catena-Poly[zinc-tris­(μ-dimethyl­carbamato-κ2O:O′)-zinc-μ-(2-phenyl­benzimidazolido-κ2N:N′]

Rodriguez, M.A.; Sava, D.F.; Nenoff, T.M.

doi:10.1107/S1600536811053177

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 1| January 2012| Pages m59-m60

doi:10.1107/S1600536811053177

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catena-Poly[zinc-tris(μ-dimethylcarbamato-κ²O:O′)-zinc-μ-(2-phenylbenzimidazolido-κ²N:N′]

Mark A. Rodriguez,^a ^* Dorina F. Sava ^b and Tina M. Nenoff ^b

^aPO Box 5800, MS 1411, Sandia National Laboratories, Albuquerque, NM 87185, USA, and ^bPO Box 5800, MS 1415, Sandia National Laboratories, Albuquerque, NM 87185, USA
^*Correspondence e-mail: marodri@sandia.gov

(Received 3 November 2011; accepted 9 December 2011; online 17 December 2011)

The crystal structure of the title compound, [Zn₂(C₁₃H₉N₂)(C₃H₆NO₂)₃]_n, displays a long chiral chain. This is composed of zinc-dimer clusters capped by dimethylcarbamate ligands, which lie on crystallographic twofold rotation axes and are polymerically linked in one dimension by 2-phenylbenzimidadole (2–PBImi) organic ligands. The two Zn²⁺ ions defining the dimetal cluster are crystallographically independent, but display very similar coordination modes and tetrahedral geometry. As such, each Zn²⁺ ion is coordinated on one side by the N-donor imidazole linker, while the other three available coordination sites are fully occupied by the O atoms from the capping dimethylcarbamates. The chirality of the chain extends along the c axis, generating a rather long 52.470 (11) Å cell axis. Interestingly, the chiral material crystallizes from completely achiral precursors. A twofold axis and 3₁ screw axis serve to generate the long asymmetric unit.

Related literature

For the structure of another zinc–adeninate compound, see: An et al. (2009 ). This structure, formed with adenine, contains a similar but not identical ligand as that of the 2-PBImi molecule. Interestingly, this Zn-adeninate structure also displays the presence of dimethylcarbamate, but in the case of the zinc-adeninate it is not a bridging molecule between Zn²⁺ cations, but is terminally tethered to the Zn²⁺ ions. The dimethylcarbamate capping molecules formed in situ during the synthesis; there is precedence for such in situ reactions (An et al. 2009; Dell'Amico et al. 2003 ).

Experimental

Crystal data

[Zn₂(C₁₃H₉N₂)(C₃H₆NO₂)₃]
M_r = 588.23
Trigonal, P 3₁ 21
a = 9.0521 (13) Å
c = 52.470 (11) Å
V = 3723.4 (11) Å³
Z = 6
Mo Kα radiation
μ = 1.98 mm⁻¹
T = 188 K
0.20 × 0.19 × 0.15 mm

Data collection

Bruker APEX CCD diffractometer
Absorption correction: numerical (SADABS; Sheldrick, 1996 ) T_min = 0.681, T_max = 0.742
26966 measured reflections
4386 independent reflections
4132 reflections with I > 2σ(I)
R_int = 0.044

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.059
S = 1.09
4386 reflections
333 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.24 e Å⁻³
Absolute structure: Flack (1983 ), 1754 Friedel pairs
Flack parameter: 0.011 (12)

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: XSHELL (Bruker, 2007) and Mercury (Macrae et al., 2008 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811053177/nk2124sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811053177/nk2124Isup2.hkl

checkCIF report

Comment top

This manuscript documents possibly the first reported structure of the linker 2-phenylbenzimidazole (2–PBImi), as well as a coordination polymer derived from this molecule. The 2-PBImi molecule was investigated as a possible linker molecule for the synthesis of metal-organic framworks (MOFs). As a result of this research, the title compound was observed. This polymeric chain structure is derived from two tetrahedral metal centers that are capped by three dimethylcarbamates, resulting in a very rare (novel) molecular building block (MBB). There are a few published examples that display similar environments (see An, et al., 2009), but none display identical coodination. The dimethylcarbamate capping molecules formed in situ during the synthesis; there is precedence for such in situ reactions (An, et al. 2009; Dell'Amico, et al. 2003).

Figure 1 shows the MBB for the chain. A cluster composed of two Zn cations bridged by three dimethylcarbamate molecules is bracketed on either side by 2-PBImi linkers to complete the tetrahedrally coordinated Zn1 cations. A twofold axis (coincident with the a axis direction) is also shown to illustrate how the atoms in the MBB are related by symmetry. Atoms with asterisks indicate symmetry equivalent atoms within the MBB. Zn2 is also shown extending from the 2-PBImi molecule. The Zn2 metal center also binds to a second set of three dimethylcarbamate molecules. This is illustrated in Figure 2. The second set of dimethylcarbamates, which bridge the Zn2 metal center, are crystallographically unique but structurally similar to those bound to Zn1 (asterisks indicate symmetry equivalent atoms). Figure 3 shows a ball and stick representation of an individual polymer chain to illustrate the chiral behavior of the molecule. The chain propagates along the c axis direction. The observation of chirality (the compound crystallizes in the space group P3₁21) is interesting because the structure crystallized from achiral precursors Zn(CH₃COO₂)₂^.2H₂O and 2–PBImi. Presumably the sample crystallizes as a equal fraction mixture of P3₁21 and P3₂21 symmetry.

The structure is charge-neutral. The metal to 2-PBImi ligand ratio is 2:1 because each 2-PBImi ligand is shared by the two zinc cations. Therefore, each MBB requires an additional 3- for charge balance. This is accomodated by the three dimethylcarbamate anionic molecules which cap the metals. The structure repeats itself every sixth zinc cluster, resulting in the long 52.470 (11) Å c axis.

Related literature top

For the structure of another zinc–adeninate compound, see: An et al. (2009). This structure, formed with adenine, contains a similar but not identical ligand as that of the 2-PBImi molecule. Interestingly, this Zn-adeninate structure also displays the presence of dimethylcarbamate, but in the case of the zinc-adeninate it is not a bridging molecule between Zn metal atoms, but is terminally tethered to the Zn cations. The dimethylcarbamate capping molecules formed in situ during the synthesis; there is precedence for such in situ reactions (An, et al. 2009; Dell'Amico, et al. 2003).

Experimental top

The reaction mixture containing Zn(CH₃COO₂)₂^.2H₂O (0.008 g, 0.0436 mmol) and 2–PBImi (2-phenylbenzimidazole, 0.066 g, 0.3398 mmol) in 3 mL of N,N'-dimethylformamide (DMF) was placed in a convection oven at 115° C for 72 h inside capped scintillation vials. The capped vials were removed from the oven, and allowed to stand at room temperature over a period of approximately two weeks, after which time pale yellow block-shaped crystals formed.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: XSHELL (Bruker, 2007) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the molecular building block (MBB) for the title compound, with labels and 50% probability displacement ellipsoids for non-H atoms. A twofold rotation axis extends through the polymeric chain parallel to the N4—C14 bond (and coincident with the a axis) and relates atoms by symmetry. For clarity of the MBB, dimethylcarbamate molecules attached to the Zn2 metal center have been removed. Atom labels containing asterisks indicate symmetry equivalent atoms.
	Fig. 2. Capped stick image of the entire asymmetric unit for the title compound. This plot shows the second set of demethylcarbamate molecules which coordinate to the Zn2 atom. Atom labels containing asterisks indicate symmetry equivalent atoms.
	Fig. 3. A ball-and-stick representation of a single chiral chain for the title compound. The chain propagates in the c axis direction.

catena-Poly[zinc-tris(µ-dimethylcarbamato-κ²O:O')- zinc-µ-(2-phenylbenzimidazolido-κ²N:N'] top

Crystal data top

[Zn₂(C₁₃H₉N₂)(C₃H₆NO₂)₃]	D_x = 1.574 Mg m⁻³
M_r = 588.23	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P3₁21	Cell parameters from 200 reflections
Hall symbol: P 31 2"	θ = 1–25.0°
a = 9.0521 (13) Å	µ = 1.98 mm⁻¹
c = 52.470 (11) Å	T = 188 K
V = 3723.4 (11) Å³	Prism, colourless
Z = 6	0.20 × 0.19 × 0.15 mm
F(000) = 1812

Data collection top

Bruker APEX CCD diffractometer	4386 independent reflections
Radiation source: fine-focus sealed tube	4132 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.3°
Absorption correction: numerical (SADABS; Sheldrick, 1996)	h = −10→10
T_min = 0.681, T_max = 0.742	k = −10→10
26966 measured reflections	l = −62→62

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.029	H-atom parameters constrained
wR(F²) = 0.059	w = 1/[σ²(F_o²) + (0.0139P)² + 2.9151P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max = 0.001
4386 reflections	Δρ_max = 0.25 e Å⁻³
333 parameters	Δρ_min = −0.24 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1754 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.011 (12)

Crystal data top

[Zn₂(C₁₃H₉N₂)(C₃H₆NO₂)₃]	Z = 6
M_r = 588.23	Mo Kα radiation
Trigonal, P3₁21	µ = 1.98 mm⁻¹
a = 9.0521 (13) Å	T = 188 K
c = 52.470 (11) Å	0.20 × 0.19 × 0.15 mm
V = 3723.4 (11) Å³

Data collection top

Bruker APEX CCD diffractometer	4386 independent reflections
Absorption correction: numerical (SADABS; Sheldrick, 1996)	4132 reflections with I > 2σ(I)
T_min = 0.681, T_max = 0.742	R_int = 0.044
26966 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	H-atom parameters constrained
wR(F²) = 0.059	Δρ_max = 0.25 e Å⁻³
S = 1.09	Δρ_min = −0.24 e Å⁻³
4386 reflections	Absolute structure: Flack (1983), 1754 Friedel pairs
333 parameters	Absolute structure parameter: 0.011 (12)
0 restraints

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	0.61691 (5)	0.56462 (5)	0.031021 (7)	0.02259 (10)
Zn2	0.88114 (5)	0.62957 (5)	0.139747 (7)	0.02319 (10)
O1	0.5750 (3)	0.3622 (3)	0.01178 (4)	0.0358 (6)
O2	0.8274 (3)	0.7528 (3)	0.01830 (4)	0.0354 (6)
O3	0.5961 (3)	0.4199 (3)	−0.03014 (4)	0.0338 (6)
O4	0.7517 (3)	0.4560 (3)	0.16515 (4)	0.0436 (7)
O5	0.9058 (3)	0.5436 (3)	0.20106 (4)	0.0392 (7)
O6	0.8978 (4)	0.8375 (3)	0.15205 (5)	0.0457 (8)
N1	0.6497 (3)	0.5170 (3)	0.06693 (4)	0.0211 (6)
N2	0.7528 (3)	0.5425 (3)	0.10704 (5)	0.0213 (6)
N3	0.5940 (4)	0.1848 (4)	−0.01588 (5)	0.0345 (8)
N4	1.0043 (5)	1.0043 (5)	0.0000	0.0365 (11)
N5	0.6591 (4)	0.2963 (4)	0.20013 (5)	0.0329 (7)
N6	1.0000	1.1032 (5)	0.1667	0.0411 (12)
C1	0.7521 (5)	0.8882 (5)	0.07206 (7)	0.0370 (9)
H1	0.6428	0.8215	0.0655	0.042 (11)*
C2	0.8316 (6)	1.0654 (5)	0.07046 (8)	0.0474 (11)
H2	0.7766	1.1172	0.0627	0.042 (10)*
C3	0.9932 (6)	1.1629 (5)	0.08049 (9)	0.0562 (12)
H3	1.0462	1.2813	0.0798	0.051 (11)*
C4	1.0773 (6)	1.0865 (5)	0.09152 (7)	0.0464 (11)
H4	1.1870	1.1536	0.0979	0.053 (13)*
C5	0.9985 (5)	0.9104 (5)	0.09305 (6)	0.0338 (9)
H5	1.0550	0.8595	0.1005	0.029 (10)*
C6	0.8346 (5)	0.8100 (4)	0.08340 (6)	0.0252 (7)
C7	0.7473 (4)	0.6227 (4)	0.08569 (6)	0.0220 (7)
C8	0.6498 (4)	0.3696 (4)	0.10177 (6)	0.0229 (7)
C9	0.6048 (5)	0.2254 (5)	0.11655 (6)	0.0317 (8)
H9	0.6466	0.2351	0.1330	0.055 (12)*
C10	0.4971 (5)	0.0683 (5)	0.10609 (7)	0.0403 (10)
H10	0.4649	−0.0295	0.1157	0.041 (11)*
C11	0.4348 (5)	0.0531 (5)	0.08119 (7)	0.0391 (9)
H11	0.3630	−0.0549	0.0745	0.030 (9)*
C12	0.4772 (5)	0.1935 (4)	0.06647 (7)	0.0320 (9)
H12	0.4346	0.1824	0.0500	0.030 (9)*
C13	0.5861 (4)	0.3535 (4)	0.07689 (6)	0.0240 (7)
C14	0.8556 (5)	0.8556 (5)	0.0000	0.0238 (11)
C15	1.1260 (5)	1.0518 (6)	0.02054 (7)	0.0562 (13)
H15A	1.0726	0.9779	0.0349	0.084*
H15B	1.1649	1.1677	0.0254	0.084*
H15C	1.2213	1.0412	0.0150	0.084*
C16	0.5881 (4)	0.3284 (4)	−0.01132 (6)	0.0274 (8)
C17	0.5966 (6)	0.1272 (6)	−0.04163 (7)	0.0547 (13)
H17A	0.5995	0.2086	−0.0536	0.082*
H17B	0.4961	0.0186	−0.0444	0.082*
H17C	0.6960	0.1162	−0.0438	0.082*
C18	0.5903 (7)	0.0760 (6)	0.00490 (8)	0.0587 (13)
H18A	0.6551	0.1457	0.0190	0.088*
H18B	0.6388	0.0086	−0.0008	0.088*
H18C	0.4744	0.0021	0.0101	0.088*
C19	0.7772 (4)	0.4385 (4)	0.18828 (6)	0.0234 (7)
C20	0.5019 (5)	0.1739 (6)	0.18801 (8)	0.0565 (13)
H20A	0.4878	0.2209	0.1724	0.085*
H20B	0.4078	0.1475	0.1992	0.085*
H20C	0.5053	0.0717	0.1844	0.085*
C21	0.6793 (6)	0.2625 (6)	0.22652 (8)	0.0561 (12)
H21A	0.7903	0.3467	0.2324	0.084*
H21B	0.6671	0.1512	0.2279	0.084*
H21C	0.5936	0.2672	0.2367	0.084*
C22	1.0000	0.9526 (5)	0.1667	0.0290 (12)
C23	0.8890 (7)	1.1336 (6)	0.15050 (9)	0.0641 (14)
H23A	0.8378	1.0447	0.1380	0.096*
H23B	0.9541	1.2417	0.1421	0.096*
H23C	0.8013	1.1346	0.1607	0.096*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0257 (2)	0.0255 (2)	0.01562 (18)	0.01208 (19)	−0.00268 (16)	0.00245 (17)
Zn2	0.0258 (2)	0.0255 (2)	0.01727 (18)	0.01204 (18)	−0.00601 (17)	−0.00255 (17)
O1	0.0619 (18)	0.0346 (15)	0.0162 (12)	0.0280 (14)	−0.0006 (12)	−0.0010 (11)
O2	0.0279 (14)	0.0389 (16)	0.0295 (13)	0.0093 (13)	0.0012 (11)	0.0153 (12)
O3	0.0531 (18)	0.0337 (14)	0.0236 (13)	0.0285 (13)	0.0013 (12)	0.0060 (11)
O4	0.0392 (16)	0.0460 (17)	0.0177 (13)	0.0003 (13)	−0.0042 (11)	0.0034 (12)
O5	0.0289 (14)	0.0438 (17)	0.0234 (13)	0.0020 (13)	−0.0076 (11)	0.0032 (12)
O6	0.065 (2)	0.0420 (17)	0.0432 (16)	0.0371 (16)	−0.0322 (15)	−0.0236 (13)
N1	0.0237 (15)	0.0214 (15)	0.0150 (12)	0.0089 (12)	−0.0049 (11)	0.0008 (11)
N2	0.0255 (15)	0.0233 (16)	0.0140 (13)	0.0114 (13)	−0.0020 (11)	0.0008 (11)
N3	0.053 (2)	0.0324 (18)	0.0274 (16)	0.0284 (17)	−0.0003 (14)	0.0015 (14)
N4	0.0324 (18)	0.0324 (18)	0.027 (2)	0.003 (2)	−0.0074 (11)	0.0074 (11)
N5	0.0287 (18)	0.0302 (18)	0.0310 (17)	0.0083 (15)	0.0013 (13)	0.0035 (14)
N6	0.048 (3)	0.0290 (18)	0.053 (3)	0.0238 (15)	−0.019 (2)	−0.0094 (12)
C1	0.038 (2)	0.034 (2)	0.039 (2)	0.0182 (19)	−0.0060 (19)	0.0007 (18)
C2	0.056 (3)	0.033 (2)	0.056 (3)	0.024 (2)	−0.008 (2)	0.005 (2)
C3	0.069 (3)	0.018 (2)	0.073 (3)	0.015 (2)	−0.009 (3)	0.001 (2)
C4	0.047 (3)	0.032 (2)	0.042 (2)	0.006 (2)	−0.011 (2)	−0.003 (2)
C5	0.036 (2)	0.031 (2)	0.0310 (19)	0.0140 (19)	−0.0028 (17)	0.0045 (17)
C6	0.032 (2)	0.0218 (18)	0.0216 (16)	0.0135 (16)	−0.0013 (15)	−0.0028 (15)
C7	0.0218 (17)	0.0267 (19)	0.0179 (15)	0.0124 (16)	−0.0007 (13)	−0.0016 (15)
C8	0.0258 (18)	0.0242 (19)	0.0212 (17)	0.0143 (16)	−0.0003 (14)	0.0013 (14)
C9	0.043 (2)	0.033 (2)	0.0199 (17)	0.0193 (19)	−0.0058 (16)	0.0012 (16)
C10	0.058 (3)	0.026 (2)	0.031 (2)	0.017 (2)	0.0017 (18)	0.0065 (17)
C11	0.042 (2)	0.027 (2)	0.037 (2)	0.0088 (19)	−0.005 (2)	−0.0027 (18)
C12	0.035 (2)	0.025 (2)	0.0264 (19)	0.0077 (17)	−0.0073 (16)	−0.0012 (15)
C13	0.0241 (18)	0.0249 (19)	0.0170 (16)	0.0077 (16)	−0.0013 (14)	0.0007 (14)
C14	0.026 (2)	0.026 (2)	0.023 (2)	0.015 (2)	0.0012 (10)	−0.0012 (10)
C15	0.034 (3)	0.065 (3)	0.039 (2)	0.001 (2)	−0.012 (2)	0.006 (2)
C16	0.025 (2)	0.026 (2)	0.0276 (19)	0.0097 (17)	0.0011 (15)	0.0037 (15)
C17	0.089 (4)	0.061 (3)	0.031 (2)	0.051 (3)	−0.005 (2)	−0.011 (2)
C18	0.101 (4)	0.050 (3)	0.046 (3)	0.054 (3)	0.015 (3)	0.013 (2)
C19	0.0269 (19)	0.0233 (18)	0.0231 (18)	0.0150 (17)	0.0023 (15)	0.0000 (15)
C20	0.041 (3)	0.044 (3)	0.049 (3)	−0.006 (2)	0.006 (2)	0.000 (2)
C21	0.054 (3)	0.066 (3)	0.047 (3)	0.029 (3)	0.008 (2)	0.028 (2)
C22	0.025 (3)	0.022 (2)	0.040 (3)	0.0127 (14)	−0.002 (2)	−0.0010 (12)
C23	0.098 (4)	0.066 (3)	0.060 (3)	0.065 (3)	−0.026 (3)	−0.016 (3)

Geometric parameters (Å, º) top

Zn1—O2	1.932 (2)	C3—C4	1.386 (6)
Zn1—O3ⁱ	1.942 (2)	C3—H3	0.9300
Zn1—O1	1.956 (2)	C4—C5	1.385 (5)
Zn1—N1	1.988 (2)	C4—H4	0.9300
Zn2—O6	1.923 (3)	C5—C6	1.391 (5)
Zn2—O5ⁱⁱ	1.933 (2)	C5—H5	0.9300
Zn2—O4	1.944 (2)	C6—C7	1.474 (4)
Zn2—N2	2.000 (3)	C8—C9	1.393 (5)
O1—C16	1.270 (4)	C8—C13	1.405 (4)
O2—C14	1.271 (3)	C9—C10	1.374 (5)
O3—C16	1.267 (4)	C9—H9	0.9300
O3—Zn1ⁱ	1.942 (2)	C10—C11	1.402 (5)
O4—C19	1.260 (4)	C10—H10	0.9300
O5—C19	1.266 (4)	C11—C12	1.368 (5)
O5—Zn2ⁱⁱ	1.933 (2)	C11—H11	0.9300
O6—C22	1.251 (3)	C12—C13	1.393 (5)
N1—C7	1.349 (4)	C12—H12	0.9300
N1—C13	1.394 (4)	C14—O2ⁱ	1.271 (3)
N2—C7	1.349 (4)	C15—H15A	0.9600
N2—C8	1.391 (4)	C15—H15B	0.9600
N3—C16	1.349 (4)	C15—H15C	0.9600
N3—C17	1.452 (4)	C17—H17A	0.9600
N3—C18	1.458 (5)	C17—H17B	0.9600
N4—C14	1.346 (6)	C17—H17C	0.9600
N4—C15ⁱ	1.444 (4)	C18—H18A	0.9600
N4—C15	1.445 (4)	C18—H18B	0.9600
N5—C19	1.346 (4)	C18—H18C	0.9600
N5—C20	1.443 (5)	C20—H20A	0.9600
N5—C21	1.450 (5)	C20—H20B	0.9600
N6—C22	1.363 (6)	C20—H20C	0.9600
N6—C23ⁱⁱ	1.442 (5)	C21—H21A	0.9600
N6—C23	1.442 (5)	C21—H21B	0.9600
C1—C6	1.393 (5)	C21—H21C	0.9600
C1—C2	1.394 (5)	C22—O6ⁱⁱ	1.251 (3)
C1—H1	0.9300	C23—H23A	0.9600
C2—C3	1.380 (6)	C23—H23B	0.9600
C2—H2	0.9300	C23—H23C	0.9600

O2—Zn1—O3ⁱ	115.83 (11)	C8—C9—H9	121.0
O2—Zn1—O1	106.95 (11)	C9—C10—C11	121.1 (3)
O3ⁱ—Zn1—O1	111.27 (11)	C9—C10—H10	119.4
O2—Zn1—N1	109.29 (10)	C11—C10—H10	119.4
O3ⁱ—Zn1—N1	107.59 (10)	C12—C11—C10	121.5 (4)
O1—Zn1—N1	105.43 (10)	C12—C11—H11	119.2
O6—Zn2—O5ⁱⁱ	116.22 (13)	C10—C11—H11	119.2
O6—Zn2—O4	106.34 (12)	C11—C12—C13	117.9 (3)
O5ⁱⁱ—Zn2—O4	110.93 (12)	C11—C12—H12	121.0
O6—Zn2—N2	114.79 (11)	C13—C12—H12	121.0
O5ⁱⁱ—Zn2—N2	102.32 (10)	C12—C13—N1	131.2 (3)
O4—Zn2—N2	105.86 (11)	C12—C13—C8	120.9 (3)
C16—O1—Zn1	136.1 (2)	N1—C13—C8	107.9 (3)
C14—O2—Zn1	130.9 (2)	O2—C14—O2ⁱ	124.4 (4)
C16—O3—Zn1ⁱ	129.2 (2)	O2—C14—N4	117.8 (2)
C19—O4—Zn2	133.4 (2)	O2ⁱ—C14—N4	117.8 (2)
C19—O5—Zn2ⁱⁱ	135.6 (2)	N4—C15—H15A	109.5
C22—O6—Zn2	133.2 (3)	N4—C15—H15B	109.5
C7—N1—C13	104.8 (2)	H15A—C15—H15B	109.5
C7—N1—Zn1	130.8 (2)	N4—C15—H15C	109.5
C13—N1—Zn1	123.9 (2)	H15A—C15—H15C	109.5
C7—N2—C8	104.8 (3)	H15B—C15—H15C	109.5
C7—N2—Zn2	132.1 (2)	O3—C16—O1	124.6 (3)
C8—N2—Zn2	123.0 (2)	O3—C16—N3	118.3 (3)
C16—N3—C17	121.8 (3)	O1—C16—N3	117.1 (3)
C16—N3—C18	121.3 (3)	N3—C17—H17A	109.5
C17—N3—C18	116.9 (3)	N3—C17—H17B	109.5
C14—N4—C15ⁱ	122.0 (2)	H17A—C17—H17B	109.5
C14—N4—C15	122.0 (2)	N3—C17—H17C	109.5
C15ⁱ—N4—C15	116.0 (5)	H17A—C17—H17C	109.5
C19—N5—C20	122.6 (3)	H17B—C17—H17C	109.5
C19—N5—C21	121.3 (3)	N3—C18—H18A	109.5
C20—N5—C21	116.0 (3)	N3—C18—H18B	109.5
C22—N6—C23ⁱⁱ	122.6 (2)	H18A—C18—H18B	109.5
C22—N6—C23	122.6 (2)	N3—C18—H18C	109.5
C23ⁱⁱ—N6—C23	114.8 (5)	H18A—C18—H18C	109.5
C6—C1—C2	120.7 (4)	H18B—C18—H18C	109.5
C6—C1—H1	119.6	O4—C19—O5	125.0 (3)
C2—C1—H1	119.6	O4—C19—N5	117.2 (3)
C3—C2—C1	119.0 (4)	O5—C19—N5	117.8 (3)
C3—C2—H2	120.5	N5—C20—H20A	109.5
C1—C2—H2	120.5	N5—C20—H20B	109.5
C2—C3—C4	120.7 (4)	H20A—C20—H20B	109.5
C2—C3—H3	119.6	N5—C20—H20C	109.5
C4—C3—H3	119.6	H20A—C20—H20C	109.5
C5—C4—C3	120.2 (4)	H20B—C20—H20C	109.5
C5—C4—H4	119.9	N5—C21—H21A	109.5
C3—C4—H4	119.9	N5—C21—H21B	109.5
C4—C5—C6	119.9 (4)	H21A—C21—H21B	109.5
C4—C5—H5	120.0	N5—C21—H21C	109.5
C6—C5—H5	120.0	H21A—C21—H21C	109.5
C5—C6—C1	119.4 (3)	H21B—C21—H21C	109.5
C5—C6—C7	120.3 (3)	O6—C22—O6ⁱⁱ	124.9 (5)
C1—C6—C7	120.3 (3)	O6—C22—N6	117.6 (2)
N1—C7—N2	114.3 (3)	O6ⁱⁱ—C22—N6	117.6 (2)
N1—C7—C6	122.7 (3)	N6—C23—H23A	109.5
N2—C7—C6	122.9 (3)	N6—C23—H23B	109.5
N2—C8—C9	131.4 (3)	H23A—C23—H23B	109.5
N2—C8—C13	108.1 (3)	N6—C23—H23C	109.5
C9—C8—C13	120.5 (3)	H23A—C23—H23C	109.5
C10—C9—C8	118.1 (3)	H23B—C23—H23C	109.5
C10—C9—H9	121.0

O2—Zn1—O1—C16	−41.4 (4)	C7—N2—C8—C13	0.2 (4)
O3ⁱ—Zn1—O1—C16	86.0 (4)	Zn2—N2—C8—C13	−177.1 (2)
N1—Zn1—O1—C16	−157.7 (3)	N2—C8—C9—C10	179.2 (3)
O3ⁱ—Zn1—O2—C14	−36.3 (3)	C13—C8—C9—C10	−0.1 (5)
O1—Zn1—O2—C14	88.3 (3)	C8—C9—C10—C11	0.4 (6)
N1—Zn1—O2—C14	−158.0 (2)	C9—C10—C11—C12	−0.7 (6)
O6—Zn2—O4—C19	−62.3 (4)	C10—C11—C12—C13	0.5 (6)
O5ⁱⁱ—Zn2—O4—C19	64.9 (4)	C11—C12—C13—N1	−179.2 (4)
N2—Zn2—O4—C19	175.1 (3)	C11—C12—C13—C8	−0.2 (5)
O5ⁱⁱ—Zn2—O6—C22	−37.6 (3)	C7—N1—C13—C12	179.3 (4)
O4—Zn2—O6—C22	86.4 (3)	Zn1—N1—C13—C12	−7.3 (6)
N2—Zn2—O6—C22	−156.9 (3)	C7—N1—C13—C8	0.2 (4)
O2—Zn1—N1—C7	33.4 (3)	Zn1—N1—C13—C8	173.6 (2)
O3ⁱ—Zn1—N1—C7	−93.2 (3)	N2—C8—C13—C12	−179.5 (3)
O1—Zn1—N1—C7	148.0 (3)	C9—C8—C13—C12	−0.1 (5)
O2—Zn1—N1—C13	−138.1 (3)	N2—C8—C13—N1	−0.3 (4)
O3ⁱ—Zn1—N1—C13	95.4 (3)	C9—C8—C13—N1	179.2 (3)
O1—Zn1—N1—C13	−23.5 (3)	Zn1—O2—C14—O2ⁱ	−19.90 (16)
O6—Zn2—N2—C7	39.0 (3)	Zn1—O2—C14—N4	160.10 (16)
O5ⁱⁱ—Zn2—N2—C7	−87.8 (3)	C15ⁱ—N4—C14—O2	177.0 (3)
O4—Zn2—N2—C7	156.0 (3)	C15—N4—C14—O2	−3.0 (3)
O6—Zn2—N2—C8	−144.5 (2)	C15ⁱ—N4—C14—O2ⁱ	−3.0 (3)
O5ⁱⁱ—Zn2—N2—C8	88.7 (3)	C15—N4—C14—O2ⁱ	177.0 (3)
O4—Zn2—N2—C8	−27.5 (3)	Zn1ⁱ—O3—C16—O1	−8.1 (5)
C6—C1—C2—C3	−0.6 (6)	Zn1ⁱ—O3—C16—N3	172.0 (2)
C1—C2—C3—C4	1.4 (7)	Zn1—O1—C16—O3	−18.9 (6)
C2—C3—C4—C5	−1.2 (7)	Zn1—O1—C16—N3	161.0 (3)
C3—C4—C5—C6	0.2 (6)	C17—N3—C16—O3	−4.6 (6)
C4—C5—C6—C1	0.6 (5)	C18—N3—C16—O3	178.3 (4)
C4—C5—C6—C7	−178.0 (3)	C17—N3—C16—O1	175.5 (4)
C2—C1—C6—C5	−0.4 (6)	C18—N3—C16—O1	−1.7 (6)
C2—C1—C6—C7	178.2 (3)	Zn2—O4—C19—O5	1.1 (6)
C13—N1—C7—N2	−0.1 (4)	Zn2—O4—C19—N5	−178.3 (3)
Zn1—N1—C7—N2	−172.8 (2)	Zn2ⁱⁱ—O5—C19—O4	−7.3 (6)
C13—N1—C7—C6	−177.6 (3)	Zn2ⁱⁱ—O5—C19—N5	172.1 (3)
Zn1—N1—C7—C6	9.7 (5)	C20—N5—C19—O4	−5.1 (5)
C8—N2—C7—N1	0.0 (4)	C21—N5—C19—O4	178.3 (4)
Zn2—N2—C7—N1	176.9 (2)	C20—N5—C19—O5	175.5 (4)
C8—N2—C7—C6	177.5 (3)	C21—N5—C19—O5	−1.1 (5)
Zn2—N2—C7—C6	−5.6 (5)	Zn2—O6—C22—O6ⁱⁱ	−15.56 (19)
C5—C6—C7—N1	−140.8 (3)	Zn2—O6—C22—N6	164.44 (19)
C1—C6—C7—N1	40.7 (5)	C23ⁱⁱ—N6—C22—O6	179.5 (3)
C5—C6—C7—N2	41.9 (5)	C23—N6—C22—O6	−0.5 (3)
C1—C6—C7—N2	−136.6 (3)	C23ⁱⁱ—N6—C22—O6ⁱⁱ	−0.5 (3)
C7—N2—C8—C9	−179.1 (4)	C23—N6—C22—O6ⁱⁱ	179.5 (3)
Zn2—N2—C8—C9	3.6 (5)

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

Experimental details

Crystal data
Chemical formula	[Zn₂(C₁₃H₉N₂)(C₃H₆NO₂)₃]
M_r	588.23
Crystal system, space group	Trigonal, P3₁21
Temperature (K)	188
a, c (Å)	9.0521 (13), 52.470 (11)
V (Å³)	3723.4 (11)
Z	6
Radiation type	Mo Kα
µ (mm⁻¹)	1.98
Crystal size (mm)	0.20 × 0.19 × 0.15

Data collection
Diffractometer	Bruker APEX CCD diffractometer
Absorption correction	Numerical (SADABS; Sheldrick, 1996)
T_min, T_max	0.681, 0.742
No. of measured, independent and observed [I > 2σ(I)] reflections	26966, 4386, 4132
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.059, 1.09
No. of reflections	4386
No. of parameters	333
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.24
Absolute structure	Flack (1983), 1754 Friedel pairs
Absolute structure parameter	0.011 (12)

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008), XSHELL (Bruker, 2007) and Mercury (Macrae et al., 2008).

Acknowledgements

The authors thank Charles Campana of Bruker AXS, Inc. for his assistance with this structure, and Timothy J. Boyle (Sandia) for his help with the chemical scheme. This work was supported by the US DOE-NE/FCRD-SWG. Sandia is a multiprogram laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the United States Department of Energy's National Nuclear Security Administration under contract DE—AC04–94 A L85000.

References

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