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The asymmetric unit of the title compound, poly[(dimethylamine-κN)[μ3-(E)-2,6-dimethyl-4-styryl­pyridine-3,5-dicar­boxyl­ato-κ3O3:O3′:O5]zinc(II)], [Zn(C17H13NO4)(C2H7N)]n, con­sists of one crystallographically independent distorted tetrahedral ZnII cation, one (E)-2,6-dimethyl-4-styryl­pyridine-3,5-dicarboxyl­ate (mspda2−) ligand and one coordinated dimethyl­amine mol­ecule. Two S- and R-type chiral units are generated from the axially prochiral mspda2− ligand through C—H...O hydrogen bonds. The R-type chiral units assemble a left-handed (M) Zn–mspda helical chain, while the right-handed (P) Zn–mspda helical chain is constructed from neighbouring S-type chiral units. The P- and M-type helical chains are inter­linked by carboxyl­ate O atoms to form a one-dimensional ladder. Inter­chain N—H...O hydrogen bonds extend these one-dimensional ladders into a two-dimensional supra­molecular architecture. The title compound exhibits luminescence at λmax = 432 nm upon excitation at 365 nm.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112006051/em3046sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270112006051/em3046Isup2.hkl
Contains datablock I

CCDC reference: 879429

Comment top

The construction of metal–organic coordination polymers has attracted intense attention, owing to their intriguing network topologies and useful properties (gas storage, catalysis, photosensitivity, molecular recognition etc.), which are intimately related to their structures (Yaghi et al., 2003; O'Keeffe et al., 2008; Ockwig et al., 2005). Helices and atropisomeric units in metal complexes are two of the main aspects in the study of structural isomerism and, compared with the former, the latter has not been well explored (Kesanli & Lin, 2003; Han & Hong, 2005). For the structural construction of metal complexes, besides coordination bonds, secondary forces such as hydrogen-bonding and ππ stacking must also be considered.

Compared with common pyridine dicarboxylic acids (PDAs), highly substituted PDAs have not been effectively utilized in the construction of supramolecular polymers (Huang, He, Liang et al., 2007). In our previous work, 2,6-dimethyl-4-(2-thiophenyl)pyridine-3,5-dicarboxylate, 2,6-dimethyl-4-phenylpyridine-3,5-dicarboxylate and 2,6-dimethyl-4-(4-pyridinyl)pyridine-3,5-dicarboxylate were employed in the construction of luminescent metal compounds (Huang, He, Wang et al., 2007). Only a few reports exist of coordination polymers related to (E)-2,6-dimethyl-4-styrylpyridine-3,5-dicarboxylic acid (H2mspda) (Zhang et al., 2011; Huang et al., 2010). In this work, we report a new photoluminescent complex, poly[(dimethylamine-κN)[µ3-(E)-2,6-dimethyl-4-styrylpyridine-3,5-dicarboxylato]zinc(II)], (I), with a helical motif, assembled by distinct chiral units from an axially prochiral ligand through C—H···O hydrogen bonds.

The asymmetric unit of (I) contains one crystallographically independent ZnII cation, one mspda2- ligand and one coordinated dimethylamine molecule (Fig. 1). The N—H bond of the dimethylamine is confirmed by a characteristic peak (3176 cm-1) in the FT–IR spectrum of (I). It should be noted that the hydrolysis of dimethylformamide is observed in the formation of (I). Similar cases have also been discovered in some anionic metal–organic frameworks with aromatic polycarboxylates (Rosi et al., 2005; Chen et al., 2003). The geometry around atom Zn1 is a distorted tetrahedron (ZnNO3), with the four binding sites occupied by three O atoms (O1, O3 and O4) from three equivalent mspda2- ligands and one N atom (N2) from the coordinated dimethylamine molecule. All the Zn—O and Zn—N bond lengths are in agreement with those reported in other ZnII complexes of N,O-mixed ligands (Wang et al., 2007).

As shown in Fig. 1, the mspda2- anion serves as an exo-tridenate ligand and bridges three Zn atoms through atoms O1, O3 and O4, leaving the uncoordinated carboxylate O atom involved in an N2—H···O2i hydrogen bond [symmetry code: (i) x + 1, y, z]. The Zn···Zn separations over the mspda2- bridge are 8.0331 (14) and 9.134 (2) Å. The C9—C10 bond of 1.320 (4) Å is assigned as a CC double bond, with the mspda2- ligand displaying a trans conformation (E). The C6H5—CHCH dihedral angle in mspda2- is 19.76 (14)°, and that between the pyridine and phenyl rings is 68.03 (14)°. Thus, the pyridine and phenyl rings in the mspda2- ligand are not coplanar, with the major twist occuring about the C8—C9 bond (Table 1).

It is interesting that S- and R-type chiral units co-exist in the structure of (I) (Fig. 2). In the mspda2- ligand, according to the Cahn–Ingold–Prelog sequence rule (Cahn et al., 1966), atom C10 has priority over atom H9, and the two carboxylate (CO2-) groups may exist in different chemical environments within the metal complex. Thus, the mspda2- ligand is an axially prochiral ligand. In the structure of (I), one CO2- group (denoted as C17i) of the mspda2- anion is coordinated to two Zn2+ centres while the other (C1) is coordinated to only one Zn2+ centre, and thus atom C17i has priority over atom C1. In crystal engineering, C—H···O contacts are electrostatic and they occur within certain distance (C—H···O = 3.0–4.0 Å) and angle (C—H···O = 90–180°) ranges (Desiraju, 1991; Taylor & Kennard, 1982). Therefore, we believe that there are reliable C—H···O in (I) interactions because of the C9—H9···O1ii angle and the short C9···O1ii distance [Table 1; symmetry code: (ii) -x + 1, -y + 1, -z + 1]. The rotation of C6H5—CHCH around the aryl-carbon bond (C8—C9) controls the C—H···O hydrogen bonds to a certain degree. Thus, there are two types of chiral units (S and R) that co-exist in the same crystal lattice (Fig. 3).

Another interesting feature is the presence of P- and M-type helical chains comprising the S- and R-chiral units separately. It should be emphasized that the R-chiral units assemble a left-handed (M) Zn–mspda2- helical chain with a helical pitch of 9.134 Å, while the right-handed (P) Zn–mspda2- helical chain is constructed from the connection of neighbouring S-chiral units (Fig. 3). Thus, the P- and M-type helices assembled by distinct separate S- and R-chiral units are interlinked by atoms O4 to form a one-dimensional ladder. To our knowledge, such an arrangement of helical chains has rarely been reported among Zn frameworks (Yashima et al., 2008; Bishop, 2008).

The configuration of the chiral units in (I) is similar to those of atropisomeric [M(Hsmpdc)2(H2O)4].6H2O, (II) [smpdc is 2,6-dimethyl-4-(thiophen-2-yl)pyridine-3,5-dicarboxylate, M = ?; Huang, He, Liang et al., 2007), [M(H-mpypdc)(Cl)(H2O)3]n, (III) [mpypdc is 2,6-dimethyl-4-(pyridin-4-yl)pyridine-3,5-dicarboxylate, M = ?; Huang & Hu, 2007] and {Cd3(phen)3(HL)2(H2O)2.4.25H2O}n, (IV) [H4L = p-terphenyl-type 4,4'-(1,4-phenylene)bis(2,6-dimethyl-3,5-pyridine-dicarboxylic acid); Huang et al., 2009]. However, the structure of (I) is quite different from these structures. For example, (II) has an interesting hydrogen-bonded M2+(H2O)8 ionic cluster, which links the Hsmpdc ligands into a one-dimensional supramolecular motif. Compound (III) displays wave-like motifs generated from the Hmpypdc ligands. The R- and S-components composed of [M(Hmpypdc)] are arranged alternately [Please check rephrasing] in the one-dimensional coordination polymer. In complex (IV), the T-type secondary building units construct independent one-dimensional metal–organic nanotubes (MONTs) with 63 topology, containing distinct axially asymmetric [R-Cd3(HL) and S-Cd3(HL)] subunits. In (I), the construction of atropisomeric type units from axially prochiral ligands through hydrogen bonds is the major feature of interest.

Interchain hydrogen bonds between the coordinated dimethylamine molecules and mspda2- ligands [N2···O2iii; symmetry code: (i) -x + 1, -y, -z + 1] extend the one-dimensional ladders of (I) into a two-dimensional supramolecular architecture (Fig. 4).

The photoluminescent emission maximum of free H2mspda was observed at 496 nm (em). The emission spectra of (I) in the solid state at room temperature are shown in Fig. 5. Excitation at 365 nm leads to a broad fluorescent emission band at 432 nm. The distinct maximum emission wavelength indicates that the mechanism of photoluminescence can be assigned to ligand–metal charge transfer (LMCT) (Hu et al., 2010; Zhou et al., 2008).

Related literature top

For related literature, see: Bishop (2008); Cahn et al. (1966); Chen et al. (2003); Desiraju (1991); Han & Hong (2005); Hu et al. (2010); Huang & Hu (2007); Huang et al. (2009, 2010); Huang, He, Liang, Sun & Hu (2007); Huang, He, Wang, Pan & Hu (2007); Kesanli & Lin (2003); O'Keeffe et al. (2008); Ockwig et al. (2005); Rosi et al. (2005); Taylor & Kennard (1982); Wang et al. (2007); Yaghi et al. (2003); Yashima et al. (2008); Zhang et al. (2011); Zhou et al. (2008).

Experimental top

A mixture of Zn(NO3)2.6H2O (60 mg, 0.2 mmol), H2mspda (59 mg, 0.2 mmol), imidazole (14 mg, 0.2 mmol), Et3N (0.02 ml) and dimethylformamide (10 ml) was sealed in a 25 ml Teflon-lined stainless steel reactor and directly heated to 413 K for 2 d, then cooled to room temperature. The crystals were washed with methanol to yield 20 mg of (I) (yield ~25% based on the H2mspda ligand).

Refinement top

The methyl H atoms were constrained to an ideal geometry, with C—H = 0.96 Å and with Uiso(H) = 1.5Ueq(C), but were allowed to rotate freely. Other H atoms attached to C atoms were refined using a riding model, with C—H = 0.93 Å (CH) and Uiso(H) = 1.2Ueq(parent atom). The N-bound H atom was freely refined.

Computing details top

Data collection: APEX2 (Bruker, 2010); cell refinement: APEX2 (Bruker, 2010); data reduction: SAINT-Plus (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2008) and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. Part of the structure of the mspda2- ligand and ZnII centres in (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (i) x + 1, y, z; (ii) -x + 1, -y + 1, -z + 1.]
[Figure 2] Fig. 2. The absolute conformations of the chiral units comprising [Zn(mspda)]n, shown as mirror images. [Symmetry codes: (i) x + 1, y, z; (ii) -x + 1, -y + 1, -z + 1; (iii) -x + 2, -y + 1, -z + 1.]
[Figure 3] Fig. 3. View of the one-dimensional ladders comprising P- and M-type helices, which are assembled by distinct separate S- and R-atropisomeric units, with Zn2+ ions as nodes.
[Figure 4] Fig. 4. View of the two-dimensional supramolecular network of (I). Dashed lines represent N2···O2i hydrogen bonds and polyhedra the ZnNO3 groups. [Symmetry code: (i) x + 1, y, z.]
[Figure 5] Fig. 5. Photoluminescent spectra of (I) (λem at 432 nm, upon λex at 365 nm). I is relative intensity, em denotes emission and ex denotes excitation
poly[(dimethylamine-κN)[µ3-(E)-2,6-dimethyl-4- styrylpyridine-3,5-dicarboxylato- κ3O3:O3':O5]zinc(II)] top
Crystal data top
[Zn(C17H13NO4)(C2H7N)]Z = 2
Mr = 405.76F(000) = 420
Triclinic, P1Dx = 1.434 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 9.134 (2) ÅCell parameters from 1490 reflections
b = 9.694 (2) Åθ = 2.7–23.1°
c = 11.735 (3) ŵ = 1.33 mm1
α = 80.602 (4)°T = 298 K
β = 87.611 (4)°Block, orange
γ = 66.518 (4)°0.28 × 0.25 × 0.22 mm
V = 939.9 (4) Å3
Data collection top
Bruker APEXII CCD area-detector
diffractometer
3295 independent reflections
Radiation source: fine-focus sealed tube2691 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.021
ω scansθmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
h = 1010
Tmin = 0.707, Tmax = 0.758k = 911
5025 measured reflectionsl = 1312
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.091H atoms treated by a mixture of independent and constrained refinement
S = 1.07 w = 1/[σ2(Fo2) + (0.0426P)2 + 0.0029P]
where P = (Fo2 + 2Fc2)/3
3295 reflections(Δ/σ)max = 0.002
243 parametersΔρmax = 0.32 e Å3
1 restraintΔρmin = 0.31 e Å3
Crystal data top
[Zn(C17H13NO4)(C2H7N)]γ = 66.518 (4)°
Mr = 405.76V = 939.9 (4) Å3
Triclinic, P1Z = 2
a = 9.134 (2) ÅMo Kα radiation
b = 9.694 (2) ŵ = 1.33 mm1
c = 11.735 (3) ÅT = 298 K
α = 80.602 (4)°0.28 × 0.25 × 0.22 mm
β = 87.611 (4)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer
3295 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
2691 reflections with I > 2σ(I)
Tmin = 0.707, Tmax = 0.758Rint = 0.021
5025 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0391 restraint
wR(F2) = 0.091H atoms treated by a mixture of independent and constrained refinement
S = 1.07Δρmax = 0.32 e Å3
3295 reflectionsΔρmin = 0.31 e Å3
243 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
xyzUiso*/Ueq
Zn10.18549 (4)0.30228 (4)0.53051 (3)0.03462 (14)
O10.3329 (2)0.3717 (2)0.4424 (2)0.0469 (6)
O20.4374 (3)0.1398 (2)0.3973 (2)0.0484 (6)
O30.0213 (2)0.2818 (2)0.44043 (19)0.0428 (5)
O40.0823 (2)0.4697 (2)0.62438 (18)0.0395 (5)
N10.6595 (3)0.3871 (3)0.1472 (2)0.0404 (6)
N20.2617 (3)0.1183 (3)0.6545 (2)0.0424 (7)
H20.340 (3)0.051 (3)0.628 (3)0.056 (11)*
C10.4359 (3)0.2687 (3)0.3939 (3)0.0347 (7)
C20.5617 (3)0.3120 (3)0.3293 (3)0.0309 (7)
C30.5544 (4)0.3429 (3)0.2087 (3)0.0356 (7)
C40.4256 (4)0.3313 (4)0.1402 (3)0.0557 (10)
H4A0.42630.37730.06140.084*
H4B0.32370.38330.17230.084*
H4C0.44450.22600.14310.084*
C50.7741 (4)0.4051 (3)0.2036 (3)0.0349 (7)
C60.8874 (4)0.4544 (4)0.1275 (3)0.0568 (10)
H6A0.90940.40440.06070.085*
H6B0.98520.42730.16990.085*
H6C0.83980.56270.10350.085*
C70.7876 (3)0.3787 (3)0.3238 (2)0.0290 (6)
C80.6815 (3)0.3277 (3)0.3890 (3)0.0308 (7)
C90.6987 (3)0.2934 (3)0.5161 (3)0.0371 (7)
H90.70970.36730.55240.045*
C100.7005 (4)0.1702 (4)0.5844 (3)0.0427 (8)
H100.68520.09680.55010.051*
C110.7248 (4)0.1402 (4)0.7107 (3)0.0436 (8)
C120.6999 (5)0.2556 (4)0.7737 (3)0.0614 (11)
H120.66290.35590.73620.074*
C130.7288 (6)0.2248 (6)0.8909 (4)0.0839 (14)
H130.71360.30370.93180.101*
C140.7795 (6)0.0797 (6)0.9468 (4)0.0905 (15)
H140.79880.05941.02620.109*
C150.8026 (6)0.0374 (6)0.8876 (4)0.0916 (16)
H150.83710.13710.92630.110*
C160.7739 (5)0.0056 (4)0.7694 (3)0.0645 (11)
H160.78840.08480.72900.077*
C170.0831 (3)0.3990 (3)0.3845 (3)0.0331 (7)
C180.3220 (5)0.1458 (5)0.7596 (4)0.0737 (12)
H18A0.23580.21890.79520.111*
H18B0.40310.18440.73930.111*
H18C0.36640.05200.81270.111*
C190.1382 (4)0.0566 (4)0.6850 (4)0.0647 (11)
H19A0.18220.03500.74040.097*
H19B0.10330.03430.61680.097*
H19C0.04900.13050.71760.097*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0309 (2)0.0362 (2)0.0394 (2)0.01660 (15)0.00111 (15)0.00423 (16)
O10.0388 (13)0.0425 (13)0.0642 (16)0.0209 (10)0.0182 (12)0.0139 (12)
O20.0492 (14)0.0432 (13)0.0621 (16)0.0276 (11)0.0091 (12)0.0112 (12)
O30.0377 (12)0.0412 (12)0.0512 (14)0.0180 (10)0.0115 (11)0.0021 (11)
O40.0475 (13)0.0400 (12)0.0403 (13)0.0264 (10)0.0059 (10)0.0094 (10)
N10.0432 (16)0.0530 (16)0.0279 (15)0.0228 (13)0.0016 (12)0.0037 (13)
N20.0341 (15)0.0390 (16)0.0481 (18)0.0093 (12)0.0034 (13)0.0049 (14)
C10.0292 (16)0.0431 (18)0.0331 (18)0.0165 (14)0.0057 (14)0.0026 (15)
C20.0307 (16)0.0320 (15)0.0316 (17)0.0133 (13)0.0018 (13)0.0074 (13)
C30.0381 (17)0.0391 (17)0.0294 (17)0.0155 (14)0.0062 (14)0.0025 (14)
C40.056 (2)0.078 (3)0.044 (2)0.039 (2)0.0114 (18)0.0007 (19)
C50.0359 (17)0.0399 (17)0.0304 (18)0.0167 (14)0.0044 (14)0.0064 (14)
C60.060 (2)0.088 (3)0.036 (2)0.045 (2)0.0130 (18)0.010 (2)
C70.0284 (15)0.0328 (15)0.0263 (16)0.0123 (12)0.0013 (12)0.0056 (13)
C80.0337 (16)0.0304 (15)0.0302 (17)0.0142 (13)0.0024 (13)0.0065 (13)
C90.0433 (18)0.0432 (18)0.0326 (18)0.0242 (15)0.0058 (14)0.0099 (15)
C100.048 (2)0.047 (2)0.0386 (19)0.0232 (16)0.0001 (16)0.0095 (16)
C110.049 (2)0.050 (2)0.037 (2)0.0255 (16)0.0025 (16)0.0047 (16)
C120.084 (3)0.057 (2)0.041 (2)0.025 (2)0.006 (2)0.0125 (19)
C130.132 (4)0.087 (3)0.041 (3)0.050 (3)0.008 (3)0.017 (2)
C140.124 (4)0.104 (4)0.040 (3)0.044 (3)0.005 (3)0.004 (3)
C150.137 (5)0.078 (3)0.051 (3)0.038 (3)0.016 (3)0.007 (3)
C160.092 (3)0.054 (2)0.049 (2)0.032 (2)0.004 (2)0.002 (2)
C170.0299 (16)0.0465 (19)0.0275 (17)0.0197 (15)0.0109 (13)0.0092 (15)
C180.075 (3)0.077 (3)0.060 (3)0.025 (2)0.021 (2)0.005 (2)
C190.061 (2)0.059 (2)0.074 (3)0.030 (2)0.007 (2)0.004 (2)
Geometric parameters (Å, º) top
Zn1—O11.927 (2)C10—H100.9300
Zn1—O31.961 (2)C11—C161.369 (4)
Zn1—O42.004 (2)C11—C121.379 (4)
Zn1—N22.008 (3)C9—H90.9300
O2—C11.238 (3)C16—C151.383 (6)
O3—C171.255 (4)C16—H160.9300
O4—C17i1.263 (3)C6—H6A0.9600
O1—C11.265 (3)C6—H6B0.9600
N1—C31.340 (4)C6—H6C0.9600
N1—C51.344 (4)C14—C151.367 (6)
C1—C21.509 (4)C14—H140.9300
C2—C81.394 (4)C15—H150.9300
C2—C31.396 (4)C4—H4A0.9600
C8—C71.402 (4)C4—H4B0.9600
C8—C91.475 (4)C4—H4C0.9600
C17—O4i1.263 (3)C12—H120.9300
C17—C7ii1.497 (4)N2—C181.476 (5)
C7—C51.394 (4)N2—C191.480 (4)
C7—C17iii1.497 (4)N2—H20.841 (18)
C5—C61.508 (4)C19—H19A0.9600
C3—C41.502 (4)C19—H19B0.9600
C13—C141.352 (6)C19—H19C0.9600
C13—C121.372 (6)C18—H18A0.9600
C13—H130.9300C18—H18B0.9600
C10—C91.320 (4)C18—H18C0.9600
C10—C111.472 (5)
O1—Zn1—O3115.82 (10)C11—C16—C15121.3 (4)
O1—Zn1—O4101.18 (8)C11—C16—H16119.3
O3—Zn1—O4109.50 (9)C15—C16—H16119.3
O1—Zn1—N2121.58 (10)C5—C6—H6A109.5
O3—Zn1—N2105.88 (10)C5—C6—H6B109.5
O4—Zn1—N2101.31 (10)H6A—C6—H6B109.5
C17—O3—Zn1119.2 (2)C5—C6—H6C109.5
C17i—O4—Zn1131.48 (18)H6A—C6—H6C109.5
C1—O1—Zn1112.53 (18)H6B—C6—H6C109.5
C3—N1—C5118.8 (3)C13—C14—C15120.6 (4)
O2—C1—O1124.0 (3)C13—C14—H14119.7
O2—C1—C2120.6 (3)C15—C14—H14119.7
O1—C1—C2115.5 (2)C14—C15—C16119.1 (4)
C8—C2—C3119.6 (3)C14—C15—H15120.5
C8—C2—C1120.6 (3)C16—C15—H15120.5
C3—C2—C1119.8 (3)C3—C4—H4A109.5
C2—C8—C7117.5 (3)C3—C4—H4B109.5
C2—C8—C9122.5 (3)H4A—C4—H4B109.5
C7—C8—C9120.0 (3)C3—C4—H4C109.5
O3—C17—O4i123.5 (3)H4A—C4—H4C109.5
O3—C17—C7ii117.2 (3)H4B—C4—H4C109.5
O4i—C17—C7ii119.3 (3)C13—C12—C11121.1 (4)
C5—C7—C8119.5 (3)C13—C12—H12119.4
C5—C7—C17iii121.1 (2)C11—C12—H12119.4
C8—C7—C17iii119.3 (3)C18—N2—C19109.9 (3)
N1—C5—C7122.2 (3)C18—N2—Zn1113.0 (2)
N1—C5—C6115.2 (3)C19—N2—Zn1112.4 (2)
C7—C5—C6122.6 (3)C18—N2—H2106 (2)
N1—C3—C2122.3 (3)C19—N2—H2108 (2)
N1—C3—C4115.9 (3)Zn1—N2—H2107 (2)
C2—C3—C4121.8 (3)N2—C19—H19A109.5
C14—C13—C12120.0 (4)N2—C19—H19B109.5
C14—C13—H13120.0H19A—C19—H19B109.5
C12—C13—H13120.0N2—C19—H19C109.5
C9—C10—C11125.0 (3)H19A—C19—H19C109.5
C9—C10—H10117.5H19B—C19—H19C109.5
C11—C10—H10117.5N2—C18—H18A109.5
C16—C11—C12117.8 (3)N2—C18—H18B109.5
C16—C11—C10120.2 (3)H18A—C18—H18B109.5
C12—C11—C10121.9 (3)N2—C18—H18C109.5
C10—C9—C8127.7 (3)H18A—C18—H18C109.5
C10—C9—H9116.2H18B—C18—H18C109.5
C8—C9—H9116.2
O1—Zn1—O3—C1766.1 (2)C17iii—C7—C5—N1179.7 (3)
O4—Zn1—O3—C1747.4 (2)C8—C7—C5—C6177.6 (3)
N2—Zn1—O3—C17155.9 (2)C17iii—C7—C5—C60.3 (4)
O1—Zn1—O4—C17i13.4 (3)C5—N1—C3—C21.3 (4)
O3—Zn1—O4—C17i109.3 (3)C5—N1—C3—C4177.5 (3)
N2—Zn1—O4—C17i139.2 (3)C8—C2—C3—N10.2 (4)
O3—Zn1—O1—C175.7 (2)C1—C2—C3—N1177.6 (3)
O4—Zn1—O1—C1166.0 (2)C8—C2—C3—C4178.6 (3)
N2—Zn1—O1—C155.2 (2)C1—C2—C3—C41.2 (4)
Zn1—O1—C1—O23.6 (4)C9—C10—C11—C16159.5 (3)
Zn1—O1—C1—C2176.4 (2)C9—C10—C11—C1220.3 (5)
O2—C1—C2—C8107.5 (3)C11—C10—C9—C8177.3 (3)
O1—C1—C2—C872.5 (4)C2—C8—C9—C1049.1 (5)
O2—C1—C2—C375.2 (4)C7—C8—C9—C10131.2 (3)
O1—C1—C2—C3104.8 (3)C12—C11—C16—C151.9 (6)
C3—C2—C8—C71.8 (4)C10—C11—C16—C15177.9 (4)
C1—C2—C8—C7175.5 (2)C12—C13—C14—C150.1 (8)
C3—C2—C8—C9178.5 (3)C13—C14—C15—C160.2 (8)
C1—C2—C8—C94.2 (4)C11—C16—C15—C140.7 (8)
Zn1—O3—C17—O4i5.4 (4)C14—C13—C12—C111.4 (7)
Zn1—O3—C17—C7ii175.88 (17)C16—C11—C12—C132.2 (6)
C2—C8—C7—C52.8 (4)C10—C11—C12—C13177.6 (4)
C9—C8—C7—C5177.5 (3)O1—Zn1—N2—C1872.9 (3)
C2—C8—C7—C17iii179.3 (2)O3—Zn1—N2—C18152.1 (2)
C9—C8—C7—C17iii0.5 (4)O4—Zn1—N2—C1837.9 (3)
C3—N1—C5—C70.3 (4)O1—Zn1—N2—C19161.9 (2)
C3—N1—C5—C6179.7 (3)O3—Zn1—N2—C1926.9 (3)
C8—C7—C5—N11.8 (4)O4—Zn1—N2—C1987.3 (2)
Symmetry codes: (i) x, y+1, z+1; (ii) x1, y, z; (iii) x+1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O2iv0.84 (2)2.19 (2)3.010 (3)167 (3)
C9—H9···O1v0.932.413.258 (4)151
Symmetry codes: (iv) x+1, y, z+1; (v) x+1, y+1, z+1.

Experimental details

Crystal data
Chemical formula[Zn(C17H13NO4)(C2H7N)]
Mr405.76
Crystal system, space groupTriclinic, P1
Temperature (K)298
a, b, c (Å)9.134 (2), 9.694 (2), 11.735 (3)
α, β, γ (°)80.602 (4), 87.611 (4), 66.518 (4)
V3)939.9 (4)
Z2
Radiation typeMo Kα
µ (mm1)1.33
Crystal size (mm)0.28 × 0.25 × 0.22
Data collection
DiffractometerBruker APEXII CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.707, 0.758
No. of measured, independent and
observed [I > 2σ(I)] reflections
5025, 3295, 2691
Rint0.021
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.091, 1.07
No. of reflections3295
No. of parameters243
No. of restraints1
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.32, 0.31

Computer programs: APEX2 (Bruker, 2010), SAINT-Plus (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2008) and ORTEP-3 (Farrugia, 1997), PLATON (Spek, 2009).

Selected geometric parameters (Å, º) top
Zn1—O11.927 (2)Zn1—O42.004 (2)
Zn1—O31.961 (2)Zn1—N22.008 (3)
C2—C8—C9—C1049.1 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O2i0.841 (18)2.19 (2)3.010 (3)167 (3)
C9—H9···O1ii0.932.413.258 (4)151.2
Symmetry codes: (i) x+1, y, z+1; (ii) x+1, y+1, z+1.
 

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