research communications
μ4-benzene-1,3,5-tricarboxylato)dizincate] 1-methylpyrrolidin-2-one disolvate]
of poly[bis(ammonium) [bis(aDepartment of Biology & Chemistry, New Mexico Highlands University, Las Vegas, NM 87701, USA, and bInstitute of Applied Physics, Academy of Sciences of Moldova, Academy str. 5, MD2028 Chisinau, Republic of Moldova
*Correspondence e-mail: fonari.xray@gmail.com
The title three-dimensional metal–organic framework (MOF) compound, {(NH4)2[Zn2(C9H3O6)2]·2C5H9NO}n, features an anionic framework constructed from Zn2+ cations and benzene-1,3,5-tricarboxylate (BTC) organic anions. Charge balance is achieved by outer sphere ammonium cations formed by degradation of di-n-butylamine in the solvothermal synthesis of the compound. Binuclear {Zn2(COO)2} entities act as the framework's secondary building units. Each ZnII atom has a tetrahedral coordination environment with an O4 set of donor atoms. The three-dimensional framework adopts a rutile-type topology and channels are filled in an alternating fashion with ordered and disordered 1-methylpyrrolidin-2-one solvent molecules and ammonium cations. The latter are held in the channels via four N—H⋯O hydrogen bonds, including three with the benzene-1,3,5-tricarboxylate ligands of the anionic framework and one with a 1-methylpyrrolidin-2-one solvent molecule.
CCDC reference: 1476509
1. Chemical context
1,3,5-Benzenetricarboxylic acid (H3BTC) has proved its efficacy as a versatile and powerful ligand for the construction of metal–organic frameworks (MOFs). Its three carboxylate groups and benzene ring can act as short and long bridges between metal ions, leading to three-dimensional assemblies with a large structural diversity (Eddaoudi et al., 2001; Almeida Paz & Klinowski, 2004; Liu et al., 2007). Since 1997 (Yaghi et al., 1997), the coordination chemistry of zinc ions and BTC ligands has represented one of the most extensively explored systems in efforts to synthesize new porous materials. The various aspects of the Zn–BTC system continue to being investigated, and diverse MOF structures have been reported. The published results reveal that the variation of starting compositions, solvents and templates as well as reaction conditions are significant and can result in the formation of completely different metal–organic framework compounds. A base is needed for deprotonation of H3BTC so that it can make use of its full coordination capacity. This base should have a low affinity for binding to metal ions to avoid competition with BTC, especially if the aim is the synthesis of porous materials. A wide range of different solvent systems and reaction conditions have been used in the construction of new coordination networks, including the use of ionothermal techniques (Xu et al., 2007), and conducting reactions in the presence of different surfactants as reaction media (Gao et al., 2014).
In our recent work (Ordonez et al., 2014), we reported 13 different Zn–BTC coordination networks that were formed as a result of the use of different cations as framework templates. Generally, only one type of secondary building unit (SBU) is observed in one compound; however, data from our and other groups (Ordonez et al., 2014; Xie, 2013; Hao et al., 2012) have shown the possibility of different SBUs in a single self-assembled system which can, in turn, result in distinct frameworks and topologies. In some cases, hydrothermal reaction conditions lead to decomposition of solvents or bases (Burrows et al., 2005), and fixation of the decomposition products in the systems can result in unexpected guests such as ammonium cations (Ordonez et al., 2014). Herein we report the structure of a new three-dimensional Zn–BTC MOF obtained serendipitously by reaction of the H3BTC ligand with zinc nitrate hexahydrate using 1-methylpyrrolidin-2-one (NMP) as a solvent and di-(n-butyl)amine as a base and a framework template. The main product of the reaction was the {Zn-BTC}{n-Bu2NH2} MOF, but a few single crystals of title compound were found as a byproduct.
2. Structural commentary
The 4)2[Zn2(C9H3O6)2]·2C5H9NO}n, contains two ZnII cations, two ammonium cations, two NMP molecules and two BTC residues (Fig. 1). The compound has a three-dimensional structure constructed from dimeric zinc carboxylate entities and BTC linkers (Fig. 2). The two zinc ions form a unit with six carboxylate units from the two symmetry-independent BTC ligands, and four additional BTC units created by the glide operations and translations. Each of the ZnII cations exhibits an O4 coordination set defined by four oxygen atoms of four coordinating BTC residues. The Zn—O distances range within 1.927 (5)–1.982 (5) Å for Zn1 and 1.926 (5)–1.969 (5) Å for Zn2. Of the six BTC residues around the Zn2 units, two act in bidentate bridging modes, and combine the two crystallographically unique ZnII ions in the binuclear cluster {Zn2(COO)2} that acts as the SBU in this compound. All of the other carboxylic oxygen atoms coordinate in a monodentate fashion (Fig. 1). The Zn1⋯Zn2 separation within the SBU is 3.542 (5) Å. The connection of alternating zinc carboxylate units and BTC linkers results in an infinite three-dimensional (3,6)-connected net, which leads to the framework having the same topology as rutile, TiO2.
of the title compound, {(NHAs a result of the lower symmetry of the SBU, the title compound crystallizes in a reduced symmetry Pn) compared to rutile (P42/mnm). Like other Zn–BTC frameworks with rtl-topology (Xie et al., 2005; Ordonez et al., 2014), this framework is also porous. There are rectangular channels paralle to the [100] axis, with an approximate dimension of 7.472 x 9.543 Å in which per two ammonium cations and two NMP molecules (ordered and disordered ones) reside (Fig. 2). Seven hydrogen-bonding interactions are observed between both of the ammonium cations and the carboxylic framework, N⋯O distances being in the range 2.713 (7)–3.104 (7) Å; two link each of the ammonium cations with each an NMP molecule (Table 1). The source of the ammonium cations is considered to be from the degradation of di-(n-butyl)amine during the reaction.
(3. Database survey
A literature overview (Xu et al., 2007) reported 41 different Zn–BTC MOFs with a total of 13 types of connectivity modes of BTC with Zn. The 13 modes span all of the possible features of bonds between carboxylic groups and Zn atoms. Modes with bimetallic Zn coordination were most frequently found, followed by modes with three Zn and with four Zn atoms. A search of the CSD (Groom et al., 2016; ConQuest 1.18, Version 5.37, updates November, 2015) for structures reported after 2007 revealed at least 60 additional {Zn–BTC} carboxylic networks. The title compound occupies a place in the reticular series of the complexes {Zn–BTC}{Base} for Base = Me2NH2+, Et2NH2+, n-Bu2NH2+, Et3NH+, (PhCH2)Me3N+, and BMIM = 1-butyl-3-methylimidazole (Ordonez et al., 2014). As a result of the size of the templates, the reticular networks differ by the packing modes of the cations in the channels, and correspondingly by channel size within the framework. {Zn/Cd–BTC} networks with the same rtl topology have also been reported (Xie et al., 2005; Zhao et al., 2007).
4. Synthesis and crystallization
A mixture of Zn(NO3)2·6H2O (0.343 g, 1.15 mmol), H3BTC (0.244g, 1.16 mmol), di-(n-butyl)amine (0.142 g, 1.10 mmol), and 1-methylpyrrolidin-2-one (NMP, 10 mL) was prepared in a capped vial. The solution was transferred to a 23 mL Teflon-lined acid digestion vessel and placed in an oven at 423 K for four days. The crystals produced were collected in a vial, washed with fresh NMP, and sonicated to remove impurities from the crystals. The main product of the reaction was the MOF {Zn–BTC}{n-Bu2NH2}; only few single crystals of the title compound were found as a byproduct. Those crystals were plate shaped and colorless. Synthetic details are given in Ordonez et al. (2014).
5. details
Crystal data, data collection and structure . C-bound H atoms were calculated in geometrically idealized positions and refined riding on their parent atoms, with Uiso(H) = 1.2Ueq(C) (aromatic) and 1.5Ueq(C) (methyl), and with C—H = 0.95 Å (aromatic) and 0.98 Å (methyl). The methyl H atoms were allowed to rotate around the corresponding C—C bond. N-bound H atoms in ammonium cations were found in a difference map and refined using geometrical restraints to fix the N—H distances, and with an isotropic displacement parameter of Uiso(H) = 1.5Ueq(N). One of the NMP molecules is disordered over two positions with partial occupancies 0.903 (8) and 0.097 (8). The geometries of the major and minor NMP moieties were restrained to be similar using a SAME command. The displacement parameters for the disordered NMP molecule were restrained to be similar to each other using a SIMU command with a standard deviation of 0.01 Å2.
details are summarized in Table 2
|
Supporting information
CCDC reference: 1476509
10.1107/S2056989016007027/zl2661sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989016007027/zl2661Isup2.hkl
1,3,5-Benzenetricarboxylic acid (H3BTC) has proved its efficacy as a versatile and powerful ligand for the construction of metal–organic frameworks (MOFs). Its three carboxylate groups and benzene ring can act as short and long bridges between metal centers, leading to three-dimensional assemblies with a large structural diversity (Eddaoudi et al., 2001; Almeida Paz & Klinowski, 2004; Liu et al., 2007). Since 1997 (Yaghi et al., 1997), the coordination chemistry of zinc ions and BTC ligands has represented one of the most extensively explored systems in efforts to synthesize new porous materials. The various aspects of the Zn–BTC system continue to being investigated, and diverse MOF structures have been reported. The published results reveal that the variation of starting compositions, solvents and templates as well as reaction conditions are significant and can result in the formation of completely different metal–organic framework compounds. A base is needed for deprotonation of H3BTC so that it can make use of its full coordination capacity. This base should have a low affinity for binding to metal ions to avoid competition with BTC, especially if the aim is the synthesis of porous materials. A wide range of different solvent systems and reaction conditions have been used in the construction of new coordination networks, including the use of ionothermal techniques (Xu et al., 2007), and conducting reactions in the presence of different surfactants as reaction media (Gao et al., 2014).
In our recent work (Ordonez et al., 2014), we reported 13 different Zn–BTC coordination networks that were formed as a result of the use of different cations as framework templates. Generally, only one type of secondary building unit (SBU) is observed in one compound; however, data from our and other groups (Ordonez et al., 2014; Xie, 2013; Hao et al., 2012) have shown the possibility of different SBUs in a single self-assembled system which can, in turn, result in distinct frameworks and topologies. In some cases, hydrothermal reaction conditions lead to decomposition of solvents or bases (Burrows et al., 2005), and fixation of the decomposition products in the systems can result in unexpected guests such as ammonium cations (Ordonez et al., 2014). Herein we report the structure of a new three-dimensional Zn–BTC MOF obtained serendipitously by reaction of the H3BTC ligand with zinc(II) nitrate hexahydrate using 1-methylpyrrolidin-2-one as a solvent and di-(n-butyl)amine as a base and a framework template. The main product of the reaction was the {Zn-BTC}{n-Bu2NH2} MOF, but a few single crystals of title compound were found as a byproduct.
The
of the title compound, {(NH4)2[Zn2(C9H3NO6)2]·2C5H9NO}n, contains two ZnII cations, two ammonium cations, two NMP molecules and two BTC residues (Fig. 1). The X-ray study revealed that the compound has a three-dimensional structure constructed from dimeric zinc carboxylate clusters and BTC linkers (Fig. 2). The two zinc ions form a cluster with six carboxylate units from the two symmetry-independent BTC ligands, and four additional BTC units created by the glide operations and translations. Each of the ZnII cations exhibits an O4 coordination set defined by four oxygen atoms of four coordinating BTC residues. The Zn—O distances range within 1.927 (5)–1.982 (5) Å for Zn1 and 1.926 (5)–1.969 (5) Å for Zn2. Of the six BTC residues around the Zn2 cluster, two act in bidentate bridging modes, and combine the two crystallographically unique Zn atoms in the binuclear cluster {Zn2(COO)2} that acts as the SBU in this compound. All of the other carboxylic oxygen atoms coordinate in a monodentate fashion (Fig. 1). The Zn1···Zn2 separation within the SBU is 3.542 (5) Å. The connection of alternating zinc carboxylate clusters and BTC linkers results in an infinite three-dimensional (3,6)-connected net, which leads to the framework having the same topology as rutile, TiO2.As a result of the lower symmetry of the SBU, the title compound crystallizes in a reduced symmetry
(Pn) compared to rutile (P42/mnm). Like other Zn–BTC frameworks with rtl-topology (Xie et al., 2005; Ordonez et al., 2014), this framework is also porous. There are rectangular channels along the [100] axis, with an approximate dimension of 7.472 x 9.543 Å in which per two ammonium cations and two NMP molecules (ordered and disordered ones) reside (Fig. 2). Seven hydrogen-bonding interactions are observed between both of the ammonium cations and the carboxylic framework, N···O distances being in the range 2.713 (7)–3.104 (7) Å; two link each of the ammonium cations with each an NMP molecule (Table 1). The source of the ammonium cations is considered to be from the degradation of di-(n-butyl)amine during the reaction.A literature overview (Xu et al., 2007) reported 41 different Zn–BTC MOFs with a total of 13 types of connectivity modes of BTC with Zn. The 13 modes span all of the possible features of bonds between carboxylic groups and Zn atoms. Modes with bimetallic Zn coordination were most frequently found, followed by modes with three Zn and with four Zn atoms. A search of the CSD (Groom et al., 2016; ConQuest 1.18, Version 5.37, updates November, 2015) for structures reported after 2007 revealed at least 60 additional {Zn–BTC} carboxylic networks. The title compound occupies a place in the reticular series of the complexes {Zn–BTC}{Base} for Base = Me2NH2+, Et2NH2+, n-Bu2NH2+, Et3NH+, (PhCH2)Me3N+, and BMIM = 1-butyl-3-methylimidazole (Ordonez et al., 2014). As a result of the size of the templates, the reticular networks differ by the packing modes of the cations in the channels, and correspondingly by channel size within the framework. {Zn/Cd–BTC} networks with the same rtl topology have also been reported (Xie et al., 2005; Zhao et al., 2007).
A mixture of Zn(NO3)2·6H2O (0.343 g, 1.15 mmol), H3BTC (0.244g, 1.16 mmol), di-(n-butyl)amine (0.142 g, 1.10 mmol), and 1-methylpyrrolidin-2-one (NMP, 10 mL) was prepared in a capped vial. The solution was transferred to a 23 mL Teflon-lined acid digestion vessel and placed in an oven at 423 K for four days. The crystals produced were collected in a vial, washed with fresh NMP, and sonicated to remove impurities from the crystals. The main product of the reaction was the MOF {Zn–BTC}{n-Bu2NH2}; only few single crystals of title compound were found as a byproduct. Those crystals were plate shaped and colorless. Synthetic details are given in Ordonez et al. (2014).
Crystal data, data collection and structure
details are summarized in Table 2. C-bound H atoms were calculated in geometrically idealized positions and refined riding on their parent atoms, with Uiso(H) = 1.2Ueq(C) (aromatic) and 1.5Ueq(C) (methyl), and with C—H = 0.95 Å (aromatic) and 0.98 Å (methyl). The methyl H atoms were allowed to rotate around the corresponding C—C bond. N-bound H atoms in ammonium cations were found in a difference map and refined using geometrical restraints to fix the N—H distances, and with an isotropic displacement parameter of Uiso(H) = 1.5Ueq(N). One of the NMP molecules is disordered over two positions with partial occupancies 0.903 (8) and 0.097 (8). The geometries of the major and minor NMP moieties were restrained to be similar using a SAME command. The displacement parameters for the disordered NMP molecule were restrained to be similar to each other using a SIMU command with a standard deviation of 0.01 Å2.1,3,5-Benzenetricarboxylic acid (H3BTC) has proved its efficacy as a versatile and powerful ligand for the construction of metal–organic frameworks (MOFs). Its three carboxylate groups and benzene ring can act as short and long bridges between metal centers, leading to three-dimensional assemblies with a large structural diversity (Eddaoudi et al., 2001; Almeida Paz & Klinowski, 2004; Liu et al., 2007). Since 1997 (Yaghi et al., 1997), the coordination chemistry of zinc ions and BTC ligands has represented one of the most extensively explored systems in efforts to synthesize new porous materials. The various aspects of the Zn–BTC system continue to being investigated, and diverse MOF structures have been reported. The published results reveal that the variation of starting compositions, solvents and templates as well as reaction conditions are significant and can result in the formation of completely different metal–organic framework compounds. A base is needed for deprotonation of H3BTC so that it can make use of its full coordination capacity. This base should have a low affinity for binding to metal ions to avoid competition with BTC, especially if the aim is the synthesis of porous materials. A wide range of different solvent systems and reaction conditions have been used in the construction of new coordination networks, including the use of ionothermal techniques (Xu et al., 2007), and conducting reactions in the presence of different surfactants as reaction media (Gao et al., 2014).
In our recent work (Ordonez et al., 2014), we reported 13 different Zn–BTC coordination networks that were formed as a result of the use of different cations as framework templates. Generally, only one type of secondary building unit (SBU) is observed in one compound; however, data from our and other groups (Ordonez et al., 2014; Xie, 2013; Hao et al., 2012) have shown the possibility of different SBUs in a single self-assembled system which can, in turn, result in distinct frameworks and topologies. In some cases, hydrothermal reaction conditions lead to decomposition of solvents or bases (Burrows et al., 2005), and fixation of the decomposition products in the systems can result in unexpected guests such as ammonium cations (Ordonez et al., 2014). Herein we report the structure of a new three-dimensional Zn–BTC MOF obtained serendipitously by reaction of the H3BTC ligand with zinc(II) nitrate hexahydrate using 1-methylpyrrolidin-2-one as a solvent and di-(n-butyl)amine as a base and a framework template. The main product of the reaction was the {Zn-BTC}{n-Bu2NH2} MOF, but a few single crystals of title compound were found as a byproduct.
The
of the title compound, {(NH4)2[Zn2(C9H3NO6)2]·2C5H9NO}n, contains two ZnII cations, two ammonium cations, two NMP molecules and two BTC residues (Fig. 1). The X-ray study revealed that the compound has a three-dimensional structure constructed from dimeric zinc carboxylate clusters and BTC linkers (Fig. 2). The two zinc ions form a cluster with six carboxylate units from the two symmetry-independent BTC ligands, and four additional BTC units created by the glide operations and translations. Each of the ZnII cations exhibits an O4 coordination set defined by four oxygen atoms of four coordinating BTC residues. The Zn—O distances range within 1.927 (5)–1.982 (5) Å for Zn1 and 1.926 (5)–1.969 (5) Å for Zn2. Of the six BTC residues around the Zn2 cluster, two act in bidentate bridging modes, and combine the two crystallographically unique Zn atoms in the binuclear cluster {Zn2(COO)2} that acts as the SBU in this compound. All of the other carboxylic oxygen atoms coordinate in a monodentate fashion (Fig. 1). The Zn1···Zn2 separation within the SBU is 3.542 (5) Å. The connection of alternating zinc carboxylate clusters and BTC linkers results in an infinite three-dimensional (3,6)-connected net, which leads to the framework having the same topology as rutile, TiO2.As a result of the lower symmetry of the SBU, the title compound crystallizes in a reduced symmetry
(Pn) compared to rutile (P42/mnm). Like other Zn–BTC frameworks with rtl-topology (Xie et al., 2005; Ordonez et al., 2014), this framework is also porous. There are rectangular channels along the [100] axis, with an approximate dimension of 7.472 x 9.543 Å in which per two ammonium cations and two NMP molecules (ordered and disordered ones) reside (Fig. 2). Seven hydrogen-bonding interactions are observed between both of the ammonium cations and the carboxylic framework, N···O distances being in the range 2.713 (7)–3.104 (7) Å; two link each of the ammonium cations with each an NMP molecule (Table 1). The source of the ammonium cations is considered to be from the degradation of di-(n-butyl)amine during the reaction.A literature overview (Xu et al., 2007) reported 41 different Zn–BTC MOFs with a total of 13 types of connectivity modes of BTC with Zn. The 13 modes span all of the possible features of bonds between carboxylic groups and Zn atoms. Modes with bimetallic Zn coordination were most frequently found, followed by modes with three Zn and with four Zn atoms. A search of the CSD (Groom et al., 2016; ConQuest 1.18, Version 5.37, updates November, 2015) for structures reported after 2007 revealed at least 60 additional {Zn–BTC} carboxylic networks. The title compound occupies a place in the reticular series of the complexes {Zn–BTC}{Base} for Base = Me2NH2+, Et2NH2+, n-Bu2NH2+, Et3NH+, (PhCH2)Me3N+, and BMIM = 1-butyl-3-methylimidazole (Ordonez et al., 2014). As a result of the size of the templates, the reticular networks differ by the packing modes of the cations in the channels, and correspondingly by channel size within the framework. {Zn/Cd–BTC} networks with the same rtl topology have also been reported (Xie et al., 2005; Zhao et al., 2007).
A mixture of Zn(NO3)2·6H2O (0.343 g, 1.15 mmol), H3BTC (0.244g, 1.16 mmol), di-(n-butyl)amine (0.142 g, 1.10 mmol), and 1-methylpyrrolidin-2-one (NMP, 10 mL) was prepared in a capped vial. The solution was transferred to a 23 mL Teflon-lined acid digestion vessel and placed in an oven at 423 K for four days. The crystals produced were collected in a vial, washed with fresh NMP, and sonicated to remove impurities from the crystals. The main product of the reaction was the MOF {Zn–BTC}{n-Bu2NH2}; only few single crystals of title compound were found as a byproduct. Those crystals were plate shaped and colorless. Synthetic details are given in Ordonez et al. (2014).
detailsCrystal data, data collection and structure
details are summarized in Table 2. C-bound H atoms were calculated in geometrically idealized positions and refined riding on their parent atoms, with Uiso(H) = 1.2Ueq(C) (aromatic) and 1.5Ueq(C) (methyl), and with C—H = 0.95 Å (aromatic) and 0.98 Å (methyl). The methyl H atoms were allowed to rotate around the corresponding C—C bond. N-bound H atoms in ammonium cations were found in a difference map and refined using geometrical restraints to fix the N—H distances, and with an isotropic displacement parameter of Uiso(H) = 1.5Ueq(N). One of the NMP molecules is disordered over two positions with partial occupancies 0.903 (8) and 0.097 (8). The geometries of the major and minor NMP moieties were restrained to be similar using a SAME command. The displacement parameters for the disordered NMP molecule were restrained to be similar to each other using a SIMU command with a standard deviation of 0.01 Å2.Data collection: APEX2 (Bruker, 2014); cell
SAINT-Plus (Bruker, 2009); data reduction: SAINT-Plus (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: publCIF (Westrip, 2010).Fig. 1. A portion of the crystal structure of the title complex, displaying the atomic labeling. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: A 1/2 + x, 2 - y, 1/2 + z; B: 1 + x, y, z; C: x - 1/2, 1 - y, z - 1/2; D: x - 1, y, z.] | |
Fig. 2. Three-dimensional structure in the unit cell viewed along the c axis. Hydrogen-bonding interactions are shown as dashed lines. C-bound H atoms are omitted for clarity. |
(NH4)2[Zn2(C9H3O6)2]·2C5H9NO | F(000) = 800 |
Mr = 779.31 | Dx = 1.635 Mg m−3 |
Monoclinic, Pn | Mo Kα radiation, λ = 0.71073 Å |
a = 9.470 (4) Å | Cell parameters from 3722 reflections |
b = 12.351 (5) Å | θ = 4.3–26.2° |
c = 13.575 (5) Å | µ = 1.59 mm−1 |
β = 94.327 (5)° | T = 100 K |
V = 1583.2 (10) Å3 | Prism, colorless |
Z = 2 | 0.45 × 0.35 × 0.25 mm |
Bruker SMART APEXII CCD area-detector diffractometer | 5263 reflections with I > 2σ(I) |
phi and ω scans | Rint = 0.038 |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | θmax = 26.0°, θmin = 4.3° |
Tmin = 0.628, Tmax = 0.784 | h = −11→11 |
13257 measured reflections | k = −15→15 |
6013 independent reflections | l = −16→16 |
Refinement on F2 | Hydrogen site location: mixed |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.033 | w = 1/[σ2(Fo2) + (0.029P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.068 | (Δ/σ)max = 0.002 |
S = 0.99 | Δρmax = 0.38 e Å−3 |
6013 reflections | Δρmin = −0.33 e Å−3 |
525 parameters | Absolute structure: Refined as an inversion twin. |
236 restraints | Absolute structure parameter: 0.102 (18) |
(NH4)2[Zn2(C9H3O6)2]·2C5H9NO | V = 1583.2 (10) Å3 |
Mr = 779.31 | Z = 2 |
Monoclinic, Pn | Mo Kα radiation |
a = 9.470 (4) Å | µ = 1.59 mm−1 |
b = 12.351 (5) Å | T = 100 K |
c = 13.575 (5) Å | 0.45 × 0.35 × 0.25 mm |
β = 94.327 (5)° |
Bruker SMART APEXII CCD area-detector diffractometer | 6013 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | 5263 reflections with I > 2σ(I) |
Tmin = 0.628, Tmax = 0.784 | Rint = 0.038 |
13257 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.068 | Δρmax = 0.38 e Å−3 |
S = 0.99 | Δρmin = −0.33 e Å−3 |
6013 reflections | Absolute structure: Refined as an inversion twin. |
525 parameters | Absolute structure parameter: 0.102 (18) |
236 restraints |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. Refined as a 2-component inversion twin. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Zn1 | 0.89147 (5) | 0.67955 (5) | 0.05911 (4) | 0.00955 (18) | |
Zn2 | 0.62372 (5) | 0.81579 (5) | 0.17921 (4) | 0.00980 (19) | |
O1 | 0.9514 (6) | 0.8118 (3) | 0.1336 (4) | 0.0115 (12) | |
O2 | 0.8070 (6) | 0.8139 (3) | 0.2567 (4) | 0.0138 (12) | |
O3 | 0.8606 (5) | 0.5625 (4) | 0.1496 (3) | 0.0156 (11) | |
O4 | 1.0719 (5) | 0.5942 (4) | 0.2254 (4) | 0.0213 (11) | |
O5 | 0.7069 (6) | 0.6839 (3) | −0.0140 (4) | 0.0126 (12) | |
O6 | 0.5633 (6) | 0.6808 (3) | 0.1113 (4) | 0.0129 (12) | |
O7 | 0.6608 (5) | 0.9254 (4) | 0.0835 (3) | 0.0139 (10) | |
O8 | 0.4502 (5) | 0.8860 (4) | 0.0057 (4) | 0.0224 (12) | |
O9 | 0.4623 (5) | 0.8233 (3) | 0.2583 (4) | 0.0127 (12) | |
O10 | 0.5241 (4) | 0.9792 (3) | 0.3323 (3) | 0.0177 (10) | |
O11 | 1.0529 (6) | 0.6840 (3) | −0.0191 (4) | 0.0134 (12) | |
O12 | 0.9855 (4) | 0.5564 (3) | −0.1286 (3) | 0.0193 (10) | |
O13 | 0.2466 (6) | 0.0795 (4) | 0.1181 (3) | 0.0482 (14) | |
C1 | 0.9235 (8) | 0.8327 (5) | 0.2208 (6) | 0.0115 (16) | |
C2 | 1.0366 (7) | 0.8843 (5) | 0.2878 (5) | 0.0127 (15) | |
C3 | 1.1771 (7) | 0.8723 (5) | 0.2683 (5) | 0.0110 (15) | |
H3 | 1.2011 | 0.8307 | 0.2132 | 0.013* | |
C4 | 1.2836 (7) | 0.9213 (5) | 0.3297 (5) | 0.0115 (14) | |
C5 | 1.2461 (7) | 0.9836 (5) | 0.4080 (5) | 0.0113 (14) | |
H5 | 1.3177 | 1.0186 | 0.4492 | 0.014* | |
C6 | 1.1059 (7) | 0.9959 (5) | 0.4271 (5) | 0.0134 (15) | |
C7 | 0.9997 (8) | 0.9460 (5) | 0.3666 (5) | 0.0120 (15) | |
H7 | 0.9031 | 0.9544 | 0.3795 | 0.014* | |
C8 | 0.9530 (7) | 0.5524 (5) | 0.2213 (5) | 0.0128 (15) | |
C9 | 0.9120 (7) | 0.4837 (5) | 0.3048 (5) | 0.0134 (15) | |
C10 | 0.7684 (8) | 0.4637 (5) | 0.3179 (5) | 0.0129 (14) | |
H10 | 0.6968 | 0.4899 | 0.2710 | 0.015* | |
C11 | 1.0130 (8) | 0.4415 (6) | 0.3723 (6) | 0.0147 (15) | |
H11 | 1.1102 | 0.4529 | 0.3628 | 0.018* | |
C12 | 0.5904 (8) | 0.6637 (5) | 0.0231 (6) | 0.0113 (16) | |
C13 | 0.4770 (7) | 0.6170 (5) | −0.0465 (5) | 0.0097 (15) | |
C14 | 0.3341 (7) | 0.6340 (5) | −0.0316 (5) | 0.0114 (15) | |
H14 | 0.3079 | 0.6720 | 0.0251 | 0.014* | |
C15 | 0.2317 (7) | 0.5949 (5) | −0.1000 (5) | 0.0108 (14) | |
C16 | 0.5650 (8) | 0.9342 (6) | 0.0106 (6) | 0.0158 (16) | |
C17 | 0.4354 (7) | 0.9100 (5) | 0.3065 (5) | 0.0109 (14) | |
C18 | 1.0761 (7) | 0.6109 (5) | −0.0831 (5) | 0.0133 (14) | |
C19 | 0.2289 (7) | 0.1747 (5) | 0.0954 (5) | 0.0292 (14) | |
C20 | 0.1892 (9) | 0.2178 (6) | −0.0067 (5) | 0.0386 (17) | |
H20A | 0.0926 | 0.1944 | −0.0305 | 0.046* | |
H20B | 0.2569 | 0.1927 | −0.0539 | 0.046* | |
C21 | 0.1961 (8) | 0.3402 (6) | 0.0056 (6) | 0.0429 (18) | |
H21A | 0.2857 | 0.3690 | −0.0170 | 0.051* | |
H21B | 0.1157 | 0.3754 | −0.0328 | 0.051* | |
C22 | 0.1882 (8) | 0.3598 (5) | 0.1150 (6) | 0.0431 (19) | |
H22A | 0.2520 | 0.4195 | 0.1385 | 0.052* | |
H22B | 0.0903 | 0.3774 | 0.1306 | 0.052* | |
C23 | 0.2518 (9) | 0.2404 (6) | 0.2649 (5) | 0.0419 (18) | |
H23A | 0.1586 | 0.2397 | 0.2918 | 0.063* | |
H23B | 0.3087 | 0.2996 | 0.2952 | 0.063* | |
H23C | 0.2997 | 0.1713 | 0.2796 | 0.063* | |
N1 | 0.2347 (6) | 0.2561 (4) | 0.1594 (4) | 0.0314 (13) | |
N2 | 0.6628 (5) | 0.0862 (4) | 0.4962 (4) | 0.0220 (11) | |
H1N | 0.628 (7) | 0.062 (5) | 0.438 (3) | 0.033* | |
H2N | 0.749 (4) | 0.105 (5) | 0.483 (5) | 0.033* | |
H3N | 0.620 (6) | 0.145 (4) | 0.515 (5) | 0.033* | |
H4N | 0.687 (7) | 0.036 (4) | 0.539 (4) | 0.033* | |
N3 | 0.3320 (5) | 0.6331 (4) | 0.3316 (4) | 0.0197 (11) | |
H5N | 0.249 (4) | 0.624 (5) | 0.302 (4) | 0.029* | |
H6N | 0.369 (6) | 0.683 (4) | 0.296 (4) | 0.029* | |
H7N | 0.393 (6) | 0.580 (4) | 0.328 (4) | 0.029* | |
H8N | 0.326 (7) | 0.660 (5) | 0.392 (3) | 0.029* | |
C1S | 0.3028 (9) | 0.7644 (7) | 0.5883 (6) | 0.030 (2) | 0.903 (8) |
C2S | 0.3572 (11) | 0.8553 (9) | 0.6562 (9) | 0.032 (2) | 0.903 (8) |
H2S1 | 0.3523 | 0.9255 | 0.6209 | 0.038* | 0.903 (8) |
H2S2 | 0.4565 | 0.8417 | 0.6812 | 0.038* | 0.903 (8) |
C3S | 0.2619 (8) | 0.8556 (6) | 0.7391 (5) | 0.0324 (17) | 0.903 (8) |
H3S1 | 0.3059 | 0.8161 | 0.7970 | 0.039* | 0.903 (8) |
H3S2 | 0.2409 | 0.9306 | 0.7592 | 0.039* | 0.903 (8) |
C4S | 0.1267 (13) | 0.7981 (13) | 0.6975 (11) | 0.036 (2) | 0.903 (8) |
H4S1 | 0.0865 | 0.7520 | 0.7481 | 0.043* | 0.903 (8) |
H4S2 | 0.0541 | 0.8506 | 0.6717 | 0.043* | 0.903 (8) |
C5S | 0.0917 (12) | 0.6515 (11) | 0.5659 (10) | 0.059 (3) | 0.903 (8) |
H5S1 | 0.0244 | 0.6870 | 0.5178 | 0.089* | 0.903 (8) |
H5S2 | 0.0396 | 0.6105 | 0.6132 | 0.089* | 0.903 (8) |
H5S3 | 0.1522 | 0.6022 | 0.5313 | 0.089* | 0.903 (8) |
N1S | 0.1793 (8) | 0.7334 (6) | 0.6184 (5) | 0.0355 (18) | 0.903 (8) |
O1S | 0.3602 (7) | 0.7270 (8) | 0.5180 (5) | 0.034 (2) | 0.903 (8) |
C1P | 0.258 (6) | 0.737 (6) | 0.557 (4) | 0.034 (4) | 0.097 (8) |
C2P | 0.130 (9) | 0.665 (7) | 0.572 (8) | 0.037 (5) | 0.097 (8) |
H2P1 | 0.0741 | 0.6512 | 0.5091 | 0.045* | 0.097 (8) |
H2P2 | 0.1604 | 0.5951 | 0.6025 | 0.045* | 0.097 (8) |
C3P | 0.046 (5) | 0.730 (5) | 0.641 (5) | 0.038 (5) | 0.097 (8) |
H3P1 | −0.0295 | 0.7714 | 0.6038 | 0.046* | 0.097 (8) |
H3P2 | 0.0018 | 0.6813 | 0.6884 | 0.046* | 0.097 (8) |
C4P | 0.153 (10) | 0.806 (13) | 0.696 (9) | 0.035 (4) | 0.097 (8) |
H4P1 | 0.1800 | 0.7795 | 0.7637 | 0.042* | 0.097 (8) |
H4P2 | 0.1148 | 0.8802 | 0.6996 | 0.042* | 0.097 (8) |
C5P | 0.392 (9) | 0.875 (8) | 0.650 (8) | 0.029 (9) | 0.097 (8) |
H5P1 | 0.4522 | 0.8697 | 0.5945 | 0.043* | 0.097 (8) |
H5P2 | 0.4478 | 0.8561 | 0.7115 | 0.043* | 0.097 (8) |
H5P3 | 0.3577 | 0.9499 | 0.6548 | 0.043* | 0.097 (8) |
N1P | 0.272 (5) | 0.802 (4) | 0.635 (4) | 0.032 (3) | 0.097 (8) |
O1P | 0.337 (7) | 0.732 (8) | 0.490 (4) | 0.037 (10) | 0.097 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0067 (4) | 0.0131 (4) | 0.0089 (4) | −0.0007 (3) | 0.0011 (3) | 0.0001 (3) |
Zn2 | 0.0068 (4) | 0.0136 (4) | 0.0091 (4) | −0.0013 (3) | 0.0008 (3) | −0.0002 (3) |
O1 | 0.011 (3) | 0.016 (3) | 0.008 (3) | −0.0017 (17) | 0.000 (2) | −0.0005 (18) |
O2 | 0.007 (3) | 0.019 (3) | 0.015 (3) | −0.0018 (18) | −0.002 (2) | 0.0015 (19) |
O3 | 0.014 (3) | 0.020 (2) | 0.013 (3) | −0.0026 (19) | −0.002 (2) | 0.007 (2) |
O4 | 0.013 (3) | 0.026 (3) | 0.024 (3) | −0.0063 (19) | −0.001 (2) | 0.013 (2) |
O5 | 0.011 (3) | 0.019 (3) | 0.008 (3) | 0.0001 (19) | 0.001 (2) | −0.0017 (18) |
O6 | 0.014 (3) | 0.014 (3) | 0.011 (3) | 0.0023 (17) | 0.000 (2) | −0.0006 (18) |
O7 | 0.011 (3) | 0.018 (2) | 0.013 (3) | 0.0013 (19) | 0.000 (2) | 0.0035 (19) |
O8 | 0.011 (3) | 0.029 (3) | 0.027 (3) | −0.005 (2) | −0.001 (2) | 0.013 (2) |
O9 | 0.005 (3) | 0.014 (3) | 0.019 (3) | 0.0011 (17) | 0.003 (2) | −0.0007 (19) |
O10 | 0.010 (2) | 0.021 (2) | 0.022 (2) | −0.0048 (17) | 0.0041 (17) | −0.0047 (18) |
O11 | 0.015 (3) | 0.017 (3) | 0.009 (3) | −0.0019 (18) | 0.007 (2) | −0.0046 (18) |
O12 | 0.007 (2) | 0.022 (2) | 0.029 (3) | −0.0042 (18) | 0.0008 (18) | −0.010 (2) |
O13 | 0.083 (4) | 0.022 (3) | 0.036 (3) | 0.008 (2) | −0.015 (3) | 0.001 (2) |
C1 | 0.009 (4) | 0.008 (3) | 0.017 (4) | 0.003 (3) | 0.000 (3) | 0.000 (3) |
C2 | 0.007 (4) | 0.014 (3) | 0.017 (4) | 0.000 (3) | 0.003 (3) | −0.001 (3) |
C3 | 0.013 (4) | 0.009 (3) | 0.011 (4) | −0.002 (3) | −0.002 (3) | 0.002 (3) |
C4 | 0.011 (3) | 0.011 (3) | 0.013 (3) | −0.001 (2) | 0.001 (3) | 0.003 (3) |
C5 | 0.009 (3) | 0.013 (3) | 0.011 (3) | −0.003 (2) | −0.005 (2) | 0.001 (2) |
C6 | 0.014 (4) | 0.012 (3) | 0.013 (4) | 0.000 (3) | −0.001 (3) | 0.000 (3) |
C7 | 0.009 (4) | 0.012 (3) | 0.015 (4) | −0.001 (3) | 0.002 (3) | −0.002 (3) |
C8 | 0.012 (4) | 0.015 (3) | 0.011 (3) | 0.002 (3) | 0.001 (3) | 0.001 (3) |
C9 | 0.012 (4) | 0.014 (3) | 0.014 (4) | 0.000 (3) | 0.003 (3) | −0.001 (3) |
C10 | 0.011 (3) | 0.013 (3) | 0.016 (3) | −0.004 (2) | 0.002 (2) | 0.001 (3) |
C11 | 0.009 (4) | 0.018 (3) | 0.017 (4) | −0.003 (3) | 0.001 (3) | 0.001 (3) |
C12 | 0.010 (4) | 0.011 (3) | 0.012 (4) | 0.000 (3) | −0.006 (3) | 0.004 (3) |
C13 | 0.011 (4) | 0.011 (3) | 0.007 (4) | −0.001 (3) | −0.002 (3) | −0.001 (3) |
C14 | 0.009 (4) | 0.014 (3) | 0.013 (4) | 0.003 (3) | 0.007 (3) | −0.001 (3) |
C15 | 0.007 (3) | 0.010 (3) | 0.015 (3) | 0.001 (2) | 0.002 (3) | −0.002 (3) |
C16 | 0.012 (4) | 0.016 (3) | 0.020 (4) | 0.003 (3) | 0.005 (3) | 0.004 (3) |
C17 | 0.011 (3) | 0.016 (3) | 0.006 (3) | 0.004 (3) | 0.000 (2) | −0.001 (2) |
C18 | 0.011 (3) | 0.013 (3) | 0.016 (3) | 0.000 (2) | 0.002 (2) | 0.006 (3) |
C19 | 0.039 (4) | 0.026 (3) | 0.022 (3) | 0.009 (3) | 0.002 (3) | −0.003 (3) |
C20 | 0.050 (5) | 0.040 (4) | 0.028 (4) | 0.013 (4) | 0.010 (3) | 0.002 (3) |
C21 | 0.036 (4) | 0.044 (5) | 0.047 (5) | 0.001 (3) | −0.002 (3) | 0.020 (4) |
C22 | 0.043 (5) | 0.017 (3) | 0.069 (5) | 0.005 (3) | 0.001 (4) | −0.002 (4) |
C23 | 0.053 (5) | 0.047 (5) | 0.025 (4) | −0.009 (4) | 0.001 (3) | −0.014 (3) |
N1 | 0.045 (4) | 0.021 (3) | 0.029 (3) | −0.001 (2) | 0.008 (3) | −0.003 (2) |
N2 | 0.018 (3) | 0.019 (3) | 0.028 (3) | 0.005 (2) | −0.001 (2) | −0.011 (2) |
N3 | 0.014 (3) | 0.018 (3) | 0.027 (3) | 0.001 (2) | −0.001 (2) | 0.003 (2) |
C1S | 0.026 (4) | 0.034 (4) | 0.029 (4) | 0.005 (3) | 0.002 (3) | 0.007 (4) |
C2S | 0.032 (5) | 0.032 (5) | 0.030 (4) | 0.002 (4) | −0.001 (4) | −0.002 (4) |
C3S | 0.034 (4) | 0.034 (4) | 0.029 (4) | 0.004 (3) | 0.003 (3) | −0.002 (3) |
C4S | 0.032 (5) | 0.040 (4) | 0.034 (4) | 0.007 (4) | 0.007 (4) | 0.002 (4) |
C5S | 0.053 (7) | 0.063 (7) | 0.059 (6) | −0.016 (6) | −0.012 (6) | −0.015 (5) |
N1S | 0.028 (4) | 0.041 (4) | 0.039 (4) | −0.001 (3) | 0.005 (3) | 0.000 (3) |
O1S | 0.032 (4) | 0.041 (4) | 0.030 (4) | 0.010 (3) | −0.005 (3) | −0.008 (4) |
C1P | 0.028 (8) | 0.038 (8) | 0.035 (8) | 0.004 (8) | 0.000 (8) | 0.004 (8) |
C2P | 0.031 (9) | 0.042 (9) | 0.038 (9) | −0.002 (9) | 0.001 (9) | 0.000 (9) |
C3P | 0.033 (8) | 0.042 (8) | 0.039 (8) | −0.002 (8) | 0.005 (8) | 0.002 (8) |
C4P | 0.031 (7) | 0.039 (7) | 0.034 (7) | 0.003 (7) | 0.005 (7) | 0.001 (7) |
C5P | 0.031 (15) | 0.033 (15) | 0.022 (15) | 0.005 (15) | −0.004 (15) | −0.003 (14) |
N1P | 0.030 (6) | 0.035 (6) | 0.032 (6) | 0.004 (6) | 0.001 (6) | 0.001 (6) |
O1P | 0.041 (17) | 0.038 (16) | 0.032 (17) | 0.017 (16) | −0.006 (16) | −0.001 (17) |
Zn1—O3 | 1.933 (5) | C20—H20A | 0.9900 |
Zn1—O11 | 1.927 (5) | C20—H20B | 0.9900 |
Zn1—O5 | 1.944 (5) | C21—C22 | 1.513 (11) |
Zn1—O1 | 1.982 (5) | C21—H21A | 0.9900 |
Zn2—O7 | 1.926 (5) | C21—H21B | 0.9900 |
Zn2—O9 | 1.935 (5) | C22—N1 | 1.469 (8) |
Zn2—O2 | 1.960 (5) | C22—H22A | 0.9900 |
Zn2—O6 | 1.969 (5) | C22—H22B | 0.9900 |
O1—C1 | 1.259 (9) | C23—N1 | 1.443 (9) |
O2—C1 | 1.261 (9) | C23—H23A | 0.9800 |
O3—C8 | 1.265 (8) | C23—H23B | 0.9800 |
O4—C8 | 1.237 (8) | C23—H23C | 0.9800 |
O5—C12 | 1.272 (9) | N2—H1N | 0.88 (3) |
O6—C12 | 1.261 (9) | N2—H2N | 0.88 (3) |
O7—C16 | 1.296 (8) | N2—H3N | 0.88 (3) |
O8—C16 | 1.237 (8) | N2—H4N | 0.86 (3) |
O9—C17 | 1.290 (7) | N3—H5N | 0.86 (3) |
O10—C17 | 1.231 (7) | N3—H6N | 0.87 (3) |
O11—C18 | 1.283 (8) | N3—H7N | 0.88 (3) |
O12—C18 | 1.222 (8) | N3—H8N | 0.89 (3) |
O13—C19 | 1.224 (7) | C1S—O1S | 1.223 (11) |
C1—C2 | 1.494 (10) | C1S—N1S | 1.325 (8) |
C2—C7 | 1.381 (9) | C1S—C2S | 1.517 (14) |
C2—C3 | 1.384 (9) | C2S—C3S | 1.495 (13) |
C3—C4 | 1.397 (9) | C2S—H2S1 | 0.9900 |
C3—H3 | 0.9500 | C2S—H2S2 | 0.9900 |
C4—C5 | 1.380 (9) | C3S—C4S | 1.533 (13) |
C4—C17i | 1.501 (9) | C3S—H3S1 | 0.9900 |
C5—C6 | 1.381 (9) | C3S—H3S2 | 0.9900 |
C5—H5 | 0.9500 | C4S—N1S | 1.457 (11) |
C6—C7 | 1.392 (10) | C4S—H4S1 | 0.9900 |
C6—C16ii | 1.500 (10) | C4S—H4S2 | 0.9900 |
C7—H7 | 0.9500 | C5S—N1S | 1.459 (11) |
C8—C9 | 1.490 (9) | C5S—H5S1 | 0.9800 |
C9—C11 | 1.376 (10) | C5S—H5S2 | 0.9800 |
C9—C10 | 1.407 (9) | C5S—H5S3 | 0.9800 |
C10—C15iii | 1.395 (9) | C1P—O1P | 1.22 (3) |
C10—H10 | 0.9500 | C1P—N1P | 1.33 (3) |
C11—C13iii | 1.382 (9) | C1P—C2P | 1.52 (3) |
C11—H11 | 0.9500 | C2P—C3P | 1.50 (3) |
C12—C13 | 1.492 (10) | C2P—H2P1 | 0.9900 |
C13—C11iv | 1.382 (9) | C2P—H2P2 | 0.9900 |
C13—C14 | 1.400 (9) | C3P—C4P | 1.53 (3) |
C14—C15 | 1.378 (9) | C3P—H3P1 | 0.9900 |
C14—H14 | 0.9500 | C3P—H3P2 | 0.9900 |
C15—C10iv | 1.395 (9) | C4P—N1P | 1.46 (3) |
C15—C18v | 1.521 (9) | C4P—H4P1 | 0.9900 |
C16—C6vi | 1.500 (10) | C4P—H4P2 | 0.9900 |
C17—C4v | 1.501 (9) | C5P—N1P | 1.46 (3) |
C18—C15i | 1.521 (9) | C5P—H5P1 | 0.9800 |
C19—N1 | 1.327 (7) | C5P—H5P2 | 0.9800 |
C19—C20 | 1.505 (9) | C5P—H5P3 | 0.9800 |
C20—C21 | 1.522 (9) | ||
O3—Zn1—O11 | 122.4 (2) | H21A—C21—H21B | 108.8 |
O3—Zn1—O5 | 99.9 (2) | N1—C22—C21 | 103.1 (5) |
O11—Zn1—O5 | 116.0 (2) | N1—C22—H22A | 111.1 |
O3—Zn1—O1 | 110.1 (2) | C21—C22—H22A | 111.1 |
O11—Zn1—O1 | 92.8 (2) | N1—C22—H22B | 111.1 |
O5—Zn1—O1 | 116.7 (2) | C21—C22—H22B | 111.1 |
O7—Zn2—O9 | 122.16 (19) | H22A—C22—H22B | 109.1 |
O7—Zn2—O2 | 99.8 (2) | N1—C23—H23A | 109.5 |
O9—Zn2—O2 | 114.1 (2) | N1—C23—H23B | 109.5 |
O7—Zn2—O6 | 109.9 (2) | H23A—C23—H23B | 109.5 |
O9—Zn2—O6 | 94.9 (2) | N1—C23—H23C | 109.5 |
O2—Zn2—O6 | 117.1 (2) | H23A—C23—H23C | 109.5 |
C1—O1—Zn1 | 125.2 (5) | H23B—C23—H23C | 109.5 |
C1—O2—Zn2 | 123.8 (5) | C19—N1—C23 | 123.0 (6) |
C8—O3—Zn1 | 115.7 (4) | C19—N1—C22 | 113.3 (5) |
C12—O5—Zn1 | 124.5 (5) | C23—N1—C22 | 122.1 (6) |
C12—O6—Zn2 | 120.9 (5) | H1N—N2—H2N | 101 (6) |
C16—O7—Zn2 | 114.9 (4) | H1N—N2—H3N | 113 (6) |
C17—O9—Zn2 | 121.0 (4) | H2N—N2—H3N | 107 (6) |
C18—O11—Zn1 | 122.4 (4) | H1N—N2—H4N | 115 (6) |
O1—C1—O2 | 125.3 (7) | H2N—N2—H4N | 97 (6) |
O1—C1—C2 | 117.9 (7) | H3N—N2—H4N | 120 (6) |
O2—C1—C2 | 116.8 (7) | H5N—N3—H6N | 103 (6) |
C7—C2—C3 | 120.7 (6) | H5N—N3—H7N | 117 (6) |
C7—C2—C1 | 119.7 (7) | H6N—N3—H7N | 102 (6) |
C3—C2—C1 | 119.6 (6) | H5N—N3—H8N | 111 (6) |
C2—C3—C4 | 120.1 (6) | H6N—N3—H8N | 107 (6) |
C2—C3—H3 | 120.0 | H7N—N3—H8N | 115 (6) |
C4—C3—H3 | 120.0 | O1S—C1S—N1S | 125.9 (9) |
C5—C4—C3 | 119.0 (7) | O1S—C1S—C2S | 127.0 (9) |
C5—C4—C17i | 121.3 (6) | N1S—C1S—C2S | 107.1 (7) |
C3—C4—C17i | 119.6 (6) | C1S—C2S—C3S | 105.2 (7) |
C4—C5—C6 | 120.9 (6) | C1S—C2S—H2S1 | 110.7 |
C4—C5—H5 | 119.6 | C3S—C2S—H2S1 | 110.7 |
C6—C5—H5 | 119.6 | C1S—C2S—H2S2 | 110.7 |
C7—C6—C5 | 120.2 (6) | C3S—C2S—H2S2 | 110.7 |
C7—C6—C16ii | 119.0 (6) | H2S1—C2S—H2S2 | 108.8 |
C5—C6—C16ii | 120.8 (6) | C4S—C3S—C2S | 104.9 (7) |
C2—C7—C6 | 119.2 (7) | C4S—C3S—H3S1 | 110.8 |
C2—C7—H7 | 120.4 | C2S—C3S—H3S1 | 110.8 |
C6—C7—H7 | 120.4 | C4S—C3S—H3S2 | 110.8 |
O4—C8—O3 | 124.6 (6) | C2S—C3S—H3S2 | 110.8 |
O4—C8—C9 | 119.5 (6) | H3S1—C3S—H3S2 | 108.8 |
O3—C8—C9 | 115.9 (6) | N1S—C4S—C3S | 101.7 (7) |
C11—C9—C10 | 118.6 (7) | N1S—C4S—H4S1 | 111.4 |
C11—C9—C8 | 120.9 (7) | C3S—C4S—H4S1 | 111.4 |
C10—C9—C8 | 120.4 (6) | N1S—C4S—H4S2 | 111.4 |
C15iii—C10—C9 | 119.6 (6) | C3S—C4S—H4S2 | 111.4 |
C15iii—C10—H10 | 120.2 | H4S1—C4S—H4S2 | 109.3 |
C9—C10—H10 | 120.2 | N1S—C5S—H5S1 | 109.5 |
C13iii—C11—C9 | 121.9 (7) | N1S—C5S—H5S2 | 109.5 |
C13iii—C11—H11 | 119.0 | H5S1—C5S—H5S2 | 109.5 |
C9—C11—H11 | 119.0 | N1S—C5S—H5S3 | 109.5 |
O5—C12—O6 | 126.0 (7) | H5S1—C5S—H5S3 | 109.5 |
O5—C12—C13 | 115.4 (7) | H5S2—C5S—H5S3 | 109.5 |
O6—C12—C13 | 118.5 (7) | C1S—N1S—C5S | 122.2 (8) |
C11iv—C13—C14 | 119.6 (6) | C1S—N1S—C4S | 115.4 (8) |
C11iv—C13—C12 | 119.9 (7) | C5S—N1S—C4S | 121.8 (8) |
C14—C13—C12 | 120.5 (6) | O1P—C1P—N1P | 126 (4) |
C15—C14—C13 | 119.3 (6) | O1P—C1P—C2P | 128 (4) |
C15—C14—H14 | 120.4 | N1P—C1P—C2P | 106 (3) |
C13—C14—H14 | 120.4 | C3P—C2P—C1P | 104 (3) |
C14—C15—C10iv | 121.0 (6) | C3P—C2P—H2P1 | 110.9 |
C14—C15—C18v | 119.6 (6) | C1P—C2P—H2P1 | 110.9 |
C10iv—C15—C18v | 119.4 (6) | C3P—C2P—H2P2 | 111.0 |
O8—C16—O7 | 124.3 (7) | C1P—C2P—H2P2 | 111.0 |
O8—C16—C6vi | 120.8 (7) | H2P1—C2P—H2P2 | 109.0 |
O7—C16—C6vi | 114.9 (6) | C4P—C3P—C2P | 105 (3) |
O10—C17—O9 | 124.3 (6) | C4P—C3P—H3P1 | 110.7 |
O10—C17—C4v | 121.3 (6) | C2P—C3P—H3P1 | 110.7 |
O9—C17—C4v | 114.4 (6) | C4P—C3P—H3P2 | 110.7 |
O12—C18—O11 | 125.5 (6) | C2P—C3P—H3P2 | 110.7 |
O12—C18—C15i | 120.2 (6) | H3P1—C3P—H3P2 | 108.8 |
O11—C18—C15i | 114.2 (6) | C3P—C4P—N1P | 102 (3) |
O13—C19—N1 | 124.4 (6) | C3P—C4P—H4P1 | 111.3 |
O13—C19—C20 | 126.3 (6) | N1P—C4P—H4P1 | 111.3 |
N1—C19—C20 | 109.3 (6) | C3P—C4P—H4P2 | 111.3 |
C19—C20—C21 | 104.2 (6) | N1P—C4P—H4P2 | 111.3 |
C19—C20—H20A | 110.9 | H4P1—C4P—H4P2 | 109.2 |
C21—C20—H20A | 110.9 | N1P—C5P—H5P1 | 109.5 |
C19—C20—H20B | 110.9 | N1P—C5P—H5P2 | 109.5 |
C21—C20—H20B | 110.9 | H5P1—C5P—H5P2 | 109.5 |
H20A—C20—H20B | 108.9 | N1P—C5P—H5P3 | 109.5 |
C22—C21—C20 | 105.2 (6) | H5P1—C5P—H5P3 | 109.5 |
C22—C21—H21A | 110.7 | H5P2—C5P—H5P3 | 109.5 |
C20—C21—H21A | 110.7 | C1P—N1P—C5P | 122 (4) |
C22—C21—H21B | 110.7 | C1P—N1P—C4P | 116 (3) |
C20—C21—H21B | 110.7 | C5P—N1P—C4P | 122 (4) |
Symmetry codes: (i) x+1, y, z; (ii) x+1/2, −y+2, z+1/2; (iii) x+1/2, −y+1, z+1/2; (iv) x−1/2, −y+1, z−1/2; (v) x−1, y, z; (vi) x−1/2, −y+2, z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H8N···O1P | 0.89 (3) | 1.60 (7) | 2.47 (6) | 167 (7) |
N3—H8N···O1S | 0.89 (3) | 1.91 (3) | 2.779 (9) | 166 (6) |
N3—H7N···O12vii | 0.88 (3) | 1.97 (4) | 2.786 (6) | 154 (6) |
N3—H6N···O9 | 0.87 (3) | 2.03 (3) | 2.867 (7) | 161 (6) |
N3—H5N···O4v | 0.86 (3) | 1.94 (3) | 2.800 (7) | 174 (6) |
N2—H4N···O13viii | 0.86 (3) | 1.85 (3) | 2.713 (7) | 173 (6) |
N2—H3N···O11vii | 0.88 (3) | 2.24 (4) | 3.025 (7) | 148 (6) |
N2—H3N···O1vii | 0.88 (3) | 2.41 (5) | 3.104 (7) | 136 (6) |
N2—H2N···O8iii | 0.88 (3) | 1.91 (4) | 2.737 (7) | 156 (6) |
N2—H1N···O10ix | 0.88 (3) | 1.97 (3) | 2.825 (7) | 163 (6) |
Symmetry codes: (iii) x+1/2, −y+1, z+1/2; (v) x−1, y, z; (vii) x−1/2, −y+1, z+1/2; (viii) x+1/2, −y, z+1/2; (ix) x, y−1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H8N···O1P | 0.89 (3) | 1.60 (7) | 2.47 (6) | 167 (7) |
N3—H8N···O1S | 0.89 (3) | 1.91 (3) | 2.779 (9) | 166 (6) |
N3—H7N···O12i | 0.88 (3) | 1.97 (4) | 2.786 (6) | 154 (6) |
N3—H6N···O9 | 0.87 (3) | 2.03 (3) | 2.867 (7) | 161 (6) |
N3—H5N···O4ii | 0.86 (3) | 1.94 (3) | 2.800 (7) | 174 (6) |
N2—H4N···O13iii | 0.86 (3) | 1.85 (3) | 2.713 (7) | 173 (6) |
N2—H3N···O11i | 0.88 (3) | 2.24 (4) | 3.025 (7) | 148 (6) |
N2—H3N···O1i | 0.88 (3) | 2.41 (5) | 3.104 (7) | 136 (6) |
N2—H2N···O8iv | 0.88 (3) | 1.91 (4) | 2.737 (7) | 156 (6) |
N2—H1N···O10v | 0.88 (3) | 1.97 (3) | 2.825 (7) | 163 (6) |
Symmetry codes: (i) x−1/2, −y+1, z+1/2; (ii) x−1, y, z; (iii) x+1/2, −y, z+1/2; (iv) x+1/2, −y+1, z+1/2; (v) x, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | (NH4)2[Zn2(C9H3O6)2]·2C5H9NO |
Mr | 779.31 |
Crystal system, space group | Monoclinic, Pn |
Temperature (K) | 100 |
a, b, c (Å) | 9.470 (4), 12.351 (5), 13.575 (5) |
β (°) | 94.327 (5) |
V (Å3) | 1583.2 (10) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.59 |
Crystal size (mm) | 0.45 × 0.35 × 0.25 |
Data collection | |
Diffractometer | Bruker SMART APEXII CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2009) |
Tmin, Tmax | 0.628, 0.784 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13257, 6013, 5263 |
Rint | 0.038 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.068, 0.99 |
No. of reflections | 6013 |
No. of parameters | 525 |
No. of restraints | 236 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.38, −0.33 |
Absolute structure | Refined as an inversion twin. |
Absolute structure parameter | 0.102 (18) |
Computer programs: APEX2 (Bruker, 2014), SAINT-Plus (Bruker, 2009), SHELXTL (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), ORTEP-3 for Windows (Farrugia, 2012), publCIF (Westrip, 2010).
Acknowledgements
The authors are grateful for NSF support via DMR-0934212 and DMR-1523611 (PREM), and EPSCoR IIA-1301346.
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