Two new dimeric cadmium(II) and zinc(II) sulfate complexes with 2,4,6-tris(2-pyridyl)-1,3,5-triazine and 2,2:6′,2′′-ter­pyridine

The structures of two new sulfate complexes are reported, namely di-μ-sulfato-κ³O,O′:O′′-bis{aqua­[2,4,6-tris(2-pyridyl)-1,3,5-triazine-κ³N¹,N²,N⁶]­cadmium(II)} tetra­hydrate, [Cd₂(SO₄)₂(C₁₆H₁₂N₆)₂(H₂O)₂]·4H₂O, and di-μ-sulfato-κ²O:O′-bis­[(2,2′:6′,2′′-ter­pyridine-κ³N¹,N^1′,N^1′′)­zinc(II)] dihydrate, [Cd₂(SO₄)₂(C₁₅H₁₁N₃)₂]·2H₂O, the former being the first report of a Cd(tpt) complex [tpt is 2,4,6-tris(2-pyridyl)-1,3,5-triazine]. Both compounds crystallize in the space group P and form centrosymmetric dimeric structures. In the cadmium complex, the metal center is heptacoordinated in the form of a pentagonal bipyramid, while in the zinc complex, the metal ion is in a fivefold environment, the coordination geometry being intermediate between square pyramidal and trigonal bipyramidal. Packing of the dimers leads to the formation of planar structures strongly linked by hydrogen bonding.

S1. Comment

The study of Cd^II and Zn^II coordination compounds with sulfur oxoanions as ligands has been ongoing for many years. A number of structures, interesting from a stereochemical point of view, have been synthesized, as many of these anions (sulfite, sulfate, thiosulfate, tetrathionate, etc.) behave as versatile ligands when coordinating to d¹⁰ metal centers. The sulfate ion, in particular, is quite attractive in this respect; it has been reported as coordinating to transition metals through one, two or three O atoms, giving rise to monomeric, dimeric or polymeric structures and, in spite of extensive studies, the full binding capability of the anion does not seem to be exhausted.

A search in the November 2002 Version of the Cambridge Structural Database (CSD; Allen, 2002) returned 33 organometallic complexes in which the sulfate group is attached either to Zn^II or Cd^II. The 16 Zn^II complexes reported in the CSD are almost equally distributed between compounds displaying monomeric monodentate (M—O—SO₃) and polymeric bridging (M—O—SO₂—O—M) modes, with only three exceptions, which we will refer to by their CSD refcodes, viz. a dimer (MASVUX; Harvey et al., 2000), a one-dinemsional polymeric M—O—SO₂—O—M structure (LOPNIN; Plater et al., 2000), where the sulfate group binds through three O atoms, two to the same metal center in a chelate fashion, and a polynuclear monomeric structure (VABMEK; Ali et al., 1998), in which the sulfate group binds to three different Zn^II ions. Complexes with Cd^II, in contrast, show only a few examples of monomeric structures, the preferred coordination being polymeric of the M—O—SO₂—O—M type. The only two exceptions [TIRXAT (Rahmani et al., 1996) and COXQUB (Huang et al., 1999)] organize as polymers built up by three O atoms, binding to three different metal centers. Continuing our research on this type of compounds, we report herein the structures of two new sulfate complexes, namely [Cd(SO₄)(tpt)(H₂O)·2H₂O]₂, (I), and [Zn(SO₄)(tpy)·H₂O]₂, (II) [tpt is 2,4,6-tris(2-pyridyl)-1,3,5-triazine and tpy is 2,2':6',2''-terpyridine]. The former is the first report of a Cd(tpt) complex.

Both compounds crystallize in the space group P1 and form dimeric centrosymmetric structures. Complex (I) presents a heptacoordinated environment around the metal ion, formed by three N atoms from the tridentate tpt ligand, one aqua O atom and three O atoms from two symmetry-related sulfate ions, each of which binds to two metal centers, thus generating the dimeric structure (Fig. 1). In the two other Cd complexes incorporating tridentate sulfate ligands reported previously (TIRXAT and COXQUB), the anion binds to three different metal centers, generating polymeric structures. The coordination polyhedra in (I) can be described as a distorted pentagonal bipyramid, with the equatorial plane formed by atoms N1, N2, N3, O1 and O2 [maximum deviation of 0.04 (1) Å for N2], and angles subtended at the Cd site ranging from 58.6 (3) to 83.6 (3)° (ideal 72°). The axial sites are occupied by atoms O1W and O4(-x, −y, −z), and they subtend an angle of 166.1 (3)° to the cation.

The ligand is almost planar and acts in a tridentate manner, with the central Cd—N distance [2.337 (4) Å] being considerably shorter than the lateral Cd—N distances [2.437 (4) and 2.415 (4) Å]. Comparison with similar cases in the literature becomes difficult since there are no other reports of heptacoordinated cadmium(II) complexes with tpt or related tridentate ligands. There are, however, some examples where the heptacoordinated cation binds to a similar base [2,4-bis(4-pyridyl)-1,3,5-triazine] acting in a bridging manner, which display Cd—N distances in the range 2.28–2.32 Å (XESHOS, XESHUY and XESJAG; Barnett et al., 2001). The larger values in (I) could be attributed to the steric hindrance introduced by the planar tridentate bite.

Coordination does not affect the dimensions of the sulfate moiety; moreover, no significant differences are observed among the S—O distances involving either coordinated or non-coordinated O atoms. In fact, the mean S—O distance [1.463 (3) Å] is similar to that reported for the free anion [a search in the CSD gave a mean value of 1.472 (8) Å for 118 structures with R < 0.05]. The tpt ligand does not show any abnormal characteristics, with its three bound rings being basically coplanar; the atoms deviate from an ideal plane on average by less than 0.02 (1) Å. The terminal pyridyl ring deviates from planarity by less than 0.01 (1) Å and subtends an angle of 3.6 (1)° to the ideal plane. The structure is stabilized by hydrogen bonding with the two independent hydrate molecules (see Table 2).

The structure of (II) is also dimeric. The coordination is such that three N atoms from tpy and two O atoms from two symmetry-related sulfate ions complete a distorted fivefold environment around the metal ion (Fig. 2). The geometry lies midway between square pyramidal and trigonal bipyramidal. As in the case of (I), a considerable difference is observed in the Zn—N distances, that to the central N atom of tpy being the shortest [2.074 (3) versus 2.167 (3) and 2.201 (3) Å]. Similar results have been obtained in other pentacoordinated Zn–tpy complexes, viz. 2.209, 2.115 and 2.170 Å in DOLVIJ (Harrison et al., 1986), 2.181, 2.097 and 2.155 Å in OFABOM (Finn & Zubieta, 2002), and 2.169, 2.066 and 2.164 Å, and 2.158, 2.062 and 2.172 Å in XEZZIL (Hagrman & Zubieta, 2001).

As the zinc complex is pentacoordinated, larger valence bond values (Brown & Altermatt, 1985) for the Zn—O bonds are expected compared to those in the heptacoordinated cadmium complex, and, accordingly, a larger effect on the corresponding S—O_coord distances of the sulfate group is predicted. In fact, the regular geometry displayed by the anion in (I) is lost in (II), where a clear difference is observed between the mean S—O_coord and S—O_uncoord distances [1.490 (6) and 1.427 (6) Å, respectively]. Since (II) is the first reported structure containing pentacoordinated Zn cations bridged by sulfate anions in a Zn—O—SO₂—O—Zn mode, it was not possible to make a fair comparison with other Zn complexes displaying analogous cation environments. We could trace, however, both tetra- and hexacoordinated Zn structures with a similar sulfate coordination. These structures clearly confirm the effect of bond valence; in the only tetracoordinated case of this sort reported so far (MASVUX; Harvey et al., 2000), the difference between the two types of S—O bonds is enhanced, being even larger than in the present pentacoordinated case [1.506 (6) and 1.439 (2) Å, respectively]; in the five hexacoordinated structures reported, in contrast, there is almost no trend differentiating the two kinds of bonds, their mean values being 1.47 (2) and 1.48 (3) Å, respectively, indistinguishable from each other and from the already mentioned average for the free ligand [1.472 (8) Å]. The geometry of the tpy ligand geometry and the internal parameters are unexceptional. There is one hydrogen-bonded crystallization water molecule in the structure (Table 4).

The packing is rather similar in both structures. As the dimers build up around a symmetry center, the planar molecules [tpt in (I) and tpy in (II)] are aligned parallel to each other. Cell symmetry preserves the orientation of the dimeric units, which stack with sets of parallel planes sharing one part of the double molecular units. This distribution (illustrated in Fig. 3) consists of a set of interleaved planar arrays at a nearly graphitic distance (3.4 Å). The linking agent is the extensive hydrogen-bonding network involving all the available water molecules acting as donors and, together with some N atoms of the organic ligand and sulfate O atoms, as acceptors, in some cases. The most important of these interactions are reported in Tables 2 and 4.

S2. Experimental

Both compounds were obtained by direct mixing of an aqueous solution of the cation sulfate (3CdSO₄·8H₂O or ZnSO₄·7H₂O), with a methanolic solution of the corresponding organic ligand (tpt or tpy), both in a 0.025 M concentration. A crop of tiny crystals appeared readily, but they were not found adequate for X-ray diffraction and dissolved (those of compound (I) in hot water and those of compound (II) in a 1:1 mixture of hot water and dimethylformamide). On standing, small specimens suitable for the structural study were collected.

S3. Refinement

H atoms were located at calculated positions, riding on their host atoms. Water H atoms were found in a difference Fourier synthesis and were refined with restrained O—H (0.80 Å) and H···H (> 1.30 Å) distances, and U_iso = 1.2U_eq(O).

Computing details

For both compounds, data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: MSC/AFC Diffractometer Control Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL/PC (Sheldrick, 1994); software used to prepare material for publication: XP in SHELXTL/PC.

Figures

	Fig. 1. Ellipsoid plot (50% probability level) showing the dimeric unit of (I).
	Fig. 2. Ellipsoid plot (50% probability level) showing the dimeric unit of (II).
	Fig. 3. Schematic packing view of (II) along the planes, which are seen as horizontal lines. Selected dimers are drawn in heavy full lines so as to distinguish them from the background.

(I) di-µ-sulfato-κ³O,O':O''-bis{aqua[2,4,6-tris(2-pyridyl)-1,3,5-triazine- κ³N¹,N²,N⁶]cadmium(II)} tetrahydrate

Crystal data

[Cd2(SO4)2(C16H12N6)2(H2O)2]·4H2O	Z = 1
Mr = 1149.68	F(000) = 576
Triclinic, P1	Dx = 1.810 Mg m^−3
a = 8.870 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.640 (2) Å	Cell parameters from 28 reflections
c = 12.685 (2) Å	θ = 7.5–15°
α = 103.36 (2)°	µ = 1.19 mm^−1
β = 98.79 (2)°	T = 293 K
γ = 110.45 (2)°	Prism, colorless
V = 1055.0 (4) Å^3	0.20 × 0.12 × 0.05 mm

Data collection

Rigaku AFC-7S diffractometer	1996 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.039
Graphite monochromator	θmax = 26.0°, θmin = 1.7°
ω/2θ scans	h = −5→10
Absorption correction: ψ scan (MSC/AFC Diffractometer Control Software; Molecular Structure Corp, 1988)	k = −13→12
Tmin = 0.83, Tmax = 0.90	l = −15→13
5842 measured reflections	2 standard reflections every 98 reflections
4010 independent reflections	intensity decay: <2%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.038	Hydrogen site location: mixed
wR(F^2) = 0.056	H atoms treated by a mixture of independent and constrained refinement
S = 0.88	w = 1/[σ^2(Fo^2))^2] where P = (Fo^2 + 2Fc^2)/3
4010 reflections	(Δ/σ)max = 0.003
319 parameters	Δρmax = 0.44 e Å^−3
13 restraints	Δρmin = −0.40 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cd	0.09400 (5)	−0.00222 (4)	0.18610 (3)	0.03625 (13)
S	0.00314 (17)	−0.20524 (14)	−0.04017 (11)	0.0375 (4)
O1	0.1698 (4)	−0.0991 (3)	0.0215 (3)	0.0594 (11)
O2	−0.1051 (4)	−0.1890 (3)	0.0335 (3)	0.0545 (11)
O3	0.0025 (4)	−0.3469 (3)	−0.0661 (3)	0.0571 (11)
O4	−0.0531 (4)	−0.1834 (3)	−0.1466 (3)	0.0507 (10)
N1	0.3901 (5)	0.1383 (4)	0.2518 (3)	0.0351 (11)
N2	0.1686 (5)	0.1413 (4)	0.3715 (3)	0.0326 (11)
N3	−0.1425 (5)	−0.0291 (4)	0.2678 (3)	0.0348 (11)
N4	0.3769 (4)	0.3160 (4)	0.5268 (3)	0.0364 (11)
N5	0.0946 (5)	0.2232 (4)	0.5364 (3)	0.0331 (11)
N6	0.1894 (5)	0.3838 (4)	0.7523 (3)	0.0396 (12)
C1	0.4981 (7)	0.1347 (5)	0.1910 (4)	0.0456 (15)
H1A	0.4584	0.0750	0.1176	0.055*
C2	0.6676 (7)	0.2155 (6)	0.2314 (4)	0.0494 (16)
H2A	0.7397	0.2095	0.1863	0.059*
C3	0.7262 (6)	0.3036 (5)	0.3381 (5)	0.0487 (16)
H3A	0.8395	0.3588	0.3672	0.058*
C4	0.6154 (6)	0.3106 (5)	0.4037 (4)	0.0430 (15)
H4A	0.6528	0.3705	0.4770	0.052*
C5	0.4491 (6)	0.2268 (5)	0.3574 (4)	0.0309 (13)
C6	0.3253 (6)	0.2276 (5)	0.4227 (4)	0.0308 (13)
C7	0.2555 (6)	0.3077 (5)	0.5802 (4)	0.0305 (13)
C8	0.0597 (6)	0.1433 (5)	0.4310 (4)	0.0285 (13)
C9	−0.1169 (6)	0.0460 (5)	0.3737 (4)	0.0303 (13)
C10	−0.2433 (6)	0.0343 (5)	0.4278 (4)	0.0373 (15)
H10A	−0.2211	0.0869	0.5022	0.045*
C11	−0.4025 (6)	−0.0575 (5)	0.3683 (4)	0.0434 (15)
H11A	−0.4905	−0.0677	0.4018	0.052*
C12	−0.4304 (6)	−0.1341 (5)	0.2584 (5)	0.0482 (16)
H12A	−0.5376	−0.1966	0.2171	0.058*
C13	−0.2995 (7)	−0.1179 (5)	0.2101 (4)	0.0432 (15)
H13A	−0.3194	−0.1695	0.1357	0.052*
C14	0.3090 (6)	0.3974 (5)	0.6976 (4)	0.0315 (13)
C15	0.4727 (6)	0.4876 (5)	0.7468 (4)	0.0390 (14)
H15A	0.5528	0.4934	0.7065	0.047*
C16	0.5164 (6)	0.5707 (5)	0.8589 (4)	0.0489 (16)
H16A	0.6260	0.6326	0.8946	0.059*
C17	0.3939 (7)	0.5585 (5)	0.9145 (4)	0.0476 (16)
H17A	0.4184	0.6136	0.9884	0.057*
C18	0.2333 (6)	0.4631 (5)	0.8591 (4)	0.0462 (15)
H18A	0.1515	0.4538	0.8982	0.055*
O1W	0.1327 (4)	−0.1701 (3)	0.2716 (3)	0.0444 (10)
H1WA	0.056 (4)	−0.204 (4)	0.301 (4)	0.053*
H1WB	0.158 (5)	−0.237 (3)	0.237 (3)	0.053*
O2W	0.8622 (5)	0.5577 (5)	0.6671 (3)	0.0977 (16)
H2WA	0.898 (4)	0.536 (3)	0.727 (2)	0.117*
H2WB	0.865 (4)	0.636 (3)	0.684 (3)	0.117*
O3W	0.1977 (4)	0.6324 (3)	0.1193 (3)	0.0541 (12)
H3WA	0.142 (5)	0.541 (3)	0.109 (4)	0.065*
H3WB	0.134 (5)	0.647 (4)	0.065 (3)	0.065*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd	0.0368 (3)	0.0375 (2)	0.0315 (2)	0.01291 (19)	0.01062 (17)	0.00717 (18)
S	0.0427 (10)	0.0338 (9)	0.0334 (9)	0.0145 (8)	0.0095 (7)	0.0071 (7)
O1	0.039 (2)	0.058 (3)	0.056 (3)	0.007 (2)	0.006 (2)	−0.004 (2)
O2	0.050 (3)	0.063 (3)	0.037 (2)	0.017 (2)	0.0170 (19)	−0.003 (2)
O3	0.079 (3)	0.038 (2)	0.051 (3)	0.030 (2)	0.005 (2)	0.0043 (19)
O4	0.077 (3)	0.048 (2)	0.031 (2)	0.031 (2)	0.0064 (19)	0.0128 (18)
N1	0.040 (3)	0.038 (3)	0.034 (3)	0.018 (2)	0.021 (2)	0.011 (2)
N2	0.023 (3)	0.033 (3)	0.034 (3)	0.004 (2)	0.005 (2)	0.009 (2)
N3	0.028 (3)	0.033 (3)	0.032 (3)	0.005 (2)	0.002 (2)	0.005 (2)
N4	0.029 (3)	0.040 (3)	0.034 (3)	0.009 (2)	0.014 (2)	0.006 (2)
N5	0.027 (3)	0.035 (3)	0.029 (3)	0.007 (2)	0.008 (2)	0.003 (2)
N6	0.040 (3)	0.038 (3)	0.027 (3)	0.009 (2)	0.007 (2)	−0.004 (2)
C1	0.054 (4)	0.043 (4)	0.040 (4)	0.015 (3)	0.022 (3)	0.013 (3)
C2	0.041 (4)	0.064 (4)	0.055 (4)	0.024 (3)	0.030 (3)	0.024 (3)
C3	0.030 (4)	0.055 (4)	0.061 (4)	0.013 (3)	0.016 (3)	0.019 (3)
C4	0.035 (4)	0.042 (4)	0.052 (4)	0.014 (3)	0.014 (3)	0.015 (3)
C5	0.031 (3)	0.031 (3)	0.032 (3)	0.012 (3)	0.007 (3)	0.015 (3)
C6	0.027 (3)	0.034 (3)	0.040 (4)	0.014 (3)	0.015 (3)	0.021 (3)
C7	0.036 (4)	0.026 (3)	0.031 (3)	0.011 (3)	0.012 (3)	0.011 (3)
C8	0.027 (3)	0.029 (3)	0.035 (3)	0.013 (3)	0.013 (3)	0.013 (3)
C9	0.032 (4)	0.029 (3)	0.028 (3)	0.011 (3)	0.007 (3)	0.008 (3)
C10	0.031 (4)	0.038 (4)	0.033 (3)	0.009 (3)	0.005 (3)	0.003 (3)
C11	0.030 (4)	0.054 (4)	0.043 (4)	0.015 (3)	0.012 (3)	0.010 (3)
C12	0.021 (3)	0.047 (4)	0.064 (5)	0.003 (3)	0.006 (3)	0.013 (3)
C13	0.042 (4)	0.035 (4)	0.037 (4)	0.010 (3)	0.003 (3)	−0.002 (3)
C14	0.033 (4)	0.028 (3)	0.028 (3)	0.009 (3)	0.011 (3)	0.001 (3)
C15	0.034 (4)	0.044 (4)	0.039 (4)	0.015 (3)	0.014 (3)	0.012 (3)
C16	0.036 (4)	0.051 (4)	0.041 (4)	0.008 (3)	0.001 (3)	0.002 (3)
C17	0.046 (4)	0.045 (4)	0.034 (4)	0.009 (3)	0.007 (3)	−0.004 (3)
C18	0.046 (4)	0.047 (4)	0.041 (4)	0.012 (3)	0.017 (3)	0.011 (3)
O1W	0.047 (3)	0.040 (2)	0.046 (3)	0.015 (2)	0.0190 (18)	0.013 (2)
O2W	0.084 (3)	0.122 (4)	0.056 (3)	0.016 (3)	0.019 (2)	0.009 (3)
O3W	0.050 (3)	0.041 (2)	0.057 (3)	0.015 (2)	0.000 (2)	0.004 (2)

Geometric parameters (Å, º)

Cd—O4^i	2.278 (3)	C3—H3A	0.9300
Cd—N2	2.337 (4)	C4—C5	1.374 (5)
Cd—O2	2.354 (3)	C4—H4A	0.9300
Cd—O1W	2.387 (4)	C5—C6	1.475 (6)
Cd—O1	2.407 (3)	C7—C14	1.471 (6)
Cd—N1	2.417 (4)	C8—C9	1.492 (6)
Cd—N3	2.437 (4)	C9—C10	1.386 (6)
S—O3	1.465 (3)	C10—C11	1.374 (5)
S—O2	1.463 (3)	C10—H10A	0.9300
S—O1	1.464 (3)	C11—C12	1.378 (6)
S—O4	1.465 (3)	C11—H11A	0.9300
O4—Cd^i	2.278 (3)	C12—C13	1.371 (7)
N1—C1	1.323 (6)	C12—H12A	0.9300
N1—C5	1.347 (5)	C13—H13A	0.9300
N2—C8	1.316 (5)	C14—C15	1.375 (6)
N2—C6	1.324 (5)	C15—C16	1.402 (6)
N3—C9	1.334 (5)	C15—H15A	0.9300
N3—C13	1.348 (5)	C16—C17	1.369 (6)
N4—C6	1.334 (5)	C16—H16A	0.9300
N4—C7	1.345 (5)	C17—C18	1.381 (6)
N5—C8	1.330 (5)	C17—H17A	0.9300
N5—C7	1.336 (5)	C18—H18A	0.9300
N6—C18	1.334 (5)	O1W—H1WA	0.84 (2)
N6—C14	1.339 (6)	O1W—H1WB	0.86 (2)
C1—C2	1.386 (6)	O2W—H2WA	0.89 (2)
C1—H1A	0.9300	O2W—H2WB	0.80 (2)
C2—C3	1.356 (6)	O3W—H3WA	0.89 (2)
C2—H2A	0.9300	O3W—H3WB	0.90 (2)
C3—C4	1.392 (6)
O4^i—Cd—N2	83.30 (12)	C5—C4—C3	118.3 (5)
O4^i—Cd—O2	100.08 (11)	C5—C4—H4A	120.8
N2—Cd—O2	149.95 (13)	C3—C4—H4A	120.8
O4^i—Cd—O1W	166.07 (12)	N1—C5—C4	122.6 (5)
N2—Cd—O1W	83.48 (13)	N1—C5—C6	116.2 (5)
O2—Cd—O1W	89.24 (12)	C4—C5—C6	121.1 (5)
O4^i—Cd—O1	101.15 (12)	N2—C6—N4	124.7 (5)
N2—Cd—O1	150.50 (12)	N2—C6—C5	116.7 (5)
O2—Cd—O1	58.61 (11)	N4—C6—C5	118.6 (4)
O1W—Cd—O1	92.53 (12)	N5—C7—N4	125.5 (5)
O4^i—Cd—N1	90.00 (12)	N5—C7—C14	118.6 (5)
N2—Cd—N1	68.18 (14)	N4—C7—C14	115.9 (5)
O2—Cd—N1	141.05 (12)	N2—C8—N5	125.6 (4)
O1W—Cd—N1	89.15 (12)	N2—C8—C9	116.0 (5)
O1—Cd—N1	82.59 (12)	N5—C8—C9	118.4 (5)
O4^i—Cd—N3	85.05 (12)	N3—C9—C10	123.0 (5)
N2—Cd—N3	66.86 (14)	N3—C9—C8	114.9 (5)
O2—Cd—N3	83.59 (12)	C10—C9—C8	122.0 (5)
O1W—Cd—N3	85.74 (12)	C11—C10—C9	118.0 (5)
O1—Cd—N3	142.20 (11)	C11—C10—H10A	121.0
N1—Cd—N3	135.04 (13)	C9—C10—H10A	121.0
O3—S—O2	111.2 (2)	C10—C11—C12	119.3 (5)
O3—S—O1	110.57 (19)	C10—C11—H11A	120.4
O2—S—O1	105.5 (2)	C12—C11—H11A	120.4
O3—S—O4	107.48 (19)	C13—C12—C11	119.7 (5)
O2—S—O4	110.7 (2)	C13—C12—H12A	120.1
O1—S—O4	111.3 (2)	C11—C12—H12A	120.1
S—O1—Cd	96.77 (17)	N3—C13—C12	121.6 (5)
S—O2—Cd	99.08 (17)	N3—C13—H13A	119.2
S—O4—Cd^i	131.70 (19)	C12—C13—H13A	119.2
C1—N1—C5	117.8 (5)	N6—C14—C15	123.0 (5)
C1—N1—Cd	124.5 (4)	N6—C14—C7	115.8 (5)
C5—N1—Cd	117.7 (3)	C15—C14—C7	121.2 (5)
C8—N2—C6	115.9 (5)	C14—C15—C16	118.7 (5)
C8—N2—Cd	122.9 (3)	C14—C15—H15A	120.7
C6—N2—Cd	121.2 (4)	C16—C15—H15A	120.7
C9—N3—C13	118.3 (5)	C17—C16—C15	118.4 (5)
C9—N3—Cd	119.2 (3)	C17—C16—H16A	120.8
C13—N3—Cd	122.5 (3)	C15—C16—H16A	120.8
C6—N4—C7	114.2 (4)	C16—C17—C18	118.9 (5)
C8—N5—C7	114.0 (4)	C16—C17—H17A	120.5
C18—N6—C14	117.6 (4)	C18—C17—H17A	120.5
N1—C1—C2	123.2 (5)	N6—C18—C17	123.4 (5)
N1—C1—H1A	118.4	N6—C18—H18A	118.3
C2—C1—H1A	118.4	C17—C18—H18A	118.3
C3—C2—C1	118.7 (5)	Cd—O1W—H1WA	113 (3)
C3—C2—H2A	120.7	Cd—O1W—H1WB	121 (3)
C1—C2—H2A	120.7	H1WA—O1W—H1WB	109 (2)
C2—C3—C4	119.4 (5)	H2WA—O2W—H2WB	112 (3)
C2—C3—H3A	120.3	H3WA—O3W—H3WB	101 (2)
C4—C3—H3A	120.3
O3—S—O1—Cd	−120.61 (18)	Cd—N1—C1—C2	−179.3 (4)
O2—S—O1—Cd	−0.2 (2)	N1—C1—C2—C3	−0.5 (8)
O4—S—O1—Cd	119.97 (18)	C1—C2—C3—C4	−0.1 (8)
O4^i—Cd—O1—S	−94.93 (17)	C2—C3—C4—C5	0.2 (8)
N2—Cd—O1—S	168.9 (2)	C1—N1—C5—C4	−0.9 (7)
O2—Cd—O1—S	0.16 (15)	Cd—N1—C5—C4	179.4 (3)
O1W—Cd—O1—S	87.72 (18)	C1—N1—C5—C6	−179.8 (4)
N1—Cd—O1—S	176.54 (19)	Cd—N1—C5—C6	0.6 (5)
N3—Cd—O1—S	1.4 (3)	C3—C4—C5—N1	0.3 (7)
O3—S—O2—Cd	120.19 (17)	C3—C4—C5—C6	179.1 (5)
O1—S—O2—Cd	0.2 (2)	C8—N2—C6—N4	−1.7 (7)
O4—S—O2—Cd	−120.37 (18)	Cd—N2—C6—N4	177.6 (3)
O4^i—Cd—O2—S	96.83 (19)	C8—N2—C6—C5	180.0 (4)
N2—Cd—O2—S	−169.1 (2)	Cd—N2—C6—C5	−0.6 (6)
O1W—Cd—O2—S	−93.59 (18)	C7—N4—C6—N2	2.6 (7)
O1—Cd—O2—S	−0.16 (15)	C7—N4—C6—C5	−179.2 (4)
N1—Cd—O2—S	−5.9 (3)	N1—C5—C6—N2	0.0 (7)
N3—Cd—O2—S	−179.4 (2)	C4—C5—C6—N2	−178.8 (4)
O3—S—O4—Cd^i	178.8 (2)	N1—C5—C6—N4	−178.4 (4)
O2—S—O4—Cd^i	57.2 (3)	C4—C5—C6—N4	2.8 (7)
O1—S—O4—Cd^i	−59.9 (3)	C8—N5—C7—N4	0.1 (7)
O4^i—Cd—N1—C1	−97.5 (4)	C8—N5—C7—C14	−178.0 (4)
N2—Cd—N1—C1	179.7 (4)	C6—N4—C7—N5	−1.7 (7)
O2—Cd—N1—C1	8.7 (5)	C6—N4—C7—C14	176.4 (4)
O1W—Cd—N1—C1	96.4 (4)	C6—N2—C8—N5	−0.2 (7)
O1—Cd—N1—C1	3.7 (4)	Cd—N2—C8—N5	−179.6 (3)
N3—Cd—N1—C1	179.5 (4)	C6—N2—C8—C9	−179.8 (4)
O4^i—Cd—N1—C5	82.2 (3)	Cd—N2—C8—C9	0.8 (6)
N2—Cd—N1—C5	−0.6 (3)	C7—N5—C8—N2	0.9 (7)
O2—Cd—N1—C5	−171.7 (3)	C7—N5—C8—C9	−179.4 (4)
O1W—Cd—N1—C5	−83.9 (3)	C13—N3—C9—C10	1.7 (7)
O1—Cd—N1—C5	−176.6 (3)	Cd—N3—C9—C10	−178.1 (4)
N3—Cd—N1—C5	−0.8 (4)	C13—N3—C9—C8	−179.1 (4)
O4^i—Cd—N2—C8	87.3 (4)	Cd—N3—C9—C8	1.2 (5)
O2—Cd—N2—C8	−11.3 (5)	N2—C8—C9—N3	−1.3 (6)
O1W—Cd—N2—C8	−88.3 (4)	N5—C8—C9—N3	179.0 (4)
O1—Cd—N2—C8	−171.9 (3)	N2—C8—C9—C10	178.0 (5)
N1—Cd—N2—C8	180.0 (4)	N5—C8—C9—C10	−1.7 (7)
N3—Cd—N2—C8	−0.2 (4)	N3—C9—C10—C11	−1.2 (8)
O4^i—Cd—N2—C6	−92.0 (4)	C8—C9—C10—C11	179.6 (4)
O2—Cd—N2—C6	169.4 (3)	C9—C10—C11—C12	0.3 (8)
O1W—Cd—N2—C6	92.4 (4)	C10—C11—C12—C13	0.0 (8)
O1—Cd—N2—C6	8.8 (5)	C9—N3—C13—C12	−1.3 (7)
N1—Cd—N2—C6	0.7 (3)	Cd—N3—C13—C12	178.4 (4)
N3—Cd—N2—C6	−179.5 (4)	C11—C12—C13—N3	0.5 (8)
O4^i—Cd—N3—C9	−85.4 (3)	C18—N6—C14—C15	0.5 (8)
N2—Cd—N3—C9	−0.6 (3)	C18—N6—C14—C7	179.8 (4)
O2—Cd—N3—C9	173.8 (3)	N5—C7—C14—N6	1.5 (7)
O1W—Cd—N3—C9	84.1 (3)	N4—C7—C14—N6	−176.8 (4)
O1—Cd—N3—C9	172.7 (3)	N5—C7—C14—C15	−179.2 (4)
N1—Cd—N3—C9	−0.4 (4)	N4—C7—C14—C15	2.5 (7)
O4^i—Cd—N3—C13	94.8 (4)	N6—C14—C15—C16	−0.8 (8)
N2—Cd—N3—C13	179.7 (4)	C7—C14—C15—C16	179.9 (4)
O2—Cd—N3—C13	−5.9 (4)	C14—C15—C16—C17	−0.1 (8)
O1W—Cd—N3—C13	−95.6 (4)	C15—C16—C17—C18	1.3 (8)
O1—Cd—N3—C13	−7.0 (5)	C14—N6—C18—C17	0.8 (8)
N1—Cd—N3—C13	179.9 (3)	C16—C17—C18—N6	−1.8 (8)
C5—N1—C1—C2	1.0 (8)

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3W—H3WA···O3^i	0.89 (2)	1.90 (2)	2.784 (5)	170 (4)
O3W—H3WB···O3^ii	0.90 (2)	1.91 (2)	2.800 (4)	171 (4)
O2W—H2WB···O4^iii	0.80 (2)	2.34 (3)	2.956 (5)	134 (3)
O2W—H2WA···O3^iii	0.89 (2)	2.50 (3)	3.206 (5)	137 (3)
O1W—H1WA···N6^iv	0.84 (2)	2.21 (3)	2.881 (5)	136 (4)
O1W—H1WB···O3W^v	0.86 (2)	1.96 (3)	2.791 (5)	162 (4)

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

(II) di-µ-sulfato-κ²O:O'-bis[(2,2':6',2''-terpyridine- κ³N¹,N^1',N^1'')zinc(II)] dihydrate

Crystal data

[Cd2(SO4)2(C15H11N3)2]·2H2O	Z = 1
Mr = 825.43	F(000) = 420
Triclinic, P1	Dx = 1.800 Mg m^−3
a = 9.700 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.755 (2) Å	Cell parameters from 30 reflections
c = 10.324 (2) Å	θ = 7.5–15°
α = 110.34 (2)°	µ = 1.79 mm^−1
β = 116.59 (2)°	T = 293 K
γ = 98.83 (2)°	Prism, colorless
V = 761.4 (4) Å^3	0.24 × 0.16 × 0.10 mm

Data collection

Rigaku AFC-7S diffractometer	2008 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.039
Graphite monochromator	θmax = 26.0°, θmin = 2.4°
ω/2θ scans	h = −11→11
Absorption correction: ψ scan (MSC/AFC Diffractometer Control Software; Molecular Structure Corp, 1988)	k = −12→4
Tmin = 0.79, Tmax = 0.86	l = −11→12
4216 measured reflections	2 standard reflections every 98 reflections
2890 independent reflections	intensity decay: <2%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.040	Hydrogen site location: mixed
wR(F^2) = 0.073	H atoms treated by a mixture of independent and constrained refinement
S = 0.85	w = 1/[σ^2(Fo^2) + (0.0178P)^2] where P = (Fo^2 + 2Fc^2)/3
2890 reflections	(Δ/σ)max = 0.004
234 parameters	Δρmax = 0.41 e Å^−3
3 restraints	Δρmin = −0.35 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Zn	0.76317 (5)	0.85637 (5)	0.90932 (5)	0.03576 (15)
S	1.07896 (11)	1.02598 (11)	1.26397 (12)	0.0368 (2)
O1	0.9204 (3)	0.8918 (3)	1.1321 (3)	0.0613 (8)
O2	1.0570 (3)	1.1164 (3)	1.3913 (3)	0.0640 (8)
O3	1.2096 (3)	0.9697 (3)	1.3206 (4)	0.0722 (9)
O4	1.1123 (3)	1.1279 (3)	1.1934 (3)	0.0431 (7)
N1	0.7047 (3)	0.6013 (3)	0.8129 (4)	0.0379 (8)
N2	0.6833 (3)	1.0545 (4)	0.9480 (4)	0.0388 (8)
N3	0.5075 (3)	0.7529 (3)	0.7496 (3)	0.0340 (7)
C1	0.8151 (5)	0.5312 (5)	0.8482 (5)	0.0472 (11)
H1A	0.9260	0.5939	0.9286	0.057*
C2	0.7722 (5)	0.3712 (5)	0.7711 (5)	0.0497 (11)
H2A	0.8521	0.3264	0.7978	0.060*
C3	0.6085 (5)	0.2790 (5)	0.6538 (5)	0.0488 (11)
H3A	0.5760	0.1702	0.6002	0.059*
C4	0.4921 (5)	0.3477 (4)	0.6155 (5)	0.0437 (10)
H4A	0.3804	0.2866	0.5372	0.052*
C5	0.5458 (4)	0.5102 (4)	0.6965 (4)	0.0334 (9)
C6	0.4318 (4)	0.5967 (4)	0.6603 (4)	0.0338 (9)
C7	0.2630 (4)	0.5270 (5)	0.5452 (4)	0.0442 (10)
H7A	0.2107	0.4181	0.4844	0.053*
C8	0.1744 (5)	0.6239 (5)	0.5230 (5)	0.0521 (11)
H8A	0.0612	0.5802	0.4440	0.063*
C9	0.2521 (4)	0.7834 (5)	0.6163 (5)	0.0486 (11)
H9A	0.1918	0.8483	0.6023	0.058*
C10	0.4199 (4)	0.8476 (5)	0.7310 (5)	0.0394 (9)
C11	0.5197 (5)	1.0156 (5)	0.8442 (5)	0.0396 (9)
C12	0.4499 (5)	1.1292 (5)	0.8477 (5)	0.0520 (11)
H12A	0.3371	1.1020	0.7756	0.062*
C13	0.5517 (6)	1.2840 (5)	0.9610 (5)	0.0565 (12)
H13A	0.5069	1.3620	0.9653	0.068*
C14	0.7174 (5)	1.3244 (5)	1.0669 (5)	0.0541 (11)
H14A	0.7865	1.4284	1.1440	0.065*
C15	0.7781 (5)	1.2044 (5)	1.0550 (5)	0.0487 (11)
H15A	0.8909	1.2300	1.1254	0.058*
O1W	0.8391 (4)	0.7034 (3)	0.2766 (4)	0.0644 (10)
H1WA	0.858 (5)	0.757 (4)	0.367 (4)	0.077*
H1WB	0.879 (5)	0.757 (4)	0.249 (5)	0.077*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn	0.0322 (2)	0.0287 (3)	0.0355 (3)	0.0065 (2)	0.0160 (2)	0.0095 (2)
S	0.0342 (5)	0.0292 (6)	0.0348 (5)	0.0071 (5)	0.0155 (4)	0.0091 (5)
O1	0.0527 (16)	0.0488 (19)	0.0361 (16)	−0.0186 (15)	0.0050 (14)	0.0154 (15)
O2	0.081 (2)	0.059 (2)	0.0511 (18)	0.0186 (18)	0.0463 (17)	0.0136 (17)
O3	0.0602 (19)	0.062 (2)	0.104 (3)	0.0366 (18)	0.0391 (19)	0.049 (2)
O4	0.0459 (15)	0.0377 (16)	0.0613 (18)	0.0169 (14)	0.0375 (14)	0.0267 (15)
N1	0.0332 (17)	0.0287 (19)	0.0353 (18)	0.0036 (15)	0.0110 (15)	0.0122 (16)
N2	0.0385 (18)	0.0292 (19)	0.045 (2)	0.0117 (16)	0.0248 (16)	0.0120 (17)
N3	0.0322 (17)	0.0309 (18)	0.0364 (18)	0.0084 (15)	0.0197 (15)	0.0132 (16)
C1	0.041 (2)	0.047 (3)	0.044 (2)	0.016 (2)	0.015 (2)	0.022 (2)
C2	0.061 (3)	0.044 (3)	0.051 (3)	0.024 (2)	0.030 (2)	0.027 (2)
C3	0.070 (3)	0.028 (2)	0.049 (3)	0.016 (2)	0.036 (2)	0.015 (2)
C4	0.043 (2)	0.031 (2)	0.042 (2)	0.002 (2)	0.020 (2)	0.011 (2)
C5	0.036 (2)	0.028 (2)	0.030 (2)	0.0047 (18)	0.0186 (18)	0.0085 (18)
C6	0.035 (2)	0.032 (2)	0.031 (2)	0.0081 (19)	0.0188 (18)	0.0126 (19)
C7	0.034 (2)	0.040 (3)	0.042 (2)	0.001 (2)	0.016 (2)	0.014 (2)
C8	0.030 (2)	0.062 (3)	0.048 (3)	0.010 (2)	0.015 (2)	0.022 (3)
C9	0.037 (2)	0.056 (3)	0.056 (3)	0.022 (2)	0.025 (2)	0.028 (3)
C10	0.039 (2)	0.045 (3)	0.044 (2)	0.018 (2)	0.027 (2)	0.023 (2)
C11	0.047 (2)	0.036 (2)	0.043 (2)	0.019 (2)	0.030 (2)	0.016 (2)
C12	0.058 (3)	0.051 (3)	0.064 (3)	0.030 (3)	0.040 (2)	0.030 (3)
C13	0.090 (4)	0.046 (3)	0.066 (3)	0.043 (3)	0.055 (3)	0.034 (3)
C14	0.073 (3)	0.034 (3)	0.055 (3)	0.019 (3)	0.039 (3)	0.015 (2)
C15	0.054 (3)	0.035 (3)	0.049 (3)	0.011 (2)	0.031 (2)	0.011 (2)
O1W	0.087 (2)	0.041 (2)	0.061 (2)	0.0178 (19)	0.041 (2)	0.0203 (17)

Geometric parameters (Å, º)

Zn—O4^i	1.952 (2)	C4—C5	1.385 (5)
Zn—O1	1.970 (3)	C4—H4A	0.9300
Zn—N3	2.074 (3)	C5—C6	1.487 (4)
Zn—N2	2.166 (3)	C6—C7	1.382 (4)
Zn—N1	2.201 (3)	C7—C8	1.381 (5)
S—O3	1.422 (3)	C7—H7A	0.9300
S—O2	1.434 (3)	C8—C9	1.366 (5)
S—O1	1.483 (3)	C8—H8A	0.9300
S—O4	1.496 (2)	C9—C10	1.375 (5)
O4—Zn^i	1.952 (2)	C9—H9A	0.9300
N1—C5	1.337 (4)	C10—C11	1.469 (5)
N1—C1	1.340 (4)	C11—C12	1.383 (5)
N2—C15	1.327 (4)	C12—C13	1.379 (5)
N2—C11	1.350 (4)	C12—H12A	0.9300
N3—C6	1.336 (4)	C13—C14	1.367 (5)
N3—C10	1.353 (4)	C13—H13A	0.9300
C1—C2	1.373 (5)	C14—C15	1.381 (5)
C1—H1A	0.9300	C14—H14A	0.9300
C2—C3	1.371 (5)	C15—H15A	0.9300
C2—H2A	0.9300	O1W—H1WA	0.81 (3)
C3—C4	1.377 (5)	O1W—H1WB	0.81 (3)
C3—H3A	0.9300
O4^i—Zn—O1	107.54 (10)	C3—C4—H4A	120.9
O4^i—Zn—N3	115.24 (11)	C5—C4—H4A	120.9
O1—Zn—N3	134.66 (11)	N1—C5—C4	122.4 (3)
O4^i—Zn—N2	107.83 (10)	N1—C5—C6	114.9 (3)
O1—Zn—N2	104.58 (12)	C4—C5—C6	122.7 (3)
N3—Zn—N2	76.52 (12)	N3—C6—C7	121.3 (4)
O4^i—Zn—N1	91.75 (10)	N3—C6—C5	113.7 (3)
O1—Zn—N1	90.39 (11)	C7—C6—C5	124.9 (3)
N3—Zn—N1	74.44 (11)	C8—C7—C6	118.0 (4)
N2—Zn—N1	149.88 (11)	C8—C7—H7A	121.0
O3—S—O2	112.92 (19)	C6—C7—H7A	121.0
O3—S—O1	109.95 (17)	C9—C8—C7	120.4 (4)
O2—S—O1	108.10 (17)	C9—C8—H8A	119.8
O3—S—O4	110.37 (16)	C7—C8—H8A	119.8
O2—S—O4	107.69 (16)	C8—C9—C10	119.6 (4)
O1—S—O4	107.63 (15)	C8—C9—H9A	120.2
S—O1—Zn	128.49 (16)	C10—C9—H9A	120.2
S—O4—Zn^i	135.32 (15)	N3—C10—C9	120.0 (4)
C5—N1—C1	118.1 (3)	N3—C10—C11	113.9 (3)
C5—N1—Zn	115.7 (2)	C9—C10—C11	126.1 (4)
C1—N1—Zn	125.9 (2)	N2—C11—C12	121.1 (4)
C15—N2—C11	119.1 (3)	N2—C11—C10	116.8 (3)
C15—N2—Zn	127.0 (3)	C12—C11—C10	122.0 (4)
C11—N2—Zn	113.8 (3)	C13—C12—C11	118.3 (4)
C6—N3—C10	120.6 (3)	C13—C12—H12A	120.8
C6—N3—Zn	120.9 (2)	C11—C12—H12A	120.8
C10—N3—Zn	118.4 (2)	C14—C13—C12	120.9 (4)
N1—C1—C2	123.0 (4)	C14—C13—H13A	119.5
N1—C1—H1A	118.5	C12—C13—H13A	119.5
C2—C1—H1A	118.5	C13—C14—C15	117.3 (4)
C3—C2—C1	118.4 (4)	C13—C14—H14A	121.3
C3—C2—H2A	120.8	C15—C14—H14A	121.3
C1—C2—H2A	120.8	N2—C15—C14	123.1 (4)
C2—C3—C4	119.9 (4)	N2—C15—H15A	118.4
C2—C3—H3A	120.0	C14—C15—H15A	118.4
C4—C3—H3A	120.0	H1WA—O1W—H1WB	110 (3)
C3—C4—C5	118.2 (4)
O3—S—O1—Zn	−126.3 (2)	C1—N1—C5—C4	1.6 (5)
O2—S—O1—Zn	110.1 (2)	Zn—N1—C5—C4	175.1 (3)
O4—S—O1—Zn	−6.0 (3)	C1—N1—C5—C6	−178.0 (3)
O4^i—Zn—O1—S	53.6 (2)	Zn—N1—C5—C6	−4.5 (4)
N3—Zn—O1—S	−146.17 (19)	C3—C4—C5—N1	−1.9 (5)
N2—Zn—O1—S	−60.8 (2)	C3—C4—C5—C6	177.7 (3)
N1—Zn—O1—S	145.6 (2)	C10—N3—C6—C7	0.8 (5)
O3—S—O4—Zn^i	26.6 (3)	Zn—N3—C6—C7	−175.4 (2)
O2—S—O4—Zn^i	150.3 (2)	C10—N3—C6—C5	−179.7 (3)
O1—S—O4—Zn^i	−93.4 (2)	Zn—N3—C6—C5	4.1 (4)
O4^i—Zn—N1—C5	−110.8 (2)	N1—C5—C6—N3	0.6 (4)
O1—Zn—N1—C5	141.7 (3)	C4—C5—C6—N3	−179.1 (3)
N3—Zn—N1—C5	5.0 (2)	N1—C5—C6—C7	−180.0 (3)
N2—Zn—N1—C5	20.8 (4)	C4—C5—C6—C7	0.3 (5)
O4^i—Zn—N1—C1	62.1 (3)	N3—C6—C7—C8	1.0 (5)
O1—Zn—N1—C1	−45.4 (3)	C5—C6—C7—C8	−178.4 (3)
N3—Zn—N1—C1	177.9 (3)	C6—C7—C8—C9	−1.9 (6)
N2—Zn—N1—C1	−166.3 (3)	C7—C8—C9—C10	1.0 (6)
O4^i—Zn—N2—C15	−70.2 (3)	C6—N3—C10—C9	−1.7 (5)
O1—Zn—N2—C15	44.1 (3)	Zn—N3—C10—C9	174.6 (3)
N3—Zn—N2—C15	177.3 (3)	C6—N3—C10—C11	176.9 (3)
N1—Zn—N2—C15	161.6 (3)	Zn—N3—C10—C11	−6.8 (4)
O4^i—Zn—N2—C11	106.7 (3)	C8—C9—C10—N3	0.7 (6)
O1—Zn—N2—C11	−139.0 (2)	C8—C9—C10—C11	−177.7 (4)
N3—Zn—N2—C11	−5.8 (2)	C15—N2—C11—C12	0.0 (5)
N1—Zn—N2—C11	−21.5 (4)	Zn—N2—C11—C12	−177.2 (3)
O4^i—Zn—N3—C6	79.6 (3)	C15—N2—C11—C10	−178.6 (3)
O1—Zn—N3—C6	−79.5 (3)	Zn—N2—C11—C10	4.2 (4)
N2—Zn—N3—C6	−176.8 (3)	N3—C10—C11—N2	1.4 (5)
N1—Zn—N3—C6	−4.9 (2)	C9—C10—C11—N2	179.9 (3)
O4^i—Zn—N3—C10	−96.7 (2)	N3—C10—C11—C12	−177.2 (3)
O1—Zn—N3—C10	104.2 (3)	C9—C10—C11—C12	1.3 (6)
N2—Zn—N3—C10	6.9 (2)	N2—C11—C12—C13	−0.3 (6)
N1—Zn—N3—C10	178.8 (3)	C10—C11—C12—C13	178.2 (3)
C5—N1—C1—C2	−0.3 (5)	C11—C12—C13—C14	0.1 (6)
Zn—N1—C1—C2	−173.1 (3)	C12—C13—C14—C15	0.4 (6)
N1—C1—C2—C3	−0.7 (6)	C11—N2—C15—C14	0.6 (6)
C1—C2—C3—C4	0.3 (6)	Zn—N2—C15—C14	177.3 (3)
C2—C3—C4—C5	0.9 (6)	C13—C14—C15—N2	−0.7 (6)

Symmetry code: (i) −x+2, −y+2, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WB···O1^ii	0.81 (3)	2.17 (3)	2.957 (4)	166 (4)
O1W—H1WA···O2^i	0.81 (3)	2.04 (3)	2.834 (4)	169 (4)

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