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A nonclassical tetra­zole isostere of glycine, viz. zwitterionic 5-ammonio­methyl-1H-tetra­zolide, C2H5N5, (I), crystallizes in the chiral P31 space group, similar to γ-glycine. The crystal packing of (I) is determined by a set of classical hydrogen bonds, forming a three-dimensional network that is practically the same as that in γ-glycine. The CuII complex of (I), poly[[bis­(μ2-5-amino­methyl-1H-tetra­zolido-κ3N1,N5:N4)copper(II)] dihydrate], {[Cu(C2H4N5)2]·2H2O}n, (II), is a layered coordination polymer formed as a result of tetra­zole ring bridges. The CuII cations lie on inversion centres, are surrounded by four anions and adopt elongated octa­hedral coordination. Water mol­ecules are located in the inter­layer space and connect the layers into a three-dimensional network via a system of hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109055164/eg3037sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270109055164/eg3037Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270109055164/eg3037IIsup3.hkl
Contains datablock II

CCDC references: 774016; 774017

Comment top

The tetrazole ring is extensively used in molecular design and in the synthesis of modified amino acids and peptidomimetics, because the tetrazol-5-yl group, –CN4H, is a nonclassical isostere for the carboxylic acid group, –COOH. These functional groups have similar chemical properties and may be interchangeable, resulting in compounds with similar biological properties. Moreover, the tetrazol-1,5-diyl group, –CN4–, is a cis-amide –C(O)N– surrogate (Ostrovskii et al., 2008). In particular, 5-aminomethyltetrazole and its derivatives form an interesting class of tetrazole analogues of natural α-amino acids. Moreover, they are the precursors of dipeptides, attractive as catalysts for the direct asymmetric intermolecular aldol reaction (Zheng, Li et al., 2006). However, very little has appeared in the literature concerning their structure. Only a few examples of 5-aminomethyltetrazole derivatives have been structurally characterized. These are zwitterionic 5-(piperidiniomethyl)-1H-tetrazolide (Lyakhov et al., 2003), 1-phenyl-5-(piperidinomethyl)-1H-tetrazole (Lyakhov et al., 2004) and (S)-N-(1H-tetrazol-5-ylmethyl)pyrrolidine-2-carboxamide dihydrate (Zheng, Zhang et al., 2006). In spite of interest in the coordination chemistry of these compounds, mainly potentiometric and spectroscopic (UV-vis, circular dichroism and electron paramagnetic resonance) studies have been undertaken (Lodyga-Chruscinska et al., 2006, and references therein), and only the structure of a copper(II) chloride complex with N,N-dimethyl-1-(1-methyl-1H-tetrazol-5-yl) methanamine has been reported (Ivashkevich et al., 2002).

The present paper is concerned with 5-methylaminotetrazole, existing in the crystal in zwitterionic form as 5-(ammoniomethyl)-1H-tetrazolide, (I). The compound is a tetrazol-5-yl analogue of the simplest α-amino acid, glycine. Here we present also a CuII complex of (I), poly[[[bis(µ-5-aminomethyltetrazolato-κ3N1,N':N4)]copper(II)] dihydrate], (II). It should be noted that compound (I) was synthesized 50 years ago (McManus & Herbst, 1959). As to its metal derivatives, they are hitherto unknown.

Compound (I), whose molecules are achiral in solution, crystallizes in the enantiomeric pair of chiral space groups P31 and P32. It may be expected that the distribution of the crystalline product between the two space groups is essentially statistical.

Zwitterions (I) are produced when the H atom of the tetrazole ring is transferred to the amine group N atom (Fig. 1). As a consequence, the tetrazole ring is rather symmetrical (Table 1). The C5—N1 and C5—N4 bond lengths are practically the same, and a similar situation is observed for the N1—N2 and N3—N4 bonds. The N2N3 bond is the shortest in the ring. The tetrazole ring is essentially planar, to within 0.0021 (10) Å, so the ring symmetry is close to C2v. The obtained ring geometry corresponds to charge delocalization in the N1—C5—N4 fragment.

All H atoms of the NH3 groups are involved in classical intermolecular hydrogen bonding (Table 2). Bifurcated hydrogen bonds [N7—H7B···N2ii and N7—H7B···N3ii; symmetry code: (ii) x, y, z + 1] connect the zwitterions into chains running along the c axis. These chains are bonded through lateral hydrogen bonds (N7—H7A···N1i and N7—H7C···N4iii; symmetry codes: (i) -y, x - y, z + 1/3; (iii) -y, x - y - 1, z + 1/3) to form a three-dimensional network (Fig. 2).

It is of interest to compare the structure of (I) with that of glycine, which crystallizes in three polymorphic forms, α (P21/n), β (P21) and γ (P31), reported previously (Boldyreva et al., 2003, and references therein). The analysis showed that the structure of (I) was very close to that of γ-glycine. Both compounds are achiral but crystallize in the same chiral space group P31 (P32). In (I), the values of the cell dimensions are somewhat higher than those in γ-glycine, in agreement with the sizes of the molecules. In both compounds, the crystal packing is practically the same, being determined by similar hydrogen bonds [N—H···N in (I) and N—H···O in γ-glycine].

The asymmetric unit of complex (II) is shown in Fig. 3. The CuII cations lie on inversion centres and are surrounded by four anions to form an elongated octahedral coordination (Table 3). The tetrazole ring N4 atoms of two tetrazolate anions lie in axial positions of the octahedron. Two other anions in the CuII environment are coordinated bidentately via atoms N1 and N7, occupying equatorial sites of the octahedron. Within 3σ, the tetrazole ring bond lengths are the same as those in (I). Moreover, the complexing has practically no influence on the C5-substituent conformation. Complex (II) is a layered coordination polymer, with layers parallel to the bc plane. Within a layer, each ligand acts as a bridge between adjacent Cu cations, separated by ca 6.35 Å (Fig. 4). Water molecules, located in the interlayer space, connect the layers into a three-dimensional network via a system of hydrogen bonds, each molecule acting as both a donor and an acceptor of H atoms (Fig. 5 and Table 4). Although the water molecules are not coordinated to the Cu atoms, the solvent molecules play an important role in the crystal packing. According to the thermal analysis data, the complex shows high thermal stability and does not reveal water loss up to decomposition, which takes place as an exothermal process at 514 K. Note that the only reported CuII complex of glycine (Casari et al., 2004, and references therein) is different from (II) in composition and crystal structure, including the CuII coordination environment, polymeric structure and hydrogen-bond system.

Related literature top

For related literature, see: Boldyreva et al. (2003); Casari et al. (2004); Ivashkevich et al. (2002); Lodyga-Chruscinska, Sanna, Micera, Chruscinski, Olejnik, Nachman & Zabrocki (2006); Lyakhov et al. (2003, 2004); McManus & Herbst (1959); Ostrovskii et al. (2008); Vereshchagin et al. (2006); Zheng, Li, Zhang, Yang, Wang, Wang, Bai & Liu (2006); Zheng, Zhang, Wang, Yang & Li (2006).

Experimental top

5-Chloromethyltetrazole (1 g, 8.4 mmol), synthesized from chloroacetonitrile, sodium azide and aluminium chloride according to the method reported by Vereshchagin et al. (2006), was dissolved in 25% aqueous ammonia (5 ml). The resulting solution was kept at room temperature for 1 d and evaporated under vacuum. The residue was recrystallized from a water–ethanol solution (10:1), yielding colourless crystals of (I) (yield 85%, 1.1 g; m.p. 560–561 K). Analysis found: C 24.31, H 5.11, N 70.71%; calculated for C2H5N5: C 24.24, H 5.09, N 70.67%. 1H NMR (500 MHz, DMSO-d6): δ 4.10 (s, 2H, CH2). 13C NMR (125 MHz, DMSO-d6): δ 35.2 (CH2), 156.1 (Ctetrazole).

To obtain (II), a mixture of water (20 ml), 5-aminomethyltetrazole (99 mg, 1 mmol) and copper(II) oxide (40 mg, 0.5 mmol) was refluxed for 15 h. The resulting solution was filtered, and after slow cooling, blue crystals of (II) suitable for X-ray analysis were obtained (yield 50%, 78 mg). Analysis found: C 16.39, H 4.02, N 47.60%; calculated for C4H8CuN10: C 16.24, H 4.09, N 47.36%.

Refinement top

For (I), the systematic absences permitted the space groups P31 and P32 as possible ones. In the absence of significant resonant scattering, it was impossible to distinguish between these enantiomeric space groups. In view of this, Friedel pairs were merged and the space group P31 was used. All H atoms of (I) were placed in calculated positions (C—H = 0.97 Å and N—H = 0.89 Å) and refined using a riding model [Uiso(H) = 1.2Ueq(parent)]. In (II), H atoms of the water molecules were located from a difference map and refined with DFIX restraints for the O—H [0.88 (s.u. value?) Å] and H···H [1.41(s.u. value?) Å] distances [Uiso(H) = 1.5Ueq(O)]. The remaining H atoms of (II) were placed in calculated positions (C—H = 0.97 Å and N—H = 0.90 Å) and refined using a riding model [Uiso(H) = 1.2Ueq(parent)].

Computing details top

For both compounds, data collection: R3m Software (Nicolet, 1980); cell refinement: R3m Software (Nicolet, 1980). Data reduction: R3m Software (Nicolet, 1980) for (I); OMNIBUS (Gałdecka, 2002) for (II). For both compounds, program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The zwitterion in the crystal structure of (I), with the atom numbering. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as spheres of arbitrary radii.
[Figure 2] Fig. 2. The crystal structure of (I), viewed along the c axis. Dashed lines show hydrogen bonds. The methylene H atoms have been omitted for clarity.
[Figure 3] Fig. 3. The atom numbering in the asymmetric unit of (II). Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as spheres of arbitrary radii.
[Figure 4] Fig. 4. A coordination layer in the structure of (II), parallel to the bc plane.
[Figure 5] Fig. 5. The crystal structure of (II), viewed along the b axis. Dashed lines represent hydrogen bonds. Only H atoms participating in hydrogen bonds are shown.
(I) 5-ammoniomethyl-1H-tetrazolide top
Crystal data top
C2H5N5Dx = 1.548 Mg m3
Mr = 99.11Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P31Cell parameters from 25 reflections
Hall symbol: P 31θ = 16.2–20.2°
a = 7.3048 (11) ŵ = 0.12 mm1
c = 6.9003 (14) ÅT = 294 K
V = 318.87 (9) Å3Prism, colourless
Z = 30.52 × 0.34 × 0.32 mm
F(000) = 156
Data collection top
Nicolet R3m four-circle
diffractometer
Rint = 0.022
Radiation source: fine-focus sealed tubeθmax = 30.0°, θmin = 3.2°
Graphite monochromatorh = 810
ω/2θ scansk = 810
1076 measured reflectionsl = 90
624 independent reflections2 standard reflections every 100 reflections
611 reflections with I > 2σ(I) intensity decay: none
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.078H-atom parameters constrained
S = 1.11 w = 1/[σ2(Fo2) + (0.0587P)2 + 0.0056P]
where P = (Fo2 + 2Fc2)/3
624 reflections(Δ/σ)max < 0.001
65 parametersΔρmax = 0.18 e Å3
1 restraintΔρmin = 0.20 e Å3
Crystal data top
C2H5N5Z = 3
Mr = 99.11Mo Kα radiation
Hexagonal, P31µ = 0.12 mm1
a = 7.3048 (11) ÅT = 294 K
c = 6.9003 (14) Å0.52 × 0.34 × 0.32 mm
V = 318.87 (9) Å3
Data collection top
Nicolet R3m four-circle
diffractometer
Rint = 0.022
1076 measured reflections2 standard reflections every 100 reflections
624 independent reflections intensity decay: none
611 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0291 restraint
wR(F2) = 0.078H-atom parameters constrained
S = 1.11Δρmax = 0.18 e Å3
624 reflectionsΔρmin = 0.20 e Å3
65 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
xyzUiso*/Ueq
N10.22468 (17)0.00931 (18)0.65217 (17)0.0295 (2)
N20.2746 (2)0.0337 (2)0.46962 (18)0.0340 (3)
N30.4554 (2)0.0278 (3)0.46749 (17)0.0429 (3)
N40.5299 (2)0.0011 (3)0.65017 (17)0.0397 (3)
C50.38522 (19)0.01011 (18)0.75824 (17)0.0265 (2)
C60.4073 (2)0.0440 (3)0.9722 (2)0.0368 (3)
H6A0.47370.03091.02660.044*
H6B0.49790.19340.99900.044*
N70.19875 (19)0.03152 (18)1.06593 (15)0.0286 (2)
H7A0.14350.04611.02520.034*
H7B0.21510.01971.19400.034*
H7C0.11250.16631.03480.034*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0305 (5)0.0415 (6)0.0216 (5)0.0217 (4)0.0000 (4)0.0006 (4)
N20.0364 (6)0.0500 (7)0.0205 (5)0.0253 (5)0.0009 (4)0.0022 (4)
N30.0426 (7)0.0722 (9)0.0245 (6)0.0366 (7)0.0029 (4)0.0009 (5)
N40.0355 (6)0.0654 (8)0.0281 (6)0.0328 (6)0.0007 (4)0.0006 (5)
C50.0281 (5)0.0312 (5)0.0216 (5)0.0157 (4)0.0015 (4)0.0011 (4)
C60.0368 (6)0.0514 (8)0.0229 (6)0.0225 (6)0.0059 (5)0.0078 (5)
N70.0405 (6)0.0341 (5)0.0179 (4)0.0236 (5)0.0014 (4)0.0012 (4)
Geometric parameters (Å, º) top
N1—C51.3284 (16)C6—N71.4841 (19)
N1—N21.3478 (17)C6—H6A0.9700
N2—N31.2995 (19)C6—H6B0.9700
N3—N41.3479 (17)N7—H7A0.8900
N4—C51.3288 (16)N7—H7B0.8900
C5—C61.4926 (17)N7—H7C0.8900
C5—N1—N2104.26 (11)N7—C6—H6B109.4
N3—N2—N1110.11 (11)C5—C6—H6B109.4
N2—N3—N4108.91 (11)H6A—C6—H6B108.0
C5—N4—N3104.95 (11)C6—N7—H7A109.5
N1—C5—N4111.77 (12)C6—N7—H7B109.5
N1—C5—C6125.39 (11)H7A—N7—H7B109.5
N4—C5—C6122.83 (11)C6—N7—H7C109.5
N7—C6—C5111.32 (11)H7A—N7—H7C109.5
N7—C6—H6A109.4H7B—N7—H7C109.5
C5—C6—H6A109.4
C5—N1—N2—N30.36 (16)N3—N4—C5—N10.31 (18)
N1—N2—N3—N40.6 (2)N3—N4—C5—C6178.77 (14)
N2—N3—N4—C50.5 (2)N1—C5—C6—N723.31 (19)
N2—N1—C5—N40.02 (15)N4—C5—C6—N7157.74 (14)
N2—N1—C5—C6179.07 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N7—H7A···N1i0.892.072.9443 (15)169
N7—H7B···N2ii0.891.972.8417 (18)168
N7—H7B···N3ii0.892.603.3379 (17)141
N7—H7C···N4iii0.891.972.8300 (18)162
Symmetry codes: (i) y, xy, z+1/3; (ii) x, y, z+1; (iii) y, xy1, z+1/3.
(II) poly[[bis(µ2-5-aminomethyl-1H-tetrazolido- κ3N1,N5:N4)copper(II)] dihydrate] top
Crystal data top
[Cu(C2H4N5)2]·2H2OF(000) = 302
Mr = 295.79Dx = 1.815 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 25 reflections
a = 7.0452 (18) Åθ = 17.4–25.2°
b = 8.907 (2) ŵ = 2.03 mm1
c = 9.059 (2) ÅT = 294 K
β = 107.80 (2)°Block, blue
V = 541.3 (2) Å30.38 × 0.34 × 0.28 mm
Z = 2
Data collection top
Nicolet R3m four-circle
diffractometer
1406 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.012
Graphite monochromatorθmax = 30.1°, θmin = 3.0°
ω/2θ scansh = 99
Absorption correction: ψ scan
(North et al., 1968)
k = 012
Tmin = 0.483, Tmax = 0.563l = 012
1681 measured reflections2 standard reflections every 100 reflections
1590 independent reflections intensity decay: none
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.025Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.076H atoms treated by a mixture of independent and constrained refinement
S = 1.11 w = 1/[σ2(Fo2) + (0.0433P)2 + 0.208P]
where P = (Fo2 + 2Fc2)/3
1590 reflections(Δ/σ)max < 0.001
85 parametersΔρmax = 0.36 e Å3
3 restraintsΔρmin = 0.56 e Å3
Crystal data top
[Cu(C2H4N5)2]·2H2OV = 541.3 (2) Å3
Mr = 295.79Z = 2
Monoclinic, P21/cMo Kα radiation
a = 7.0452 (18) ŵ = 2.03 mm1
b = 8.907 (2) ÅT = 294 K
c = 9.059 (2) Å0.38 × 0.34 × 0.28 mm
β = 107.80 (2)°
Data collection top
Nicolet R3m four-circle
diffractometer
1406 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.012
Tmin = 0.483, Tmax = 0.5632 standard reflections every 100 reflections
1681 measured reflections intensity decay: none
1590 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0253 restraints
wR(F2) = 0.076H atoms treated by a mixture of independent and constrained refinement
S = 1.11Δρmax = 0.36 e Å3
1590 reflectionsΔρmin = 0.56 e Å3
85 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
xyzUiso*/Ueq
Cu10.00000.00000.00000.02128 (10)
N10.11094 (18)0.10998 (14)0.20149 (13)0.0217 (2)
N20.2743 (2)0.11299 (16)0.32578 (15)0.0277 (3)
N30.2449 (2)0.20914 (17)0.42555 (16)0.0313 (3)
N40.0614 (2)0.27161 (16)0.36870 (15)0.0281 (3)
C50.0154 (2)0.20769 (17)0.23077 (16)0.0221 (3)
C60.2151 (2)0.22943 (19)0.11343 (18)0.0288 (3)
H6A0.31600.24670.16430.035*
H6B0.21280.31490.04760.035*
N70.25832 (19)0.08992 (15)0.02071 (14)0.0236 (2)
H7A0.34250.11010.07410.028*
H7B0.31760.02310.06690.028*
O10.5998 (2)0.0454 (2)0.27623 (17)0.0449 (4)
H1A0.516 (4)0.010 (3)0.302 (4)0.067*
H1B0.649 (4)0.108 (3)0.350 (3)0.067*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.02003 (14)0.02418 (15)0.01836 (14)0.00115 (8)0.00399 (9)0.00694 (8)
N10.0232 (6)0.0224 (5)0.0180 (5)0.0026 (4)0.0042 (4)0.0017 (4)
N20.0280 (6)0.0287 (6)0.0223 (6)0.0044 (5)0.0015 (5)0.0036 (5)
N30.0341 (7)0.0319 (7)0.0225 (6)0.0061 (6)0.0004 (5)0.0054 (5)
N40.0327 (7)0.0283 (6)0.0210 (6)0.0056 (5)0.0045 (5)0.0061 (5)
C50.0250 (6)0.0211 (6)0.0193 (6)0.0024 (5)0.0052 (5)0.0023 (5)
C60.0269 (7)0.0296 (7)0.0265 (7)0.0083 (6)0.0033 (6)0.0060 (6)
N70.0217 (5)0.0269 (6)0.0208 (5)0.0000 (5)0.0043 (4)0.0027 (4)
O10.0425 (8)0.0638 (9)0.0304 (7)0.0195 (8)0.0142 (6)0.0106 (7)
Geometric parameters (Å, º) top
Cu1—N12.0075 (12)N4—C51.3284 (18)
Cu1—N1i2.0075 (12)N4—Cu1iv2.4605 (14)
Cu1—N7i2.0488 (13)C5—C61.494 (2)
Cu1—N72.0488 (13)C6—N71.479 (2)
Cu1—N4ii2.4605 (14)C6—H6A0.9700
Cu1—N4iii2.4606 (14)C6—H6B0.9700
N1—C51.3283 (18)N7—H7A0.9000
N1—N21.3419 (18)N7—H7B0.9000
N2—N31.3066 (19)O1—H1A0.852 (17)
N3—N41.357 (2)O1—H1B0.856 (16)
N1—Cu1—N1i180.0C5—N4—N3104.36 (13)
N1—Cu1—N7i99.45 (5)C5—N4—Cu1iv136.71 (10)
N1i—Cu1—N7i80.55 (5)N3—N4—Cu1iv116.33 (10)
N1—Cu1—N780.55 (5)N1—C5—N4111.32 (13)
N1i—Cu1—N799.45 (5)N1—C5—C6119.05 (13)
N7i—Cu1—N7180.0N4—C5—C6129.62 (14)
N1—Cu1—N4ii92.35 (5)N7—C6—C5106.31 (12)
N1i—Cu1—N4ii87.65 (5)N7—C6—H6A110.5
N7i—Cu1—N4ii90.76 (5)C5—C6—H6A110.5
N7—Cu1—N4ii89.24 (5)N7—C6—H6B110.5
N1—Cu1—N4iii87.65 (5)C5—C6—H6B110.5
N1i—Cu1—N4iii92.35 (5)H6A—C6—H6B108.7
N7i—Cu1—N4iii89.24 (5)C6—N7—Cu1110.25 (9)
N7—Cu1—N4iii90.76 (5)C6—N7—H7A109.6
N4ii—Cu1—N4iii180.0Cu1—N7—H7A109.6
C5—N1—N2105.93 (12)C6—N7—H7B109.6
C5—N1—Cu1113.76 (10)Cu1—N7—H7B109.6
N2—N1—Cu1140.21 (10)H7A—N7—H7B108.1
N3—N2—N1108.48 (12)H1A—O1—H1B108 (2)
N2—N3—N4109.90 (13)
N7i—Cu1—N1—C5166.13 (11)Cu1—N1—C5—N4176.79 (10)
N7—Cu1—N1—C513.87 (11)N2—N1—C5—C6179.38 (14)
N4ii—Cu1—N1—C5102.71 (11)Cu1—N1—C5—C62.31 (18)
N4iii—Cu1—N1—C577.29 (11)N3—N4—C5—N10.23 (18)
N7i—Cu1—N1—N218.28 (17)Cu1iv—N4—C5—N1160.20 (12)
N7—Cu1—N1—N2161.72 (17)N3—N4—C5—C6179.21 (16)
N4ii—Cu1—N1—N272.88 (17)Cu1iv—N4—C5—C620.8 (3)
N4iii—Cu1—N1—N2107.12 (17)N1—C5—C6—N724.03 (19)
C5—N1—N2—N30.21 (17)N4—C5—C6—N7154.89 (16)
Cu1—N1—N2—N3175.59 (13)C5—C6—N7—Cu133.33 (15)
N1—N2—N3—N40.08 (19)N1—Cu1—N7—C626.92 (10)
N2—N3—N4—C50.09 (19)N1i—Cu1—N7—C6153.08 (10)
N2—N3—N4—Cu1iv164.89 (11)N4ii—Cu1—N7—C6119.43 (10)
N2—N1—C5—N40.28 (17)N4iii—Cu1—N7—C660.57 (10)
Symmetry codes: (i) x, y, z; (ii) x, y1/2, z1/2; (iii) x, y+1/2, z+1/2; (iv) x, y+1/2, z1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N7—H7A···O10.902.223.037 (2)150
N7—H7B···O1v0.902.233.037 (2)149
O1—H1A···N2i0.85 (2)2.01 (2)2.842 (2)167 (3)
O1—H1B···N3vi0.86 (2)2.14 (2)2.969 (2)163 (3)
Symmetry codes: (i) x, y, z; (v) x+1, y, z; (vi) x+1, y, z+1.

Experimental details

(I)(II)
Crystal data
Chemical formulaC2H5N5[Cu(C2H4N5)2]·2H2O
Mr99.11295.79
Crystal system, space groupHexagonal, P31Monoclinic, P21/c
Temperature (K)294294
a, b, c (Å)7.3048 (11), 7.3048 (11), 6.9003 (14)7.0452 (18), 8.907 (2), 9.059 (2)
α, β, γ (°)90, 90, 12090, 107.80 (2), 90
V3)318.87 (9)541.3 (2)
Z32
Radiation typeMo KαMo Kα
µ (mm1)0.122.03
Crystal size (mm)0.52 × 0.34 × 0.320.38 × 0.34 × 0.28
Data collection
DiffractometerNicolet R3m four-circle
diffractometer
Nicolet R3m four-circle
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.483, 0.563
No. of measured, independent and
observed [I > 2σ(I)] reflections
1076, 624, 611 1681, 1590, 1406
Rint0.0220.012
(sin θ/λ)max1)0.7040.705
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.078, 1.11 0.025, 0.076, 1.11
No. of reflections6241590
No. of parameters6585
No. of restraints13
H-atom treatmentH-atom parameters constrainedH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.18, 0.200.36, 0.56

Computer programs: R3m Software (Nicolet, 1980), OMNIBUS (Gałdecka, 2002), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Selected bond lengths (Å) for (I) top
N1—C51.3284 (16)N3—N41.3479 (17)
N1—N21.3478 (17)N4—C51.3288 (16)
N2—N31.2995 (19)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N7—H7A···N1i0.892.072.9443 (15)169.2
N7—H7B···N2ii0.891.972.8417 (18)168.0
N7—H7B···N3ii0.892.603.3379 (17)141.1
N7—H7C···N4iii0.891.972.8300 (18)162.2
Symmetry codes: (i) y, xy, z+1/3; (ii) x, y, z+1; (iii) y, xy1, z+1/3.
Selected bond lengths (Å) for (II) top
Cu1—N12.0075 (12)Cu1—N4i2.4605 (14)
Cu1—N72.0488 (13)
Symmetry code: (i) x, y1/2, z1/2.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N7—H7A···O10.902.223.037 (2)150.
N7—H7B···O1ii0.902.233.037 (2)149.
O1—H1A···N2iii0.852 (17)2.005 (19)2.842 (2)167 (3)
O1—H1B···N3iv0.856 (16)2.141 (19)2.969 (2)163 (3)
Symmetry codes: (ii) x+1, y, z; (iii) x, y, z; (iv) x+1, y, z+1.
 

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