(Ethyl­enediamine-κ2N,N′)bis­[3-(2-pyridyl)-5-(4-pyrid­yl)-1,2,4-triazolato-κ2N2,N3]zinc(II) methanol solvate dihydrate

Cheng, L.; Sun, Y.-Y.; Zhang, Y.-W.; Wang, J.-Q.

doi:10.1107/S1600536809001688

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 2| February 2009| Page m206

doi:10.1107/S1600536809001688

Open

access

(Ethylenediamine-κ²N,N′)bis[3-(2-pyridyl)-5-(4-pyridyl)-1,2,4-triazolato-κ²N²,N³]zinc(II) methanol solvate dihydrate

Lin Cheng,^a ^* Yan-Yan Sun,^b Ya-Wen Zhang ^b and Jian-Quan Wang ^a

^aDepartment of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, People's Republic of China, and ^bDepartment of Chemistry and Chemical Engineering, State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: cep02chl@yahoo.com.cn

(Received 4 December 2008; accepted 14 January 2009; online 17 January 2009)

The asymmetric unit of the title compound, [Zn(C₁₂H₈N₅)₂(C₂H₈N₂)]·CH₃OH·2H₂O, contains a Zn^II cation, octahedrally coordinated by two 3-(2-pyridyl)-5-(4-pyridyl)-1,2,4-triazolate anions, a chelating ethane-1,2-diamine molecule, a methanol solvent molecule, and two crystal water molecules. In the crystal packing, complex molecules are linked by hydrogen bonds into a two-dimensional layer.

Related literature

For related structures, see: Wang et al. (2005 ). For general background, see: Kesanli & Lin (2003 ).

Experimental

Crystal data

[Zn(C₁₂H₈N₅)₂(C₂H₈N₂)]·CH₄O·2H₂O
M_r = 638.02
Triclinic, $[P \overline 1]$
a = 8.3323 (8) Å
b = 13.0268 (12) Å
c = 14.9444 (14) Å
α = 66.404 (2)°
β = 79.751 (2)°
γ = 81.437 (2)°
V = 1457.3 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.90 mm⁻¹
T = 293 (2) K
0.25 × 0.22 × 0.16 mm

Data collection

Bruker APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2000 ) T_min = 0.807, T_max = 0.870
11395 measured reflections
5643 independent reflections
4532 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.130
S = 1.04
5643 reflections
388 parameters
H-atom parameters constrained
Δρ_max = 0.61 e Å⁻³
Δρ_min = −0.56 e Å⁻³

Table 1
Selected bond lengths (Å)

Zn1—N7	2.096 (3)
Zn1—N2	2.103 (2)
Zn1—N11	2.133 (3)
Zn1—N12	2.148 (3)
Zn1—N1	2.269 (3)
Zn1—N6	2.293 (3)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N11—H11B⋯O1Wⁱ	0.90	2.27	3.166 (4)	172
N11—H11C⋯O2Wⁱⁱ	0.90	2.17	3.034 (4)	161
N12—H12B⋯N5ⁱⁱⁱ	0.90	2.54	3.321 (4)	146
N12—H12C⋯O1W	0.90	2.45	3.331 (4)	165
O1—H1B⋯N4^iv	0.90	2.02	2.897 (4)	163
O1W—H1WA⋯N3^v	0.85	2.04	2.887 (4)	171
O1W—H1WB⋯N8	0.85	2.09	2.859 (4)	150
O2W—H2WA⋯O1	0.85	1.94	2.778 (4)	169
O2W—H2WB⋯O1W	0.85	2.00	2.787 (4)	153
Symmetry codes: (i) x+1, y, z; (ii) -x+1, -y+1, -z+1; (iii) -x+2, -y+2, -z+1; (iv) -x+1, -y+2, -z+1; (v) x-1, y, z.

Data collection: SMART (Bruker, 2000 ); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809001688/kp2199sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809001688/kp2199Isup2.hkl

checkCIF report

Comment top

Recently, there has been significant interest in the rational design and synthesis of chiral coordination polymers due to their potential functions, such as enantioselective separations and catalysis, which could be obtained by using chiral and achiral ligands (Kesanli et al. 2003; Wang et al. 2005). The use of achiral ligands is more attractive since usually such ligands are easier to be generated. Asymmetric ligands, as achiral ligands, have been widely used to construct those non-centrosymmetrical polymers. Unfortunately, here, we synthesed a centrosymmetrical complex Zn(C₁₂H₈N₅)₂(C₂H₈N₂).CH₃OH.2H₂O, with an asymmetric 3-(2-pyridyl)-5-(4-pyridyl)-4_H-1,2,4-triazole ligand.

The asymmetric unit of the title compound, contains one Zn^II cation, two 3-(2-pyridyl)-5-(4-pyridyl)-1,2,4-triazolato anions, one chelating ethane-1,2-diamine, methanol solvate and two crystal water molecules. The complex is mononuclear with Zn^II in a distorted octahedral geometry of two chelating triazolato anions, and one chelating ethane-1,2-diamine ligand. Each triazolato group acts as a bidentate chelating ligand whereas the N atom of 4-pyridyl group does not take part in coordination (Table 1and Fig. 1). In the crystal, the complex molecules are linked by N—H···O, O—H···N and O—H···O hydrogen bonds into a two-dimensional layer (Table 2 and Fig. 2).

Related literature top

For related structures, see: Wang et al. (2005). For general background, see: Kesanli & Lin (2003).

Experimental top

A mixture of 3-(2-pyridyl)-5-(4-pyridyl)-4_H-1,2,4-triazole (0.0446 g, 0.2 mmol), ZnSO₄.7 H₂O (0.0288 g, 0.1 mmol), ethane-1,2-diamine (0.1 ml), methanol (2 ml) and water (2 ml) was stirred for 0.5 h at room temperature, and then filtered. The filtrate was allowed to evaporate slowly at room temperature. After 2 weeks, colourless needle crystals were obtained in 34% yield (0.0217 g) based on Zn^II.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Coordination environment of Zn^II with the 30% displacement ellipsoids.
	Fig. 2. The two-dimensional hydrogen bond network of the title compound.

(Ethylenediamine-κ²N,N')bis[3-(2-pyridyl)-5-(4-pyridyl)-1,2,4- triazolato-κ²N²,N³]zinc(II) methanol solvate dihydrate top

Crystal data top

[Zn(C₁₂H₈N₅)₂(C₂H₈N₂)]·CH₃O·2H₂O	Z = 2
M_r = 638.02	F(000) = 664
Triclinic, P1	D_x = 1.454 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.3323 (8) Å	Cell parameters from 783 reflections
b = 13.0268 (12) Å	θ = 2.5–28.0°
c = 14.9444 (14) Å	µ = 0.90 mm⁻¹
α = 66.404 (2)°	T = 293 K
β = 79.751 (2)°	Needle, colourless
γ = 81.437 (2)°	0.25 × 0.22 × 0.16 mm
V = 1457.3 (2) Å³

Data collection top

Bruker APEX CCD diffractometer	5643 independent reflections
Radiation source: fine-focus sealed tube	4532 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ϕ and ω scans	θ_max = 26.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	h = −10→10
T_min = 0.807, T_max = 0.870	k = −16→16
11395 measured reflections	l = −18→18

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.130	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0579P)² + 0.853P] where P = (F_o² + 2F_c²)/3
5643 reflections	(Δ/σ)_max < 0.001
388 parameters	Δρ_max = 0.61 e Å⁻³
0 restraints	Δρ_min = −0.56 e Å⁻³

Crystal data top

[Zn(C₁₂H₈N₅)₂(C₂H₈N₂)]·CH₃O·2H₂O	γ = 81.437 (2)°
M_r = 638.02	V = 1457.3 (2) Å³
Triclinic, P1	Z = 2
a = 8.3323 (8) Å	Mo Kα radiation
b = 13.0268 (12) Å	µ = 0.90 mm⁻¹
c = 14.9444 (14) Å	T = 293 K
α = 66.404 (2)°	0.25 × 0.22 × 0.16 mm
β = 79.751 (2)°

Data collection top

Bruker APEX CCD diffractometer	5643 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	4532 reflections with I > 2σ(I)
T_min = 0.807, T_max = 0.870	R_int = 0.030
11395 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.130	H-atom parameters constrained
S = 1.04	Δρ_max = 0.61 e Å⁻³
5643 reflections	Δρ_min = −0.56 e Å⁻³
388 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
Zn1	0.71857 (5)	0.78434 (3)	0.29062 (3)	0.03871 (14)
C1	0.4382 (5)	0.9641 (3)	0.1713 (3)	0.0551 (10)
H1A	0.4027	0.9023	0.1664	0.066*
C2	0.3536 (5)	1.0670 (4)	0.1313 (3)	0.0636 (11)
H2A	0.2637	1.0748	0.0993	0.076*
C3	0.4042 (5)	1.1584 (3)	0.1393 (3)	0.0609 (11)
H3A	0.3492	1.2293	0.1127	0.073*
C4	0.5377 (4)	1.1433 (3)	0.1875 (3)	0.0477 (9)
H4A	0.5729	1.2036	0.1949	0.057*
C5	0.6183 (4)	1.0380 (3)	0.2245 (2)	0.0357 (7)
C6	0.7672 (4)	1.0124 (3)	0.2716 (2)	0.0350 (7)
C7	0.9746 (4)	1.0178 (3)	0.3288 (2)	0.0364 (7)
C8	1.0995 (4)	1.0544 (3)	0.3656 (2)	0.0378 (7)
C9	1.1963 (4)	0.9778 (3)	0.4322 (3)	0.0456 (8)
H9A	1.1866	0.9012	0.4534	0.055*
C10	1.3081 (4)	1.0159 (3)	0.4672 (3)	0.0549 (10)
H10A	1.3723	0.9627	0.5123	0.066*
C11	1.2366 (5)	1.1968 (3)	0.3747 (3)	0.0597 (11)
H11A	1.2510	1.2728	0.3531	0.072*
C12	1.1207 (5)	1.1674 (3)	0.3365 (3)	0.0512 (9)
H12A	1.0575	1.2223	0.2918	0.061*
C13	1.0318 (4)	0.8471 (3)	0.1141 (3)	0.0522 (9)
H13A	1.0659	0.8844	0.1482	0.063*
C14	1.1280 (5)	0.8449 (3)	0.0311 (3)	0.0601 (11)
H14A	1.2243	0.8807	0.0088	0.072*
C15	1.0810 (5)	0.7890 (3)	−0.0194 (3)	0.0552 (10)
H15A	1.1451	0.7859	−0.0761	0.066*
C16	0.9368 (4)	0.7374 (3)	0.0155 (3)	0.0447 (8)
H16A	0.9026	0.6980	−0.0166	0.054*
C17	0.8445 (4)	0.7457 (3)	0.0990 (2)	0.0372 (7)
C18	0.6844 (4)	0.6996 (3)	0.1399 (2)	0.0360 (7)
C19	0.4638 (4)	0.6307 (3)	0.1630 (2)	0.0370 (7)
C20	0.3338 (4)	0.5731 (3)	0.1523 (3)	0.0389 (8)
C21	0.2038 (4)	0.5364 (3)	0.2252 (3)	0.0484 (9)
H21A	0.1938	0.5495	0.2828	0.058*
C22	0.0886 (5)	0.4799 (3)	0.2112 (3)	0.0583 (10)
H22A	0.0012	0.4566	0.2608	0.070*
C23	0.2181 (5)	0.4939 (4)	0.0620 (3)	0.0633 (11)
H23A	0.2245	0.4800	0.0051	0.076*
C24	0.3379 (5)	0.5521 (3)	0.0684 (3)	0.0527 (10)
H24A	0.4212	0.5771	0.0164	0.063*
C25	0.8006 (5)	0.6203 (3)	0.4815 (3)	0.0540 (10)
H25A	0.8431	0.6727	0.5008	0.065*
H25B	0.8377	0.5446	0.5230	0.065*
C26	0.6162 (5)	0.6348 (3)	0.4945 (3)	0.0562 (10)
H26A	0.5734	0.5796	0.4789	0.067*
H26B	0.5750	0.6239	0.5623	0.067*
N1	0.5690 (3)	0.9484 (2)	0.2168 (2)	0.0425 (7)
N2	0.8401 (3)	0.9090 (2)	0.3005 (2)	0.0379 (6)
N3	0.9767 (3)	0.9114 (2)	0.3379 (2)	0.0391 (6)
N4	0.8461 (3)	1.0852 (2)	0.2877 (2)	0.0384 (6)
N5	1.3297 (4)	1.1242 (3)	0.4403 (3)	0.0584 (9)
N6	0.8917 (3)	0.7990 (2)	0.1493 (2)	0.0425 (7)
N7	0.6034 (3)	0.7089 (2)	0.2217 (2)	0.0392 (6)
N8	0.4580 (3)	0.6639 (2)	0.2376 (2)	0.0405 (6)
N9	0.6030 (3)	0.6513 (2)	0.0994 (2)	0.0411 (7)
N10	0.0943 (4)	0.4566 (3)	0.1321 (3)	0.0618 (9)
N11	0.8616 (3)	0.6409 (2)	0.3777 (2)	0.0418 (7)
H11B	0.9644	0.6557	0.3761	0.050*
H11C	0.8363	0.5759	0.3779	0.050*
N12	0.5630 (3)	0.7487 (2)	0.4287 (2)	0.0466 (7)
H12B	0.5435	0.7894	0.4666	0.056*
H12C	0.4597	0.7511	0.4173	0.056*
C27	0.3055 (11)	0.6293 (5)	0.7695 (7)	0.204 (5)
H27A	0.2189	0.6451	0.8151	0.245*
H27B	0.4091	0.6254	0.7908	0.245*
H27C	0.2926	0.5587	0.7666	0.245*
O1	0.2993 (5)	0.7199 (3)	0.6702 (3)	0.1036 (12)
H1B	0.2698	0.7879	0.6733	0.124*
O1W	0.2078 (3)	0.7151 (2)	0.37517 (18)	0.0555 (7)
H1WA	0.1489	0.7772	0.3615	0.067*
H1WB	0.2587	0.7179	0.3197	0.067*
O2W	0.1847 (4)	0.6019 (2)	0.5789 (2)	0.0810 (10)
H2WA	0.2278	0.6300	0.6105	0.097*
H2WB	0.1918	0.6143	0.5181	0.097*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0371 (2)	0.0371 (2)	0.0476 (2)	−0.00668 (16)	−0.01032 (17)	−0.01898 (18)
C1	0.052 (2)	0.050 (2)	0.069 (3)	−0.0071 (18)	−0.028 (2)	−0.020 (2)
C2	0.054 (2)	0.061 (3)	0.076 (3)	−0.001 (2)	−0.039 (2)	−0.016 (2)
C3	0.053 (2)	0.050 (2)	0.074 (3)	0.0077 (19)	−0.027 (2)	−0.014 (2)
C4	0.046 (2)	0.039 (2)	0.059 (2)	−0.0010 (16)	−0.0134 (18)	−0.0178 (17)
C5	0.0318 (17)	0.0397 (18)	0.0380 (17)	−0.0050 (14)	−0.0062 (14)	−0.0158 (15)
C6	0.0333 (17)	0.0350 (18)	0.0391 (17)	−0.0033 (14)	−0.0081 (14)	−0.0149 (14)
C7	0.0344 (18)	0.0375 (18)	0.0420 (18)	−0.0040 (14)	−0.0065 (14)	−0.0192 (15)
C8	0.0310 (17)	0.0443 (19)	0.0476 (19)	−0.0059 (14)	−0.0057 (15)	−0.0262 (16)
C9	0.0368 (19)	0.047 (2)	0.061 (2)	−0.0030 (16)	−0.0128 (17)	−0.0254 (18)
C10	0.042 (2)	0.064 (3)	0.068 (3)	0.0016 (19)	−0.0218 (19)	−0.031 (2)
C11	0.060 (3)	0.051 (2)	0.083 (3)	−0.013 (2)	−0.019 (2)	−0.035 (2)
C12	0.053 (2)	0.043 (2)	0.067 (2)	−0.0042 (17)	−0.0212 (19)	−0.0254 (19)
C13	0.044 (2)	0.052 (2)	0.064 (2)	−0.0126 (18)	−0.0050 (19)	−0.024 (2)
C14	0.041 (2)	0.063 (3)	0.070 (3)	−0.0196 (19)	0.003 (2)	−0.019 (2)
C15	0.043 (2)	0.066 (3)	0.055 (2)	−0.0031 (19)	0.0010 (18)	−0.025 (2)
C16	0.0366 (19)	0.053 (2)	0.047 (2)	−0.0043 (16)	−0.0047 (15)	−0.0214 (17)
C17	0.0324 (17)	0.0382 (18)	0.0387 (17)	−0.0017 (14)	−0.0086 (14)	−0.0112 (15)
C18	0.0346 (17)	0.0354 (18)	0.0393 (17)	−0.0014 (14)	−0.0034 (14)	−0.0168 (15)
C19	0.0341 (18)	0.0350 (18)	0.0436 (18)	−0.0027 (14)	−0.0032 (15)	−0.0177 (15)
C20	0.0337 (18)	0.0342 (18)	0.052 (2)	0.0006 (14)	−0.0074 (15)	−0.0208 (16)
C21	0.045 (2)	0.053 (2)	0.052 (2)	−0.0113 (17)	−0.0020 (17)	−0.0247 (18)
C22	0.047 (2)	0.058 (2)	0.070 (3)	−0.0210 (19)	0.003 (2)	−0.023 (2)
C23	0.064 (3)	0.069 (3)	0.076 (3)	−0.016 (2)	−0.006 (2)	−0.046 (2)
C24	0.046 (2)	0.062 (2)	0.064 (2)	−0.0148 (19)	0.0027 (18)	−0.039 (2)
C25	0.055 (2)	0.054 (2)	0.050 (2)	0.0056 (19)	−0.0161 (18)	−0.0174 (19)
C26	0.054 (2)	0.059 (3)	0.053 (2)	−0.014 (2)	0.0035 (19)	−0.019 (2)
N1	0.0390 (16)	0.0405 (16)	0.0522 (17)	−0.0042 (13)	−0.0187 (13)	−0.0166 (14)
N2	0.0332 (15)	0.0340 (15)	0.0532 (17)	−0.0018 (12)	−0.0155 (13)	−0.0199 (13)
N3	0.0335 (15)	0.0385 (16)	0.0516 (17)	−0.0014 (12)	−0.0130 (13)	−0.0212 (13)
N4	0.0373 (15)	0.0340 (15)	0.0491 (16)	−0.0019 (12)	−0.0140 (13)	−0.0181 (13)
N5	0.0494 (19)	0.066 (2)	0.076 (2)	−0.0097 (17)	−0.0190 (17)	−0.0386 (19)
N6	0.0380 (16)	0.0419 (16)	0.0487 (17)	−0.0085 (13)	−0.0056 (13)	−0.0169 (14)
N7	0.0336 (15)	0.0425 (16)	0.0463 (16)	−0.0072 (12)	−0.0037 (12)	−0.0213 (13)
N8	0.0341 (15)	0.0464 (17)	0.0470 (16)	−0.0084 (13)	0.0008 (12)	−0.0252 (14)
N9	0.0357 (15)	0.0474 (17)	0.0475 (16)	−0.0072 (13)	−0.0029 (13)	−0.0254 (14)
N10	0.054 (2)	0.061 (2)	0.084 (2)	−0.0211 (17)	−0.0054 (19)	−0.038 (2)
N11	0.0400 (16)	0.0351 (15)	0.0536 (17)	−0.0051 (12)	−0.0088 (13)	−0.0188 (13)
N12	0.0365 (16)	0.0554 (19)	0.0568 (18)	−0.0042 (14)	−0.0047 (14)	−0.0313 (16)
C27	0.250 (10)	0.067 (4)	0.335 (13)	0.000 (5)	−0.219 (10)	−0.048 (6)
O1	0.139 (3)	0.066 (2)	0.123 (3)	0.013 (2)	−0.044 (3)	−0.051 (2)
O1W	0.0514 (16)	0.0555 (16)	0.0523 (15)	0.0069 (12)	−0.0001 (12)	−0.0199 (13)
O2W	0.119 (3)	0.068 (2)	0.0630 (19)	−0.0367 (19)	−0.0044 (18)	−0.0249 (16)

Geometric parameters (Å, º) top

Zn1—N7	2.096 (3)	C16—H16A	0.9300
Zn1—N2	2.103 (2)	C17—N6	1.343 (4)
Zn1—N11	2.133 (3)	C17—C18	1.473 (4)
Zn1—N12	2.148 (3)	C18—N7	1.329 (4)
Zn1—N1	2.269 (3)	C18—N9	1.341 (4)
Zn1—N6	2.293 (3)	C19—N8	1.340 (4)
C1—N1	1.334 (4)	C19—N9	1.347 (4)
C1—C2	1.370 (5)	C19—C20	1.470 (4)
C1—H1A	0.9300	C20—C24	1.379 (5)
C2—C3	1.376 (6)	C20—C21	1.381 (5)
C2—H2A	0.9300	C21—C22	1.382 (5)
C3—C4	1.379 (5)	C21—H21A	0.9300
C3—H3A	0.9300	C22—N10	1.324 (5)
C4—C5	1.374 (5)	C22—H22A	0.9300
C4—H4A	0.9300	C23—N10	1.325 (5)
C5—N1	1.347 (4)	C23—C24	1.377 (5)
C5—C6	1.465 (4)	C23—H23A	0.9300
C6—N2	1.324 (4)	C24—H24A	0.9300
C6—N4	1.347 (4)	C25—N11	1.470 (4)
C7—N3	1.335 (4)	C25—C26	1.507 (5)
C7—N4	1.348 (4)	C25—H25A	0.9700
C7—C8	1.475 (4)	C25—H25B	0.9700
C8—C9	1.374 (5)	C26—N12	1.468 (5)
C8—C12	1.387 (5)	C26—H26A	0.9700
C9—C10	1.380 (5)	C26—H26B	0.9700
C9—H9A	0.9300	N2—N3	1.364 (3)
C10—N5	1.335 (5)	N7—N8	1.366 (4)
C10—H10A	0.9300	N11—H11B	0.8999
C11—N5	1.330 (5)	N11—H11C	0.9001
C11—C12	1.374 (5)	N12—H12B	0.9006
C11—H11A	0.9300	N12—H12C	0.8999
C12—H12A	0.9300	C27—O1	1.485 (8)
C13—N6	1.330 (4)	C27—H27A	0.9600
C13—C14	1.361 (5)	C27—H27B	0.9600
C13—H13A	0.9300	C27—H27C	0.9600
C14—C15	1.372 (5)	O1—H1B	0.9002
C14—H14A	0.9300	O1W—H1WA	0.8500
C15—C16	1.379 (5)	O1W—H1WB	0.8506
C15—H15A	0.9300	O2W—H2WA	0.8501
C16—C17	1.379 (5)	O2W—H2WB	0.8506

N7—Zn1—N2	156.47 (11)	N8—C19—N9	114.0 (3)
N7—Zn1—N11	99.48 (10)	N8—C19—C20	123.6 (3)
N2—Zn1—N11	98.05 (10)	N9—C19—C20	122.4 (3)
N7—Zn1—N12	101.58 (10)	C24—C20—C21	116.9 (3)
N2—Zn1—N12	96.28 (11)	C24—C20—C19	121.0 (3)
N11—Zn1—N12	81.99 (11)	C21—C20—C19	122.2 (3)
N7—Zn1—N1	89.05 (10)	C20—C21—C22	119.0 (3)
N2—Zn1—N1	74.90 (10)	C20—C21—H21A	120.5
N11—Zn1—N1	170.61 (10)	C22—C21—H21A	120.5
N12—Zn1—N1	92.50 (11)	N10—C22—C21	124.5 (4)
N7—Zn1—N6	75.35 (10)	N10—C22—H22A	117.7
N2—Zn1—N6	88.45 (10)	C21—C22—H22A	117.7
N11—Zn1—N6	92.21 (10)	N10—C23—C24	124.0 (4)
N12—Zn1—N6	172.96 (10)	N10—C23—H23A	118.0
N1—Zn1—N6	93.77 (10)	C24—C23—H23A	118.0
N1—C1—C2	123.1 (3)	C23—C24—C20	119.8 (4)
N1—C1—H1A	118.5	C23—C24—H24A	120.1
C2—C1—H1A	118.5	C20—C24—H24A	120.1
C1—C2—C3	118.7 (3)	N11—C25—C26	109.3 (3)
C1—C2—H2A	120.6	N11—C25—H25A	109.8
C3—C2—H2A	120.6	C26—C25—H25A	109.8
C2—C3—C4	118.9 (4)	N11—C25—H25B	109.8
C2—C3—H3A	120.5	C26—C25—H25B	109.8
C4—C3—H3A	120.5	H25A—C25—H25B	108.3
C5—C4—C3	119.2 (3)	N12—C26—C25	108.8 (3)
C5—C4—H4A	120.4	N12—C26—H26A	109.9
C3—C4—H4A	120.4	C25—C26—H26A	109.9
N1—C5—C4	122.0 (3)	N12—C26—H26B	109.9
N1—C5—C6	113.5 (3)	C25—C26—H26B	109.9
C4—C5—C6	124.5 (3)	H26A—C26—H26B	108.3
N2—C6—N4	113.5 (3)	C1—N1—C5	118.1 (3)
N2—C6—C5	119.7 (3)	C1—N1—Zn1	127.8 (2)
N4—C6—C5	126.8 (3)	C5—N1—Zn1	114.1 (2)
N3—C7—N4	114.2 (3)	C6—N2—N3	106.6 (2)
N3—C7—C8	121.6 (3)	C6—N2—Zn1	117.1 (2)
N4—C7—C8	124.1 (3)	N3—N2—Zn1	136.0 (2)
C9—C8—C12	117.5 (3)	C7—N3—N2	104.7 (3)
C9—C8—C7	121.1 (3)	C6—N4—C7	101.1 (3)
C12—C8—C7	121.4 (3)	C11—N5—C10	115.7 (3)
C8—C9—C10	119.3 (3)	C13—N6—C17	117.3 (3)
C8—C9—H9A	120.4	C13—N6—Zn1	129.4 (2)
C10—C9—H9A	120.4	C17—N6—Zn1	113.2 (2)
N5—C10—C9	124.1 (4)	C18—N7—N8	106.3 (2)
N5—C10—H10A	117.9	C18—N7—Zn1	117.0 (2)
C9—C10—H10A	117.9	N8—N7—Zn1	136.7 (2)
N5—C11—C12	124.6 (4)	C19—N8—N7	104.7 (2)
N5—C11—H11A	117.7	C18—N9—C19	101.3 (3)
C12—C11—H11A	117.7	C22—N10—C23	115.9 (3)
C11—C12—C8	118.9 (4)	C25—N11—Zn1	107.1 (2)
C11—C12—H12A	120.6	C25—N11—H11B	99.2
C8—C12—H12A	120.6	Zn1—N11—H11B	112.6
N6—C13—C14	123.6 (4)	C25—N11—H11C	97.5
N6—C13—H13A	118.2	Zn1—N11—H11C	113.1
C14—C13—H13A	118.2	H11B—N11—H11C	123.5
C13—C14—C15	119.1 (4)	C26—N12—Zn1	107.1 (2)
C13—C14—H14A	120.5	C26—N12—H12B	104.9
C15—C14—H14A	120.5	Zn1—N12—H12B	127.8
C14—C15—C16	118.8 (4)	C26—N12—H12C	110.1
C14—C15—H15A	120.6	Zn1—N12—H12C	107.7
C16—C15—H15A	120.6	H12B—N12—H12C	98.5
C17—C16—C15	118.5 (3)	O1—C27—H27A	109.5
C17—C16—H16A	120.7	O1—C27—H27B	109.5
C15—C16—H16A	120.7	H27A—C27—H27B	109.5
N6—C17—C16	122.7 (3)	O1—C27—H27C	109.5
N6—C17—C18	113.9 (3)	H27A—C27—H27C	109.5
C16—C17—C18	123.4 (3)	H27B—C27—H27C	109.5
N7—C18—N9	113.8 (3)	C27—O1—H1B	112.0
N7—C18—C17	120.1 (3)	H1WA—O1W—H1WB	104.0
N9—C18—C17	126.0 (3)	H2WA—O2W—H2WB	133.0

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11B···O1Wⁱ	0.90	2.27	3.166 (4)	172
N11—H11C···O2Wⁱⁱ	0.90	2.17	3.034 (4)	161
N12—H12B···N5ⁱⁱⁱ	0.90	2.54	3.321 (4)	146
N12—H12C···O1W	0.90	2.45	3.331 (4)	165
O1—H1B···N4^iv	0.90	2.02	2.897 (4)	163
O1W—H1WA···N3^v	0.85	2.04	2.887 (4)	171
O1W—H1WB···N8	0.85	2.09	2.859 (4)	150
O2W—H2WA···O1	0.85	1.94	2.778 (4)	169
O2W—H2WB···O1W	0.85	2.00	2.787 (4)	153

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

Experimental details

Crystal data
Chemical formula	[Zn(C₁₂H₈N₅)₂(C₂H₈N₂)]·CH₃O·2H₂O
M_r	638.02
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	8.3323 (8), 13.0268 (12), 14.9444 (14)
α, β, γ (°)	66.404 (2), 79.751 (2), 81.437 (2)
V (Å³)	1457.3 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.90
Crystal size (mm)	0.25 × 0.22 × 0.16

Data collection
Diffractometer	Bruker APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2000)
T_min, T_max	0.807, 0.870
No. of measured, independent and observed [I > 2σ(I)] reflections	11395, 5643, 4532
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.130, 1.04
No. of reflections	5643
No. of parameters	388
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.61, −0.56

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Zn1—N7	2.096 (3)	Zn1—N12	2.148 (3)
Zn1—N2	2.103 (2)	Zn1—N1	2.269 (3)
Zn1—N11	2.133 (3)	Zn1—N6	2.293 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11B···O1Wⁱ	0.90	2.27	3.166 (4)	172.0
N11—H11C···O2Wⁱⁱ	0.90	2.17	3.034 (4)	161.3
N12—H12B···N5ⁱⁱⁱ	0.90	2.54	3.321 (4)	145.6
N12—H12C···O1W	0.90	2.45	3.331 (4)	164.9
O1—H1B···N4^iv	0.90	2.02	2.897 (4)	163.0
O1W—H1WA···N3^v	0.85	2.04	2.887 (4)	171.0
O1W—H1WB···N8	0.85	2.09	2.859 (4)	149.8
O2W—H2WA···O1	0.85	1.94	2.778 (4)	169.0
O2W—H2WB···O1W	0.85	2.00	2.787 (4)	153.0

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

Acknowledgements

The authors thank the Program for Young Excellent Talents in Southeast University for a financial support.

References

Bruker (2000). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Kesanli, B. & Lin, W. (2003). Coord. Chem. Rev. 246, 305–326. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2000). 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
Wang, Y.-T., Tong, M.-L., Fan, H.-H., Wang, H.-Z. & Chen, X.-M. (2005). Dalton Trans. pp. 424–426. 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.