H–d-Phe–d-Pro–Gly methyl ester hydro­chloride monohydrate

Doi, M.; Ichimiya, Y.; Asano, A.

doi:10.1107/S160053680800528X

organic compounds

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ISSN: 2056-9890

Volume 64| Part 4| April 2008| Page o704

doi:10.1107/S160053680800528X

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H–D-Phe–D-Pro–Gly methyl ester hydrochloride monohydrate

Mitsunobu Doi,^a ^* Yuko Ichimiya ^a and Akiko Asano ^a

^aOsaka University of Pharmaceutical Sciences, 4-20-1 Nasahara, Takatsuki, Osaka 569-1094, Japan
^*Correspondence e-mail: doit@gly.oups.ac.jp

(Received 13 February 2008; accepted 25 February 2008; online 12 March 2008)

The conformation of the title tripeptide methyl ester hydrochloride monohydrate, 1-[2-(methoxycarbonylmethylaminocarbonyl)pyrrolidin-1-ylcarbonyl]-2-phenylethanaminium chloride monohydrate, C₁₇H₂₄N₃O₄⁺·Cl⁻·H₂O, is extended, but the structure cannot be classified as any typical secondary structure. Interactions through water molecules and chloride ions were formed, in addition to peptide–peptide hydrogen bonds, stabilizing the molecular packing. In comparison with the previous β-turn structure of the Phe–D-Pro–Gly analogue [Doi, Ichimiya & Asano (2007 ). Acta Cryst. E63, o4691], it was suggested that the difference between the chiralities of Phe and Pro residues of the title compound is important to induce the β-turn structure.

Related literature

For related literature, see: Cremer & Pople (1975 ); Doi, Fujita et al. (2001 ); Doi, Ichimiya et al. (2007); Espinosa & Gellman (2000 ); Llamas-Saiz et al. (2007 ); Tamaki et al. (1985 ); Yamada et al. (2002 ).

Experimental

Crystal data

C₁₇H₂₄N₃O₄⁺·Cl⁻·H₂O
M_r = 387.86
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.3707 (5) Å
b = 9.6667 (7) Å
c = 27.099 (2) Å
V = 1930.8 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 90 (2) K
0.40 × 0.35 × 0.35 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.874, T_max = 0.923
23047 measured reflections
4553 independent reflections
4540 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.087
S = 0.85
4553 reflections
237 parameters
H-atom parameters constrained
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.21 e Å⁻³
Absolute structure: Flack (1983 ), 1920 Friedel pairs
Flack parameter: 0.03 (4)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N10—H10A⋯O1	0.91	1.96	2.845 (2)	166
N10—H10C⋯Cl	0.91	2.31	3.112 (1)	147
N10—H10B⋯O18ⁱ	0.91	1.94	2.755 (1)	148
O1—H2⋯Clⁱⁱ	0.77	2.43	3.201 (1)	177
N30—H30⋯Clⁱⁱⁱ	0.88	2.43	3.299 (1)	171
O1—H1⋯Cl^iv	0.82	2.33	3.139 (1)	165
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[-x, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) x+1, y, z.

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT-Plus (Bruker, 1998);; data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680800528X/pv2069sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680800528X/pv2069Isup2.hkl

checkCIF report

Comment top

The β-turn structures were formed at D-Pro residue in a Gramicidin S and its analogue (Doi et al., 2001; Yamada et al., 2002; Llamas-Saiz, et al., 2007), and a motif including D-Pro promoted β-hairpin in the protein GB1 analogue (Espinosa & Gellman, 2000). A tripeptide motif of Boc–Phe–D-Pro–Gly–OMe (Boc = t-butyloxycarbonyl; OMe = methylester) was designed from these peptides, and the β-turn structure was elucidated (Doi et al., 2007). Moreover, the CD spectra of Gramicidin S analogues suggested that the chiral combination of Phe and Pro residues contributes to the β-turn formation (Tamaki et al., 1985). Title peptide (I) was designed to highlight the chirality of the Phe residue in this tripeptide β-turn motif.

The molecular structure of (I) is shown in Fig. 1. The peptide is a chloride salt and its N-terminal (N10 atom) is protonated. The peptide molecule is somewhat extended, but the structure is not classified to any typical secondary structures from torsion angles. The Pro residue shows a ring puckering with amplitude of Q2 = 0.361 (2) Å and phase of ϕ2 = 293.1 (2) ° (Cremer & Pople, 1975), which is slightly different from those of the β-turn structure of Boc–Phe–D-Pro–Gly–OMe (Doi et al., 2007).

A peptide-peptide hydrogen bond is formed between N10 and O18 atoms. This interaction makes the molecular arrangement propagated along the b axis, but no sheet structure is created (Fig. 2). Molecular packing is stabilized by the interactions with chloride ion (Cl) and water molecule (O1).

CD spectra of (I) showed no clear proof of special structures existed in acetonitril solution (data not shown), and the structure of (I) was somewhat extended. In contrast to the β-turn structure of the diastereomeric tripeptide (Boc–Phe–D-Pro–Gly–OMe), these results indicate that the chirality of Phe different from that of Pro is important for folding of this tripeptide motif.

Related literature top

For related literature, see: Cremer & Pople (1975); Doi, Fujita et al. (2001); Doi, Ichimiya et al. (2007); Espinosa & Gellman (2000); Llamas-Saiz et al. (2007); Tamaki et al. (1985); Yamada et al. (2002).

Experimental top

The title compound was synthesized by a conventional liquid-phase method and the protected peptide, Boc–D-Phe–D-Pro–Gly–OMe (Boc = t-Butyloxycarboxy; OMe = methylester), was obtained. Boc group was removed by using HCl/dioxane, and the hydrocloride salt was obtained. Crystals were grown from aqueous acetonitrile solutions by vapor diffusion method.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SMART (Bruker, 1998); data reduction: SAINT-Plus (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. A view of (I) with displacement ellipsoids drawn at the 50% probability level with the aid of PLATON (Spek, 2003). Dotted lines represent hydrogen bonds.
	Fig. 2. Packing diagram of (I). Side chains of amino acids are omitted for clarity. Dotted lines represent hydrogen bonds. Circles and filled-circles represent chloride ion (Cl) and water (O1) molecules.

1-[2-(methoxycarbonylmethylaminocarbonyl)pyrrolidin-1-ylcarbonyl]-2- phenylethanaminium chloride monohydrate top

Crystal data top

C₁₇H₂₄N₃O₄⁺·Cl⁻·H₂O	F(000) = 824
M_r = 387.86	D_x = 1.334 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 8392 reflections
a = 7.3707 (5) Å	θ = 2.3–28.3°
b = 9.6667 (7) Å	µ = 0.23 mm⁻¹
c = 27.099 (2) Å	T = 90 K
V = 1930.8 (2) Å³	Cubic, colourless
Z = 4	0.40 × 0.35 × 0.35 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	4553 independent reflections
Radiation source: MacScience, M18XCE rotating anode	4540 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
Detector resolution: 8.366 pixels mm^-1	θ_max = 27.9°, θ_min = 2.6°
ω–scan	h = −9→9
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −12→12
T_min = 0.874, T_max = 0.923	l = −35→35
23047 measured reflections

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)] = 0.032	H-atom parameters constrained
wR(F²) = 0.088	w = 1/[σ²(F_o²) + (0.0703P)² + 0.8632P] where P = (F_o² + 2F_c²)/3
S = 0.85	(Δ/σ)_max = 0.001
4553 reflections	Δρ_max = 0.46 e Å⁻³
237 parameters	Δρ_min = −0.21 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1920 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.03 (4)

Crystal data top

C₁₇H₂₄N₃O₄⁺·Cl⁻·H₂O	V = 1930.8 (2) Å³
M_r = 387.86	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.3707 (5) Å	µ = 0.23 mm⁻¹
b = 9.6667 (7) Å	T = 90 K
c = 27.099 (2) Å	0.40 × 0.35 × 0.35 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	4553 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	4540 reflections with I > 2σ(I)
T_min = 0.874, T_max = 0.923	R_int = 0.020
23047 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	H-atom parameters constrained
wR(F²) = 0.088	Δρ_max = 0.46 e Å⁻³
S = 0.85	Δρ_min = −0.21 e Å⁻³
4553 reflections	Absolute structure: Flack (1983), 1920 Friedel pairs
237 parameters	Absolute structure parameter: 0.03 (4)
0 restraints

Special details top

Geometry. Cremer & Pople Puckering Parameters [D. Cremer & J.A. Pople, J.Amer.Chem.Soc., 97, (1975), 1354–1358] ——————————————————————- Q(2) = 0.3608 (15) A ng., Phi(2) = 293.1 (2) Deg

The equation of the plane is of the form: P * x + Q * y + R * z - S = 0 where P, Q, R, S are constants and x, y, z are fractional coordinates.

P = 5.153 (2), Q = 1.935 (5), R = -18.602 (8), S = -9.378 (8) Atom Distance x y z X Y Z * O(18): -0.0397 (9) 0.4138 0.9441 0.7191 3.0500 9.1267 19.4869 * N(20): 0.0350 (11) 0.2674 0.8185 0.6615 1.9711 7.9123 17.9252 * C(10): 0.0337 (12) 0.4982 0.7074 0.7139 3.6722 6.8378 19.3462 * C(18): -0.0103 (12) 0.3858 0.8324 0.6981 2.8434 8.0464 18.9186 * C(20): 0.0268 (13) 0.1632 0.9399 0.6457 1.2030 9.0862 17.4973 * C(23): -0.0454 (14) 0.2080 0.6914 0.6361 1.5330 6.6837 17.2377

P = 4.443 (3), Q = 0.711 (4), R = 21.531 (8), S = 15.452 (5) Atom Distance x y z X Y Z * O(24): 0.1064 (11) 0.4222 1.0289 0.6015 3.1119 9.9466 16.2998 * N(30): 0.0315 (11) 0.2213 1.1812 0.6344 1.6313 11.4182 17.1924 * C(20): -0.1560 (13) 0.1632 0.9399 0.6457 1.2030 9.0862 17.4973 * C(24): 0.0232 (13) 0.2849 1.0527 0.6252 2.1002 10.1765 16.9412 * C(30): -0.1661 (14) 0.2878 1.2994 0.6076 2.1213 12.5607 16.4662 * H(30): 0.16108 0.1378 1.1928 0.6573 1.0157 11.5304 17.8122

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
Cl	0.11272 (5)	0.69212 (3)	0.784634 (14)	0.02274 (9)
N10	0.52851 (16)	0.72346 (11)	0.76814 (4)	0.0135 (2)
H10A	0.6034	0.7967	0.7737	0.020*
H10B	0.5802	0.6451	0.7803	0.020*
H10C	0.4203	0.7384	0.7834	0.020*
C10	0.49822 (17)	0.70736 (13)	0.71391 (4)	0.0131 (2)
H10	0.4307	0.6198	0.7070	0.016*
C11	0.68581 (19)	0.70458 (16)	0.68855 (5)	0.0175 (3)
H11A	0.7301	0.8008	0.6851	0.021*
H11B	0.7720	0.6545	0.7101	0.021*
C12	0.68628 (19)	0.63705 (14)	0.63820 (5)	0.0165 (3)
C13	0.6299 (2)	0.70899 (16)	0.59619 (5)	0.0199 (3)
H13	0.5899	0.8021	0.5990	0.024*
C14	0.6322 (2)	0.6449 (2)	0.55034 (6)	0.0310 (4)
H14	0.5924	0.6939	0.5219	0.037*
C15	0.6927 (3)	0.5092 (2)	0.54597 (7)	0.0399 (5)
H15	0.6951	0.4658	0.5145	0.048*
C16	0.7488 (3)	0.43792 (18)	0.58701 (8)	0.0391 (5)
H16	0.7901	0.3452	0.5839	0.047*
C17	0.7457 (2)	0.50079 (16)	0.63329 (7)	0.0261 (3)
H17	0.7841	0.4507	0.6616	0.031*
C18	0.38577 (18)	0.83238 (13)	0.69813 (4)	0.0132 (2)
O18	0.41380 (14)	0.94414 (10)	0.71910 (3)	0.0177 (2)
N20	0.26742 (16)	0.81851 (11)	0.66147 (4)	0.0138 (2)
C20	0.16322 (18)	0.93995 (13)	0.64568 (5)	0.0140 (3)
H20	0.0887	0.9764	0.6736	0.017*
C22	0.1285 (2)	0.74806 (14)	0.58840 (5)	0.0187 (3)
H22A	0.0379	0.6835	0.5744	0.022*
H22B	0.2248	0.7646	0.5636	0.022*
C21	0.0392 (2)	0.88425 (14)	0.60427 (5)	0.0183 (3)
H21A	−0.0852	0.8679	0.6167	0.022*
H21B	0.0335	0.9501	0.5763	0.022*
C23	0.20798 (19)	0.69142 (14)	0.63610 (5)	0.0160 (3)
H23A	0.1153	0.6413	0.6556	0.019*
H23B	0.3115	0.6289	0.6295	0.019*
C24	0.28494 (18)	1.05274 (13)	0.62516 (5)	0.0143 (2)
O24	0.42220 (15)	1.02895 (11)	0.60149 (4)	0.0226 (2)
N30	0.22132 (17)	1.18119 (12)	0.63443 (4)	0.0175 (2)
H30	0.1378	1.1928	0.6573	0.021*
C30	0.2878 (2)	1.29938 (15)	0.60763 (5)	0.0206 (3)
H30A	0.4206	1.2903	0.6031	0.025*
H30B	0.2650	1.3841	0.6272	0.025*
C31	0.1982 (2)	1.31382 (14)	0.55761 (5)	0.0183 (3)
O31	0.09911 (18)	1.22970 (12)	0.53927 (4)	0.0269 (2)
O32	0.24639 (17)	1.43362 (11)	0.53707 (4)	0.0248 (2)
C32	0.1767 (3)	1.4570 (2)	0.48750 (6)	0.0367 (4)
H32A	0.2270	1.3875	0.4650	0.055*
H32B	0.2121	1.5496	0.4763	0.055*
H32C	0.0441	1.4498	0.4878	0.055*
O1	0.81122 (14)	0.92109 (10)	0.78001 (4)	0.0195 (2)
H1	0.9029	0.8722	0.7787	0.023*
H2	0.8324	0.9851	0.7638	0.023*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl	0.01806 (16)	0.01737 (15)	0.03278 (18)	−0.00004 (13)	0.00761 (14)	−0.00212 (13)
N10	0.0160 (5)	0.0120 (5)	0.0123 (5)	0.0004 (4)	−0.0018 (4)	0.0010 (4)
C10	0.0151 (5)	0.0122 (5)	0.0119 (5)	0.0002 (5)	−0.0010 (5)	0.0010 (5)
C11	0.0148 (6)	0.0220 (7)	0.0157 (6)	−0.0005 (5)	0.0005 (5)	−0.0006 (5)
C12	0.0135 (5)	0.0168 (6)	0.0191 (6)	−0.0028 (5)	0.0032 (5)	−0.0043 (5)
C13	0.0174 (6)	0.0246 (7)	0.0178 (6)	−0.0043 (6)	0.0012 (5)	−0.0029 (5)
C14	0.0218 (7)	0.0511 (10)	0.0202 (7)	−0.0096 (8)	0.0021 (6)	−0.0081 (7)
C15	0.0281 (8)	0.0539 (12)	0.0375 (9)	−0.0133 (9)	0.0105 (7)	−0.0320 (9)
C16	0.0241 (8)	0.0245 (8)	0.0686 (13)	−0.0067 (7)	0.0142 (9)	−0.0251 (9)
C17	0.0175 (6)	0.0179 (7)	0.0429 (9)	−0.0013 (6)	0.0049 (7)	−0.0024 (6)
C18	0.0145 (5)	0.0123 (5)	0.0127 (5)	−0.0018 (5)	0.0024 (5)	0.0026 (4)
O18	0.0226 (5)	0.0122 (4)	0.0182 (4)	−0.0010 (4)	−0.0045 (4)	0.0000 (4)
N20	0.0166 (5)	0.0092 (5)	0.0157 (5)	−0.0006 (4)	−0.0014 (4)	0.0010 (4)
C20	0.0162 (6)	0.0119 (6)	0.0140 (5)	0.0011 (5)	0.0000 (5)	0.0023 (4)
C22	0.0217 (7)	0.0187 (6)	0.0157 (6)	−0.0025 (5)	−0.0052 (5)	−0.0013 (5)
C21	0.0182 (6)	0.0174 (6)	0.0194 (6)	−0.0035 (5)	−0.0053 (5)	0.0025 (5)
C23	0.0174 (6)	0.0124 (6)	0.0183 (6)	−0.0031 (5)	−0.0027 (5)	−0.0003 (5)
C24	0.0170 (6)	0.0130 (6)	0.0130 (5)	−0.0010 (5)	−0.0026 (5)	0.0017 (5)
O24	0.0220 (5)	0.0192 (5)	0.0266 (5)	−0.0012 (4)	0.0077 (4)	0.0041 (4)
N30	0.0227 (6)	0.0128 (5)	0.0169 (5)	−0.0005 (5)	0.0011 (4)	0.0021 (4)
C30	0.0268 (7)	0.0137 (6)	0.0214 (6)	−0.0047 (6)	−0.0040 (5)	0.0038 (5)
C31	0.0215 (6)	0.0153 (6)	0.0181 (6)	0.0031 (6)	0.0039 (5)	0.0006 (5)
O31	0.0353 (6)	0.0221 (5)	0.0233 (5)	−0.0015 (5)	−0.0060 (5)	−0.0025 (4)
O32	0.0299 (6)	0.0211 (5)	0.0233 (5)	0.0000 (5)	−0.0007 (5)	0.0089 (4)
C32	0.0483 (11)	0.0399 (9)	0.0218 (7)	0.0074 (9)	0.0005 (7)	0.0101 (7)
O1	0.0186 (5)	0.0172 (4)	0.0227 (5)	0.0001 (4)	0.0005 (4)	0.0003 (4)

Geometric parameters (Å, º) top

N10—C10	1.4947 (16)	C20—C21	1.5441 (18)
N10—H10A	0.9100	C20—H20	1.0000
N10—H10B	0.9100	C22—C23	1.5209 (18)
N10—H10C	0.9100	C22—C21	1.533 (2)
C10—C18	1.5265 (17)	C22—H22A	0.9900
C10—C11	1.5442 (18)	C22—H22B	0.9900
C10—H10	1.0000	C21—H21A	0.9900
C11—C12	1.5125 (18)	C21—H21B	0.9900
C11—H11A	0.9900	C23—H23A	0.9900
C11—H11B	0.9900	C23—H23B	0.9900
C12—C17	1.394 (2)	C24—O24	1.2197 (17)
C12—C13	1.397 (2)	C24—N30	1.3509 (17)
C13—C14	1.388 (2)	N30—C30	1.4397 (17)
C13—H13	0.9500	N30—H30	0.8800
C14—C15	1.391 (3)	C30—C31	1.5144 (19)
C14—H14	0.9500	C30—H30A	0.9900
C15—C16	1.372 (3)	C30—H30B	0.9900
C15—H15	0.9500	C31—O31	1.2006 (19)
C16—C17	1.394 (3)	C31—O32	1.3329 (17)
C16—H16	0.9500	O32—C32	1.456 (2)
C17—H17	0.9500	C32—H32A	0.9800
C18—O18	1.2381 (16)	C32—H32B	0.9800
C18—N20	1.3289 (17)	C32—H32C	0.9800
N20—C20	1.4666 (16)	O1—H1	0.825
N20—C23	1.4745 (17)	O1—H2	0.775
C20—C24	1.5176 (18)

C10—N10—H10A	109.5	N20—C20—H20	110.4
C10—N10—H10B	109.5	C24—C20—H20	110.4
H10A—N10—H10B	109.5	C21—C20—H20	110.4
C10—N10—H10C	109.5	C23—C22—C21	103.65 (11)
H10A—N10—H10C	109.5	C23—C22—H22A	111.0
H10B—N10—H10C	109.5	C21—C22—H22A	111.0
N10—C10—C18	105.90 (10)	C23—C22—H22B	111.0
N10—C10—C11	107.80 (10)	C21—C22—H22B	111.0
C18—C10—C11	112.04 (10)	H22A—C22—H22B	109.0
N10—C10—H10	110.3	C22—C21—C20	104.43 (11)
C18—C10—H10	110.3	C22—C21—H21A	110.9
C11—C10—H10	110.3	C20—C21—H21A	110.9
C12—C11—C10	114.26 (11)	C22—C21—H21B	110.9
C12—C11—H11A	108.7	C20—C21—H21B	110.9
C10—C11—H11A	108.7	H21A—C21—H21B	108.9
C12—C11—H11B	108.7	N20—C23—C22	102.16 (10)
C10—C11—H11B	108.7	N20—C23—H23A	111.3
H11A—C11—H11B	107.6	C22—C23—H23A	111.3
C17—C12—C13	119.06 (14)	N20—C23—H23B	111.3
C17—C12—C11	119.64 (14)	C22—C23—H23B	111.3
C13—C12—C11	121.30 (13)	H23A—C23—H23B	109.2
C14—C13—C12	120.25 (15)	O24—C24—N30	123.99 (13)
C14—C13—H13	119.9	O24—C24—C20	123.20 (12)
C12—C13—H13	119.9	N30—C24—C20	112.77 (12)
C13—C14—C15	120.05 (18)	C24—N30—C30	121.16 (12)
C13—C14—H14	120.0	C24—N30—H30	119.4
C15—C14—H14	120.0	C30—N30—H30	119.4
C16—C15—C14	120.10 (16)	N30—C30—C31	112.10 (12)
C16—C15—H15	120.0	N30—C30—H30A	109.2
C14—C15—H15	120.0	C31—C30—H30A	109.2
C15—C16—C17	120.34 (17)	N30—C30—H30B	109.2
C15—C16—H16	119.8	C31—C30—H30B	109.2
C17—C16—H16	119.8	H30A—C30—H30B	107.9
C16—C17—C12	120.20 (17)	O31—C31—O32	125.29 (13)
C16—C17—H17	119.9	O31—C31—C30	124.98 (13)
C12—C17—H17	119.9	O32—C31—C30	109.73 (12)
O18—C18—N20	122.73 (12)	C31—O32—C32	115.22 (13)
O18—C18—C10	118.15 (11)	O32—C32—H32A	109.5
N20—C18—C10	119.07 (11)	O32—C32—H32B	109.5
C18—N20—C20	118.75 (11)	H32A—C32—H32B	109.5
C18—N20—C23	128.88 (11)	O32—C32—H32C	109.5
C20—N20—C23	112.05 (10)	H32A—C32—H32C	109.5
N20—C20—C24	111.86 (11)	H32B—C32—H32C	109.5
N20—C20—C21	104.05 (10)	H1—O1—H2	105.56
C24—C20—C21	109.51 (11)

N10—C10—C11—C12	158.2 (1)	C23—N20—C20—C24	−122.61 (12)
C18—C10—C11—C12	−85.66 (14)	C18—N20—C20—C21	−178.58 (11)
C10—C11—C12—C17	−99.94 (15)	C23—N20—C20—C21	−4.49 (14)
C10—C11—C12—C13	80.71 (17)	C23—C22—C21—C20	34.16 (14)
C17—C12—C13—C14	0.4 (2)	N20—C20—C21—C22	−18.6 (1)
C11—C12—C13—C14	179.76 (13)	C24—C20—C21—C22	101.18 (12)
C12—C13—C14—C15	−0.8 (2)	C18—N20—C23—C22	−160.99 (13)
C13—C14—C15—C16	0.5 (3)	C20—N20—C23—C22	25.66 (14)
C14—C15—C16—C17	0.0 (3)	C21—C22—C23—N20	−36.02 (13)
C15—C16—C17—C12	−0.4 (3)	N20—C20—C24—O24	35.04 (17)
C13—C12—C17—C16	0.1 (2)	C21—C20—C24—O24	−79.78 (16)
C11—C12—C17—C16	−179.22 (14)	N20—C20—C24—N30	−147.2 (1)
N10—C10—C18—O18	34.80 (15)	C21—C20—C24—N30	98.00 (13)
C11—C10—C18—O18	−82.47 (14)	O24—C24—N30—C30	14.4 (2)
N10—C10—C18—N20	−147.7 (1)	C20—C24—N30—C30	−163.4 (1)
C11—C10—C18—N20	95.02 (14)	C24—N30—C30—C31	80.9 (2)
O18—C18—N20—C20	−1.09 (19)	N30—C30—C31—O31	−8.2 (2)
C10—C18—N20—C20	−178.5 (1)	N30—C30—C31—O32	172.0 (1)
O18—C18—N20—C23	−174.05 (12)	O31—C31—O32—C32	−3.0 (2)
C10—C18—N20—C23	8.58 (19)	C30—C31—O32—C32	176.89 (14)
C18—N20—C20—C24	63.3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N10—H10A···O1	0.91	1.96	2.845 (2)	166
N10—H10C···Cl	0.91	2.31	3.112 (1)	147
N10—H10B···O18ⁱ	0.91	1.94	2.755 (1)	148
O1—H2···Clⁱⁱ	0.77	2.43	3.201 (1)	177
N30—H30···Clⁱⁱⁱ	0.88	2.43	3.299 (1)	171
O1—H1···Cl^iv	0.82	2.33	3.139 (1)	165

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

Experimental details

Crystal data
Chemical formula	C₁₇H₂₄N₃O₄⁺·Cl⁻·H₂O
M_r	387.86
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	90
a, b, c (Å)	7.3707 (5), 9.6667 (7), 27.099 (2)
V (Å³)	1930.8 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.23
Crystal size (mm)	0.40 × 0.35 × 0.35

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.874, 0.923
No. of measured, independent and observed [I > 2σ(I)] reflections	23047, 4553, 4540
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.088, 0.85
No. of reflections	4553
No. of parameters	237
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.21
Absolute structure	Flack (1983), 1920 Friedel pairs
Absolute structure parameter	0.03 (4)

Computer programs: SMART (Bruker, 1998), SAINT-Plus (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N10—H10A···O1	0.91	1.96	2.845 (2)	166
N10—H10C···Cl	0.91	2.31	3.112 (1)	147
N10—H10B···O18ⁱ	0.91	1.94	2.755 (1)	148
O1—H2···Clⁱⁱ	0.77	2.43	3.201 (1)	177
N30—H30···Clⁱⁱⁱ	0.88	2.43	3.299 (1)	171
O1—H1···Cl^iv	0.82	2.33	3.139 (1)	165

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

References

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Volume 64| Part 4| April 2008| Page o704

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