An unusual coordination polymer containing Cu⁺ ions and featuring possible Cu...Cu `cuprophilic' inter­actions: poly[di-[mu]-chlorido-([mu]₄-3,5-di­amino­benzoato-[kappa]⁴O:O':N:N')tricopper(I)(3 Cu-Cu)]

Compounds containing copper(I) are of inter­est for their role in biological pro­cesses. The nature of short (< ~3.2 Å) Cu...Cu contacts within these com­pounds has been debated, being either described as weakly attractive (bonding) `cuprophilic' inter­actions, or simply as short metal-metal distances constrained by ligand geometry or largely ionic in nature. The title three-dimensional Cu<sup>+</sup>-containing coordination polymer, [Cu<sub>3</sub>(C<sub>7</sub>H<sub>7</sub>N<sub>2</sub>O<sub>2</sub>)Cl<sub>2</sub>]<sub>n</sub>, was formed from the in situ reduction of CuCl<sub>2</sub> in the presence of 3,5-di­amino­benzoic acid and KOH under hydro­thermal conditions. Its complex crystal structure contains ten distinct Cu<sup>I</sup> atoms, two of which lie on crystallographic inversion centres. The copper coordination geometries include near-linear CuOCl and CuN<sub>2</sub>, T-shaped CuOCl<sub>2</sub> and distorted tetra­hedral CuOCl<sub>3</sub> groups. Each Cu<sup>I</sup> atom is also associated with two adjacent metal atoms, with Cu...Cu distances varying from 2.7350 (14) to 3.2142 (13) Å; if all these are regarded as `cuprophilic' inter­actions, then infinite [01] zigzag chains of Cu^I atoms occur in the crystal. The structure is consolidated by N-H...Cl hydrogen bonds.

S1. Introduction

Compounds containing copper(I) (electronic configuration [Ar]3d¹⁰) are of inter­est for their role in biological processes (Tsukihara et al., 1995) and the presence of short (< ~3.2 Å) Cu···Cu contacts in their crystal structures (Arkhireeva et al., 1990; Zheng et al., 2005; Sundararaman et al., 2005; Doshi et al., 2012, Cotton et al., 1998; Carvajal et al., 2004). The nature of these contacts has been debated, with some authors (Zheng et al., 2005; Sundararaman et al., 2005; Doshi et al., 2012) describing them as weakly attractive (bonding) `cuprophilic' inter­actions akin to the well-established argentophilic Ag···Ag (Barreiro et al., 2013) and aurophilic Au···Au (Schmidbaur & Schier, 2012) weak bonds in silver(I) and gold(I) compounds, respectively. However, other workers have questioned whether these Cu···Cu contacts represent bonds at all and suggested that the short metal–metal distances observed are either constrained by the ligand geometry (Cotton et al., 1998) or are largely ionic in nature (Carvajal et al., 2004).

Here, we describe the hydro­thermal synthesis and crystal structure of the three-dimensional coordination polymer [Cu₃(C₇H₇N₂O₂)Cl₂]_n, (1), which arose from the unexpected reduction of the CuCl₂ starting material to Cu⁺ under basic conditions; C₇H₇N₂O₂^- is the 3,5-di­amino­benzoate anion.

S2. Experimental

S2.1. Synthesis and crystallization

A mixture of CuCl₂ (134 mg, 1.0 mmol) and 3,5-di­amino­benzoic acid (304 mg, 2.0 mmol) was added to 1 M KOH (2.0 ml) with stirring to yield a pale-blue solution. This mixture was heated to 423 K in a 23 ml Teflon-lined autoclave for 15 h and then cooled to room temperature over a period of several hours. Colourless blocks of (1) were recovered from the reaction by filtration and rinsing with water and acetone.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. The crystal quality was only fair, which may correlate with the rather high residuals and the larger than expected difference-map features (Δρ min. max. = -2.7 and 3.4 e Å^-3, respectively). The H atoms were placed geometrically (C—H = 0.95 Å and N—H = 0.92 Å) and refined as riding atoms, with the constraint U_iso(H) = U_eq(carrier). This structure has a strong subcell (C2/c, a = 13.077, b = 10.894, c = 7.209 Å, β = 94.64° and V = 1023.6 ų), but refinements in this space group, in which the asymmetric unit contains two Cu^I atoms (one with symmetry 1), two Cl atoms and half a ligand molecule, led to much higher residuals [R(F) ~0.20], large difference Fourier peaks (~±6 e Å^-3) in the vicinity of the Cu^I atoms and many systematic absence violations and was therefore rejected. The structural models were analysed and verified with PLATON (Spek, 2009).

S3. Results and discussion

The lack of colour of the crystals of (1) is consistent with the 3d¹⁰ electron configuration of the Cu⁺ ion (Doshi et al., 2012; Kappenstein & Hugel, 1978). The precise nature of the redox reaction that generated the cuprous ions is unknown, but similar reductions of Cu²⁺ → Cu⁺ in the presence of a nitro­gen-containing ligand under hydro­thermal conditions have been reported by other workers (Xin et al., 2013) and indeed this type of reduction has been described as a `recommended route' (Peng et al., 2010) to cuprous–halide compounds from Cu²⁺-containing starting materials. The asymmetric unit of (1), which contains no fewer than ten crystallographically independent Cu^I atoms (eight of which lie on general positions and two on crystallographic inversion centres), as well as three benzoate ligands and six chloride ions, is shown in Fig. 1.

The copper coordination geometries in (1) can be split into several distinct types. Atoms Cu1–Cu6 are bonded to various combinations of benzoate O atoms and chloride ions (Table 1). In this complex structure, all these Cu^I atoms are surrounded by a number of O and Cl atoms at distances around or slightly shorter that the Bondi (1964) van der Waals radii sum of Cu···O = 2.92 Å and Cu···Cl = 3.15 Å, but by using the Brown criterion of 0.04 of a bond-valence unit to indicate a significant chemical bond to a univalent cation (Brown, 2002), the following conclusions can be drawn: Cu1 and Cu2 are bonded to a benzoate O atom and two chloride ions in a distorted T-shape, whereas Cu3 and Cu5 are bonded to one O atom and three chloride ions in very distorted tetra­hedral arrangements (Fig. 2). The Cu4 and Cu6 coordination geometries are ambiguous; they have two well-defined short bonds to one O and one chloride ion in an approximately linear arrangement [O—Cu—Cl = 161.90 (15) and 151.94 (15)° for Cu4 and Cu6, respectively], but also one (for Cu4) and two (for Cu6) very long Cu—Cl contacts, which are right on the borderline of being considered as bonds.

In every case, the Cu^I atom also has two short Cu···Cu contacts to adjacent metal atoms with the separations indicated in the caption of Fig. 1; these are further discussed below. Bond-valence sums (Brown & Altermatt, 1985) for atoms Cu1 (1.05), Cu2 (1.04), Cu3 (1.03), Cu4 (1.01), Cu5 (1.05) and Cu6 (1.05) are in excellent agreement with the expected value of 1.00 for the cuprous ion, confirming that reduction from Cu²⁺ has occurred.

The other group of metal atoms, Cu7–Cu10 (Cu7 and Cu10 lie on crystallographic inversion centres) are bonded to two ligand N atoms (Cu—N < 2.00 Å) in a linear or near-linear geometry [N—Cu—N = 180, 177.8 (2), 176.6 (2) and 180° for Cu7, Cu8, Cu9 and Cu10, respectively]. Again, these atoms have a number of Cu···O and Cu···Cl contacts slightly shorter that the van der Waals radii sums noted above, with some of the former being just significant as bonds based on the Brown bond-valence criterion (Table 1). Even when the long Cu—O bonds are included, this group of Cu^I atoms appear to be substanti­ally `under-bonded' (Saines et al., 2006), with their BVS values of 0.66 (Cu7), 0.74 (Cu8), 0.72 (Cu9) and 0.71 (Cu10) all significantly smaller than the expected value of 1.00. Considering just the Cu—N bonds and Cu···Cu contacts, each of atoms Cu7–Cu10 has an approximate `square-planar' trans-Cu₂N₂ coordination geometry.

The carboxyl­ate group of the C1-containing benzoate ligand is slightly rotated from the plane of the aromatic ring, by 1.3 (5)°; the equivalent values for the for the C8- and C15-containing anions are much larger, at 18.4 (4) and 18.5 (4)°, respectively. The C—O carboxyl­ate bond lengths indicate substantial delocalization in each case such that the two C—O bond lengths are almost equal (Table 2). For each ligand, the Cu^I atoms bonded to the O atoms are displaced in an opposite sense from the CO₂ plane: for the C7/O1/O2 group, atoms Cu1 and Cu2 are displaced by -0.36 (2) and 0.44 (2) Å, respectively; for C14/O3/O4, Cu3 and Cu4 are displaced by -0.58 (2) and 0.44 (2) Å, respectively; for C21/O5/O6, Cu5 and Cu6 are displaced by -0.57 (2) and 0.48 (2) Å, respectively. Neglecting the borderline long Cu—O bonds, each benzoate ligand bonds to four nearby Cu^I atoms in a µ₄N,N',O,O'-mode. The same µ₄ ligand-bonding mode (but with a totally different overall structure) has been seen in [Mn(C₇H₇N₂O₂)(N₃)] (Chen et al., 2009). Each chloride ion in (1) is bonded to two Cu^I atoms, with Cu—Cl < 2.5 Å and Cl—Cu—Cl < 125°, but a third metal atom is also present within 3.1 Å.

The packing in (1) is a dense three-dimensional polymeric network without any identifiable channels or voids. When viewed down the [101] direction (Fig. 3), chains of Cu^I atoms (involving Cu1–Cu6) and chloride ions are apparent, which are shown in more detail in Fig. 4, where four-, six- and eight-atom loops (Peng et al., 2010) are apparent in the chains. The packing is consolidated by N—H···Cl hydrogen bonds (Table 2), with all 12 N—H groups participating in such an inter­action (mean H···Cl = 2.62 Å and mean N—H···Cl = 165°) Any possible aromatic π–π stacking in the crystal of (1) must be extremely weak, as the shortest separation of the centroids of the benzene rings is greater than 4.0 Å.

The Cu···Cu contacts (or bonds?) in (1) merit some further discussion. As might be expected, the shortest separations occur between pairs of metal atoms bridged by a benzoate ligand: this type of inter­action has been termed `semi supported' by Schmidbaur & Schier (2012): the relevant data for (1) are Cu1···Cu2 = 2.7454 (13) Å, Cu3···Cu4 = 2.7350 (14) Å and Cu5···Cu6 = 2.7551 (15) Å. These separations are significantly shorter than those in the recently reported semi-supported (by one bulky benzoate ligand) linear polymer [Cu(C<sub>16</sub>H<sub>23</sub>O<sub>2</sub>)]<sub>n</sub> (Hietsoi et al., 2011), with Cu···Cu = 2.9397 (5) Å, but are much longer than the `fully supported' (by two bridging benzoate ligands) Cu···Cu distance of 2.493 Å (s.u. value not stated) in the dimeric compound [Cu₂(C₁₆H₂₃O₂)₂(C₆H₄Cl₂)₂] (Batsanov, 2001).

The `unsupported' (no bridging ligands) Cu···Cu contacts in (1) between the Cu^I atoms associated with the benzoate ligands (Cu1–Cu6) and the Cu^I atoms showing a local linear N—Cu—N geometry (Cu7–Cu10) show considerable variation in their lengths, with the Cu4···Cu9 [2.8145 (12) Å] and Cu6···Cu10 [2.8455 (10) Å] separations being almost as short as the semi-supported bonds. Conversely, the Cu1···Cu7 [3.0169 (9) Å] and Cu2···Cu8 [3.0174 (12) Å] links are of inter­mediate length, and the Cu5···Cu9 [3.1067 (12) Å] and Cu3···Cu8 [3.2142 (13) Å] contacts are the longest. If all of these contacts, which are significantly shorter than twice the van der Waals radius of 1.92 Å for Cu⁺ according to Batsanov (2001), are regarded as cuprophilic Cu···Cu inter­actions/bonds, then infinite [101] zigzag chains of Cu^I atoms occur (Fig. 5). Yet another way to visualize the structure is in terms of the Cu⁺ and Cl^- ions: when these are considered together, an unusual three-dimensional cationic open framework of stoichiometry [Cu₃Cl₂]⁺ results (including the Cu···Cu links), which surrounds [101] channels (Fig. 6).

S4. Conclusions

The serendipitous redox synthesis and crystal structure of [Cu₃(C₇H₇N₂O₂)Cl₂] have been described. A wide variety of copper coordination polyhedra occur, including CuOCl₂ (T-shape), CuOCl₃ (tetra­hedral) and CuN₂ (linear), which obviously correlate with the different functional groups (carboxyl­ate and amine) of the ligand. Every Cu^I atom has two near neighbours and if all these are regarded as cuprophilic bonds, then infinite zigzag Cu···Cu chains occur in the crystal.

Structure description

Compounds containing copper(I) (electronic configuration [Ar]3d¹⁰) are of inter­est for their role in biological processes (Tsukihara et al., 1995) and the presence of short (< ~3.2 Å) Cu···Cu contacts in their crystal structures (Arkhireeva et al., 1990; Zheng et al., 2005; Sundararaman et al., 2005; Doshi et al., 2012, Cotton et al., 1998; Carvajal et al., 2004). The nature of these contacts has been debated, with some authors (Zheng et al., 2005; Sundararaman et al., 2005; Doshi et al., 2012) describing them as weakly attractive (bonding) `cuprophilic' inter­actions akin to the well-established argentophilic Ag···Ag (Barreiro et al., 2013) and aurophilic Au···Au (Schmidbaur & Schier, 2012) weak bonds in silver(I) and gold(I) compounds, respectively. However, other workers have questioned whether these Cu···Cu contacts represent bonds at all and suggested that the short metal–metal distances observed are either constrained by the ligand geometry (Cotton et al., 1998) or are largely ionic in nature (Carvajal et al., 2004).

Here, we describe the hydro­thermal synthesis and crystal structure of the three-dimensional coordination polymer [Cu₃(C₇H₇N₂O₂)Cl₂]_n, (1), which arose from the unexpected reduction of the CuCl₂ starting material to Cu⁺ under basic conditions; C₇H₇N₂O₂^- is the 3,5-di­amino­benzoate anion.

The lack of colour of the crystals of (1) is consistent with the 3d¹⁰ electron configuration of the Cu⁺ ion (Doshi et al., 2012; Kappenstein & Hugel, 1978). The precise nature of the redox reaction that generated the cuprous ions is unknown, but similar reductions of Cu²⁺ → Cu⁺ in the presence of a nitro­gen-containing ligand under hydro­thermal conditions have been reported by other workers (Xin et al., 2013) and indeed this type of reduction has been described as a `recommended route' (Peng et al., 2010) to cuprous–halide compounds from Cu²⁺-containing starting materials. The asymmetric unit of (1), which contains no fewer than ten crystallographically independent Cu^I atoms (eight of which lie on general positions and two on crystallographic inversion centres), as well as three benzoate ligands and six chloride ions, is shown in Fig. 1.

The copper coordination geometries in (1) can be split into several distinct types. Atoms Cu1–Cu6 are bonded to various combinations of benzoate O atoms and chloride ions (Table 1). In this complex structure, all these Cu^I atoms are surrounded by a number of O and Cl atoms at distances around or slightly shorter that the Bondi (1964) van der Waals radii sum of Cu···O = 2.92 Å and Cu···Cl = 3.15 Å, but by using the Brown criterion of 0.04 of a bond-valence unit to indicate a significant chemical bond to a univalent cation (Brown, 2002), the following conclusions can be drawn: Cu1 and Cu2 are bonded to a benzoate O atom and two chloride ions in a distorted T-shape, whereas Cu3 and Cu5 are bonded to one O atom and three chloride ions in very distorted tetra­hedral arrangements (Fig. 2). The Cu4 and Cu6 coordination geometries are ambiguous; they have two well-defined short bonds to one O and one chloride ion in an approximately linear arrangement [O—Cu—Cl = 161.90 (15) and 151.94 (15)° for Cu4 and Cu6, respectively], but also one (for Cu4) and two (for Cu6) very long Cu—Cl contacts, which are right on the borderline of being considered as bonds.

In every case, the Cu^I atom also has two short Cu···Cu contacts to adjacent metal atoms with the separations indicated in the caption of Fig. 1; these are further discussed below. Bond-valence sums (Brown & Altermatt, 1985) for atoms Cu1 (1.05), Cu2 (1.04), Cu3 (1.03), Cu4 (1.01), Cu5 (1.05) and Cu6 (1.05) are in excellent agreement with the expected value of 1.00 for the cuprous ion, confirming that reduction from Cu²⁺ has occurred.

The other group of metal atoms, Cu7–Cu10 (Cu7 and Cu10 lie on crystallographic inversion centres) are bonded to two ligand N atoms (Cu—N < 2.00 Å) in a linear or near-linear geometry [N—Cu—N = 180, 177.8 (2), 176.6 (2) and 180° for Cu7, Cu8, Cu9 and Cu10, respectively]. Again, these atoms have a number of Cu···O and Cu···Cl contacts slightly shorter that the van der Waals radii sums noted above, with some of the former being just significant as bonds based on the Brown bond-valence criterion (Table 1). Even when the long Cu—O bonds are included, this group of Cu^I atoms appear to be substanti­ally `under-bonded' (Saines et al., 2006), with their BVS values of 0.66 (Cu7), 0.74 (Cu8), 0.72 (Cu9) and 0.71 (Cu10) all significantly smaller than the expected value of 1.00. Considering just the Cu—N bonds and Cu···Cu contacts, each of atoms Cu7–Cu10 has an approximate `square-planar' trans-Cu₂N₂ coordination geometry.

The carboxyl­ate group of the C1-containing benzoate ligand is slightly rotated from the plane of the aromatic ring, by 1.3 (5)°; the equivalent values for the for the C8- and C15-containing anions are much larger, at 18.4 (4) and 18.5 (4)°, respectively. The C—O carboxyl­ate bond lengths indicate substantial delocalization in each case such that the two C—O bond lengths are almost equal (Table 2). For each ligand, the Cu^I atoms bonded to the O atoms are displaced in an opposite sense from the CO₂ plane: for the C7/O1/O2 group, atoms Cu1 and Cu2 are displaced by -0.36 (2) and 0.44 (2) Å, respectively; for C14/O3/O4, Cu3 and Cu4 are displaced by -0.58 (2) and 0.44 (2) Å, respectively; for C21/O5/O6, Cu5 and Cu6 are displaced by -0.57 (2) and 0.48 (2) Å, respectively. Neglecting the borderline long Cu—O bonds, each benzoate ligand bonds to four nearby Cu^I atoms in a µ₄N,N',O,O'-mode. The same µ₄ ligand-bonding mode (but with a totally different overall structure) has been seen in [Mn(C₇H₇N₂O₂)(N₃)] (Chen et al., 2009). Each chloride ion in (1) is bonded to two Cu^I atoms, with Cu—Cl < 2.5 Å and Cl—Cu—Cl < 125°, but a third metal atom is also present within 3.1 Å.

The packing in (1) is a dense three-dimensional polymeric network without any identifiable channels or voids. When viewed down the [101] direction (Fig. 3), chains of Cu^I atoms (involving Cu1–Cu6) and chloride ions are apparent, which are shown in more detail in Fig. 4, where four-, six- and eight-atom loops (Peng et al., 2010) are apparent in the chains. The packing is consolidated by N—H···Cl hydrogen bonds (Table 2), with all 12 N—H groups participating in such an inter­action (mean H···Cl = 2.62 Å and mean N—H···Cl = 165°) Any possible aromatic π–π stacking in the crystal of (1) must be extremely weak, as the shortest separation of the centroids of the benzene rings is greater than 4.0 Å.

The Cu···Cu contacts (or bonds?) in (1) merit some further discussion. As might be expected, the shortest separations occur between pairs of metal atoms bridged by a benzoate ligand: this type of inter­action has been termed `semi supported' by Schmidbaur & Schier (2012): the relevant data for (1) are Cu1···Cu2 = 2.7454 (13) Å, Cu3···Cu4 = 2.7350 (14) Å and Cu5···Cu6 = 2.7551 (15) Å. These separations are significantly shorter than those in the recently reported semi-supported (by one bulky benzoate ligand) linear polymer [Cu(C<sub>16</sub>H<sub>23</sub>O<sub>2</sub>)]<sub>n</sub> (Hietsoi et al., 2011), with Cu···Cu = 2.9397 (5) Å, but are much longer than the `fully supported' (by two bridging benzoate ligands) Cu···Cu distance of 2.493 Å (s.u. value not stated) in the dimeric compound [Cu₂(C₁₆H₂₃O₂)₂(C₆H₄Cl₂)₂] (Batsanov, 2001).

The `unsupported' (no bridging ligands) Cu···Cu contacts in (1) between the Cu^I atoms associated with the benzoate ligands (Cu1–Cu6) and the Cu^I atoms showing a local linear N—Cu—N geometry (Cu7–Cu10) show considerable variation in their lengths, with the Cu4···Cu9 [2.8145 (12) Å] and Cu6···Cu10 [2.8455 (10) Å] separations being almost as short as the semi-supported bonds. Conversely, the Cu1···Cu7 [3.0169 (9) Å] and Cu2···Cu8 [3.0174 (12) Å] links are of inter­mediate length, and the Cu5···Cu9 [3.1067 (12) Å] and Cu3···Cu8 [3.2142 (13) Å] contacts are the longest. If all of these contacts, which are significantly shorter than twice the van der Waals radius of 1.92 Å for Cu⁺ according to Batsanov (2001), are regarded as cuprophilic Cu···Cu inter­actions/bonds, then infinite [101] zigzag chains of Cu^I atoms occur (Fig. 5). Yet another way to visualize the structure is in terms of the Cu⁺ and Cl^- ions: when these are considered together, an unusual three-dimensional cationic open framework of stoichiometry [Cu₃Cl₂]⁺ results (including the Cu···Cu links), which surrounds [101] channels (Fig. 6).

The serendipitous redox synthesis and crystal structure of [Cu₃(C₇H₇N₂O₂)Cl₂] have been described. A wide variety of copper coordination polyhedra occur, including CuOCl₂ (T-shape), CuOCl₃ (tetra­hedral) and CuN₂ (linear), which obviously correlate with the different functional groups (carboxyl­ate and amine) of the ligand. Every Cu^I atom has two near neighbours and if all these are regarded as cuprophilic bonds, then infinite zigzag Cu···Cu chains occur in the crystal.

Synthesis and crystallization

A mixture of CuCl₂ (134 mg, 1.0 mmol) and 3,5-di­amino­benzoic acid (304 mg, 2.0 mmol) was added to 1 M KOH (2.0 ml) with stirring to yield a pale-blue solution. This mixture was heated to 423 K in a 23 ml Teflon-lined autoclave for 15 h and then cooled to room temperature over a period of several hours. Colourless blocks of (1) were recovered from the reaction by filtration and rinsing with water and acetone.

Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 1. The crystal quality was only fair, which may correlate with the rather high residuals and the larger than expected difference-map features (Δρ min. max. = -2.7 and 3.4 e Å^-3, respectively). The H atoms were placed geometrically (C—H = 0.95 Å and N—H = 0.92 Å) and refined as riding atoms, with the constraint U_iso(H) = U_eq(carrier). This structure has a strong subcell (C2/c, a = 13.077, b = 10.894, c = 7.209 Å, β = 94.64° and V = 1023.6 ų), but refinements in this space group, in which the asymmetric unit contains two Cu^I atoms (one with symmetry 1), two Cl atoms and half a ligand molecule, led to much higher residuals [R(F) ~0.20], large difference Fourier peaks (~±6 e Å^-3) in the vicinity of the Cu^I atoms and many systematic absence violations and was therefore rejected. The structural models were analysed and verified with PLATON (Spek, 2009).

Computing details

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and ATOMS (Dowty, 2004); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

Figures

	Fig. 1. The asymmetric unit of (1), showing displacement ellipsoids at the 50% probability level. The N—H···Cl hydrogen bonds are indicated by double dashed lines. The Cu···Cu separations (bronze double dashed lines, Å) are as follows: Cu1···Cu2 = 2.7454 (13), Cu3···Cu4 = 2.7350 (14), Cu5···Cu6 = 2.7551 (15), Cu1···Cu7 = 3.0169 (9), Cu2···Cu8 = 3.0174 (12), Cu3···Cu8 = 3.2142 (13), Cu4···Cu9 = 2.8145 (12), Cu5···Cu9 = 3.1067 (12), Cu6···Cu10 = 2.845 (10). The Cu···Cu···Cu angles (°) are as follows: Cu7···Cu1···Cu2 = 142.08 (3), Cu1···Cu2···Cu8 = 147.34 (4), Cu2···Cu8···Cu3 = 175.11 (4), Cu8···Cu3···Cu4 = 136.27 (4), Cu3···Cu4···Cu9 = 149.88 (5), Cu4···Cu9···Cu5 = 174.23 (4), Cu9···Cu5···Cu6 = 135.11 (4), Cu5···Cu6···Cu10 = 143.90 (4), Cu1···Cu7···Cu1^i = 180, Cu6···Cu10···Cu6^ii = 180 [symmetry codes: (i) -x+1, -y, -z; (ii) -x, -y, -z+2.]
	Fig. 2. The coordination environment of atom Cu3 in (1), showing its CuOCl3 tetrahedron (solid lines for Cu—O and Cu—Cl bonds and open lines connecting vertices) and dashed lines indicating short Cu···Cu contacts to Cu4 (`semi-supported' via the bridging –CO2 group) and Cu8 (unsupported); note how these pass through the tetrahedral faces. For symmetry codes, see Table 1.
	Fig. 3. The packing in (1), viewed approximately down [101], showing the Cu/Cl chains. Colour key: Cu orange, Cl green, C dark grey, H white, N blue and O red. C-bound H atoms have been omitted for clarity. [Can versions of Figs. 3–6 be supplied with a white background?]
	Fig. 4. Fragment of a [101] Cu/Cl chain (key: Cu orange and Cl green) in (1), showing the constituent four-, six- and eight-membered rings.
	Fig. 5. Zigzag Cu···Cu chains, which propagate in the [101] direction, in the crystal of (1).
	Fig. 6. The [Cu3Cl2]^+ network in (1), showing the formation of [101] channels.

Poly[di-µ-chlorido-(µ-3,5-diaminobenzoato-κ²O:O')tricopper(I)(3 Cu—Cu)]

Crystal data

[Cu3(C7H7CN2O2)Cl2]	F(000) = 2400
Mr = 412.67	Dx = 2.677 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 14.4127 (2) Å	Cell parameters from 23785 reflections
b = 10.8942 (2) Å	θ = 1.0–30.0°
c = 20.2348 (4) Å	µ = 6.68 mm^−1
β = 104.8395 (7)°	T = 180 K
V = 3071.20 (9) Å^3	Block, colourless
Z = 12	0.39 × 0.16 × 0.14 mm

Data collection

Bruker APEXII CCD diffractometer	4798 reflections with I > 2σ(I)
ω scans	Rint = 0.069
Absorption correction: multi-scan (SADABS; Bruker, 2004)	θmax = 26.0°, θmin = 2.1°
Tmin = 0.181, Tmax = 0.455	h = −17→17
16907 measured reflections	k = −12→13
5987 independent reflections	l = −22→24

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.069	H-atom parameters constrained
wR(F^2) = 0.202	w = 1/[σ^2(Fo^2) + (0.1163P)^2 + 23.2868P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
5987 reflections	Δρmax = 3.40 e Å^−3
436 parameters	Δρmin = −2.71 e Å^−3

Special details

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.

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

	x	y	z	Uiso*/Ueq
Cu1	0.46131 (6)	−0.15788 (7)	0.11250 (4)	0.0217 (2)
Cu2	0.37595 (6)	−0.15297 (7)	0.21918 (5)	0.0228 (2)
Cu3	0.26100 (8)	0.15557 (9)	0.44481 (5)	0.0351 (3)
Cu4	0.25123 (7)	0.12385 (8)	0.57694 (5)	0.0286 (3)
Cu5	0.08697 (7)	−0.14980 (8)	0.77262 (5)	0.0325 (3)
Cu6	0.08418 (7)	−0.12935 (8)	0.90781 (5)	0.0275 (3)
Cu7	0.5000	0.0000	0.0000	0.0177 (3)
Cu8	0.32887 (5)	−0.00559 (7)	0.33262 (4)	0.0199 (2)
Cu9	0.17070 (5)	0.00558 (7)	0.67278 (4)	0.0206 (2)
Cu10	0.0000	0.0000	1.0000	0.0205 (3)
C1	0.4207 (4)	0.2083 (6)	0.1627 (3)	0.0097 (12)
C2	0.4815 (4)	0.2722 (5)	0.1312 (3)	0.0104 (11)
H2	0.5227	0.2291	0.1094	0.013*
C3	0.4813 (4)	0.3997 (5)	0.1322 (3)	0.0106 (11)
C4	0.4220 (4)	0.4639 (6)	0.1635 (3)	0.0113 (12)
H4	0.4218	0.5511	0.1634	0.014*
C5	0.3622 (4)	0.3990 (5)	0.1954 (3)	0.0107 (11)
C6	0.3601 (4)	0.2720 (5)	0.1953 (3)	0.0096 (11)
H6	0.3185	0.2288	0.2168	0.012*
C7	0.4201 (4)	0.0721 (6)	0.1633 (3)	0.0110 (12)
N1	0.5492 (4)	0.4670 (5)	0.1044 (3)	0.0145 (10)
H1A	0.5233	0.5407	0.0883	0.017*
H1B	0.5606	0.4243	0.0686	0.017*
N2	0.2977 (4)	0.4666 (5)	0.2273 (3)	0.0147 (11)
H2A	0.3248	0.5405	0.2419	0.018*
H2B	0.2915	0.4243	0.2647	0.018*
C8	0.2549 (4)	−0.2226 (5)	0.4944 (3)	0.0092 (11)
C9	0.3132 (4)	−0.2847 (5)	0.4599 (3)	0.0104 (11)
H9	0.3537	−0.2406	0.4379	0.013*
C10	0.3110 (4)	−0.4128 (5)	0.4583 (3)	0.0106 (11)
C11	0.2500 (4)	−0.4779 (5)	0.4887 (3)	0.0109 (11)
H11	0.2471	−0.5649	0.4857	0.013*
C12	0.1938 (4)	−0.4154 (5)	0.5231 (3)	0.0095 (11)
C13	0.1960 (4)	−0.2881 (5)	0.5268 (3)	0.0112 (11)
H13	0.1577	−0.2459	0.5514	0.013*
C14	0.2570 (4)	−0.0856 (5)	0.4979 (3)	0.0099 (11)
N3	0.3797 (4)	−0.4791 (5)	0.4304 (3)	0.0142 (11)
H3A	0.3906	−0.4368	0.3943	0.017*
H3B	0.3554	−0.5539	0.4152	0.017*
N4	0.1299 (4)	−0.4819 (5)	0.5553 (3)	0.0134 (10)
H4A	0.1282	−0.4423	0.5946	0.016*
H4B	0.1548	−0.5580	0.5670	0.016*
C15	0.0841 (3)	0.2246 (6)	0.8298 (3)	0.0093 (12)
C16	0.1397 (4)	0.2878 (5)	0.7943 (3)	0.0093 (11)
H16	0.1787	0.2441	0.7710	0.011*
C17	0.1380 (4)	0.4154 (5)	0.7931 (3)	0.0106 (11)
C18	0.0782 (4)	0.4802 (6)	0.8243 (3)	0.0100 (12)
H18	0.0752	0.5672	0.8217	0.012*
C19	0.0224 (4)	0.4157 (5)	0.8595 (3)	0.0101 (11)
C20	0.0262 (4)	0.2895 (5)	0.8635 (3)	0.0102 (11)
H20	−0.0103	0.2467	0.8891	0.012*
C21	0.0866 (3)	0.0876 (6)	0.8327 (3)	0.0089 (12)
N5	0.2042 (4)	0.4809 (5)	0.7630 (3)	0.0146 (11)
H5A	0.1786	0.5553	0.7479	0.018*
H5B	0.2121	0.4382	0.7262	0.018*
N6	−0.0426 (4)	0.4826 (5)	0.8907 (3)	0.0142 (11)
H6A	−0.0168	0.5576	0.9039	0.017*
H6B	−0.0469	0.4417	0.9290	0.017*
O1	0.4743 (3)	0.0166 (4)	0.1325 (2)	0.0180 (10)
O2	0.3656 (3)	0.0181 (4)	0.1938 (2)	0.0206 (10)
O3	0.2921 (4)	−0.0264 (4)	0.4563 (2)	0.0199 (10)
O4	0.2252 (4)	−0.0391 (4)	0.5446 (2)	0.0216 (10)
O5	0.1191 (3)	0.0303 (4)	0.7893 (2)	0.0167 (9)
O6	0.0561 (3)	0.0371 (4)	0.8790 (2)	0.0172 (9)
Cl1	0.39320 (11)	−0.29137 (15)	0.03396 (8)	0.0225 (4)
Cl2	0.43913 (10)	−0.29010 (13)	0.29733 (8)	0.0172 (3)
Cl3	0.27191 (12)	0.25776 (14)	0.34882 (8)	0.0214 (4)
Cl4	0.26239 (11)	0.28564 (14)	0.63859 (8)	0.0202 (4)
Cl5	0.10718 (11)	−0.25623 (14)	0.68104 (7)	0.0186 (3)
Cl6	0.08403 (13)	−0.28007 (15)	0.97701 (8)	0.0267 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0264 (5)	0.0164 (4)	0.0250 (5)	−0.0048 (3)	0.0116 (4)	−0.0076 (3)
Cu2	0.0257 (5)	0.0185 (4)	0.0285 (5)	0.0069 (3)	0.0145 (4)	0.0101 (3)
Cu3	0.0522 (7)	0.0215 (5)	0.0343 (6)	0.0021 (4)	0.0159 (5)	0.0124 (4)
Cu4	0.0384 (6)	0.0200 (5)	0.0280 (5)	−0.0033 (4)	0.0099 (4)	−0.0105 (4)
Cu5	0.0354 (6)	0.0252 (5)	0.0399 (6)	−0.0039 (4)	0.0151 (5)	−0.0167 (4)
Cu6	0.0326 (5)	0.0203 (5)	0.0271 (5)	−0.0019 (4)	0.0027 (4)	0.0122 (4)
Cu7	0.0091 (6)	0.0185 (6)	0.0275 (6)	0.0053 (4)	0.0085 (5)	0.0021 (5)
Cu8	0.0108 (5)	0.0220 (5)	0.0294 (5)	−0.0067 (3)	0.0096 (4)	−0.0035 (3)
Cu9	0.0117 (5)	0.0254 (5)	0.0267 (5)	0.0080 (3)	0.0084 (4)	0.0065 (3)
Cu10	0.0109 (6)	0.0262 (6)	0.0254 (6)	−0.0074 (4)	0.0066 (5)	−0.0058 (5)
C1	0.007 (3)	0.011 (3)	0.008 (3)	0.0022 (19)	−0.002 (2)	0.000 (2)
C2	0.005 (2)	0.017 (3)	0.009 (3)	0.001 (2)	0.001 (2)	0.000 (2)
C3	0.008 (3)	0.013 (3)	0.010 (3)	−0.004 (2)	0.000 (2)	0.001 (2)
C4	0.009 (3)	0.013 (3)	0.012 (3)	−0.004 (2)	0.002 (2)	0.000 (2)
C5	0.006 (3)	0.014 (3)	0.009 (3)	0.000 (2)	−0.003 (2)	−0.004 (2)
C6	0.007 (3)	0.013 (3)	0.008 (3)	−0.005 (2)	0.001 (2)	−0.003 (2)
C7	0.009 (3)	0.013 (3)	0.011 (3)	0.002 (2)	0.002 (2)	−0.002 (2)
N1	0.010 (2)	0.016 (2)	0.020 (3)	−0.003 (2)	0.008 (2)	0.004 (2)
N2	0.017 (3)	0.009 (2)	0.023 (3)	0.000 (2)	0.012 (2)	−0.002 (2)
C8	0.005 (2)	0.012 (3)	0.010 (3)	0.001 (2)	−0.001 (2)	0.000 (2)
C9	0.005 (3)	0.013 (3)	0.013 (3)	−0.003 (2)	0.003 (2)	−0.001 (2)
C10	0.008 (3)	0.012 (3)	0.011 (3)	0.005 (2)	0.001 (2)	−0.004 (2)
C11	0.008 (3)	0.009 (3)	0.016 (3)	0.002 (2)	0.002 (2)	0.003 (2)
C12	0.005 (2)	0.009 (3)	0.014 (3)	−0.002 (2)	0.001 (2)	0.003 (2)
C13	0.012 (3)	0.009 (3)	0.013 (3)	0.003 (2)	0.004 (2)	−0.002 (2)
C14	0.004 (2)	0.012 (3)	0.012 (3)	−0.002 (2)	−0.001 (2)	0.000 (2)
N3	0.014 (3)	0.011 (2)	0.020 (3)	0.002 (2)	0.008 (2)	−0.004 (2)
N4	0.015 (3)	0.010 (2)	0.017 (3)	−0.0028 (19)	0.008 (2)	0.002 (2)
C15	0.002 (3)	0.013 (3)	0.012 (3)	0.0006 (19)	0.000 (2)	0.001 (2)
C16	0.008 (3)	0.009 (3)	0.011 (3)	0.001 (2)	0.003 (2)	0.002 (2)
C17	0.005 (2)	0.010 (3)	0.016 (3)	0.000 (2)	0.001 (2)	0.002 (2)
C18	0.006 (3)	0.010 (3)	0.014 (3)	0.0021 (19)	0.003 (2)	0.002 (2)
C19	0.004 (2)	0.011 (3)	0.014 (3)	−0.001 (2)	0.001 (2)	−0.006 (2)
C20	0.009 (3)	0.011 (3)	0.012 (3)	0.000 (2)	0.005 (2)	−0.003 (2)
C21	0.005 (3)	0.011 (3)	0.011 (3)	0.0014 (18)	0.001 (2)	0.000 (2)
N5	0.017 (3)	0.012 (2)	0.018 (3)	−0.003 (2)	0.009 (2)	0.002 (2)
N6	0.015 (3)	0.011 (2)	0.021 (3)	0.0056 (19)	0.013 (2)	0.000 (2)
O1	0.018 (2)	0.013 (2)	0.026 (2)	0.0008 (17)	0.0106 (19)	−0.0006 (18)
O2	0.023 (2)	0.014 (2)	0.028 (3)	0.0032 (18)	0.013 (2)	0.0036 (19)
O3	0.027 (3)	0.012 (2)	0.026 (2)	0.0021 (18)	0.018 (2)	0.0005 (19)
O4	0.034 (3)	0.015 (2)	0.022 (2)	−0.002 (2)	0.018 (2)	−0.0061 (19)
O5	0.023 (2)	0.011 (2)	0.020 (2)	−0.0025 (18)	0.0128 (19)	−0.0040 (18)
O6	0.027 (2)	0.011 (2)	0.019 (2)	0.0030 (18)	0.0140 (19)	0.0021 (17)
Cl1	0.0208 (8)	0.0233 (8)	0.0202 (8)	−0.0011 (6)	−0.0007 (6)	−0.0058 (6)
Cl2	0.0145 (7)	0.0169 (7)	0.0179 (7)	0.0024 (5)	0.0000 (6)	0.0044 (6)
Cl3	0.0226 (8)	0.0234 (8)	0.0159 (7)	0.0000 (6)	0.0008 (6)	0.0040 (6)
Cl4	0.0204 (8)	0.0179 (7)	0.0178 (7)	0.0031 (6)	−0.0031 (6)	−0.0070 (6)
Cl5	0.0181 (7)	0.0209 (7)	0.0147 (7)	0.0019 (6)	0.0005 (6)	−0.0047 (6)
Cl6	0.0313 (9)	0.0233 (8)	0.0182 (8)	−0.0106 (7)	−0.0070 (7)	0.0095 (6)

Geometric parameters (Å, º)

Cu1—O1	1.943 (4)	C7—O2	1.261 (7)
Cu1—Cl1	2.1921 (17)	C7—O1	1.270 (7)
Cu1—Cl5^i	2.3928 (17)	N1—Cu9^viii	1.957 (5)
Cu1—Cu2	2.7454 (13)	N1—H1A	0.9200
Cu1—Cu7	3.0169 (9)	N1—H1B	0.9200
Cu2—O2	1.929 (5)	N2—Cu8^iii	1.938 (5)
Cu2—Cl2	2.1964 (16)	N2—H2A	0.9200
Cu2—Cl3^ii	2.4246 (18)	N2—H2B	0.9200
Cu2—Cu8	3.0174 (12)	C8—C13	1.395 (8)
Cu3—O3	2.033 (5)	C8—C9	1.398 (8)
Cu3—Cl3	2.2788 (18)	C8—C14	1.494 (8)
Cu3—Cl1^iii	2.439 (2)	C9—C10	1.395 (8)
Cu3—Cl6^iv	2.485 (2)	C9—H9	0.9500
Cu3—Cu4	2.7350 (14)	C10—C11	1.390 (8)
Cu4—O4	1.896 (5)	C10—N3	1.453 (7)
Cu4—Cl4	2.1415 (17)	C11—C12	1.376 (8)
Cu4—Cl1^iii	2.7981 (19)	C11—H11	0.9500
Cu4—Cu9	2.8145 (12)	C12—C13	1.389 (8)
Cu5—O5	2.024 (4)	C12—N4	1.452 (7)
Cu5—Cl5	2.2672 (17)	C13—H13	0.9500
Cu5—Cl2^v	2.4009 (18)	C14—O4	1.257 (7)
Cu5—Cl4^vi	2.5373 (18)	C14—O3	1.263 (7)
Cu5—Cu6	2.7551 (15)	N3—Cu10^vi	1.946 (5)
Cu6—O6	1.916 (4)	N3—H3A	0.9200
Cu6—Cl6	2.1583 (18)	N3—H3B	0.9200
Cu6—Cl4^vi	2.7735 (19)	N4—Cu7^ii	1.929 (5)
Cu6—Cl2^v	2.7828 (18)	N4—H4A	0.9200
Cu6—Cu10	2.8455 (10)	N4—H4B	0.9200
Cu7—N4^i	1.929 (5)	C15—C16	1.387 (8)
Cu7—N4^iii	1.929 (5)	C15—C20	1.398 (8)
Cu7—Cu1^vii	3.0168 (9)	C15—C21	1.494 (9)
Cu8—N2^ii	1.938 (5)	C16—C17	1.391 (8)
Cu8—N6^viii	1.939 (6)	C16—H16	0.9500
Cu8—O3	2.697 (4)	C17—C18	1.385 (8)
Cu9—N5^vi	1.953 (5)	C17—N5	1.444 (7)
Cu9—N1^ix	1.957 (5)	C18—C19	1.394 (8)
Cu9—O5	2.661 (4)	C18—H18	0.9500
Cu10—N3^v	1.946 (5)	C19—C20	1.377 (8)
Cu10—N3^iv	1.946 (5)	C19—N6	1.453 (7)
Cu10—O6	2.798 (4)	C20—H20	0.9500
Cu10—O6^x	2.798 (4)	C21—O6	1.258 (7)
Cu10—Cu6^x	2.8455 (10)	C21—O5	1.260 (7)
C1—C2	1.395 (8)	N5—Cu9^iv	1.953 (5)
C1—C6	1.406 (8)	N5—H5A	0.9200
C1—C7	1.484 (9)	N5—H5B	0.9200
C2—C3	1.389 (8)	N6—Cu8^ix	1.939 (6)
C2—H2	0.9500	N6—H6A	0.9200
C3—C4	1.378 (8)	N6—H6B	0.9200
C3—N1	1.448 (7)	Cl1—Cu3^ii	2.439 (2)
C4—C5	1.394 (8)	Cl2—Cu5^i	2.4010 (18)
C4—H4	0.9500	Cl3—Cu2^iii	2.4246 (18)
C5—C6	1.384 (8)	Cl4—Cu5^iv	2.5373 (18)
C5—N2	1.458 (7)	Cl5—Cu1^v	2.3929 (17)
C6—H6	0.9500	Cl6—Cu3^vi	2.485 (2)
O1—Cu1—Cl1	143.31 (15)	C10—C11—H11	120.3
O1—Cu1—Cl5^i	103.78 (15)	C11—C12—C13	120.9 (5)
Cl1—Cu1—Cl5^i	108.94 (6)	C11—C12—N4	120.3 (5)
O2—Cu2—Cl2	147.00 (16)	C13—C12—N4	118.8 (5)
O2—Cu2—Cl3^ii	103.86 (15)	C12—C13—C8	119.6 (5)
Cl2—Cu2—Cl3^ii	106.14 (6)	C12—C13—H13	120.2
O3—Cu3—Cl3	120.86 (15)	C8—C13—H13	120.2
O3—Cu3—Cl1^iii	113.26 (14)	O4—C14—O3	125.4 (6)
Cl3—Cu3—Cl1^iii	107.42 (7)	O4—C14—C8	115.5 (5)
O3—Cu3—Cl6^iv	93.82 (16)	O3—C14—C8	119.0 (5)
Cl3—Cu3—Cl6^iv	99.08 (7)	C10—N3—Cu10^vi	110.3 (4)
Cl1^iii—Cu3—Cl6^iv	122.15 (7)	C10—N3—H3A	109.6
O4—Cu4—Cl4	161.90 (15)	Cu10^vi—N3—H3A	109.6
O5—Cu5—Cl5	124.08 (14)	C10—N3—H3B	109.6
O5—Cu5—Cl2^v	113.99 (14)	Cu10^vi—N3—H3B	109.6
Cl5—Cu5—Cl2^v	109.72 (7)	H3A—N3—H3B	108.1
O5—Cu5—Cl4^vi	91.90 (14)	C12—N4—Cu7^ii	115.0 (4)
Cl5—Cu5—Cl4^vi	99.86 (6)	C12—N4—H4A	108.5
Cl2^v—Cu5—Cl4^vi	114.90 (7)	Cu7^ii—N4—H4A	108.5
O6—Cu6—Cl6	151.94 (15)	C12—N4—H4B	108.5
N4^i—Cu7—N4^iii	180.0	Cu7^ii—N4—H4B	108.5
N2^ii—Cu8—N6^viii	177.8 (2)	H4A—N4—H4B	107.5
N5^vi—Cu9—N1^ix	176.6 (2)	C16—C15—C20	119.9 (6)
N3^v—Cu10—N3^iv	180.0 (3)	C16—C15—C21	120.3 (5)
C2—C1—C6	120.4 (6)	C20—C15—C21	119.8 (5)
C2—C1—C7	120.6 (5)	C15—C16—C17	119.7 (5)
C6—C1—C7	119.0 (5)	C15—C16—H16	120.2
C3—C2—C1	119.2 (5)	C17—C16—H16	120.2
C3—C2—H2	120.4	C18—C17—C16	120.8 (5)
C1—C2—H2	120.4	C18—C17—N5	119.7 (5)
C4—C3—C2	121.2 (5)	C16—C17—N5	119.4 (5)
C4—C3—N1	118.9 (5)	C17—C18—C19	119.0 (6)
C2—C3—N1	119.7 (5)	C17—C18—H18	120.5
C3—C4—C5	119.0 (6)	C19—C18—H18	120.5
C3—C4—H4	120.5	C20—C19—C18	120.9 (5)
C5—C4—H4	120.5	C20—C19—N6	119.7 (5)
C6—C5—C4	121.4 (5)	C18—C19—N6	119.3 (5)
C6—C5—N2	119.3 (5)	C19—C20—C15	119.7 (5)
C4—C5—N2	119.2 (5)	C19—C20—H20	120.2
C5—C6—C1	118.6 (5)	C15—C20—H20	120.2
C5—C6—H6	120.7	O6—C21—O5	124.4 (6)
C1—C6—H6	120.7	O6—C21—C15	117.2 (5)
O2—C7—O1	123.7 (6)	O5—C21—C15	118.4 (5)
O2—C7—C1	118.5 (5)	C17—N5—Cu9^iv	112.6 (4)
O1—C7—C1	117.8 (5)	C17—N5—H5A	109.1
C3—N1—Cu9^viii	111.9 (4)	Cu9^iv—N5—H5A	109.1
C3—N1—H1A	109.2	C17—N5—H5B	109.1
Cu9^viii—N1—H1A	109.2	Cu9^iv—N5—H5B	109.1
C3—N1—H1B	109.2	H5A—N5—H5B	107.8
Cu9^viii—N1—H1B	109.2	C19—N6—Cu8^ix	115.1 (4)
H1A—N1—H1B	107.9	C19—N6—H6A	108.5
C5—N2—Cu8^iii	114.0 (4)	Cu8^ix—N6—H6A	108.5
C5—N2—H2A	108.8	C19—N6—H6B	108.5
Cu8^iii—N2—H2A	108.8	Cu8^ix—N6—H6B	108.5
C5—N2—H2B	108.8	H6A—N6—H6B	107.5
Cu8^iii—N2—H2B	108.8	C7—O1—Cu1	122.0 (4)
H2A—N2—H2B	107.6	C7—O2—Cu2	124.5 (4)
C13—C8—C9	120.2 (5)	C14—O3—Cu3	117.4 (4)
C13—C8—C14	119.8 (5)	C14—O4—Cu4	124.0 (4)
C9—C8—C14	120.0 (5)	C21—O5—Cu5	119.1 (4)
C10—C9—C8	118.8 (5)	C21—O6—Cu6	123.6 (4)
C10—C9—H9	120.6	Cu1—Cl1—Cu3^ii	106.78 (7)
C8—C9—H9	120.6	Cu2—Cl2—Cu5^i	105.19 (7)
C11—C10—C9	120.9 (5)	Cu3—Cl3—Cu2^iii	115.93 (8)
C11—C10—N3	119.3 (5)	Cu4—Cl4—Cu5^iv	124.31 (8)
C9—C10—N3	119.5 (5)	Cu5—Cl5—Cu1^v	113.33 (7)
C12—C11—C10	119.5 (5)	Cu6—Cl6—Cu3^vi	118.53 (8)
C12—C11—H11	120.3
C6—C1—C2—C3	−0.2 (8)	C20—C19—N6—Cu8^ix	−88.0 (6)
C7—C1—C2—C3	−179.2 (5)	C18—C19—N6—Cu8^ix	90.3 (6)
C1—C2—C3—C4	−0.1 (8)	O2—C7—O1—Cu1	12.7 (7)
C1—C2—C3—N1	175.3 (5)	C1—C7—O1—Cu1	−166.7 (4)
C2—C3—C4—C5	0.8 (8)	Cl1—Cu1—O1—C7	93.3 (5)
N1—C3—C4—C5	−174.7 (5)	Cl5^i—Cu1—O1—C7	−114.0 (4)
C3—C4—C5—C6	−1.1 (8)	Cu2—Cu1—O1—C7	−22.7 (4)
C3—C4—C5—N2	−178.6 (5)	Cu7—Cu1—O1—C7	139.2 (5)
C4—C5—C6—C1	0.7 (8)	O1—C7—O2—Cu2	16.1 (8)
N2—C5—C6—C1	178.2 (5)	C1—C7—O2—Cu2	−164.5 (4)
C2—C1—C6—C5	0.0 (8)	Cl2—Cu2—O2—C7	89.9 (5)
C7—C1—C6—C5	179.0 (5)	Cl3^ii—Cu2—O2—C7	−115.3 (5)
C2—C1—C7—O2	178.4 (5)	Cu1—Cu2—O2—C7	−24.6 (5)
C6—C1—C7—O2	−0.6 (8)	Cu8—Cu2—O2—C7	140.2 (5)
C2—C1—C7—O1	−2.2 (8)	O4—C14—O3—Cu3	−18.7 (8)
C6—C1—C7—O1	178.8 (5)	C8—C14—O3—Cu3	163.5 (4)
C4—C3—N1—Cu9^viii	87.5 (6)	Cl3—Cu3—O3—C14	−158.1 (4)
C2—C3—N1—Cu9^viii	−88.0 (6)	Cl1^iii—Cu3—O3—C14	−28.6 (5)
C6—C5—N2—Cu8^iii	−85.6 (6)	Cl6^iv—Cu3—O3—C14	98.9 (4)
C4—C5—N2—Cu8^iii	92.0 (5)	Cu4—Cu3—O3—C14	28.9 (4)
C13—C8—C9—C10	0.3 (8)	O3—C14—O4—Cu4	−16.1 (8)
C14—C8—C9—C10	179.1 (5)	C8—C14—O4—Cu4	161.7 (4)
C8—C9—C10—C11	1.8 (8)	Cl4—Cu4—O4—C14	−166.7 (4)
C8—C9—C10—N3	−172.2 (5)	Cu3—Cu4—O4—C14	29.5 (5)
C9—C10—C11—C12	−2.5 (9)	Cu9—Cu4—O4—C14	−167.2 (5)
N3—C10—C11—C12	171.4 (5)	O6—C21—O5—Cu5	18.9 (7)
C10—C11—C12—C13	1.1 (9)	C15—C21—O5—Cu5	−161.4 (4)
C10—C11—C12—N4	−179.8 (5)	Cl5—Cu5—O5—C21	164.7 (4)
C11—C12—C13—C8	1.1 (9)	Cl2^v—Cu5—O5—C21	26.4 (5)
N4—C12—C13—C8	−178.1 (5)	Cl4^vi—Cu5—O5—C21	−92.0 (4)
C9—C8—C13—C12	−1.8 (8)	Cu6—Cu5—O5—C21	−29.9 (4)
C14—C8—C13—C12	179.5 (5)	O5—C21—O6—Cu6	17.4 (7)
C13—C8—C14—O4	18.2 (8)	C15—C21—O6—Cu6	−162.3 (4)
C9—C8—C14—O4	−160.5 (5)	Cl6—Cu6—O6—C21	169.6 (3)
C13—C8—C14—O3	−163.8 (5)	Cu5—Cu6—O6—C21	−30.6 (4)
C9—C8—C14—O3	17.5 (8)	Cu10—Cu6—O6—C21	168.2 (5)
C11—C10—N3—Cu10^vi	−89.8 (6)	O1—Cu1—Cl1—Cu3^ii	−90.7 (2)
C9—C10—N3—Cu10^vi	84.3 (6)	Cl5^i—Cu1—Cl1—Cu3^ii	117.39 (7)
C11—C12—N4—Cu7^ii	−93.8 (6)	Cu2—Cu1—Cl1—Cu3^ii	15.68 (8)
C13—C12—N4—Cu7^ii	85.3 (6)	Cu7—Cu1—Cl1—Cu3^ii	−131.23 (6)
C20—C15—C16—C17	0.5 (8)	O2—Cu2—Cl2—Cu5^i	−90.0 (3)
C21—C15—C16—C17	−178.8 (5)	Cl3^ii—Cu2—Cl2—Cu5^i	115.39 (7)
C15—C16—C17—C18	−3.0 (9)	Cu1—Cu2—Cl2—Cu5^i	15.51 (8)
C15—C16—C17—N5	172.9 (5)	Cu8—Cu2—Cl2—Cu5^i	−136.75 (6)
C16—C17—C18—C19	2.7 (8)	O3—Cu3—Cl3—Cu2^iii	118.45 (18)
N5—C17—C18—C19	−173.1 (5)	Cl1^iii—Cu3—Cl3—Cu2^iii	−13.58 (10)
C17—C18—C19—C20	0.0 (8)	Cl6^iv—Cu3—Cl3—Cu2^iii	−141.53 (7)
C17—C18—C19—N6	−178.3 (5)	Cu4—Cu3—Cl3—Cu2^iii	−80.2 (2)
C18—C19—C20—C15	−2.4 (8)	O4—Cu4—Cl4—Cu5^iv	95.9 (5)
N6—C19—C20—C15	175.9 (5)	Cu3—Cu4—Cl4—Cu5^iv	−102.07 (9)
C16—C15—C20—C19	2.1 (8)	Cu9—Cu4—Cl4—Cu5^iv	96.38 (9)
C21—C15—C20—C19	−178.6 (5)	O5—Cu5—Cl5—Cu1^v	−120.24 (18)
C16—C15—C21—O6	161.7 (5)	Cl2^v—Cu5—Cl5—Cu1^v	19.58 (10)
C20—C15—C21—O6	−17.6 (7)	Cl4^vi—Cu5—Cl5—Cu1^v	140.66 (7)
C16—C15—C21—O5	−18.1 (7)	Cu6—Cu5—Cl5—Cu1^v	92.79 (15)
C20—C15—C21—O5	162.6 (5)	O6—Cu6—Cl6—Cu3^vi	−107.5 (3)
C18—C17—N5—Cu9^iv	91.0 (6)	Cu5—Cu6—Cl6—Cu3^vi	97.29 (9)
C16—C17—N5—Cu9^iv	−84.9 (6)	Cu10—Cu6—Cl6—Cu3^vi	−106.27 (8)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1^xi	0.92	2.64	3.517 (6)	160
N1—H1B···Cl1^vii	0.92	2.74	3.657 (6)	176
N2—H2A···Cl2^xi	0.92	2.53	3.422 (5)	164
N2—H2B···Cl3	0.92	2.54	3.440 (5)	165
N3—H3A···Cl2	0.92	2.75	3.661 (6)	173
N3—H3B···Cl3^xii	0.92	2.57	3.471 (5)	168
N4—H4A···Cl5	0.92	2.73	3.612 (5)	160
N4—H4B···Cl4^xii	0.92	2.49	3.354 (5)	156
N5—H5A···Cl5^xi	0.92	2.52	3.423 (5)	168
N5—H5B···Cl4	0.92	2.65	3.557 (6)	168
N6—H6A···Cl6^xi	0.92	2.51	3.382 (6)	159
N6—H6B···Cl6^x	0.92	2.73	3.634 (6)	167

Symmetry codes: (vii) −x+1, −y, −z; (x) −x, −y, −z+2; (xi) x, y+1, z; (xii) x, y−1, z.