N,N-Diethyl-2-hy­droxy­ethanaminium 5-(5-chloro-2,4-dinitro­phen­yl)-2,6-dioxo-1,2,3,6-tetra­hydro­pyrimidin-4-olate hemihydrate

Babykala, R.; Kalaivani, D.

doi:10.1107/S1600536812003248

N,N-Diethyl-2-hydroxyethanaminium 5-(5-chloro-2,4-dinitrophenyl)-2,6-dioxo-1,2,3,6-tetrahydropyrimidin-4-olate hemihydrate

The asymmetric unit of the title salt, C₆H₁₆NO⁺·C₁₀H₄ClN₄O₇⁻·0.5H₂O, contains two cations, two anions and one water molecule. In one independent anion, one nitro group is rotationally disordered over two orientations in a 0.657 (8):0.343 (8) ratio. In the crystal, intermolecular N—H

O and O—H

O hydrogen bonds link all the components into ribbons extending along [100].

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536812003248/cv5228sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536812003248/cv5228Isup2.hkl Contains datablock I
	Chemical Markup Language (CML) file https://doi.org/10.1107/S1600536812003248/cv5228Isup3.cml Supplementary material

CCDC reference: 838895

checkCIF report

Key indicators

Single-crystal X-ray study
T = 294 K
Mean (C-C) = 0.003 Å
Disorder in main residue
R factor = 0.043
wR factor = 0.138
Data-to-parameter ratio = 12.0

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT220_ALERT_2_B Large Non-Solvent    O     Ueq(max)/Ueq(min) ...        4.2 Ratio

Alert level C
PLAT041_ALERT_1_C Calc. and Reported SumFormula    Strings  Differ          ?
PLAT042_ALERT_1_C Calc. and Reported MoietyFormula Strings  Differ          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       0.50 Ratio
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.22
PLAT213_ALERT_2_C Atom O15'            has ADP max/min Ratio .....        3.2 prola
PLAT213_ALERT_2_C Atom O16'            has ADP max/min Ratio .....        3.2 prola
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O15    --  N9      ..        6.2 su
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N9
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N4
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors of         N10
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          1
              C10 H4 Cl N4 O7
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          2
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.595          3

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          3
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT007_ALERT_5_G Note: Number of Unrefined D-H Atoms ............          4
PLAT301_ALERT_3_G Note: Main Residue  Disorder ...................          5 Perc.
PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd.  #          4
              C6 H16 N O
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          4
PLAT909_ALERT_3_G Percentage of Observed Data at Theta(Max) still          54 Perc.

   0 ALERT level A = Most likely a serious problem - resolve or explain
   1 ALERT level B = A potentially serious problem, consider carefully
  13 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   7 ALERT level G = General information/check it is not something unexpected

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   8 ALERT type 2 Indicator that the structure model may be wrong or deficient
   5 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

Comment top

Pyrimidine derivatives play a significant role in many biological systems (Hueso et al., 2003). Barbiturates are pyrimidine derivatives which have been used as hypnotic drugs, anaesthetics, sleeping agents and for the treatment of anxiety, epilepsy and other psychiatric disorders (Colorado & Brodbelt, 1996). In continuation of our systematic studies of molecular salts containing various derivatives of barbiturates (Kalaivani et al., 2008; Kalaivani & Malarvizhi, 2009; Kalaivani & Buvaneswari, 2010; Buvaneswari & Kalaivani, 2011), we present here the title compound (I).

In (I) (Fig. 1), all bond lengths and angles are normal and comparable with those observed in the related compounds (Kalaivani & Malarvizhi, 2009; Buvaneswari & Kalaivani, 2011). The crystal packing (Fig. 2) exhibits a number of N—H···O and O—H···O hydrogen bonds with various ring motifs such as R₂²(8), R₂²(9), R₃²(8) and R₄⁴(13), respectively. These hydrogen bonds link all moieties into ribbons extended in [100].

Related literature top

For details of the pharmacological properties of pyrimidine derivatives, see: Hueso et al. (2003); Colorado & Brodbelt (1996); Kalaivani et al. (2008); Kalaivani & Buvaneswari (2010). For the crystal structures of related compounds, see: Kalaivani & Malarvizhi (2009); Buvaneswari & Kalaivani (2011).

Experimental top

Analytical grade 1,3-dichloro-4,6-dinitrobenzene (DCDNB) and barbituric acid were used as supplied by Aldrich company. N,N-Diethylethanolamine was distilled under reduced pressure and the fraction boiling over at its boiling point was used for the preparation of the title molecular salt. DCDNB (2.01 g, 0.01 mol) in 15 ml absolute ethanol was mixed with barbituric acid (1.28 g, 0.01 mol) in 30 ml of absolute ethanol. N,N-diethylethanolamine (2.36 g, 0.02 mol) was added to the above mixture at 313 K and shaken well for 5–6 h. The solution was filtered and kept as such at room temperature for 48 h. On standing, reddish orange crystals come out from the solution. The crystals were powdered well and washed with copious amount of ethanol and dry ether and recrystallized from absolute alcohol (yield of pure crystals 80%, m.p. 503 K). Good quality crystals (red orange blocks) for single-crystal X-ray studies were obtained by slow evaporation of ethanol at room temperature.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The content of asymmetric part of (I) showing the atomic numbering and 30% probability displacement ellipsoids. For the disordered nitro group, only major part is shown.
	Fig. 2. A portion of the crystal packing showing hydrogen bonds as dotted lines.

N,N-Diethyl-2-hydroxyethanaminium 5-(5-chloro-2,4-dinitrophenyl)-2,6-dioxo-1,2,3,6-tetrahydropyrimidin-4-olate hemihydrate top

Crystal data top

C₆H₁₆NO⁺·C₁₀H₄ClN₄O₇⁻·0.5H₂O	Z = 4
M_r = 454.83	F(000) = 948
Triclinic, P1	D_x = 1.482 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 12.3775 (7) Å	Cell parameters from 6078 reflections
b = 12.8109 (8) Å	θ = 2.5–27.0°
c = 13.5834 (9) Å	µ = 0.25 mm⁻¹
α = 101.497 (4)°	T = 294 K
β = 99.142 (3)°	Block, red
γ = 99.718 (3)°	0.30 × 0.25 × 0.20 mm
V = 2038.6 (2) Å³

Data collection top

Bruker Kappa APEXII CCD diffractometer	7179 independent reflections
Radiation source: fine-focus sealed tube	5639 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ω and ϕ scans	θ_max = 25.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −14→14
T_min = 0.901, T_max = 0.942	k = −15→15
36654 measured reflections	l = −16→16

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.138	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0773P)² + 0.6949P] where P = (F_o² + 2F_c²)/3
7179 reflections	(Δ/σ)_max < 0.001
598 parameters	Δρ_max = 0.72 e Å⁻³
4 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₆H₁₆NO⁺·C₁₀H₄ClN₄O₇⁻·0.5H₂O	γ = 99.718 (3)°
M_r = 454.83	V = 2038.6 (2) Å³
Triclinic, P1	Z = 4
a = 12.3775 (7) Å	Mo Kα radiation
b = 12.8109 (8) Å	µ = 0.25 mm⁻¹
c = 13.5834 (9) Å	T = 294 K
α = 101.497 (4)°	0.30 × 0.25 × 0.20 mm
β = 99.142 (3)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	7179 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	5639 reflections with I > 2σ(I)
T_min = 0.901, T_max = 0.942	R_int = 0.031
36654 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	4 restraints
wR(F²) = 0.138	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.72 e Å⁻³
7179 reflections	Δρ_min = −0.32 e Å⁻³
598 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	Occ. (<1)
C1	0.73604 (16)	0.44594 (17)	−0.05043 (16)	0.0343 (5)
C2	0.60151 (16)	0.40344 (17)	0.05684 (15)	0.0309 (4)
C3	0.65908 (16)	0.32478 (16)	0.08526 (15)	0.0307 (4)
C4	0.75520 (16)	0.30658 (16)	0.04682 (16)	0.0330 (4)
C5	0.62072 (15)	0.26499 (16)	0.15797 (15)	0.0309 (4)
C6	0.59379 (16)	0.32162 (17)	0.24693 (16)	0.0331 (4)
H6	0.6024	0.3968	0.2582	0.040*
C7	0.55516 (17)	0.27072 (18)	0.31856 (16)	0.0369 (5)
C8	0.54654 (19)	0.15898 (19)	0.30541 (17)	0.0407 (5)
C9	0.57638 (18)	0.10095 (19)	0.22112 (18)	0.0423 (5)
H9	0.5736	0.0267	0.2131	0.051*
C10	0.61032 (17)	0.15297 (17)	0.14886 (16)	0.0356 (5)
C11	0.3083 (2)	0.2680 (2)	0.1612 (2)	0.0532 (6)
H11A	0.3635	0.3322	0.1995	0.064*
H11B	0.3476	0.2110	0.1388	0.064*
C12	0.23267 (19)	0.23115 (19)	0.23035 (18)	0.0448 (5)
H12A	0.2757	0.2063	0.2839	0.054*
H12B	0.2042	0.2925	0.2629	0.054*
C13	0.1698 (2)	0.0418 (2)	0.1186 (2)	0.0518 (6)
H13A	0.1032	−0.0071	0.0756	0.062*
H13B	0.2191	0.0628	0.0739	0.062*
C14	0.2266 (3)	−0.0185 (3)	0.1866 (3)	0.0890 (11)
H14A	0.2944	0.0280	0.2278	0.133*
H14B	0.2441	−0.0813	0.1456	0.133*
H14C	0.1781	−0.0414	0.2303	0.133*
C15	0.0554 (2)	0.1188 (2)	0.2403 (2)	0.0544 (6)
H15A	0.0367	0.1866	0.2717	0.065*
H15B	0.0904	0.0894	0.2947	0.065*
C16	−0.0505 (3)	0.0396 (3)	0.1822 (3)	0.0785 (9)
H16A	−0.0810	0.0644	0.1236	0.118*
H16B	−0.1039	0.0350	0.2261	0.118*
H16C	−0.0341	−0.0309	0.1600	0.118*
N1	0.78912 (15)	0.37048 (15)	−0.01912 (14)	0.0371 (4)
N2	0.64328 (14)	0.45918 (15)	−0.01195 (14)	0.0347 (4)
N3	0.62568 (17)	0.08057 (16)	0.05553 (17)	0.0474 (5)
N4	0.5033 (2)	0.0960 (2)	0.37474 (18)	0.0619 (6)
N5	0.13683 (15)	0.14164 (15)	0.17278 (14)	0.0383 (4)
H5	0.1002	0.1682	0.1228	0.046*
O1	0.77048 (13)	0.49917 (13)	−0.10940 (13)	0.0454 (4)
O2	0.81174 (12)	0.24002 (13)	0.06849 (13)	0.0452 (4)
O3	0.51542 (12)	0.42531 (13)	0.08530 (12)	0.0404 (4)
O4	0.58787 (16)	0.09712 (15)	−0.02727 (14)	0.0595 (5)
O5	0.67161 (17)	0.00520 (15)	0.06664 (17)	0.0685 (6)
O6	0.5307 (3)	0.0114 (2)	0.3777 (2)	0.1097 (10)
O7	0.4287 (2)	0.12591 (19)	0.41688 (18)	0.0825 (7)
O8	0.24764 (14)	0.29216 (14)	0.07518 (13)	0.0521 (4)
H8	0.2158	0.3415	0.0939	0.078*
O9	1.00189 (14)	0.19327 (14)	0.01618 (15)	0.0494 (4)
Cl1	0.52193 (6)	0.35212 (5)	0.42199 (5)	0.05531 (19)
H9A	0.9462 (17)	0.210 (2)	0.040 (2)	0.069 (9)*
H9B	1.030 (2)	0.241 (2)	−0.013 (3)	0.100 (13)*
H2	0.604 (2)	0.501 (2)	−0.0340 (18)	0.042 (7)*
H1	0.847 (2)	0.3646 (18)	−0.0432 (17)	0.034 (6)*
C17	1.03464 (17)	0.41704 (18)	−0.14752 (16)	0.0368 (5)
C18	1.16333 (15)	0.44983 (15)	−0.26248 (15)	0.0288 (4)
C19	1.10360 (16)	0.52326 (16)	−0.29751 (15)	0.0305 (4)
C20	1.01060 (16)	0.54779 (17)	−0.25484 (15)	0.0324 (4)
C21	1.13552 (15)	0.57684 (16)	−0.37742 (15)	0.0298 (4)
C22	1.13816 (17)	0.68886 (17)	−0.36557 (17)	0.0349 (5)
H22	1.1219	0.7271	−0.3059	0.042*
C23	1.16361 (19)	0.74390 (17)	−0.43818 (18)	0.0413 (5)
C24	1.19176 (19)	0.68958 (19)	−0.52631 (18)	0.0438 (5)
C25	1.19514 (18)	0.58186 (18)	−0.54005 (17)	0.0394 (5)
H25	1.2168	0.5457	−0.5978	0.047*
C26	1.16608 (16)	0.52740 (16)	−0.46732 (15)	0.0313 (4)
C27	1.3675 (3)	0.2472 (3)	−0.1336 (2)	0.0674 (8)
H27A	1.4013	0.2112	−0.0839	0.081*
H27B	1.4104	0.3210	−0.1199	0.081*
C28	1.3701 (3)	0.1885 (3)	−0.2380 (2)	0.0689 (8)
H28A	1.3201	0.1178	−0.2534	0.083*
H28B	1.4451	0.1762	−0.2395	0.083*
C29	1.4321 (2)	0.2946 (2)	−0.3634 (2)	0.0583 (7)
H29A	1.4687	0.2376	−0.3916	0.070*
H29B	1.4018	0.3248	−0.4192	0.070*
C30	1.5159 (3)	0.3808 (3)	−0.2878 (3)	0.0836 (10)
H30A	1.4789	0.4318	−0.2518	0.125*
H30B	1.5664	0.4178	−0.3226	0.125*
H30C	1.5571	0.3489	−0.2399	0.125*
C31	1.2477 (3)	0.1671 (2)	−0.4101 (2)	0.0680 (8)
H31A	1.2399	0.2005	−0.4682	0.082*
H31B	1.2727	0.0997	−0.4309	0.082*
C32	1.1376 (3)	0.1425 (3)	−0.3805 (3)	0.0822 (10)
H32A	1.1450	0.1089	−0.3233	0.123*
H32B	1.0849	0.0938	−0.4374	0.123*
H32C	1.1117	0.2088	−0.3618	0.123*
N6	0.98182 (15)	0.49133 (16)	−0.18171 (15)	0.0394 (4)
N7	1.12560 (14)	0.40106 (15)	−0.18818 (14)	0.0353 (4)
N8	1.16366 (16)	0.40985 (15)	−0.49451 (13)	0.0381 (4)
N9	1.2163 (3)	0.7445 (2)	−0.6078 (2)	0.0779 (8)
N10	1.33782 (18)	0.24545 (16)	−0.31949 (16)	0.0493 (5)
H10	1.3060	0.3004	−0.2917	0.059*
O10	1.00397 (14)	0.36887 (15)	−0.08398 (13)	0.0519 (4)
O11	0.95065 (12)	0.61060 (13)	−0.27829 (12)	0.0418 (4)
O12	1.24892 (11)	0.42489 (11)	−0.29138 (11)	0.0335 (3)
O13	1.08502 (14)	0.34754 (13)	−0.48101 (13)	0.0483 (4)
O14	1.24008 (15)	0.38142 (14)	−0.53307 (13)	0.0555 (5)
O15	1.1439 (4)	0.7960 (5)	−0.6401 (4)	0.118 (2)	0.670 (9)
O16	1.2847 (6)	0.7283 (7)	−0.6494 (7)	0.142 (5)	0.670 (9)
O15'	1.3101 (9)	0.8218 (9)	−0.5731 (7)	0.125 (5)	0.330 (9)
O16'	1.2011 (14)	0.7054 (10)	−0.6879 (7)	0.133 (8)	0.330 (9)
O17	1.25677 (16)	0.24953 (16)	−0.12333 (14)	0.0623 (5)
H17	1.2564	0.2834	−0.0655	0.094*
Cl2	1.16163 (7)	0.88047 (5)	−0.41687 (6)	0.0707 (2)
H7	1.161 (2)	0.355 (2)	−0.1702 (19)	0.043 (7)*
H6A	0.928 (2)	0.5042 (19)	−0.1581 (18)	0.036 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0309 (10)	0.0399 (12)	0.0377 (11)	0.0116 (9)	0.0126 (9)	0.0136 (9)
C2	0.0273 (10)	0.0387 (11)	0.0304 (10)	0.0113 (8)	0.0090 (8)	0.0106 (9)
C3	0.0272 (10)	0.0351 (11)	0.0329 (11)	0.0087 (8)	0.0094 (8)	0.0104 (9)
C4	0.0283 (10)	0.0350 (11)	0.0401 (11)	0.0101 (9)	0.0107 (9)	0.0130 (9)
C5	0.0221 (9)	0.0381 (11)	0.0357 (11)	0.0096 (8)	0.0062 (8)	0.0128 (9)
C6	0.0286 (10)	0.0380 (11)	0.0356 (11)	0.0109 (8)	0.0074 (9)	0.0109 (9)
C7	0.0328 (10)	0.0487 (13)	0.0322 (11)	0.0118 (9)	0.0088 (9)	0.0116 (9)
C8	0.0422 (12)	0.0496 (13)	0.0372 (12)	0.0119 (10)	0.0125 (10)	0.0206 (10)
C9	0.0433 (12)	0.0390 (12)	0.0518 (14)	0.0142 (10)	0.0144 (11)	0.0182 (10)
C10	0.0322 (10)	0.0397 (12)	0.0382 (12)	0.0115 (9)	0.0117 (9)	0.0098 (9)
C11	0.0386 (12)	0.0547 (15)	0.0649 (17)	0.0085 (11)	0.0021 (12)	0.0181 (13)
C12	0.0474 (13)	0.0452 (13)	0.0415 (13)	0.0132 (10)	0.0049 (10)	0.0094 (10)
C13	0.0555 (14)	0.0512 (14)	0.0495 (14)	0.0158 (12)	0.0194 (12)	0.0027 (11)
C14	0.101 (3)	0.070 (2)	0.103 (3)	0.051 (2)	0.014 (2)	0.0113 (19)
C15	0.0640 (16)	0.0570 (15)	0.0549 (15)	0.0191 (13)	0.0339 (13)	0.0196 (12)
C16	0.0639 (18)	0.088 (2)	0.088 (2)	−0.0028 (16)	0.0363 (17)	0.0307 (19)
N1	0.0301 (9)	0.0450 (11)	0.0484 (11)	0.0180 (8)	0.0207 (8)	0.0201 (9)
N2	0.0307 (9)	0.0432 (10)	0.0410 (10)	0.0189 (8)	0.0147 (8)	0.0196 (8)
N3	0.0462 (11)	0.0405 (11)	0.0575 (14)	0.0067 (9)	0.0253 (10)	0.0060 (10)
N4	0.0846 (17)	0.0630 (15)	0.0533 (13)	0.0228 (13)	0.0316 (12)	0.0280 (11)
N5	0.0423 (10)	0.0432 (10)	0.0362 (10)	0.0150 (8)	0.0146 (8)	0.0148 (8)
O1	0.0426 (8)	0.0569 (10)	0.0557 (10)	0.0232 (7)	0.0266 (8)	0.0332 (8)
O2	0.0372 (8)	0.0490 (9)	0.0673 (11)	0.0240 (7)	0.0249 (8)	0.0309 (8)
O3	0.0340 (8)	0.0566 (10)	0.0459 (9)	0.0254 (7)	0.0198 (7)	0.0246 (7)
O4	0.0692 (12)	0.0605 (12)	0.0431 (10)	0.0026 (9)	0.0183 (9)	0.0026 (9)
O5	0.0776 (13)	0.0476 (11)	0.0946 (15)	0.0287 (10)	0.0454 (12)	0.0139 (10)
O6	0.166 (3)	0.0938 (18)	0.129 (2)	0.0676 (19)	0.090 (2)	0.0805 (18)
O7	0.1039 (17)	0.0817 (15)	0.0758 (14)	0.0151 (13)	0.0538 (13)	0.0256 (12)
O8	0.0519 (10)	0.0570 (10)	0.0532 (10)	0.0116 (8)	0.0154 (8)	0.0223 (8)
O9	0.0389 (9)	0.0554 (10)	0.0675 (12)	0.0219 (8)	0.0200 (8)	0.0280 (9)
Cl1	0.0693 (4)	0.0612 (4)	0.0400 (3)	0.0161 (3)	0.0252 (3)	0.0086 (3)
C17	0.0343 (11)	0.0450 (12)	0.0384 (12)	0.0144 (9)	0.0127 (9)	0.0169 (10)
C18	0.0287 (10)	0.0291 (10)	0.0292 (10)	0.0074 (8)	0.0068 (8)	0.0059 (8)
C19	0.0308 (10)	0.0320 (10)	0.0326 (10)	0.0107 (8)	0.0094 (8)	0.0103 (8)
C20	0.0315 (10)	0.0349 (11)	0.0338 (11)	0.0121 (9)	0.0078 (9)	0.0096 (9)
C21	0.0237 (9)	0.0319 (10)	0.0345 (11)	0.0083 (8)	0.0041 (8)	0.0082 (8)
C22	0.0342 (11)	0.0327 (11)	0.0408 (12)	0.0101 (9)	0.0106 (9)	0.0101 (9)
C23	0.0428 (12)	0.0297 (11)	0.0535 (14)	0.0083 (9)	0.0098 (10)	0.0140 (10)
C24	0.0460 (13)	0.0455 (13)	0.0468 (13)	0.0073 (10)	0.0150 (11)	0.0241 (11)
C25	0.0381 (11)	0.0443 (13)	0.0388 (12)	0.0096 (10)	0.0124 (10)	0.0117 (10)
C26	0.0300 (10)	0.0309 (10)	0.0345 (11)	0.0084 (8)	0.0067 (8)	0.0096 (9)
C27	0.0680 (18)	0.088 (2)	0.0527 (16)	0.0331 (16)	0.0112 (14)	0.0186 (15)
C28	0.086 (2)	0.0715 (19)	0.0711 (19)	0.0483 (17)	0.0276 (16)	0.0301 (16)
C29	0.0615 (16)	0.0704 (18)	0.0538 (16)	0.0268 (14)	0.0279 (13)	0.0156 (13)
C30	0.0648 (19)	0.096 (3)	0.080 (2)	0.0135 (18)	0.0264 (17)	−0.0080 (19)
C31	0.094 (2)	0.0429 (15)	0.0690 (19)	0.0187 (15)	0.0204 (17)	0.0095 (13)
C32	0.081 (2)	0.0540 (18)	0.103 (3)	0.0091 (16)	0.002 (2)	0.0162 (18)
N6	0.0351 (10)	0.0512 (12)	0.0476 (11)	0.0238 (9)	0.0221 (9)	0.0245 (9)
N7	0.0353 (9)	0.0413 (10)	0.0408 (10)	0.0191 (8)	0.0156 (8)	0.0204 (8)
N8	0.0470 (11)	0.0368 (10)	0.0306 (9)	0.0148 (9)	0.0029 (8)	0.0070 (8)
N9	0.118 (2)	0.0601 (16)	0.078 (2)	0.0223 (17)	0.0525 (19)	0.0383 (16)
N10	0.0656 (13)	0.0449 (11)	0.0542 (12)	0.0313 (10)	0.0286 (10)	0.0203 (10)
O10	0.0513 (9)	0.0700 (11)	0.0608 (11)	0.0309 (9)	0.0327 (8)	0.0438 (9)
O11	0.0402 (8)	0.0490 (9)	0.0500 (9)	0.0259 (7)	0.0164 (7)	0.0231 (7)
O12	0.0322 (7)	0.0352 (8)	0.0412 (8)	0.0154 (6)	0.0153 (6)	0.0138 (6)
O13	0.0550 (10)	0.0349 (8)	0.0498 (10)	0.0011 (7)	0.0026 (8)	0.0108 (7)
O14	0.0700 (11)	0.0579 (11)	0.0498 (10)	0.0366 (9)	0.0221 (9)	0.0103 (8)
O15	0.149 (4)	0.155 (5)	0.118 (4)	0.090 (3)	0.066 (3)	0.110 (4)
O16	0.160 (6)	0.184 (9)	0.188 (9)	0.113 (7)	0.139 (7)	0.141 (8)
O15'	0.154 (9)	0.103 (7)	0.093 (6)	−0.068 (6)	0.040 (6)	0.032 (6)
O16'	0.221 (16)	0.107 (9)	0.039 (5)	−0.058 (11)	0.027 (7)	0.020 (4)
O17	0.0757 (13)	0.0789 (13)	0.0519 (11)	0.0432 (11)	0.0218 (9)	0.0299 (10)
Cl2	0.0971 (6)	0.0333 (3)	0.0919 (6)	0.0188 (3)	0.0292 (4)	0.0254 (3)

Geometric parameters (Å, º) top

C1—O1	1.231 (2)	C17—O10	1.228 (2)
C1—N1	1.355 (3)	C17—N6	1.356 (3)
C1—N2	1.357 (3)	C17—N7	1.358 (3)
C2—O3	1.246 (2)	C18—O12	1.255 (2)
C2—N2	1.395 (3)	C18—N7	1.389 (3)
C2—C3	1.408 (3)	C18—C19	1.400 (3)
C3—C4	1.409 (3)	C19—C20	1.422 (3)
C3—C5	1.454 (3)	C19—C21	1.465 (3)
C4—O2	1.241 (2)	C20—O11	1.236 (2)
C4—N1	1.394 (3)	C20—N6	1.396 (3)
C5—C10	1.398 (3)	C21—C26	1.398 (3)
C5—C6	1.399 (3)	C21—C22	1.406 (3)
C6—C7	1.377 (3)	C22—C23	1.368 (3)
C6—H6	0.9300	C22—H22	0.9300
C7—C8	1.390 (3)	C23—C24	1.386 (3)
C7—Cl1	1.725 (2)	C23—Cl2	1.721 (2)
C8—C9	1.374 (3)	C24—C25	1.364 (3)
C8—N4	1.464 (3)	C24—N9	1.468 (3)
C9—C10	1.372 (3)	C25—C26	1.377 (3)
C9—H9	0.9300	C25—H25	0.9300
C10—N3	1.473 (3)	C26—N8	1.471 (3)
C11—O8	1.403 (3)	C27—O17	1.404 (3)
C11—C12	1.512 (3)	C27—C28	1.476 (4)
C11—H11A	0.9700	C27—H27A	0.9700
C11—H11B	0.9700	C27—H27B	0.9700
C12—N5	1.491 (3)	C28—N10	1.482 (3)
C12—H12A	0.9700	C28—H28A	0.9700
C12—H12B	0.9700	C28—H28B	0.9700
C13—C14	1.486 (4)	C29—C30	1.474 (4)
C13—N5	1.497 (3)	C29—N10	1.495 (3)
C13—H13A	0.9700	C29—H29A	0.9700
C13—H13B	0.9700	C29—H29B	0.9700
C14—H14A	0.9600	C30—H30A	0.9600
C14—H14B	0.9600	C30—H30B	0.9600
C14—H14C	0.9600	C30—H30C	0.9600
C15—N5	1.498 (3)	C31—C32	1.482 (5)
C15—C16	1.508 (4)	C31—N10	1.568 (4)
C15—H15A	0.9700	C31—H31A	0.9700
C15—H15B	0.9700	C31—H31B	0.9700
C16—H16A	0.9600	C32—H32A	0.9600
C16—H16B	0.9600	C32—H32B	0.9600
C16—H16C	0.9600	C32—H32C	0.9600
N1—H1	0.84 (2)	N6—H6A	0.81 (2)
N2—H2	0.85 (3)	N7—H7	0.84 (3)
N3—O4	1.221 (3)	N8—O13	1.213 (2)
N3—O5	1.223 (3)	N8—O14	1.225 (2)
N4—O6	1.194 (3)	N9—O16'	1.076 (9)
N4—O7	1.235 (3)	N9—O16	1.115 (5)
N5—H5	0.9100	N9—O15	1.275 (5)
O8—H8	0.8200	N9—O15'	1.343 (8)
O9—H9A	0.844 (10)	N10—H10	0.9100
O9—H9B	0.847 (10)	O17—H17	0.8200

O1—C1—N1	121.94 (18)	O12—C18—N7	116.88 (17)
O1—C1—N2	122.51 (19)	O12—C18—C19	125.81 (18)
N1—C1—N2	115.54 (18)	N7—C18—C19	117.30 (17)
O3—C2—N2	117.45 (17)	C18—C19—C20	120.00 (18)
O3—C2—C3	125.94 (18)	C18—C19—C21	121.25 (17)
N2—C2—C3	116.58 (16)	C20—C19—C21	118.75 (17)
C2—C3—C4	120.63 (18)	O11—C20—N6	116.96 (17)
C2—C3—C5	119.26 (17)	O11—C20—C19	126.90 (19)
C4—C3—C5	120.07 (17)	N6—C20—C19	116.09 (17)
O2—C4—N1	118.45 (17)	C26—C21—C22	114.50 (18)
O2—C4—C3	125.05 (19)	C26—C21—C19	126.22 (17)
N1—C4—C3	116.49 (17)	C22—C21—C19	119.28 (17)
C10—C5—C6	115.15 (18)	C23—C22—C21	122.7 (2)
C10—C5—C3	125.52 (18)	C23—C22—H22	118.6
C6—C5—C3	119.31 (18)	C21—C22—H22	118.6
C7—C6—C5	122.8 (2)	C22—C23—C24	119.8 (2)
C7—C6—H6	118.6	C22—C23—Cl2	118.85 (18)
C5—C6—H6	118.6	C24—C23—Cl2	121.37 (17)
C6—C7—C8	119.43 (19)	C25—C24—C23	120.1 (2)
C6—C7—Cl1	116.87 (17)	C25—C24—N9	118.2 (2)
C8—C7—Cl1	123.70 (16)	C23—C24—N9	121.7 (2)
C9—C8—C7	119.59 (19)	C24—C25—C26	119.1 (2)
C9—C8—N4	116.3 (2)	C24—C25—H25	120.5
C7—C8—N4	124.1 (2)	C26—C25—H25	120.5
C10—C9—C8	119.8 (2)	C25—C26—C21	123.73 (19)
C10—C9—H9	120.1	C25—C26—N8	114.20 (18)
C8—C9—H9	120.1	C21—C26—N8	121.99 (17)
C9—C10—C5	123.18 (19)	O17—C27—C28	110.3 (3)
C9—C10—N3	114.93 (19)	O17—C27—H27A	109.6
C5—C10—N3	121.68 (18)	C28—C27—H27A	109.6
O8—C11—C12	111.63 (19)	O17—C27—H27B	109.6
O8—C11—H11A	109.3	C28—C27—H27B	109.6
C12—C11—H11A	109.3	H27A—C27—H27B	108.1
O8—C11—H11B	109.3	C27—C28—N10	114.6 (2)
C12—C11—H11B	109.3	C27—C28—H28A	108.6
H11A—C11—H11B	108.0	N10—C28—H28A	108.6
N5—C12—C11	111.96 (19)	C27—C28—H28B	108.6
N5—C12—H12A	109.2	N10—C28—H28B	108.6
C11—C12—H12A	109.2	H28A—C28—H28B	107.6
N5—C12—H12B	109.2	C30—C29—N10	113.5 (2)
C11—C12—H12B	109.2	C30—C29—H29A	108.9
H12A—C12—H12B	107.9	N10—C29—H29A	108.9
C14—C13—N5	115.1 (2)	C30—C29—H29B	108.9
C14—C13—H13A	108.5	N10—C29—H29B	108.9
N5—C13—H13A	108.5	H29A—C29—H29B	107.7
C14—C13—H13B	108.5	C29—C30—H30A	109.5
N5—C13—H13B	108.5	C29—C30—H30B	109.5
H13A—C13—H13B	107.5	H30A—C30—H30B	109.5
C13—C14—H14A	109.5	C29—C30—H30C	109.5
C13—C14—H14B	109.5	H30A—C30—H30C	109.5
H14A—C14—H14B	109.5	H30B—C30—H30C	109.5
C13—C14—H14C	109.5	C32—C31—N10	111.7 (2)
H14A—C14—H14C	109.5	C32—C31—H31A	109.3
H14B—C14—H14C	109.5	N10—C31—H31A	109.3
N5—C15—C16	112.4 (2)	C32—C31—H31B	109.3
N5—C15—H15A	109.1	N10—C31—H31B	109.3
C16—C15—H15A	109.1	H31A—C31—H31B	107.9
N5—C15—H15B	109.1	C31—C32—H32A	109.5
C16—C15—H15B	109.1	C31—C32—H32B	109.5
H15A—C15—H15B	107.9	H32A—C32—H32B	109.5
C15—C16—H16A	109.5	C31—C32—H32C	109.5
C15—C16—H16B	109.5	H32A—C32—H32C	109.5
H16A—C16—H16B	109.5	H32B—C32—H32C	109.5
C15—C16—H16C	109.5	C17—N6—C20	126.19 (18)
H16A—C16—H16C	109.5	C17—N6—H6A	117.4 (17)
H16B—C16—H16C	109.5	C20—N6—H6A	116.4 (17)
C1—N1—C4	125.43 (17)	C17—N7—C18	125.73 (18)
C1—N1—H1	113.6 (15)	C17—N7—H7	118.2 (17)
C4—N1—H1	120.9 (15)	C18—N7—H7	115.9 (17)
C1—N2—C2	125.29 (18)	O13—N8—O14	124.30 (19)
C1—N2—H2	118.9 (16)	O13—N8—C26	118.52 (17)
C2—N2—H2	115.6 (16)	O14—N8—C26	117.12 (18)
O4—N3—O5	124.6 (2)	O16'—N9—O16	57.1 (8)
O4—N3—C10	118.05 (19)	O16'—N9—O15	81.8 (10)
O5—N3—C10	117.3 (2)	O16—N9—O15	121.3 (4)
O6—N4—O7	122.9 (2)	O16'—N9—O15'	115.5 (8)
O6—N4—C8	118.8 (2)	O16—N9—O15'	67.1 (7)
O7—N4—C8	117.6 (2)	O15—N9—O15'	103.5 (7)
C12—N5—C13	114.51 (18)	O16'—N9—C24	125.0 (6)
C12—N5—C15	110.22 (18)	O16—N9—C24	121.6 (4)
C13—N5—C15	113.58 (18)	O15—N9—C24	116.0 (3)
C12—N5—H5	105.9	O15'—N9—C24	110.0 (4)
C13—N5—H5	105.9	C28—N10—C29	115.2 (2)
C15—N5—H5	105.9	C28—N10—C31	110.8 (2)
C11—O8—H8	109.5	C29—N10—C31	108.0 (2)
H9A—O9—H9B	111.6 (17)	C28—N10—H10	107.5
O10—C17—N6	122.98 (19)	C29—N10—H10	107.5
O10—C17—N7	122.42 (19)	C31—N10—H10	107.5
N6—C17—N7	114.59 (18)	C27—O17—H17	109.5

O3—C2—C3—C4	179.2 (2)	O12—C18—C19—C21	2.3 (3)
N2—C2—C3—C4	1.3 (3)	N7—C18—C19—C21	−178.60 (18)
O3—C2—C3—C5	−3.0 (3)	C18—C19—C20—O11	−180.0 (2)
N2—C2—C3—C5	179.08 (18)	C21—C19—C20—O11	0.5 (3)
C2—C3—C4—O2	179.2 (2)	C18—C19—C20—N6	−2.7 (3)
C5—C3—C4—O2	1.5 (3)	C21—C19—C20—N6	177.79 (18)
C2—C3—C4—N1	0.4 (3)	C18—C19—C21—C26	43.5 (3)
C5—C3—C4—N1	−177.35 (18)	C20—C19—C21—C26	−137.0 (2)
C2—C3—C5—C10	136.1 (2)	C18—C19—C21—C22	−135.7 (2)
C4—C3—C5—C10	−46.2 (3)	C20—C19—C21—C22	43.7 (3)
C2—C3—C5—C6	−45.7 (3)	C26—C21—C22—C23	2.8 (3)
C4—C3—C5—C6	132.0 (2)	C19—C21—C22—C23	−177.86 (19)
C10—C5—C6—C7	−2.7 (3)	C21—C22—C23—C24	−2.1 (3)
C3—C5—C6—C7	178.89 (18)	C21—C22—C23—Cl2	178.70 (16)
C5—C6—C7—C8	2.8 (3)	C22—C23—C24—C25	−0.6 (3)
C5—C6—C7—Cl1	−178.12 (15)	Cl2—C23—C24—C25	178.48 (18)
C6—C7—C8—C9	−0.2 (3)	C22—C23—C24—N9	178.1 (3)
Cl1—C7—C8—C9	−179.13 (17)	Cl2—C23—C24—N9	−2.8 (3)
C6—C7—C8—N4	−178.0 (2)	C23—C24—C25—C26	2.5 (3)
Cl1—C7—C8—N4	3.1 (3)	N9—C24—C25—C26	−176.3 (2)
C7—C8—C9—C10	−2.5 (3)	C24—C25—C26—C21	−1.7 (3)
N4—C8—C9—C10	175.5 (2)	C24—C25—C26—N8	175.07 (19)
C8—C9—C10—C5	2.6 (3)	C22—C21—C26—C25	−0.9 (3)
C8—C9—C10—N3	−172.2 (2)	C19—C21—C26—C25	179.86 (19)
C6—C5—C10—C9	0.0 (3)	C22—C21—C26—N8	−177.43 (17)
C3—C5—C10—C9	178.3 (2)	C19—C21—C26—N8	3.3 (3)
C6—C5—C10—N3	174.38 (18)	O17—C27—C28—N10	68.8 (4)
C3—C5—C10—N3	−7.3 (3)	O10—C17—N6—C20	−178.8 (2)
O8—C11—C12—N5	51.5 (3)	N7—C17—N6—C20	2.0 (3)
O1—C1—N1—C4	−179.6 (2)	O11—C20—N6—C17	178.2 (2)
N2—C1—N1—C4	0.8 (3)	C19—C20—N6—C17	0.7 (3)
O2—C4—N1—C1	179.5 (2)	O10—C17—N7—C18	177.9 (2)
C3—C4—N1—C1	−1.6 (3)	N6—C17—N7—C18	−3.0 (3)
O1—C1—N2—C2	−178.4 (2)	O12—C18—N7—C17	−179.7 (2)
N1—C1—N2—C2	1.2 (3)	C19—C18—N7—C17	1.1 (3)
O3—C2—N2—C1	179.7 (2)	C25—C26—N8—O13	−134.9 (2)
C3—C2—N2—C1	−2.2 (3)	C21—C26—N8—O13	42.0 (3)
C9—C10—N3—O4	135.0 (2)	C25—C26—N8—O14	42.5 (2)
C5—C10—N3—O4	−39.9 (3)	C21—C26—N8—O14	−140.6 (2)
C9—C10—N3—O5	−42.1 (3)	C25—C24—N9—O16'	29.0 (14)
C5—C10—N3—O5	143.1 (2)	C23—C24—N9—O16'	−149.7 (13)
C9—C8—N4—O6	25.7 (4)	C25—C24—N9—O16	−40.6 (8)
C7—C8—N4—O6	−156.4 (3)	C23—C24—N9—O16	140.7 (8)
C9—C8—N4—O7	−144.8 (3)	C25—C24—N9—O15	127.6 (4)
C7—C8—N4—O7	33.1 (4)	C23—C24—N9—O15	−51.2 (5)
C11—C12—N5—C13	58.8 (3)	C25—C24—N9—O15'	−115.3 (8)
C11—C12—N5—C15	−171.7 (2)	C23—C24—N9—O15'	65.9 (8)
C14—C13—N5—C12	66.5 (3)	C27—C28—N10—C29	106.6 (3)
C14—C13—N5—C15	−61.3 (3)	C27—C28—N10—C31	−130.3 (3)
C16—C15—N5—C12	172.3 (2)	C30—C29—N10—C28	−62.9 (3)
C16—C15—N5—C13	−57.7 (3)	C30—C29—N10—C31	172.6 (3)
O12—C18—C19—C20	−177.21 (19)	C32—C31—N10—C28	71.2 (3)
N7—C18—C19—C20	1.9 (3)	C32—C31—N10—C29	−161.6 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5···O9ⁱ	0.91	1.85	2.749 (2)	167
O8—H8···O1ⁱⁱ	0.82	1.98	2.674 (2)	141
O9—H9A···O2	0.84 (1)	1.85 (1)	2.691 (2)	171 (3)
O9—H9B···O10	0.85 (1)	2.11 (2)	2.850 (2)	146 (3)
N2—H2···O3ⁱⁱ	0.85 (3)	1.99 (3)	2.826 (2)	168 (2)
N1—H1···O10	0.84 (2)	2.10 (2)	2.933 (2)	171 (2)
N10—H10···O12	0.91	1.85	2.698 (2)	154
O17—H17···O8ⁱⁱⁱ	0.82	1.91	2.667 (2)	153
N7—H7···O17	0.84 (3)	2.07 (3)	2.911 (2)	176 (2)
N6—H6A···O1	0.81 (2)	2.16 (2)	2.947 (2)	167 (2)

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

Experimental details

Crystal data
Chemical formula	C₆H₁₆NO⁺·C₁₀H₄ClN₄O₇⁻·0.5H₂O
M_r	454.83
Crystal system, space group	Triclinic, P1
Temperature (K)	294
a, b, c (Å)	12.3775 (7), 12.8109 (8), 13.5834 (9)
α, β, γ (°)	101.497 (4), 99.142 (3), 99.718 (3)
V (Å³)	2038.6 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.25
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.901, 0.942
No. of measured, independent and observed [I > 2σ(I)] reflections	36654, 7179, 5639
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.138, 1.07
No. of reflections	7179
No. of parameters	598
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.72, −0.32

Computer programs: APEX2 (Bruker, 2004), APEX2 and SAINT (Bruker, 2004), SAINT and XPREP (Bruker, 2004), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2008).