catena-Poly[[[diaqua­copper(II)]-bis­[μ2-1,3-bis­(1,2,4-triazol-1-yl)propane]] dinitrate monohydrate]

Feng, W.; Zhao, X.-J.; Yang, E.-C.

doi:10.1107/S1600536809035958

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 10| October 2009| Pages m1198-m1199

doi:10.1107/S1600536809035958

Open

access

catena-Poly[[[diaquacopper(II)]-bis[μ₂-1,3-bis(1,2,4-triazol-1-yl)propane]] dinitrate monohydrate]

Wen Feng,^a Xiao-Jun Zhao ^a and En-Cui Yang ^a ^*

^aCollege of Chemistry and Life Science, Tianjin Key Laboratory of Structure and Performance for Functional Molecule, Tianjin Normal University, Tianjin 300387, People's Republic of China
^*Correspondence e-mail: encui_yang@yahoo.com.cn

(Received 31 August 2009; accepted 5 September 2009; online 12 September 2009)

The title Cu^II coordination polymer, {[Cu(C₇H₁₀N₆)₂(H₂O)₂](NO₃)₂·H₂O}_n, was obtained by the reaction of equimolar Cu(NO₃)₂·4H₂O and 1,3-bis(1,2,4-triazol-1-yl)propane (btp) in a water–methanol solvent. The Cu^II atom is located on a centre of inversion and has an elongated octahedral coordination geometry formed by four N atoms from four symmetry-related btp ligands and two coordinated water molecules. Adjacent Cu^II atoms are connected by btp ligands, generating a double-stranded chain. The nitrate anion is disordered over two positions in a 0.828 (7):0.172 (2) ratio.

Related literature

For the structures and applications of functional metal complexes in coordination and materials science, see: Blake et al. (1999 ); Evans & Lin (2001 ); James (2003 ); Janiak (2003 ); Mitziet al. (2001 ); Moulton & Zaworotko (2001 ); Papaefstathiou & MacGillivray (2003 ). For the structures of btp-based metal complexes, see: Wang et al. (2006 ); Yin et al. (2006 ); Zhu et al. (2009 ); Van Albada et al. (2000 ); Tian et al. (2008 ); Zhao et al. (2002 ); Gu et al. (2008 ).

Experimental

Crystal data

[Cu(C₇H₁₀N₆)₂(H₂O)₂](NO₃)₂·H₂O
M_r = 598.03
Monoclinic, C 2/c
a = 11.177 (3) Å
b = 12.449 (3) Å
c = 17.312 (4) Å
β = 91.655 (4)°
V = 2408.0 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.98 mm⁻¹
T = 296 K
0.24 × 0.18 × 0.16 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.798, T_max = 0.858
5954 measured reflections
2115 independent reflections
1874 reflections with I > 2σ(I)
R_int = 0.014

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.112
S = 1.07
2115 reflections
184 parameters
26 restraints
H-atom parameters constrained
Δρ_max = 0.93 e Å⁻³
Δρ_min = −0.56 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Cu1—N6ⁱ	1.998 (2)
Cu1—N3	2.035 (3)
Cu1—O4	2.456 (3)
Symmetry code: (i) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ .

Data collection: APEX2 (Bruker, 2003 ); cell refinement: SAINT (Bruker, 2001 ); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg & Berndt, 1999 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809035958/bt5049sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809035958/bt5049Isup2.hkl

checkCIF report

Comment top

Recently, rapid progress has been made on the the construction and applications of the functional metal complexes in diverse science fields (Blake et al., 1999; Evans et al., 2001; James et al., 2003; Janiak et al., 2003; Mitzi et al., 2001; Moulton et al., 2001; Papaefstathiou et al., 2003). In this regard, 1,3-bis(1,2,4-triazol-1-yl)propane(btp), one of the most popular derivatives of 1,2,4-triazole, has received more and more attention in the fields of coordination chemistry and material science due to its multiple binding sites, flexible skeleton and intense fluorescence emission behavior (Wang et al., 2006; Yin et al., 2006; Zhu et al., 2009). Indeed, bearing two triazolyl groups being connected by a flexible propane linker, btp ligand in the transitional metal complexes has exhibited variable bi- (Van Albada et al., 2000), tri- and tetra-dentate (Tian et al., 2008) coordination modes as well as commonly observed anti-anti, anti-gauche, and gauche-gauche conformations. Thus, a variety of interesting structures ranged from the discrete binuclear, infinite one-dimensional Z-shaped, ladder-like, double-, and triple-stranded chains to two-dimensional grid-like layer, have been generated. Obviously, the structural diversity of the btp-based metal complexes depends strongly on the binding features of the metal ions and the functional ligands. Herein, to further investigate the binding behavior of the btp ligand, a double-stranded Cu^IIcoordination chain, (I), was obtained by the reaction of Cu(NO₃)₂. 4H₂O and btp in mixed water-methanol medium.

X-ray structural analysis reveals that I consists of a one-dimensional double-stranded cationic chain and a disorder NO₃^-for charge compensation. The Cu^II atom locates at special position and is in an elongated octahedral coordination geometry constructed by four triazole nitrogen atoms (N3, N3A, N6B, N6C) from four symmetry-related btp ligands in an equatorial plane and two coordinated water molecules occupying the apical positions (see Figure 1). The Cu–N distances are ca. 0.5 Å shorter than that of Cu–O separation due to the Jahn–Teller effect (see Table 1).

Pairs of neutral btp ligands adopt an exo-bidentate (µ₂-btp-κ¹N⁴:κ¹N^4') binding mode to connect the adjacent Cu^II atoms into an infinite double-stranded chain along the diagonal of the crystallographic ab plane (see Figure 2). As a result, the closed 20–membered [Cu₂(btp)₂] metallomacrocycles are alternately generated with the nearest Cu···Cu separation of 8.3654 (13) Å. Such the polymeric chain has ever been obtained in the complexes of [Co(btp)₂(NCS)₂]_n (Zhao et al., 2002), [Fe(btp)₂(NCS)₂]_n (Gu et al., 2008), and [Zn(btp)₂(dca)₂]_n (Zhu et al., 2009), although the metal center and the coligand are different from each other. Notably, the torsion angles of N1/C3/C4/C5 and C3/C4/C5/N4 are -65.695 (18)° and 108.753 (16)°, respectively. And the dihedral angle between the two triazole rings is 84.057 (16)°, which suggests a scarcely observed gauche-eclipsed conformation of the btp ligand.

Related literature top

For the structures and applications of functional metal complexes in coordination and materials science, see: Blake et al. (1999); Evans et al. (2001); James et al. (2003); Janiak et al. (2003); Mitzi et al. (2001); Moulton et al. (2001); Papaefstathiou et al. (2003). For the structures of btp-based metal complexes, see: Wang et al. (2006); Yin et al. (2006); Zhu et al. (2009); Van Albada et al. (2000); Tian et al. (2008); Zhao et al. (2002); Gu et al. (2008).

Experimental top

To an aqueous solution (10 ml) of Cu(NO₃)₂^.4H₂O (30.8 mg, 0.1 mmol) was slowly added a methanol solution (10 ml) of btp (17.8 mg, 0.1 mmol) with constant stirring. The resulting mixture was further stirred for half an hour and then filtered. Upon slow evaporation of the filtrate at room tempreture, blue block-shaped crystals suitable for single-crystal X-ray diffraction analysis were isolated directly within two weeks, washed with ethanol and dried in air (yield: 40% based on Cu^IIsalt). Elemental analysis calculated for C₇H₁₃Cu_0.5N₇O_4.5: C, 28.12; H, 4.38; N, 32.79%; found: C, 28.22; H, 4.29; N, 32.61%.

Computing details top

Data collection: APEX2 (Bruker, 2003); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg & Berndt, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The local coordination environment of the Cu^II atom in I. Displacement ellipsoids were drawn at 30% probability. [Symmetry codes: (A) –x + 3/2, –y + 1/2, –z, (B) x + 1/2, y + 1/2, z, (C) –x + 2, –y + 1, –z.]
	Fig. 2. Part of the chain of the title compound.

catena-Poly[[[diaquacopper(II)]-bis[µ₂-1,3-bis(1,2,4-triazol-1- yl)propane]] dinitrate monohydrate] top

Crystal data top

[Cu(C₇H₁₀N₆)₂(H₂O)₂](NO₃)₂·H₂O	F(000) = 1236
M_r = 598.03	D_x = 1.650 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.177 (3) Å	Cell parameters from 3805 reflections
b = 12.449 (3) Å	θ = 2.5–27.7°
c = 17.312 (4) Å	µ = 0.98 mm⁻¹
β = 91.655 (4)°	T = 296 K
V = 2408.0 (9) Å³	Block, blue
Z = 4	0.24 × 0.18 × 0.16 mm

Data collection top

Bruker APEXII area-detector diffractometer	2115 independent reflections
Radiation source: fine-focus sealed tube	1874 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.014
phi and ω scans	θ_max = 25.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→13
T_min = 0.798, T_max = 0.858	k = −14→14
5954 measured reflections	l = −20→14

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.112	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0519P)² + 7.175P] where P = (F_o² + 2F_c²)/3
2115 reflections	(Δ/σ)_max < 0.001
184 parameters	Δρ_max = 0.93 e Å⁻³
26 restraints	Δρ_min = −0.56 e Å⁻³

Crystal data top

[Cu(C₇H₁₀N₆)₂(H₂O)₂](NO₃)₂·H₂O	V = 2408.0 (9) Å³
M_r = 598.03	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 11.177 (3) Å	µ = 0.98 mm⁻¹
b = 12.449 (3) Å	T = 296 K
c = 17.312 (4) Å	0.24 × 0.18 × 0.16 mm
β = 91.655 (4)°

Data collection top

Bruker APEXII area-detector diffractometer	2115 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1874 reflections with I > 2σ(I)
T_min = 0.798, T_max = 0.858	R_int = 0.014
5954 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	26 restraints
wR(F²) = 0.112	H-atom parameters constrained
S = 1.07	Δρ_max = 0.93 e Å⁻³
2115 reflections	Δρ_min = −0.56 e Å⁻³
184 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)
Cu1	1.0000	0.5000	0.0000	0.0316 (2)
N1	1.1092 (2)	0.1933 (2)	0.06359 (16)	0.0348 (6)
N2	1.1152 (3)	0.1788 (2)	−0.01363 (17)	0.0422 (7)
N3	1.0493 (2)	0.3437 (2)	0.01382 (15)	0.0337 (6)
N4	0.8317 (2)	0.0666 (2)	0.09733 (15)	0.0341 (6)
N5	0.8401 (2)	0.1305 (2)	0.03421 (16)	0.0415 (7)
N6	0.6637 (2)	0.0474 (2)	0.03457 (16)	0.0339 (6)
C1	1.0779 (3)	0.2711 (3)	−0.0409 (2)	0.0407 (8)
H1	1.0716	0.2857	−0.0936	0.049*
C2	1.0699 (3)	0.2906 (2)	0.07910 (19)	0.0350 (7)
H2	1.0585	0.3178	0.1284	0.042*
C3	1.1409 (3)	0.1067 (3)	0.1175 (2)	0.0405 (8)
H3A	1.1547	0.1370	0.1686	0.049*
H3B	1.2151	0.0740	0.1018	0.049*
C4	1.0458 (3)	0.0208 (3)	0.1216 (2)	0.0386 (8)
H4A	1.0769	−0.0380	0.1531	0.046*
H4B	1.0297	−0.0070	0.0700	0.046*
C5	0.9283 (3)	0.0588 (3)	0.1550 (2)	0.0433 (8)
H5A	0.9050	0.0093	0.1951	0.052*
H5B	0.9406	0.1287	0.1787	0.052*
C6	0.7370 (3)	0.1162 (3)	−0.0014 (2)	0.0382 (7)
H6	0.7158	0.1505	−0.0476	0.046*
C7	0.7269 (3)	0.0179 (3)	0.0965 (2)	0.0376 (7)
H7	0.7015	−0.0299	0.1339	0.045*
N7	0.2452 (3)	0.3129 (3)	0.2674 (2)	0.0646 (10)
O1	0.293 (2)	0.2228 (13)	0.2776 (16)	0.147 (3)	0.172 (7)
O2	0.1369 (11)	0.3192 (19)	0.2856 (14)	0.1018 (18)	0.172 (7)
O3	0.2982 (18)	0.3883 (13)	0.2421 (14)	0.229 (6)	0.172 (7)
O1'	0.2728 (6)	0.2639 (6)	0.3235 (3)	0.147 (3)	0.828 (7)
O2'	0.3137 (4)	0.3107 (5)	0.2130 (3)	0.1018 (18)	0.828 (7)
O3'	0.1580 (7)	0.3633 (8)	0.2599 (3)	0.229 (6)	0.828 (7)
O4	0.9447 (3)	0.5006 (2)	0.13626 (15)	0.0523 (7)
H4'	0.9082	0.4529	0.1616	0.078*
H4"	0.9664	0.5569	0.1606	0.078*
O5	0.0000	0.6545 (3)	0.2500	0.0667 (11)
H5	0.0564	0.7003	0.2495	0.100*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0248 (3)	0.0273 (3)	0.0426 (3)	−0.0009 (2)	−0.0023 (2)	0.0017 (2)
N1	0.0295 (13)	0.0296 (14)	0.0451 (16)	0.0009 (11)	−0.0017 (11)	0.0012 (12)
N2	0.0463 (16)	0.0349 (15)	0.0457 (17)	0.0025 (13)	0.0070 (13)	−0.0027 (13)
N3	0.0293 (13)	0.0293 (13)	0.0426 (15)	−0.0003 (11)	−0.0003 (11)	0.0004 (12)
N4	0.0284 (13)	0.0361 (14)	0.0377 (14)	−0.0019 (11)	−0.0006 (11)	−0.0006 (12)
N5	0.0334 (14)	0.0441 (16)	0.0468 (16)	−0.0076 (13)	−0.0021 (12)	0.0088 (13)
N6	0.0278 (13)	0.0299 (14)	0.0438 (15)	−0.0016 (11)	−0.0010 (11)	0.0004 (12)
C1	0.0440 (19)	0.0373 (18)	0.0409 (18)	−0.0026 (15)	0.0050 (15)	0.0000 (15)
C2	0.0314 (16)	0.0310 (16)	0.0424 (18)	0.0002 (13)	−0.0004 (13)	−0.0018 (14)
C3	0.0303 (16)	0.0353 (17)	0.055 (2)	0.0033 (14)	−0.0073 (14)	0.0066 (16)
C4	0.0363 (17)	0.0300 (16)	0.049 (2)	0.0015 (14)	−0.0071 (15)	0.0054 (14)
C5	0.0358 (18)	0.055 (2)	0.0386 (18)	−0.0058 (16)	−0.0068 (14)	0.0005 (16)
C6	0.0337 (17)	0.0366 (17)	0.0443 (18)	−0.0014 (14)	−0.0027 (14)	0.0063 (15)
C7	0.0327 (17)	0.0372 (18)	0.0428 (18)	−0.0054 (14)	0.0007 (14)	0.0049 (14)
N7	0.075 (3)	0.070 (2)	0.049 (2)	0.006 (2)	−0.0036 (18)	−0.0077 (19)
O1	0.186 (6)	0.172 (6)	0.086 (4)	0.005 (5)	0.028 (4)	0.069 (5)
O2	0.113 (4)	0.117 (4)	0.077 (3)	0.031 (3)	0.038 (3)	0.014 (3)
O3	0.254 (9)	0.362 (13)	0.073 (4)	0.241 (10)	0.020 (5)	−0.005 (6)
O1'	0.186 (6)	0.172 (6)	0.086 (4)	0.005 (5)	0.028 (4)	0.069 (5)
O2'	0.113 (4)	0.117 (4)	0.077 (3)	0.031 (3)	0.038 (3)	0.014 (3)
O3'	0.254 (9)	0.362 (13)	0.073 (4)	0.241 (10)	0.020 (5)	−0.005 (6)
O4	0.0625 (17)	0.0489 (15)	0.0459 (15)	−0.0062 (12)	0.0086 (12)	−0.0015 (12)
O5	0.070 (3)	0.052 (2)	0.078 (3)	0.000	−0.008 (2)	0.000

Geometric parameters (Å, º) top

Cu1—N6ⁱ	1.998 (2)	C3—C4	1.512 (5)
Cu1—N6ⁱⁱ	1.998 (2)	C3—H3A	0.9700
Cu1—N3ⁱⁱⁱ	2.035 (3)	C3—H3B	0.9700
Cu1—N3	2.035 (3)	C4—C5	1.526 (5)
Cu1—O4	2.456 (3)	C4—H4A	0.9700
N1—C2	1.319 (4)	C4—H4B	0.9700
N1—N2	1.352 (4)	C5—H5A	0.9700
N1—C3	1.462 (4)	C5—H5B	0.9700
N2—C1	1.306 (4)	C6—H6	0.9300
N3—C2	1.324 (4)	C7—H7	0.9300
N3—C1	1.355 (4)	N7—O3'	1.164 (6)
N4—C7	1.318 (4)	N7—O1'	1.180 (5)
N4—N5	1.357 (4)	N7—O3	1.199 (11)
N4—C5	1.452 (4)	N7—O2'	1.232 (5)
N5—C6	1.304 (4)	N7—O1	1.253 (10)
N6—C7	1.319 (4)	N7—O2	1.261 (10)
N6—C6	1.350 (4)	O4—H4'	0.8499
N6—Cu1^iv	1.998 (2)	O4—H4"	0.8500
C1—H1	0.9300	O5—H5	0.8500
C2—H2	0.9300

N6ⁱ—Cu1—N6ⁱⁱ	180.0	C3—C4—C5	114.4 (3)
N6ⁱ—Cu1—N3ⁱⁱⁱ	89.71 (11)	C3—C4—H4A	108.7
N6ⁱⁱ—Cu1—N3ⁱⁱⁱ	90.29 (11)	C5—C4—H4A	108.7
N6ⁱ—Cu1—N3	90.29 (11)	C3—C4—H4B	108.7
N6ⁱⁱ—Cu1—N3	89.71 (10)	C5—C4—H4B	108.7
N3ⁱⁱⁱ—Cu1—N3	180.0	H4A—C4—H4B	107.6
N6ⁱ—Cu1—O4	88.00 (10)	N4—C5—C4	113.1 (3)
N6ⁱⁱ—Cu1—O4	92.00 (10)	N4—C5—H5A	109.0
N3ⁱⁱⁱ—Cu1—O4	92.03 (10)	C4—C5—H5A	109.0
N3—Cu1—O4	87.97 (10)	N4—C5—H5B	109.0
C2—N1—N2	110.5 (3)	C4—C5—H5B	109.0
C2—N1—C3	128.6 (3)	H5A—C5—H5B	107.8
N2—N1—C3	120.9 (3)	N5—C6—N6	114.1 (3)
C1—N2—N1	102.5 (3)	N5—C6—H6	122.9
C2—N3—C1	103.0 (3)	N6—C6—H6	122.9
C2—N3—Cu1	128.1 (2)	N4—C7—N6	109.6 (3)
C1—N3—Cu1	128.6 (2)	N4—C7—H7	125.2
C7—N4—N5	110.1 (3)	N6—C7—H7	125.2
C7—N4—C5	128.3 (3)	O3'—N7—O1'	124.8 (5)
N5—N4—C5	121.6 (3)	O3'—N7—O3	87.6 (11)
C6—N5—N4	102.7 (3)	O1'—N7—O3	125.8 (13)
C7—N6—C6	103.5 (3)	O3'—N7—O2'	117.6 (5)
C7—N6—Cu1^iv	128.7 (2)	O1'—N7—O2'	117.6 (5)
C6—N6—Cu1^iv	127.7 (2)	O3—N7—O2'	54.1 (11)
N2—C1—N3	114.4 (3)	O3'—N7—O1	148.4 (13)
N2—C1—H1	122.8	O1'—N7—O1	47.2 (12)
N3—C1—H1	122.8	O3—N7—O1	122.6 (9)
N1—C2—N3	109.6 (3)	O2'—N7—O1	79.3 (10)
N1—C2—H2	125.2	O3'—N7—O2	35.7 (10)
N3—C2—H2	125.2	O1'—N7—O2	93.3 (10)
N1—C3—C4	113.2 (3)	O3—N7—O2	122.0 (9)
N1—C3—H3A	108.9	O2'—N7—O2	144.5 (12)
C4—C3—H3A	108.9	O1—N7—O2	115.4 (8)
N1—C3—H3B	108.9	Cu1—O4—H4'	129.2
C4—C3—H3B	108.9	Cu1—O4—H4"	113.7
H3A—C3—H3B	107.8	H4'—O4—H4"	117.1

C2—N1—N2—C1	−0.1 (3)	C3—N1—C2—N3	−178.7 (3)
C3—N1—N2—C1	178.5 (3)	C1—N3—C2—N1	0.5 (3)
N6ⁱ—Cu1—N3—C2	71.7 (3)	Cu1—N3—C2—N1	−175.0 (2)
N6ⁱⁱ—Cu1—N3—C2	−108.3 (3)	C2—N1—C3—C4	102.6 (4)
N3ⁱⁱⁱ—Cu1—N3—C2	142 (3)	N2—N1—C3—C4	−75.7 (4)
O4—Cu1—N3—C2	−16.3 (3)	N1—C3—C4—C5	−65.6 (4)
N6ⁱ—Cu1—N3—C1	−102.6 (3)	C7—N4—C5—C4	122.2 (4)
N6ⁱⁱ—Cu1—N3—C1	77.4 (3)	N5—N4—C5—C4	−58.5 (4)
N3ⁱⁱⁱ—Cu1—N3—C1	−32 (4)	C3—C4—C5—N4	108.7 (3)
O4—Cu1—N3—C1	169.4 (3)	N4—N5—C6—N6	−0.2 (4)
C7—N4—N5—C6	0.3 (4)	C7—N6—C6—N5	0.0 (4)
C5—N4—N5—C6	−179.1 (3)	Cu1^iv—N6—C6—N5	−178.7 (2)
N1—N2—C1—N3	0.4 (4)	N5—N4—C7—N6	−0.2 (4)
C2—N3—C1—N2	−0.5 (4)	C5—N4—C7—N6	179.1 (3)
Cu1—N3—C1—N2	174.9 (2)	C6—N6—C7—N4	0.1 (4)
N2—N1—C2—N3	−0.2 (4)	Cu1^iv—N6—C7—N4	178.9 (2)

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

Experimental details

Crystal data
Chemical formula	[Cu(C₇H₁₀N₆)₂(H₂O)₂](NO₃)₂·H₂O
M_r	598.03
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	11.177 (3), 12.449 (3), 17.312 (4)
β (°)	91.655 (4)
V (Å³)	2408.0 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.98
Crystal size (mm)	0.24 × 0.18 × 0.16

Data collection
Diffractometer	Bruker APEXII area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.798, 0.858
No. of measured, independent and observed [I > 2σ(I)] reflections	5954, 2115, 1874
R_int	0.014
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.112, 1.07
No. of reflections	2115
No. of parameters	184
No. of restraints	26
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.93, −0.56

Computer programs: APEX2 (Bruker, 2003), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg & Berndt, 1999), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Cu1—N6ⁱ	1.998 (2)	Cu1—N3	2.035 (3)
Cu1—N6ⁱⁱ	1.998 (2)	Cu1—O4	2.456 (3)
Cu1—N3ⁱⁱⁱ	2.035 (3)

N6ⁱ—Cu1—N6ⁱⁱ	180.0	N3ⁱⁱⁱ—Cu1—N3	180.0
N6ⁱ—Cu1—N3ⁱⁱⁱ	89.71 (11)	N6ⁱ—Cu1—O4	88.00 (10)
N6ⁱⁱ—Cu1—N3ⁱⁱⁱ	90.29 (11)	N6ⁱⁱ—Cu1—O4	92.00 (10)
N6ⁱ—Cu1—N3	90.29 (11)	N3ⁱⁱⁱ—Cu1—O4	92.03 (10)
N6ⁱⁱ—Cu1—N3	89.71 (10)	N3—Cu1—O4	87.97 (10)

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

Acknowledgements

This work was supported financially by the Advance Project of Young Teachers in Tianjin Normal university (to ECY).

References

Blake, A. J., Champness, N. R., Hubberstey, P., Li, W. S., Withersby, M. A. & Schröder, M. (1999). Coord. Chem. Rev. 183, 117–138. Web of Science CrossRef CAS Google Scholar
Brandenburg, K. & Berndt, M. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2001). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2003). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Evans, O. R. & Lin, W.-B. (2001). Chem. Mater. 13, 3009–3017. Web of Science CSD CrossRef CAS Google Scholar
Gu, Z.-G., Xu, Y.-F., Zhou, X.-H., Zuo, J.-L. & You, X.-Z. (2008). Cryst. Growth Des. 8, 1306–1312. Web of Science CSD CrossRef CAS Google Scholar
James, S. L. (2003). Chem. Soc. Rev. 32, 276–288. Web of Science CrossRef PubMed CAS Google Scholar
Janiak, C. (2003). Dalton. Trans. pp. 2781–2804. Web of Science CrossRef Google Scholar
Mitzi, D. B. (2001). Dalton. Trans. pp. 1–12. CrossRef Google Scholar
Moulton, B. & Zaworotko, M. J. (2001). Chem. Rev. 101, 1629–1658. Web of Science CrossRef PubMed CAS Google Scholar
Papaefstathiou, G. S. & MacGillivray, L. R. (2003). Coord. Chem. Rev. 246, 169–184. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tian, A.-X., Ying, J., Peng, J., Sha, J.-Q., Han, Z.-G., Ma, J.-F., Su, Z.-M., Hu, N.-H. & Jia, H.-Q. (2008). Inorg. Chem. 47, 3274-3283. Web of Science CSD CrossRef PubMed CAS Google Scholar
Van Albada, G. A., Guijt, R. C., Haasnoot, J. G., Lutz, M., Spek, A. L. & Reedijk, J. (2000). Eur. J. Inorg. Chem. pp. 121–126. CrossRef Google Scholar
Wang, X.-L., Qin, C., Wang, E.-B., Su, Z.-M., Li, Y.-G. & Xu, L. (2006). Angew. Chem. Int. Ed. 45, 7411–7414. Web of Science CSD CrossRef CAS Google Scholar
Yin, G., Zhang, Y.-P., Li, B.-L. & Zhang, Y. (2006). J. Mol. Struct. 837, 263–268. Web of Science CSD CrossRef Google Scholar
Zhao, Q.-H., Li, H.-F., Wang, X.-F. & Chen, Z.-D. (2002). New J. Chem. 26, 1709–1710. Web of Science CSD CrossRef CAS Google Scholar
Zhu, X., Liu, K., Yang, Y., Li, B.-L. & Zhang, Y. (2009). J. Coord. Chem., 62, 2358–2366. Web of Science CSD CrossRef CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.