cis-Diaqua-bis(2,2',2''-tripyridylamine)zinc(II) bis-(perchlorate).

In the title compound, [Zn(2,2',2''-tpa)(2)(H(2)O)(2)](ClO(4))(2) (2,2',2''-tpa is 2,2',2''-tripyridylamine, C(15)H(12)N(4)), the Zn center lies on a twofold axis and is coordinated octa-hedrally by two water mol-ecules and two bidentate 2,2',2''-tpa ligands. The perchlorate anions are linked to the coordinated water mol-ecules in the complex cations via O-H⋯O hydrogen bonds.

Related literature

For general background, see: Liu et al. (1997 ▶). For related structures, see: Yang et al. (1999 ▶).

Experimental

Crystal data

[Zn(C15H12N4)2(H2O)2](ClO4)2

M = 796.89

Monoclinic,

a = 18.687 (3) Å

b = 19.305 (4) Å

c = 10.8910 (19) Å

β = 121.689 (3)°

V = 3343.2 (11) Å3

Z = 4

Mo Kα radiation

μ = 0.96 mm−1

T = 200 K

0.35 × 0.22 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.775, T max = 0.825

7752 measured reflections

2940 independent reflections

1861 reflections with I > 2σ(I)

R int = 0.068

Refinement

R[F 2 > 2σ(F 2)] = 0.057

wR(F 2) = 0.143

S = 0.92

2940 reflections

239 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.86 e Å−3

Δρmin = −0.41 e Å−3

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809042688/nk2005sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809042688/nk2005Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Zn(C15H12N4)2(H2O)2](ClO4)2	F(000) = 1632
Mr = 796.89	Dx = 1.583 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 7889 reflections
a = 18.687 (3) Å	θ = 2.2–27.9°
b = 19.305 (4) Å	µ = 0.96 mm−1
c = 10.8910 (19) Å	T = 200 K
β = 121.689 (3)°	Block, colorless
V = 3343.2 (11) Å3	0.35 × 0.22 × 0.20 mm
Z = 4

Bruker SMART CCD area-detector diffractometer	2940 independent reflections
Radiation source: fine-focus sealed tube	1861 reflections with I > 2σ(I)
graphite	Rint = 0.068
Detector resolution: 8.366 pixels mm-1	θmax = 25.0°, θmin = 2.1°
phi and ω scans	h = −22→21
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −18→22
Tmin = 0.775, Tmax = 0.825	l = −12→12
7752 measured reflections

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.143	H atoms treated by a mixture of independent and constrained refinement
S = 0.92	w = 1/[σ2(Fo2) + (0.0705P)2] where P = (Fo2 + 2Fc2)/3
2940 reflections	(Δ/σ)max < 0.001
239 parameters	Δρmax = 0.86 e Å−3
2 restraints	Δρmin = −0.41 e Å−3

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.

	x	y	z	Uiso*/Ueq
N1	0.5518 (2)	0.28833 (19)	0.9789 (4)	0.0386 (9)
C1	0.5611 (3)	0.2247 (2)	1.0527 (5)	0.0419 (12)
C2	0.5981 (3)	0.2230 (3)	1.1989 (5)	0.0560 (15)
H2	0.6182	0.2634	1.2530	0.067*
C3	0.6054 (4)	0.1604 (3)	1.2652 (6)	0.0726 (19)
H3	0.6305	0.1579	1.3648	0.087*
C4	0.5750 (4)	0.1018 (3)	1.1816 (7)	0.0750 (19)
H4	0.5783	0.0591	1.2237	0.090*
C5	0.5400 (4)	0.1072 (3)	1.0366 (6)	0.0612 (16)
H5	0.5209	0.0671	0.9811	0.073*
N2	0.5317 (2)	0.16820 (19)	0.9694 (4)	0.0428 (10)
C6	0.6036 (3)	0.2977 (2)	0.9218 (5)	0.0382 (11)
C7	0.6595 (3)	0.3515 (3)	0.9666 (5)	0.0533 (14)
H7	0.6629	0.3836	1.0331	0.064*
C8	0.7103 (3)	0.3570 (3)	0.9116 (6)	0.0670 (17)
H8	0.7474	0.3940	0.9378	0.080*
C9	0.7060 (3)	0.3072 (3)	0.8166 (6)	0.0598 (16)
H9	0.7410	0.3096	0.7799	0.072*
C10	0.6500 (3)	0.2550 (3)	0.7783 (5)	0.0455 (12)
H10	0.6476	0.2211	0.7155	0.055*
N3	0.5972 (2)	0.25002 (18)	0.8277 (4)	0.0350 (9)
Zn1	0.5000	0.17445 (4)	0.7500	0.0376 (3)
O1W	0.4117 (3)	0.0899 (2)	0.7028 (5)	0.0598 (10)
H1W	0.387 (4)	0.066 (3)	0.626 (5)	0.10 (3)*
H2W	0.384 (4)	0.088 (3)	0.742 (6)	0.10 (3)*
C11	0.5002 (3)	0.3407 (2)	0.9806 (5)	0.0416 (12)
N4	0.4849 (3)	0.3960 (2)	0.8930 (4)	0.0573 (12)
C12	0.4310 (3)	0.4453 (3)	0.8870 (6)	0.0569 (15)
H12	0.4197	0.4841	0.8288	0.068*
C13	0.3930 (4)	0.4387 (3)	0.9659 (7)	0.0664 (17)
H13	0.3549	0.4717	0.9595	0.080*
C14	0.4128 (4)	0.3824 (3)	1.0536 (6)	0.0696 (17)
H14	0.3890	0.3776	1.1097	0.084*
C15	0.4662 (3)	0.3336 (2)	1.0602 (5)	0.0494 (13)
H15	0.4790	0.2953	1.1200	0.059*
Cl1	0.79396 (8)	0.44302 (7)	0.37729 (14)	0.0488 (4)
O2	0.8198 (5)	0.3778 (3)	0.3894 (6)	0.200 (4)
O3	0.7209 (4)	0.4465 (5)	0.3674 (8)	0.222 (4)
O4	0.8513 (5)	0.4778 (3)	0.4996 (5)	0.159 (3)
O5	0.7854 (3)	0.4721 (3)	0.2524 (4)	0.1048 (17)

	U11	U22	U33	U12	U13	U23
N1	0.048 (2)	0.032 (2)	0.036 (2)	0.0059 (18)	0.022 (2)	−0.0005 (17)
C1	0.051 (3)	0.040 (3)	0.041 (3)	0.015 (2)	0.028 (3)	0.008 (2)
C2	0.071 (4)	0.056 (4)	0.044 (3)	0.023 (3)	0.032 (3)	0.008 (3)
C3	0.103 (5)	0.078 (5)	0.049 (4)	0.027 (4)	0.049 (4)	0.018 (3)
C4	0.119 (6)	0.057 (4)	0.074 (4)	0.027 (4)	0.067 (4)	0.029 (3)
C5	0.094 (5)	0.040 (3)	0.071 (4)	0.012 (3)	0.058 (4)	0.014 (3)
N2	0.060 (3)	0.034 (2)	0.048 (3)	0.007 (2)	0.037 (2)	0.0080 (19)
C6	0.034 (3)	0.035 (3)	0.033 (3)	0.003 (2)	0.009 (2)	0.007 (2)
C7	0.050 (3)	0.047 (3)	0.043 (3)	−0.003 (3)	0.011 (3)	0.002 (3)
C8	0.041 (3)	0.065 (4)	0.067 (4)	−0.016 (3)	0.009 (3)	0.015 (3)
C9	0.034 (3)	0.076 (4)	0.064 (4)	0.002 (3)	0.022 (3)	0.024 (3)
C10	0.045 (3)	0.048 (3)	0.046 (3)	0.007 (3)	0.027 (3)	0.011 (2)
N3	0.035 (2)	0.033 (2)	0.037 (2)	0.0035 (17)	0.0185 (19)	0.0030 (17)
Zn1	0.0483 (5)	0.0296 (4)	0.0440 (5)	0.000	0.0307 (4)	0.000
O1W	0.077 (3)	0.049 (3)	0.071 (3)	−0.019 (2)	0.051 (3)	−0.009 (2)
C11	0.042 (3)	0.034 (3)	0.033 (3)	0.009 (2)	0.009 (2)	−0.002 (2)
N4	0.054 (3)	0.056 (3)	0.048 (3)	0.008 (2)	0.018 (2)	−0.004 (2)
C12	0.055 (4)	0.049 (3)	0.055 (4)	0.015 (3)	0.020 (3)	0.005 (3)
C13	0.071 (4)	0.056 (4)	0.078 (4)	0.023 (3)	0.044 (4)	0.000 (3)
C14	0.087 (5)	0.069 (4)	0.069 (4)	0.017 (4)	0.053 (4)	0.006 (3)
C15	0.074 (4)	0.036 (3)	0.044 (3)	0.021 (3)	0.035 (3)	0.010 (2)
Cl1	0.0522 (8)	0.0533 (9)	0.0487 (8)	0.0061 (6)	0.0319 (7)	0.0047 (6)
O2	0.349 (10)	0.089 (4)	0.096 (4)	0.114 (6)	0.070 (5)	0.005 (3)
O3	0.115 (5)	0.399 (12)	0.223 (8)	0.073 (6)	0.138 (6)	0.137 (8)
O4	0.281 (8)	0.097 (4)	0.063 (3)	−0.065 (5)	0.066 (4)	−0.025 (3)
O5	0.093 (3)	0.166 (5)	0.057 (3)	−0.016 (3)	0.040 (3)	0.027 (3)

N1—C11	1.404 (5)	C10—H10	0.9300
N1—C6	1.411 (6)	N3—Zn1	2.128 (4)
N1—C1	1.428 (5)	Zn1—N3i	2.128 (4)
C1—N2	1.338 (6)	Zn1—N2i	2.142 (4)
C1—C2	1.364 (6)	Zn1—O1W	2.182 (4)
C2—C3	1.376 (7)	Zn1—O1Wi	2.182 (4)
C2—H2	0.9300	O1W—H1W	0.85 (4)
C3—C4	1.374 (8)	O1W—H2W	0.83 (2)
C3—H3	0.9300	C11—C15	1.325 (6)
C4—C5	1.359 (7)	C11—N4	1.358 (6)
C4—H4	0.9300	N4—C12	1.364 (6)
C5—N2	1.352 (6)	C12—C13	1.379 (7)
C5—H5	0.9300	C12—H12	0.9300
N2—Zn1	2.142 (4)	C13—C14	1.364 (8)
C6—N3	1.335 (5)	C13—H13	0.9300
C6—C7	1.368 (7)	C14—C15	1.346 (7)
C7—C8	1.366 (7)	C14—H14	0.9300
C7—H7	0.9300	C15—H15	0.9300
C8—C9	1.384 (8)	Cl1—O3	1.314 (5)
C8—H8	0.9300	Cl1—O2	1.330 (5)
C9—C10	1.352 (7)	Cl1—O4	1.369 (5)
C9—H9	0.9300	Cl1—O5	1.401 (4)
C10—N3	1.352 (5)
C11—N1—C6	123.2 (4)	N3—Zn1—N2i	99.25 (14)
C11—N1—C1	119.6 (4)	N3i—Zn1—N2i	85.21 (14)
C6—N1—C1	116.7 (4)	N3—Zn1—N2	85.21 (14)
N2—C1—C2	123.2 (5)	N3i—Zn1—N2	99.25 (14)
N2—C1—N1	115.8 (4)	N2i—Zn1—N2	173.5 (2)
C2—C1—N1	121.0 (5)	N3—Zn1—O1W	171.28 (15)
C1—C2—C3	118.9 (5)	N3i—Zn1—O1W	92.16 (15)
C1—C2—H2	120.6	N2i—Zn1—O1W	87.87 (16)
C3—C2—H2	120.6	N2—Zn1—O1W	87.30 (16)
C4—C3—C2	118.9 (5)	N3—Zn1—O1Wi	92.16 (15)
C4—C3—H3	120.6	N3i—Zn1—O1Wi	171.28 (15)
C2—C3—H3	120.6	N2i—Zn1—O1Wi	87.30 (16)
C5—C4—C3	119.0 (5)	N2—Zn1—O1Wi	87.87 (16)
C5—C4—H4	120.5	O1W—Zn1—O1Wi	83.1 (2)
C3—C4—H4	120.5	Zn1—O1W—H1W	126 (4)
N2—C5—C4	123.0 (5)	Zn1—O1W—H2W	120 (5)
N2—C5—H5	118.5	H1W—O1W—H2W	109 (6)
C4—C5—H5	118.5	C15—C11—N4	123.1 (4)
C1—N2—C5	116.9 (4)	C15—C11—N1	120.2 (4)
C1—N2—Zn1	119.0 (3)	N4—C11—N1	116.7 (4)
C5—N2—Zn1	122.6 (3)	C11—N4—C12	117.4 (4)
N3—C6—C7	122.7 (5)	N4—C12—C13	121.1 (5)
N3—C6—N1	116.3 (4)	N4—C12—H12	119.5
C7—C6—N1	120.9 (5)	C13—C12—H12	119.5
C8—C7—C6	118.6 (5)	C14—C13—C12	118.0 (5)
C8—C7—H7	120.7	C14—C13—H13	121.0
C6—C7—H7	120.7	C12—C13—H13	121.0
C7—C8—C9	119.5 (5)	C15—C14—C13	121.2 (5)
C7—C8—H8	120.2	C15—C14—H14	119.4
C9—C8—H8	120.2	C13—C14—H14	119.4
C10—C9—C8	118.7 (5)	C11—C15—C14	119.3 (5)
C10—C9—H9	120.6	C11—C15—H15	120.4
C8—C9—H9	120.6	C14—C15—H15	120.4
N3—C10—C9	122.5 (5)	O3—Cl1—O2	111.4 (6)
N3—C10—H10	118.7	O3—Cl1—O4	107.6 (5)
C9—C10—H10	118.7	O2—Cl1—O4	108.1 (4)
C6—N3—C10	117.8 (4)	O3—Cl1—O5	108.4 (4)
C6—N3—Zn1	119.5 (3)	O2—Cl1—O5	109.0 (4)
C10—N3—Zn1	122.6 (3)	O4—Cl1—O5	112.4 (3)
N3—Zn1—N3i	93.45 (19)
C11—N1—C1—N2	115.9 (5)	C9—C10—N3—Zn1	173.1 (4)
C6—N1—C1—N2	−71.3 (5)	C6—N3—Zn1—N3i	56.2 (3)
C11—N1—C1—C2	−64.4 (6)	C10—N3—Zn1—N3i	−119.1 (4)
C6—N1—C1—C2	108.4 (5)	C6—N3—Zn1—N2i	141.9 (3)
N2—C1—C2—C3	−0.5 (8)	C10—N3—Zn1—N2i	−33.4 (4)
N1—C1—C2—C3	179.8 (5)	C6—N3—Zn1—N2	−42.8 (3)
C1—C2—C3—C4	−0.1 (9)	C10—N3—Zn1—N2	141.9 (4)
C2—C3—C4—C5	1.1 (9)	C6—N3—Zn1—O1Wi	−130.5 (3)
C3—C4—C5—N2	−1.6 (9)	C10—N3—Zn1—O1Wi	54.2 (4)
C2—C1—N2—C5	0.1 (7)	C1—N2—Zn1—N3	30.8 (3)
N1—C1—N2—C5	179.8 (4)	C5—N2—Zn1—N3	−135.2 (4)
C2—C1—N2—Zn1	−166.8 (4)	C1—N2—Zn1—N3i	−61.9 (3)
N1—C1—N2—Zn1	12.9 (5)	C5—N2—Zn1—N3i	132.0 (4)
C4—C5—N2—C1	1.0 (8)	C1—N2—Zn1—O1W	−153.6 (4)
C4—C5—N2—Zn1	167.3 (4)	C5—N2—Zn1—O1W	40.3 (4)
C11—N1—C6—N3	−129.6 (4)	C1—N2—Zn1—O1Wi	123.2 (4)
C1—N1—C6—N3	57.8 (5)	C5—N2—Zn1—O1Wi	−42.9 (4)
C11—N1—C6—C7	53.0 (6)	C6—N1—C11—C15	−166.6 (5)
C1—N1—C6—C7	−119.5 (5)	C1—N1—C11—C15	5.8 (7)
N3—C6—C7—C8	0.7 (7)	C6—N1—C11—N4	16.3 (6)
N1—C6—C7—C8	177.9 (4)	C1—N1—C11—N4	−171.4 (4)
C6—C7—C8—C9	−2.2 (8)	C15—C11—N4—C12	−0.8 (7)
C7—C8—C9—C10	1.5 (8)	N1—C11—N4—C12	176.2 (4)
C8—C9—C10—N3	0.9 (8)	C11—N4—C12—C13	−0.7 (8)
C7—C6—N3—C10	1.6 (7)	N4—C12—C13—C14	1.9 (9)
N1—C6—N3—C10	−175.7 (4)	C12—C13—C14—C15	−1.7 (9)
C7—C6—N3—Zn1	−174.0 (3)	N4—C11—C15—C14	1.0 (8)
N1—C6—N3—Zn1	8.7 (5)	N1—C11—C15—C14	−175.9 (5)
C9—C10—N3—C6	−2.4 (7)	C13—C14—C15—C11	0.3 (9)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O2ii	0.93	2.43	3.336 (8)	166
O1W—H2W···O5iii	0.83 (2)	2.23 (4)	2.939 (6)	143 (6)
O1W—H1W···O4iv	0.85 (4)	2.07 (5)	2.868 (6)	158 (6)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H2W⋯O5i	0.83 (2)	2.23 (4)	2.939 (6)	143 (6)
O1W—H1W⋯O4ii	0.85 (4)	2.07 (5)	2.868 (6)	158 (6)

Symmetry codes: (i) ; (ii) .