Mixed-ligand Mn^II and Cu^II complexes with alternating 2,2'-bi­pyrimidine and terephthalate bridges

The novel polymeric complexes catena-poly[[di­aqua­man­gan­ese(II)]-[mu]-2,2'-bi­pyrimidine-[kappa]⁴N¹,N^1':N³,N^3'-[di­aqua­man­gan­ese(II)]-bis­([mu]-terephthalato-[kappa]²O¹:O⁴)], [Mn₂(C₈H₄O₄)₂(C₈H₆N₄)(H₂O)₄]_n, (I), and catena-poly[[[aquacopper(II)]-[mu]-aqua-[mu]-hydroxido-[mu]-terephthalato-[kappa]²O¹:O^1'-copper(II)-[mu]-aqua-[mu]-hydroxido-[mu]-terephthalato-[kappa]²O¹:O^1'-[aqua­copper(II)]-[mu]-2,2'-bi­pyrimidine-[kappa]⁴N¹,N^1':N³,N^3'] tetra­hydrate], {[Cu₃(C₈H₄O₄)₂(OH)₂(C₈H₆N₄)(H₂O)₄]·4H₂O}_n, (II), containing bridging 2,2'-bi­pyrimidine (bpym) ligands coordinated as bis-chelates, have been prepared via a ligand-exchange reaction. In both cases, quite unusual coordination modes of the terephthalate (tpht^2-) anions were found. In (I), two tpht^2- anions acting as bis-monodentate ligands bridge the Mn^II centres in a parallel fashion. In (II), the tpht^2- anions act as endo-bridges and connect two Cu^II centres in combination with additional aqua and hydroxide bridges. In this way, the binuclear [Mn₂(tpht)₂(bpym)(H₂O)₄] entity in (I) and the trinuclear [Cu₃(tpht)₂(OH)₂(bpym)(H₂O)₄]·4H₂O coordination entity in (II) build up one-dimensional polymeric chains along the b axis. In (I), the Mn^II cation lies on a twofold axis, whereas the four central C atoms of the bpym ligand are located on a mirror plane. In (II), the central Cu^II cation is also on a special position (site symmetry ). In the crystal structures, the packing of the chains is further strengthened by a system of hydrogen bonds [in both (I) and (II)] and weak face-to-face [pi]-[pi] inter­actions [in (I)], forming three-dimensional metal-organic frameworks. The Mn^II cation in (I) has a trigonally deformed octa­hedral geometry, whereas the Cu^II cations in (II) are in distorted octa­hedral environments. The Cu^II polyhedra are inclined relative to each other and share common edges.

S1. Introduction

In coordination chemistry, the dianion of terephthalic acid (denoted tpht^2-; systematic name: benzene-1,4-di­carboxyl­ate) is a well known linker between two metal sites, with wide application in producing metal–organic frameworks (MOFs), materials from the Institut Lavoisier (MILs), zeolite-like metal–organic frameworks (ZMOFs), porous coordination polymers (PCPs) and similar functional materials (Janiak & Vieth, 2010). Comparable with other benzene­dicarboxyl­ates (see, for example, Baca & Decurtins, 2012), tpht can coordinate up to eight metal centres (Lu et al., 2012), resulting in enormously diverse structural architectures of various dimensionalities. In addition to their many useful properties, some tpht^2- complexes exhibit inter­esting magnetic inter­actions. Bakalbassis et al. (1985, 1988) showed for the first time that moderately strong magnetic inter­actions between two tpht-linked Cu^II sites could exist even if they are about 11 Å apart. In our previous studies of mixed-ligand complexes containing benzene polycarboxyl­ates, tpht^2- anions were, as a rule, bis-monodentate ligands yielding chain complexes (Karanović et al., 2002; Rogan et al., 2004), although there were also two examples of discrete complexes with one chelating and one uncoordinated carboxyl­ate group (Rogan et al., 2000).

2,2'-Bi­pyrimidine (bpym) is a rigid ligand with four N atoms as potential donor sites. Bpym can act as a terminal or a bridging ligand (Rodríguez-Martín et al., 2001; Alborés & Rentschler, 2013) coordinating as a mono- or bis-chelate, respectively. A survey of the Cambridge Structural Database (CSD, Version?; Groom & Allen, 2014) showed that these two modes of coordination appear with approximately the same frequency. Some recent examples (Thuéry, 2013; Thuéry & Rivière, 2013) simultaneously contain both types of bpym mode of coordination. This could result in complexes of various dimensionalities, with inter­esting optical and magnetic properties, especially in the case of lanthanide compounds (Zucchi, 2011).

So far, our research was focused on bulky aromatic di­amines, such as 2,2'-bi­pyridine (bipy), 1,10-phenanthroline (phen) and 2,2'-di­pyridyl­amine (dpya), which are typical terminal ligands (Rogan et al., 2000, 2006, 2011; Rogan & Poleti, 2004). Therefore, the choice of bpym, since it is similar to bipy, but with a possible bridging function, is logical for a continuation of our studies. The title complexes [Mn₂(tpht)₂(bpym)(H₂O)₄]_n, (I), and {[Cu₃(tpht)₂(OH)₂(bpym)(H₂O)₄].4H₂O}_n, (II), have been prepared and their structures determined.

S2. Experimental

S2.1. Synthesis and crystallization

For the synthesis of complex (I), an EtOH solution (5 ml) of bpym (0.0157 g, 0.1 mmol) was added dropwise to an aqueous solution (100 ml) containing Mn(CH₃COO)₂.4H₂O (0.0245 g, 0.1 mmol) and the resulting solution stirred for 10 min. The mixture was light yellow with pH ~7. An aqueous solution (50 ml) of Na₂tpht (0.0210 g, 0.1 mmol) was added slowly with continuous mixing. The final solution was filtered, transferred to a crystallization dish and left under ambient conditions for slow evaporation. Yellow single crystals of (I) of suitable size were obtained after five months.

Complex (II) was prepared in an analogous manner but starting with an aqueous solution containing Cu(NO₃)₂.3H₂O (0.0188 g, 0.1 mmol). The inter­mediate mixture was light blue with pH ~5. Although the first very small crystals of (II) appeared after only 4 d, a further three months were necessary to obtain green single crystals of suitable size for X-ray analysis.

In both cases the yield was very small, and only a few crystals of each complex were obtained. The complexes are insoluble in H₂O, EtOH and di­methyl sulfoxide.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. All C-bound H atoms were generated geometrically and refined using a riding model, with C—H = 0.93 Å, and with U_iso(H) = 1.2U_eq(C). The H atoms of the coordinated water molecules and bridging OH groups were located in difference maps and refined with O—H = 0.85 Å. Two of the solvent water molecules in (II) were treated in different ways. For the first (O8), the H atoms were found in a difference map and refined with O—H = 0.85 Å and U_iso(H) = 1.5U_eq(O). The other water molecule (O9) was problematic since, according to the program PLATON (Spek, 2009), it is located in a void with a volume of 56 ų, which is larger than usual (40 ų) for a hydrogen-bonded water molecule. One H atom was located easily in a difference map, while the position of the other was calculated with the program HYDROGEN (Nardelli, 1999) using 0.45 e^- as the partial atomic charge. Both H atoms were then added to the structural model with fixed coordinates and with U_iso(H) = 1.5U_eq(O). However, this water molecule acts as a hydrogen-bond donor only once, because there are no suitable acceptors in its vicinity. Large displacement parameters also indicate a possible disorder of the O9 water molecule, but this was not accounted for in the refinement.

S3. Results and discussion

In [Mn₂(tpht)₂(bpym)(H₂O)₄]_n, (I), only a quarter of the 2,2'-bi­pyrimidine (bpym) ligand, half of a terephthalate (tpht^2-) ligand, half of an Mn^II cation and one aqua ligand belong to the asymmetric unit. However, the basic building unit should be presented as the binuclear {[Mn₂(tpht)₂(bpym)(H₂O)₄]}_n entity (Fig. 1). It can be understood as an [Mn₂(bpym)(H₂O)₄] unit bridged by two tpht^2- anions, or vice versa as an [Mn₂(tpht)₂(H₂O)₄] unit bridged by a bpym ligand. In this way, one-dimensional chains extending along the [010] direction are formed. Mn···Mn distances along the chain are alternately 6.1705 (10) and 9.4645 (12) Å, while the distances between the chains are 6.4420 (10) and 7.3991 (11) Å. This means that no direct or strong magnetic inter­actions should be expected.

The Mn^II centre is in a trigonally distorted o­cta­hedral coordination, with the Mn—N bonds being the longest and the Mn—O(carboxyl­ate) bonds on the opposite side of the equatorial plane being the shortest. The trans O3—Mn1—O3ⁱ [symmetry code: (i) -x + 2, y, -z] angle involving the aqua ligands is 170.32 (7)° (Table 2). The N1—Mn1—N1ⁱ angle of 70.76 (6)° deviates significantly from 90° due to the formation of a five-membered chelate ring and long Mn—N bond distances (Table 2).

The bond distances and angles within the ligands are as expected. The aromatic rings of the tpht^2- and bpym ligands are perfectly planar due to symmetry constraints. The angle between their two least-squares planes is only 17.84 (7)°, whereas the angles between the aromatic tpht^2- ring and the carboxyl­ate groups are 27.10 (7)°. Thus, the whole chain is rather planar, not taking into account the two coordinated water molecules in apical positions. Also, the two aromatic rings of the tpht^2- ligands that bridge the Mn^II cations in a parallel fashion are perfectly coplanar.

In the structure of (I), there are only two hydrogen bonds of the inter­chain type. They are found between the coordinating water molecules and the noncoordinating carboxyl­ate O atoms (Fig. 2 and Table 3), and form centrosymmetric R₄²(8) rings [for graph-set notation, see Bernstein et al. (1995)]. Additional inter­actions between chains are face-to-face weak π–π contacts, as shown in Fig. 2.

The most inter­esting feature of (I) is the existence of a double tpht^2- bridge, which, together with the coordinated Mn^II cations, makes an 18-membered ring (Fig. 1). Although tpht^2- anions are typical bridging ligands and their bis-monodentate coordination mode is quite common, parallel double bridges are extremely rare; only one similar complex has been reported so far, a mixed-valence two-dimensional vanadium(IV,V) complex, [V₄O₄(OH)₂(tpht)₄].DMF (DMF is di­methyl­formamide), the structure of which was solved ab initio from synchrotron powder diffraction data (Djerdj et al., 2012). Even in that case the tpht^2- anions are tridentate, since one of the carboxyl­ate groups coordinates as a monobridge. Therefore, complex (I) can be considered as unprecedented.

Similar to (I), the structure of (II) should be presented as a trinuclear {[Cu₃(tpht)₂(OH)₂(bpym)(H₂O)₄].4H₂O}_n complex entity with tpht^2- anions coordinating via only one of their carboxyl­ate groups (Fig. 3). The entities further polymerize into chains parallel to the b-axis direction, due to the bridging role of the bpym ligand. These chains are inter­connected by hydrogen bonds involving all water molecules and bridging OH groups, as well as O atoms from uncoordinated tpht^2- carboxyl­ate groups, resulting in a three-dimensional framework of moderate-to-weak hydrogen bonds (Fig. 4 and Table 5). It is inter­esting that the O8 and O9 water molecules and their symmetry-related congeners make a small four-membered cluster located around the symmetry centre at (1/2, 1/2, 0).

The central atom Cu1 of (II) is on a special position (site symmetry 1) and is directly surrounded by two Cu2 atoms in general positions at distances of 3.0434 (3) Å. The intra­chain distance between two Cu2 atoms across the bpym ligand is longer [5.5452 (6) Å], while the shortest inter­chain Cu···Cu contacts vary between 6.7148 (5) and 7.5620 (5) Å. Both Cu^II cations are in an expected elongated pseudo-o­cta­hedral coordination, although Cu1 is surrounded by six O atoms and Cu2 is surrounded by four O and two N atoms. One aqua and one hydroxide ligand bridge two Cu^II cations, i.e. the Cu^II polyhedra share common edges (Fig. 5). In both o­cta­hedra, the water molecules are at the longest distances and define the apical positions. The angle between the equatorial planes of the polyhedra is 67.14 (5)°, so the polyhedra are strongly inclined towards each other. The Cu2—N bond lengths in (II) are much shorter than the Mn1—N bond lengths in (I). The N1—Cu1—N2 bond angle is closer to 90° (Table 4).

Cu^II complexes with different combinations of hydroxide (OH) and aqua (H₂O) bridges are quite common and the crystal structures of about 500 such complexes are present in the CSD. Structures with two hydroxide bridges are prevalent, whereas complexes with two aqua bridges are rare. In this way, binuclear complexes usually arise, although examples of more complicated polynuclear species with, for example, discrete Cu₁₅ clusters are also known (Fang et al., 2010). The microporous complex [Cu₃(dmtrz)₂(HCOO)(µ₂-O)(µ₃-OH)(H₂O)₃(µ₂-H₂O)].H₂O (where dmtrz is di­methyl­triazolate), simultaneously containing aqua, hydroxide and oxide (O^2-) species that triply bridge two symmetry-related Cu^II cations, was also described recently (Xia et al., 2013).

It is of inter­est that, in the cases of combined hydroxide and aqua bridges, additional carboxyl­ate anions are often present. In this way, Cu^II sites are actually triply bridged, with carboxyl­ate groups further supporting more common binuclear or less common polynuclear units, as in (II). One overview and a possible classification of binuclear five-coordinated Cu^II complexes has been published by Youngme et al. (2008). Many of these compounds contain the already mentioned dpya, phen and bipy as N,N'-chelating ligands (Wu et al., 1992; Chailuecha et al., 2006; Chen et al., 2008; Youngme et al., 2008; Li et al., 2009; Wannarit et al., 2013). Six-coordinated complexes of this type are also known (Elliot et al., 1998; Xiao et al., 2008) but are not so common. In all cases, the Cu···Cu distances range between about 2.9 and 3.4 Å, suggesting the presence of moderate magnetic inter­actions between Cu^II cations.

The situation where only one of the tpht^2- carboxyl­ate groups coordinates is quite uncommon. Among about 800 first-row transition metal tpht^2- complexes found in the CSD, there are only 13 (less than 2%) similar examples. Only one Cu^II complex, namely {[Cu₂(tpht)₂(H₂O)₄].2H₂O}_n (Deakin et al., 1999), with tpht^2- anions as endo-bridges, together with two additional bridging water molecules, has been described so far. In this complex, the Cu···Cu distances are 3.1520 (7) Å and a moderate anti­ferromagnetic coupling (J/k_B = -9.1 K) typical for chains was found.

In summary, introducing bpym instead of dpya, bipy or phen as terminal ligands, in combination with tpht^2- anions, results in chain complexes with alternating bpym and tpht^2- ligands and quite unusual architectures, especially regarding the coordination of the tpht^2- anions.

Computing details

For both compounds, data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SIR2011 (Burla et al., 2012); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015) and WinGX (Farrugia, 2012); molecular graphics: Mercury (Macrae et al., 2008), ORTEP-3 for Windows (Farrugia, 2012) and ATOMS (Dowty, 2006); software used to prepare material for publication: publCIF (Westrip, 2010), PLATON (Spek, 2009) and PARST (Nardelli, 1995).

Figures

	Fig. 1. The binuclear complex entity of (I), showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) -x + 2, y, -z; (ii) x, -y, z; (iii) -x + 2, -y + 1, -z; (iv) x, -y + 1, z; (v) -x + 2, -y, -z.]
	Fig. 2. (a) A projection of the structure of (I) onto the ab plane, with hydrogen bonds shown as dotted lines. (b) A projection of the structure of (I) onto the ac plane, showing the π–π interactions (dotted lines) and the centroid-to-centroid distances (in ångström). Cg1 denotes the centroids of the pyrimidine rings and Cg2 those of the tpht aromatic rings.
	Fig. 3. The trinuclear complex entity of (II), showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) -x, -y, -z + 1; (ii) -x, -y + 1, -z + 1; (iii) x, y + 1, z.]
	Fig. 4. A projection of the structure of (II) onto the ab plane, with hydrogen bonds shown as dotted lines.
	Fig. 5. A polyhedral representation of the trinuclear core of (II), showing the mutual orientation of the distorted Cu^II octahedra. For the sake of clarity, only Cu^II atoms are labelled. [Symmetry code: (i) -x, -y, -z + 1.]

(I) catena-Poly[[diaquamanganese(II)]-µ-2,2'-bipyrimidine-κ⁴N¹,N^1':N³,N^3'-[diaquamanganese(II)]-bis(µ-terephthalato-κ²O¹:O⁴)],

Crystal data

[Mn2(C8H4O4)2(C8H6N4)(H2O)4]	F(000) = 680
Mr = 668.34	Dx = 1.696 Mg m^−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
a = 14.4270 (3) Å	Cell parameters from 7117 reflections
b = 15.6350 (3) Å	θ = 4.1–28.7°
c = 6.4420 (1) Å	µ = 1.04 mm^−1
β = 115.789 (2)°	T = 294 K
V = 1308.37 (5) Å^3	Prism, yellow
Z = 2	0.44 × 0.32 × 0.12 mm

Data collection

Oxford Gemini S diffractometer with Sapphire3 CCD area detector	1333 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1284 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
Detector resolution: 16.3280 pixels mm^-1	θmax = 26.0°, θmin = 4.1°
ω scans	h = −17→17
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −19→19
Tmin = 0.756, Tmax = 1.000	l = −7→7
12759 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.024	Hydrogen site location: mixed
wR(F^2) = 0.066	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0385P)^2 + 0.9699P] where P = (Fo^2 + 2Fc^2)/3
1333 reflections	(Δ/σ)max = 0.001
107 parameters	Δρmax = 0.30 e Å^−3
2 restraints	Δρmin = −0.23 e Å^−3

Special details

Experimental. CrysAlis PRO (Agilent Technologies, 2014) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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.

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

	x	y	z	Uiso*/Ueq
Mn1	1.0000	0.19733 (2)	0.0000	0.03014 (13)
O1	0.93763 (11)	0.28058 (9)	0.1567 (3)	0.0567 (4)
O2	0.82353 (9)	0.27461 (7)	0.3003 (2)	0.0420 (3)
O3	0.85749 (10)	0.18562 (9)	−0.3125 (2)	0.0451 (3)
H3A	0.8528 (18)	0.2172 (14)	−0.415 (3)	0.066 (7)*
H3B	0.8046 (14)	0.1948 (13)	−0.303 (4)	0.058 (7)*
N1	0.94283 (9)	0.07584 (7)	0.1191 (2)	0.0287 (3)
C1	0.87734 (12)	0.31443 (9)	0.2247 (3)	0.0338 (3)
C2	0.87117 (11)	0.41076 (9)	0.2154 (2)	0.0309 (3)
C3	0.89433 (12)	0.45565 (10)	0.0583 (3)	0.0366 (3)
H3	0.9100	0.4261	−0.0477	0.044*
C4	0.84600 (12)	0.45565 (10)	0.3696 (3)	0.0372 (4)
H4	0.8290	0.4261	0.4736	0.045*
C5	0.88655 (12)	0.07539 (9)	0.2396 (3)	0.0336 (3)
H5	0.8665	0.1271	0.2789	0.040*
C6	0.96834 (14)	0.0000	0.0666 (3)	0.0239 (4)
C7	0.85806 (17)	0.0000	0.3059 (4)	0.0357 (5)
H7	0.8207	0.0000	0.3927	0.043*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.03450 (19)	0.02257 (18)	0.0454 (2)	0.000	0.02865 (15)	0.000
O1	0.0626 (8)	0.0420 (7)	0.0905 (10)	0.0065 (6)	0.0565 (8)	−0.0119 (7)
O2	0.0480 (6)	0.0314 (6)	0.0587 (7)	0.0062 (5)	0.0345 (6)	0.0074 (5)
O3	0.0370 (6)	0.0558 (8)	0.0500 (7)	0.0069 (5)	0.0258 (5)	0.0148 (6)
N1	0.0334 (6)	0.0243 (6)	0.0367 (6)	0.0007 (5)	0.0229 (5)	−0.0005 (5)
C1	0.0345 (8)	0.0321 (8)	0.0406 (8)	0.0046 (6)	0.0219 (6)	−0.0029 (6)
C2	0.0303 (7)	0.0313 (7)	0.0377 (7)	0.0019 (6)	0.0210 (6)	−0.0016 (6)
C3	0.0423 (8)	0.0416 (8)	0.0385 (7)	0.0006 (7)	0.0293 (7)	−0.0039 (6)
C4	0.0536 (9)	0.0313 (8)	0.0441 (8)	0.0010 (7)	0.0376 (8)	0.0027 (6)
C5	0.0409 (8)	0.0277 (7)	0.0441 (8)	0.0019 (6)	0.0296 (7)	−0.0035 (6)
C6	0.0244 (9)	0.0239 (9)	0.0270 (9)	0.000	0.0144 (7)	0.000
C7	0.0405 (11)	0.0361 (11)	0.0443 (11)	0.000	0.0314 (10)	0.000

Geometric parameters (Å, º)

Mn1—O1	2.0770 (12)	C2—C3	1.387 (2)
Mn1—O1^i	2.0770 (12)	C2—C4	1.388 (2)
Mn1—O3	2.1709 (13)	C3—C3^ii	1.387 (3)
Mn1—O3^i	2.1709 (13)	C3—H3	0.9300
Mn1—N1	2.3298 (11)	C4—C4^ii	1.387 (3)
Mn1—N1^i	2.3298 (12)	C4—H4	0.9300
O1—C1	1.2487 (19)	C5—C7	1.3761 (18)
O2—C1	1.2478 (19)	C5—H5	0.9300
O3—H3A	0.806 (16)	C6—N1^iii	1.3283 (14)
O3—H3B	0.806 (16)	C6—C6^iv	1.501 (3)
N1—C6	1.3284 (14)	C7—C5^iii	1.3761 (18)
N1—C5	1.3452 (17)	C7—H7	0.9300
C1—C2	1.508 (2)
O1—Mn1—O1^i	102.39 (8)	O2—C1—O1	124.89 (15)
O1—Mn1—O3	93.90 (6)	O2—C1—C2	118.52 (13)
O1^i—Mn1—O3	92.16 (6)	O1—C1—C2	116.58 (14)
O1—Mn1—O3^i	92.16 (6)	C3—C2—C4	119.20 (14)
O1^i—Mn1—O3^i	93.90 (6)	C3—C2—C1	120.36 (13)
O3—Mn1—O3^i	170.32 (7)	C4—C2—C1	120.40 (13)
O1—Mn1—N1	93.47 (5)	C2—C3—C3^ii	120.41 (9)
O1^i—Mn1—N1	164.02 (5)	C2—C3—H3	119.8
O3—Mn1—N1	84.75 (4)	C3^ii—C3—H3	119.8
O3^i—Mn1—N1	87.36 (5)	C4^ii—C4—C2	120.38 (9)
O1—Mn1—N1^i	164.02 (5)	C4^ii—C4—H4	119.8
O1^i—Mn1—N1^i	93.47 (5)	C2—C4—H4	119.8
O3—Mn1—N1^i	87.36 (5)	N1—C5—C7	121.35 (13)
O3^i—Mn1—N1^i	84.75 (4)	N1—C5—H5	119.3
N1—Mn1—N1^i	70.76 (6)	C7—C5—H5	119.3
Mn1—O3—H3A	114.7 (17)	N1^iii—C6—N1	126.42 (16)
Mn1—O3—H3B	117.4 (16)	N1^iii—C6—C6^iv	116.79 (8)
H3A—O3—H3B	102 (2)	N1—C6—C6^iv	116.79 (8)
C6—N1—C5	116.49 (12)	C5—C7—C5^iii	117.88 (18)
C6—N1—Mn1	117.83 (9)	C5—C7—H7	121.1
C5—N1—Mn1	125.68 (9)	C5^iii—C7—H7	121.1

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O2^v	0.81 (2)	1.91 (2)	2.708 (2)	168 (2)
O3—H3B···O2^vi	0.81 (2)	1.92 (2)	2.719 (2)	174 (2)

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

(II) catena-Poly[[[aquacopper(II)]-µ-aqua-µ-hydroxido-µ-terephthalato-κ²O¹:O^1'-copper(II)-µ-aqua-µ-hydroxido-µ-terephthalato-κ²O¹:O^1'-[aquacopper(II)]-µ-2,2'-bipyrimidine-κ⁴N¹,N^1':N³,N^3'] tetrahydrate]

Crystal data

[Cu3(C8H4O4)2(OH)2(C8H6N4)(H2O)4]·4H2O	Z = 1
Mr = 855.15	F(000) = 435
Triclinic, P1	Dx = 1.844 Mg m^−3
a = 6.7148 (2) Å	Cu Kα radiation, λ = 1.54178 Å
b = 10.7900 (3) Å	Cell parameters from 4736 reflections
c = 11.7620 (5) Å	θ = 4.9–72.5°
α = 69.565 (3)°	µ = 3.21 mm^−1
β = 75.167 (3)°	T = 295 K
γ = 81.404 (3)°	Rod, translucent green
V = 770.25 (5) Å^3	0.63 × 0.23 × 0.12 mm

Data collection

Oxford Gemini S CCD area-detector diffractometer	3036 independent reflections
Radiation source: Enhance (Cu) X-ray source	2885 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
Detector resolution: 16.3280 pixels mm^-1	θmax = 72.1°, θmin = 4.4°
ω scans	h = −8→8
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −13→9
Tmin = 0.487, Tmax = 1.000	l = −14→14
8206 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.030	Hydrogen site location: mixed
wR(F^2) = 0.086	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0468P)^2 + 0.7262P] where P = (Fo^2 + 2Fc^2)/3
3036 reflections	(Δ/σ)max < 0.001
249 parameters	Δρmax = 0.61 e Å^−3
9 restraints	Δρmin = −0.36 e Å^−3

Special details

Experimental. CrysAlis PRO (Agilent Technologies, 2014) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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.

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

	x	y	z	Uiso*/Ueq
Cu1	0.0000	0.0000	0.5000	0.02179 (13)
Cu2	−0.06720 (5)	0.30070 (3)	0.41875 (3)	0.02385 (11)
O1	0.0838 (3)	0.05372 (15)	0.31075 (13)	0.0294 (3)
O2	0.0370 (3)	0.27565 (15)	0.25681 (13)	0.0298 (3)
O3	0.3524 (3)	0.33471 (17)	−0.36946 (15)	0.0373 (4)
O4	0.4082 (3)	0.11759 (17)	−0.32075 (15)	0.0386 (4)
O5	0.2310 (3)	0.16542 (18)	0.47498 (16)	0.0323 (4)
H5A	0.327 (3)	0.167 (3)	0.413 (2)	0.031 (7)*
H5B	0.273 (5)	0.156 (3)	0.537 (2)	0.043 (9)*
O6	−0.3930 (3)	0.41295 (18)	0.38533 (18)	0.0395 (4)
H6A	−0.391 (5)	0.4912 (19)	0.379 (3)	0.037 (8)*
H6B	−0.473 (4)	0.377 (3)	0.451 (2)	0.050 (9)*
O7	−0.2095 (2)	0.14152 (14)	0.48389 (14)	0.0230 (3)
H7A	−0.304 (3)	0.132 (3)	0.539 (2)	0.027 (7)*
O8	0.5818 (3)	0.1520 (2)	0.2934 (2)	0.0430 (4)
H8A	0.588 (6)	0.074 (2)	0.297 (4)	0.065*
H8B	0.655 (5)	0.151 (4)	0.341 (3)	0.065*
O9	0.6362 (6)	0.3844 (4)	0.0706 (3)	0.1041 (11)
H9A	0.5926	0.3230	0.1357	0.156*
H9B	0.7713	0.3779	0.0530	0.156*
N1	0.1136 (3)	0.65456 (18)	0.41706 (17)	0.0241 (4)
N2	0.0682 (3)	0.47817 (18)	0.35082 (17)	0.0255 (4)
C1	0.0862 (3)	0.1677 (2)	0.23341 (19)	0.0244 (4)
C2	0.1563 (3)	0.1811 (2)	0.09742 (19)	0.0258 (4)
C3	0.1813 (4)	0.3044 (2)	0.0080 (2)	0.0364 (6)
H3	0.1538	0.3798	0.0320	0.044*
C4	0.2467 (4)	0.3172 (2)	−0.1164 (2)	0.0363 (6)
H4	0.2648	0.4010	−0.1752	0.044*
C5	0.2856 (3)	0.2065 (2)	−0.15496 (19)	0.0247 (4)
C6	0.2580 (6)	0.0838 (3)	−0.0660 (2)	0.0535 (9)
H6	0.2829	0.0084	−0.0900	0.064*
C7	0.1935 (7)	0.0712 (3)	0.0589 (2)	0.0599 (10)
H7	0.1750	−0.0126	0.1177	0.072*
C8	0.3532 (3)	0.2209 (2)	−0.29157 (19)	0.0255 (4)
C9	0.0503 (3)	0.5366 (2)	0.43620 (19)	0.0219 (4)
C10	0.1958 (4)	0.7240 (2)	0.2994 (2)	0.0293 (5)
H10	0.2371	0.8086	0.2813	0.035*
C11	0.2204 (4)	0.6720 (2)	0.2043 (2)	0.0351 (5)
H11	0.2782	0.7203	0.1226	0.042*
C12	0.1570 (4)	0.5466 (2)	0.2339 (2)	0.0326 (5)
H12	0.1762	0.5088	0.1716	0.039*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0326 (2)	0.0164 (2)	0.0148 (2)	−0.00029 (16)	−0.00166 (17)	−0.00615 (16)
Cu2	0.0381 (2)	0.01706 (17)	0.01669 (17)	−0.00609 (13)	0.00014 (13)	−0.00857 (12)
O1	0.0470 (9)	0.0234 (8)	0.0153 (7)	−0.0006 (7)	−0.0019 (6)	−0.0074 (6)
O2	0.0490 (9)	0.0231 (8)	0.0166 (7)	−0.0057 (7)	0.0007 (6)	−0.0099 (6)
O3	0.0601 (11)	0.0290 (9)	0.0191 (8)	−0.0053 (8)	−0.0018 (7)	−0.0072 (7)
O4	0.0627 (12)	0.0302 (9)	0.0217 (8)	−0.0002 (8)	−0.0009 (8)	−0.0141 (7)
O5	0.0356 (9)	0.0392 (9)	0.0258 (8)	−0.0017 (7)	−0.0059 (7)	−0.0162 (7)
O6	0.0509 (11)	0.0263 (9)	0.0346 (10)	−0.0017 (8)	0.0007 (8)	−0.0094 (8)
O7	0.0299 (8)	0.0179 (7)	0.0194 (7)	−0.0031 (6)	0.0009 (6)	−0.0076 (6)
O8	0.0484 (11)	0.0384 (10)	0.0464 (11)	−0.0033 (8)	−0.0099 (9)	−0.0190 (9)
O9	0.100 (2)	0.087 (2)	0.098 (2)	−0.0194 (19)	−0.020 (2)	0.0080 (19)
N1	0.0307 (9)	0.0192 (8)	0.0227 (9)	−0.0030 (7)	−0.0040 (7)	−0.0079 (7)
N2	0.0344 (9)	0.0212 (9)	0.0218 (9)	−0.0029 (7)	−0.0017 (7)	−0.0109 (7)
C1	0.0310 (10)	0.0250 (11)	0.0183 (10)	−0.0027 (8)	−0.0024 (8)	−0.0101 (8)
C2	0.0351 (11)	0.0250 (11)	0.0170 (10)	−0.0022 (8)	−0.0021 (8)	−0.0091 (8)
C3	0.0618 (16)	0.0234 (11)	0.0232 (11)	−0.0049 (11)	−0.0010 (11)	−0.0116 (9)
C4	0.0618 (16)	0.0247 (11)	0.0183 (10)	−0.0053 (11)	−0.0007 (10)	−0.0067 (9)
C5	0.0303 (10)	0.0268 (11)	0.0173 (10)	−0.0013 (8)	−0.0021 (8)	−0.0100 (8)
C6	0.110 (3)	0.0237 (12)	0.0220 (12)	0.0012 (14)	−0.0022 (14)	−0.0126 (10)
C7	0.130 (3)	0.0207 (12)	0.0182 (12)	−0.0009 (15)	−0.0011 (15)	−0.0051 (10)
C8	0.0302 (10)	0.0289 (11)	0.0183 (10)	−0.0037 (8)	−0.0014 (8)	−0.0107 (9)
C9	0.0282 (10)	0.0177 (9)	0.0211 (10)	−0.0014 (8)	−0.0033 (8)	−0.0094 (8)
C10	0.0386 (12)	0.0233 (11)	0.0247 (11)	−0.0095 (9)	−0.0043 (9)	−0.0050 (9)
C11	0.0469 (14)	0.0331 (13)	0.0223 (11)	−0.0129 (10)	−0.0010 (10)	−0.0059 (9)
C12	0.0467 (13)	0.0314 (12)	0.0207 (10)	−0.0075 (10)	−0.0007 (9)	−0.0125 (9)

Geometric parameters (Å, º)

Cu1—O7	1.9076 (15)	O9—H9A	0.836
Cu1—O7^i	1.9076 (15)	O9—H9B	0.875
Cu1—O1^i	2.0402 (14)	N1—C9	1.328 (3)
Cu1—O1	2.0402 (14)	N1—C10	1.338 (3)
Cu1—O5^i	2.4301 (18)	N1—Cu2^ii	2.0875 (18)
Cu1—O5	2.4302 (18)	N2—C9	1.334 (3)
Cu1—Cu2^i	3.0433 (3)	N2—C12	1.340 (3)
Cu1—Cu2	3.0433 (3)	C1—C2	1.508 (3)
Cu2—O7	1.9096 (15)	C2—C7	1.379 (3)
Cu2—O2	1.9522 (15)	C2—C3	1.379 (3)
Cu2—N2	2.0521 (18)	C3—C4	1.380 (3)
Cu2—N1^ii	2.0875 (18)	C3—H3	0.9300
Cu2—O5	2.3891 (18)	C4—C5	1.387 (3)
Cu2—O6	2.392 (2)	C4—H4	0.9300
O1—C1	1.248 (3)	C5—C6	1.374 (3)
O2—C1	1.267 (3)	C5—C8	1.512 (3)
O3—C8	1.250 (3)	C6—C7	1.384 (4)
O4—C8	1.255 (3)	C6—H6	0.9300
O5—H5A	0.835 (17)	C7—H7	0.9300
O5—H5B	0.816 (18)	C9—C9^ii	1.465 (4)
O6—H6A	0.823 (18)	C10—C11	1.382 (3)
O6—H6B	0.825 (18)	C10—H10	0.9300
O7—H7A	0.770 (17)	C11—C12	1.379 (3)
O8—H8A	0.827 (19)	C11—H11	0.9300
O8—H8B	0.833 (19)	C12—H12	0.9300
O7—Cu1—O7^i	180.0	Cu2—O5—H5B	125 (2)
O7—Cu1—O1^i	91.05 (6)	Cu1—O5—H5B	115 (2)
O7^i—Cu1—O1^i	88.95 (6)	H5A—O5—H5B	112 (3)
O7—Cu1—O1	88.95 (6)	Cu2—O6—H6A	109 (2)
O7^i—Cu1—O1	91.05 (6)	Cu2—O6—H6B	103 (2)
O1^i—Cu1—O1	180.0	H6A—O6—H6B	108 (3)
O7—Cu1—O5^i	94.13 (6)	Cu1—O7—Cu2	105.74 (7)
O7^i—Cu1—O5^i	85.87 (6)	Cu1—O7—H7A	116 (2)
O1^i—Cu1—O5^i	84.51 (6)	Cu2—O7—H7A	121 (2)
O1—Cu1—O5^i	95.49 (6)	H8A—O8—H8B	104 (4)
O7—Cu1—O5	85.87 (6)	H9A—O9—H9B	109
O7^i—Cu1—O5	94.13 (6)	C9—N1—C10	116.64 (18)
O1^i—Cu1—O5	95.49 (6)	C9—N1—Cu2^ii	112.64 (14)
O1—Cu1—O5	84.51 (6)	C10—N1—Cu2^ii	130.72 (15)
O5^i—Cu1—O5	180.0	C9—N2—C12	116.34 (19)
O7—Cu1—Cu2^i	142.85 (5)	C9—N2—Cu2	113.73 (14)
O7^i—Cu1—Cu2^i	37.15 (5)	C12—N2—Cu2	129.75 (16)
O1^i—Cu1—Cu2^i	77.04 (4)	O1—C1—O2	126.72 (19)
O1—Cu1—Cu2^i	102.96 (4)	O1—C1—C2	117.84 (18)
O5^i—Cu1—Cu2^i	50.24 (4)	O2—C1—C2	115.43 (19)
O5—Cu1—Cu2^i	129.76 (4)	C7—C2—C3	118.3 (2)
O7—Cu1—Cu2	37.15 (5)	C7—C2—C1	121.1 (2)
O7^i—Cu1—Cu2	142.85 (5)	C3—C2—C1	120.60 (19)
O1^i—Cu1—Cu2	102.96 (4)	C2—C3—C4	120.8 (2)
O1—Cu1—Cu2	77.04 (4)	C2—C3—H3	119.6
O5^i—Cu1—Cu2	129.76 (4)	C4—C3—H3	119.6
O5—Cu1—Cu2	50.24 (4)	C3—C4—C5	120.8 (2)
Cu2^i—Cu1—Cu2	180.0	C3—C4—H4	119.6
O7—Cu2—O2	92.02 (7)	C5—C4—H4	119.6
O7—Cu2—N2	176.41 (7)	C6—C5—C4	118.3 (2)
O2—Cu2—N2	89.72 (7)	C6—C5—C8	120.9 (2)
O7—Cu2—N1^ii	98.71 (7)	C4—C5—C8	120.7 (2)
O2—Cu2—N1^ii	166.90 (7)	C5—C6—C7	120.7 (2)
N2—Cu2—N1^ii	80.00 (7)	C5—C6—H6	119.6
O7—Cu2—O5	87.00 (6)	C7—C6—H6	119.6
O2—Cu2—O5	85.67 (7)	C2—C7—C6	121.0 (2)
N2—Cu2—O5	96.26 (7)	C2—C7—H7	119.5
N1^ii—Cu2—O5	87.40 (6)	C6—C7—H7	119.5
O7—Cu2—O6	85.93 (7)	O3—C8—O4	123.4 (2)
O2—Cu2—O6	98.20 (7)	O3—C8—C5	118.45 (19)
N2—Cu2—O6	90.71 (7)	O4—C8—C5	118.1 (2)
N1^ii—Cu2—O6	90.09 (7)	N1—C9—N2	126.60 (19)
O5—Cu2—O6	172.05 (6)	N1—C9—C9^ii	116.8 (2)
O7—Cu2—Cu1	37.11 (5)	N2—C9—C9^ii	116.6 (2)
O2—Cu2—Cu1	79.98 (5)	N1—C10—C11	121.0 (2)
N2—Cu2—Cu1	146.43 (5)	N1—C10—H10	119.5
N1^ii—Cu2—Cu1	104.19 (5)	C11—C10—H10	119.5
O5—Cu2—Cu1	51.44 (4)	C12—C11—C10	118.1 (2)
O6—Cu2—Cu1	122.22 (5)	C12—C11—H11	120.9
C1—O1—Cu1	128.12 (14)	C10—C11—H11	120.9
C1—O2—Cu2	128.09 (14)	N2—C12—C11	121.2 (2)
Cu2—O5—Cu1	78.32 (5)	N2—C12—H12	119.4
Cu2—O5—H5A	112.4 (19)	C11—C12—H12	119.4
Cu1—O5—H5A	108.3 (19)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O8	0.83 (2)	1.95 (2)	2.770 (3)	169 (2)
O5—H5B···O4^iii	0.82 (3)	1.99 (3)	2.805 (3)	172 (3)
O6—H6A···O3^iv	0.82 (2)	1.90 (2)	2.714 (3)	173 (2)
O6—H6B···O3^v	0.82 (2)	2.06 (2)	2.857 (2)	161 (2)
O7—H7A···O4^v	0.77 (2)	2.18 (2)	2.950 (2)	174 (2)
O8—H8A···O4^vi	0.83 (3)	1.98 (2)	2.805 (3)	175 (3)
O8—H8B···O7^vii	0.83 (4)	2.07 (4)	2.895 (3)	170 (3)
O9—H9A···O8	0.84	2.10	2.913 (4)	162

Symmetry codes: (iii) x, y, z+1; (iv) −x, −y+1, −z; (v) x−1, y, z+1; (vi) −x+1, −y, −z; (vii) x+1, y, z.