catena-Poly[[[aqua­(pyrazine-2-carboxamide-κ² N ¹,O)zinc]-μ-pyrazine-2-carboxamide-κ³ N ¹,O:N ⁴] dinitrate]

Abstract

In the crystal of the title compound, {[Zn(C₅H₅N₃O)₂(H₂O)](NO₃)₂}_n, the Zn^II cation is N,O-chelated by two pyrazine-2-carboxamide (PCA) ligands and is further coordinated by one water mol­ecule and by one pyrazine-N atom from an adjacent PCA ligand in a distorted ZnN₃O₃ octa­hedral geometry. One of the two independent PCA ligands bridges two Zn^II cations, forming a zigzag polymeric chain running along the c axis. In the crystal, the NO₃ ⁻ anions link to the chain via O—H⋯O and N—H⋯O hydrogen bonding. Weak inter­molecular C—H⋯O inter­actions also occur.

Related literature  

For related structures, see: Shirvan & Haydari Dezfuli (2012 ▶); Abu-Youssef et al. (2006 ▶); Azhdari Tehrani et al. (2010 ▶); Goher & Mautner (2000 ▶); Kristiansson (2002 ▶); Mir Mohammad Sadegh et al. (2010 ▶); Munakata et al. (1997 ▶); Pacigova et al. (2008 ▶).

Experimental  

Crystal data  

• [Zn(C₅H₅N₃O)₂(H₂O)](NO₃)₂

• M _r = 453.67

• Monoclinic,

• a = 10.4889 (11) Å

• b = 15.7477 (16) Å

• c = 9.9332 (10) Å

• β = 97.664 (8)°

• V = 1626.1 (3) ų

• Z = 4

• Mo Kα radiation

• μ = 1.58 mm⁻¹

• T = 298 K

• 0.23 × 0.12 × 0.10 mm

Data collection  

• Bruker APEXII CCD area detector diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.070, T _max = 0.240

• 9288 measured reflections

• 3192 independent reflections

• 2088 reflections with I > 2σ(I)

• R _int = 0.123

Refinement  

• R[F ² > 2σ(F ²)] = 0.076

• wR(F ²) = 0.103

• S = 1.06

• 3192 reflections

• 261 parameters

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.46 e Å⁻³

• Δρ_min = −0.52 e Å⁻³

Data collection: APEX2 (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: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

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

Table 1. Selected bond lengths (Å).

Zn1—O1	2.064 (3)
Zn1—O2	2.073 (3)
Zn1—O3	2.042 (6)
Zn1—N1	2.180 (5)
Zn1—N4	2.193 (5)
Zn1—N5i	2.179 (5)

Symmetry code: (i) .

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3B⋯O8ii	0.76 (7)	2.05 (7)	2.810 (8)	177 (7)
O3—H3C⋯O4	0.75 (6)	2.06 (7)	2.781 (8)	162 (9)
N3—H3D⋯O3ii	0.86	2.50	3.193 (8)	138
N3—H3D⋯O5ii	0.86	2.42	3.163 (8)	144
N3—H3E⋯O7	0.86	2.08	2.937 (8)	172
N6—H6B⋯O4iii	0.86	2.07	2.913 (7)	166
N6—H6C⋯O5iv	0.86	2.41	3.231 (8)	161
C1—H1⋯O8v	0.93	2.39	3.292 (8)	162
C3—H3⋯O7	0.93	2.31	3.227 (8)	169
C6—H6⋯O6vi	0.93	2.60	3.295 (8)	132
C7—H7⋯O5vi	0.93	2.49	3.362 (8)	156
C8—H8⋯O4iii	0.93	2.39	3.298 (7)	167

Symmetry codes: (ii) ; (iii) ; (iv) ; (v) ; (vi) .

supplementary crystallographic information

Comment

In a recent paper, we reported the synthesis and crystal structure of [ZnBr₂(pzc)₂] (Shirvan & Haydari Dezfuli, 2012), where pzc is the pyrazine-2-carboxamide. Pyrazine-2-carboxamide is a good ligand, and a few complexes with pzc have been prepared, such as that of mercury (Azhdari Tehrani et al., 2010; Mir Mohammad Sadegh et al., 2010) and vanadium (Pacigova et al., 2008), manganese (Abu-Youssef et al., 2006) and copper (Kristiansson, 2002; Munakata et al., 1997; Goher & Mautner, 2000). Here, we report the synthesis and structure of the title compound.

The asymmetric unit of the title compound, (Fig. 1), contains one Zn^II cation, two pyrazine-2-carboxamide ligands, one water molecule and two NO₃^- counter-ions. The Zn^II atom is six-coordinated in a distorted octahedral configuration by two N and two O atoms from two pyrazine-2-carboxamide ligands and one O atom from one water molecule. The sixth coordination site is occupied by N atom from one bridging pyrazine-2-carboxamide ligand. The Zn—O and Zn—N bond lengths and angles are collected in Table 1.

In the crystal structure, intra and intermolecular O—H···O, N—H···O and C—H···O hydrogen bonds (Table 2, Fig. 2) may stabilize the structure.

Experimental

A solution of pyrazine-2-carboxamide (0.25 g, 2.0 mmol) in methanol (10 ml) was added to a solution of Zn(NO₃)₂.4H₂O (0.26 g, 1.0 mmol) in methanol (10 ml) and the resulting colorless solution was stirred for 15 min at room temperature. This solution was left to evaporate slowly at room temperature. After one week, colorless block crystals of the title compound were isolated (yield 0.36 g, 79.3%).

Refinement

Water H atoms were located in a difference Fourier map and refined isotropically. Other H atoms were positioned geometrically with C—H = 0.93 and N—H = 0.86 Å, and constrained to ride on their parent atoms with U_iso(H) = 1.2U_eq(N,C).

Figures

Fig. 1.

The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (b) x,3/2 - y,1/2 + z].

Fig. 2.

Unit-cell packing diagram for title molecule. Hydrogen bonds are shown as dashed lines.

Crystal data

[Zn(C5H5N3O)2(H2O)](NO3)2	F(000) = 920
Mr = 453.67	Dx = 1.853 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9288 reflections
a = 10.4889 (11) Å	θ = 2.4–26.0°
b = 15.7477 (16) Å	µ = 1.58 mm−1
c = 9.9332 (10) Å	T = 298 K
β = 97.664 (8)°	Block, colorless
V = 1626.1 (3) Å3	0.23 × 0.12 × 0.10 mm
Z = 4

Data collection

Bruker APEXII CCD area detector diffractometer	3192 independent reflections
Radiation source: fine-focus sealed tube	2088 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.123
ω scans	θmax = 26.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −12→12
Tmin = 0.070, Tmax = 0.240	k = −19→19
9288 measured reflections	l = −12→11

Refinement

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)] = 0.076	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.103	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0237P)2] where P = (Fo2 + 2Fc2)/3
3192 reflections	(Δ/σ)max = 0.006
261 parameters	Δρmax = 0.46 e Å−3
0 restraints	Δρmin = −0.52 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.

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.7871 (6)	0.4587 (4)	0.1320 (7)	0.0329 (15)
H1	0.8748	0.4701	0.1417	0.039*
C2	0.7334 (6)	0.4048 (5)	0.0291 (7)	0.0445 (17)
H2	0.7859	0.3819	−0.0300	0.053*
C3	0.5393 (6)	0.4184 (4)	0.1012 (7)	0.0387 (16)
H3	0.4526	0.4043	0.0946	0.046*
C4	0.5906 (5)	0.4738 (3)	0.2038 (6)	0.0210 (12)
C5	0.5169 (5)	0.5161 (3)	0.3017 (6)	0.0237 (13)
C6	0.6418 (5)	0.7234 (4)	0.1580 (7)	0.0248 (14)
H6	0.5624	0.7048	0.1782	0.030*
C7	0.6463 (5)	0.7868 (4)	0.0610 (7)	0.0292 (15)
H7	0.5699	0.8084	0.0154	0.035*
C8	0.8651 (5)	0.7831 (3)	0.0990 (6)	0.0240 (14)
H8	0.9445	0.8033	0.0814	0.029*
C9	0.8615 (5)	0.7189 (3)	0.1932 (6)	0.0189 (12)
C10	0.9758 (5)	0.6759 (3)	0.2712 (6)	0.0207 (13)
N1	0.7158 (4)	0.4940 (3)	0.2159 (5)	0.0246 (12)
N2	0.6089 (5)	0.3848 (4)	0.0128 (6)	0.0483 (16)
N3	0.3939 (5)	0.5002 (3)	0.3014 (6)	0.0366 (14)
H3D	0.3515	0.5264	0.3571	0.044*
H3E	0.3558	0.4637	0.2454	0.044*
N4	0.7479 (4)	0.6893 (3)	0.2219 (5)	0.0228 (12)
N5	0.7584 (4)	0.8170 (3)	0.0325 (5)	0.0225 (11)
N6	1.0915 (4)	0.7048 (3)	0.2613 (5)	0.0317 (13)
H6C	1.1576	0.6814	0.3071	0.038*
H6B	1.1012	0.7472	0.2090	0.038*
N7	0.7146 (5)	0.3192 (3)	0.4190 (7)	0.0350 (13)
N8	0.1273 (5)	0.4024 (4)	0.1241 (6)	0.0361 (13)
O1	0.5749 (3)	0.5684 (2)	0.3812 (4)	0.0300 (11)
O2	0.9561 (3)	0.6152 (2)	0.3448 (4)	0.0252 (9)
O3	0.8371 (5)	0.5012 (4)	0.5193 (6)	0.0397 (13)
H3C	0.850 (7)	0.456 (4)	0.503 (8)	0.04 (3)*
H3B	0.853 (6)	0.510 (4)	0.595 (7)	0.03 (2)*
O4	0.8335 (4)	0.3362 (3)	0.4190 (5)	0.0437 (12)
O5	0.6640 (5)	0.3426 (4)	0.5181 (7)	0.080 (2)
O6	0.6571 (5)	0.2815 (4)	0.3235 (6)	0.0633 (16)
O7	0.2393 (5)	0.3816 (3)	0.1188 (7)	0.0622 (15)
O8	0.1027 (5)	0.4586 (4)	0.2039 (6)	0.0669 (17)
O9	0.0400 (5)	0.3687 (4)	0.0522 (8)	0.098 (3)
Zn1	0.76855 (6)	0.58798 (4)	0.37477 (7)	0.02037 (17)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.021 (3)	0.037 (3)	0.042 (4)	0.001 (3)	0.007 (3)	−0.005 (3)
C2	0.044 (4)	0.049 (4)	0.041 (4)	0.003 (4)	0.008 (3)	−0.020 (4)
C3	0.030 (3)	0.048 (4)	0.038 (4)	−0.012 (3)	0.004 (3)	−0.020 (4)
C4	0.020 (3)	0.028 (3)	0.015 (3)	−0.003 (2)	0.000 (2)	−0.001 (3)
C5	0.023 (3)	0.023 (3)	0.025 (4)	−0.003 (2)	−0.001 (3)	0.005 (3)
C6	0.018 (3)	0.025 (3)	0.033 (4)	−0.004 (2)	0.007 (3)	0.006 (3)
C7	0.013 (3)	0.035 (4)	0.039 (4)	0.001 (2)	0.001 (3)	0.003 (3)
C8	0.021 (3)	0.019 (3)	0.033 (4)	0.001 (2)	0.007 (3)	−0.001 (3)
C9	0.017 (3)	0.020 (3)	0.018 (3)	−0.002 (2)	0.001 (2)	−0.001 (2)
C10	0.022 (3)	0.021 (3)	0.020 (3)	0.003 (2)	0.004 (2)	−0.004 (3)
N1	0.021 (2)	0.030 (3)	0.023 (3)	−0.001 (2)	0.003 (2)	0.003 (2)
N2	0.038 (3)	0.060 (4)	0.046 (4)	−0.004 (3)	0.003 (3)	−0.021 (3)
N3	0.023 (3)	0.052 (3)	0.035 (4)	−0.004 (2)	0.009 (2)	−0.011 (3)
N4	0.020 (2)	0.020 (3)	0.029 (3)	0.000 (2)	0.006 (2)	0.003 (2)
N5	0.022 (2)	0.024 (2)	0.021 (3)	0.005 (2)	0.004 (2)	−0.002 (2)
N6	0.015 (2)	0.039 (3)	0.041 (4)	0.001 (2)	0.003 (2)	0.017 (3)
N7	0.027 (3)	0.025 (3)	0.053 (4)	0.002 (2)	0.004 (3)	−0.004 (3)
N8	0.030 (3)	0.035 (3)	0.042 (4)	0.003 (3)	0.002 (3)	0.001 (3)
O1	0.022 (2)	0.034 (3)	0.035 (3)	−0.0099 (18)	0.0051 (19)	−0.017 (2)
O2	0.020 (2)	0.025 (2)	0.031 (3)	0.0002 (16)	0.0029 (18)	0.0098 (18)
O3	0.053 (3)	0.034 (3)	0.030 (4)	0.009 (3)	0.000 (3)	0.005 (3)
O4	0.024 (2)	0.052 (3)	0.056 (4)	0.001 (2)	0.007 (2)	−0.017 (3)
O5	0.063 (4)	0.087 (4)	0.103 (5)	−0.015 (3)	0.057 (4)	−0.041 (4)
O6	0.045 (3)	0.077 (4)	0.063 (4)	−0.022 (3)	−0.009 (3)	−0.006 (3)
O7	0.028 (3)	0.065 (3)	0.094 (4)	−0.006 (3)	0.010 (3)	−0.022 (3)
O8	0.052 (3)	0.088 (4)	0.056 (4)	0.018 (3)	−0.009 (3)	−0.039 (3)
O9	0.026 (3)	0.135 (6)	0.127 (6)	0.003 (3)	−0.007 (3)	−0.092 (5)
Zn1	0.0182 (3)	0.0208 (3)	0.0216 (3)	−0.0026 (3)	0.0009 (2)	−0.0004 (4)

Geometric parameters (Å, º)

Zn1—O1	2.064 (3)	N4—C9	1.345 (7)
Zn1—O2	2.073 (3)	N4—C6	1.320 (7)
Zn1—O3	2.042 (6)	N5—C8	1.333 (7)
Zn1—N1	2.180 (5)	N5—C7	1.333 (7)
Zn1—N4	2.193 (5)	N6—C10	1.312 (7)
Zn1—N5i	2.179 (5)	N3—H3E	0.8600
O1—C5	1.243 (6)	N3—H3D	0.8600
O2—C10	1.237 (6)	N6—H6B	0.8600
O3—H3B	0.76 (7)	N6—H6C	0.8600
O3—H3C	0.75 (6)	C1—C2	1.389 (10)
O4—N7	1.276 (7)	C3—C4	1.394 (9)
O5—N7	1.235 (9)	C4—C5	1.479 (8)
O6—N7	1.210 (9)	C6—C7	1.393 (9)
O7—N8	1.227 (8)	C8—C9	1.382 (7)
O8—N8	1.238 (9)	C9—C10	1.500 (8)
O9—N8	1.207 (9)	C1—H1	0.9300
N1—C4	1.341 (7)	C2—H2	0.9300
N1—C1	1.315 (8)	C3—H3	0.9300
N2—C2	1.332 (8)	C6—H6	0.9300
N2—C3	1.325 (9)	C7—H7	0.9300
N3—C5	1.314 (7)	C8—H8	0.9300
Zn1···H3Dii	3.5800	N4···C10	2.385 (7)
O1···O3	3.092 (6)	N4···N5i	3.074 (7)
O1···N1	2.627 (6)	N5···N4viii	3.074 (7)
O1···N4	3.192 (6)	N5···O3viii	2.987 (8)
O1···C4	2.330 (7)	N5···O1viii	2.907 (6)
O1···O5ii	3.148 (7)	N5···N4	2.766 (7)
O1···N5i	2.907 (6)	N5···O2viii	3.154 (6)
O1···C7i	2.932 (7)	N6···O6ix	3.117 (7)
O2···C9	2.350 (6)	N6···O4ix	2.913 (7)
O2···O3	2.892 (7)	N6···O4iii	3.233 (7)
O2···N4	2.629 (6)	N6···O5iii	3.231 (8)
O2···C8i	3.240 (7)	N7···C4	3.383 (8)
O2···O3iii	3.018 (7)	N7···O3	3.243 (8)
O2···O4iii	3.095 (6)	N8···C8v	3.323 (8)
O2···N5i	3.154 (6)	N8···C9v	3.406 (8)
O3···N1	3.113 (8)	N2···H6vii	2.8100
O3···O5	3.087 (8)	N3···H3Bii	2.92 (6)
O3···N5i	2.987 (8)	N3···H3	2.6900
O3···O2iii	3.018 (7)	N5···H3Bviii	2.94 (6)
O3···O1	3.092 (6)	N6···H8	2.6900
O3···O2	2.892 (7)	N7···H6Ciii	2.8700
O3···O4	2.781 (8)	N7···H3C	2.65 (7)
O3···O8ii	2.810 (8)	N7···H6Biv	2.7000
O3···N7	3.243 (8)	N8···H1vi	2.8800
O3···N3ii	3.193 (8)	N8···H3E	2.7100
O4···O3	2.781 (8)	C1···O9x	3.199 (9)
O4···C8iv	3.298 (7)	C1···O8x	3.292 (8)
O4···N6iii	3.233 (7)	C2···O9x	3.244 (8)
O4···O2iii	3.095 (6)	C3···O6	3.213 (9)
O4···N6iv	2.913 (7)	C3···O7	3.227 (8)
O5···C7v	3.362 (8)	C3···C4vii	3.580 (9)
O5···N6iii	3.231 (8)	C3···C3vii	3.299 (9)
O5···N3ii	3.163 (8)	C4···C3vii	3.580 (9)
O5···O1ii	3.148 (7)	C4···O6	3.294 (8)
O5···O3	3.087 (8)	C4···N7	3.383 (8)
O6···N6iv	3.117 (7)	C6···N2vii	3.392 (8)
O6···C4	3.294 (8)	C6···O6xi	3.295 (8)
O6···C3	3.213 (9)	C7···O5xi	3.362 (8)
O6···C6v	3.295 (8)	C8···N8xi	3.323 (8)
O7···C3	3.227 (8)	C8···O9vii	3.059 (8)
O7···N3	2.937 (8)	C8···O8xi	3.378 (8)
O8···C8v	3.378 (8)	C8···O4ix	3.298 (7)
O8···C1vi	3.292 (8)	C9···N8xi	3.406 (8)
O8···N3	3.148 (8)	C9···O9vii	3.096 (9)
O8···O3ii	2.810 (8)	C10···O9vii	3.271 (10)
O9···C9vii	3.096 (9)	C3···H3E	2.6500
O9···C2vi	3.244 (8)	C8···H6B	2.6300
O9···C8vii	3.059 (8)	H1···O8x	2.3900
O9···C1vi	3.199 (9)	H1···O9x	2.6000
O9···C10vii	3.271 (10)	H1···N8x	2.8800
O1···H7i	2.3600	H2···O9x	2.6900
O2···H3Ciii	2.62 (7)	H3···N3	2.6900
O2···H3Biii	2.82 (6)	H3···H3E	2.1300
O2···H8i	2.6900	H3···O7	2.3100
O3···H3Dii	2.5000	H3B···O2iii	2.82 (6)
O4···H3C	2.06 (7)	H3B···H3Dii	2.3300
O4···H6Ciii	2.7200	H3B···O8ii	2.05 (7)
O4···H6Biv	2.0700	H3B···N3ii	2.92 (6)
O4···H8iv	2.3900	H3C···O5	2.66 (7)
O5···H3C	2.66 (7)	H3C···O4	2.06 (7)
O5···H6Ciii	2.4100	H3C···N7	2.65 (7)
O5···H7v	2.4900	H3C···O2iii	2.62 (7)
O5···H3Dii	2.4200	H3D···Zn1ii	3.5800
O6···H6v	2.6000	H3D···H3Bii	2.3300
O6···H6Biv	2.6500	H3D···O3ii	2.5000
O7···H3	2.3100	H3D···O5ii	2.4200
O7···H3E	2.0800	H3E···O7	2.0800
O8···H3E	2.6300	H3E···O8	2.6300
O8···H1vi	2.3900	H3E···N8	2.7100
O8···H3Bii	2.05 (7)	H3E···C3	2.6500
O9···H2vi	2.6900	H3E···H3	2.1300
O9···H1vi	2.6000	H6···N2vii	2.8100
N1···C5	2.382 (7)	H6···O6xi	2.6000
N1···O1	2.627 (6)	H6B···O6ix	2.6500
N1···N2	2.772 (8)	H6B···O4ix	2.0700
N1···N4	3.094 (7)	H6B···N7ix	2.7000
N1···O3	3.113 (8)	H6B···H8	2.1300
N2···N1	2.772 (8)	H6B···C8	2.6300
N2···C6vii	3.392 (8)	H6C···O5iii	2.4100
N3···O5ii	3.163 (8)	H6C···O4iii	2.7200
N3···O7	2.937 (8)	H6C···N7iii	2.8700
N3···O3ii	3.193 (8)	H7···O5xi	2.4900
N3···O8	3.148 (8)	H7···O1viii	2.3600
N4···N1	3.094 (7)	H8···O4ix	2.3900
N4···O1	3.192 (6)	H8···O2viii	2.6900
N4···O2	2.629 (6)	H8···N6	2.6900
N4···N5	2.766 (7)	H8···H6B	2.1300
O1—Zn1—O2	172.71 (15)	O4—N7—O5	117.5 (6)
O1—Zn1—O3	97.70 (18)	O4—N7—O6	119.2 (6)
O1—Zn1—N1	76.42 (15)	O5—N7—O6	123.3 (6)
O1—Zn1—N4	97.09 (15)	O8—N8—O9	119.1 (6)
O1—Zn1—N5i	86.43 (15)	O7—N8—O8	120.0 (6)
O2—Zn1—O3	89.28 (18)	O7—N8—O9	120.8 (6)
O2—Zn1—N1	100.98 (15)	N1—C1—C2	121.0 (6)
O2—Zn1—N4	76.01 (15)	N2—C2—C1	121.9 (6)
O2—Zn1—N5i	95.71 (15)	N2—C3—C4	122.8 (6)
O3—Zn1—N1	94.9 (2)	C3—C4—C5	125.3 (5)
O3—Zn1—N4	165.13 (19)	N1—C4—C5	115.2 (5)
O3—Zn1—N5i	90.0 (2)	N1—C4—C3	119.5 (5)
N1—Zn1—N4	90.03 (18)	O1—C5—C4	117.5 (5)
N1—Zn1—N5i	162.62 (16)	O1—C5—N3	121.7 (5)
N4—Zn1—N5i	89.34 (18)	N3—C5—C4	120.8 (5)
Zn1—O1—C5	118.7 (3)	N4—C6—C7	121.4 (5)
Zn1—O2—C10	118.8 (3)	N5—C7—C6	121.0 (5)
H3B—O3—H3C	112 (8)	N5—C8—C9	122.1 (5)
Zn1—O3—H3C	123 (6)	C8—C9—C10	126.0 (5)
Zn1—O3—H3B	126 (5)	N4—C9—C10	113.8 (5)
C1—N1—C4	118.4 (5)	N4—C9—C8	120.2 (5)
Zn1—N1—C4	112.1 (4)	O2—C10—C9	118.0 (5)
Zn1—N1—C1	129.4 (4)	N6—C10—C9	119.2 (5)
C2—N2—C3	116.3 (6)	O2—C10—N6	122.8 (5)
Zn1—N4—C6	128.9 (4)	C2—C1—H1	120.00
Zn1—N4—C9	113.0 (3)	N1—C1—H1	119.00
C6—N4—C9	118.1 (5)	N2—C2—H2	119.00
Zn1viii—N5—C8	120.9 (4)	C1—C2—H2	119.00
C7—N5—C8	117.3 (5)	N2—C3—H3	119.00
Zn1viii—N5—C7	121.8 (4)	C4—C3—H3	119.00
C5—N3—H3E	120.00	C7—C6—H6	119.00
H3D—N3—H3E	120.00	N4—C6—H6	119.00
C5—N3—H3D	120.00	N5—C7—H7	120.00
C10—N6—H6B	120.00	C6—C7—H7	119.00
C10—N6—H6C	120.00	C9—C8—H8	119.00
H6B—N6—H6C	120.00	N5—C8—H8	119.00
O3—Zn1—O1—C5	−92.4 (4)	Zn1—O2—C10—N6	170.5 (4)
N1—Zn1—O1—C5	0.9 (4)	Zn1—O2—C10—C9	−8.1 (6)
N4—Zn1—O1—C5	89.2 (4)	Zn1—N1—C4—C5	−2.1 (6)
N5i—Zn1—O1—C5	178.1 (4)	C1—N1—C4—C3	−1.8 (8)
O3—Zn1—O2—C10	−171.7 (4)	C4—N1—C1—C2	3.0 (9)
N1—Zn1—O2—C10	93.4 (4)	Zn1—N1—C4—C3	176.1 (4)
N4—Zn1—O2—C10	6.2 (4)	Zn1—N1—C1—C2	−174.5 (5)
N5i—Zn1—O2—C10	−81.7 (4)	C1—N1—C4—C5	−180.0 (5)
O1—Zn1—N1—C1	178.4 (6)	C2—N2—C3—C4	1.9 (10)
O2—Zn1—N1—C1	5.4 (6)	C3—N2—C2—C1	−0.8 (10)
O3—Zn1—N1—C1	−84.9 (5)	Zn1—N4—C9—C8	−179.9 (4)
N4—Zn1—N1—C1	81.1 (5)	Zn1—N4—C6—C7	−178.8 (5)
O1—Zn1—N1—C4	0.8 (4)	C6—N4—C9—C10	−180.0 (5)
O2—Zn1—N1—C4	−172.3 (4)	Zn1—N4—C9—C10	0.3 (6)
O3—Zn1—N1—C4	97.5 (4)	C6—N4—C9—C8	−0.1 (8)
N4—Zn1—N1—C4	−96.5 (4)	C9—N4—C6—C7	1.6 (9)
O1—Zn1—N4—C6	−0.4 (5)	C8—N5—C7—C6	1.0 (9)
O2—Zn1—N4—C6	177.3 (6)	Zn1viii—N5—C7—C6	177.2 (5)
N1—Zn1—N4—C6	76.0 (5)	Zn1viii—N5—C8—C9	−175.8 (4)
N5i—Zn1—N4—C6	−86.7 (5)	C7—N5—C8—C9	0.4 (8)
O1—Zn1—N4—C9	179.3 (4)	N1—C1—C2—N2	−1.7 (11)
O2—Zn1—N4—C9	−3.0 (4)	N2—C3—C4—C5	177.3 (6)
N1—Zn1—N4—C9	−104.3 (4)	N2—C3—C4—N1	−0.7 (9)
N5i—Zn1—N4—C9	93.0 (4)	N1—C4—C5—N3	−178.8 (5)
O1viii—Zn1viii—N5—C7	14.9 (5)	N1—C4—C5—O1	3.0 (7)
O2viii—Zn1viii—N5—C7	−158.1 (5)	C3—C4—C5—N3	3.2 (9)
O3viii—Zn1viii—N5—C7	112.6 (5)	C3—C4—C5—O1	−175.1 (5)
N4viii—Zn1viii—N5—C7	−82.2 (5)	N4—C6—C7—N5	−2.1 (10)
O1viii—Zn1viii—N5—C8	−169.1 (4)	N5—C8—C9—N4	−0.9 (8)
O2viii—Zn1viii—N5—C8	17.9 (4)	N5—C8—C9—C10	178.9 (5)
O3viii—Zn1viii—N5—C8	−71.4 (4)	N4—C9—C10—O2	5.0 (7)
N4viii—Zn1viii—N5—C8	93.8 (4)	C8—C9—C10—N6	6.5 (8)
Zn1—O1—C5—N3	179.4 (4)	N4—C9—C10—N6	−173.6 (5)
Zn1—O1—C5—C4	−2.3 (6)	C8—C9—C10—O2	−174.9 (5)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3B···O8ii	0.76 (7)	2.05 (7)	2.810 (8)	177 (7)
O3—H3C···O4	0.75 (6)	2.06 (7)	2.781 (8)	162 (9)
N3—H3D···O3ii	0.86	2.50	3.193 (8)	138
N3—H3D···O5ii	0.86	2.42	3.163 (8)	144
N3—H3E···O7	0.86	2.08	2.937 (8)	172
N6—H6B···O4ix	0.86	2.07	2.913 (7)	166
N6—H6C···O5iii	0.86	2.41	3.231 (8)	161
C1—H1···O8x	0.93	2.39	3.292 (8)	162
C3—H3···O7	0.93	2.31	3.227 (8)	169
C6—H6···O6xi	0.93	2.60	3.295 (8)	132
C7—H7···O5xi	0.93	2.49	3.362 (8)	156
C8—H8···O4ix	0.93	2.39	3.298 (7)	167

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