Crystal structures of 4-(pyrimidin-2-yl)piperazin-1-ium chloride and 4-(pyrimidin-2-yl)piperazin-1-ium nitrate

The title salts, C₈H₁₃N₄⁺·Cl⁻, (I), and C₈H₁₃N₄⁺·NO₃⁻, (II), contain linked pyridinium–piperazine heterocycles. In the crystal of (I), weak N—H...Cl inter­actions lead to zigzag chains along [100] while in the crystal of (II), bifurcated N—H...(O,O) hydrogen bonds and weak C—H...O inter­actions collectively link the components into infinite chains along [100].

Key indicators

Structure: I

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.035
• wR factor = 0.091
• Data-to-parameter ratio = 15.5

Structure: II

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.058
• wR factor = 0.163
• Data-to-parameter ratio = 13.4

checkCIF/PLATON results

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Datablock: I


Alert level C
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds ...............     0.0043 Ang.

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF     Please Do !
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          2 Report
PLAT033_ALERT_4_G Flack x Value Deviates > 2*sigma from Zero .....      0.056
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          5 Note

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

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Datablock: II


Alert level C
PLAT242_ALERT_2_C Low       Ueq as Compared to Neighbors for .....         N5 Check
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      3.702 Check
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         16 Report

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF     Please Do !
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          2 Report
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         14 Note

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

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

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S1. Chemical context

Pyrimidine-containing compounds exhibit various biological activities (Goldmann & Stoltefuss, 1991) and related fused heterocycles are unique classes of heterocyclic compounds that exhibit a broad spectrum of biological activities such as anti­cancer (Amin et al., 2009; Pandey et al., 2004), anti­viral (Ibrahim & El-Metwally, 2010), anti­bacterial (Kuyper et al., 1996) and anti-oxidant (Padmaja et al., 2009), anti­depressant (Kim et al., 2010) and possess anti-inflammatory effects (Clark et al., 2007). In addition, several piperazine derivatives have reached the stage of clinical application; among the known drugs that are used to treat anxiety is a pyrimidinylpiperazinyl compound, bu­spirone and BuSpar® (Tollefson et al., 1991). Our research group has published a number of papers on incorporated heterocyclic ring structures, viz. imatinibium dipicrate (Jasinski et al., 2010), 1-(2-hy­droxy­ethyl)-4-[3-(2-tri­fluoro­methyl-9H-thioxanthen-9-yl­idene)propyl]­piperazine-1,4-diium dichloride, which is the di­hydro­chloride salt of flupentixol (Siddegowda et al., 2011a) and opipramolium fumarate (Siddegowda et al., 2011b). Other related crystal structures are 4-(pyrimidin-2-yl)piperazin-1-ium (E)-3-carb­oxy­prop-2-enoate (Yamuna et al., 2014a), flupentixol tartarate and enrofloxacinium oxalate (Yamuna et al., 2014b,c). As part of our ongoing studies in this area, we report herein the crystal structures of the title salts, (I) and (II).

S2. Structural commentary

The structure of (I) and its atom numbering are shown in Fig. 1. It consists of a pyrimidylpiperazine cation joined by the C1/N3 atoms of each unit and a chloride anion. The C1—N3 bond is 1.373 (3) Å long, which compares favorably with similar ionic structures containing this cation [1.369 (3) (Yamuna et al., 2014a), and 1.36 (6) and 1.37 (1) Å (Ding et al., 2014)]. The N3/C5/C6/N4/C7/C8 piperazine unit adopts a slightly distorted chair conformation with protonation at the N4 nitro­gen atom. The structure of (II) and its atom numbering are shown in Fig. 2. Similarly, it consists of a pyrimidylpiperazine cation joined by the C1/N3 atoms of each unit and a nitrate anion. The C1—N3 bond is 1.369 (3) Å, also in the range of the related structures described above. The N3/C5/C6/N4/C7/C8 piperazine unit also adopts a slightly distorted chair conformation with protonation at the N4 atom.

S3. Supra­molecular features

In the crystal of (I), N4—H4A···Cl1 and N4—H4B···Cl1 inter­actions are observed between chloride anions and pyrimidylpiperazine cations, forming zigzag chains along [100] (Fig. 3 and Table 1). In the crystal of (II), both of the H atoms on the N4 atom of the pyrimidylpiperazine cation are bifurcated, forming N—H···(O,O) hydrogen bonds (Fig. 4 and Table 2). Additional C—H···O inter­actions between the pyrimidyl unit and the nitrate anion are present which, in concert with the N—H···O hydrogen bonds between the piperazine group and nitrate anions, form infinite chains along [100].

S4. Database survey

A search of the Cambridge Structural Database (Version 5.35, last update May 2014: Allen 2002) revealed only three structures containing the 4-(pyrimidin-2-yl)piperazin-1-ium cation similar to the structures reported here. These include the salts of 4-(pyrimidin-2-yl)piperazin-1-ium 3-carb­oxy­prop-2-enoate (Yamuna et al. 2014a), 4-(pyrimidin-2-yl)piperazin-1-ium hydrogen D-tartrate monohydrate (Ding et al., 2014) and 4-(pyrimidin-2-yl)piperazin-1-ium hydrogen L-tartrate monohydrate (Ding et al. 2014). The 3-carb­oxy­prop-2-enoate complex crystallizes in space group P2₁/c while the two hydrogen (D and L)-tartrate monohydrate salts both crystallize in the P2₁2₁2₁. In comparison, title salt (I) crystallizes in P2₁2₁2₁ while (II) crystallizes in space group P2₁/c. In addition, as a related observation, 109 structures containing the pyrimidine–piperazine unit were also identified in this search. Some of these include, uniquely, the 4-(pyrimidin-2-yl)piperazin-1-yl unit itself. These include 1-[4-(pyrimidin-2-yl)piperazin-1-yl]ethanone, (1-methyl-1H-pyrrol-2-yl)[4-(pyrimidin-2-yl)piperazin-1-yl]methanone, [4-(pyrimidin-2-yl)piperazin-1-yl](2-thienyl)methanone, (4-fluoro­phenyl)[4-(pyrimidin-2-yl)piperazin-1-yl]methanone (Spencer et al., 2011), (E)-1-phenyl-3-[4-(pyrimidin-2-yl)piperazin-1-yl]propan-1-one oxime (Kolasa et al., 2006), N-(4-chloro­phenyl)-4-(pyrimidin-2-yl)piperazine-1-carboxamide (Li, 2011) and 6-{3-[4-(pyrimidin-2-yl)piperazin-1-yl]propyl}-2,3-di­hydro-5H-[1,4]dithiino[2,3-c]pyrrole-5,7(6H)-dione (Bielenica et al., 2011).

S5. Synthesis and crystallization

For the preparation of title salt (I), a mixture of 1-(pyrimidin-2-yl)piperazine (0.2 g) and concentrated hydro­chloric acid (5 ml) was stirred well over a magnetic stirrer at room temperature for 10 min and then warmed at 313 K for another 10 min. A white precipitate was obtained, which was dried in the open air overnight and then dissolved in hot di­methyl sulfoxide solvent. After few days, colourless blocks were obtained on slow evaporation (m.p. above 563 K).

For the preparation of title salt (II), a mixture of 1-(pyrimidin-2-yl)piperazine, from Sigma–Aldrich (0.2 g), and concentrated nitric acid (5 ml) was stirred well over a magnetic stirrer at room temperature for 10 min. A white precipitate was obtained immediately, which was dried in the open air overnight and then dissolved in water. After a few days, colourless blocks were obtained on slow evaporation (m.p. 463–470 K).

S6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. In both (I) and (II), all of the H atoms were placed in their calculated positions and then refined using a riding model with C—H bond lengths of 0.93 (CH) or 0.97 Å (CH₂) and N—H bond lengths of 0.97 Å. Isotropic displacement parameters for these atoms were set at 1.2U_eq(CH,CH₂,NH).

Related literature

For related literature, see: Allen (2002); Amin et al. (2009); Bielenica et al. (2011); Clark et al. (2007); Ding et al. (2014); Goldmann & Stoltefuss (1991); Ibrahim & El-Metwally (2010); Jasinski et al. (2010); Kim et al. (2010); Kolasa et al. (2006); Kuyper et al. (1996); Li (2011); Padmaja et al. (2009); Pandey et al. (2004); Siddegowda et al. (2011a, 2011b); Spencer et al. (2011); Tollefson et al. (1991); Yamuna et al. (2014a, 2014b, 2014c).

Computing details

For both compounds, data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis RED (Agilent, 2012); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures

	Fig. 1. ORTEP drawing of C8H13N4^+.Cl^-, (I), showing 30% probability displacement ellipsoids.
	Fig. 2. ORTEP drawing of C8H13N4^+.NO3^-, (II), showing 30% probability displacement ellipsoids.
	Fig. 3. Molecular packing for C8H13N4^+.Cl^-, (I), viewed along the b axis. Dashed lines indicate N—H···Cl interactions forming zigzag chains along the a axis (see Table 1 for details). H atoms not involved in hydrogen bonding have been omitted for clarity.
	Fig. 4. Molecular packing for C8H13N4^+.NO3^-, (II), viewed along the c axis. Dashed lines indicate N—H···O hydrogen bonds and additional C—H···O interactions forming infinite chains along [100] (see Table 2 for details). H atoms not involved in hydrogen bonding have been omitted for clarity.

(I) 4-(Pyrimidin-2-yl)piperazin-1-ium chloride

Crystal data

C8H13N4^+·Cl^−	Dx = 1.395 Mg m^−3
Mr = 200.67	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, P212121	Cell parameters from 2676 reflections
a = 6.84764 (17) Å	θ = 4.6–71.5°
b = 7.27667 (18) Å	µ = 3.21 mm^−1
c = 19.1751 (5) Å	T = 173 K
V = 955.46 (4) Å^3	Irregular, colourless
Z = 4	0.26 × 0.14 × 0.08 mm
F(000) = 424

Data collection

Agilent Agilent Eos Gemini diffractometer	1841 independent reflections
Radiation source: Enhance (Cu) X-ray Source	1761 reflections with I > 2σ(I)
Detector resolution: 16.0416 pixels mm^-1	Rint = 0.045
ω scans	θmax = 71.4°, θmin = 4.6°
Absorption correction: multi-scan (CrysAlis RED; Agilent, 2012)	h = −8→8
Tmin = 0.417, Tmax = 1.000	k = −8→4
5514 measured reflections	l = −23→23

Refinement

Refinement on F^2	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0504P)^2 + 0.1163P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.035	(Δ/σ)max < 0.001
wR(F^2) = 0.091	Δρmax = 0.23 e Å^−3
S = 1.08	Δρmin = −0.20 e Å^−3
1841 reflections	Extinction correction: SHELXL2012 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
119 parameters	Extinction coefficient: 0.0073 (13)
0 restraints	Absolute structure: Flack x determined using 687 quotients [(I^+)-(I^-)]/[(I^+)+(I^-)] (Parsons et al. (2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.056 (15)
Hydrogen site location: inferred from neighbouring sites

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.08383 (9)	0.49612 (9)	0.48653 (3)	0.0262 (2)
N1	0.6948 (4)	0.6820 (3)	0.81551 (12)	0.0251 (5)
N2	0.9664 (4)	0.5690 (3)	0.74930 (13)	0.0286 (6)
N3	0.6688 (3)	0.6293 (3)	0.69659 (12)	0.0224 (5)
N4	0.4359 (4)	0.6322 (3)	0.57422 (12)	0.0258 (5)
H4A	0.3467	0.5800	0.5451	0.031*
H4B	0.4718	0.7422	0.5556	0.031*
C1	0.7813 (4)	0.6281 (4)	0.75588 (14)	0.0208 (5)
C2	0.8040 (4)	0.6746 (4)	0.87274 (15)	0.0269 (6)
H2	0.7471	0.7097	0.9159	0.032*
C3	0.9968 (5)	0.6181 (4)	0.87217 (16)	0.0318 (7)
H3	1.0742	0.6147	0.9133	0.038*
C4	1.0692 (5)	0.5668 (4)	0.80773 (17)	0.0330 (7)
H4	1.2013	0.5274	0.8052	0.040*
C5	0.7582 (4)	0.5944 (4)	0.62855 (14)	0.0245 (6)
H5A	0.8701	0.5096	0.6341	0.029*
H5B	0.8076	0.7111	0.6088	0.029*
C6	0.6103 (4)	0.5108 (4)	0.57949 (14)	0.0278 (6)
H6A	0.6694	0.4948	0.5328	0.033*
H6B	0.5705	0.3883	0.5969	0.033*
C7	0.3448 (4)	0.6631 (4)	0.64394 (14)	0.0246 (6)
H7A	0.2964	0.5449	0.6628	0.030*
H7B	0.2323	0.7475	0.6392	0.030*
C8	0.4936 (4)	0.7449 (4)	0.69357 (14)	0.0233 (6)
H8A	0.5297	0.8698	0.6777	0.028*
H8B	0.4359	0.7553	0.7407	0.028*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0230 (3)	0.0300 (4)	0.0255 (3)	−0.0007 (3)	−0.0033 (2)	0.0015 (3)
N1	0.0252 (12)	0.0254 (11)	0.0246 (11)	−0.0008 (10)	−0.0007 (10)	−0.0015 (9)
N2	0.0240 (14)	0.0310 (12)	0.0309 (12)	0.0064 (10)	0.0001 (10)	0.0014 (10)
N3	0.0184 (11)	0.0255 (11)	0.0233 (11)	0.0044 (9)	0.0015 (9)	−0.0022 (10)
N4	0.0228 (12)	0.0290 (11)	0.0256 (11)	−0.0051 (10)	−0.0032 (10)	0.0005 (10)
C1	0.0217 (13)	0.0157 (11)	0.0251 (13)	0.0000 (10)	0.0013 (11)	0.0022 (10)
C2	0.0342 (16)	0.0238 (13)	0.0229 (13)	−0.0013 (12)	0.0000 (12)	−0.0001 (11)
C3	0.0353 (16)	0.0287 (14)	0.0314 (14)	−0.0017 (14)	−0.0114 (14)	0.0056 (12)
C4	0.0238 (14)	0.0339 (14)	0.0413 (17)	0.0072 (13)	−0.0056 (14)	0.0062 (13)
C5	0.0208 (13)	0.0292 (14)	0.0233 (13)	0.0030 (11)	0.0031 (11)	−0.0032 (11)
C6	0.0256 (14)	0.0316 (14)	0.0261 (13)	0.0000 (14)	0.0035 (10)	−0.0058 (12)
C7	0.0200 (13)	0.0272 (13)	0.0267 (14)	−0.0009 (11)	−0.0007 (11)	0.0007 (11)
C8	0.0186 (13)	0.0244 (12)	0.0268 (13)	0.0046 (12)	−0.0004 (12)	−0.0027 (11)

Geometric parameters (Å, º)

N1—C1	1.346 (4)	C3—H3	0.9500
N1—C2	1.329 (4)	C3—C4	1.383 (4)
N2—C1	1.344 (4)	C4—H4	0.9500
N2—C4	1.323 (4)	C5—H5A	0.9900
N3—C1	1.373 (3)	C5—H5B	0.9900
N3—C5	1.463 (3)	C5—C6	1.510 (4)
N3—C8	1.466 (3)	C6—H6A	0.9900
N4—H4A	0.9100	C6—H6B	0.9900
N4—H4B	0.9100	C7—H7A	0.9900
N4—C6	1.489 (4)	C7—H7B	0.9900
N4—C7	1.492 (3)	C7—C8	1.516 (4)
C2—H2	0.9500	C8—H8A	0.9900
C2—C3	1.383 (4)	C8—H8B	0.9900
C2—N1—C1	116.2 (2)	N3—C5—H5B	109.6
C4—N2—C1	115.2 (3)	N3—C5—C6	110.2 (2)
C1—N3—C5	120.2 (2)	H5A—C5—H5B	108.1
C1—N3—C8	119.7 (2)	C6—C5—H5A	109.6
C5—N3—C8	114.0 (2)	C6—C5—H5B	109.6
H4A—N4—H4B	108.0	N4—C6—C5	110.0 (2)
C6—N4—H4A	109.4	N4—C6—H6A	109.7
C6—N4—H4B	109.4	N4—C6—H6B	109.7
C6—N4—C7	111.3 (2)	C5—C6—H6A	109.7
C7—N4—H4A	109.4	C5—C6—H6B	109.7
C7—N4—H4B	109.4	H6A—C6—H6B	108.2
N1—C1—N3	117.0 (2)	N4—C7—H7A	109.7
N2—C1—N1	126.0 (2)	N4—C7—H7B	109.7
N2—C1—N3	116.9 (2)	N4—C7—C8	109.9 (2)
N1—C2—H2	118.6	H7A—C7—H7B	108.2
N1—C2—C3	122.9 (3)	C8—C7—H7A	109.7
C3—C2—H2	118.6	C8—C7—H7B	109.7
C2—C3—H3	122.3	N3—C8—C7	110.4 (2)
C2—C3—C4	115.5 (3)	N3—C8—H8A	109.6
C4—C3—H3	122.3	N3—C8—H8B	109.6
N2—C4—C3	124.2 (3)	C7—C8—H8A	109.6
N2—C4—H4	117.9	C7—C8—H8B	109.6
C3—C4—H4	117.9	H8A—C8—H8B	108.1
N3—C5—H5A	109.6
N1—C2—C3—C4	−0.8 (4)	C4—N2—C1—N1	−0.6 (4)
N3—C5—C6—N4	55.8 (3)	C4—N2—C1—N3	−178.9 (3)
N4—C7—C8—N3	−54.5 (3)	C5—N3—C1—N1	172.5 (2)
C1—N1—C2—C3	1.0 (4)	C5—N3—C1—N2	−9.0 (4)
C1—N2—C4—C3	0.8 (4)	C5—N3—C8—C7	55.2 (3)
C1—N3—C5—C6	151.9 (2)	C6—N4—C7—C8	57.4 (3)
C1—N3—C8—C7	−152.4 (2)	C7—N4—C6—C5	−58.1 (3)
C2—N1—C1—N2	−0.3 (4)	C8—N3—C1—N1	21.8 (4)
C2—N1—C1—N3	178.0 (2)	C8—N3—C1—N2	−159.8 (2)
C2—C3—C4—N2	−0.2 (5)	C8—N3—C5—C6	−55.8 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···Cl1	0.91	2.21	3.102 (2)	167
N4—H4B···Cl1^i	0.91	2.21	3.114 (2)	175

Symmetry code: (i) x+1/2, −y+3/2, −z+1.

(II) 4-(Pyrimidin-2-yl)piperazin-1-ium nitrate

Crystal data

C8H13N4^+·NO3^−	F(000) = 480
Mr = 227.23	Dx = 1.469 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54184 Å
a = 10.5272 (6) Å	Cell parameters from 2763 reflections
b = 7.2230 (3) Å	θ = 6.2–71.4°
c = 14.1575 (7) Å	µ = 0.98 mm^−1
β = 107.341 (6)°	T = 173 K
V = 1027.58 (9) Å^3	Irregular, colourless
Z = 4	0.22 × 0.16 × 0.06 mm

Data collection

Agilent Agilent Eos Gemini diffractometer	1960 independent reflections
Radiation source: Cu Kα	1752 reflections with I > 2σ(I)
Detector resolution: 16.0416 pixels mm^-1	Rint = 0.040
ω scans	θmax = 71.0°, θmin = 4.4°
Absorption correction: multi-scan (CrysAlis RED; Agilent, 2012)	h = −9→12
Tmin = 0.727, Tmax = 1.000	k = −8→8
6218 measured reflections	l = −17→16

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.058	w = 1/[σ^2(Fo^2) + (0.0789P)^2 + 0.9595P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.163	(Δ/σ)max < 0.001
S = 1.10	Δρmax = 0.42 e Å^−3
1960 reflections	Δρmin = −0.25 e Å^−3
146 parameters	Extinction correction: SHELXL2012 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0099 (14)
Primary atom site location: structure-invariant direct methods

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.4119 (2)	0.6964 (4)	0.41222 (17)	0.0615 (7)
O2	0.50951 (18)	0.6257 (2)	0.30424 (14)	0.0381 (5)
O3	0.55020 (17)	0.8884 (2)	0.37996 (13)	0.0323 (5)
N5	0.49103 (17)	0.7390 (3)	0.36677 (13)	0.0238 (4)
N1	0.00592 (19)	0.2396 (3)	0.48106 (14)	0.0291 (5)
N2	−0.11846 (18)	0.3821 (3)	0.32856 (15)	0.0273 (5)
N3	0.10930 (18)	0.3372 (3)	0.36702 (14)	0.0268 (5)
N4	0.33344 (18)	0.3134 (3)	0.29632 (15)	0.0278 (5)
H4A	0.3814	0.2536	0.2617	0.033*
H4B	0.3777	0.4191	0.3216	0.033*
C1	−0.0049 (2)	0.3204 (3)	0.39365 (16)	0.0220 (5)
C2	−0.1085 (3)	0.2126 (3)	0.50188 (19)	0.0346 (6)
H2	−0.1054	0.1544	0.5627	0.042*
C3	−0.2307 (2)	0.2647 (4)	0.4398 (2)	0.0362 (6)
H3	−0.3111	0.2420	0.4553	0.043*
C4	−0.2290 (2)	0.3519 (3)	0.3537 (2)	0.0329 (6)
H4	−0.3113	0.3927	0.3097	0.039*
C5	0.2387 (2)	0.2876 (4)	0.43489 (16)	0.0282 (5)
H5A	0.2266	0.2035	0.4867	0.034*
H5B	0.2848	0.4005	0.4676	0.034*
C6	0.3222 (2)	0.1932 (3)	0.37877 (17)	0.0270 (5)
H6A	0.4121	0.1674	0.4242	0.032*
H6B	0.2808	0.0738	0.3519	0.032*
C7	0.1993 (2)	0.3620 (3)	0.22801 (17)	0.0277 (5)
H7A	0.1537	0.2483	0.1960	0.033*
H7B	0.2095	0.4461	0.1755	0.033*
C8	0.1166 (2)	0.4552 (3)	0.28517 (17)	0.0276 (5)
H8A	0.1571	0.5756	0.3112	0.033*
H8B	0.0258	0.4789	0.2407	0.033*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0614 (14)	0.0836 (17)	0.0562 (13)	−0.0362 (13)	0.0431 (11)	−0.0184 (12)
O2	0.0436 (10)	0.0314 (10)	0.0460 (11)	−0.0072 (8)	0.0238 (8)	−0.0153 (8)
O3	0.0379 (9)	0.0249 (9)	0.0353 (9)	−0.0045 (7)	0.0129 (7)	−0.0021 (7)
N5	0.0175 (9)	0.0301 (10)	0.0240 (9)	−0.0015 (7)	0.0064 (7)	0.0012 (8)
N1	0.0292 (10)	0.0327 (11)	0.0282 (10)	0.0020 (8)	0.0126 (8)	0.0038 (8)
N2	0.0210 (9)	0.0270 (10)	0.0331 (11)	0.0037 (7)	0.0071 (8)	0.0001 (8)
N3	0.0189 (9)	0.0380 (11)	0.0243 (9)	0.0068 (8)	0.0075 (7)	0.0087 (8)
N4	0.0231 (9)	0.0278 (10)	0.0368 (11)	−0.0042 (8)	0.0153 (8)	−0.0045 (8)
C1	0.0207 (10)	0.0220 (10)	0.0246 (11)	0.0023 (8)	0.0087 (8)	−0.0035 (8)
C2	0.0416 (14)	0.0328 (13)	0.0372 (13)	−0.0021 (11)	0.0235 (11)	−0.0014 (10)
C3	0.0300 (13)	0.0340 (13)	0.0525 (15)	−0.0049 (10)	0.0247 (11)	−0.0130 (12)
C4	0.0224 (11)	0.0304 (12)	0.0456 (15)	0.0020 (9)	0.0098 (10)	−0.0063 (11)
C5	0.0208 (11)	0.0395 (13)	0.0234 (11)	0.0087 (9)	0.0054 (9)	0.0023 (9)
C6	0.0219 (10)	0.0296 (12)	0.0293 (11)	0.0038 (9)	0.0074 (9)	0.0014 (9)
C7	0.0291 (11)	0.0305 (12)	0.0255 (11)	−0.0013 (9)	0.0111 (9)	0.0039 (9)
C8	0.0267 (11)	0.0290 (12)	0.0283 (11)	0.0033 (9)	0.0098 (9)	0.0080 (9)

Geometric parameters (Å, º)

O1—N5	1.233 (3)	C2—C3	1.376 (4)
O2—N5	1.263 (2)	C3—H3	0.9500
O3—N5	1.232 (2)	C3—C4	1.377 (4)
N1—C1	1.342 (3)	C4—H4	0.9500
N1—C2	1.337 (3)	C5—H5A	0.9900
N2—C1	1.349 (3)	C5—H5B	0.9900
N2—C4	1.333 (3)	C5—C6	1.512 (3)
N3—C1	1.369 (3)	C6—H6A	0.9900
N3—C5	1.459 (3)	C6—H6B	0.9900
N3—C8	1.459 (3)	C7—H7A	0.9900
N4—H4A	0.9100	C7—H7B	0.9900
N4—H4B	0.9100	C7—C8	1.512 (3)
N4—C6	1.487 (3)	C8—H8A	0.9900
N4—C7	1.496 (3)	C8—H8B	0.9900
C2—H2	0.9500
O1—N5—O2	118.2 (2)	C3—C4—H4	118.2
O3—N5—O1	121.9 (2)	N3—C5—H5A	109.7
O3—N5—O2	119.82 (18)	N3—C5—H5B	109.7
C2—N1—C1	115.6 (2)	N3—C5—C6	109.86 (18)
C4—N2—C1	115.5 (2)	H5A—C5—H5B	108.2
C1—N3—C5	121.45 (19)	C6—C5—H5A	109.7
C1—N3—C8	121.92 (18)	C6—C5—H5B	109.7
C5—N3—C8	114.01 (18)	N4—C6—C5	110.12 (18)
H4A—N4—H4B	108.0	N4—C6—H6A	109.6
C6—N4—H4A	109.4	N4—C6—H6B	109.6
C6—N4—H4B	109.4	C5—C6—H6A	109.6
C6—N4—C7	111.33 (17)	C5—C6—H6B	109.6
C7—N4—H4A	109.4	H6A—C6—H6B	108.2
C7—N4—H4B	109.4	N4—C7—H7A	109.7
N1—C1—N2	126.0 (2)	N4—C7—H7B	109.7
N1—C1—N3	116.88 (19)	N4—C7—C8	109.99 (18)
N2—C1—N3	117.06 (19)	H7A—C7—H7B	108.2
N1—C2—H2	118.3	C8—C7—H7A	109.7
N1—C2—C3	123.4 (2)	C8—C7—H7B	109.7
C3—C2—H2	118.3	N3—C8—C7	109.85 (18)
C2—C3—H3	122.1	N3—C8—H8A	109.7
C2—C3—C4	115.8 (2)	N3—C8—H8B	109.7
C4—C3—H3	122.1	C7—C8—H8A	109.7
N2—C4—C3	123.6 (2)	C7—C8—H8B	109.7
N2—C4—H4	118.2	H8A—C8—H8B	108.2
N1—C2—C3—C4	−1.3 (4)	C4—N2—C1—N1	−2.7 (3)
N3—C5—C6—N4	55.5 (3)	C4—N2—C1—N3	175.4 (2)
N4—C7—C8—N3	−55.3 (2)	C5—N3—C1—N1	−6.3 (3)
C1—N1—C2—C3	−0.7 (4)	C5—N3—C1—N2	175.4 (2)
C1—N2—C4—C3	0.2 (3)	C5—N3—C8—C7	56.9 (3)
C1—N3—C5—C6	141.1 (2)	C6—N4—C7—C8	56.9 (2)
C1—N3—C8—C7	−141.2 (2)	C7—N4—C6—C5	−57.0 (2)
C2—N1—C1—N2	2.9 (3)	C8—N3—C1—N1	−166.9 (2)
C2—N1—C1—N3	−175.2 (2)	C8—N3—C1—N2	14.8 (3)
C2—C3—C4—N2	1.6 (4)	C8—N3—C5—C6	−57.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···O2^i	0.91	1.92	2.829 (3)	177
N4—H4A···O3^i	0.91	2.52	3.138 (3)	126
N4—H4B···O1	0.91	2.35	3.197 (3)	155
N4—H4B···O2	0.91	2.10	2.900 (3)	146
C3—H3···O1^ii	0.95	2.46	3.240 (3)	140
C4—H4···O2^iii	0.95	2.51	3.291 (3)	139

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