[(1,4,8,11-Tetraazacyclotetradeca-1,4,8,11-tetrayl)tetraacetamide-κ⁶N¹,N⁴,N⁸,N¹¹,O¹,O⁸]copper(II) sulfate 4.5-hydrate

The crystal structure of the title copper(II) complex, [Cu(C₁₈H₃₆N₈O₄)]SO₄·4.5H₂O, formed with the tetra­amide cyclam derivative 2-(4,8,11-triscarbamoyl­methyl-1,4,8,11-tetra­aza­cyclo­tetradec-1-yl)­acet­amide (TETAM), is described. The macrocycle lies on an inversion centre occupied by the hexacoordinated Cu atom. The four macrocyclic tertiary amines form the equatorial plane of an axially Jahn–Teller elongated octahedron. Two O atoms belonging to two diagonally opposite amide groups occupy the apical positions, giving rise to a trans-III stereochemistry, while both the remaining pendant side arms extend outwards from the macrocyclic cavity and are engaged in hydrogen bonds with sulfate anions and co-crystallized water mol­ecules.

S1. Comment

Owing to their novel physico-chemical and structural properties, substituted tetraaza macrocycles have attracted widespread interest and have provided practical solutions to challenging everyday problems, where selective metal-complex formation plays a key role. For example, lanthanide complexes of N-carbamoyl-substituted cyclen derivatives were found to exhibit interesting chiroptical properties (Parker & Williams, 1996) or to promote RNA cleavage efficiently (Amin et al., 1994). In contrast, the 14-membered cyclam analogues bearing dangling amide groups have been studied much less extensively, while crystallographic data are scarce (Meyer et al., 1998). A monoacetamide cyclam-based copper(II) complex has been structurally characterized by means of infrared and visible absorption spectroscopy (Kaden, 1984); the pH-dependent solution behaviour observed suggested the formation of a square-planar tetracoordinated species below pH 10, while apical ligation of the deprotonated amide N atom at higher pH values afforded a pentacoordinated square-pyramidal species. The crystal structure of the title copper(II) complex of 2-(4,8,11-triscarbamoylmethyl-1,4,8,11-tetraazacyclotetradec-1-yl)-acetamide, (I), is reported herein in order to investigate further the structural features related to the presence of pendant acetamide arms attached to the cyclam scaffold. \sch

Compound (I) crystallizes in the centrosymmetric space group C2/c, with half a molecular unit belonging to the asymmetric unit. The second half unit is generated by an inversion centre at (3/4, 1/4, 1/2), which is occupied by the Cu atom, leading to a planar N₄ basal coordination. According to the extended Dale nomenclature developed for heteroatom-containing macrocycles (Meyer et al., 1998), the cyclam fragment exhibits an anangular [3',4',3',4']-C ring conformation with four pseudocorners located at C1, C4, and the symmetry-related atoms C1' and C4', delimiting a parallelogram of 4.98 (C1···C4) by 3.84 Å (C1···C4') with a C4···C1···C4' angle of 99.4°. Starting at τ₁, defined as the N1—C1—C2—N2 torsion angle, the following sequence along the cycle is observed: 59.2 (2), -169.6 (1), 175.6 (2), -66.2 (2), 67.3 (2), -174.2 (1) and 157.9 (1)°. It can be easily observed that this macrocyclic conformation forces the amine N atoms to adopt a type-III configuration according to Bosnich's formalism (Bosnich et al., 1965; Frémond et al., 2000), which results in a trans layout of the four acetamide substituents. The five- and six-membered chelate rings have been characterized by puckering analysis (Cremer & Pople, 1975). For both independent five-membered chelate rings (N1—C1—C2—N2—Cu and N2—C21—C22—O22—Cu), the closest pucker descriptor is a half-chair twisted along C1—C2 (Q = 0.465 Å and ϕ = 91.8°) and N2—C21 (Q = 0.238 Å and ϕ = 311.0°), respectively. The six-membered chelate ring (N2—C3—C4—C5—N1'-Cu) exhibits a chair conformation, in agreement with the observed puckering parameters (Q = 0.657 Å, θ = 174.6° and ϕ = 166.0°). The average bond distances [Csp³—Csp³ = 1.520 (5) Å and Csp³—N = 1.493 (5) Å] are typical of tetraaza macrocycles (Meyer et al., 1998).

The coordination sphere around the metal centre exhibits a distorted octahedral geometry. The distances and angles within the basal plane reveal a regular rectangular arrangement of the four N atoms [Cu—N1 = 2.152 (1) Å, Cu—N2 = 2.049 (2) Å and N1—Cu—N2 = 86.24 (5)°]. Two acetamide O atoms complete the octahedron at the apical positions [Cu—O22 = 2.356 (1) Å, N1—Cu—O22 = 85.72 (4)° and N2—Cu—O22 = 78.49 (5)°]. The axial elongation results from the well known Jahn-Teller effect. The acetamide C═O groups show a double-bond character whether the carbonyl is coordinated [1.241 (2) Å] or not [1.231 (2) Å]. The calculated N2/C21/C22/(N23,O22) mean plane exhibits a higher r.m.s. deviation (0.1346 Å) than the one corresponding to N1/C11/C12/(N13,O12) (0.0972 Å), due to the Cu—O22 interaction. The angle between these mean planes [88.71 (6)°] is very close to the N1—Cu—N2 coordination angle [86.24 (5)°].

The hydrogen-bonding pattern found in the structure of (I) seems responsible for the above arrangement. In particular, the specific orientation of the uncoordinated acetamide moiety is due to the N13—H131···OW1—HW11···O12 hydrogen bonds, which involve a water molecule as both acceptor and donor in the same asymmetric unit (Table 1). The sulfate anions bridge the complexes and water molecules by means of their O atoms, giving rise to a hydrogen-bond network. Indeed, they act as acceptors in medium strength interactions (H···O 1.783–2.052 Å).

In order to obtain a more accurate description of the amide and water H atoms, their bond distances were restrained to the mean values derived from neutron experiments: N—H = 1.009 Å (Wilson & Prince, 1999) and OW—HW = 0.970 Å (Blessing, 1988). Table 1 shows the dissociation energies (D_E) corresponding to the N—H···O and OW—HW···O contacts, which were calculated according to the simple expression obtained for X—H···O (X is C, N or O) closed-shell hydrogen-bond interactions: D_E (kJ mol¹) = 25000 × exp[-3.6 × d(H···O) (Å)] (Espinosa et al., 1998). At this stage, it has to be noted that weaker C—H···O interactions have not been taken into account. Inspection of the D_E values reported in Table 1 leads to an estimated interaction energy between the OW1 water molecule and the C11/C12/(O12,N13) acetamide group of roughly 33 kJ mol¹. The interaction energy corresponding to a sulfate anion bridging TETAM and water molecules is approximately 134 kJ mol¹. Thus, it might be concluded that the crystal cohesion in (I) is mainly ensured by the hydrogen-bond network involving the sulfate counter-ions.

S2. Experimental

The free ligand TETAM was prepared according to the method of Guilard et al. (2001). A methanol solution (20 ml) containing CuSO₄·5H₂O (180 mg, 0.72 mmol) and TETAM (300 mg, 0.70 mmol) was stirred for 30 min at room temperature. Evaporation of the solvent afforded a blue solid, (I), which was recrystallized in a water-methanol mixture (1:1 v/v). X-ray quality crystals of (I) were obtained by slow evaporation of this mixture at room temperature.

S3. Refinement

All H atoms (except those of the disordered water molecule) were found in the difference Fourier map and refined with a global isotropic displacement parameter of 0.038 (1) Ų. The positions of the H(—N) and HW atoms were constrained using the DFIX and DANG (only for HW atoms) instructions of the SHELXL97 program (Sheldrick, 1997). A disordered water molecule was found in the structure, exhibiting a site occupancy factor of 0.25. The corresponding atom OW3 is located 2.757, 2.868 and 2.969 Å from two equivalent O12 atoms and a symmetry-related OW3 atom, respectively. Since atoms HW31 and HW32 were not found, the corresponding data have not been included in Table 1.

Computing details

Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO; program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

Fig. 1. A view of the cation of (I) showing the atom-numbering scheme and with 50% probability displacement ellipsoids. For sake of clarity, H atoms have been omitted.

[(1,4,8,11-tetraazacyclotetradeca-1,4,8,11-tetrayl)tetraacetamide- κ⁶N¹,N⁴,N⁸,N¹¹,O¹,O⁸]copper(II) sulfate 4.5-hydrate

Crystal data

[Cu(C18H36N8O4)]SO4·4.5H2O	F(000) = 1416
Mr = 669.22	Cell parameters refined using SCALEPACK part of DENZO (Otwinowski & Minor, 1997).
Monoclinic, C2/c	Dx = 1.568 Mg m^−3
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 18.8609 (3) Å	Cell parameters from 12370 reflections
b = 15.4691 (4) Å	θ = 1.4–27.6°
c = 11.6010 (2) Å	µ = 0.92 mm^−1
β = 123.145 (9)°	T = 173 K
V = 2833.99 (10) Å^3	Prism, dark blue
Z = 4	0.2 × 0.2 × 0.2 mm

Data collection

Nonius KappaCCD area-detector diffractometer	2814 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.027
Graphite monochromator	θmax = 27.6°, θmin = 3.4°
ϕ scans	h = 0→24
12370 measured reflections	k = 0→19
3235 independent reflections	l = −15→12

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.113	w = 1/[σ^2(Fo^2) + (0.0856P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max = 0.001
3235 reflections	Δρmax = 0.72 e Å^−3
260 parameters	Δρmin = −0.62 e Å^−3
10 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0073 (9)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu	0.7500	0.2500	0.5000	0.02178 (14)
N1	0.68238 (8)	0.12936 (9)	0.43164 (14)	0.0244 (3)
N2	0.72349 (10)	0.24882 (8)	0.64928 (16)	0.0228 (3)
C1	0.63774 (10)	0.12574 (11)	0.50541 (18)	0.0274 (3)
C2	0.69670 (11)	0.15814 (11)	0.65100 (18)	0.0284 (4)
C3	0.80044 (11)	0.26758 (13)	0.78898 (18)	0.0290 (4)
C4	0.84142 (11)	0.35537 (12)	0.80452 (17)	0.0307 (4)
C5	0.88070 (11)	0.36818 (12)	0.72099 (17)	0.0286 (4)
C11	0.74237 (10)	0.05608 (11)	0.47609 (19)	0.0266 (3)
C12	0.70588 (11)	−0.03519 (11)	0.45356 (18)	0.0280 (4)
O12	0.63074 (8)	−0.05338 (8)	0.37207 (16)	0.0408 (3)
N13	0.76542 (10)	−0.09446 (10)	0.52979 (18)	0.0321 (3)
C21	0.65330 (10)	0.30842 (11)	0.61847 (17)	0.0252 (3)
C22	0.59261 (10)	0.32408 (10)	0.46578 (17)	0.0239 (3)
O22	0.61532 (7)	0.31541 (8)	0.38419 (12)	0.0261 (3)
N23	0.51561 (9)	0.34921 (11)	0.42823 (15)	0.0319 (3)
H1	0.7877 (15)	0.0643 (15)	0.575 (2)	0.0383 (12)*
H2	0.7676 (13)	0.0567 (14)	0.423 (2)	0.0383 (12)*
H3	0.6219 (13)	0.0671 (14)	0.504 (2)	0.0383 (12)*
H4	0.5878 (15)	0.1662 (15)	0.450 (2)	0.0383 (12)*
H5	0.7491 (14)	0.1209 (15)	0.700 (2)	0.0383 (12)*
H6	0.6683 (14)	0.1563 (15)	0.696 (2)	0.0383 (12)*
H7	0.6758 (14)	0.3668 (15)	0.660 (2)	0.0383 (12)*
H8	0.6230 (14)	0.2871 (16)	0.656 (2)	0.0383 (12)*
H9	0.8445 (14)	0.2231 (16)	0.813 (2)	0.0383 (12)*
H10	0.7811 (15)	0.2642 (14)	0.852 (3)	0.0383 (12)*
H11	0.8878 (14)	0.3596 (14)	0.900 (2)	0.0383 (12)*
H12	0.8026 (14)	0.4059 (16)	0.788 (2)	0.0383 (12)*
H13	0.9190 (13)	0.3148 (15)	0.736 (2)	0.0383 (12)*
H14	0.9171 (13)	0.4184 (14)	0.751 (2)	0.0383 (12)*
H131	0.7509 (11)	−0.1578 (3)	0.511 (2)	0.0383 (12)*
H132	0.8241 (6)	−0.0716 (14)	0.5979 (18)	0.0383 (12)*
H231	0.4731 (10)	0.3669 (14)	0.3300 (8)	0.0383 (12)*
H232	0.5062 (14)	0.3625 (14)	0.5040 (16)	0.0383 (12)*
S	1.0000	−0.07390 (4)	0.7500	0.02473 (16)
O1	0.96754 (8)	−0.12914 (9)	0.62661 (12)	0.0325 (3)
O2	0.93037 (8)	−0.01978 (9)	0.73052 (14)	0.0371 (3)
OW1	0.63414 (10)	−0.23629 (9)	0.37416 (16)	0.0365 (3)
HW11	0.6109 (10)	−0.1785 (4)	0.361 (2)	0.0383 (12)*
HW12	0.5909 (8)	−0.2781 (8)	0.356 (2)	0.0383 (12)*
OW2	0.35575 (8)	0.47418 (9)	0.36816 (14)	0.0351 (3)
HW21	0.3902 (8)	0.4901 (14)	0.3330 (16)	0.0383 (12)*
HW22	0.3914 (8)	0.4463 (12)	0.4569 (10)	0.0383 (12)*
OW3	0.0088 (4)	0.4298 (5)	0.0952 (6)	0.0516 (16)	0.25

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu	0.0233 (2)	0.02190 (19)	0.02179 (19)	0.00166 (8)	0.01339 (16)	0.00045 (8)
N1	0.0235 (7)	0.0244 (7)	0.0250 (7)	0.0015 (5)	0.0130 (6)	−0.0001 (5)
N2	0.0231 (8)	0.0240 (7)	0.0213 (7)	0.0029 (4)	0.0120 (7)	0.0011 (4)
C1	0.0272 (9)	0.0254 (8)	0.0333 (9)	−0.0007 (6)	0.0190 (8)	−0.0004 (6)
C2	0.0339 (9)	0.0264 (8)	0.0300 (8)	0.0029 (6)	0.0207 (8)	0.0039 (6)
C3	0.0285 (10)	0.0358 (9)	0.0195 (8)	0.0037 (7)	0.0111 (8)	0.0017 (6)
C4	0.0283 (9)	0.0360 (10)	0.0236 (8)	−0.0004 (6)	0.0114 (8)	−0.0046 (6)
C5	0.0245 (9)	0.0308 (8)	0.0258 (8)	−0.0010 (6)	0.0107 (7)	−0.0025 (6)
C11	0.0247 (9)	0.0223 (8)	0.0322 (8)	0.0008 (5)	0.0152 (8)	−0.0009 (6)
C12	0.0316 (9)	0.0250 (8)	0.0323 (9)	−0.0007 (6)	0.0205 (8)	−0.0020 (6)
O12	0.0302 (7)	0.0301 (7)	0.0489 (8)	−0.0038 (5)	0.0133 (7)	−0.0032 (6)
N13	0.0325 (7)	0.0240 (7)	0.0406 (8)	0.0019 (6)	0.0205 (7)	0.0040 (6)
C21	0.0261 (8)	0.0279 (8)	0.0251 (7)	0.0036 (6)	0.0161 (7)	0.0014 (6)
C22	0.0244 (8)	0.0218 (7)	0.0267 (8)	0.0010 (5)	0.0148 (7)	−0.0002 (6)
O22	0.0269 (6)	0.0275 (6)	0.0260 (6)	0.0038 (4)	0.0159 (5)	0.0023 (4)
N23	0.0248 (8)	0.0444 (9)	0.0272 (7)	0.0079 (6)	0.0146 (7)	0.0020 (6)
S	0.0241 (3)	0.0270 (3)	0.0241 (3)	0.000	0.0138 (3)	0.000
O1	0.0373 (7)	0.0355 (7)	0.0287 (6)	−0.0030 (5)	0.0206 (6)	−0.0055 (5)
O2	0.0312 (7)	0.0422 (8)	0.0362 (7)	0.0087 (5)	0.0173 (6)	−0.0025 (5)
OW1	0.0424 (8)	0.0294 (6)	0.0410 (8)	−0.0055 (5)	0.0250 (7)	−0.0037 (5)
OW2	0.0332 (7)	0.0390 (7)	0.0361 (7)	0.0013 (5)	0.0208 (6)	0.0016 (5)
OW3	0.031 (3)	0.075 (5)	0.035 (3)	−0.002 (3)	0.009 (3)	−0.009 (3)

Geometric parameters (Å, º)

Cu—N2^i	2.0484 (15)	C5—H13	1.05 (2)
Cu—N2	2.0484 (15)	C5—H14	0.97 (2)
Cu—N1	2.1521 (14)	C11—C12	1.529 (2)
Cu—N1^i	2.1521 (14)	C11—H1	0.99 (2)
Cu—O22^i	2.3557 (11)	C11—H2	0.96 (2)
Cu—O22	2.3557 (11)	C12—O12	1.231 (2)
N1—C11	1.481 (2)	C12—N13	1.341 (2)
N1—C1	1.494 (2)	N13—H131	1.0087 (10)
N1—C5^i	1.500 (2)	N13—H132	1.0087 (11)
N2—C21	1.488 (2)	C21—C22	1.513 (2)
N2—C2	1.495 (2)	C21—H7	1.00 (2)
N2—C3	1.498 (2)	C21—H8	0.95 (2)
C1—C2	1.512 (2)	C22—O22	1.241 (2)
C1—H3	0.95 (2)	C22—N23	1.326 (2)
C1—H4	1.02 (2)	N23—H231	1.0086 (10)
C2—H5	1.01 (2)	N23—H232	1.0087 (10)
C2—H6	0.93 (2)	S—O2^ii	1.4670 (12)
C3—C4	1.524 (3)	S—O2	1.4670 (12)
C3—H9	0.99 (2)	S—O1	1.4818 (13)
C3—H10	0.98 (3)	S—O1^ii	1.4818 (13)
C4—C5	1.521 (2)	OW1—HW11	0.9697 (10)
C4—H11	0.97 (2)	OW1—HW12	0.9697 (10)
C4—H12	1.02 (2)	OW2—HW21	0.9699 (10)
C5—N1^i	1.500 (2)	OW2—HW22	0.9699 (10)
N2^i—Cu—N2	180.0	C5—C4—C3	115.66 (15)
N2^i—Cu—N1	93.76 (5)	C5—C4—H11	105.6 (13)
N2—Cu—N1	86.24 (5)	C3—C4—H11	106.2 (13)
N2^i—Cu—N1^i	86.24 (5)	C5—C4—H12	109.6 (12)
N2—Cu—N1^i	93.76 (5)	C3—C4—H12	113.3 (13)
N1—Cu—N1^i	180.00 (4)	H11—C4—H12	105.6 (17)
N2^i—Cu—O22^i	78.49 (5)	N1^i—C5—C4	114.02 (13)
N2—Cu—O22^i	101.51 (5)	N1^i—C5—H13	104.4 (12)
N1—Cu—O22^i	94.28 (5)	C4—C5—H13	108.7 (12)
N1^i—Cu—O22^i	85.72 (5)	N1^i—C5—H14	110.7 (14)
N2^i—Cu—O22	101.51 (5)	C4—C5—H14	111.9 (14)
N2—Cu—O22	78.49 (5)	H13—C5—H14	106.6 (17)
N1—Cu—O22	85.72 (5)	N1—C11—C12	117.40 (13)
N1^i—Cu—O22	94.28 (5)	N1—C11—H1	108.3 (13)
O22^i—Cu—O22	180.00 (7)	C12—C11—H1	109.8 (13)
C11—N1—C1	109.54 (13)	N1—C11—H2	108.8 (13)
C11—N1—C5^i	113.11 (13)	C12—C11—H2	103.5 (13)
C1—N1—C5^i	110.21 (12)	H1—C11—H2	108.7 (18)
C11—N1—Cu	110.45 (10)	O12—C12—N13	123.19 (16)
C1—N1—Cu	103.15 (9)	O12—C12—C11	124.32 (16)
C5^i—N1—Cu	109.93 (10)	N13—C12—C11	112.46 (15)
C21—N2—C2	108.77 (14)	C12—N13—H131	119.4 (11)
C21—N2—C3	110.38 (13)	C12—N13—H132	116.3 (13)
C2—N2—C3	107.57 (13)	H131—N13—H132	124.1 (17)
C21—N2—Cu	112.82 (10)	N2—C21—C22	112.62 (13)
C2—N2—Cu	105.08 (10)	N2—C21—H7	110.8 (13)
C3—N2—Cu	111.90 (11)	C22—C21—H7	105.4 (13)
N1—C1—C2	109.08 (13)	N2—C21—H8	110.8 (14)
N1—C1—H3	107.5 (13)	C22—C21—H8	109.6 (13)
C2—C1—H3	111.2 (14)	H7—C21—H8	107.3 (19)
N1—C1—H4	103.3 (13)	O22—C22—N23	123.62 (15)
C2—C1—H4	111.5 (13)	O22—C22—C21	121.33 (13)
H3—C1—H4	113.8 (17)	N23—C22—C21	115.03 (14)
N2—C2—C1	110.10 (14)	C22—O22—Cu	109.00 (10)
N2—C2—H5	107.9 (13)	C22—N23—H231	120.1 (12)
C1—C2—H5	109.4 (13)	C22—N23—H232	117.2 (13)
N2—C2—H6	109.8 (14)	H231—N23—H232	121.3 (18)
C1—C2—H6	108.4 (14)	O2^ii—S—O2	110.41 (12)
H5—C2—H6	111.2 (18)	O2^ii—S—O1	109.90 (7)
N2—C3—C4	115.42 (14)	O2—S—O1	108.54 (7)
N2—C3—H9	109.7 (14)	O2^ii—S—O1^ii	108.54 (7)
C4—C3—H9	107.0 (14)	O2—S—O1^ii	109.90 (7)
N2—C3—H10	105.1 (14)	O1—S—O1^ii	109.56 (11)
C4—C3—H10	109.3 (13)	HW11—OW1—HW12	109.01 (16)
H9—C3—H10	110.3 (18)	HW21—OW2—HW22	108.95 (16)
N1—C1—C2—N2	59.12 (17)	N1^i—C1^i—C2^i—N2^i	−59.12 (17)
C1—C2—N2—C3	−162.62 (14)	C1^i—C2^i—N2^i—C3^i	162.62 (13)
C2—N2—C3—C4	175.60 (15)	C2^i—N2^i—C3^i—C4^i	−175.60 (15)
N2—C3—C4—C5	−66.2 (2)	N2^i—C3^i—C4^i—C5^i	66.2 (2)
C3—C4—C5—N1^i	67.3 (2)	C3^i—C4^i—C5^i—N1	−67.3 (2)
C4—C5—N1^i—C1^i	−174.20 (14)	C4^i—C5^i—N1—C1	174.20 (14)
C5—N1^i—C1^i—C2^i	157.90 (14)	C5^i—N1—C1—C2	−157.90 (14)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N13—H131···OW1	1.01 (1)	2.24 (1)	3.052 (2)	137 (1)
N13—H131···OW1^iii	1.01 (1)	2.45 (2)	3.062 (2)	119 (1)
N13—H132···O2	1.01 (2)	1.91 (2)	2.918 (2)	175 (2)
N23—H231···O22^iv	1.01 (1)	2.25 (1)	3.118 (2)	143 (2)
N23—H232···O1^v	1.01 (2)	1.93 (2)	2.918 (2)	167 (2)
OW1—HW11···O12	0.97 (1)	1.96 (1)	2.830 (2)	148 (1)
OW1—HW12···O1^iii	0.97 (2)	1.89 (2)	2.827 (2)	163 (2)
OW2—HW21···O2^vi	0.97 (2)	1.78 (2)	2.736 (2)	167 (1)
OW2—HW22···O1^v	0.97 (1)	2.05 (1)	3.013 (2)	171 (2)

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