B	0.96 (2)
C4—H4A	0.99 (2)	C15—C15ⁱ	1.514 (5)
C4—H4B	0.96 (3)	C15—H15A	0.98 (3)
C5—N6	1.456 (3)	C15—H15B	1.02 (3)
C5—H5A	0.98 (2)	O16—H16A	0.83 (3)
C5—H5B	1.02 (3)	O16—H16B	0.81 (4)
N6—C7	1.326 (3)

C2—N1—H1A	108.8 (16)	C4—C5—H5B	108.4 (13)
C2—N1—H1B	108.9 (15)	H5A—C5—H5B	110.5 (19)
H1A—N1—H1B	113 (2)	C7—N6—C5	124.57 (19)
C2—N1—H1C	110.2 (14)	C7—N6—H6	117.0 (18)
H1A—N1—H1C	109 (2)	C5—N6—H6	117.5 (18)
H1B—N1—H1C	108 (2)	N8—C7—N6	121.7 (2)
O1—C1—O2	125.56 (19)	N8—C7—N9	118.6 (2)
O1—C1—C2	118.12 (18)	N6—C7—N9	119.6 (2)
O2—C1—C2	116.31 (18)	C7—N8—H8A	125.2 (18)
N1—C2—C3	108.51 (16)	C7—N8—H8B	119.7 (17)
N1—C2—C1	109.83 (16)	H8A—N8—H8B	115 (2)
C3—C2—C1	110.22 (16)	C7—N9—H9A	119.3 (18)
N1—C2—H2	106.3 (12)	C7—N9—H9B	123.3 (18)
C3—C2—H2	112.6 (12)	H9A—N9—H9B	116 (3)
C1—C2—H2	109.3 (12)	O11—C13—O12	123.4 (2)
C4—C3—C2	113.52 (17)	O11—C13—C14	117.94 (19)
C4—C3—H3A	111.5 (13)	O12—C13—C14	118.7 (2)
C2—C3—H3A	106.2 (14)	C13—C14—C15	112.90 (19)
C4—C3—H3B	109.6 (13)	C13—C14—H14A	107.5 (16)
C2—C3—H3B	107.1 (13)	C15—C14—H14A	111.0 (17)
H3A—C3—H3B	108.7 (18)	C13—C14—H14B	111.4 (14)
C5—C4—C3	112.16 (18)	C15—C14—H14B	110.2 (14)
C5—C4—H4A	110.3 (13)	H14A—C14—H14B	103 (2)
C3—C4—H4A	109.0 (13)	C15ⁱ—C15—C14	114.0 (2)
C5—C4—H4B	108.3 (15)	C15ⁱ—C15—H15A	107.6 (15)
C3—C4—H4B	108.1 (15)	C14—C15—H15A	111.4 (15)
H4A—C4—H4B	109 (2)	C15ⁱ—C15—H15B	108.5 (14)
N6—C5—C4	110.30 (18)	C14—C15—H15B	110.0 (14)
N6—C5—H5A	108.0 (13)	H15A—C15—H15B	105 (2)
C4—C5—H5A	109.9 (13)	H16A—O16—H16B	106 (3)
N6—C5—H5B	109.8 (13)

Symmetry code: (i) −x+2, −y, −z.

(larad_m) top

Crystal data top

2(C₆H₁₅N₄O₂)·C₆H₈O₄	F(000) = 532
M_r = 494.56	D_x = 1.374 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 3711 reflections
a = 12.494 (4) Å	θ = 1.3–24.7°
b = 5.9510 (17) Å	µ = 0.11 mm⁻¹
c = 16.719 (5) Å	T = 298 K
β = 105.977 (5)°	Platy, colourless
V = 1195.1 (6) Å³	0.25 × 0.07 × 0.06 mm
Z = 2

Data collection top

Bruker SMART CCD area detector diffractometer	3711 independent reflections
Radiation source: fine-focus sealed tube	3396 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
phi and ω scans	θ_max = 24.7°, θ_min = 1.3°
Absorption correction: multi-scan Sheldrick, 1999	h = −14→14
T_min = 0.973, T_max = 0.994	k = −6→6
6142 measured reflections	l = −19→18

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)] = 0.039	All H-atom parameters refined
wR(F²) = 0.113	w = 1/[σ²(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
S = 0.86	(Δ/σ)_max = 0.012
3711 reflections	Δρ_max = 0.17 e Å⁻³
459 parameters	Δρ_min = −0.17 e Å⁻³
1 restraint	Absolute structure: Flack H.D. (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.1 (11)

Crystal data top

2(C₆H₁₅N₄O₂)·C₆H₈O₄	V = 1195.1 (6) Å³
M_r = 494.56	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 12.494 (4) Å	µ = 0.11 mm⁻¹
b = 5.9510 (17) Å	T = 298 K
c = 16.719 (5) Å	0.25 × 0.07 × 0.06 mm
β = 105.977 (5)°

Data collection top

Bruker SMART CCD area detector diffractometer	3711 independent reflections
Absorption correction: multi-scan Sheldrick, 1999	3396 reflections with I > 2σ(I)
T_min = 0.973, T_max = 0.994	R_int = 0.019
6142 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	All H-atom parameters refined
wR(F²) = 0.113	Δρ_max = 0.17 e Å⁻³
S = 0.86	Δρ_min = −0.17 e Å⁻³
3711 reflections	Absolute structure: Flack H.D. (1983), Acta Cryst. A39, 876-881
459 parameters	Absolute structure parameter: −0.1 (11)
1 restraint

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	1.01548 (17)	0.9154 (4)	0.88174 (12)	0.0240 (4)
O1	0.96221 (14)	0.5244 (3)	0.95135 (9)	0.0366 (4)
O2	0.96334 (19)	0.3583 (3)	0.83320 (12)	0.0566 (6)
C1	0.95512 (17)	0.5228 (4)	0.87500 (13)	0.0252 (5)
C2	0.93201 (17)	0.7539 (4)	0.83210 (13)	0.0233 (5)
H2	0.8586	0.8030	0.8357	0.028*
C3	0.92912 (17)	0.7552 (4)	0.74139 (12)	0.0271 (5)
H3A	0.8882	0.6244	0.7147	0.033*
H3B	1.0047	0.7426	0.7369	0.033*
C4	0.87581 (19)	0.9652 (5)	0.69515 (12)	0.0302 (6)
H4A	0.8060	0.9940	0.7080	0.036*
H4B	0.9244	1.0928	0.7146	0.036*
C5	0.85417 (19)	0.9446 (5)	0.60204 (13)	0.0309 (5)
H5A	0.8275	1.0874	0.5762	0.037*
H5B	0.9233	0.9092	0.5891	0.037*
N6	0.77239 (15)	0.7705 (4)	0.56788 (11)	0.0296 (5)
C7	0.78677 (18)	0.5905 (4)	0.52479 (13)	0.0271 (5)
N8	0.88506 (17)	0.5337 (5)	0.51713 (15)	0.0428 (6)
N9	0.69899 (17)	0.4645 (4)	0.48849 (14)	0.0385 (6)
N11	0.47199 (16)	0.3474 (4)	0.62115 (13)	0.0278 (5)
O11	0.53182 (13)	0.7147 (3)	0.55435 (10)	0.0370 (5)
O12	0.5459 (2)	0.9183 (3)	0.66813 (13)	0.0640 (7)
C11	0.53475 (19)	0.7406 (4)	0.62924 (15)	0.0304 (6)
C12	0.52925 (17)	0.5288 (4)	0.67927 (13)	0.0249 (5)
H12	0.4847	0.5617	0.7178	0.030*
C13	0.64495 (17)	0.4533 (4)	0.73018 (13)	0.0300 (5)
H13A	0.6822	0.3834	0.6928	0.036*
H13B	0.6875	0.5857	0.7535	0.036*
C14	0.6474 (2)	0.2896 (5)	0.80096 (13)	0.0345 (6)
H14A	0.5934	0.1715	0.7802	0.041*
H14B	0.7204	0.2203	0.8185	0.041*
C15	0.6223 (2)	0.3985 (5)	0.87609 (14)	0.0362 (6)
H15A	0.5539	0.4845	0.8583	0.043*
H15B	0.6120	0.2830	0.9142	0.043*
N16	0.71339 (17)	0.5462 (4)	0.91837 (12)	0.0338 (5)
C17	0.70469 (19)	0.7180 (5)	0.96698 (14)	0.0313 (6)
N18	0.60849 (18)	0.7865 (5)	0.97442 (16)	0.0460 (7)
N19	0.79692 (18)	0.8235 (5)	1.00812 (14)	0.0436 (6)
O21	0.21705 (13)	−0.2818 (3)	0.89309 (11)	0.0462 (5)
O22	0.39213 (14)	−0.3812 (4)	0.91304 (12)	0.0506 (6)
C23	0.31072 (19)	−0.2600 (5)	0.87990 (14)	0.0330 (6)
C24	0.3284 (2)	−0.0812 (6)	0.82081 (16)	0.0458 (7)
H24A	0.3886	0.0152	0.8511	0.055*
H24B	0.3534	−0.1548	0.7774	0.055*
C25	0.2318 (2)	0.0652 (5)	0.77992 (15)	0.0371 (6)
H25A	0.2083	0.1466	0.8224	0.045*
H25B	0.1702	−0.0288	0.7502	0.045*
C26	0.25825 (19)	0.2315 (5)	0.71983 (15)	0.0372 (6)
H26A	0.3203	0.3244	0.7495	0.045*
H26B	0.2813	0.1497	0.6772	0.045*
C27	0.1621 (2)	0.3808 (5)	0.67872 (16)	0.0400 (7)
H27A	0.1376	0.4559	0.7221	0.048*
H27B	0.1013	0.2860	0.6483	0.048*
C28	0.18174 (18)	0.5578 (5)	0.61971 (13)	0.0301 (6)
O29	0.27334 (13)	0.5652 (3)	0.60343 (10)	0.0388 (5)
O30	0.10253 (13)	0.6905 (3)	0.58914 (11)	0.0420 (5)
H1A	1.088 (2)	0.877 (4)	0.8829 (14)	0.036 (7)*
H1B	0.999 (2)	1.052 (5)	0.8635 (15)	0.026 (6)*
H1C	1.0151 (19)	0.908 (5)	0.9380 (15)	0.041 (7)*
H6A	0.702 (2)	0.810 (5)	0.5692 (14)	0.037 (7)*
H8A	0.8889 (17)	0.419 (5)	0.4860 (14)	0.023 (6)*
H8B	0.953 (2)	0.613 (6)	0.5431 (17)	0.065 (10)*
H9A	0.630 (2)	0.480 (5)	0.4972 (15)	0.050 (8)*
H9B	0.709 (2)	0.339 (6)	0.4639 (18)	0.058 (10)*
H11A	0.494 (2)	0.174 (6)	0.6427 (17)	0.051 (8)*
H11B	0.398 (2)	0.369 (4)	0.6104 (14)	0.034 (7)*
H11C	0.4946 (19)	0.360 (5)	0.5700 (16)	0.040 (7)*
H16A	0.7788 (19)	0.506 (5)	0.9261 (13)	0.029 (7)*
H18A	0.549 (2)	0.727 (5)	0.9525 (14)	0.028 (7)*
H18B	0.603 (2)	0.898 (6)	1.0223 (18)	0.072 (10)*
H19A	0.794 (2)	0.930 (6)	1.0417 (16)	0.042 (8)*
H19B	0.8621 (19)	0.784 (5)	1.0010 (13)	0.035 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0338 (11)	0.0160 (12)	0.0211 (10)	−0.0006 (9)	0.0058 (8)	0.0020 (8)
O1	0.0515 (10)	0.0331 (11)	0.0272 (8)	0.0077 (8)	0.0145 (7)	0.0094 (8)
O2	0.1109 (17)	0.0189 (11)	0.0342 (11)	0.0077 (11)	0.0104 (11)	−0.0028 (9)
C1	0.0250 (11)	0.0223 (14)	0.0268 (12)	−0.0021 (10)	0.0046 (9)	0.0008 (11)
C2	0.0244 (11)	0.0218 (13)	0.0227 (11)	0.0036 (9)	0.0049 (9)	−0.0012 (10)
C3	0.0307 (11)	0.0251 (13)	0.0246 (11)	0.0011 (10)	0.0061 (9)	−0.0027 (10)
C4	0.0419 (13)	0.0213 (14)	0.0256 (11)	0.0020 (11)	0.0063 (10)	−0.0017 (11)
C5	0.0430 (13)	0.0223 (13)	0.0245 (11)	−0.0012 (11)	0.0046 (10)	0.0015 (11)
N6	0.0307 (10)	0.0324 (13)	0.0250 (10)	0.0011 (9)	0.0066 (8)	−0.0036 (9)
C7	0.0296 (12)	0.0266 (15)	0.0221 (11)	0.0008 (10)	0.0022 (9)	0.0022 (11)
N8	0.0298 (12)	0.0434 (16)	0.0550 (14)	−0.0037 (11)	0.0113 (10)	−0.0242 (13)
N9	0.0291 (11)	0.0383 (15)	0.0462 (13)	−0.0027 (10)	0.0072 (10)	−0.0164 (12)
N11	0.0279 (11)	0.0238 (12)	0.0308 (11)	−0.0017 (9)	0.0066 (9)	−0.0003 (9)
O11	0.0426 (10)	0.0335 (11)	0.0387 (10)	0.0017 (8)	0.0174 (8)	0.0071 (9)
O12	0.1078 (18)	0.0206 (11)	0.0476 (12)	0.0001 (12)	−0.0054 (12)	−0.0052 (10)
C11	0.0273 (12)	0.0241 (14)	0.0355 (14)	0.0011 (11)	0.0017 (10)	0.0017 (12)
C12	0.0245 (11)	0.0241 (13)	0.0256 (11)	0.0006 (10)	0.0064 (9)	−0.0042 (10)
C13	0.0286 (11)	0.0313 (14)	0.0280 (11)	0.0020 (10)	0.0044 (9)	−0.0018 (11)
C14	0.0417 (13)	0.0268 (15)	0.0303 (12)	0.0018 (12)	0.0021 (10)	−0.0013 (12)
C15	0.0426 (13)	0.0362 (17)	0.0297 (13)	−0.0080 (12)	0.0095 (10)	−0.0006 (11)
N16	0.0285 (11)	0.0397 (13)	0.0319 (10)	0.0008 (10)	0.0063 (9)	−0.0098 (10)
C17	0.0324 (12)	0.0362 (16)	0.0255 (12)	−0.0040 (11)	0.0081 (10)	−0.0041 (12)
N18	0.0299 (12)	0.0527 (17)	0.0562 (15)	−0.0051 (12)	0.0130 (11)	−0.0271 (14)
N19	0.0333 (12)	0.0515 (17)	0.0456 (14)	−0.0072 (11)	0.0101 (10)	−0.0223 (13)
O21	0.0346 (9)	0.0459 (13)	0.0623 (12)	0.0070 (9)	0.0206 (9)	0.0232 (11)
O22	0.0304 (9)	0.0513 (14)	0.0691 (13)	0.0060 (9)	0.0118 (9)	0.0335 (11)
C23	0.0304 (12)	0.0314 (15)	0.0368 (13)	0.0016 (12)	0.0086 (10)	0.0067 (13)
C24	0.0361 (13)	0.053 (2)	0.0508 (16)	0.0046 (14)	0.0171 (12)	0.0189 (15)
C25	0.0396 (14)	0.0345 (17)	0.0399 (14)	0.0028 (12)	0.0154 (11)	0.0091 (13)
C26	0.0359 (13)	0.0380 (17)	0.0408 (14)	0.0057 (13)	0.0158 (11)	0.0128 (14)
C27	0.0371 (13)	0.0393 (18)	0.0474 (15)	0.0059 (12)	0.0178 (11)	0.0169 (14)
C28	0.0278 (12)	0.0313 (15)	0.0303 (12)	−0.0001 (11)	0.0064 (10)	0.0026 (12)
O29	0.0309 (9)	0.0404 (12)	0.0474 (10)	0.0054 (8)	0.0149 (7)	0.0181 (10)
O30	0.0290 (9)	0.0395 (12)	0.0564 (11)	0.0044 (8)	0.0099 (8)	0.0177 (10)

Geometric parameters (Å, º) top

N1—C2	1.491 (3)	C13—C14	1.527 (3)
N1—H1A	0.93 (2)	C13—H13A	0.9700
N1—H1B	0.88 (3)	C13—H13B	0.9700
N1—H1C	0.94 (2)	C14—C15	1.521 (3)
O1—C1	1.255 (3)	C14—H14A	0.9700
O2—C1	1.224 (3)	C14—H14B	0.9700
C1—C2	1.541 (3)	C15—N16	1.457 (3)
C2—C3	1.507 (3)	C15—H15A	0.9700
C2—H2	0.9800	C15—H15B	0.9700
C3—C4	1.523 (3)	N16—C17	1.329 (3)
C3—H3A	0.9700	N16—H16A	0.83 (2)
C3—H3B	0.9700	C17—N18	1.307 (3)
C4—C5	1.510 (3)	C17—N19	1.326 (3)
C4—H4A	0.9700	N18—H18A	0.81 (3)
C4—H4B	0.9700	N18—H18B	1.06 (3)
C5—N6	1.457 (3)	N19—H19A	0.85 (3)
C5—H5A	0.9700	N19—H19B	0.89 (2)
C5—H5B	0.9700	O21—C23	1.256 (3)
N6—C7	1.330 (3)	O22—C23	1.245 (3)
N6—H6A	0.92 (2)	C23—C24	1.509 (4)
C7—N8	1.314 (3)	C24—C25	1.494 (4)
C7—N9	1.329 (3)	C24—H24A	0.9700
N8—H8A	0.87 (3)	C24—H24B	0.9700
N8—H8B	0.97 (3)	C25—C26	1.511 (3)
N9—H9A	0.91 (3)	C25—H25A	0.9700
N9—H9B	0.88 (3)	C25—H25B	0.9700
N11—C12	1.496 (3)	C26—C27	1.500 (4)
N11—H11A	1.10 (3)	C26—H26A	0.9700
N11—H11B	0.90 (2)	C26—H26B	0.9700
N11—H11C	0.97 (2)	C27—C28	1.509 (3)
O11—C11	1.252 (3)	C27—H27A	0.9700
O12—C11	1.229 (3)	C27—H27B	0.9700
C11—C12	1.525 (3)	C28—O29	1.248 (3)
C12—C13	1.529 (3)	C28—O30	1.259 (3)
C12—H12	0.9800

C2—N1—H1A	112.4 (15)	C14—C13—C12	115.66 (19)
C2—N1—H1B	110.1 (17)	C14—C13—H13A	108.4
H1A—N1—H1B	112 (2)	C12—C13—H13A	108.4
C2—N1—H1C	109.3 (16)	C14—C13—H13B	108.4
H1A—N1—H1C	104 (2)	C12—C13—H13B	108.4
H1B—N1—H1C	109 (2)	H13A—C13—H13B	107.4
O2—C1—O1	126.4 (2)	C15—C14—C13	113.8 (2)
O2—C1—C2	118.85 (19)	C15—C14—H14A	108.8
O1—C1—C2	114.8 (2)	C13—C14—H14A	108.8
N1—C2—C3	112.08 (19)	C15—C14—H14B	108.8
N1—C2—C1	107.66 (18)	C13—C14—H14B	108.8
C3—C2—C1	115.00 (19)	H14A—C14—H14B	107.7
N1—C2—H2	107.2	N16—C15—C14	110.3 (2)
C3—C2—H2	107.2	N16—C15—H15A	109.6
C1—C2—H2	107.2	C14—C15—H15A	109.6
C2—C3—C4	113.64 (19)	N16—C15—H15B	109.6
C2—C3—H3A	108.8	C14—C15—H15B	109.6
C4—C3—H3A	108.8	H15A—C15—H15B	108.1
C2—C3—H3B	108.8	C17—N16—C15	125.2 (2)
C4—C3—H3B	108.8	C17—N16—H16A	111.9 (18)
H3A—C3—H3B	107.7	C15—N16—H16A	120.3 (19)
C5—C4—C3	112.7 (2)	N18—C17—N19	119.6 (3)
C5—C4—H4A	109.1	N18—C17—N16	122.0 (2)
C3—C4—H4A	109.1	N19—C17—N16	118.4 (2)
C5—C4—H4B	109.1	C17—N18—H18A	125.0 (18)
C3—C4—H4B	109.1	C17—N18—H18B	121.7 (16)
H4A—C4—H4B	107.8	H18A—N18—H18B	111 (2)
N6—C5—C4	111.7 (2)	C17—N19—H19A	120.5 (18)
N6—C5—H5A	109.3	C17—N19—H19B	120.2 (18)
C4—C5—H5A	109.3	H19A—N19—H19B	119 (3)
N6—C5—H5B	109.3	O22—C23—O21	123.3 (2)
C4—C5—H5B	109.3	O22—C23—C24	116.8 (2)
H5A—C5—H5B	107.9	O21—C23—C24	120.0 (2)
C7—N6—C5	126.87 (19)	C25—C24—C23	117.7 (2)
C7—N6—H6A	119.5 (17)	C25—C24—H24A	107.9
C5—N6—H6A	112.6 (17)	C23—C24—H24A	107.9
N8—C7—N9	119.1 (2)	C25—C24—H24B	107.9
N8—C7—N6	122.0 (2)	C23—C24—H24B	107.9
N9—C7—N6	118.9 (2)	H24A—C24—H24B	107.2
C7—N8—H8A	117.9 (14)	C24—C25—C26	112.9 (2)
C7—N8—H8B	124.4 (19)	C24—C25—H25A	109.0
H8A—N8—H8B	118 (2)	C26—C25—H25A	109.0
C7—N9—H9A	124.3 (18)	C24—C25—H25B	109.0
C7—N9—H9B	119 (2)	C26—C25—H25B	109.0
H9A—N9—H9B	115 (3)	H25A—C25—H25B	107.8
C12—N11—H11A	115.4 (15)	C27—C26—C25	113.48 (19)
C12—N11—H11B	107.9 (16)	C27—C26—H26A	108.9
H11A—N11—H11B	111 (2)	C25—C26—H26A	108.9
C12—N11—H11C	108.3 (16)	C27—C26—H26B	108.9
H11A—N11—H11C	104 (2)	C25—C26—H26B	108.9
H11B—N11—H11C	110 (2)	H26A—C26—H26B	107.7
O12—C11—O11	127.1 (3)	C26—C27—C28	117.4 (2)
O12—C11—C12	115.9 (2)	C26—C27—H27A	108.0
O11—C11—C12	117.0 (2)	C28—C27—H27A	108.0
N11—C12—C11	109.02 (19)	C26—C27—H27B	108.0
N11—C12—C13	111.08 (19)	C28—C27—H27B	108.0
C11—C12—C13	111.69 (19)	H27A—C27—H27B	107.2
N11—C12—H12	108.3	O29—C28—O30	123.7 (2)
C11—C12—H12	108.3	O29—C28—C27	119.4 (2)
C13—C12—H12	108.3	O30—C28—C27	116.88 (19)

O2—C1—C2—N1	−129.5 (2)	N11—C12—C13—C14	−75.6 (2)
O1—C1—C2—N1	51.4 (2)	C11—C12—C13—C14	162.4 (2)
O2—C1—C2—C3	−3.8 (3)	C12—C13—C14—C15	−74.6 (3)
O1—C1—C2—C3	177.07 (18)	C13—C14—C15—N16	−69.4 (3)
N1—C2—C3—C4	−72.4 (2)	C14—C15—N16—C17	156.6 (2)
C1—C2—C3—C4	164.17 (19)	C15—N16—C17—N18	−7.6 (4)
C2—C3—C4—C5	−169.23 (19)	C15—N16—C17—N19	173.2 (2)
C3—C4—C5—N6	64.8 (3)	O22—C23—C24—C25	179.6 (3)
C4—C5—N6—C7	−121.6 (2)	O21—C23—C24—C25	0.1 (4)
C5—N6—C7—N8	9.1 (4)	C23—C24—C25—C26	−177.8 (2)
C5—N6—C7—N9	−170.9 (2)	C24—C25—C26—C27	−179.6 (3)
O12—C11—C12—N11	157.6 (2)	C25—C26—C27—C28	178.0 (2)
O11—C11—C12—N11	−25.1 (3)	C26—C27—C28—O29	4.3 (4)
O12—C11—C12—C13	−79.3 (3)	C26—C27—C28—O30	−176.1 (2)
O11—C11—C12—C13	98.0 (2)

Experimental details

	(dlarad_m)	(larad_m)
Crystal data
Chemical formula	C₆H₁₅N₄O₂·0.5(C₆H₈O₄)·H₂O	2(C₆H₁₅N₄O₂)·C₆H₈O₄
M_r	265.30	494.56
Crystal system, space group	Monoclinic, P2₁/c	Monoclinic, P2₁
Temperature (K)	298	298
a, b, c (Å)	13.825 (4), 5.0531 (16), 18.804 (6)	12.494 (4), 5.9510 (17), 16.719 (5)
β (°)	102.900 (6)	105.977 (5)
V (Å³)	1280.5 (7)	1195.1 (6)
Z	4	2
Radiation type	Mo Kα	Mo Kα
µ (mm⁻¹)	0.11	0.11
Crystal size (mm)	0.59 × 0.11 × 0.02	0.25 × 0.07 × 0.06

Data collection
Diffractometer	Bruker SMART CCD area detector diffractometer	Bruker SMART CCD area detector diffractometer
Absorption correction	Multi-scan SADABS,Sheldrick, 1997	Multi-scan Sheldrick, 1999
T_min, T_max	0.937, 0.998	0.973, 0.994
No. of measured, independent and observed [I > 2σ(I)] reflections	9412, 2581, 2150	6142, 3711, 3396
R_int	0.031	0.019
(sin θ/λ)_max (Å⁻¹)	0.625	0.588

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.128, 1.05	0.039, 0.113, 0.86
No. of reflections	2581	3711
No. of parameters	247	459
No. of restraints	0	1
H-atom treatment	All H-atom parameters refined	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.17	0.17, −0.17
Absolute structure	Flack H.D. (1983), Acta Cryst. A39, 876-881	Flack H.D. (1983), Acta Cryst. A39, 876-881
Absolute structure parameter	centrosymmetric	−0.1 (11)

Computer programs: Bruker SMART, Bruker SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3, PLATON (Spek, 1990).

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