(Dicyanamido)[tris­(2-pyridylmeth­yl)amine]zinc(II) perchlorate

Li, H.; Zhao, H.Y.; Zhang, S.G.

doi:10.1107/S1600536808004741

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 3| March 2008| Page m495

doi:10.1107/S1600536808004741

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(Dicyanamido)[tris(2-pyridylmethyl)amine]zinc(II) perchlorate

Hong Li,^a ^* Hong Yan Zhao ^b and Shi Guo Zhang ^a

^aDepartment of Chemistry and Chemical Engineering, Institute of Materials Chemistry, Binzhou University, Binzhou 256603, People's Republic of China, and ^bDepartment of Chemistry, Shandong Normal University, Jinan 250014, People's Republic of China
^*Correspondence e-mail: honglizhang1968@yahoo.cn

(Received 29 January 2008; accepted 18 February 2008; online 27 February 2008)

In the title complex, [Zn(C₂N₃)(C₁₈H₁₈N₄)]ClO₄, the Zn^II ion has a slightly distorted trigonal–bipyramidal ZnN₅ coordination geometry. The crystal structure is stabilized by weak intermolecular C—H⋯O and C—H⋯N hydrogen bonds. In addition, there are relatively close contacts between the O atoms of the perchlorate anion and symmetry-related pyridine rings [O⋯Cg = 3.179 (3) and 3.236 (3) Å, where Cg is the centroid of a pyridine ring], and between the terminal N atom of the dicyanamide ligand and pyridine rings [N⋯Cg = 3.381 (4)–3.761 (3) Å]. The central N atom of the dicyanamide ligand is disordered over two sites in an approximately 0.6:0.4 ratio.

Related literature

For related literature, see: Makowska-Grzyska et al. (2003 ); Sun et al. (2003 ); Martin et al. (2001 ).

Experimental

Crystal data

[Zn(C₂N₃)(C₁₈H₁₈N₄)]ClO₄
M_r = 521.23
Monoclinic, P 2₁ /c
a = 13.931 (2) Å
b = 10.8578 (18) Å
c = 14.653 (2) Å
β = 91.590 (3)°
V = 2215.5 (6) Å³
Z = 4
Mo Kα radiation
μ = 1.27 mm⁻¹
T = 298 (2) K
0.30 × 0.20 × 0.18 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.702, T_max = 0.803
12346 measured reflections
4800 independent reflections
3352 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.106
S = 0.99
4800 reflections
308 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

N1—Zn1	2.053 (2)
N2—Zn1	2.048 (2)
N3—Zn1	2.059 (2)
N4—Zn1	2.215 (2)
N5—Zn1	2.021 (3)

N5—Zn1—N2	101.94 (10)
N5—Zn1—N1	100.96 (11)
N2—Zn1—N1	118.19 (9)
N5—Zn1—N3	100.98 (10)
N2—Zn1—N3	117.58 (9)
N1—Zn1—N3	112.99 (9)
N5—Zn1—N4	179.41 (10)
N2—Zn1—N4	78.60 (9)
N1—Zn1—N4	78.95 (9)
N3—Zn1—N4	78.55 (9)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O4ⁱ	0.93	2.53	3.272 (4)	138
C7—H7B⋯O2ⁱⁱ	0.97	2.59	3.455 (4)	148
C10—H10⋯O1ⁱⁱⁱ	0.93	2.58	3.511 (5)	179
C13—H13A⋯N6^iv	0.97	2.61	3.457 (5)	146
C16—H16⋯N7′^v	0.93	2.48	3.412 (18)	178
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x, -y+1, -z; (iii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iv) -x+1, -y+2, -z; (v) x, y-1, z.

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); 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/S1600536808004741/lh2594sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808004741/lh2594Isup2.hkl

checkCIF report

Comment top

Tris[(2-pyridyl)methylene)amine is a very common terminal ligand and many complexes containing this ligand have been reported, including some Zn(II) complexes with perchlorate anions (e.g. Makowska-Grzyska et al., 2003) such as in the title compound. The dicyanamide anion can play a role as bridging ligand to form multi-nuclear complexes (e.g. Sun et al., 2003; Martin et al., 2001). As part of our work we wanted to prepare a coordination polymer with dicyanamide group acting as a bridging ligand and tris[(2-pyridyl)methylene)amine as terminal ligand, but instead we obtained the title mononuclear five-coordinated Zn(II) complex (I) and its crystal structure is reported herein. At this time there appears to be no other published examples of crystal structures of complexes of the two above mentioned ligands both coordinated to a transition metal.

The title complex is shown in Fig. 1. The Zn^II ion is in a slightly distorted trigonal-bipyramidal coordination geometry. In the crystal structure, there are weak hydrogen bonds formed between complex cations and perchlorate anions, and between symmetry related complex cations (Fig. 2). In addition there also exists interactions between Cl—O bonds and π-rings systems and between C—N bonds and π-ring systems, and the relevant distances (Å) are as follows: Cl1—O2···Cg1ⁱ = 3.236 (3), Cl1—O2···Cg1ⁱ_perp = 3.120; Cl1—O4···Cg2ⁱ = 3.179 (3), Cl1—O4···Cg2ⁱ_perp = 3.111; C20—N6···Cg2ⁱⁱ = 3.381 (4), C20—N6···Cg2ⁱⁱ_perp = 3.360; C20—N6···Cg1ⁱⁱⁱ = 3.453 (4), C20—N6···Cg1ⁱⁱⁱ_perp = 3.156; C20—N6···Cg3ⁱⁱⁱ = 3.761 (3), C20—N6···Cg3ⁱⁱⁱ_perp = 3.365; (Cg1, Cg2 and Cg3 are the centroids of N2/C1—C5 ring, N1/C8—C12 ring and N3/C14—C18 ring, respectively; A—B···Cgj_perp is the perpendicular distance from B atom to ring j; symmetry codes: (i) x,-1 + y,z; (ii) 1 - x,2 - y,-z; (iii) 1 - x,1/2 + y,1/2 - z).

Related literature top

For related literature, see: Makowska-Grzyska et al. (2003); Sun et al. (2003); Martin et al. (2001).

Experimental top

A 10 ml me thanol solution of tris[(2-pyridyl)methylene]amine (0.2103 g, 0.72 mmol) was added into 20 ml H₂O solution containing Zn(ClO₄)6H₂O (0.2621 g, 0.70 mmol) and sodium dicyanamide (0.0645 g, 0.72 mmol), and the mixture was stirred for a few minutes. Colorless single crystals were obtained after the filtrate had been allowed to stand at room temperature for 10 d.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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. View of complex (I), showing the the atom numbering scheme with thermal ellipsoids drawn at the 30% probability level.
	Fig. 2. Part of the crystal structure showing weak hydrogen bonds as dashed lines.

(Dicyanamido)[tris(2-pyridylmethyl)amine]zinc(II) perchlorate top

Crystal data top

[Zn(C₂N₃)(C₁₈H₁₈N₄)]ClO₄	F(000) = 1064
M_r = 521.23	D_x = 1.563 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2616 reflections
a = 13.931 (2) Å	θ = 2.3–22.0°
b = 10.8578 (18) Å	µ = 1.27 mm⁻¹
c = 14.653 (2) Å	T = 298 K
β = 91.590 (3)°	Block, colorless
V = 2215.5 (6) Å³	0.30 × 0.20 × 0.18 mm
Z = 4

Data collection top

Bruker SMART APEX CCD diffractometer	4800 independent reflections
Radiation source: fine-focus sealed tube	3352 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
ϕ and ω scans	θ_max = 27.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→17
T_min = 0.702, T_max = 0.803	k = −13→12
12346 measured reflections	l = −18→16

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.106	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.053P)²] where P = (F_o² + 2F_c²)/3
4800 reflections	(Δ/σ)_max = 0.001
308 parameters	Δρ_max = 0.36 e Å⁻³
1 restraint	Δρ_min = −0.25 e Å⁻³

Crystal data top

[Zn(C₂N₃)(C₁₈H₁₈N₄)]ClO₄	V = 2215.5 (6) Å³
M_r = 521.23	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.931 (2) Å	µ = 1.27 mm⁻¹
b = 10.8578 (18) Å	T = 298 K
c = 14.653 (2) Å	0.30 × 0.20 × 0.18 mm
β = 91.590 (3)°

Data collection top

Bruker SMART APEX CCD diffractometer	4800 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3352 reflections with I > 2σ(I)
T_min = 0.702, T_max = 0.803	R_int = 0.035
12346 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	1 restraint
wR(F²) = 0.106	H-atom parameters constrained
S = 0.99	Δρ_max = 0.36 e Å⁻³
4800 reflections	Δρ_min = −0.25 e Å⁻³
308 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)
C1	0.0860 (2)	0.9139 (3)	0.2853 (2)	0.0612 (9)
H1	0.0337	0.8627	0.2947	0.073*
C2	0.1044 (3)	1.0115 (4)	0.3423 (2)	0.0697 (10)
H2	0.0648	1.0272	0.3910	0.084*
C3	0.1813 (3)	1.0854 (3)	0.3270 (2)	0.0674 (9)
H3	0.1952	1.1517	0.3654	0.081*
C4	0.2375 (2)	1.0607 (3)	0.2547 (2)	0.0545 (8)
H4	0.2894	1.1122	0.2439	0.065*
C5	0.14649 (19)	0.8927 (3)	0.21361 (19)	0.0461 (7)
C6	0.1355 (2)	0.7823 (3)	0.1528 (2)	0.0562 (8)
H6A	0.1669	0.7122	0.1816	0.067*
H6B	0.0678	0.7629	0.1445	0.067*
C7	0.1151 (2)	0.8761 (3)	0.0017 (2)	0.0629 (9)
H7A	0.0784	0.9345	0.0367	0.076*
H7B	0.0702	0.8217	−0.0301	0.076*
C8	0.1729 (2)	0.9441 (3)	−0.0664 (2)	0.0519 (7)
C9	0.1372 (3)	0.9713 (3)	−0.1530 (2)	0.0691 (9)
H9	0.0769	0.9431	−0.1722	0.083*
C10	0.1913 (4)	1.0397 (4)	−0.2098 (2)	0.0812 (11)
H10	0.1684	1.0590	−0.2683	0.097*
C11	0.2798 (3)	1.0797 (3)	−0.1801 (2)	0.0786 (11)
H11	0.3177	1.1267	−0.2180	0.094*
C12	0.3118 (3)	1.0497 (3)	−0.0937 (2)	0.0617 (8)
H12	0.3719	1.0774	−0.0736	0.074*
C13	0.2121 (2)	0.6901 (3)	0.0215 (2)	0.0628 (9)
H13A	0.2159	0.7016	−0.0439	0.075*
H13B	0.1676	0.6233	0.0324	0.075*
C14	0.3093 (2)	0.6574 (3)	0.0606 (2)	0.0554 (8)
C15	0.3413 (4)	0.5360 (3)	0.0654 (3)	0.0844 (12)
H15	0.3010	0.4718	0.0469	0.101*
C16	0.4314 (4)	0.5126 (4)	0.0972 (3)	0.1041 (15)
H16	0.4535	0.4318	0.1008	0.125*
C17	0.4900 (3)	0.6072 (4)	0.1240 (3)	0.0947 (14)
H17	0.5526	0.5922	0.1448	0.114*
C18	0.4545 (2)	0.7252 (3)	0.1195 (2)	0.0681 (9)
H18	0.4936	0.7899	0.1392	0.082*
C19	0.4657 (2)	1.1134 (3)	0.1232 (2)	0.0594 (8)
C20	0.5964 (3)	1.2341 (3)	0.1587 (2)	0.0670 (9)
Cl1	0.13251 (5)	0.26686 (7)	0.06625 (5)	0.0551 (2)
N1	0.25963 (17)	0.9822 (2)	−0.03743 (15)	0.0474 (6)
N2	0.22133 (15)	0.9657 (2)	0.19860 (14)	0.0425 (5)
N3	0.36571 (17)	0.7501 (2)	0.08790 (16)	0.0500 (6)
N4	0.17686 (15)	0.8038 (2)	0.06381 (15)	0.0461 (6)
N5	0.42095 (18)	1.0295 (3)	0.11270 (19)	0.0626 (7)
N6	0.6718 (3)	1.2592 (3)	0.1805 (2)	0.1036 (12)
N7	0.5015 (14)	1.214 (2)	0.157 (3)	0.066 (7)	0.40 (7)
N7'	0.5148 (16)	1.2179 (15)	0.116 (3)	0.100 (5)	0.60 (7)
O1	0.1054 (2)	0.3925 (2)	0.06831 (17)	0.0854 (8)
O2	0.08216 (17)	0.2017 (2)	0.13439 (16)	0.0821 (7)
O3	0.23268 (17)	0.2569 (3)	0.0827 (2)	0.0980 (8)
O4	0.1080 (2)	0.2177 (2)	−0.02084 (16)	0.0905 (8)
Zn1	0.30405 (2)	0.92245 (3)	0.08979 (2)	0.04138 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0467 (17)	0.086 (3)	0.0509 (19)	0.0100 (16)	0.0088 (14)	0.0197 (18)
C2	0.081 (3)	0.086 (3)	0.0423 (19)	0.024 (2)	0.0134 (17)	0.0048 (18)
C3	0.089 (3)	0.067 (2)	0.0456 (19)	0.0119 (19)	0.0039 (18)	−0.0042 (16)
C4	0.0615 (19)	0.056 (2)	0.0459 (18)	0.0023 (14)	−0.0017 (15)	0.0004 (14)
C5	0.0401 (15)	0.0575 (18)	0.0404 (16)	0.0022 (13)	−0.0029 (12)	0.0081 (13)
C6	0.0447 (17)	0.068 (2)	0.0564 (19)	−0.0167 (15)	0.0066 (14)	0.0053 (15)
C7	0.0424 (17)	0.090 (2)	0.056 (2)	−0.0105 (16)	−0.0095 (15)	0.0053 (18)
C8	0.0528 (18)	0.0588 (19)	0.0437 (17)	0.0085 (14)	−0.0041 (14)	0.0003 (14)
C9	0.083 (2)	0.076 (2)	0.048 (2)	0.0142 (19)	−0.0125 (18)	−0.0030 (18)
C10	0.123 (4)	0.075 (3)	0.045 (2)	0.025 (2)	−0.006 (2)	0.0083 (18)
C11	0.120 (3)	0.062 (2)	0.055 (2)	0.005 (2)	0.020 (2)	0.0158 (17)
C12	0.074 (2)	0.0515 (19)	0.061 (2)	−0.0001 (16)	0.0158 (17)	0.0026 (15)
C13	0.074 (2)	0.056 (2)	0.059 (2)	−0.0263 (17)	0.0047 (17)	−0.0095 (15)
C14	0.075 (2)	0.0442 (17)	0.0481 (17)	−0.0047 (15)	0.0153 (15)	−0.0035 (14)
C15	0.119 (4)	0.046 (2)	0.089 (3)	0.001 (2)	0.030 (3)	0.0011 (19)
C16	0.138 (4)	0.067 (3)	0.108 (4)	0.043 (3)	0.033 (3)	0.018 (3)
C17	0.090 (3)	0.100 (4)	0.095 (3)	0.048 (3)	0.007 (2)	0.012 (3)
C18	0.061 (2)	0.073 (2)	0.070 (2)	0.0125 (17)	0.0050 (18)	0.0036 (18)
C19	0.0489 (18)	0.0545 (18)	0.074 (2)	−0.0062 (12)	−0.0102 (16)	0.0012 (17)
C20	0.071 (2)	0.058 (2)	0.072 (2)	−0.0248 (18)	−0.0010 (19)	−0.0053 (17)
Cl1	0.0535 (4)	0.0568 (5)	0.0552 (5)	−0.0035 (3)	0.0042 (4)	0.0010 (4)
N1	0.0524 (14)	0.0476 (14)	0.0424 (13)	0.0022 (11)	0.0063 (11)	0.0037 (11)
N2	0.0419 (13)	0.0463 (13)	0.0391 (13)	0.0032 (10)	−0.0033 (10)	0.0028 (10)
N3	0.0524 (15)	0.0494 (14)	0.0484 (15)	0.0025 (11)	0.0044 (11)	0.0023 (11)
N4	0.0411 (13)	0.0553 (15)	0.0421 (13)	−0.0109 (11)	0.0025 (10)	0.0002 (11)
N5	0.0485 (15)	0.0609 (16)	0.0784 (19)	−0.0141 (11)	0.0000 (13)	−0.0056 (14)
N6	0.090 (2)	0.118 (3)	0.103 (3)	−0.050 (2)	0.010 (2)	−0.037 (2)
N7	0.060 (6)	0.040 (8)	0.096 (15)	−0.005 (5)	−0.014 (8)	0.007 (6)
N7'	0.089 (7)	0.082 (6)	0.128 (15)	−0.040 (5)	−0.042 (8)	0.052 (7)
O1	0.107 (2)	0.0644 (16)	0.0849 (19)	0.0212 (14)	0.0130 (15)	0.0035 (13)
O2	0.0737 (16)	0.1009 (19)	0.0720 (16)	−0.0049 (13)	0.0058 (13)	0.0369 (14)
O3	0.0550 (15)	0.0947 (19)	0.144 (2)	−0.0051 (13)	0.0035 (15)	0.0138 (17)
O4	0.110 (2)	0.098 (2)	0.0639 (16)	−0.0235 (16)	0.0170 (14)	−0.0221 (14)
Zn1	0.03599 (18)	0.0427 (2)	0.0454 (2)	−0.00542 (13)	0.00088 (13)	−0.00063 (14)

Geometric parameters (Å, º) top

C1—C2	1.368 (5)	C13—C14	1.498 (4)
C1—C5	1.384 (4)	C13—H13A	0.9700
C1—H1	0.9300	C13—H13B	0.9700
C2—C3	1.362 (5)	C14—N3	1.332 (4)
C2—H2	0.9300	C14—C15	1.392 (5)
C3—C4	1.362 (4)	C15—C16	1.352 (6)
C3—H3	0.9300	C15—H15	0.9300
C4—N2	1.334 (3)	C16—C17	1.363 (6)
C4—H4	0.9300	C16—H16	0.9300
C5—N2	1.333 (3)	C17—C18	1.374 (5)
C5—C6	1.499 (4)	C17—H17	0.9300
C6—N4	1.458 (3)	C18—N3	1.336 (4)
C6—H6A	0.9700	C18—H18	0.9300
C6—H6B	0.9700	C19—N5	1.112 (4)
C7—N4	1.463 (4)	C19—N7	1.294 (17)
C7—C8	1.495 (4)	C19—N7'	1.331 (14)
C7—H7A	0.9700	C20—N6	1.122 (4)
C7—H7B	0.9700	C20—N7'	1.298 (16)
C8—N1	1.335 (4)	C20—N7	1.34 (2)
C8—C9	1.382 (4)	Cl1—O3	1.414 (2)
C9—C10	1.359 (5)	Cl1—O4	1.416 (2)
C9—H9	0.9300	Cl1—O1	1.416 (2)
C10—C11	1.367 (6)	Cl1—O2	1.424 (2)
C10—H10	0.9300	N1—Zn1	2.053 (2)
C11—C12	1.369 (5)	N2—Zn1	2.048 (2)
C11—H11	0.9300	N3—Zn1	2.059 (2)
C12—N1	1.334 (4)	N4—Zn1	2.215 (2)
C12—H12	0.9300	N5—Zn1	2.021 (3)
C13—N4	1.472 (4)

C2—C1—C5	119.0 (3)	C16—C15—C14	119.3 (4)
C2—C1—H1	120.5	C16—C15—H15	120.4
C5—C1—H1	120.5	C14—C15—H15	120.4
C3—C2—C1	119.4 (3)	C15—C16—C17	120.0 (4)
C3—C2—H2	120.3	C15—C16—H16	120.0
C1—C2—H2	120.3	C17—C16—H16	120.0
C2—C3—C4	118.9 (3)	C16—C17—C18	118.5 (4)
C2—C3—H3	120.5	C16—C17—H17	120.7
C4—C3—H3	120.5	C18—C17—H17	120.7
N2—C4—C3	122.7 (3)	N3—C18—C17	122.3 (4)
N2—C4—H4	118.6	N3—C18—H18	118.9
C3—C4—H4	118.6	C17—C18—H18	118.9
N2—C5—C1	121.4 (3)	N5—C19—N7	162.3 (19)
N2—C5—C6	116.4 (2)	N5—C19—N7'	166.9 (17)
C1—C5—C6	122.0 (3)	N6—C20—N7'	166.3 (18)
N4—C6—C5	111.5 (2)	N6—C20—N7	163.6 (17)
N4—C6—H6A	109.3	O3—Cl1—O4	109.71 (18)
C5—C6—H6A	109.3	O3—Cl1—O1	109.44 (17)
N4—C6—H6B	109.3	O4—Cl1—O1	108.92 (16)
C5—C6—H6B	109.3	O3—Cl1—O2	110.20 (16)
H6A—C6—H6B	108.0	O4—Cl1—O2	109.48 (16)
N4—C7—C8	111.2 (2)	O1—Cl1—O2	109.07 (16)
N4—C7—H7A	109.4	C12—N1—C8	118.5 (3)
C8—C7—H7A	109.4	C12—N1—Zn1	125.4 (2)
N4—C7—H7B	109.4	C8—N1—Zn1	115.97 (19)
C8—C7—H7B	109.4	C5—N2—C4	118.6 (3)
H7A—C7—H7B	108.0	C5—N2—Zn1	116.86 (19)
N1—C8—C9	121.7 (3)	C4—N2—Zn1	124.6 (2)
N1—C8—C7	116.1 (2)	C14—N3—C18	118.9 (3)
C9—C8—C7	122.1 (3)	C14—N3—Zn1	116.6 (2)
C10—C9—C8	119.2 (4)	C18—N3—Zn1	124.2 (2)
C10—C9—H9	120.4	C6—N4—C7	113.7 (2)
C8—C9—H9	120.4	C6—N4—C13	112.7 (2)
C9—C10—C11	119.3 (3)	C7—N4—C13	112.7 (2)
C9—C10—H10	120.4	C6—N4—Zn1	105.89 (16)
C11—C10—H10	120.4	C7—N4—Zn1	104.41 (17)
C10—C11—C12	119.1 (3)	C13—N4—Zn1	106.58 (17)
C10—C11—H11	120.4	C19—N5—Zn1	160.0 (3)
C12—C11—H11	120.4	C19—N7—C20	120.9 (14)
N1—C12—C11	122.2 (3)	C20—N7'—C19	121.4 (13)
N1—C12—H12	118.9	N5—Zn1—N2	101.94 (10)
C11—C12—H12	118.9	N5—Zn1—N1	100.96 (11)
N4—C13—C14	110.3 (2)	N2—Zn1—N1	118.19 (9)
N4—C13—H13A	109.6	N5—Zn1—N3	100.98 (10)
C14—C13—H13A	109.6	N2—Zn1—N3	117.58 (9)
N4—C13—H13B	109.6	N1—Zn1—N3	112.99 (9)
C14—C13—H13B	109.6	N5—Zn1—N4	179.41 (10)
H13A—C13—H13B	108.1	N2—Zn1—N4	78.60 (9)
N3—C14—C15	121.0 (3)	N1—Zn1—N4	78.95 (9)
N3—C14—C13	117.1 (3)	N3—Zn1—N4	78.55 (9)
C15—C14—C13	121.9 (3)

C5—C1—C2—C3	0.2 (5)	C14—C13—N4—Zn1	34.9 (3)
C1—C2—C3—C4	0.6 (5)	N7—C19—N5—Zn1	63 (5)
C2—C3—C4—N2	−1.0 (5)	N7'—C19—N5—Zn1	−71 (7)
C2—C1—C5—N2	−0.6 (4)	N5—C19—N7—C20	138.7 (19)
C2—C1—C5—C6	175.2 (3)	N7'—C19—N7—C20	−61 (3)
N2—C5—C6—N4	−27.9 (3)	N6—C20—N7—C19	−134 (2)
C1—C5—C6—N4	156.1 (3)	N7'—C20—N7—C19	65 (3)
N4—C7—C8—N1	−33.0 (4)	N6—C20—N7'—C19	141 (3)
N4—C7—C8—C9	150.0 (3)	N7—C20—N7'—C19	−62 (2)
N1—C8—C9—C10	−0.7 (5)	N5—C19—N7'—C20	−142 (3)
C7—C8—C9—C10	176.1 (3)	N7—C19—N7'—C20	66 (3)
C8—C9—C10—C11	0.1 (6)	C19—N5—Zn1—N2	−60.5 (8)
C9—C10—C11—C12	0.1 (6)	C19—N5—Zn1—N1	61.7 (8)
C10—C11—C12—N1	0.2 (5)	C19—N5—Zn1—N3	178.0 (8)
N4—C13—C14—N3	−30.8 (4)	C5—N2—Zn1—N5	−167.30 (19)
N4—C13—C14—C15	151.5 (3)	C4—N2—Zn1—N5	12.5 (2)
N3—C14—C15—C16	−0.8 (5)	C5—N2—Zn1—N1	83.2 (2)
C13—C14—C15—C16	176.8 (4)	C4—N2—Zn1—N1	−97.0 (2)
C14—C15—C16—C17	−0.1 (7)	C5—N2—Zn1—N3	−58.0 (2)
C15—C16—C17—C18	1.3 (7)	C4—N2—Zn1—N3	121.8 (2)
C16—C17—C18—N3	−1.6 (6)	C5—N2—Zn1—N4	12.47 (18)
C11—C12—N1—C8	−0.8 (5)	C4—N2—Zn1—N4	−167.7 (2)
C11—C12—N1—Zn1	175.7 (2)	C12—N1—Zn1—N5	14.7 (3)
C9—C8—N1—C12	1.0 (4)	C8—N1—Zn1—N5	−168.7 (2)
C7—C8—N1—C12	−176.0 (3)	C12—N1—Zn1—N2	124.8 (2)
C9—C8—N1—Zn1	−175.8 (2)	C8—N1—Zn1—N2	−58.7 (2)
C7—C8—N1—Zn1	7.2 (3)	C12—N1—Zn1—N3	−92.3 (2)
C1—C5—N2—C4	0.2 (4)	C8—N1—Zn1—N3	84.2 (2)
C6—C5—N2—C4	−175.8 (2)	C12—N1—Zn1—N4	−164.7 (3)
C1—C5—N2—Zn1	−180.0 (2)	C8—N1—Zn1—N4	11.9 (2)
C6—C5—N2—Zn1	4.0 (3)	C14—N3—Zn1—N5	−170.4 (2)
C3—C4—N2—C5	0.6 (4)	C18—N3—Zn1—N5	15.8 (3)
C3—C4—N2—Zn1	−179.2 (2)	C14—N3—Zn1—N2	79.8 (2)
C15—C14—N3—C18	0.6 (4)	C18—N3—Zn1—N2	−94.1 (3)
C13—C14—N3—C18	−177.2 (3)	C14—N3—Zn1—N1	−63.4 (2)
C15—C14—N3—Zn1	−173.6 (2)	C18—N3—Zn1—N1	122.8 (2)
C13—C14—N3—Zn1	8.6 (3)	C14—N3—Zn1—N4	9.3 (2)
C17—C18—N3—C14	0.7 (5)	C18—N3—Zn1—N4	−164.6 (3)
C17—C18—N3—Zn1	174.4 (3)	C6—N4—Zn1—N2	−25.66 (18)
C5—C6—N4—C7	−79.4 (3)	C7—N4—Zn1—N2	94.61 (19)
C5—C6—N4—C13	150.8 (2)	C13—N4—Zn1—N2	−145.91 (19)
C5—C6—N4—Zn1	34.7 (3)	C6—N4—Zn1—N1	−147.68 (19)
C8—C7—N4—C6	153.5 (3)	C7—N4—Zn1—N1	−27.42 (18)
C8—C7—N4—C13	−76.7 (3)	C13—N4—Zn1—N1	92.06 (19)
C8—C7—N4—Zn1	38.6 (3)	C6—N4—Zn1—N3	95.86 (18)
C14—C13—N4—C6	−80.8 (3)	C7—N4—Zn1—N3	−143.9 (2)
C14—C13—N4—C7	148.9 (2)	C13—N4—Zn1—N3	−24.39 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O4ⁱ	0.93	2.53	3.272 (4)	138
C7—H7B···O2ⁱⁱ	0.97	2.59	3.455 (4)	148
C10—H10···O1ⁱⁱⁱ	0.93	2.58	3.511 (5)	179
C13—H13A···N6^iv	0.97	2.61	3.457 (5)	146
C16—H16···N7′^v	0.93	2.48	3.412 (18)	178

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

Experimental details

Crystal data
Chemical formula	[Zn(C₂N₃)(C₁₈H₁₈N₄)]ClO₄
M_r	521.23
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	13.931 (2), 10.8578 (18), 14.653 (2)
β (°)	91.590 (3)
V (Å³)	2215.5 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.27
Crystal size (mm)	0.30 × 0.20 × 0.18

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.702, 0.803
No. of measured, independent and observed [I > 2σ(I)] reflections	12346, 4800, 3352
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.106, 0.99
No. of reflections	4800
No. of parameters	308
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.25

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

N1—Zn1	2.053 (2)	N4—Zn1	2.215 (2)
N2—Zn1	2.048 (2)	N5—Zn1	2.021 (3)
N3—Zn1	2.059 (2)

N5—Zn1—N2	101.94 (10)	N1—Zn1—N3	112.99 (9)
N5—Zn1—N1	100.96 (11)	N5—Zn1—N4	179.41 (10)
N2—Zn1—N1	118.19 (9)	N2—Zn1—N4	78.60 (9)
N5—Zn1—N3	100.98 (10)	N1—Zn1—N4	78.95 (9)
N2—Zn1—N3	117.58 (9)	N3—Zn1—N4	78.55 (9)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O4ⁱ	0.93	2.53	3.272 (4)	137.5
C7—H7B···O2ⁱⁱ	0.97	2.59	3.455 (4)	148.1
C10—H10···O1ⁱⁱⁱ	0.93	2.58	3.511 (5)	178.7
C13—H13A···N6^iv	0.97	2.61	3.457 (5)	146.0
C16—H16···N7'^v	0.93	2.48	3.412 (18)	178.1

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

Acknowledgements

The authors thank the Natural Science Foundation of Shandong Province of China (grant No. Y2007B26).

References

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